Title of Invention

"ULTRAVIOLET LIGHT (UV) ABSORBING COMPOUNDS AND COMPOSITIONS CONTAINING UV ABSORBING COMPOUNDS"

Abstract Hydroxybenzotriazole-based compounds are useful for ultraviolet light absorbing additives for a variety of applications. Such compounds have particular usefulness in various applications, including plastics, automotive, coatings, and food packaging applications. Such inventive compound exhibit excellent UV radiation absorbing activity, high thermal stability, excellent low fogging, low extraction/low migration rates, and high lightfastness levels, particularly when incorporated within certain media and/or on the surface of certain substrates, particularly polyesters, polyoiefins, and polyurethanes. Block copolymer chain or chains consisting of poly(oxyalkylene) and/or aliphatic polyester segments can be conveniently tailored to increase the solubility or compatibility in different solvents or resins thereby permitting the introduction of such excellent UV absorbing chromophores within diverse media and/or or diverse substrates. Compositions and articles comprising such compounds are provided as well as methods for producing such inventive compounds.
Full Text Ultraviolet Light (UV) Absorbing Compounds and
Compositions Containing UV Absorbing Compounds
Background of the Invention
Ultraviolet absorbing compounds have many uses and industrial
applications. Such compounds are useful in combination with various polymers,
including for example polyurethanes, polyolefins, PET, and the like for protecting
the polymers or products made with the polymers against degradation by
exposure to ultraviolet light.
United States Patent Nos. 5,994,431; 6,150,440 and 6,291,586 are
directed to amide functional benzotriazole UV absorbers and their application in
polyolefin, polyurethane and other films. United States Patent No. 5,459,222 to
Rodgers reports UV absorbing polyurethanes arid polyesters obtained by
reacting difunctional (i,e. two -OH groups) benzotriazole UV absorbers with
polyurethane or polyester monomers.
United States Patent No. 6,307,055 to Thanki et al discloses a diolfunctionalized
benzotriazole UV absorbers prepared from bromobenzotriazole
precursor and di(hydroxyalkyl)amine.
United States Patent Nos. 4,857,471; 4,973,702 and 5,032,498 disclose
amide functional benzotriazole UV absorbers. United States Patent No.
5,585,228 discloses a specific benzotriazole derivative as photographic element.
This specific UV absorbers are obtained from the reaction of the 4-OH group on
2H-(2,4-dihydroxyphenyl)benzotriazole with glycidyl ethers.
United States Patent No. 6,037,393 to Okumura reports novel polyester
compounds having benzotriazole group(s) obtained by ring-openfng
polymerization of lactones with hydroxyalkylphenyl benzotriazoies.
United States Patent Nos. 6,653,484 and 6,369,267 to Toan et al.
disclose benzotriazole derivatives which are substituted or bridged with
polyoxyalkylene groups obtained from the reaction of benzotriazole precursors
with alkyl caped polyethylene glycol glycidyl ether.
Detailed Description of the Invention
Reference now will be made to the embodiments of the invention, one or
more examples of which are set forth below. Each example is provided by way
of explanation of the invention, not as a limitation of the invention. In fact, it will
be apparent to those skilled in the art that various modifications and variations
can be made in this invention without departing from the scope or spirit of the
invention.
The invention is directed to UV absorbing compounds that can be used in
a wide variety of compositions or end products to provide to a coating, substrate,
or resin a UV resistant property. Ultraviolet light degrades many substances,
and thus a composition that can be used to avoid such undesirable degradation
is highly desirable.
Benzotriazole derivatives set forth herein are in general reactive,
liquid, and are polymeric-bearing amide functioning oxyalkylene and aliphatic
ester block copolymer/oligomer chain(s). The inventive UV absorbers set forth
herein typically are liquid and polymeric, but it is not required that they be liquid,
or polymeric.
The inventive UV absorbers, in one particular embodiment, bear primary
OH group(s) at the end of the respective polymer chain(s). They may be
completely reactive in polyurethane, PET and polycarbonate (PC) applications,
for example. One advantage of the invention is that the inventive UV absorbers
tend to resist extraction, migration, fogging, and leaching. Furthermore, they
may provide longer performance lifetimes than conventional UV absorbers in
many applications.
The inventive UV absorbers may bear oxyalkylene (hydrophilic) and
aliphatic ester (hydrophobia) functions, thus usually these compositions are
adjustable within the combination to provide compatibility for various media.
The inventive UV absorbers (when used in combination with other additives)
may offer a very good solution to stabilize polyurethane from NOX gas fading,
which is highly desirable.
The invention, in one embodiment, may comprise ultraviolet light
absorbing compound having the structure represented by
Ri is selected from the group of: H, F, Cl, Br, I, alkyls, aikoxy, 0=0
containing radicals represented as -C(0)-A, and SO2-containing radicals
represented as S02-A, wherein A is OH, alkyl, aikoxy, or an organic amine
group;
Rz is selected from the group of: H, Ci-Cio alkyls, or C
phenylalkyls;
Rs is selected from the group of: H, carbon and/or oxygen and/or nitrogen
conlaining chain radicals; and
R4 is selected from the group of: divalent 62-020 alkyl radicals, divalent
CrCao alky radicals which are interrupted by oxygen, sulfur or nitrogen, and
divalent oligomeric radicals; and
G is selected from one of the following: H, Ci - Cm alkyls, alkyl
carbonyls, and aryl carbonyl groups; and
Z-i is selected from (a) or (b) below:
(a) C2-C1D alkyls;
(b) divalent radicals represented by:
:
Rr and Ra each are independently selected from H or Ci -
alkyl groups;
n comprises an integer between 1 and 10;
m comprises any positive integer or fraction between 1 and 20.
Furthermore, a compound is provided in one aspect of the
invention wherein Rs comprises a carbon and/or oxygen and/or nitrogencontaining
chain radical represented by:
RI, Z-i, and G are as defined above.
In some applications of the invention, a compound is provided in
which R4 is a divalent oligomeric radical represented by:
R5
---*•>, S-\(EG/,(POMEG)..-
r.|-
wherein
EO comprises ethylene oxide or a derivative thereof;
PO comprises propylene oxide or a derivative thereof; and
R5 comprises H or Ci - do alkyl groups;
Re comprises a divalent Ci - Cm alkyl radical;
wherein x, y, and z comprise positive integers or fractional
numbers between 0 and 20, and further
wherein x + y + z is equal to or greater than 1.
RI and Ra, in some embodiments, may be bonded to specific
respective carbons, as shown below:
wherein RI, Rz, Rs, R4, Zi and G are as previously described.
A compound of the invention may also be represented by the
formula:
RI \s selected from the group of: H, F, Cl, Br, I, alkyls, alkoxy,
A and -SOz-A wherein A is OH, alkyl, alkoxy, or an organic amine group;
R2 Is selected from the group of: H, Ci - C-io alkyls, and Cy - Cao
phenylalkyls;
Ra is selected from the group of: H, carbon and/or oxygen and/or
nitrogen-containing chain radicals; and
R4 is selected from the group of: divalent C2 - C2D alkyl radicals, divalent
C^CZQ alky radicals which are interrupted by oxygen, sulfur or nitrogen, and
divalent oligomeric radicals; and
R-f and Re each are independently selected from the group of:
H and Ci - Cio alkyl groups;
n comprises an integer between 1 and 10; and
m comprises a positive integer or fraction between 1 and 20.
The invention, in one aspect, may provide an ultraviolet light absorbing
compound adapted for incorporation into polymers, said compound being
comprised of a benzotriazole moiety and at least one reactive moiety bonded to
said benzotriazole moiety, said reactive moiety being capable of reacting with
said polymer under conditions to facilitate substantial non-migration of said
compound within polymer, said reactive moiety having at least one reactive -OH
group, further wherein said compound comprises a liquid or a paste at a
temperature of up to about 45 degrees C. The reactive moiety may comprise:
(a) a proximal portion adjacent to and bonded to said benzotriazole moiety, and
(b) a distal portion positioned apart from said benzotriazole moiety, wherein said
-OH group is positioned upon said distal portion. The reactive moiety may
comprise an amine or an amide. The amine may comprise a tertiary amine.
The reactive moiety further may comprise an oxyalkylene or a derivative
thereof. The reactive moiety comprises at least one aliphatic portion. The
aliphatic portion further may comprise a copolymeric chain. The aliphatic
portion may comprise a block copolymer.
In one aspect of the invention, an ultraviolet light absorbing compound
may be adapted for incorporation into polymers. The compound may be
comprised of a benzotriazole moiety and at least one reactive moiety bonded to
the benzotriazole moiety. The reactive moiety may be capable of reacting with
the polymer under conditions to facilitate substantial non-migration of the
compound within polymer. The reactive moiety has at least one reactive -OH
group, further wherein said compound is a liquid or a paste at a temperature of
up to about 45 degrees C. The reactive moiety may (in some applications)
comprise (a) a proximal portion adjacent to and bonded to said benzotriazole
moiety, and (b) a distal portion positioned apart from said benzotriazole moiety.
An -OH group may be positioned upon the distal portion, as defined.
The compound(s) of the invention may be made in part by the process of
reacting (a) and (b), as further set forth below:
(a) the compound having the structure represented as the following
R-i and Rz are independent and are defined as above;
R is a group selected from hydrogen, alkyl and aryl; and
(b) an organic amine as represented as
In one embodiment of the invention, the compound may be made by
reacting the compound set forth in (a) with said amine in (b) to make an
intermediate or a product, said intermediate or product being illustrated as the
RL Ra, Ra, and R4 are defined as above.
In yet another embodiment of the invention, the compound(s) may be
formed in part by making said intermediate, further wherein said intermediate of
said process is further reacted with m equivalents of cyclic lactones/esters
represented as the following structure
wherein Xi is a divalent radical selected from the group of: Cj-Czo aryls,
and alkyls as represented by the following
wherein: n, m, R7 and Ra are defined as above.
Thus, those reactions result in the ultraviolet light absorbing compound of
the invention, in some embodiments.
An article may be provided in the invention which includes:
(a) at least one polymeric formulation having a thermoplastic or thermoset
component, or mixtures thereof; (b) at least one UV absorber compound, either
i) present within said polymeric formulation or
ii) adhered to the surface of said polymeric formulation. In one aspect of the
invention, the UV absorber compound may comprise a benzotriazole derivative,
further wherein at least one alkyl chain which is interrupted by oxygen, sulfur or
nitrogen; and a poly(oxyalkylene) chain, aliphatic polyester chain, or
block.copolymeric chain, consisting of poly(oxyalkylene) and aliphatic polyester
segments. The segments being attached to said UV absorber compound by
way of an amide functional group.
The compounds according to the invention may be effective light
stabilizers for organic materials, for example for coatings and a large number of
polymers. For all applications in which a liquid, oligomeric and non-migration
properties are highly desirable, the inventive compounds afford advantages
over conventional UV absorbers. These polymers may be polyurethane,
polyolefin, PET and other polyester, polycarbonate, polyamide, and the like.
Some representative polymers are provided as such: polymers of
monoolefines and diolefines, for example polyethylene {which can, if desired, be
crosslinked), polypropylene, polyisobutylene, polybut-1-ene, polymethylpent-1-
ene, polyisoprene or polybutadiene, and also polymers of cycloolefmes, for
example polymers of cyclopentene or norbornene; mixtures of such polymers,
for example, mixtures of polypropylene with polyethylene or polyisobutylene.
Copoiymers of monoolefines or diolefines with one another or with other
vinyl monomers, for example ethylene/propylene copolymers, propylene/but-1-
ene copolymers, propyiene/isobutylene copolymers, ethylene/but-1-ene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/ethyl acrylate copolymers, ethylene/alkyl methacrylate
copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid
copolymers and salts thereof (ionomers), and also terpolymers of ethylene with
propylene and a diene, such as hexadiene, dicyclopentadiene or
ethylidenenorbornene, random copolymers of styrene or alpha.-methylstyrene
with dienes or acrylic derivatives, for example styrene/butadiene,
styrene/acrylonitrile, styrene/ethyl methacrylate or
styrene/acrylonitrile/methacrylate; mixtures of high impact strength obtained
from styrene copolymers and another polymer, for example a polyacrylate, a
diene polymer or an ethylene/propylene/diene terpolymer; and also block
copolymers of styrene, for example styrene/butadiene/styrene,
styrene/isoprene/styrene, styrene/ethylene-butylene/styrene or
styrene/ethylene-propylene/styrene; graft copolymers of styrene, for example
styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene
and alkyl acrylates or alkyl 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 and mixtures thereof with the copolymers
mentioned under 5), such as are known as so-called ABS, MBS, ASA or AES
polymers; halogen-containing polymers, for example polychloroprene,
chlorinated rubber, chlorinated or chlorosulfonated polyethylene and especially
polymers formed from halogen-containing vinyl compounds, for example
polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride and polyvinylidene
fluoride and also copolymers thereof, such as vinyl chloride/vinylidene chloride,
vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate; polymers
derived from ,a/pfta.,.ibete.-unsaturated acids and derivatives thereof, such as
polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles;
including also copolymers of the monomers above, with one another or with
other unsaturated monomers, for example acrylonitrile/butadiene copolymers,
acrylonitriie/alkyl acrylate copolymers, acrylonitrile/vinyl chloride copolymers or
acrylonitrile/alkyl methacrylate/butadiene terpolymers; polymers derived from
unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as
polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallylmelamine;
homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols,
polyethylene oxide or polypropylene oxide or copolymers thereof with bisglycidyl
ethers; polyacetals, such as polyoxymethylene and also polyoxymethylenes
containing comonomers such as ethylene oxide; polyphenylene oxides and
sulfides and also mixtures of polyphenylene oxides and polystyrene;
polyurethanes derived, on the one hand, from polyethers, polyesters and
polybutadienes having terminal hydroxyl groups and, on the other hand, from
aliphatic or aromatic polyisocyanates, and also precursors thereof; polyamides
and copolyamides derived from diamines and dicarboxylic acids and/or from
aminocarboxylic acids or the corresponding lactams, such as polyamide 4,
polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-
2,4,4-trimethylhexamethylene terephthalamide and polym-phenylene
isophthalamide, and copolymers thereof with polyethers, for example
copolymers with polyethylene glycol, polypropylene glycol or polytetramethylene
glycol.
Product and End Use Applications
Appropriately stabilized compositions are thus a preferred form of the
compositions mentioned above. It is preferable to stabilize polyurethane and
coatings formed from polymers of any appropriate types in any suitable
applications, such as automotive, textile, and exterior and interior of
constructions.
The invention may be used when there are risks in being exposed to a
' . "I- :.
light such as sunlight and ultraviolet rays. Specifically, this means that they can
be used as glass-substitute products or as glass coating, for houses, equipment,
for windows of means of transport, as a coating for lighting glass and for lightsources
protecting glass, as an internal or external painting for means of
transport, as a material to produce light sources such as florescent lamps or
mercury lamps which emit ultraviolet-rays, for producing precise devices, as a
material for electrical or electronic devices,
Further, applications include a material containing compositions useful for
cutting off electromagnetic waves or the like which are generated by a variety of
displays, for food, for chemicals, Pharmaceuticals, as a coating or a container of
Pharmaceuticals. The compositions of the present invention may be used to
produce sheets or films that may be used in the agricultural field. The
compositions of the present invention may be used for printing materials, such
as colorants, in cosmetics for preventing fading, in creams for stopping sunburn,
in shampoos or rinses, or other hair care products, in sponge wears, stockings,
for making fibers used to manufacture clothes or other articles such as hats or
the like, curtains, carpets, for furniture such as wall paper, for plastic lenses,
contact lenses, artificial eyes or other medical devices, optical filters, prisms,
mirrors, optical articles for photographic material, tapes, ink or other stationery
articles, for marker boards, or as a coating for the surface of marking devices.
The stabilizing compounds are incorporated into the organic material by
the conventional methods, for example in any desired phase during the
manufacture of shaped products. They can, for example, be mixed in the form of
a liquid, a paste, a powder with other materials, suspensions or emulsions or
solutions into the polymer, which can be in the form of a powder, melt, solution,
suspension or emulsion.
Concentrations and Compositions
The stabilizer mixtures of the invention can, if desired, contain 0.1 to 15%
by weight, preferably 0.3 to 8% by weight, relative to the polymer, of the
customary additives, in particular antioxidants, other UV absorbers such as
benzotriazole-, hydroxyl benzophenone- or phenyl triazine-based, other types of
light stabilizers or mixtures thereof.
In stabilizing polyurethane foam in particular, the inventive compounds
can be used with the following classes of additives:
Class A: Benzotriazoles are (in general) those compounds that conform to
the structure represented as the following:
wherein Rg, RIO, and Rn are individually selected from hydrogen, a group having
a formula CaHbNtAjSe wherein a, b, c, d, and e are from 0 to 30, and halogen.
Class B: Hindered phenols or BHT derivatives, and related compounds
typically conform to the structure of the following:
wherein Ri2 is selected from the group consisting of hydrogen, a group having a
formula CaHbNcOdSa wherein a, b, c, d, and e may be from 0 to 30, and halogen.
Class C: Secondary diphenylarnines may conform to the structure of the
following ;
wherein Risand R^ are individually selected from the group consisting of
hydrogen, a group having a formula CaHbNcOdSe wherein a, b, c, d, and e are
from 0 to 30, and halogen.
Class D: Lactone-based antioxidants may include those compounds that
conform to the structure of the following:
wherein Ris, to Raa are individually selected from the group consisting of
hydrogen, a group having a formula CBHbNqOdSe wherein a, b, c, d, and e are
from 0 to 30, and halogen.
The following examples are illustrative of the invention, but do not in limit
the scope of the invention. Species provided below may enable a person of skill
in the art to practice the entire chemical genus represented by the specific
species presented below.
Synthetic Examples of the Invention
EXAMPLE 1
A 100 ml 3-neck round-bottom flask equipped with a mechanical stirrer, a
thermal controller and a reflux condenser was charged with about 20 g (51
mmol) of 3-(5-chloro-2H-benzotriazol-2-yl)-5-(1,1-dimethyletnyl)-4-hydroxybenzenepropanoic
acid methyl ester, 4.4 g (1.4 eq) of ethanolamine and 100 ml
of xylene. The reaction was heated to 130C under N2 blank and monitored. After
about eight (8) hours, the reaction was completed. Upon cool down to 5-10°C,
the solid precipitate was collected by filtration, and washed with cold methylene
chloride and dried overnight. 20.5 g of analytical pure product was obtained with
a melting point (mp) of about 132-135C, and an NMR (CDCI3): 11.51 (broad,
1H), 8.06 (s, 1H), 7.89 (s, 1H), 7.85 (d, 1H), 7.41 (d, 1H), 7.21 (s, 1H), 6.06 (m,
1H), 3.70 (t, 2H), 3.41 (m, 2H), 3.01 (t, 2H), 2.56 (t, 2H), 1.48 (s, 9H).
To a 250 ml 3-neck round-bottom flask equipped with a mechanical
stirrer, a thermal controller and a reflux condenser, were charged 54.5 g (141
mmol) of 3-(5-chloro-2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxybenzenepropanoic
acid methyl ester and 21.8 g (1.4 eq) of diglycolamine. After 6
hours of heating to 130-135°C with Na sweep, TLC suggested there was still
trace amount of starting material presence. 2.6 g (0.2 eq) of diglycolamine was
added and the heating was continued for 2 more hours. TLC analysis suggested
the reaction was completed. Upon cool down.to room temperature, 250 ml of
methylene chloride was introduced into the reaction mixture, and the solution
M
was washed three times with 3 x 75 ml of 3% aqueous HCI and then once with
75 ml of water. The organic layer was collected and dried with MgSC>4 and the
solvent was removed by rotary evaporator. 56 g of analytical pure product was
obtained as a pale yellow solid with a mp 84-87 °C, and NMR {CDCI3): 1 1 .52 (s,
1H), 8.07 (s, 1H), 7.89 (s, 1H), 7.85 (d, 1HJ, 7.40 (d, 1H), 7.21 (s, 1H), 6.16 (m,
1H), 3.69 (t, 2H), 3.55 (m, 6H), 3.00 (t, 2H), 2.55 (t, 2H), 1.48 (s, 9H).
To a 100 mL 3-neck round-bottom flask equipped with a mechanical
stirrer, a thermal controller and a reflux condenser, were charged 20 g {51 mmol)
of 3-(5-chloro-2H-benzotriazol-2-yI)-5-(1r1-dimethylethyl)-4-hydroxybenzenepropanoic
acid methyl ester and 12 g (1.4 eq) of polyglycolamine H-163
(available from Dixie Chemical). The reaction mixture was heated to 130-135 °C
for 6 hours with Nz sweep. TLC analysis suggested the reaction was completed.
Upon cool down to room temperature, 120 ml of methylene chloride was
introduced into the reaction mixture, and the solution was washed three times
with 3 x 40 ml of 3% aqueous HCI and then once with 40 ml of water. The
organic layer was collected and dried with MgS04 and the solvent was removed
by rotary evaporator. 22 g of analytical pure product was obtained as a paste,
with proton NMR (CDCI3): 11.51 (s, 1H), 8.08 {s, 1H), 7.90 (s, 1H), 7.85 (d, 1H),
7.41 {d, 1H), 7.22 (s, 1H), 6.28 {m, 1H), 3.71 {t, 2H), 3.57 (m, 4H), 3.49 (m, 4H),
3.00 (t, 2H), 2.52 (t, 2H), 1 .48 (s, 9H). '
To a 250 mL 3-neck round-bottom flask equipped with a mechanical
stirrer, a thermal controller and a reflux condenser, were charged 20 g {51 mmol)
of 3-(5-chloro-2H-benzotriazol-2-yl)-5-{1 „ 1 -dimethylethyl)-4-hydroxybenzenepropanoic
acid methyl ester and 22 g (1.4 eq) of 2-amino-1-butanol 5EO
[1-poly(oxyethylene)oxy-2-amino-butane, Mw 309, prepared in Milliken lab]. The
reaction mixture was heated to 130-135 °C for 6 hours with N2 sweep. TLC
analysis suggested the reaction was completed. Upon cool down to room
temperature, 150 ml of methylene chloride was introduced into the reaction
mixture, and the solution was washed three times with 3 x 40 ml of 3% aqueous
HCI and then once with 40 ml of water. The organic layer was collected and
dried with MgSO4 and the solvent was removed by rotary evaporator. 30 g of
product was obtained as a pale yellow liquid which was confirmed by NMR and

To a 100 ml 3-neck round-bottom flask equipped with a mechanical
stirrer, a thermal controller and a reflux condenser, were charged 30 g (85 mmol)
of3-(2H-benzotriazol-2-yl)-5-(1l1-dimethylethyl)-4-hydroxy-benzenepropanoic
acid methyl ester and 14.2 g (1.6 eq) of diglycolamine. After 9 hours of heating to
13Q-135C with N2 sweep, TLC analysis suggested the reaction was completed.
Upon cool down to room temperature, 200 ml of methylene chloride was
introduced into the reaction mixture, and the solution was washed three times
with 3 x 50 ml of 3% aqueous HCI and then once with 50 ml of water. The
organic layer was collected and dried with MgSCU and the solvent was removed
by rotary evaporator. 32 g of product was obtained as a viscous liquid, which
upon standing in -5 °C overnight become a pale solid with the mp of 106-109 "C.
Product purity was confirmed by NMR.
EXAMPLE 6
Accordingly, the title product was prepared from the reaction of 30 g (85
mo!) of 3-(2H~benzotriazol-2-yl)-5-(1,1-dimethyletnyl)-4-hydroxybenzenepropanoic
acid methyl ester with 8.3 g (1.6 eq) of ethanolamine, using
the similar procedure as described in Example 5, Product purity was confirmed
by NMR and directly used as intermediate for further reaction with purification.
EXAMPLE 7
Accordingly, the title product was prepared from the reaction of 30 g (85
rnol)of3-(2H-benzotriazol-2-y!)-5-(1,1-dimethyIethyl)-4-hydroxybenzenepropanoic
acid methyl ester with 19.4 g (1.4 eq) of polyglycolamine H-
163, using similar procedure as described in Example 3. Product purity was
confirmed by NMR and directly used as intermediate for further reaction with
purification.
EXAMPLE 8
Accordingly, the title product was prepared as a viscous liquid from the
reaction of 30 g (85 mol) of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-
hydroxy-benzenepropanoic acid methyl ester with 36.8 g (1.4 eq) of 2-amino-1-
butanol 5EO [1-poly(oxyethylene)oxy-2-amino-butane, Mw 309, prepared in
Milliken lab], using similar procedure as described in Example 4. Product purity
was confirmed by NMR and IR.
EXAMPLE 9
To a 500 ml 3-neck round-bottom flask equipped with a mechanical
stirrer, a thermal controller and a reflux condenser/were charged 100 g (217
mmol) of benzotriazole intermediate prepared in Example 2,74 g (3 eq) of
caprolactone, and 1 g of 50% hypophosphorous acid. The reaction mixture was
heated to 100 °C under Na for 3 hours, 174 g of product was obtained as pale
yellow liquid with a color value/absorbance value of 20.1 abs./g/L (in MeOH) at
347 nm. 71% of transesterificaton rate was obtained based on HPLC
analysis. NMR (CDCI3) and IR (on NaCI plate) confirmed the product purity.
EXAMPLE 10
o a 100 ml 3-neck round-bottom flask equipped with a mechanical
stirrer, a thermal controller and a reflux condenser, were charged 20 g (43 mmol)
of benzotriazole intermediate prepared in Example 2,19.8 g (4 eq) of
caprolactone, and 0.08 g of Pascal® FC9102 (available from Atofina Chemical).
The reaction mixture was heated to 140-150 CG under Na for 1-2 hours. 37 g of
product was obtained as pale yellow liquid with a color value/absorbance value
of 17.8 abs./g/L (in MeOH) at 347 nm. 78% of transesterificaton rate was
obtained based on HPLC analysis.
22
EXAMPLE 11
To a 100 ml 3-neck round-bottom flask equipped with a mechanical
stirrer, a thermal controller and a reflux condenser, were charged 20 g (47 mmol)
of benzotriazole intermediate prepared in Example 5,16 g (3 eq) of
caprolactone, and 0.2 g of 50% hypophosphorous acid. The reaction mixture
was heated to 100 °C under N2 for 3 hours. The mixture was cool down to room
temperature and dissolved into 150 ml of methylene chloride. The solution was
washed twice with 50 ml of water and dried over MgSCU. Upon removing
solvent, 33 g of product was obtained as pale liquid with a color
value/absorbance value of 17.6 abs./g/L (in MeOH) at 339 nm. 75% of
transesterificaton rate was obtained based on HPLC analysis.
Following the procedure as decribed in Example 11, the title product was
prepared from 20 g (47 mmol) of benzotriazole intermediate prepared in
Example 5, and 21.4 g (4 eq) of caprolactone, and 0.2 g of 50%
23
hypophosphorous acid. 28 g of product was obtained as pale yellow liquid with a
color value/absorbance value of 16.4 abs./g/L (in MeOH) at 339 nm. 72% of
transesteriflcaton rate was obtained based on HPLC analysis.
Article Production and Performance
Testing for Various Inventive Liquid
Polymeric Benzotriazole UV Absorbers
a) Pplyether Foam Article Formation
The inventive UV absorbers were incorporated with or without other
additives to produce (in one particular embodiment of the invention)
polyurethane foam in accordance with the following formulation and
procedure:
Component Amount
F3022 Polyol (from Arco Chemical) 100 grams
Water 4.53ml
DABCO 33LV (catalyst, from Air Products) 0.15 ml
DABCOT10 (catalyst) 0.32ml
L520 Silicone (from Union Carbide) 1.0 ml
80/20 Toluene diisocyanate (Bayer)(112 index) 49.0 ml
ReacTint® Blue X3LV as noted
Inventive UV Absorber as noted
Additive from Class A (UV absorbers)
Comparative (Tinuvin® 326) as noted
Comparative (Tinuvin® 1130) as noted
Additive from Class B
lrganox®1135 as noted
Additive from Class C
lrganox®5057 as noted
Additive from Class D
Irganox® HP 136 as noted
Upon mixture within a reaction vessel, the reaction created a "health"
bubble (indicating gelation and blowing, balance), and the vessel was then
1A
exposed to 185 °C (generated within a microwave oven to simulate actual heat
history encountered on an industrial production environment) for about 10 min to
form a foam bun. The resultant foam buns were then analyzed for performance,
as discussed in details below.
b) Performance Characteristics of Polvether Foams Including Inventive UV
Absorbers
The white foams made in accordance with formulation and process as
described in Section a), were all tested for standard foam performance, in terms
of rise time, tack time, and bun height, and compared with the control polyether
foams either made with existing commercial UV absorbers or made without
additive. Measurements within 5% of the control are considered acceptable for
the finished foam product. The measurements are summarized in Table 1.
Table 1. Foam Performance of Inventive or Comparative UV Absorbers
Sample
Additionally, the foams produced exhibited good resiliency and densities
measured at about 1.5 pounds per cubit foot. Thus, the inventive UV absorbers
provide acceptable polyurethane foam articles as compared with control
samples.
c) Extraction Measurements From Polvurethane Foams
The polyurethane foams produced in above section b) were analyzed for
extraction levels using the following method. The extraction test involved cutting
1 gram of the cured foam from the center of the sample and post-curing the cut
foam for another 20 minutes at 160°C in a glass jar. After cooling to room
temperature, 75 grams of methanol were then added to the glass jar that was
then capped for 1 hour. The foam was then removed and the extract solution
was analyzed under Perkin Elmer Lambda 35 UV-vis spectrophotometer for the
maximum absorption. If the solution is too concentrate, dilute it with methanol to
20%, then measure its UV-vis and calculate the absorption value of the original
solution. The results are summarized in Table 2.
Table 2. Foam Extraction Tests of
Inventive or Comparative UV Absorbers
Based on the molecular weight of these additives, 1.5 php of Tinuvin 326
is mole equivalent to 3.0 php of Tinuvin 1130, 3.8 php of inventive Example 9,
and 3.6 php of inventive Example 11. As suggested from Table 2, the inventive
27
liquid polymeric UV absorbers provide significant improvement in the foam
extraction test, comparing to comparative examples such as commercial
products Tinuvin 326 and Tinuvin 1130,
d) Protection of Colorants from UV Discoloration in Polvurethane Foam
Liquid polymeric colorant ReacTint® Blue X3LV (available from Milliken
Chemical) is widely used for the coloration of polyurethane foam, and is known
to be very prone to UV discoloration. Thus, the blue foams were made in the
presence of 1php Blue X3LV with or without inventive UV absorber, in
accordance with formulation and process as described in Section a). The foam
buns were sliced in half, and small pieces of foam samples (diameters of 10cm x
5cm x 2cm) were cut from the center of each foam bun. These foam samples
were all tested under Xenon lamp chamber (AATCC Test No. 16-1999) for
discoloration at different exposure time. Those foam samples exposed different
amount of time under Xenon light were then compared reading in CMC for delta
E with respected unexposed foam samples. The results are summarized in
Table 3. Stabilization of RTBlurX3LV with Inventive UVAbsorbers
Thus, without UV absorber, Blue X3LV was completely discolored after 1
hour of exposure under Xenon light. However, the discoloration of Blue X3LV
foam made in the presence of the inventive UV absorber (1 php) from Example 9
showed significant improvement as evidenced in delta E measurement.
e) Reduction of Discoloration in White Polvurethane Foam
Several white foams made in accordance with formulation and process as
described in Section a), in the presence of unique anti-discoloration additive
packages consists of a UV absorber selected from Class A, a phenolic
antloxidant from Class B, a secondary amine antioxidant from Class C and a
lactone antioxidant from Class D. The inventive liquid polymeric UV absorbers
are used in this unique additive package to replace the commercial UV
absorbers which are solid and/or non-reactive. Upon the foams are made with
the inventive additive packages, as well as commercially available additive
packages, the foam buns are then sliced in half, and compared the performance
against UV discoloration (Xenon lamp test according to AATCC Test No. 16-
1999) and gas fading (AATCC Test No. 23-1999).
The inventive synergistic additive composition packages are listed in Table
4. Also included in Table 4 as comparatives, are control (with no additive) and
commercially available additive packages B-75 (Ciba), CS-31 (Crompton) and
LS-1 (Ortegol), which are current best commercial products in polyurethane
industry for stabilization of white polyurethane foams.
Table 4. Additive Compositions and Loadings in Foam Formulation
Tinuvin B75 (commercially available from Ciba), loading @ 3.0
Php
CS-31 (commercially available from Crompton), loading @ 3.0
php
LS-1 (commercially available from Goldschmidt), loading @ 3.0
php
0 o 0 0
Lightfastness and gas fade test results for the inventive and comparative
sample foams are summarized in Table 5.
Table 5. Test Results for Inventive and Comparative Additive Packages
Clearly, the inventive additive packages containing the inventive liquid
polymeric UV absorbers exhibited the best overall performance against
discoloration of UV exposure and gas fade, comparing to state-of-the-art
commercial additive packages such as GG, HH and JJ. More over, when used at
equal mole loading (based on different molecular weights of respected UV
absorbers), the additive package containing the inventive liquid reactive
polymeric UV absorber has significantly better performance than that containing
solid non-reactive commercial UV absorber such as Tinuvin 326; especially
when exposed to NOX gas discoloration tests.
f) Application of the Inventive UV absorbers in PET Packaging
UV absorbers are being increasingly used in PET packaging to protect the
content from UV degradation in the food container industry. Since UV absorbers
could decompose during the injection molding process at process condition
(usually 280 °C) causing resin yellowing, the appearance (yellowness index) the
final PET articles (containing UV absorbers) becomes an indicator for the
suitability of UV absorbers in this application. Another requirement for an
acceptable UV absorber is the lightfastness of the UV absorber itself. The
inventive liquid polymeric UV absorbers were thus tested for their performance
against current best commercial products ClearShiald® UV absorbers (available
from Milliken Chemical).
In each instance noted below regarding polyester article production
applications, the inventive polymeric UV absorber was introduced within an
injection molding operation for a polyester thermoplastic, in this instance
polyethylene terephthalate (ClearTuf® 8006 PET resin from M&G). The inventive
UV absorber, in the amount noted in the related examples below, was blended
via agitation onto hot, dried PET resin pellets. The blend of UV absorber and
pellets was gravity fed into the feed throat of the machine. In the feed section,
melting was accomplished through the utilization of rotating heated (heat
transferred from the barrel of the machine) screw extruder. The rotation of the
screw provided thorough mixing of the UV absorber and molten resin together
producing a uniform plastic melt which was injected into a mold in order to form
the thermoplastic article, in this instance a 2 inch by 3 inch plaque with a uniform
thickness of 50 mils and a surface area of 12.5 in2.
Ten 50 mil-thick plaques of UV absorber-containing PET, as made above,
thermoplastic plaques of polyester terephthalate containing inventive UV
absorber were produced as described above (injection molded) were collected.
The same injection molding machine used to produce these first ten plaques was
paused during production of ten further plaques and allowed to remain idle for 15
minutes at the standard polyester processing temperatures (~277°C). At the end
of the 15-minute pause, the machine was then restarted without purging the
colored resin from the heated barrel of the machine. Ten consecutive plaques
were then collected and numbered after resumption of the injection molding
operation.
The absorbance at the UV absorber lambda max of the Control Samples
collected from the standard operation was measured by Perkin-Elmer Lambda
35 Spectrophotometer and averaged together to represent a standard
measurement for all plaques. Each of the ten consecutive Measured Sample
plaques collected after the 15-minute hold-period was measured individually and
sequentially on the spectrophotometer. The absorbance difference between the
standard measurements for the Control Samples each of the ten Measured
Sample plaques was recorded and defined as the change in absorbance (AAbs).
The thermal stability of UV absorber was measured by the percentage of UV
absorbance loss (Loss%), as calculated by the formula
Loss% = [Mbs] I [standard]
The biggest Loss% of the ten Measured Samples plaques collected after
the 15-minute hold period represents the largest absorbance difference, and is
determined to be the UV absorber's thermal stability.
The thermal stability (Loss%) of the inventive UV absorbers from Example
9, above, as well as comparative commercial UV absorbers (ClearShield® UV
absorbers) were measured, and the results are tabulated in Table 6 (the
loadings for UV absorbers were adjusted to the same heights of the absorption
peaks based on their Color Values).

A Loss% of less than 10 Is considered to be acceptable, with a result less than 2
considered to be outstanding when analyzed by this protocol. Clearly, the inventive UV
absorbers exhibited highly favorable thermal stability characteristics with no detectable loss,
particularly in comparison with current best commercial products.
For each individual inventive or comparative UV absorber compositions at
specified loadings (below), ten 50mil-thick plaques were made according to
process described as above in the previous section.
The absorbance (at each UV absorber's lambda max) of the ten plaques
collected from the standard operation was measured in Perkin-Elmer Lambda 35
Spectrophotometer and averaged together to represent the Standard
Measurement. Three sets of 2 plaques were then placed under xenon light for
20 and 40 hours exposure, respectively. Each set of the 2 plaques was
collected after the elapsed times of exposure and were measured for change in
absorbance (at each UV absorber's lambda max) individually and sequentially
on a Perkin-Elmer Spectrophotometer. The absorbance difference between the
Standard Measurement and each of the 2 sets of plaques exposed was
determined as AAbs. The lightfastness of the UV absorber incorporated was
thus measured by the percentage of UV absorbance loss (Loss%), as calculated
by the formula
Loss% = [AAbs] /[Standard]
The greater the Loss% of the plaques, the larger the absorbance
difference and is determined to be worse the UV absorber's lightfastness. The
test results are summarized in Table 7.
TABLE 7. Lightfastness of the Inventive and Comparative UV Absorbers
Under this protocol, a Loss%of at most 15% after 40 hours exposure is
highly desired. This shows that the Inventive UV absorber provides significantly
improved lightfastness characteristics over the comparative commercial
products. .
The degree of yellowing as a result of processing was determined for
selected UV absorber examples. A specified amount of inventive and
comparative UV absorbers were added to 2 kg of ClearTuf® 8006 polyester
resin. After thorough mixing, the resin was compounded on a Single-Screw
extruder and the emergent strands of material were pelletlzed. To simulate the
industrial drying process commonly practiced by the converters, the pelletized
sample was dried at 150°C under vacuum for five hours and afterwards injection
molded into175 mil thickness plaques (2 in x 3 in). The degree of yellowing of the
37
plaques, expressed as Yellowness Index (ASTM Test Method E-313) was
quantified with the aid of a MacBeth Coloreye 7000 spectrophotometer.
The yellowness of the inventive and comparative UV absorbers in 175 mil
PET plaques were measured; and the results are tabulated in Table 8.
TABLE 8. Yellowness of the
Inventive and Comparative UV Absorbers in Molded PET
Less than 5% transmission of UV radiation at 390nm in a 15 mil thick wall
container is the best UV protection currently industry can achieve. The UV
absorber loadings are adjusted based on the absorption strength to achieve this
goal. ClearShield UV 390B is a long wavelength UV absorber. When used it
alone in standard PET resin, it could not completely cover short wavelength UV
radiation. At a loading of 1450 ppm UV 390B, a portion of UV radiation between
300- 350nm is still transmitted. In the above table, only the inventive UV
absorber from Example 9 and ClearShield UV 400, at respected loadings,
achieved less than 5% transmission at 390nm.
Under this testing protocol, a Yellowness of at most 25 at the suggested
loading levels is considered to be acceptable. Thus, the inventive UV absorber
exhibited significantly better yellowness rating than the comparatives, showing
the unexpectedly good results provided thereby.
g) Application of the Inventive UV Absorbers in Polypropylene
UV absorbers are commonly used in transparent polyolefin packaging such
as films, containers, etc. to combat the harmful UV light. Two of the most widely
used commercial UV absorbers are Tinuvin® 326 and 327. Since they are low
molecular weight solids, their blooming and migration out of polypropylene
composition during and/or after the injection molding process, is one of a few
highly undesirable characteristics. The inventive liquid polymeric benzotriazole
UV absorbers are thus tested for suitability in polypropylene application. The
protocols for thermoplastic composition formation as well as their performance
' • • : •
evaluations were similar to those as described above, and in US 6,207,740.
r '
Table 9 summarized the Yellowness Index results.
aa
Table 9. Loadings and Yellowness of the Inventive and Comparative UV
A yellowness of less than 10 is considered to be highly desirable for this
application under this test protocol. Thus both inventive and comparative UV
absorbers offered acceptable yellowness performance.
Additionally, although both inventive liquid polymeric UV absorber from
Example 9 and commercial product Tinuvin 326 exhibited excellent thermal
stability and lightfastness (after 20 and 40 hours exposure to Xenon light), the
inventive UV absorber demonstrated a dramatically improved performance in
extraction and plate-out tests. Being liquid in natural and with much improved
migration, the inventive liquid polymeric UV absorber offers more desirable
characteristics for polypropylene applications such as in packaging and in films
and the like.
While specific features of the invention have been described, it will be
understood, of course, that the invention is not limited to any particular
configuration or practice since modification may well be made and other
embodiments of the principals of the invention will no doubt occur to those skilled
in the art to which the invention pertains. Therefore, it is contemplated by the
appended claims to cover any such modifications that incorporate the features of
the invention within the true meaning, spirit, and scope of such claims.
It is understood by one of ordinary skill in the art that the present
discussion is a description of exemplary embodiments only, and is not intended
as limiting the broader aspects of the present invention, which broader aspects
are embodied in the exemplary constructions. The invention is shown by
example in the appended claims.

What is claimed is:
1. An ultraviolet light absorbing compound having the structure:
wherein:
R1 is selected from the group consisting of: H, F, Cl, Br, I, alkyls, alkoxys,
C=0 containing radicals represented as -C(0)-A, and SOa -containing radicals
represented as SO2-A; wherein A may be selected from: OH, alkyl, alkoxy, or an
organic amine group;
R2 is selected from the group consisting of: H, Cn - CIQ alkyls, and C-i-
C2o phenylalkyls;
Ra is selected from the group consisting of: H, carbon-containing chain
radicals, oxygen-containing chain radicals, and nitrogen-containing chain
radicals;
R4 is selected from the group consisting of: divalent C2-C2o alkyl radicals,
divalent C4-C2o alkyl radicals interrupted by oxygen, sulfur or nitrogen, and
divalent oligomeric radicals;
G is selected from the group consisting of: H, C1 - Cm alkyls, alkyl
carbonyls, and aryl carbonyl groups; and
Z-1 is selected from (a) or (b) below:
(a) C2-C10alkyls;
(b) divalent radicals represented by:
R7 and R each are independently selected from H or C-1 -
do alkyl groups;
n comprises an integer between 1 and 10;
m comprises any positive integer or fraction between 1 and 20.
2. The compound of claim 1 wherein Rs comprises a carboncontaining
chain radicals or a carbon and oxygen-containing chain
compound represented by:
Ra, Z1, and G are as defined as in claim 1.
3. The compound of claim 1 wherein R4 is a divalent alkyl radical
represented by: , .
wherein
EO comprises ethylene oxide or a derivative thereof;
PO comprises propylene oxide or a derivative thereof; and
R5 comprises H orC1-C10 alkyl groups; and
R6 comprises a divalent C1-C10 alkyl radical;
wherein x, y, and z comprise positive integers or fractional
numbers between 0 and 20, and further wherein x + y + z is equal to or
greater than 1.
4. The compound of claim 1 wherein Ri and R2 are bonded to
specific respective carbons, as shown below:
wherein R1, R2, R3, R4, Zi and G are as defined in Claim 1, and
further wherein Z1 comprises a repeating group having an aliphatic
ester chain.
5. The compound represented by the formula:
RI is selected from the group consisting of: H, F, Cl, Br, I, alkyl, alkoxy,
C=0 containing groups represented as -C(O)-A, and SOa -containing radicals
represented as SOz-A; wherein A is'selected from OH, alkyl, alkoxy, and
organic amine groups;
R2 is selected from the group consisting of: H, C1-C10 alkyls, and C7-
. C20 phenylalkyls;
RS is selected from the group consisting of: H, carbon containing chain
radicals, and carbon/ oxygen containing chain radicals;
R4 is selected from the group consisting of: divalent C2-C20 alkyl radicals,
divalent C4-C2o alky radicals interrupted by oxygen, sulfur or nitrogen, and
divalent oligomeric radicals;
R/ and Re each are independently selected from the group consisting of: H
and C1-C10 alkyl groups;
n comprises an integer between 1 and 10; and
m comprises a positive integer or fraction thereof between 1 and 20.
6. The compound of claim 5 wherein m is at least 2.
7. The compound of claim 5 wherein n is at least 2.
8. The compound of claim 6 wherein R3 comprises H.
9. The compound of claim 7 wherein R3 comprises H.
10. The compound of claim 8 wherein RI comprises CI or H.
11. The compound of claim 9 wherein RI comprises CI or H.
12. The compound of claim 10 wherein R2 comprises a te/t-butyl
group.
13. The compound of claim 11 wherein R2 comprises a ferf-butyl
group.
14. The compound of claim 12 wherein n comprises 5.
15. The compound of claim 14 wherein m comprises at least 3,
16. The compound of claim 14 wherein R/i comprises a divalent
radical selected from the group consisting of: -CH2CH2-, -
CH2CH2OCH2CH2-, -{CH2CH20)2-CH2CH2--, and-
(CH2)30(CH2CH20)(CH2CH2)-.
17. The compound of claim 15 wherein Rt comprises a divalent
radical selected from a group consisting of: -CHzCHz-, -
CH2CH2OCH2CH2-, -(CH2CH20)2-CH2CH2-, and -
(CH2)3O(CH2CH20)(CH2CH2)-.
18. An ultraviolet light absorbing compound, said compound being
adapted for incorporation into polymers, said compound being
comprised of a benzotriazole moiety and at least one reactive
moiety bonded to said benzotriazole moiety, said reactive
moiety being capable of reacting with said polymer under
conditions to facilitate substantial non-migration of said
compound within said polymer, said reactive moiety having at
least one reactive -OH group, further wherein said compound
comprises a liquid at a temperature of about 45 degrees C.
19. The compound of claim 18 wherein said reactive moiety
comprises: (a) a proximal portion adjacent to and bonded to
, ' r.
said benzotriazole moiety, and (b) a distal portion positioned
apart from said benzotriazole moiety, wherein said -OH group
is positioned upon said distal portion.
20. The compound of claim 19 wherein said reactive moiety
further comprises an oxyalkylene or a derivative thereof.
21. The compound of claim 20 wherein said reactive moiety
further comprises at least one aliphatic copolymer chain.
22. The compound of claim 21 wherein said aliphatic portion
comprises an ether and ester block copolymer.
23. An article comprising:
(a) at least one polymeric formulation having a thermoplastic or
thermoset component, or mixtures thereof;
(b) at least one UV absorber compound, either
i) present within said polymeric formulation or
ii) adhered to the surface of said polymeric formulation,
(c) wherein said UV absorber compound comprises a benzotriazole
derivative, further wherein at least one
alkyl chain which is interrupted by oxygen, sulfur or nitrogen; and a
poly(oxyalkylene) chain,
aliphatic polyester chain, or
block copolymeric chain
consisting of poly(oxyalkylene) and aliphatic polyester segments;
said segments being attached to said UV absorber compound by
way of an amide functional group.
24. The article of claim 23 wherein said UV light absorbing compound
conforms to the structure:
:
RI is selected from the group consisting of: H, F, CI, Br, I, alkyls, alkoxys,
C=0 containing radicals represented as -C(O)-A, and SO2 -containing radicals
represented as SQa-A, wherein A is OH, alkyl, alkoxy, or an organic amine
group;
RZ is selected from the group consisting of: H, Ci - Cio alkyls, and Cy-
C2o phenylalkyls;
Ra is selected from the group consisting of: H, carbon-containing chain
radicals, oxygen-containing chain radicals, and nitrogen-containing chain
radicals;
R4 is selected from the group consisting of: divalent 62-020 alkyl radicals,
divalent C4-Czo alky radicals interrupted by oxygen, sulfur or nitrogen, and
divalent oligomeric radicals;
G is selected from the group consisting of: H, Ci - Cm alkyls, alkyl
carbonyls, and aryl carbonyl groups; and
Zi is selected from (a) or (b) below:
(a) C2-Ci0 alkyls;
(b) divalent radicals represented by:
O , R,
R7 and RB each are independently selected from H or Ci -
alkyl groups;
n comprises an integer between land 10;
m comprises any positive integer or fraction between 1 and 20.
25. The article of claim 24 wherein Ra comprises a
a) carbon- ;
b) oxygen-- ; or
c) nitrogencontaining
chain radical represented by:
O ---- Z,— G
R,
wherein R*, Z^ and G are as defined in claim 24,
26. The article of claim 25 wherein R4 is a divalent oligomeric radical
represented by:
EO comprises ethylene oxide or a derivative thereof;
PO comprises propylene oxide or a derivative thereof; and
R5 is H or Ci - Cio alkyl groups;
Re is a divalent CT - C1Q alkyl radical; and
wherein x, y, and z comprise positive integers or fractional
numbers between o and 20, and further wherein x + y + z is equal to or
greater than 1.
27. The article of claim 24 wherein said UV absorbing compound
confirms the structure as shown below, wherein Ri and R2 are bonded to
specific respective carbons:
wherein Ri, R2, Ra, RA, Zi and G are as defined in Claim 24.
28. The article of claim 27 wherein Ra comprises
a) carbonfa)
oxygen-- or
c) nitrogencontaining
chain radical represented by:
29. The article of claim 28 wherein:
R4 comprises a divalent oligomeric radical represented by:
24 wherein said UV absorbing compound
conforms the structure represented by:
RI is selected from the group consisting of: H, F, Cl, Br, I, alkyls, alkoxy,
C=0 containing radicals represented as -C(O)-A, and 862 -containing radicals
represented as SOZ-A, wherein A is OH, alkyl, alkoxy, or an organic amine
group;
Rz is selected from the group consisting of: H, Ci - Cio alkyls, and Cy-
Czo phenylalkyfs;
Ra is selected from the group consisting of: H, carbon-containing chain
radicals, oxygen-containing chain radicals, and nitrogen-containing chain
radicals;
R4 is selected from the group consisting of: divalent C2-C2o alkyl radicals,
divalent C4-C2o alky radicals interrupted by oxygen, sulfur or nitrogen, and
divalent oligorneric radicals;
Rr and RB each are independently selected from H or
d - Cio alkyl groups;
n comprises an integer between 1 and 10; and
m comprises any positive integer or fraction between 1 and 20.
31. The article of claim 30 wherein m is at least 3.
32. The article of claim 30 wherein n is at least 3.
33. The article of claim 30 wherein Rg comprises H.
34. The article of claim 30 wherein Ra comprises a carbon containing
chain radical.
35. The article of claim 30 wherein Ra comprises an oxygen containing
chain radical.
36. The article of claim 30 wherein:
RI comprises Cl or H;
Rz comprises a te/t-butyl group; and
Rr and Ra each comprise H; and
n is 5.
37. The article of claim 30 wherein
Ri comprises Cl or H;
R2 comprises terf-butyl group;
RT and Ra each comprise H; and
n comprises 5.
38. The article of claim 30 wherein
R4 comprises a divalent radical selected from a group consisting of:
- C H , -CHaCHzOCHaCIV,
-(CH2CH20)2CH2CH2-, and
-{CH2)30(CH2CH20)(CH2CH2)-.
39. The article of claim 23 wherein said polymeric formulation comprises
at least one thermoplastic component.
40. The article of claim 39 wherein said thermoplastic component
comprises at least one organic material selected from the group
consisting of: polyolefins, polyesters, polycarbonates, thermoplastic
polyurethanes, and polyamides.
41. The article of claim 23 wherein said polymeric formulation comprises
polypropylene.
42. The article of claim 23 wherein said polyester chain comprises
polyethylene terephthalate (PET).
43. The article of claim 23 wherein said polymeric formulation comprises
at least one thermoset component.
44. The article of claim 43 wherein said thermoset component comprises
at least one organic material selected from the group consisting of:
polyurethanes and acrylic resins;
wherein said organic material is capable of being cross-linked by
45. The article of claim 44 wherein said polyurethane comprises a
polyurethane foam.
46. The article of claim 23, wherein said polymeric formulation further
contains at least one said UV light absorbing compound in the amount
from about 0.1 to 15% by weight of said polymeric formulation.
47. The article of claim 46, wherein said UV light absorbing compound is
provided in the amount of 0,3 to 8% by weight of said polymeric
formulation.
48. The article of claim 46, wherein said UV light absorbing compound
is provided in the amount of 0,5 to 5% by weight of said polymeric
formulation.


Documents:

1355-delnp-2007-Abstract-(21-12-2012).pdf

1355-delnp-2007-abstract.pdf

1355-delnp-2007-assignment.pdf

1355-delnp-2007-Claims-(21-12-2012).pdf

1355-delnp-2007-claims.pdf

1355-delnp-2007-Correspondence Others-(21-12-2012).pdf

1355-DELNP-2007-Correspondence-Others.pdf

1355-delnp-2007-description (complete).pdf

1355-delnp-2007-form-1.pdf

1355-delnp-2007-form-2.pdf

1355-delnp-2007-Form-3-(21-12-2012).pdf

1355-DELNP-2007-Form-3.pdf

1355-delnp-2007-form-5.pdf

1355-delnp-2007-GPA-(21-12-2012).pdf

1355-delnp-2007-gpa.pdf

1355-delnp-2007-pct-101.pdf

1355-delnp-2007-pct-210.pdf

1355-delnp-2007-pct-220.pdf

1355-delnp-2007-pct-237.pdf

1355-delnp-2007-pct-301.pdf

1355-delnp-2007-pct-304.pdf

1355-delnp-2007-Petition-137-(21-12-2012).pdf


Patent Number 256532
Indian Patent Application Number 1355/DELNP/2007
PG Journal Number 27/2013
Publication Date 05-Jul-2013
Grant Date 28-Jun-2013
Date of Filing 20-Feb-2007
Name of Patentee MILLIKEN & COMPANY
Applicant Address 920 MILLIKEN ROAD, M-495 SPARTANBURG, SOUTH CAROLINA 29303, USA
Inventors:
# Inventor's Name Inventor's Address
1 JUSONG XIA 509 BERNNDARY COURT, MOORE, SOUTH CAROLINA 29369, USA
PCT International Classification Number C08K 5/34
PCT International Application Number PCT/US2005/029482
PCT International Filing date 2005-08-18
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/922,734 2004-08-20 U.S.A.