WO2005030856A1 - Stabilization of photochromic systems - Google Patents

Stabilization of photochromic systems Download PDF

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Publication number
WO2005030856A1
WO2005030856A1 PCT/EP2004/052238 EP2004052238W WO2005030856A1 WO 2005030856 A1 WO2005030856 A1 WO 2005030856A1 EP 2004052238 W EP2004052238 W EP 2004052238W WO 2005030856 A1 WO2005030856 A1 WO 2005030856A1
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Prior art keywords
carbon atoms
alkyl
alkylene
substituted
group
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PCT/EP2004/052238
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French (fr)
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WO2005030856A8 (en
Inventor
Mara Destro
Dario Lazzari
Dirk Simon
Manuele Vitali
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Ciba Specialty Chemicals Holding Inc.
Ciba Specialty Chemicals S.P.A.
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Application filed by Ciba Specialty Chemicals Holding Inc., Ciba Specialty Chemicals S.P.A. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to CA2538031A priority Critical patent/CA2538031C/en
Priority to CN2004800282267A priority patent/CN1860167B/en
Priority to EP04787170A priority patent/EP1709114A1/en
Priority to US10/572,154 priority patent/US20070064195A1/en
Priority to AU2004275997A priority patent/AU2004275997B2/en
Priority to BRPI0414852-5A priority patent/BRPI0414852A/en
Priority to JP2006530247A priority patent/JP4764822B2/en
Priority to KR1020067005755A priority patent/KR101099452B1/en
Publication of WO2005030856A1 publication Critical patent/WO2005030856A1/en
Publication of WO2005030856A8 publication Critical patent/WO2005030856A8/en
Priority to US12/508,641 priority patent/US8262945B2/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • 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
    • 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
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • the present invention relates to light stabilized polymer compositions comprising a photochromic dye, to a process of improving the stability and/or colour fastness of a photochromic dye, and to the use of a certain stabilizer for improving the light fastness of photochromic dyes or compositions containing them.
  • Photochromic systems comprise molecules able to change the color due to a reversible transformation of a chemical species induced by daylight.
  • Typical photochromic systems employ naphtho- or benzopyrans (chromenes), spiropyrans, spirooxazines. These molecules have found several fields of application especially in plastics (e.g. ophthalmic lenses).
  • chromenes chromenes
  • spiropyrans spirooxazines
  • plastics e.g. ophthalmic lenses.
  • One of the most severe limitations to a large scale employment of such devices is due to the intrinsically poor long term stability, e.g. the photostability of both colorless and colored forms under conditions of more or less continuous irradiation with daylight.
  • WO 96/37576 notes some stabilization of these systems using certain light stabilizers.
  • US patent 5,770,115 pertains to compositions of a carrier photochromic naphthopyran material and a stabilizer system comprising a polyphenolic antioxidant, a ultraviolet light absorber and a hindered amine light stabilizer.
  • the stabilizer system is used to improve the fatigue resistance of the photochromic naphthopyran compounds.
  • the UV absorbers are selected from the family of hydroxyphenyltriazines; thus, present invention pertains to a composition comprising a) a polymeric material containing b) a photochromic dye and c) a stabilizer comprising a hydroxyphenyl triazine UV absorber (i) conforming to formula I, II, III, IV or V
  • Y is phenyl, naphthyl, or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or Y is Z ⁇ or Z 2 ;
  • X is ⁇ or Z 2 ;
  • R ⁇ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, halogen, -SR 3 , -SOR 3 or -SO 2 R 3 ; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, -R 4 , -OR 5 , -N(R 5 ) 2 , -CORs, -COORs, -OCOR5, -CN, -NO 2 , -SR 5 , -SOR5, -SO 2 R 5 or -P(O)(OR 5 ) 2 , morpholinyl, piperidinyl, 2,2,6,6-tetramethylpipehdinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof; or said alkyl or said cycloalkyl interrupted by
  • R 3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to
  • R 4 is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms;
  • R 5 is defined as is R 4 ; or R 5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R is a group for formula
  • T is hydrogen, oxyl, hydroxyl, -OT ⁇ alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;
  • T T is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms or aryl of 6 o 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;
  • R 6 is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, -R 7 COOH or -NH-R 8 -NCO;
  • R 7 is alkylene of 2 to 14 carbon atoms or phenylene
  • R 8 is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group
  • Ri and R ⁇ are the same or different and are as defined for R ⁇
  • R 2 and R 2 " are the same or different and are as defined for R 2 ;
  • t 0 to 9;
  • L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene; or L is benzylidene; or L is -S-, -S-S-, -S-E-S-, -SO-, -SO 2 -, -SO-E-SO-, -SO 2 -E-SO 2 -, -CH 2 -NH-E- NH-CH 2 - or
  • E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by cycloalkylene of 5 to 12 carbon atoms;
  • n 2, 3 or 4;
  • Q is straight or branched alkylene of 2 to 16 carbon atoms; or said alkylene substituted by one to three hydroxy groups; or said alkylene interrupted by one to three
  • -CH CH- or -O-; or said alkylene both substituted and interrupted by combinations of the groups mentioned above; or Q is xylylene or a group -CONH-R 8 -NHCO-, -CH 2 CH(OH)CH 2 O- R 9 -OCH 2 CH(OH)CH 2 -, -CO-R 1 0-CO-, or -(CH ⁇ -COO-Rn-OOC- CHz)TM-, where m is 1 to 3; or Q is
  • R 9 is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by one to ten -O-, phenylene or a group -phenylene-G-phenylene in which G is -O-, -S-, -SO 2 -, -CH 2 - or -C(CH 3 ) 2 -;
  • Q is a group -[(CH 2 ) m COO] 3 -R ⁇ 2 where m is 1 to 3, and R 12 is an alkanetriyl of 3 to 12 carbon atoms;
  • Q is a group -[(CH 2 ) m COO] 4 -R ⁇ 3 where m is 1 to 3, and R M is an alkanetetrayl of 4 to 12 carbon atoms;
  • Zi is a group of formula
  • Z 2 is a group of formula
  • R 2 o, R21. R ⁇ and R 23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl; or R ⁇ 7 and R ⁇ 8 or R ⁇ and R 23 together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three -O- or -NR 5 -.
  • X and Y are 7. or Z 2 ;
  • Ri is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or halogen;
  • R 2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said cycloalkyl substituted by one to three -R 4 , -OR 5 , -COOR 5 , -OCOR 5 or combinations thereof; or said alkyl or cycloalkyl interrupted by one to three epoxy, -O-, -COO-, -OCO- or -CO-;
  • R is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;
  • R 5 is defined as is R ; or R is also hydrogen or straight or branched chain alkyl of 1 to
  • Z 1 is a group of formula
  • Z 2 is a group of formula
  • R ⁇ 4 , Ri5- Ri6. Ri7, Ri8, i9 > R 2 o, R21 , R_2 and R 23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, or alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl.
  • R 28 is (CH 2 -CH 2 -O-) n -R 29 ; -CH 2 -CH(OH)-CH 2 -O-R 29 ; or -CH(R 3 o)-CO-O-R 40 ; n is 0 or 1 ; R 29 is C C ⁇ 3 alkyl or C 2 -C 20 alkenyl or C 6 -C ⁇ 2 aryl or CO-C C ⁇ 8 alkyl; R 30 is H or C C 8 alkyl; R 0 is d- C 12 alkyl or C 2 -C 12 alkenyl or C 5 -C 6 cycloalkyl.
  • hydroxyphenyltriazines (i) is the compound (a) a) 2-(2-hydroxy-4-[2-ethylhexyl]oxyphenyl)-4,6-di(4-phenylphenyl)-1 ,3,5-triazine,
  • Hydroxyphenyl triazine UV absorber are described e.g. in GB-A-975966, EP-A-434608, US- 4619956, US-5298067, EP-A-530135, EP-A-520938, EP-A-531258, US-5556973, US- 5959008, US-6184375, US-6117997; for example in US-5998116, US-6255483, US- 6060543.
  • compositions wherein the hydroxyphenyl triazine UV absorber (i) is an oligo- or polyester of formula (100)
  • x 2 is a number from 1 to 50;
  • a 1 is a group of the formula (101 )
  • Di is C -C ⁇ 2 alkylene or said alkylene substituted by OH or interrupted by O or both substituted by OH and interrupted by O;
  • Li is d-C 18 alkylene; C 5 -C ⁇ 2 cycloalkylene; C 3 -C ⁇ 8 alkenylene; or one of said residues substituted by phenyl, C 7 -Cnalkylphenyl, C 5 -C ⁇ 2 cycloalkyl, OH, halogen, d-C ⁇ 8 alkoxy, C 5 - C 12 cycloalkoxy, C 3 -C ⁇ 8 alkenyloxy, COOH; the R 50 are independently of each other H, OR54 or OH, with the proviso that at least one of the R ⁇ 4 are independently of each other hydrogen, C C ⁇ 2 alkyl or a radical of formula
  • Rs 5 is H, d-C ⁇ 8 alkyl, C 2 -C 12 hydroxyalkyl;
  • R 51 is hydrogen, d-C alkyl, Cl, phenyl or a group -OR ⁇ ;
  • R 52 is hydrogen or methyl;
  • R ⁇ is hydrogen, methyl, OH or OR ⁇
  • T10 is the divalent acyl residue of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms; and which contains at least one moiety of formula (101) and at least one moiety T 10 .
  • ⁇ is d-C alkylene, especially C 2 -C alkylidene or methylene.
  • Di is advantageously C -C ⁇ 2 alkylene or C 4 -C 10 alkylene interrupted by O.
  • T 10 as the divalent acyl residue of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms includes, for example, aliphatic diacyls wherein the 2 carbonyl groups are interconnected by Cn-dsalkylene or -alkenylene or alkylene interrupted by cycloalkylene or cycloalkenylene, each of which is unsubstituted or substituted by alkyl, and containing 11 to 58 carbon atoms in total, preferably 20 to 50 carbon atoms.
  • Alkylene or alkenylene may be branched or unbranched, or, preferably not adjacent to an ethylenic double bond, interrupted by oxygen.
  • T10 is -CO-T ⁇ 0 '-CO-, wherein T 10 ' is C 20 -C 5 oalkylene or do-Csoalkylene interrupted by one or more oxygen atoms; especially preferred is unbranched do-doalkylene.
  • T10 is -CO-T ⁇ 0 '-CO-, wherein T 10 ' is alkylene interrupted by C 5 -C ⁇ 2 cycloalkylene or C 5 -C 12 cycloalkenylene or said cycloalkylene or cycloalkenylene substituted by alkyl and containing 11 to 58 carbon atoms, especially 20-50 carbon atoms, in total; especially preferred cycloalkylene is cyclohexylene; especially preferred cycloalkenylene is cyclohexenylene.
  • Valuable spacer groups T 10 ' are, for example, of the formula 102
  • R 5 6 is -(C b H 2b )- and R 5 7 is -(C c H 2c )- and R ⁇ ⁇
  • R 59 and R 60 are -(C d H 2d )-H, -(C e H 2e )-H, and -(C f H ⁇ -H, respectively, where bi is from the range 0 - 7, and each of the indices b - f is from the range 0 - 20, with the condition that the sum bi + b + c + d + e + f is from the range 15 - 45,
  • R 6 ⁇ and R 62 each are d-C 18 alkylene and each of R 63 , R ⁇ 4 , Res and R ⁇ , independently, are H or C ⁇ -C ⁇ 8 alkyl, and R 6 s and Ree together may also be a chemical bond, with the condition that the total number of carbon atoms in formula 103 ranges from 20 to 50.
  • spacer groups T 10 ' of the formula 103 wherein R 6 ⁇ and R 62 independently are alkylene of 4 - 12 carbon atoms, each of RQ 3 and R6 4 , independently, are C 4 -C 12 alkyl, while Res and R ⁇ are hydrogen.
  • the RSQ are OH; the Rs-j are hydrogen or methyl;
  • R 51 is hydrogen, methyl or a group -OR 5 ;
  • R 52 is hydrogen
  • R 53 is hydrogen, OH or methyl.
  • Terminal groups of the oligomer or polymer of formula (100) usually are
  • ester of formula (100) may conform to the formula (104)
  • x 2 is a number from 1 to 20; the number y is at least 1 and ranges from (x 2 + z - 1 ) to (x 2 + z + 1 ); z is a number from 1 to 20; and
  • Res is hydrogen, C ⁇ -C 12 alkyl; C 5 -d 2 cycloalkyl; C 2 -C 12 alkenyl; phenyl; C 7 -Cnalkylphenyl; C C 12 alkyl substituted by phenyl, OH, halogen; C ⁇ -C ⁇ 8 alkoxy, C 5 -C 12 cycloalkoxy, C 3 - C ⁇ 8 alkenyloxy or COOH; especially hydrogen or C ⁇ -C 4 alkyl; R 67 is hydrogen or d-C 8 alkyl; R 69 is hydrogen or d-C alkyl;
  • Di is C -C 8 alkylene or C 4 -C 10 alkylene interrupted by O; and T 10 ' is C 20 -C 5 oalkylene or C 20 - Csoalkylene interrupted by one or more oxygen atoms; and all other symbols are as defined for formula 100 above.
  • T10' may also be alkylene interrupted by C 5 -C ⁇ 2 cycloalkylene or said cycloalkylene, especially cyclohexylene, substituted by alkyl and containing 20-50 carbon atoms in total.
  • each of the divalent structural units identified by the indices x 2 and z bond to the structural unit -O-D identified by the index y, and/or to an end group R 6 7 or OR 67 .
  • x 2 is preferably from the range 2-50, more preferably from the range 2-20, especially 4-12; the number of triazine moieties of the formula 101 to diacid residues T 10 preferably ranges from about 1 : 3 to about 10:1 , more preferably from about 1 : 1 to about 5 : 1.
  • each of x 2 and z are preferably from the range 1 -16; more preferably, x 2 is from the range 1-10 and z is ranging from 2-12.
  • Oligomeric or polymeric esters of the invention such as those of formula 100 or 104 usually have a molecular weight within the range 1000 to 50000 g/mol, more preferably 1500 to 20000 g/mol, most preferably 2000 to 10000 g/mol (number average Mn as determined by gel permeation chromatography GPC).
  • Alkylphenyl is alkyl-substituted phenyl; C 7 -C 14 alkylphenyl embraces examples such as methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl, butylphenyl, dibutylphenyl, pentylphenyl, hexylphenyl, heptylphenyl and octylphenyl.
  • Phenylalkyl is phenyl-substituted alkyl;
  • C 7 -Cn phenylalkyl embraces examples such as benzyl, ⁇ -methylbenzyl, ⁇ -ethylbenzyl, ⁇ . ⁇ -dimethylbenzyl, phenylethyl, phenylpropyl, phenylbutyl and phenylpentyl.
  • Alkyl interrupted by O can generally comprise one or more nonadjacent oxygen atom(s).
  • a carbon atom of an alkylene chain such as D, or T 10 ' bonds to not more than 1 heteroatom.
  • the alkyl radicals are branched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1 -methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodec
  • Alkylene such as of -i or Di derives from such alkyls by abstraction of an hydrogen atom.
  • the alkenyl radicals include allyl, isopropenyl, 2- butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl; n-oct-2-enyl, n-dodec- 2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
  • the heavy chains of T 10 e.g. alkylene groups of T 10 ', may have a certain molecular distribution around their main component.
  • Ranges may be, for example, from 22-26, 28-32 or 34-38 C-atoms. It is however also possible that broader ranges are used such as for example from 20 to 40, from 30 to 50 or from 30 to 40 carbon atoms, each for T 10 ' in total.
  • the educts for preparing a compound of formula (100) or (104) are commercial products, they may vary within certain specifications. This is particularly the case for high molecular weight diacids from which the T 10 groups are derived, when T 10 is C 20 -C 6 oalkylene (which may be interrupted as described above).
  • diacids or diacid esters may also contain small amounts of chains below C 20 . Therefore mixtures of compounds wherein T ⁇ 0 is a mixture containing up to 10% of diacyl chains below 20 carbon atoms and 90 to 100% of diacyl chains between 20 and 60, particularly between 20 and 40 carbon atoms are also subject of the invention. Percentage is weight percent, based on the total mixture.
  • Present invention also pertains to an oligoester or polyester which is obtained by reacting a tris-aryl-triazine of the formula (105)
  • Hydroxyphenyl triazine UV absorber (i) of formula (100) - (105) may be prepared as described in the international patent application with application no. EP2004/050804.
  • hydroxyphenyl triazine UV absorber (i) of the formula I, II, III, IV or V Preferred further light stabilizers to be employed are sterically hindered amines (HALS), especially selected from oligomeric and monodispersed HALS, oligomeric HALS of the alkoxyamine class (NOR-HALS), and low basicity HALS like piperazinones (such as products described in WO 00/31069), morpholinones (see WO 99/14206), piperazinediones (see DE- A-19924984), and thioimidazolidinones (see WO 01/62739).
  • HALS sterically hindered amines
  • present invention specifically pertains to a composition
  • a composition comprising a) a polymeric material containing b) a photochromic dye and c) a stabilizer combination of i) a hydroxyphenyl triazine UV absorber and ii) at least one further light stabilizer selected from the sterically hindered amines (HALS).
  • HALS sterically hindered amines
  • compositions of the invention are useful for all applications wherein a photochromic effect is to be achieved. Some examples are described below:
  • Optical devices such as particular types of ophthalmic lenses, referred to as "photochromatic", where the beneficial neutralization of harmful UV solar radiation and the anti-glare effect are effective only when needed, allowing the use of the sunglasses with the photochromatic lenses also indoor.
  • Such lenses are often made of polyacrylates, cellulose esters, polyvinylalcohol, polyurethanes, polycarbonates, polyesters such as polyethyleneterephtala.es, polyvinylbutyrate, polystyrenes and related copolymers such as styrene-methacrylate or styrene-acrylonitrile.
  • the systems may further be applied in optical films as seen in WO 97/32225, and United States Patent Nos. 4,871 ,784 and 5,217,794 which are incorporated herein by reference.
  • the photochromic system can be present either in the plastic window or used in a film that is laminated onto or embedded in a glass or plastic window.
  • Typical materials used in these contexts are polyethyleneterephtalate, glycole modified polyethyleneterephtalate, polycarbonate, polymethylmethacrylate, polyvinylbutyral, and/or as described in WO 92/01557, Japanese Nos. 75-33286; 93- 143668; 95-3217 and 96-143831 , and United States Patent No. 5,643,676 which is incorporated herein by reference, for films and glazings; or as seen in Japanese Nos. 80-40018; 90-192118; 90-335037; 90-335038; 92-110128 and 94-127591 , and
  • greenhouse plastic covers can be additivated with photochromes, aiming at reducing light intensity inside the greenhouse, that eventually turns into heat, as excessive heat may be detrimental to some crops and/or inhibit growth.
  • Low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer (EVA) and ethylene-butyl acrylate copolymer and blends of the mentioned polymers are typical materials for plastic covers used in agriculture.
  • Photochromic coatings • Construction elements or articles containing photochromic parts for the purpose of labelling, signalling, decoration etc.
  • polymeric material of component a may be selected from polymers listed below:
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1 -ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a) radical polymerisation normally under high pressure and at elevated temperature.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
  • ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/ vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LDPE/
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block copo
  • 6b Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • 6c Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpoly
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
  • cyclic ethers such as polyalkylene glycols, polyethy- lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g.
  • polyethylene glycol polypropylene glycol or polytetramethylene glycol
  • polyamides or copolyamides modified with EPDM or ABS polyamides condensed during processing
  • RIM polyamide systems polyamides condensed during processing
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding iactones for example polyethylene terephthalate (PET), polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl- terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • PET polyethylene terephthalate
  • PAN polybutylene terephthalate
  • PAN poly-1 ,4-dimethylolcyclohexane terephthalate
  • PAN polyalkylene naphthalate
  • block copolyether esters derived from hydroxyl- terminated polyethers and also polyesters modified with polycarbonates or MBS.
  • PET polybutylene terephthalate
  • PEN polyethylenenaphthalenate
  • PTT polytrimethylene terephthalate
  • isophthalic acid di- ethylene glycol, 1 ,4-bis(hydroxymethyl)cyclohexane.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydhc alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
  • Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acry- lates, urethane acrylates or polyester acrylates.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, P
  • Polymeric material useable for the present invention is preferably synthetic organic polymeric material, for example, material commonly used for electronic applications.
  • Polyolefines such as polyethylene and polypropylene, polycarbonate, polyesters such as polyethylene terephthalate (PET) and its copolyesters; styrene polymers or copolymers such as polystyrene or high impact polystyrene (PS-HIPS); or the specific polymers mentioned above.
  • PET polyethylene terephthalate
  • PS-HIPS high impact polystyrene
  • the photochromic dye is usually selected from naphtho- and benzopyranes (chromenes), or from spiropyranes or spirooxazines; these components are commercial available.
  • Photochromic spiro-indolino-oxazine compounds useful in the invention have the general structural formula (I'):
  • Ri and R 2 each represent independently a C C 5 alkyl group, linear or branched; a phenyl group; or R and R 2 , together with the carbon atom to which they are connected, jointly represent a cycloalkyl(C 4 -C 7 )group, bicycloalkyl(C 6 -Cn)group, or tricycloalkyl(C 7 -C 13 )group;
  • R 3 represents a hydrogen atom; a d-C 5 alkyl group, linear or branched; a similar d-C 5 alkyl group substituted with from 1 to 5 halogen atoms chosen from fluorine, chlorine, bromine or iodine, hydroxy groups, d-C 5 alkoxy groups, C C 5 carboxy alkyl groups, cyano groups; a C 2 -C 5 alkenyl group; a phenyl group; or benzyl group;
  • R 4 to R 7 stand independently for a hydrogen atom; a C ⁇ -C 5 alkyl group, linear or branched; a similar d-C 5 alkyl group substituted with from 1 to 5 halogen atoms chosen from fluorine, chlorine, bromine or iodine, hydroxy groups, C ⁇ .C 5 alkoxy groups, d-C 5 carboxy alkyl groups, cyano groups; a C 2 -C 5 alkenyl group; a phenyl group; a benzyl group; a halogen atom chosen from either fluorine, chlorine, bromine or iodine; a hydroxy group; a C ⁇ -C 5 alkoxy group; an amino group; a monoalkyl(C ⁇ -C 5 )amino group; a dialkyl(C C 5 )amino group; a cyclo-alkyl(C 3 -C ⁇ 0 )amino group; a pipe
  • R 8 repesents a hydrogen atom; a linear or branched alkyl(d-C 5 )group; a phenyl group; a halogen atom chosen from either fluorine, chlorine, bromine; an alkoxy(C C 5 )group; or a phenoxy group;
  • A represents an arenic, monocyclic or polycyclic group, chosen from those that can be defined with formula (II'), (III'), (IV) or (V):
  • two contiguous points from R 9 to R ⁇ 2 represent the condensation position between the oxazinic nucleus in the general formula (I 1 ) and the other two groups and R ⁇ 3 -Ri6 have the same meaning as R -R 7 in the general formula (I'); or two contiguous groups together are alkylene of 3-6 carbon atoms, or a corresponding azaalkylene or oxaalkylene; or three contiguous groups jointly represent an alkane-triyl, i.e. 3-valent saturated hydrocarbon residue, of 4-8 carbon atoms, or a corresponding aza- or oxa-alkane-triyl.
  • one of the carbon atoms, along with bonding hydrogens, if present, are replaced by oxygen, nitrogen or NH.
  • Ri and R 2 each represent independently a methyl, ethyl, propyl or phenyl group, or together with the carbon atom to which they are connected, jointly represent a cyclohexyl group or a bi- or tricycloalkyl of 7-11 carbon atoms;
  • R 3 represents a methyl, ethyl, propyl, phenyl, benzyl, 2-allyl, 2-hydroxyethyl or 2-carboxy- methyl group
  • R 4 to R7 either the same or different, each stand independently for the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N-di- methylcarboxamide, cyano, nitro or phenyl group;
  • R 8 represents the hydrogen atom, the chlorine atom, methyl, phenyl, or methoxy group;
  • A is one of the groups with formula (IT), (III'), (IV) or (V) where:
  • R 9 to R 12 represent the condensation position between the oxazinic nucleus in the general formula (I') and the other two groups in addition to R I3 -R I ⁇ each represent independently the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, ethyl, propyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N-dimethylcarboxamide, cyano, nitro or phenyl group.
  • spiro-indolino-oxazine photochromic compounds useful in the present invention are: 1 ',3'-dihydro-5,7-dimethoxy-1 'n-propyl-3'ethyl-3',4',5'-(and 3',5',6')-trimethyl-spiro[2H-1 ,4- benzoxazine-2,2'-[2H]indole] (VI');
  • Naphthopyran photochromic compounds usually have the general structural formula (IX'):
  • Ri to Rn each stand independently for a hydrogen atom; a d-C alkyl group, linear or branched; a similar d-C 5 alkyl group substituted with from 1 to 5 halogen atoms chosen from fluorine, chlorine, bromine or iodine, hydroxy groups, C C 5 alkoxy groups, C C 5 carboxy alkyl groups, cyano groups; a C 2 -C 5 alkenyl group; a phenyl group; a benzyl group; a halogen atom chosen from either fluorine, chlorine, bromine or iodine; a hydroxy group; a d-C 5 alkoxy group; an amino group; a monoalkyl(d-C 5 )amino group; a dialkyl(d-C 5 )amino group; a cyclo-alkyl(C 3 -C 10 )amino group; a piperidine, piperazine or morpho
  • A represents an arenic polycyclic group, chosen from those that can be defined with formula (X'):
  • R 12 to R 15 represent the condensation position between the pyran nucleus in the general formula (IX 1 ) and the other two groups in addition to R 16 -R 19 have the same meaning as R 1 -R 11 in the general formula (IX').
  • Ri to Rn each stand independently for the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N- dimethylcarboxamide, cyano, nitro or phenyl group;
  • A is one of the groups with formula (X 1 ) where:
  • R 12 to R 15 represent the condensation position between the pyran nucleus in the general formula (IX') and the other two groups in addition to R 1 6-R19 each represent independently the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, ethyl, propyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N-dimethylcarboxamide, cyano, nitro or phenyl group.
  • naphtopyran photochromic compounds useful in the present invention are:
  • Preferred naphthopyranes also include those of the formulae
  • each of R 31 , R 32 , R ⁇ , R ⁇ , R 35 independently may be hydrogen, a hydrocarbon of 1 to 18 carbon atoms such as phenyl, naphthyl, alkyl, optionally substituted by OH, CrCealkoxy; NR'R"; -NO 2 ; where R' and R" independently are H or d-C ⁇ alkyl, C 4 -C 12 cycloalkyl, C 7 - C 13 phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene.
  • Benzopyranes another class of chromenes, include those of the formula
  • each of R 41 , R 42 , R 3 , R ⁇ , R 45 independently may be hydrogen, a hydrocarbon of 1 to 18 carbon atoms such as phenyl, naphthyl, alkyl, optionally substituted by OH, C C 6 alkoxy; NR'R"; -NO 2 ; where R' and R" independently are H or C ⁇ -C 12 alkyl, C 4 -C ⁇ 2 cycloalkyl, C 7 - C ⁇ 3 phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene.
  • a chromene may be selected from naphthopyrans of the formula
  • R is H; d-C 6 alkyl; C ⁇ -C 6 alkoxy; -NR'R"; -NO2; where R' and R" independently are H or d-C ⁇ 2 alkyl, C 4 -C ⁇ 2 cycloalkyl, C 7 -C ⁇ 3 phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene.
  • Chromenel as used in the examples below is of the above formula where each R is H.
  • Preferred sterically hindered amines (HALS) of component (ii) are those comprising at least one radical of the formula IX, X and/or XI
  • G is hydrogen or methyl
  • d and G 2 are hydrogen, methyl or together are oxygen.
  • ni is a number from 1 to 4
  • G and G ⁇ independently of one another, are hydrogen or methyl
  • Gn is hydrogen, O , hydroxyl, NO, -CH 2 CN, d-C 18 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 7 -C ⁇ 2 aralkyl, C C ⁇ 8 alkoxy, C 5 -C 12 cycloalkoxy, C 7 -d 5 phenylalkoxy, C C 8 alkanoyl, C 3 -C 5 alkenoyl, CrC ⁇ 8 alkanoyloxy, benzyloxy, glycidyl or a group -CH 2 CH(OH)-Z, where Z is hydrogen, methyl or phenyl; or Gn is d-C 18 alkoxy, C 5 -C 12 cycloalkoxy or C 7 -C 15 phenylalkoxy each of which is substituted in the aliphatic part by 1-3 OH groups; Gn preferably being d- C 12 alkoxy or cyclohexyloxy
  • G 12 if ni is 1 , is hydrogen, C C ⁇ 8 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, COO and/or CONH groups, or is cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an ⁇ , ⁇ -unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ 12 groups, in which Z 12 is
  • G 12 if ni is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZ ⁇ 2 , of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical, preferred radicals including triacyl radicals of nitrilo triacetic acid of benzene tricarboxylic acid, and G ⁇ 2 , if ni is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
  • the carboxylic acid radicals mentioned above are in each case taken to mean radicals of the formula (-CO) x R, where x is as defined above for ni, and the meaning of R arises from the definition given above.
  • Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • C ⁇ -C ⁇ 8 alkoxy Gn is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
  • C 5 -C ⁇ 2 cycloalkoxy G is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.
  • C 7 -C 9 phenylalkoxy is, for example, benzyloxy.
  • Gn as C ⁇ -C 18 alkoxy, C -d 2 cycloalkoxy or C 7 -C ⁇ 5 phenylalkoxy substituted in the aliphatic part by 1-3 OH groups is a radical formed by abstraction of an carbon-bonded hydrogen atom preferably from 2-methyl-2-propanol (tert.-butanol), 2-propanol, 2,2-dimethyl-1-propanol, 2- methyl-2-butanol, ethanol, 1 -propanol, 1-butanol, 1-pentanol, 1 -hexanol, 1 -nonanol, 1 - decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1 -hexanol, cyclo- hexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1 -ethanol
  • d 2 is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
  • d 2 is a monovalent silyl radical, it is, for example, a radical of the formula -(C j H 2j )-Si(Z') 2 Z", in which j is an integer in the range from 2 to 5, and Z' and Z", independently of one another, are d-C alkyl or d-C alkoxy.
  • d 2 is a divalent radical of a dicarboxylic acid, it is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl(3,5-di-tert-butyl ⁇ .-hydroxybenzyl)malonyl or bicycloheptenedicarbonyl radical or a group of the formula
  • G 12 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical.
  • G ⁇ 2 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1 ,2,3,4-tetracarboxylic acid or of pyromellitic acid.
  • d 2 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.
  • n 2 is the number 1 , 2 or 3, and G, Gi and Gn are as defined under (a'), d 3 is hydrogen, C C 12 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C ⁇ -C ⁇ 8 alkanoyl, C 3 -C 5 alkenoyl, benzoyl or a group of the formula
  • G ⁇ 4 if n 2 is 1 , is hydrogen, C ⁇ -C 18 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl, C ⁇ -C 4 alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group or group of the formula -CONH-Z, or G 14 is glycidyl, a group of the formula -CH 2 -CH(OH)-Z or of the formula -CONH- Z, in which Z is hydrogen, methyl or phenyl or CH 2 -OZ ⁇ with Z 14 being hydrogen or d- C 18 alkyl;
  • G ⁇ 4 if n 2 is 2, is C 2 -C ⁇ 2 alkylene, C 6 -C ⁇ 2 arylene, xylylene, a -CH 2 -CH(OH)-CH 2 group or a -CH 2 -CH(OH)-CH 2 -O-D-O- group, in which D is C 2 -C 10 alkylene, C 6 -C 15 arylene, C 6 -C 12 cycloalkylene, or, provided that d 3 is not alkanoyl, alkenoyl or benzoyl, G 1 can alternatively be 1-oxo-C 2 -C ⁇ 2 alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternatively the group -CO-, G 1 , if n 2 is 3, is a group
  • radicals G ⁇ 3 , d 4 and D are given below.
  • Any C 5 -C 7 cycloalkyl substituents are, in particular, cyclohexyl.
  • C 7 -C 8 aralkyl G 13 is, in particular, phenylethyl or especially benzyl.
  • C 2 -C 5 hydroxyalkyl G 13 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.
  • C -C 18 alkanoyl G ⁇ 3 is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and C 3 -C 5 alkenoyl d 3 is, in particular, acryloyl.
  • C 2 -C 8 alkenyl G 14 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
  • G 14 as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide -substituted C C alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
  • Any C 2 -C ⁇ 2 alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • Any C 6 -C ⁇ 5 arylene substituents are, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
  • C 6 -C 12 cycloalkylene is, in particular, cyclohexylene.
  • G M as 1 -oxo-C 2 -C ⁇ 2 alkylene is preferably a group
  • n 3 is the number 1 or 2
  • G, Gi and Gn are as defined under (a')
  • G 15 and G ' 15 if n 3 is 1 are independently d-C 12 alkyl, C 2 -C 12 alkenyl, C 7 -C ⁇ 2 aralkyl, or G 15 is also hydrogen, or G 15 and G ' ⁇ 5 together are C 2 -C 8 alkylene, C -C ⁇ 5 alkenylene, C 2 -C 8 hydroxyalkylene or C 4 - C ⁇ acyloxyalkylene, and if n 3 is 2, G 15 and G ' 15 together are the (-CH 2 ) 2 C(CH 2 -) 2 group.
  • G 15 and G ' ⁇ 5 is, for example, ethylene, 1 - methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
  • C 4 -C 22 acyloxyalkylene G 15 and G ' 15 is, for example, 2-ethyl-2-acetoxymethylpropylene.
  • n 4 is the number 1 or 2
  • G, d and Gn are as defined under (a')
  • G 16 is hydrogen, d-C 12 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl, and
  • G 17 if n 4 is 1 , is hydrogen, C ⁇ -C 12 alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C 2 -C hydroxyalkyl, C 2 -C 6 alkoxyalkyl, C 6 -C 10 aryl, glycidyl or a group of the formula
  • Ti and T 2 independently of one another, are hydrogen, d-C 18 alkyl or unsubstituted or halogen- or d-C 4 alkyl-substituted C 6 -C ⁇ 0 aryl or CrCgaralkyl, or
  • Any C ⁇ -C 12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Ci 8 alkyl substituents can be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • Any C 2 -C 6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
  • C 3 -C 5 alkenyl d 7 is, for example, 1 -propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
  • C 7 -C 9 aralkyl G 17 , T ⁇ and T 2 are, in particular, phenethyl or especially benzyl. If Ti and T 2 together with the carbon atom form a cycloalkane ring, this can be, for example, a cyclo- pentane, cyclohexane, cyclooctane or cyclododecane ring.
  • C 2 -C hydroxyalkyl G 17 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • C 6 -C ⁇ 0 aryl G 17 , T- ⁇ and T 2 are, in particular, phenyl or ⁇ - or ⁇ -naphthyl, which are unsubstituted or substituted by halogen or d-dalkyl.
  • C 2 -C 12 alkylene d 7 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • C -C 12 alkenylene G ⁇ 7 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.
  • C 6 -C 12 arylene G 17 is, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
  • C 2 -C 12 alkanoyl D" is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.
  • C 2 -C 10 alkylene, C 6 -C 15 arylene or C 6 -C ⁇ 2 cycloalkylene D' have, for example, one of the definitions given for D under (b').
  • n 5 is the number 1 or 2
  • d 8 is a group of the formula
  • E is -O- or -ND'"-
  • A is C 2 -C 6 alkylene or -(CH 2 ) 3 -O- and
  • Xi is the number 0 or 1 ,
  • D' is hydrogen, C C 12 alkyl, C 2 -C ⁇ 2 alkylene-N(D V ) 2 , C 2 -C 5 hydroxyalkyl or C 5 -C 7 cycloalkyl, where D v , independently, is hydrogen or butyl,
  • G 19 is identical to G ⁇ 8 or is one of the groups -N(G 21 )(G 22 ), -OG 23 , -N(H)(CH 2 OG 23 ) or -N(CH 2 OG 23 ) 2 ,
  • G 21 is hydrogen, C C ⁇ 2 alkyl, cyclohexyl, benzyl or C C -hydroxyalkyl or a group of the formula
  • G 22 is d-C ⁇ 2 alkyl, cyclohexyl, benzyl or C C 4 hydroxyalkyl
  • G 23 is hydrogen, d-C ⁇ 2 alkyl or phenyl
  • G 21 and G 22 together are C 4 -C 5 alkylene or C 4 -C 5 oxaalkylene, for example -CH 2 CH 2 -O-CH 2 CH 2 - , or a group of the formula -CH 2 CH 2 -N(Gn)-CH 2 CH 2 -.
  • Any C C ⁇ 2 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • Any C 5 -C 7 cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.
  • C 2 -C 6 alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
  • G 21 and G 22 together are C 4 -C 5 alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
  • Gn is as defined under (a').
  • Oligomeric or polymeric compounds whose recurring structural unit contains a 2,2,6,6- tetraalkylpiperidinyl radical, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof which contain such radicals.
  • 2,2, 6, 6-polyalkylpiperidine compounds from this class are the compounds of the following formulae, to m M is a number from 2 to about 200, preferably 2 to 100, for example 2 to 50, 2 to 40, 3 to 40 or 4 to 10.
  • end groups which saturate the free valences in the oligomeric or polymeric compounds listed below depend on the processes used for the preparation of said compounds.
  • the end groups can also in addition be modified after the synthesis of the compounds.
  • polymeric compounds examples are:
  • G 24 , G 25 , G 26 , G 27 and G 28 independently of one another, are a direct bond or d-C 10 alkylene, Gn is as defined under (a') and m 17 is a number from 1 to 50.
  • index rri ⁇ 8 ranges from 1 to 15;
  • R ⁇ 2 is C 2 -C 12 alkylene, C -C ⁇ 2 alkenylene, C 5 -C 7 cycloalkylene, C 5 -C 7 cycloalkylene- di(C ⁇ -C 4 alkylene), C ⁇ -C alkylenedi(C 5 -C 7 cycloalkylene), phenylenedi(C C 4 alkylene) or C 4 -C 12 alkylene interrupted by 1 ,4-piperazinediyl, -O- or >N-X- ⁇ with X 1 being d-C ⁇ 2 acyl or (d-C 12 alkoxy)carbonyl or having one of the definitions of R 14 given below except hydrogen; or R 12 is a group of the formula (2g ' ) or (2g");
  • X 2 being C C ⁇ 8 alkyl, C 5 -d 2 cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 d-C alkyl; phenyl which is unsubstituted or substituted by 1 , 2 or 3 d-C 4 alkyl or d-dalkoxy; C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 d-C alkyl; and the radicals X 3 being independently of one another C 2 -C 12 alkylene; the radicals A are independently of one another -OR ⁇ 3 , -N(R 1 )(R 15 ) or a group of the formula (2g"');
  • R ⁇ 3 , R M and R ⁇ 5 which are identical or different, are hydrogen, C C ⁇ 8 alkyl, C 5 -d 2 cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 d-C 4 alkyl; C 3 -C ⁇ 8 alkenyl, phenyl which is unsubstituted or substituted by 1 , 2 or 3 C C 4 alkyl or C C 4 alkoxy; C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 C ⁇ -C alkyl; tetrahydrofurfuryl or C 2 -C alkyl which is substituted in the 2, 3 or 4 position by -OH, d-C 8 alkoxy, di(d-C 4 alkyl)amino or a group of the formula (2g ⁇ v );
  • Y being -O-, -CH 2 -, -CH 2 CH 2 - or >N-CH 3 , or -N(R 14 )(R 15 ) is additionally a group of the formula (2g ⁇ v );
  • X is -O- or >N-R i6 ;
  • Ri 6 is hydrogen, C C ⁇ 8 alkyl, C 3 -C 18 alkenyl, C 5 -C ⁇ 2 cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 d-C 4 alkyl; C 7 -Cgphenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 C ⁇ -C 4 alkyl; tetrahydrofurfuryl, a group of the formula (2g v ),
  • Rn has one of the definitions given for R 16 ; and the radicals B have independently of one another one of the definitions given for A.
  • Gn is as defined under (a')
  • G 29 and G 32 independently of one another, are a direct bond or a -N(X 1 )-CO-X 2 -CO-N(X 3 )- group
  • X 3 independently of one another, are hydrogen, d-C 8 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or a group of the formula
  • G 30 , G 3 ⁇ , G ⁇ and G 35 independently of one another, are hydrogen, Ci-doalkyl, C 5 -C 12 cycloalkyl or phenyl, G is hydrogen, C Csoalkyl, C 5 -C 12 cycloalkyl, C 7 -Cgphenylalkyl, phenyl or a group of the formula (3g), and m ⁇ 9 is a number from 1 to 50.
  • the end group bonded to the 2,5-dioxopyrrolidine ring can be, for example, hydrogen
  • the end group bonded to the ⁇ (G M KG ⁇ )- radical can be, for example,
  • m' 20 , m" 20 and m'" 20 are a number from 2 to 12
  • G ⁇ is hydrogen, C C ⁇ 2 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -C 9 phenylalkyl
  • Gn is as defined under (a').
  • reaction product can be represented for example by a compound of the following 3 formulae. It can also be in the form of a mixture of these three compounds: 5) A compound of the formula (5g)
  • Gn is as defined under (a')
  • G 37 is d-C ⁇ 0 alkyl, C 5 -d 2 cycloalkyl, d-C alkyl- substituted C -C ⁇ 2 cycloalkyl, phenyl or d-doalkyl-substituted phenyl
  • G ⁇ is C 3 -C 10 alkylene and m 2 ⁇ is a number from 1 to 50.
  • the terminal group bonded to the silicon atom can be, for example, (G 37 ) 3 Si-O-, and the terminal group bonded to the oxygen can be, for example, - Si(G 37 ) 3 .
  • the compounds of the formula (5g) can also be in the form of cyclic compounds if m 2 ⁇ is a number from 3 to 10, i.e. the free valences shown in the structural formula then form a direct bond.
  • T 3 is ethylene or 1 ,2-propylene, is the repeating structural unit derived from an alpha-olefin copolymer with an alkyl acrylate or methacrylate; preferably a copolymer of ethylene and ethyl acrylate, and where k is 2 to 100.
  • n 1 to 100
  • G 50 is straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms, with the proviso that in formula (7g) successive hindered amine moieties can be oriented in either a head to head or head to tail fashion;
  • T is hydrogen or
  • G 55 is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenylene or -NH-alkylene-NH- of 2 to 18 carbon atoms including 5-amino-1-aminomethyl-1 ,3,3-trimethylcyclohexane and -NH-xylylene-NH-;
  • T 5 is alkyl of 1 to 4 carbon atoms; - G 50 -OH
  • alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2- ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n- heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1 -methyl hepty I, 3-methylheptyl, n-octyl, 2-ethyl- hexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, dec
  • n 6 is the number 1 or 2
  • G and Gn are as defined under (a 1 )
  • d 4 is as defined under (b"), but G M cannot be -CONH-Z and -CH 2 -CH(OH)-CH 2 -O-D-O-.
  • radicals G 39 independently of one another, are a group of the formula (1i-1 )
  • G 40 is d-C ⁇ 2 alkyl or C 5 -C 12 cycloalkyl
  • G 4 ⁇ is C 2 -C ⁇ 2 alkylene
  • G 2 is as defined for Gn above.
  • Alkyl is for example d-dalkyl, in particular methyl, ethyl, propyl or butyl.
  • Cycloalkyl is preferably cyclohexyl.
  • Alkylene is for example ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamethylene.
  • Alkenyl is preferably allyl.
  • Phenylalkyl is preferably benzyl.
  • Acyl is preferably acetyl.
  • G, Gn are as defined above and when n 7 is 1 , T 7 is hydrogen, d-C ⁇ alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C 2 - C 4 hydroxyalkyl, C 2 -C 6 alkoxyalkyl, C 6 -C ⁇ 0 aryl, glycidyl, a group of the formula -(CH 2 ) t -COO-Q or of the formula -(CH 2 ) r O-CO-Q wherein t is 1 or 2, and Q is C C 4 alkyl or phenyl; or when n 7 is 2, T 7 is C 2 -C 12 alkylene, C 6 -C 12 arylene, a group -CH 2 CH(OH)-CH 2 -O-X-O-CH 2 - CH(OH)-CH 2 - wherein X is C 2 -C ⁇ oalkylene
  • G, Gn are as defined above.
  • G, Gn are as defined above.
  • HALS examples are the compounds bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4- piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4- hydroxybenzylmalonate, the condensate of 1 -(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6- tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino
  • N-(2,2,6,6- tetramethyl-4-piperidyl)-n-dodecylsuccinimide N-(1 ,2,2,6,6-pentamethyl-4-piperidyl)-n- dodecylsuccinimide
  • Preferred HALS are of molecular weight 400 g/mol or higher; especially preferred are oligomeric HALS of the classes mentioned above, e.g. of molecular weight of 1000 g/mol or higher, e.g. 1500 - 15000 g/mol.
  • NOR-HALS alkoxyamine class
  • compound H1 as used in the examples below (also disclosed in Example 2 of US-6117995).
  • An appropriate combination of the photochromic dyes with UV absorber and a HALS provides an exceptional improvement of the long-term photostability, achieving a lifetime thirty times longer than the unstabilized system.
  • the components used in the invention can be pure or mixtures of compounds.
  • Components (c) to be used within present invention basically are known materials, many are commercially available.
  • Optional further ingredients include further stabilizers, antioxidants, softeners, flame retardants etc. as commonly used for polymeric material, such as the following components:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylundec
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydro ⁇ uinones and alkylated hvdro ⁇ uinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hvdroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4 , -thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4,4 , -thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • O-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • Hvdroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-buty
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdro ⁇ yphenyl.propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane,
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanedi- ol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1 -phos
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl,propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-triox
  • esters of 3.5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha-2,6,7-trioxabicycl
  • vitamin C 1.18.
  • a inic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1 -ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1 -methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine,
  • azol-2-ylphenyl 2-[2'-hydroxy-3'-( ⁇ , ⁇ -dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-( ⁇ , ⁇ -dimethylbenzyl)phenyl]ben- zotriazole.
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2'-thiobis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanol
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphos
  • Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba-Geigy), tris(nonylphenyl) phosphite,
  • Hvdroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
  • Thiosvnergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ - dodecyl
  • Polyamide stabilisers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • additives such as listed components listed above under 1. - 11. and 14. are often added in concentrations of from 0.01 to 10 %, based on the overall weight of the composition (components a, b and c). Further additives of items 12. and 13., such as fillers or flame retardants, may be contained in much higher amounts, e.g. from 0.1 to about 50 % or even 80 % by weight of the total composition.
  • compositions of the present invention do not contain polyphenolic antioxidants.
  • polyphenolic antioxidants are for example described in U.S. 5,770,115.
  • the polymeric material usually contains 0.001 to 10% by weight, most preferably 0.01 to 5% by weight of the stabilizer component (c).
  • the polymeric material can contain mixtures of two or more of the HALS (ii) and/or the hydroxyphenyl UV absorber (i).
  • the amount of photochromic dye in the polymeric material usually is in the range of about 0.001 to 10% by weight, most preferably 0.01 to 5% by weight, with respect to the total weight of the polymeric material.
  • the polymeric material can contain mixtures of two or more photochromic dyes.
  • the ratio of component (c) to component (b) can e.g. be in the range of 0.01 to 100 parts, preferably 0.1 to 10 parts, of stabilizer (c) per part of photochromic dye (b).
  • the ratio of UVA component (i) to HALS component (ii) can e.g. be in the range of 0.01 to 100 parts, most preferably 0.1 to 2 parts, of UV absorber (i) per part of HALS (ii).
  • compositions can be made in which components (b) and especially (c) are enriched in a part of the polymeric material, e.g. in the surface areas, or wherein the UV absorber component (i) is enriched in the surface areas while the remaining components are mixed homogenously.
  • components (b) and especially (c) are enriched in a part of the polymeric material, e.g. in the surface areas, or wherein the UV absorber component (i) is enriched in the surface areas while the remaining components are mixed homogenously.
  • 2- or multilayer systems wherein the UV absorber (i) is enriched in an upper layer containing no photochromic dye, while a lower layer contains the dye (b) and HALS (ii), and the UV absorber merely as an optional component.
  • additives/components of the invention and optional further components may be added to the polymer material individually or mixed with one another. If desired, the individual components can be mixed with one another before incorporation into the polymer for example by dry blending, compaction or in the melt.
  • the incorporation of the components of the invention and optional further components into the polymer is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
  • the additives of the invention and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved, melted (soaking process) or dispersed additve or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
  • the incorporation can be carried out in any heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
  • a stirrer e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
  • the incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.
  • the addition of the additive or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
  • the process is preferably carried out in an extruder by introducing the additive during processing.
  • processing machines are single-screw extruders, contrarotating and corotating twin-screw extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
  • Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffex- trusion, Vol. 1 Unen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
  • the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
  • the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm.
  • the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
  • the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
  • Components to be added can be premixed or added individually.
  • the additives/components of the invention and optional further additives can also be sprayed onto the polymer material. They are able to dilute other additives (for example the conventional additives indicated above) or their melts so that they can be sprayed also together with these additives onto the material. Addition by spraying during the deactivation of the polymerization catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst.
  • spherically polymerized polyolefins it may, for example, be advantageous to apply the additives of the invention, optionally together with other additives, by spraying.
  • the components of the invention and optional further additives can also be added to the polymer in the form of a concentrate, e.g. a masterbatch, which contains the components in a concentration of, for example, about 1 % to about 40% and preferably 2 % to about 20 % by weight incorporated in a polymer.
  • a concentrate e.g. a masterbatch
  • the polymer must not be necessarily of identical structure than the polymer where the additives are added finally.
  • the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
  • Incorporation can take place prior to or during the shaping operation, or by applying the dissolved, melted (soaking process) or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices.
  • a further possibility for incorporating the additives of the invention into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking.
  • the additive of the invention can be added as it is or else in encapsulated form (for example in waxes, oils or polymers).
  • the materials containing the additives/components of the invention described herein can be used for the production of moldings, rotomolded articles, injection molded articles, blow molded articles, films, tapes, mono-filaments, fibers, nonwovens, profiles, adhesives or putties, surface coatings and the like.
  • the invention also pertains to a process for stabilizing a photochromic system containing a photochromic dye in a polymer matrix against colour fading induced by irradiation, which process comprises incorporation of a hydroxyphenyl triazine UV absorber and optionally a sterically hindered amine light stabilizer into the polymer matrix and/or into a polymer layer covering said polymer matrix, as well as to the use of a hydroxyphenyl triazine UV absorber and optionally a sterically hindered amine for improving the stability of a photochromic system containing a photochromic dye in a polymer matrix.
  • Preferred processes and uses are in analogy to the compositions described further above or in the examples.
  • Compound HALS H1 is of the formula
  • Compound HALS H2 is of the formula
  • Chromene 2 is of the formula (Rodenstock No. N3)
  • the mixtures are blow extruded (using a mono layer Formac Lab. 25 blow extruder) at 160°C and films of 200 micron thickness are obtained.
  • the films thus prepared are mounted on a white card and exposed outdoor in the sunshine; a film with formulation 1 covered with a 150 micron thickness film containing 0.15% of the UV absorber UV1 is exposed in the same conditions (formulation: 1 plus UV1 ).
  • the covering film is a LDPE film containing as the only added additive 0.15 % of UV1.
  • the covering film is prepared by mixing 15g of UV1 and 9850 g of LDPE Riblene FF 29 supplied by Polimeri Europa; they are mixed in a 'turbomixer' for 10 minutes and blow extruded with a
  • the table below shows the performance of the three sample films as regards the persistency of the color after light irradiation: the stabilizing effect of UV1 on the chromenel itself and on the chromenel mixed with HALS H1 is evident.
  • the formulations are prepared as in example 1 but with a different chromene.
  • the formulation compositions and results are shown in the tables below.
  • formulations are prepared as in example 1 but a different sterically hindered amine is used in this example and UV1 is mixed with the other components, i.e. formulation 7 does not have a covering film.

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Abstract

Photochromic compositions are disclosed comprising a polymeric material, a photochromic dye, a hydroxyphenyl triazine UV absorber and, optionally, a further light stabilizer selected from the sterically hindered amines. These systems provide a reversible photochromic effect and show improved light stabilization and color fastness.

Description

STABILIZATION OF PHOTOCHROMIC SYSTEMS
The present invention relates to light stabilized polymer compositions comprising a photochromic dye, to a process of improving the stability and/or colour fastness of a photochromic dye, and to the use of a certain stabilizer for improving the light fastness of photochromic dyes or compositions containing them.
Photochromic systems comprise molecules able to change the color due to a reversible transformation of a chemical species induced by daylight.
Typical photochromic systems employ naphtho- or benzopyrans (chromenes), spiropyrans, spirooxazines. These molecules have found several fields of application especially in plastics (e.g. ophthalmic lenses). One of the most severe limitations to a large scale employment of such devices is due to the intrinsically poor long term stability, e.g. the photostability of both colorless and colored forms under conditions of more or less continuous irradiation with daylight. WO 96/37576 notes some stabilization of these systems using certain light stabilizers.
US patent 5,770,115 pertains to compositions of a carrier photochromic naphthopyran material and a stabilizer system comprising a polyphenolic antioxidant, a ultraviolet light absorber and a hindered amine light stabilizer. The stabilizer system is used to improve the fatigue resistance of the photochromic naphthopyran compounds.
It has now been found that an improved light stabilization and color fastness of photochromic systems and the dyes used, e.g. of marks and colorations on polymeric materials such as plastics and elastomers, may be achieved using a specific UV absorber and optional further stabilizer.
The UV absorbers are selected from the family of hydroxyphenyltriazines; thus, present invention pertains to a composition comprising a) a polymeric material containing b) a photochromic dye and c) a stabilizer comprising a hydroxyphenyl triazine UV absorber (i) conforming to formula I, II, III, IV or V
Figure imgf000003_0001
Figure imgf000003_0002
Figure imgf000003_0003
Figure imgf000004_0001
wherein
Y is phenyl, naphthyl, or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or Y is Z^ or Z2;
X is \ or Z2;
Rϊ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, halogen, -SR3, -SOR3or -SO2R3; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, -R4, -OR5, -N(R5)2, -CORs, -COORs, -OCOR5, -CN, -NO2, -SR5, -SOR5, -SO2R5 or -P(O)(OR5)2, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpipehdinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four phenylene, -O-, -NR5-, -CONR5-, -COO-, -OCO- or -CO groups or combinations thereof; or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above;
R3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to
12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms;
R4 is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms;
R5 is defined as is R4; or R5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R is a group for formula
Figure imgf000005_0001
T is hydrogen, oxyl, hydroxyl, -OT^ alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;
TT is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms or aryl of 6 o 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;
R2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said cycloalkyl substituted by one to four halogen, epoxy, glycidyloxy, furyloxy, -R4, -OR5, -N(R5)2, -CON(R5)2, -COR5, -COOR5, -OCOR5, -OCOC(R5)=C(R5)2, -C(R5)=CCOOR5, -CN, -NCO, or
Figure imgf000005_0002
or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four epoxy, -O-, -NR5-, -CONR5-, -COO-, -OCO-, -CO-, -C(R5)=C(R5)COO-, -OCOC(R5)=C(R5)-, - C(R5)=C(R5)-, phenylene or phenylene-G-phenylene in which G is -O-, -S-, -SO2-, -CH2- or - C(CH3)2- or combinations thereof, or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R2 is -SO2R3 or -COR6;
R6 is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, -R7COOH or -NH-R8-NCO;
R7 is alkylene of 2 to 14 carbon atoms or phenylene;
R8 is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group
Figure imgf000006_0001
Ri and R^ are the same or different and are as defined for R^
R2 and R2" are the same or different and are as defined for R2;
X, X' are the same or different and are as defined for X; Y and Y' are the same or different and are as defined for Y;
t is 0 to 9;
L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene; or L is benzylidene; or L is -S-, -S-S-, -S-E-S-, -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CH2-NH-E- NH-CH2- or
Figure imgf000007_0001
E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by cycloalkylene of 5 to 12 carbon atoms;
n is 2, 3 or 4;
when n is 2; Q is straight or branched alkylene of 2 to 16 carbon atoms; or said alkylene substituted by one to three hydroxy groups; or said alkylene interrupted by one to three
-CH=CH- or -O-; or said alkylene both substituted and interrupted by combinations of the groups mentioned above; or Q is xylylene or a group -CONH-R8-NHCO-, -CH2CH(OH)CH2O- R9-OCH2CH(OH)CH2-, -CO-R10-CO-, or -(CH^-COO-Rn-OOC- CHz)™-, where m is 1 to 3; or Q is
Figure imgf000007_0002
R9 is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by one to ten -O-, phenylene or a group -phenylene-G-phenylene in which G is -O-, -S-, -SO2-, -CH2- or -C(CH3)2-;
R10 is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by one to four -O-, -S- or -CH=CH-; or R10 is arylene of 6 to 12 carbon atoms; Rn is alkylene of 2 to 20 carbon atoms or said alkylene interrupted by one to eight -O-;
when n is 3, Q is a group -[(CH2)mCOO]3-Rι2 where m is 1 to 3, and R12 is an alkanetriyl of 3 to 12 carbon atoms;
when n is 4, Q is a group -[(CH2)mCOO]4-Rι3 where m is 1 to 3, and RM is an alkanetetrayl of 4 to 12 carbon atoms;
Zi is a group of formula
Figure imgf000008_0001
Z2 is a group of formula
Figure imgf000008_0002
where η and r2 are 1 ;
Ri4, Ri5, Ri6, Ri7, Ri8> Ri9. R2o, R21. R^ and R23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl; or Rι7 and Rι8or R^ and R23 together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three -O- or -NR5-. In another embodiment of the instant invention, the s-triazine UV absorbers are those of formula I where
X and Y are 7. or Z2;
Ri is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or halogen;
R2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said cycloalkyl substituted by one to three -R4, -OR5, -COOR5, -OCOR5 or combinations thereof; or said alkyl or cycloalkyl interrupted by one to three epoxy, -O-, -COO-, -OCO- or -CO-;
R is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;
R5 is defined as is R ; or R is also hydrogen or straight or branched chain alkyl of 1 to
24 carbon atoms;
Z1 is a group of formula
Figure imgf000009_0001
Z2 is a group of formula
Figure imgf000010_0001
where η and r2 are each 1 ; and
Rι4, Ri5- Ri6. Ri7, Ri8, i9> R2o, R21 , R_2 and R23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, or alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl.
Preferred are, for example, those conforming to the general structure
Figure imgf000010_0002
wherein
R28 is (CH2-CH2-O-)n-R29; -CH2-CH(OH)-CH2-O-R29; or -CH(R3o)-CO-O-R40; n is 0 or 1 ; R29 is C Cι3alkyl or C2 -C20alkenyl or C6-Cι2aryl or CO-C Cι8alkyl; R30 is H or C C8alkyl; R 0 is d- C12alkyl or C2-C12alkenyl or C5-C6cycloalkyl.
A further example of hydroxyphenyltriazines (i) is the compound (a) a) 2-(2-hydroxy-4-[2-ethylhexyl]oxyphenyl)-4,6-di(4-phenylphenyl)-1 ,3,5-triazine,
Compound UV1 as used in the examples below is identical with the above compound a (also disclosed as compound A8 of US-6060543).
Hydroxyphenyl triazine UV absorber are described e.g. in GB-A-975966, EP-A-434608, US- 4619956, US-5298067, EP-A-530135, EP-A-520938, EP-A-531258, US-5556973, US- 5959008, US-6184375, US-6117997; for example in US-5998116, US-6255483, US- 6060543.
Of interest are also such compositions wherein the hydroxyphenyl triazine UV absorber (i) is an oligo- or polyester of formula (100)
-[-A^O-D O- (100)
in which x2 is a number from 1 to 50;
A1 is a group of the formula (101 )
Figure imgf000011_0001
or has one of the meanings given for T10;
Di is C -Cι2 alkylene or said alkylene substituted by OH or interrupted by O or both substituted by OH and interrupted by O;
Li is d-C18alkylene; C5-Cι2cycloalkylene; C3-Cι8alkenylene; or one of said residues substituted by phenyl, C7-Cnalkylphenyl, C5-Cι2cycloalkyl, OH, halogen, d-Cι8alkoxy, C5- C12cycloalkoxy, C3-Cι8alkenyloxy, COOH; the R50 are independently of each other H, OR54 or OH, with the proviso that at least one of
Figure imgf000011_0002
the Rπ4 are independently of each other hydrogen, C Cι2alkyl or a radical of formula
-L CO-O-Rss;
Rs5 is H, d-Cι8alkyl, C2-C12hydroxyalkyl; R51 is hydrogen, d-C alkyl, Cl, phenyl or a group -OR^; R52 is hydrogen or methyl;
R∞ is hydrogen, methyl, OH or OR^; and
T10 is the divalent acyl residue of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms; and which contains at least one moiety of formula (101) and at least one moiety T10.
In a preferred compound, ^ is d-C alkylene, especially C2-C alkylidene or methylene. Di is advantageously C -Cι2alkylene or C4-C10alkylene interrupted by O.
T10 as the divalent acyl residue of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms includes, for example, aliphatic diacyls wherein the 2 carbonyl groups are interconnected by Cn-dsalkylene or -alkenylene or alkylene interrupted by cycloalkylene or cycloalkenylene, each of which is unsubstituted or substituted by alkyl, and containing 11 to 58 carbon atoms in total, preferably 20 to 50 carbon atoms. Alkylene or alkenylene may be branched or unbranched, or, preferably not adjacent to an ethylenic double bond, interrupted by oxygen. In preferred compounds, T10 is -CO-Tι0'-CO-, wherein T10' is C20-C5oalkylene or do-Csoalkylene interrupted by one or more oxygen atoms; especially preferred is unbranched do-doalkylene. In further preferred compounds, T10 is -CO-Tι0'-CO-, wherein T10' is alkylene interrupted by C5-Cι2cycloalkylene or C5-C12cycloalkenylene or said cycloalkylene or cycloalkenylene substituted by alkyl and containing 11 to 58 carbon atoms, especially 20-50 carbon atoms, in total; especially preferred cycloalkylene is cyclohexylene; especially preferred cycloalkenylene is cyclohexenylene. Valuable spacer groups T10' are, for example, of the formula 102
Figure imgf000012_0001
wherein R56 is -(CbH2b)- and R57 is -(CcH2c)- and Rδβ, R59 and R60 are -(CdH2d)-H, -(CeH2e)-H, and -(CfH^-H, respectively, where bi is from the range 0 - 7, and each of the indices b - f is from the range 0 - 20, with the condition that the sum bi + b + c + d + e + f is from the range 15 - 45,
or of the formula 103
Figure imgf000013_0001
wherein
R6ι and R62 each are d-C18alkylene and each of R63, Rβ4, Res and R^, independently, are H or Cι-Cι8alkyl, and R6s and Ree together may also be a chemical bond, with the condition that the total number of carbon atoms in formula 103 ranges from 20 to 50.
Of special technical importance are spacer groups T10' of the formula 103 wherein R6ι and R62 independently are alkylene of 4 - 12 carbon atoms, each of RQ3 and R64, independently, are C4-C12alkyl, while Res and R^ are hydrogen.
In the compounds of present formula (100), most preferably, the RSQ are OH; the Rs-j are hydrogen or methyl;
R51 is hydrogen, methyl or a group -OR5 ;
R52 is hydrogen;
R53 is hydrogen, OH or methyl.
Terminal groups of the oligomer or polymer of formula (100) usually are
-O-D OR67, or -OR67 if bonded to Ai (left side of formula 100), or -A OR67, such as -Tι0'-COOR67 or -[formula 101]-OR67, or -R67 if bonded to O (right side of formula 100), where R67 is H or d-C8alkyl.
For example, the ester of formula (100) may conform to the formula (104)
Figure imgf000014_0001
(104) in which x2 is a number from 1 to 20; the number y is at least 1 and ranges from (x2 + z - 1 ) to (x2 + z + 1 ); z is a number from 1 to 20; and
Res is hydrogen, Cι-C12alkyl; C5-d2cycloalkyl; C2-C12alkenyl; phenyl; C7-Cnalkylphenyl; C C12alkyl substituted by phenyl, OH, halogen; Cι-Cι8alkoxy, C5-C12cycloalkoxy, C3- Cι8alkenyloxy or COOH; especially hydrogen or Cι-C4alkyl; R67 is hydrogen or d-C8alkyl; R69 is hydrogen or d-C alkyl;
Di is C -C8alkylene or C4-C10alkylene interrupted by O; and T10' is C20-C5oalkylene or C20- Csoalkylene interrupted by one or more oxygen atoms; and all other symbols are as defined for formula 100 above.
T10' may also be alkylene interrupted by C5-Cι2cycloalkylene or said cycloalkylene, especially cyclohexylene, substituted by alkyl and containing 20-50 carbon atoms in total.
In the oligo- or polyester of formula (104), each of the divalent structural units identified by the indices x2 and z bond to the structural unit -O-D identified by the index y, and/or to an end group R67 or OR67.
In compounds of the formula (100), x2 is preferably from the range 2-50, more preferably from the range 2-20, especially 4-12; the number of triazine moieties of the formula 101 to diacid residues T10 preferably ranges from about 1 : 3 to about 10:1 , more preferably from about 1 : 1 to about 5 : 1. In compounds of the formula (104), each of x2 and z are preferably from the range 1 -16; more preferably, x2 is from the range 1-10 and z is ranging from 2-12. Oligomeric or polymeric esters of the invention such as those of formula 100 or 104 usually have a molecular weight within the range 1000 to 50000 g/mol, more preferably 1500 to 20000 g/mol, most preferably 2000 to 10000 g/mol (number average Mn as determined by gel permeation chromatography GPC).
Alkylphenyl is alkyl-substituted phenyl; C7-C14alkylphenyl embraces examples such as methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl, butylphenyl, dibutylphenyl, pentylphenyl, hexylphenyl, heptylphenyl and octylphenyl.
Phenylalkyl is phenyl-substituted alkyl; C7-Cn phenylalkyl embraces examples such as benzyl, α-methylbenzyl, α-ethylbenzyl, α.α-dimethylbenzyl, phenylethyl, phenylpropyl, phenylbutyl and phenylpentyl.
Alkyl interrupted by O can generally comprise one or more nonadjacent oxygen atom(s). Preferably, a carbon atom of an alkylene chain such as D, or T10' bonds to not more than 1 heteroatom.
Within the scope of the stated definitions, the alkyl radicals are branched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1 -methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
Alkylene such as of -i or Di derives from such alkyls by abstraction of an hydrogen atom.
Within the scope of the stated definitions, the alkenyl radicals include allyl, isopropenyl, 2- butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl; n-oct-2-enyl, n-dodec- 2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl. The heavy chains of T10, e.g. alkylene groups of T10', may have a certain molecular distribution around their main component. Ranges may be, for example, from 22-26, 28-32 or 34-38 C-atoms. It is however also possible that broader ranges are used such as for example from 20 to 40, from 30 to 50 or from 30 to 40 carbon atoms, each for T10' in total.
Since the educts for preparing a compound of formula (100) or (104) are commercial products, they may vary within certain specifications. This is particularly the case for high molecular weight diacids from which the T10 groups are derived, when T10 is C20-C6oalkylene (which may be interrupted as described above).
Commercially available diacids or diacid esters may also contain small amounts of chains below C20. Therefore mixtures of compounds wherein Tι0 is a mixture containing up to 10% of diacyl chains below 20 carbon atoms and 90 to 100% of diacyl chains between 20 and 60, particularly between 20 and 40 carbon atoms are also subject of the invention. Percentage is weight percent, based on the total mixture.
Present invention also pertains to an oligoester or polyester which is obtained by reacting a tris-aryl-triazine of the formula (105)
Figure imgf000016_0001
and a compound of the formula R67-O-Tι0-O-R67, where Yi is CO and all other all symbols are as defined above, with a diol HO-D OH.
Hydroxyphenyl triazine UV absorber (i) of formula (100) - (105) may be prepared as described in the international patent application with application no. EP2004/050804.
Preference is given to hydroxyphenyl triazine UV absorber (i) of the formula I, II, III, IV or V. Preferred further light stabilizers to be employed are sterically hindered amines (HALS), especially selected from oligomeric and monodispersed HALS, oligomeric HALS of the alkoxyamine class (NOR-HALS), and low basicity HALS like piperazinones (such as products described in WO 00/31069), morpholinones (see WO 99/14206), piperazinediones (see DE- A-19924984), and thioimidazolidinones (see WO 01/62739).
Thus, present invention specifically pertains to a composition comprising a) a polymeric material containing b) a photochromic dye and c) a stabilizer combination of i) a hydroxyphenyl triazine UV absorber and ii) at least one further light stabilizer selected from the sterically hindered amines (HALS).
The compositions of the invention are useful for all applications wherein a photochromic effect is to be achieved. Some examples are described below:
• Optical devices such as particular types of ophthalmic lenses, referred to as "photochromatic", where the beneficial neutralization of harmful UV solar radiation and the anti-glare effect are effective only when needed, allowing the use of the sunglasses with the photochromatic lenses also indoor. Such lenses are often made of polyacrylates, cellulose esters, polyvinylalcohol, polyurethanes, polycarbonates, polyesters such as polyethyleneterephtala.es, polyvinylbutyrate, polystyrenes and related copolymers such as styrene-methacrylate or styrene-acrylonitrile. The systems may further be applied in optical films as seen in WO 97/32225, and United States Patent Nos. 4,871 ,784 and 5,217,794 which are incorporated herein by reference.
• Additional applications can be in the field of glazing, where filtration of visible light triggered by the UV part of the solar radiation may enhance the comfort inside a building or vehicle and/or contribute to reduce costs for conditioning an indoor environment. The photochromic system can be present either in the plastic window or used in a film that is laminated onto or embedded in a glass or plastic window. Typical materials used in these contexts are polyethyleneterephtalate, glycole modified polyethyleneterephtalate, polycarbonate, polymethylmethacrylate, polyvinylbutyral, and/or as described in WO 92/01557, Japanese Nos. 75-33286; 93- 143668; 95-3217 and 96-143831 , and United States Patent No. 5,643,676 which is incorporated herein by reference, for films and glazings; or as seen in Japanese Nos. 80-40018; 90-192118; 90-335037; 90-335038; 92-110128 and 94-127591 , and
United States Patent No. 5,618,863 which is incorporated herein by reference, for windscreens/vehicle glazings and intermediate layers.
• Also greenhouse plastic covers can be additivated with photochromes, aiming at reducing light intensity inside the greenhouse, that eventually turns into heat, as excessive heat may be detrimental to some crops and/or inhibit growth. Low density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer (EVA) and ethylene-butyl acrylate copolymer and blends of the mentioned polymers are typical materials for plastic covers used in agriculture.
• Photochromic coatings. • Construction elements or articles containing photochromic parts for the purpose of labelling, signalling, decoration etc.
In general, the polymeric material of component a) may be selected from polymers listed below:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1 -ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1 ), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1 -olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/ vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene- acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal- kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).
6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/sty- rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propy- lene/styrene.
6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH). 6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy- lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadi- enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). 17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding iactones, for example polyethylene terephthalate (PET), polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl- terminated polyethers; and also polyesters modified with polycarbonates or MBS. Specific examples are PET, polybutylene terephthalate (PBT), polyethylenenaphthalenate (PEN), polytrimethylene terephthalate (PTT), and their copolyesters, for example with isophthalic acid, di- ethylene glycol, 1 ,4-bis(hydroxymethyl)cyclohexane.
19. Polycarbonates and polyester carbonates.
20. Polyketones.
21. Polysulfones, polyether sulfones and polyether ketones.
22. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
23. Drying and non-drying alkyd resins.
24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydhc alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
25. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry- lates, urethane acrylates or polyester acrylates.
26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. 27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
28. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
29. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
Polymeric material useable for the present invention is preferably synthetic organic polymeric material, for example, material commonly used for electronic applications.
In particular the following polymers are preferred:
Polyolefines such as polyethylene and polypropylene, polycarbonate, polyesters such as polyethylene terephthalate (PET) and its copolyesters; styrene polymers or copolymers such as polystyrene or high impact polystyrene (PS-HIPS); or the specific polymers mentioned above.
The photochromic dye is usually selected from naphtho- and benzopyranes (chromenes), or from spiropyranes or spirooxazines; these components are commercial available.
Photochromic spiro-indolino-oxazine compounds useful in the invention have the general structural formula (I'):
Figure imgf000025_0001
where:
Ri and R2, either the same or different, each represent independently a C C5alkyl group, linear or branched; a phenyl group; or R and R2, together with the carbon atom to which they are connected, jointly represent a cycloalkyl(C4-C7)group, bicycloalkyl(C6-Cn)group, or tricycloalkyl(C7-C13)group;
R3 represents a hydrogen atom; a d-C5alkyl group, linear or branched; a similar d-C5alkyl group substituted with from 1 to 5 halogen atoms chosen from fluorine, chlorine, bromine or iodine, hydroxy groups, d-C5alkoxy groups, C C5carboxy alkyl groups, cyano groups; a C2-C5alkenyl group; a phenyl group; or benzyl group;
from R4 to R7, either the same or different, each stand independently for a hydrogen atom; a Cι-C5alkyl group, linear or branched; a similar d-C5alkyl group substituted with from 1 to 5 halogen atoms chosen from fluorine, chlorine, bromine or iodine, hydroxy groups, Cι.C5alkoxy groups, d-C5carboxy alkyl groups, cyano groups; a C2-C5alkenyl group; a phenyl group; a benzyl group; a halogen atom chosen from either fluorine, chlorine, bromine or iodine; a hydroxy group; a Cι-C5alkoxy group; an amino group; a monoalkyl(Cι-C5)amino group; a dialkyl(C C5)amino group; a cyclo-alkyl(C3-Cι0)amino group; a pipe dine, piperazine or morpholine group; a carboxyl group; a carboxy alkyl(C C5)group; a carboxy alkenyl(C2-C5)group; a carboxamide group; a substituted carboxamide N-alkyl(C C5)group; a substituted carboxamide N,N-di-alkyl(CrC5)group; a cyano group; a nitro group; a sulfonic group; a (Cι-Cs)alkyl sulfonic group; an aryl sulfonic group chosen from benzene sulfonic, p-toluene sulfonic, p-chlorotoluene sulfonic groups; an aryl group chosen from phenyl, biphenyl, naphthyl groups;
R8 repesents a hydrogen atom; a linear or branched alkyl(d-C5)group; a phenyl group; a halogen atom chosen from either fluorine, chlorine, bromine; an alkoxy(C C5)group; or a phenoxy group; A represents an arenic, monocyclic or polycyclic group, chosen from those that can be defined with formula (II'), (III'), (IV) or (V):
Figure imgf000026_0001
(II') (III') (IV) (V)
two contiguous points from R9 to Rι2 represent the condensation position between the oxazinic nucleus in the general formula (I1) and the other two groups and Rι3-Ri6 have the same meaning as R -R7 in the general formula (I'); or two contiguous groups together are alkylene of 3-6 carbon atoms, or a corresponding azaalkylene or oxaalkylene; or three contiguous groups jointly represent an alkane-triyl, i.e. 3-valent saturated hydrocarbon residue, of 4-8 carbon atoms, or a corresponding aza- or oxa-alkane-triyl.
In the oxa- or aza-residues, one of the carbon atoms, along with bonding hydrogens, if present, are replaced by oxygen, nitrogen or NH.
Preferably in formula (I'):
Ri and R2, either the same or different, each represent independently a methyl, ethyl, propyl or phenyl group, or together with the carbon atom to which they are connected, jointly represent a cyclohexyl group or a bi- or tricycloalkyl of 7-11 carbon atoms;
R3 represents a methyl, ethyl, propyl, phenyl, benzyl, 2-allyl, 2-hydroxyethyl or 2-carboxy- methyl group;
from R4 to R7, either the same or different, each stand independently for the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N-di- methylcarboxamide, cyano, nitro or phenyl group; R8 represents the hydrogen atom, the chlorine atom, methyl, phenyl, or methoxy group; and/or
A is one of the groups with formula (IT), (III'), (IV) or (V) where:
two contiguous points from R9 to R12 represent the condensation position between the oxazinic nucleus in the general formula (I') and the other two groups in addition to RI3-RIΘ each represent independently the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, ethyl, propyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N-dimethylcarboxamide, cyano, nitro or phenyl group.
Specific examples of preferred spiro-indolino-oxazine photochromic compounds useful in the present invention are: 1 ',3'-dihydro-5,7-dimethoxy-1 'n-propyl-3'ethyl-3',4',5'-(and 3',5',6')-trimethyl-spiro[2H-1 ,4- benzoxazine-2,2'-[2H]indole] (VI');
1 ,3-dihydro-1 ,3,3,4,5-(and 1 ,3,3,5,6)-pentamethylspiro[2H-indole-2,3'-[3H]pyrido[3,2- f][1 ,4]benzoxazine] (VII');
1 ,3-dihydro-1 ,3,3,4,5-(and 1 ,3,3,5,6)-pentamethylspiro[2H-indole-2,3'-[3H]naphth[2, 1 ■ b][1 ,4]oxazine (VIII'):
Figure imgf000027_0001
(VI')
Figure imgf000028_0001
or
Figure imgf000028_0002
Naphthopyran photochromic compounds usually have the general structural formula (IX'):
Figure imgf000028_0003
(IX1) where:
Ri to Rn, either the same or different, each stand independently for a hydrogen atom; a d-C alkyl group, linear or branched; a similar d-C5alkyl group substituted with from 1 to 5 halogen atoms chosen from fluorine, chlorine, bromine or iodine, hydroxy groups, C C5alkoxy groups, C C5carboxy alkyl groups, cyano groups; a C2-C5alkenyl group; a phenyl group; a benzyl group; a halogen atom chosen from either fluorine, chlorine, bromine or iodine; a hydroxy group; a d-C5alkoxy group; an amino group; a monoalkyl(d-C5)amino group; a dialkyl(d-C5)amino group; a cyclo-alkyl(C3-C10)amino group; a piperidine, piperazine or morpholine group; a carboxyl group; a carboxy alkyl(C C5)group; a carboxy alkenyl(C2-C5)group; a carboxamide group; a substituted carboxamide N-alkyl(C C5)group; a substituted carboxamide N,N-di-alkyl(d-C5)group; a cyano group; a nitro group; a sulfonic group; a (d-C5)alkyl sulfonic group; an aryl sulfonic group chosen from benzene sulfonic, p-toluene sulfonic, p-chlorotoluene sulfonic groups; an aryl group chosen from phenyl, biphenyl, naphthyl groups;
A represents an arenic polycyclic group, chosen from those that can be defined with formula (X'):
Figure imgf000029_0001
(X')
two contiguous points from R12 to R15 represent the condensation position between the pyran nucleus in the general formula (IX1) and the other two groups in addition to R16-R19 have the same meaning as R1-R11 in the general formula (IX').
Preferably in formula (IX'): Ri to Rn, either the same or different, each stand independently for the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N- dimethylcarboxamide, cyano, nitro or phenyl group;
A is one of the groups with formula (X1) where:
two contiguous points from R12 to R15 represent the condensation position between the pyran nucleus in the general formula (IX') and the other two groups in addition to R16-R19 each represent independently the hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl, ethyl, propyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl, N,N-dimethylcarboxamide, cyano, nitro or phenyl group.
Specific examples of preferred naphtopyran photochromic compounds useful in the present invention are:
3,3-diphenyl-3H-naphtho[2,1-b]pyran (XI');
3-(2-fluorophenyl)-3-(3-methyl-4-methoxyphenyl)-5-acetoxy-3H-naphtho[2,1-b]pyran (XII'):
Figure imgf000030_0001
(XI')
Figure imgf000031_0001
(XII')
3(2-fluorophenyl)-3-(4-methoxyphenyl)-3H-naphtho[2,1-b]pyran;
3(2-fluorophenyl)-3(4'-methoxyphenyl)-8-methoxy-3H-naptho[2,1-b]pyran; 3(2,4-dimethoxyphenyl)-3,4'-methoxyphenyl)-3H-naphto[2,1-b]pyran; 3(2-fluorophenyl-3(3,4-dimethoxyphenyl)3H-naptho[2,1-b]pyran; 3(2-methyl-4-methoxyphenyl)-3-(4-methoxyphenyl)-3H-naphto[2,1 -b]pyran; 3-(2-methylphenyl)-3(4-methoxyphenyl)-3H-naphtho[2,1-b]pyran; 3-phenyl-3(2,4-dimethoxyphenyl)-3H-naphtho[2,1-b]pyran; and 3(2,6-difluorophenyl)-3(4-methoxyphenyl)-3H-naphtho[2,1-b]pyran.
Preferred naphthopyranes also include those of the formulae
Figure imgf000031_0002
and
Figure imgf000031_0003
where each of R31, R32, R^, R^, R35 independently may be hydrogen, a hydrocarbon of 1 to 18 carbon atoms such as phenyl, naphthyl, alkyl, optionally substituted by OH, CrCealkoxy; NR'R"; -NO2; where R' and R" independently are H or d-C^alkyl, C4-C12cycloalkyl, C7- C13phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene. Benzopyranes, another class of chromenes, include those of the formula
Figure imgf000032_0001
where each of R41, R42, R 3, R^, R45 independently may be hydrogen, a hydrocarbon of 1 to 18 carbon atoms such as phenyl, naphthyl, alkyl, optionally substituted by OH, C C6alkoxy; NR'R"; -NO2; where R' and R" independently are H or Cι-C12alkyl, C4-Cι2cycloalkyl, C7- Cι3phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene.
For example, a chromene may be selected from naphthopyrans of the formula
Figure imgf000032_0002
wherein R is H; d-C6alkyl; Cι-C6alkoxy; -NR'R"; -NO2; where R' and R" independently are H or d-Cι2alkyl, C4-Cι2cycloalkyl, C7-Cι3phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene. Chromenel as used in the examples below is of the above formula where each R is H.
Preference is given to photochromic dyes (b) that do not contain mercury.
Preferred sterically hindered amines (HALS) of component (ii) are those comprising at least one radical of the formula IX, X and/or XI
Figure imgf000033_0001
(IX) (X) (XI) in which
G is hydrogen or methyl, and d and G2 are hydrogen, methyl or together are oxygen.
Of particular interest are systems comprising as component (ii) at least one compound from the group of the sterically hindered amines as described under the following classes (a') to (I') which comprise at least one radical of the formula II or III:
(a') A compound of the formula (1a)
Figure imgf000033_0002
in which ni is a number from 1 to 4, G and Gι, independently of one another, are hydrogen or methyl,
Gn is hydrogen, O , hydroxyl, NO, -CH2CN, d-C18alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-Cι2aralkyl, C Cι8alkoxy, C5-C12cycloalkoxy, C7-d5phenylalkoxy, C C8alkanoyl, C3-C5alkenoyl, CrCι8alkanoyloxy, benzyloxy, glycidyl or a group -CH2CH(OH)-Z, where Z is hydrogen, methyl or phenyl; or Gn is d-C18alkoxy, C5-C12cycloalkoxy or C7-C15phenylalkoxy each of which is substituted in the aliphatic part by 1-3 OH groups; Gn preferably being d- C12alkoxy or cyclohexyloxy or C2-C8hydroxyalkoxy or hydrogen or C C alkyl or allyl or benzyl or acetyl or acryloyl; especially H, methyl, octyloxy, cyclohexyloxy or 2-hydroxy-2-methyl- propoxy, of interest is also Gn being C Cι8alkoxy, C5-Cι2cycloalkoxy, C7-Cι5phenylalkoxy, benzyloxy or Gn being C C18alkoxy, C -C12cycloalkoxy or C7-C15phenylalkoxy each of which is substituted in the aliphatic part by 1-3 OH groups;
and G12, if ni is 1 , is hydrogen, C Cι8alkyl which is uninterrupted or interrupted by one or more oxygen atoms, COO and/or CONH groups, or is cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ12 groups, in which Z12 is H, d-C20alkyl, C3-C12alkenyl, C5- C7cycloalkyl, phenyl or benzyl, Gι2, if ni is 2, is C2-Cι2alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus- containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZι2 groups,
G12, if ni is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZι2, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical, preferred radicals including triacyl radicals of nitrilo triacetic acid of benzene tricarboxylic acid, and Gι2, if ni is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
The carboxylic acid radicals mentioned above are in each case taken to mean radicals of the formula (-CO)xR, where x is as defined above for ni, and the meaning of R arises from the definition given above. Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Cι-Cι8alkoxy Gn is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. C6-d2alkoxy, in particular heptoxy and octoxy, is preferred.
C5-Cι2cycloalkoxy G is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C5-C8cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.
C7-C9phenylalkoxy is, for example, benzyloxy.
Gn as Cι-C18alkoxy, C -d2cycloalkoxy or C7-Cι5phenylalkoxy substituted in the aliphatic part by 1-3 OH groups is a radical formed by abstraction of an carbon-bonded hydrogen atom preferably from 2-methyl-2-propanol (tert.-butanol), 2-propanol, 2,2-dimethyl-1-propanol, 2- methyl-2-butanol, ethanol, 1 -propanol, 1-butanol, 1-pentanol, 1 -hexanol, 1 -nonanol, 1 - decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1 -hexanol, cyclo- hexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1 -ethanol; 1 ,2-ethanediol, 1 ,2-propanedial, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 2,2- dimethyl-1 ,3-propanediol, 1 ,2-cyclohexanediol, 1 ,3-cyclohexanediol or 1 ,4-cyclohexanediol; glycerol, 1 ,1 ,1 -tris(hydroxymethyl)methane, 2-ethyl-2-(hydroxymethyl-1 ,3-propanediol, 1 ,2,4- butanethol or 1 ,2,6-hexanetriol. Most preferred hydroxy substituted G is 2-hydroxy-2- methylpropoxy.
Examples of several Gι2 radicals are given below.
If d2 is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
If d2 is a monovalent silyl radical, it is, for example, a radical of the formula -(CjH2j)-Si(Z')2Z", in which j is an integer in the range from 2 to 5, and Z' and Z", independently of one another, are d-C alkyl or d-C alkoxy.
If d2 is a divalent radical of a dicarboxylic acid, it is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl(3,5-di-tert-butyl^.-hydroxybenzyl)malonyl or bicycloheptenedicarbonyl radical or a group of the formula
Figure imgf000036_0001
If G12 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical.
If Gι2 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1 ,2,3,4-tetracarboxylic acid or of pyromellitic acid.
If d2 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.
Preference is given to compounds of the formula (1a) in which G and d are hydrogen, Gn is hydrogen or methyl, n! is 2 and Gι2 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 carbon atoms.
(b') A compound of the formula (1 b)
Figure imgf000037_0001
in which n2 is the number 1 , 2 or 3, and G, Gi and Gn are as defined under (a'), d3 is hydrogen, C C12alkyl, C2-C5hydroxyalkyl, C5-C7cycloalkyl, C7-C8aralkyl, Cι-Cι8alkanoyl, C3-C5alkenoyl, benzoyl or a group of the formula
Figure imgf000037_0002
and Gι4, if n2 is 1 , is hydrogen, Cι-C18alkyl, C3-C8alkenyl, C5-C7cycloalkyl, Cι-C4alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group or group of the formula -CONH-Z, or G14 is glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH- Z, in which Z is hydrogen, methyl or phenyl or CH2-OZι with Z14 being hydrogen or d- C18alkyl;
Gι4, if n2 is 2, is C2-Cι2alkylene, C6-Cι2arylene, xylylene, a -CH2-CH(OH)-CH2 group or a -CH2-CH(OH)-CH2-O-D-O- group, in which D is C2-C10alkylene, C6-C15arylene, C6-C12cycloalkylene, or, provided that d3 is not alkanoyl, alkenoyl or benzoyl, G1 can alternatively be 1-oxo-C2-Cι2alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternatively the group -CO-, G1 , if n2 is 3, is a group
O
II CH,CH(OH)CH„-
-CH„CH(OH)CH_ X. / 2 2
2 2 N N
O N X O
CH2CH(OH)CH2- or, if n2 is 1 , d3 and G14 together can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1 ,2- or 1 ,3-dicarboxylic acid.
Some examples for the radicals Gι3, d4 and D are given below.
Any alkyl substituents are as defined above for (a').
Any C5-C7cycloalkyl substituents are, in particular, cyclohexyl.
C7-C8aralkyl G13 is, in particular, phenylethyl or especially benzyl.
C2-C5hydroxyalkyl G13 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.
C -C18alkanoyl Gι3 is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and C3-C5alkenoyl d3 is, in particular, acryloyl.
C2-C8alkenyl G14 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
G14 as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide -substituted C C alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
Any C2-Cι2alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
Any C6-Cι5arylene substituents are, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
C6-C12cycloalkylene is, in particular, cyclohexylene.
GM as 1 -oxo-C2-Cι2alkylene is preferably a group
Figure imgf000039_0001
CH-
(c') A compound of the formula (1c)
Figure imgf000039_0002
in which n3 is the number 1 or 2, G, Gi and Gn are as defined under (a'), and G15 and G' 15 if n3 is 1 , are independently d-C12 alkyl, C2-C12 alkenyl, C7-Cι2 aralkyl, or G15 is also hydrogen, or G15 and G'ι5 together are C2-C8alkylene, C -Cι5alkenylene, C2-C8hydroxyalkylene or C4- C^acyloxyalkylene, and if n3 is 2, G15 and G' 15 together are the (-CH2)2C(CH2-)2 group.
C2-C8alkylene or C2-C8hydroxyalkylene G15 and G'ι5 is, for example, ethylene, 1 - methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
C4-C22acyloxyalkylene G15 and G' 15 is, for example, 2-ethyl-2-acetoxymethylpropylene.
(d') A compound of the formula (1d-1 ), (1d-2) or (1d-3),
Figure imgf000040_0001
Figure imgf000040_0002
Figure imgf000040_0003
in which n4 is the number 1 or 2, G, d and Gn are as defined under (a'),
G16 is hydrogen, d-C12alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl, and
G17, if n4 is 1 , is hydrogen, Cι-C12alkyl, C3-C5alkenyl, C7-C9aralkyl, C5-C7cycloalkyl, C2-C hydroxyalkyl, C2-C6alkoxyalkyl, C6-C10aryl, glycidyl or a group of the formula
-(CH2)p-COO-Q or -(CH2)p-O-CO-Q, in which p is 1 or 2, and Q is C C4alkyl or phenyl, and G17, if n is 2, is C2-C12alkylene, C4-C12alkenylene, C6-C12arylene, a group of the formula -CH2-CH(OH)-CH2-O-D'-O-CH2-CH(OH)-CH2-, in which D' is C2-C10alkylene, C6-C15arylene or C6-Cι2cycloalkylene, or a group of the formula -CH2CH(OD")CH2-(OCH2-CH(OD")CH2)2-, in which D" is hydrogen, d-Cι8alkyl, allyl, benzyl, C2-C12alkanoyl or benzoyl,
Ti and T2, independently of one another, are hydrogen, d-C18alkyl or unsubstituted or halogen- or d-C4alkyl-substituted C6-Cι0aryl or CrCgaralkyl, or
Ti and T2 together with the carbon atom bonding them form a C5-Cι4cycloalkane ring. Any Cι-C12alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Any C Ci8alkyl substituents can be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
C3-C5alkenyl d7 is, for example, 1 -propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
C7-C9aralkyl G17, T^ and T2 are, in particular, phenethyl or especially benzyl. If Ti and T2 together with the carbon atom form a cycloalkane ring, this can be, for example, a cyclo- pentane, cyclohexane, cyclooctane or cyclododecane ring.
C2-C hydroxyalkyl G17 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
C6-Cι0aryl G17, T-\ and T2 are, in particular, phenyl or α- or β-naphthyl, which are unsubstituted or substituted by halogen or d-dalkyl.
C2-C12alkylene d7 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
C -C12alkenylene Gι7 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.
C6-C12arylene G17 is, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
C2-C12alkanoyl D" is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl. C2-C10alkylene, C6-C15arylene or C6-Cι2cycloalkylene D' have, for example, one of the definitions given for D under (b').
(e') A compound of the formula (1e)
18
N N
(1 e)
'_o
'19 N
in which n5 is the number 1 or 2, and d8 is a group of the formula
Figure imgf000042_0001
in which G and G are as defined under (a'), and Gi and G2 are hydrogen, methyl or, together, are a substituent =O,
E is -O- or -ND'"-, A is C2-C6alkylene or -(CH2)3-O- and
Xi is the number 0 or 1 ,
D'" is hydrogen, C C12alkyl, C2-Cι2alkylene-N(DV)2, C2-C5hydroxyalkyl or C5-C7cycloalkyl, where Dv, independently, is hydrogen or butyl,
G19 is identical to Gι8 or is one of the groups -N(G21)(G22), -OG23, -N(H)(CH2OG23) or -N(CH2OG23)2,
G2o, if n5 = 1 , is identical to G18 or Gι9 and, if n5 = 2, is an -E-D^-E- group, in which D^ is
C2-C8alkylene or C2-C8alkylene which is interrupted by 1 or 2 -NG21- groups,
G21 is hydrogen, C Cι2alkyl, cyclohexyl, benzyl or C C -hydroxyalkyl or a group of the formula
Figure imgf000043_0001
G22 is d-Cι2alkyl, cyclohexyl, benzyl or C C4hydroxyalkyl, and G23 is hydrogen, d-Cι2alkyl or phenyl, or G21 and G22 together are C4-C5alkylene or C4-C5oxaalkylene, for example -CH2CH2-O-CH2CH2- , or a group of the formula -CH2CH2-N(Gn)-CH2CH2-.
Some examples of the several variables in the formula (le) are given below.
Any C Cι2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert- butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
Any C5-C7cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.
C2-C6alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
If G21 and G22 together are C4-C5alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
(f) A compound of the formula (1f)
Figure imgf000044_0001
wherein Gn is as defined under (a').
(g') Oligomeric or polymeric compounds whose recurring structural unit contains a 2,2,6,6- tetraalkylpiperidinyl radical, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof which contain such radicals.
Examples of 2,2, 6, 6-polyalkylpiperidine compounds from this class are the compounds of the following formulae,
Figure imgf000044_0002
to mM is a number from 2 to about 200, preferably 2 to 100, for example 2 to 50, 2 to 40, 3 to 40 or 4 to 10.
The meanings of the end groups which saturate the free valences in the oligomeric or polymeric compounds listed below depend on the processes used for the preparation of said compounds. The end groups can also in addition be modified after the synthesis of the compounds.
Examples for polymeric compounds are:
1 ) A compound of the formula (1 g)
Figure imgf000045_0001
wherein G24, G25, G26, G27 and G28, independently of one another, are a direct bond or d-C10alkylene, Gn is as defined under (a') and m17 is a number from 1 to 50.
In the compound of the formula (1g), the end group bonded to the >C=O group can be, for example,
Figure imgf000045_0002
and the end group bonded to the oxygen can be, for example
Figure imgf000045_0003
2) Compound of the formula (2g)
Figure imgf000046_0001
in which the index rriι8 ranges from 1 to 15;
Rι2 is C2-C12alkylene, C -Cι2alkenylene, C5-C7cycloalkylene, C5-C7cycloalkylene- di(Cι-C4alkylene), Cι-C alkylenedi(C5-C7cycloalkylene), phenylenedi(C C4alkylene) or C4-C12alkylene interrupted by 1 ,4-piperazinediyl, -O- or >N-X-ι with X1 being d-Cι2acyl or (d-C12alkoxy)carbonyl or having one of the definitions of R14 given below except hydrogen; or R12 is a group of the formula (2g') or (2g");
H C C
H- I H. (2g")
O
X.
Figure imgf000046_0002
X2 being C Cι8alkyl, C5-d2cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 d-C alkyl; phenyl which is unsubstituted or substituted by 1 , 2 or 3 d-C4alkyl or d-dalkoxy; C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 d-C alkyl; and the radicals X3 being independently of one another C2-C12alkylene; the radicals A are independently of one another -ORι3, -N(R1 )(R15) or a group of the formula (2g"');
Figure imgf000047_0001
Rι3, RM and Rι5, which are identical or different, are hydrogen, C Cι8alkyl, C5-d2cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 d-C4alkyl; C3-Cι8alkenyl, phenyl which is unsubstituted or substituted by 1 , 2 or 3 C C4alkyl or C C4alkoxy; C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 Cι-C alkyl; tetrahydrofurfuryl or C2-C alkyl which is substituted in the 2, 3 or 4 position by -OH, d-C8alkoxy, di(d-C4alkyl)amino or a group of the formula (2gιv);
/ \ _,N (2gw)
with Y being -O-, -CH2-, -CH2CH2- or >N-CH3, or -N(R14)(R15) is additionally a group of the formula (2gιv); X is -O- or >N-Ri6;
Ri6 is hydrogen, C Cι8alkyl, C3-C18alkenyl, C5-Cι2cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 d-C4alkyl; C7-Cgphenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 Cι-C4alkyl; tetrahydrofurfuryl, a group of the formula (2gv),
Figure imgf000047_0002
or C2-C4alkyl which is substituted in the 2, 3 or 4 position by -OH, d-C8alkoxy, di(Cι-C alkyl)amino or a group of the formula (2gι );
Rn has one of the definitions given for R16; and the radicals B have independently of one another one of the definitions given for A.
3) A compound of the formula (3g)
Figure imgf000048_0001
in which Gn is as defined under (a'), G29 and G32, independently of one another, are a direct bond or a -N(X1)-CO-X2-CO-N(X3)- group, where and X3, independently of one another, are hydrogen, d-C8alkyl, C5-C12cycloalkyl, phenyl, C7-C9phenylalkyl or a group of the formula
Figure imgf000048_0002
and X2 is a direct bond or d-C4alkylene, G30, G3ι, G^ and G35, independently of one another, are hydrogen, Ci-doalkyl, C5-C12cycloalkyl or phenyl, G is hydrogen, C Csoalkyl, C5-C12cycloalkyl, C7-Cgphenylalkyl, phenyl or a group of the formula (3g), and mι9 is a number from 1 to 50.
In the compounds of the formula (3g), the end group bonded to the 2,5-dioxopyrrolidine ring can be, for example, hydrogen, and the end group bonded to the ^(GMKG^)- radical can be, for example,
Figure imgf000049_0001
11
4) A product obtainable by reacting an intermediate product, obtained by reaction of a polyamine of the formula (4g) with cyanuric chloride, with a compound of the formula (4g')
H2N (CH2) m N (CH-)-; N (CH2) 'm-^— NH2 (4g)
20 H 2 m' 20 H 20
Figure imgf000049_0002
in which m'20, m"20 and m'"20, independently of one another, are a number from 2 to 12, G^ is hydrogen, C Cι2alkyl, C5-C12cycloalkyl, phenyl or C7-C9phenylalkyl, and Gn is as defined under (a').
In general, the above reaction product can be represented for example by a compound of the following 3 formulae. It can also be in the form of a mixture of these three compounds:
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000050_0003
5) A compound of the formula (5g)
Figure imgf000051_0001
in which Gn is as defined under (a'), G37 is d-Cι0alkyl, C5-d2cycloalkyl, d-C alkyl- substituted C -Cι2cycloalkyl, phenyl or d-doalkyl-substituted phenyl, G^ is C3-C10alkylene and m2ι is a number from 1 to 50.
In the compounds of the formula (5g), the terminal group bonded to the silicon atom can be, for example, (G37)3Si-O-, and the terminal group bonded to the oxygen can be, for example, - Si(G37)3.
The compounds of the formula (5g) can also be in the form of cyclic compounds if m2ι is a number from 3 to 10, i.e. the free valences shown in the structural formula then form a direct bond.
6) A compound of the formula (6g)
Figure imgf000051_0002
where E is -O- or -ND'"- as defined under (e'), T3 is ethylene or 1 ,2-propylene, is the repeating structural unit derived from an alpha-olefin copolymer with an alkyl acrylate or methacrylate; preferably a copolymer of ethylene and ethyl acrylate, and where k is 2 to 100.
7) A compound of the formula (7g)
Figure imgf000052_0001
wherein m is 1 to 100;
G50 is straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms, with the proviso that in formula (7g) successive hindered amine moieties can be oriented in either a head to head or head to tail fashion;
T is hydrogen or
Figure imgf000052_0002
G55 is a straight or branched chain alkylene of 1 to 18 carbon atoms, cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenylene or -NH-alkylene-NH- of 2 to 18 carbon atoms including 5-amino-1-aminomethyl-1 ,3,3-trimethylcyclohexane and -NH-xylylene-NH-;
T5 is alkyl of 1 to 4 carbon atoms; - G50-OH
Figure imgf000052_0003
Figure imgf000052_0004
In the above shown oligomeric and polymeric compounds, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2- ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n- heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1 -methyl hepty I, 3-methylheptyl, n-octyl, 2-ethyl- hexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl; examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; an example of C7-C9phenylalkyl is benzyl; and examples of alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene,
2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
(h') A compound of the formula (1 h)
Figure imgf000053_0001
in which n6 is the number 1 or 2, G and Gn are as defined under (a1), and d4 is as defined under (b"), but GM cannot be -CONH-Z and -CH2-CH(OH)-CH2-O-D-O-.
(i1) A compound of the formula (1 i)
'39 N G 39 if (1i)
N N
'39 wherein the radicals G39, independently of one another, are a group of the formula (1i-1 )
Figure imgf000054_0001
in which G40 is d-Cι2alkyl or C5-C12cycloalkyl, G4ι is C2-Cι2alkylene and G 2 is as defined for Gn above.
Alkyl is for example d-dalkyl, in particular methyl, ethyl, propyl or butyl.
Cycloalkyl is preferably cyclohexyl.
Alkylene is for example ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamethylene.
Alkenyl is preferably allyl.
Phenylalkyl is preferably benzyl.
Acyl is preferably acetyl.
(j') A compound of the formula (1j)
Figure imgf000054_0002
wherein G, Gn are as defined above and when n7 is 1 , T7 is hydrogen, d-C^alkyl, C3-C5alkenyl, C7-C9aralkyl, C5-C7cycloalkyl, C2- C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-Cι0 aryl, glycidyl, a group of the formula -(CH2)t-COO-Q or of the formula -(CH2)rO-CO-Q wherein t is 1 or 2, and Q is C C4alkyl or phenyl; or when n7 is 2, T7 is C2-C12alkylene, C6-C12arylene, a group -CH2CH(OH)-CH2-O-X-O-CH2- CH(OH)-CH2- wherein X is C2-Cιoalkylene, C6-Cι5arylene or C6-Cι2cycloalkylene, or a group - CH2CH(OZ,)CH2-(OCH2-CH(OZ,)CH2)2- wherein Z' is hydrogen, C C18alkyl, allyl, benzyl, C2- C12alkanoyl or benzoyl.
(k') A compound of the formula (1 k)
Figure imgf000055_0001
wherein G, Gn are as defined above.
(I') A compound of the formula (11)
Figure imgf000055_0002
wherein G, Gn are as defined above.
Examples for HALS are the compounds bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4- piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4- hydroxybenzylmalonate, the condensate of 1 -(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6- tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1 ,3,5- triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl)-1 ,2,3,4-butanetetracarboxylate, 1 ,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetrame- thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl- piperidine, bis(1 ,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)- malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1 -octyl- oxy-2,2,6,6-tetramethylpipehdyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpipehdyl)succi- nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene- diamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n- butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-thazine and 1 ,2-bis(3-aminopropylamino)- ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1 ,2,2,6,6-pentamethylpiperidyl)- 1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetrame- thyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyr- rolidine-2,5-dione, 3-dodecyl-1 -(1 ,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, 5-(2- ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone, 1-(2-hydroxy-2-methylpropoxy)-4- octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1 ,3,5-tris(N-cyclohexyl-N-(2,2,6,6- tetramethylpiperazin-3-on-4-yl)amino)-s-triazine, 1 ,3,5-tris(N-cyclohexyl-N-(1 ,2,2,6,6- pentamethylpiperazin-3-on- -yl)amino)-s-triazine, the reaction product of 2,4-bis[(1- cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine with N,N'-bis(3- aminopropyl)ethylenediamine), a mixture of 4-hexadecyloxy- and 4-stearyloxy-2, 2,6,6- tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, a condensate of 1 ,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1 ,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1 ,6-hexanediamine and 2,4,6-trichloro-1 ,3,5-triazine as well as N,N-dibutylamine and 4- butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6- tetramethyl-4-piperidyl)-n-dodecylsuccinimide; N-(1 ,2,2,6,6-pentamethyl-4-piperidyl)-n- dodecylsuccinimide; 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane; 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone; a reaction product of 7,7,9,9- tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1 ,1 - bis(1 ,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis- formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a diester of 4- methoxymethylenemalonic acid with 1 ,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1 ,2,2,6,6-pentamethyl-4-aminopiperidine. Preferred HALS are of molecular weight 400 g/mol or higher; especially preferred are oligomeric HALS of the classes mentioned above, e.g. of molecular weight of 1000 g/mol or higher, e.g. 1500 - 15000 g/mol.
Especially preferred are those of the alkoxyamine class (NOR-HALS), e.g. compound H1 as used in the examples below (also disclosed in Example 2 of US-6117995).
An appropriate combination of the photochromic dyes with UV absorber and a HALS provides an exceptional improvement of the long-term photostability, achieving a lifetime thirty times longer than the unstabilized system.
The components used in the invention can be pure or mixtures of compounds.
Components (c) to be used within present invention basically are known materials, many are commercially available.
Optional further ingredients include further stabilizers, antioxidants, softeners, flame retardants etc. as commonly used for polymeric material, such as the following components:
1. Antioxidants
1.1. Alkylated monophenols. for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylundec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '- methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures there- of.
1.2. Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol. 1.3. Hydroαuinones and alkylated hvdroαuinones, for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
1.4. Tocopherols. for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
1.5. Hvdroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4,-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
1.6. Alkylidenebisphenols. for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methy- lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1 ,1 -bis(5-tert- butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- methylphenol, 1 ,1 ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1 ,1 -bis(5-tert-butyl-4- hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert- butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopenta- diene, bis[2-(3,-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha- late, 1 ,1 -bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe- nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1 ,1 ,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hvdroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl)-1 ,3,5-triazine, 1 ,3,5-ths(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso- cyanurate.
1.11. Benzylphosphonates. for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols. for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of β-(3,5-di-tert-butyl-4-hvdroχyphenyl.propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanedi- ol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert- butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1 ,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]- undecane.
1.15. Esters of β-(3,5-dicvclohexyl-4-hvdroxyphenyl,propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3.5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of β-(3,5-di-tert-butyl-4-hvdroxyphenv0propionic acid e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy- drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau- gard®XL-1 , supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C) 1.19. A inic antioxidants. for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1 -ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1 -methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)-N'-phe- nyl-p-phenylenediamine, N-(1 -methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'- phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di- sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy- diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phe- nyl-2-naphthylamine, octylated diphenylamine, for example p.p'-di-tert-octyldiphenylamine, 4- n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoyl- aminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4- dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N.N.N'.N'-tetramethy ^'-diaminodiphenylmethane, 1 ,2-bis[(2-methylphenyl)amino]ethane, 1 ,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1 ',3'-dimethylbutyl)phenyl]amine, tert- octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert- octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopro- pyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl- phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene, N,N-bis- (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)- sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and light stabilisers
2.1. 2-(2'-Hvdroχyphenyl.benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)benzo- triazole, 2-(3',5'-di-tert-butyl-2,-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2,-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5,-(2- methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl- ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy- phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1 ,1 ,3,3- tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu- tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol
300; l R ~ CH2CH2 - co° " CH-CH- f^ ^ where R _ 3'.tert_butyl-4,-hydroxy-5,-2H-benzotri-
azol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]ben- zotriazole.
2.2. 2-Hvdroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates. for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphe- nylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna- mate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycin- namate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Oxamides. for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
4. Phosphites and phosphonites. for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)- pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristea- ryl sorbitol thphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6- isooctyloxy-2,4,8, 10-tetra-tert-butyl-12H-dibenz[d,g]-1 ,3,2-dioxaphosphocin, bis(2,4-di-tert- butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1 ,3,2-dioxaphosphocin, 2,2',2"-nitrilo- [triethyltris(3,3',5,5,-tetra-tert-butyl-1 ,1,-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-te- tra-tert-butyl-1 ,r-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)- 1 ,3,2-dioxaphosphirane.
The following phosphites are especially preferred:
Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos®168, Ciba-Geigy), tris(nonylphenyl) phosphite,
Figure imgf000064_0001
Figure imgf000064_0002
(CH3)3C
Figure imgf000064_0003
Figure imgf000064_0004
Figure imgf000064_0005
5. Hvdroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones. for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.
7. Thiosvnergists. for example dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β- dodecylmercapto)propionate.
9. Polyamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1 ,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1 ,3:2,4-di(paramethyldibenzyli- dene)sorbitol, and 1 ,3:2,4-di(benzylidene)sorbitol.
12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A^.316611 ; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)- phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phe- nyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2- one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphe- nyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl- benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-di- methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
Conventional additives such as listed components listed above under 1. - 11. and 14. are often added in concentrations of from 0.01 to 10 %, based on the overall weight of the composition (components a, b and c). Further additives of items 12. and 13., such as fillers or flame retardants, may be contained in much higher amounts, e.g. from 0.1 to about 50 % or even 80 % by weight of the total composition.
Preferably, the compositions of the present invention do not contain polyphenolic antioxidants. Such polyphenolic antioxidants are for example described in U.S. 5,770,115.
The polymeric material usually contains 0.001 to 10% by weight, most preferably 0.01 to 5% by weight of the stabilizer component (c). The polymeric material can contain mixtures of two or more of the HALS (ii) and/or the hydroxyphenyl UV absorber (i). The amount of photochromic dye in the polymeric material usually is in the range of about 0.001 to 10% by weight, most preferably 0.01 to 5% by weight, with respect to the total weight of the polymeric material. The polymeric material can contain mixtures of two or more photochromic dyes.
The ratio of component (c) to component (b) can e.g. be in the range of 0.01 to 100 parts, preferably 0.1 to 10 parts, of stabilizer (c) per part of photochromic dye (b).
The ratio of UVA component (i) to HALS component (ii) can e.g. be in the range of 0.01 to 100 parts, most preferably 0.1 to 2 parts, of UV absorber (i) per part of HALS (ii).
The polymeric material, the dye (b) and the stabilizer components (c) often form a homogenous mixture. For specific applications, however, compositions can be made in which components (b) and especially (c) are enriched in a part of the polymeric material, e.g. in the surface areas, or wherein the UV absorber component (i) is enriched in the surface areas while the remaining components are mixed homogenously. Of specific technical importance are 2- or multilayer systems wherein the UV absorber (i) is enriched in an upper layer containing no photochromic dye, while a lower layer contains the dye (b) and HALS (ii), and the UV absorber merely as an optional component. These systems may be obtained by conventional techniques, e.g. coextrusion, adhesion or stacking of layers containing UV absorber (i) or UV absorber (i) and HALS (ii) on one hand, and HALS (ii) and dye (b) on the other hand, and possible further layers, which may improve further properties such as scratch resistance, surface gloss and reflection, adhesion, base colour etc.
The additives/components of the invention and optional further components may be added to the polymer material individually or mixed with one another. If desired, the individual components can be mixed with one another before incorporation into the polymer for example by dry blending, compaction or in the melt.
The incorporation of the components of the invention and optional further components into the polymer is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil. The additives of the invention and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved, melted (soaking process) or dispersed additve or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
The incorporation can be carried out in any heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel. The incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.
The addition of the additive or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
The process is preferably carried out in an extruder by introducing the additive during processing.
Particularly preferred processing machines are single-screw extruders, contrarotating and corotating twin-screw extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffex- trusion, Vol. 1 Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7). For example, the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm.
The maximum throughput is dependent on the screw diameter, the rotational speed and the driving force. The process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
Components to be added can be premixed or added individually. The additives/components of the invention and optional further additives can also be sprayed onto the polymer material. They are able to dilute other additives (for example the conventional additives indicated above) or their melts so that they can be sprayed also together with these additives onto the material. Addition by spraying during the deactivation of the polymerization catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst. In the case of spherically polymerized polyolefins it may, for example, be advantageous to apply the additives of the invention, optionally together with other additives, by spraying.
The components of the invention and optional further additives can also be added to the polymer in the form of a concentrate, e.g. a masterbatch, which contains the components in a concentration of, for example, about 1 % to about 40% and preferably 2 % to about 20 % by weight incorporated in a polymer. The polymer must not be necessarily of identical structure than the polymer where the additives are added finally. In such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
Incorporation can take place prior to or during the shaping operation, or by applying the dissolved, melted (soaking process) or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. A further possibility for incorporating the additives of the invention into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking. In this context the additive of the invention can be added as it is or else in encapsulated form (for example in waxes, oils or polymers).
The materials containing the additives/components of the invention described herein can be used for the production of moldings, rotomolded articles, injection molded articles, blow molded articles, films, tapes, mono-filaments, fibers, nonwovens, profiles, adhesives or putties, surface coatings and the like.
The invention also pertains to a process for stabilizing a photochromic system containing a photochromic dye in a polymer matrix against colour fading induced by irradiation, which process comprises incorporation of a hydroxyphenyl triazine UV absorber and optionally a sterically hindered amine light stabilizer into the polymer matrix and/or into a polymer layer covering said polymer matrix, as well as to the use of a hydroxyphenyl triazine UV absorber and optionally a sterically hindered amine for improving the stability of a photochromic system containing a photochromic dye in a polymer matrix. Preferred processes and uses are in analogy to the compositions described further above or in the examples.
Percentages refer to weight percentages except otherwise stated.
Materials used in the examples:
compound UV1 is of the formula
Figure imgf000070_0001
Compound HALS H1 is of the formula
Figure imgf000070_0002
Compound HALS H2 is of the formula
Figure imgf000071_0001
Chromenel is of the formula
Figure imgf000071_0002
Chromene 2 is of the formula (Rodenstock No. N3)
Figure imgf000071_0003
Examples:
Example 1
Each compound reported in the table below is mixed in a turbo mixer with EVA (ethylene- vinylacetate copolymers) Greenflex® ML30 pellets (containing 9% of vinyl acetate, supplied by Polimeri Europa, Italy), characterized by a melt flow index of 2.5 (190°C/16 Kg; ASTM D1238).
Figure imgf000072_0001
The mixtures are blow extruded (using a mono layer Formac Lab. 25 blow extruder) at 160°C and films of 200 micron thickness are obtained.
The films thus prepared are mounted on a white card and exposed outdoor in the sunshine; a film with formulation 1 covered with a 150 micron thickness film containing 0.15% of the UV absorber UV1 is exposed in the same conditions (formulation: 1 plus UV1 ).
The covering film is a LDPE film containing as the only added additive 0.15 % of UV1. The covering film is prepared by mixing 15g of UV1 and 9850 g of LDPE Riblene FF 29 supplied by Polimeri Europa; they are mixed in a 'turbomixer' for 10 minutes and blow extruded with a
Dolci extruder operating at 210°C.
The table below shows the performance of the three sample films as regards the persistency of the color after light irradiation: the stabilizing effect of UV1 on the chromenel itself and on the chromenel mixed with HALS H1 is evident.
Figure imgf000072_0002
Example 2
The formulations are prepared as in example 1 but with a different chromene. The formulation compositions and results are shown in the tables below.
Figure imgf000072_0003
Figure imgf000073_0001
Example 3
The formulations are prepared as in example 1 but a different sterically hindered amine is used in this example and UV1 is mixed with the other components, i.e. formulation 7 does not have a covering film.
Figure imgf000073_0002
Figure imgf000073_0003
The examples show that the lifetime of the photochromic system is dramatically enhanced by the stabilization system of the invention using a sterically hindered amine in combination with a hydroxyphenyl triazine UV absorber (i).

Claims

Claims
1. Photochromic composition comprising a) a polymeric material, b) a photochromic dye and c) a hydroxyphenyl triazine UV absorber (i) conforming to formula I, II, III, IV, V or (100)
Figure imgf000074_0001
Figure imgf000074_0002
Q
Figure imgf000075_0001
HO IV
N N
X N
Figure imgf000075_0002
Figure imgf000075_0003
wherein
Y is phenyl, naphthyl, or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or Y is Zi or Z2;
Figure imgf000075_0004
Ri is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, halogen, -SR3, -SOR3or -SO2R3; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, -R , -OR5, -N(R5)2, -COR5, -COOR5, -OCOR5, -CN, -NO2, -SR5, -SOR5, -SO2R5 or -P(O)(OR5)2, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four phenylene, -O-, -NR5-, -CONR5-, -COO-, -OCO- or -CO groups or combinations thereof; or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above;
R3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms;
R4 is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms;
R5 is defined as is R ; or R5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R5 is a group for formula
Figure imgf000076_0001
T is hydrogen, oxyl, hydroxyl, -OT1, alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;
Ti is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms or aryl of 6 o 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms; R2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said cycloalkyl substituted by one to four halogen, epoxy, glycidyloxy, furyloxy, -R4, -OR5, -N(R5)2, -CON(R5)2, -COR5, -COOR5, -OCOR5, -OCOC(R5)=C(R5)2, -C(R5)=CCOOR5, -CN, -NCO, or
Figure imgf000077_0001
or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four epoxy, -O-, -IMR5-, -CONR5-, -COO-, -OCO-, -CO-, -C(R5)=C(R5)COO-, -OCOC(R5)=C(R5)-, - C(R5)=C(R5)-, phenylene or phenylene-G-phenylene in which G is -O-, -S-, -SO2-, -CH2- or - C(CH3)2- or combinations thereof, or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R2 is -SO2R3 or -CORβ;
R6 is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, -R7COOH or -NH-R8-NCO;
R7 is alkylene of 2 to 14 carbon atoms or phenylene;
R8 is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group
Figure imgf000077_0002
RT and R/ are the same or different and are as defined for R^ R2 and R2' are the same or different and are as defined for R2;
X and X' are the same or different and are as defined for X; Y and Y' are the same or different and are as defined for Y;
t is 0 to 9;
L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene; or L is benzylidene; or L is -S-, -S-S-, -S-E-S-, -SO-, -SO2-, -SO-E-SO-, -SO2-E-SO2-, -CH2-NH-E- NH-CH2- or
Figure imgf000078_0001
E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by cycloalkylene of 5 to 12 carbon atoms;
n is 2, 3 or 4;
when n is 2; Q is straight or branched alkylene of 2 to 16 carbon atoms; or said alkylene substituted by one to three hydroxy groups; or said alkylene interrupted by one to three
-CH=CH- or -O-; or said alkylene both substituted and interrupted by combinations of the groups mentioned above; or Q is xylylene or a group -CONH-R8-NHCO-, -CH2CH(OH)CH2O- R9-OCH2CH(OH)CH2-, -CO-R10-CO-, or -(CH2)m-COO-Rn-OOC-(CH2)m-, where m is 1 to 3; or Q is
Figure imgf000079_0001
R9 is alkylene of 2 to 50 carbon atoms; or said alkylene interrupted by one to ten -O-, phenylene or a group -phenylene-G-phenylene in which G is -O-, -S-, -SO2-, -CH2- or -C(CH3)2-;
R10 is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by one to four -O-, -S- or -CH=CH-; or R10 is arylene of 6 to 12 carbon atoms;
Rn is alkylene of 2 to 20 carbon atoms or said alkylene interrupted by one to eight -O-;
when n is 3, Q is a group -[(CH2)mCOO]3-R12 where m is 1 to 3, and Rι2 is an alkanetriyl of 3 to 12 carbon atoms;
when n is 4, Q is a group -[(CH2)mCOO] -Rι3 where m is 1 to 3, and RM is an alkanetetrayl of 4 to 12 carbon atoms;
Zi is a group of formula
Figure imgf000079_0002
Z2 is a group of formula
Figure imgf000080_0001
where η and r2 are 1 ;
R.4, Ri5. Ri6, Ri7, i8. R19. R2o. R2ι> R_2 and R23 are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl; or R17 and Rι8or R^ and R23 together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three -O- or -NR5-;
x2 is a number from 1 to 50;
Ai is a group of the formula (101 )
Figure imgf000080_0002
or has one of the meanings given for T10;
Di is C4-Cι2 alkylene or said alkylene substituted by OH or interrupted by O or both substituted by OH and interrupted by O;
L1 is d-Cι8alkylene; C5-C12cycloalkylene; C3-Cι8alkenylene; or one of said residues substituted by phenyl, C7-Cnalkylphenyl, C5-C12cycloalkyl, OH, halogen, d-Cι8alkoxy, C5-
C12cycloalkoxy, C3-Cι8alkenyloxy, COOH; the R50 are independently of each other H, OR54 or OH, with the proviso that at least one of
Figure imgf000081_0001
the R54 are independently of each other hydrogen, C Cι2alkyl or a radical of formula
Figure imgf000081_0002
R55 is H, d-C18alkyl, C2-C12hydroxyalkyl;
R51 is hydrogen, d-C alkyl, Cl, phenyl or a group -OR54; R52 is hydrogen or methyl; R^ is hydrogen, methyl, OH or OR5 ; and
T10 is the divalent acyl residue of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms; and which contains at least one moiety of formula (101 ) and at least one moiety T10.
2. A composition according to claim 1 comprising a) a polymeric material containing b) a photochromic dye and c) a stabilizer combination of i) a hydroxyphenyl triazine UV absorber and ii) at least one further light stabilizer selected from the sterically hindered amines.
3. Composition according to any of claims 1 -2, which is an optical device, an architectural or vehicle glazing, a greenhouse film, a coating, or a construction element, in particular an ophthalmic lense.
4. Composition according to any of claims 1-3, wherein component (a) is selectected from polyolefines, polycarbonate, polyesters, styrene polymers or copolymers, polyacrylates, cellulose esters, polyvinylalcohol, polyurethanes; in particular from polyethylene, polypropylene, polyethylene terephthalate, polystyrene, high impact polystyrene, polyvinylbutyrate, styrene-methacrylate, styrene-acrylonitrile, glycole modified polyethyleneterephtalate, polycarbonate, polymethylmethacrylate, polyvinylbutyral, ethylene- vinyl acetate copolymer, ethylene-butyl acrylate copolymer, and blends thereof.
5. Composition according to any of claims 1 -4 containing a photochromic dye selected from the naphthopyranes, benzopyranes, spiropyranes or spirooxazines as component (b) in an amount of 0.001 to 10% by weight, with respect to the total weight of the polymeric material (a).
6. Composition of claim 2 wherein the sterically hindered amine (ii) is a compound comprising at least one radical of the formula IX, X and/or XI
Figure imgf000082_0001
(IX) (X) (XI) in which
G is hydrogen or methyl, and d and G2 are hydrogen, methyl or together are oxygen, and having a molecular weight of 400 g/mol or higher.
7. Composition of any of claims 1 -6 which is a 2- or multilayer system wherein the UV absorber (i) is enriched in an upper layer containing no photochromic dye, while a lower layer contains the dye (b) and optionally the sterically hindered amine (ii).
8. Composition of any of claims 2-7 wherein the polymeric material (a) contains 0.001 to 10% by weight of the stabilizer component (c) comprising a ratio of UVA component (i) to sterically hindered amine component (ii) in the range 0.01 to 100 parts (i) per 1 part (ii).
9. Composition of any of claims 1-8 comprising as component (d) at least one further additive selected from antioxidants, phosphites and phosphonites, processing stabilizers, fillers, pigments, dyes, clarifiers, modifiers, acid scavengers, flame retardants, further light stabilizers.
10. Process of stabilizing a photochromic system containing a photochromic dye in a polymer matrix against colour fading induced by irradiation, which process comprises incorporation of a hydroxyphenyl triazine UV absorber (i) as of claim 1 and optionally a sterically hindered amine light stabilizer into the polymer matrix and/or into a polymer layer covering said polymer matrix.
11. Use of a hydroxyphenyl triazine UV absorber (i) as of claim 1 and optionally a sterically hindered amine for improving the stability of a photochromic system containing a photochromic dye in a polymer matrix.
PCT/EP2004/052238 2003-09-29 2004-09-20 Stabilization of photochromic systems WO2005030856A1 (en)

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EP04787170A EP1709114A1 (en) 2003-09-29 2004-09-20 Stabilization of photochromic systems
US10/572,154 US20070064195A1 (en) 2003-09-29 2004-09-20 Stabilization of photochromic systems
AU2004275997A AU2004275997B2 (en) 2003-09-29 2004-09-20 Stabilization of photochromic systems
BRPI0414852-5A BRPI0414852A (en) 2003-09-29 2004-09-20 stabilization of photochromic systems
JP2006530247A JP4764822B2 (en) 2003-09-29 2004-09-20 Stabilization of photochromic systems
KR1020067005755A KR101099452B1 (en) 2003-09-29 2004-09-20 Stabilization of photochromic systems
US12/508,641 US8262945B2 (en) 2003-09-29 2009-07-24 Stabilization of photochromic systems

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EP2022820A1 (en) 2007-07-25 2009-02-11 Ems-Patent Ag Photochrome moulding material and objects made therefrom
US7667285B2 (en) 2006-12-14 2010-02-23 Motorola, Inc. Printed electronic substrate havine photochromic barrier layer
US9273213B2 (en) 2010-10-12 2016-03-01 Covestro Deutschland Ag Special UV absorbers for curable UV-protective coatings
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EP1820823A1 (en) 2006-01-27 2007-08-22 EMS-Chemie AG Photochromic moulding compositions and articles made therefrom
KR101413046B1 (en) 2006-01-27 2014-07-09 이엠에스-케미에 아게 Photochromic molding compositions and articles produced therefrom
CN100389168C (en) * 2006-04-04 2008-05-21 吉林大学 Method for making same dye molecule emit light with different colors by substrate induction
US7667285B2 (en) 2006-12-14 2010-02-23 Motorola, Inc. Printed electronic substrate havine photochromic barrier layer
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US9273213B2 (en) 2010-10-12 2016-03-01 Covestro Deutschland Ag Special UV absorbers for curable UV-protective coatings
US11357713B2 (en) 2015-07-14 2022-06-14 Conopco, Inc. Antimicrobial composition
EP3901205A1 (en) * 2020-04-20 2021-10-27 Taiwan Textile Research Institute Photochromic polypropylene fiber and preparation method thereof

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KR101099452B1 (en) 2011-12-28
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AU2004275997A1 (en) 2005-04-07
US20070064195A1 (en) 2007-03-22
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BRPI0414852A (en) 2006-11-21
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MY149850A (en) 2013-10-31
JP2007507569A (en) 2007-03-29
CA2538031C (en) 2015-03-17
JP4764822B2 (en) 2011-09-07
RU2006114602A (en) 2007-11-20
WO2005030856A8 (en) 2006-08-03
US8262945B2 (en) 2012-09-11
EP1709114A1 (en) 2006-10-11
TW200512281A (en) 2005-04-01
US20090289236A1 (en) 2009-11-26
KR20060090811A (en) 2006-08-16
CN1860167B (en) 2011-01-26

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