US20070064195A1 - Stabilization of photochromic systems - Google Patents

Stabilization of photochromic systems Download PDF

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US20070064195A1
US20070064195A1 US10/572,154 US57215404A US2007064195A1 US 20070064195 A1 US20070064195 A1 US 20070064195A1 US 57215404 A US57215404 A US 57215404A US 2007064195 A1 US2007064195 A1 US 2007064195A1
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carbon atoms
alkyl
alkylene
substituted
cycloalkyl
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Mara Destro
Dario Lazzari
Dirk Simon
Manuele Vitali
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BASF SE
BASF Corp
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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.
  • U.S. Pat. No. 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
  • 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 Z 1 or Z 2 ;
  • R 1 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 , —COR 5 , —COOR 5 , —OCOR 5 , —CN, —NO 2 , —SR 5 , —SOR 5 , —SO 2 R 5 or —P(O)(OR 5 ) 2 , morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof; or said alkyl or said cyclo
  • R 3 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;
  • 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 5 a group for formula
  • T is hydrogen, oxyl, hydroxyl, —OT 1 , 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 1 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 to 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;
  • 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 four halogen, epoxy, glycidyloxy, furyloxy, —R 4, —OR 5 , —N(R 5 ) 2 , —CON(R 5 ) 2 , —COR 5 , —COOR 5 , —OCOR 5 , —OCOC(R 5 ) ⁇ C(R 5 ) 2 , —C(R 5 ) ⁇ CCOOR 5 , —CN, —NCO, or or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four epoxy, —O—, —NR 5 —, —CONR 5 —, —COO—, —OCO—, —CO—, —C(R 5 ) ⁇ C(R 5 )COO—, —
  • 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
  • R 1 and R 1 ′ are the same or different and are as defined for R 1 ;
  • R 2 and R 2 ′ are the same or different and are as defined for R 2 ;
  • 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 is 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 10 —CO—, or —(CH 2 ) m —COO—R 11 —OOC—(CH 2 ) m —, 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 —;
  • R 10 is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by one to four —O—, —S— or —CH ⁇ CH—; or R 10 is arylene of 6 to 12 carbon atoms;
  • R 11 is alkylene of 2 to 20 carbon atoms or said alkylene interrupted by one to eight —O—;
  • Q is a group —[(CH 2 ) m COO] 3 —R 12 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 13 where m is 1 to 3, and R 14 is an alkanetetrayl of 4 to 12 carbon atoms;
  • Z 1 is a group of formula
  • Z 2 is a group of formula where
  • R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 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 17 and R 18 or R 22 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 —.
  • the s-triazine UV absorbers are those of formula I where X and Y are Z 1 or Z 2 ;
  • 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 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;
  • Z 2 is a group of formula where r 1 and r 2 are each 1;
  • R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 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.
  • hydroxyphenyltriazines (i) is the compound (a)
  • Hydroxyphenyl triazine UV absorber are described e.g. in GB-A-975966, EP-A-434608, U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,298,067, EP-A-530135, EP-A-520938, EP-A-531258, U.S. Pat. No. 5,556,973, U.S. Pat. No. 5,959,008, U.S. Pat. No. 6,184,375, U.S. Pat. No. 6,117,997; for example in U.S. Pat. No. 5,998,116, U.S. Pat. No. 6,255,483, U.S. Pat. No. 6060543.
  • T 10 is —CO—T 10 ′—CO—, wherein T 10 ′ is alkylene interrupted by C 5 -C 12 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 wherein R 56 is —(C b H 2b )— and R 57 is —(C c H 2c )— and
  • spacer groups T 10 ′ of the formula 103 wherein R 61 , and R 62 independently are alkylene of 4-12 carbon atoms, each of R 63 and R 64 , independently, are C 4 -C 12 alkyl, while R 65 and R 66 are hydrogen.
  • the R 50 are OH
  • Terminal groups of the oligomer or polymer of formula (100) usually are —O—D 1 —OR 67 , or —OR 67 if bonded to A 1 (left side of formula 100),
  • ester of formula (100) may conform to the formula (104) in which
  • T 10 ′ may also be alkylene interrupted by C 5 -C 12 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 1 — identified by the index y, and/or to an end group R 67 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 -C 11 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 1 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, dodecyl, 1,1,3,3,5,5-hexamethylhex
  • Alkylene such as of L 1 or D 1 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-octadec4-enyl.
  • the heavy chains 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 60 alkylene (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 10 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) and a compound of the formula R 67 —O—T 10 —O—R 67 , where Y 1 is CO and all other all symbols are as defined above, with a diol HO—D 1 —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.
  • hydroxyphenyl triazine UV absorber (i) of the formula I, II, III, IV or V.
  • HALS sterically hindered amines
  • oligomeric and monodispersed 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).
  • piperazinones such as products described in WO 00/31069
  • morpholinones see WO 99/14206
  • piperazinediones see DE-A-19924984
  • thioimidazolidinones see WO 01/62739.
  • present invention specifically pertains to a composition
  • a composition comprising
  • compositions of the invention are useful for all applications wherein a photochromic effect is to be achieved. Some examples are described below:
  • polymeric material of component a may be selected from polymers listed below:
  • 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:
  • Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • 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′): where:
  • one of the carbon atoms, along with bonding hydrogens, if present, are replaced by oxygen, nitrogen or NH.
  • Naphthopyran photochromic compounds usually have the general structural formula (IX′): where:
  • naphtopyran photochromic compounds useful in the present invention are:
  • Preferred naphthopyranes also include those of the formulae where each of R 31 , R 32 , R 33 , R 34 , R 35 independently may be hydrogen, a hydrocarbon of 1 to 18 carbon atoms such as phenyl, naphthyl, alkyl, optionally substituted by OH, C 1 -C 6 alkoxy; —NR′R′′; —NO 2 ; where R′ and R′′ independently are H or C 1 -C 12 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 where each of R 41 , R 42 , R 43 , R 44 , R 45 independently may be hydrogen, a hydrocarbon of 1 to 18 carbon atoms such as phenyl, naphthyl, alkyl, optionally substituted by OH, C 1 -C 6 alkoxy; —NR′R′′; —NO 2 ; where R′ and R′′ independently are H or C 1 -C 12 alkyl, C 4 -C 12 cycloalkyl, C 7 -C 13 phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene.
  • a chromene may be selected from naphthopyrans of the formula wherein R is H; C 1 -C 6 alkyl; C 1 -C 6 alkoxy; —NR′R′′; —NO2; where R′ and R′′ independently are H or C 1 -C 12 alkyl, C 4 -C 12 cycloalkyl, C 7 -C 13 phenylalkyl, or together are tetramethylene or pentamethylene or O-interrupted tetramethylene.
  • Chromene1 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 in which
  • 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 n 1 , and the meaning of R arises from the definition given above.
  • C 1 -C 18 alkoxy G 11 is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
  • C 5 -C 12 cycloalkoxy G 11 is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.
  • C 7 -C 8 phenylalkoxy is, for example, benzyloxy.
  • G 11 as C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy or C 7 -C 15 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, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1-ethanol; 1,2-ethanediol, 1,
  • G 12 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.
  • G 12 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 C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • G 12 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-4-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 12 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.
  • G 12 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.
  • 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 1 -C 18 alkanoyl G 13 is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and C 3 -C 5 alkenoyl G 13 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 1 -C 4 alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
  • Any C 2 -C 12 alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • Any C 6 -C 15 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 14 as 1-oxo-C 2 -C 12 alkylene is preferably a group (c′)
  • G 15 and G′ 15 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.
  • (d′) A compound of the formula (1d-1), (1d-2) or (1d-3), in which n 4 is the number 1 or 2, G, G 1 and G 11 are as defined under (a′),
  • Any C 1 -C 1 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 C 1 -C 18 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 G 17 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
  • T 1 and T 2 are, in particular, phenethyl or especially benzyl. If T 1 and T 2 together with the carbon atom form a cycloalkane ring, this can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
  • C 2 -C 4 hydroxyalkyl G 17 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • C 6 -C 10 aryl G 17 , T 1 and T 2 are, in particular, phenyl or ⁇ - or ⁇ -naphthyl, which are unsubstituted or substituted by halogen or C 1 -C 4 alkyl.
  • C 2 -C 12 alkylene G 17 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • C 4 -C 12 alkenylene G 17 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 5 arylene or C 6 -C 12 cycloalkylene D′ have, for example, one of the definitions given for D under (b′).
  • (e′) A compound of the formula (1e) in which n 5 is the number 1 or 2, and G 18 is a group of the formula in which G and G 11 are as defined under (a′), and G 1 and G 2 are hydrogen, methyl or, together, are a substituent ⁇ O,
  • Any C 1 -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.
  • 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.
  • (f′) A compound of the formula (1f) wherein G 11 is as defined under (a′).
  • m 1 to m 14 is a number from 2 to about 200, preferably 2 to 100, for example 2to 50, 2to 40, 3to 40or 4to 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:
  • the end group bonded to the >C ⁇ O group can be, for example, and the end group bonded to the oxygen can be, for example
  • the end group bonded to the 2,5-dioxopyrrolidine ring can be, for example, hydrogen
  • the end group bonded to the —C(G 34 )(G 35 )— radical can be, for example,
  • 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:
  • 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 21 , is a number from 3 to 10, i.e. the free valences shown in the structural formula then form a direct bond.
  • 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 4 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
  • Alkyl is for example C 1 -C 4 alkyl, in particular methyl, ethyl, propyl or butyl.
  • Cycloalkyl is preferably cyclohexyl.
  • Alkylene is for example ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2dimethyltrimethylene or hexamethylene.
  • Alkenyl is preferably allyl.
  • Phenylalkyl is preferably benzyl.
  • Acyl is preferably acetyl.
  • 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-2,6-dichloro-1,
  • 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 glmol.
  • 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.
  • Optional further ingredients include further stabilizers, antioxidants, softeners, flame retardants etc. as commonly used for polymeric material, such as the following components:
  • Tris(2,4-di-tert-butylphenyl) phosphite (Irgafoso®168, Ciba-Geigy), tris(nonylphenyl) phosphite,
  • compositions of the present invention do not contain polyphenolic antioxidants.
  • polyphenolic antioxidants are for example described in U.S. Pat No. 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 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).
  • 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 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.
  • 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 mixtures are blow extruded (using a mono layer Formac Lab. 25 blow extruder) at 160° C. and films of 200 micron thickness are obtained.
  • 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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CN113416516A (zh) * 2021-06-18 2021-09-21 北京天山新材料技术有限公司 丙烯酸酯厌氧胶、用于形成其的组合物及应用

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US20120178019A1 (en) * 2009-06-25 2012-07-12 Sabic Innovative Plastics Ip B.V. Method of making holographic recording materials and articles formed thereby
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CN113416516A (zh) * 2021-06-18 2021-09-21 北京天山新材料技术有限公司 丙烯酸酯厌氧胶、用于形成其的组合物及应用

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