U.S. patent application number 12/520896 was filed with the patent office on 2010-02-11 for near infrared absorbing phthalocyanines and their use.
This patent application is currently assigned to CIBA CORPORATION. Invention is credited to Samanta Cimitan, Markus Grob, Cesare Lorenzetti, Francesca Peri.
Application Number | 20100032608 12/520896 |
Document ID | / |
Family ID | 38102247 |
Filed Date | 2010-02-11 |
United States Patent
Application |
20100032608 |
Kind Code |
A1 |
Peri; Francesca ; et
al. |
February 11, 2010 |
NEAR INFRARED ABSORBING PHTHALOCYANINES AND THEIR USE
Abstract
The instant invention relates to novel phthalocyanines and their
use as IR-absorbers, in particular in transparent thermoplastic or
crosslinkable polymers. A further aspect of the invention is a
composition of these phthalocyanines and thermoplastic or
crosslinkable polymers and an architectural or automotive glazing
containing these phthalocyanines.
Inventors: |
Peri; Francesca; (Bologna,
IT) ; Lorenzetti; Cesare; (Grottammare, IT) ;
Cimitan; Samanta; (Ponte Di Piave (Treviso), IT) ;
Grob; Markus; (Reinach, CH) |
Correspondence
Address: |
JoAnn Villamizar;Ciba Corporation/Patent Department
540 White Plains Road, P.O. Box 2005
Tarrytown
NY
10591
US
|
Assignee: |
CIBA CORPORATION
TARRYTOWN
NY
|
Family ID: |
38102247 |
Appl. No.: |
12/520896 |
Filed: |
December 21, 2007 |
PCT Filed: |
December 21, 2007 |
PCT NO: |
PCT/EP2007/064465 |
371 Date: |
September 23, 2009 |
Current U.S.
Class: |
252/62 ; 524/88;
540/140 |
Current CPC
Class: |
Y10T 428/24694 20150115;
C07F 9/005 20130101; C07F 13/005 20130101; Y10S 977/742 20130101;
C09B 47/073 20130101; Y10T 428/2947 20150115; C09B 47/0676
20130101; Y10T 428/269 20150115; Y10S 430/145 20130101; Y10S
977/773 20130101 |
Class at
Publication: |
252/62 ; 540/140;
524/88 |
International
Class: |
E04B 1/74 20060101
E04B001/74; C09B 47/04 20060101 C09B047/04; C08K 5/3417 20060101
C08K005/3417 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 11, 2007 |
EP |
07100364.4 |
Claims
1. A compound of formula (Ia) ##STR00026## wherein R is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkyl interrupted by one or
more O atoms, benzyl or cyclohexyl; R' is hydrogen or
C.sub.1-C.sub.18alkyl; or R and R' together with the nitrogen atom
to which they are bonded form a morpholine group; and M is Mn, Zn,
V(O), Ti(O), Si, Al, Sn, Cu or Co; with the provisos that if R is
methyl and R' is hydrogen, M is not Zn, if R and R' are butyl or
octyl M is not Sn and if R and R' are methyl M is not Zn, Ti(O),
V(O), Cu or Co.
2. A compound according to claim 1 wherein M is Mn, Cu, V(O), Co or
Al.
3. A compound according to claim 1 wherein R is
C.sub.1-C.sub.18alkyl; R' is H and M is Mn, Cu, V(O), Co or Al.
4. A compound according to claim 1 wherein R is CH.sub.3 R' is
hydrogen and M is Mn, V(O), Cu or Co.
5. A transparent or translucent composition comprising a) a
compound of formula (I) ##STR00027## wherein R is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkyl interrupted by one or
more O atoms, benzyl or cyclohexyl; R' is hydrogen or
C.sub.1-C.sub.18alkyl; R and R' together with the nitrogen atom to
which they are bonded form a morpholine group; and M is Mn, Zn,
V(O), Ti(O), Si, Al, Sn, Cu or Co; which is dispersed in b) a
thermoplastic or crosslinkable polymer.
6. A composition according to claim 5 wherein the thermoplastic or
crosslinkable polymer comprises polycarbonate, a coating or
coextruded layer on polycarbonate polyesters acrylics halogenated
polymers, polyolefins, aromatic homopolymers, copolymers derived
from vinyl aromatic monomers, polyvinylacetales or blends, alloys
or co-polymers thereof.
7. A composition according to claim 5, wherein the thermoplastic or
crosslinkable polymer comprises polycarbonate,
polymethylmethacrylate, polyethyleneterephthalate,
polyvinylchloride, transparent ABS, polyvinylidene fluoride,
styrene-acrylnitril copolymer, polypropylene, polyethylene or
mixtures thereof.
8. A composition according to claim 5 wherein the compound of
formula (I) is present in an amount from 0.01 to 10% by weight,
based on the weight of the thermoplastic or crosslinkable
polymer.
9. A composition according to claim 5, containing as further
component a conventional additive selected from antioxidants, flame
retardants, clarifiers, UV absorbers and/sterically hindered
amines.
10. A composition according to claim 5 containing as further
component solid nano-scaled particles of a thickness of less than
200 nm, which consist of an oxide of zinc and/or a nitride of a
transition metal of group III, IV, V or VI of the periodic system,
each of which is doped with one or more of the elements belonging
to main groups III or IV of the periodic system, or consist of
undoped vanadium nitride or scandium nitride.
11. A composition according to claim 10 comprising a nitride which
is selected from nitrides of scandium, yttrium, lanthanum,
lanthanides, titanium, zirconium, hafnium, vanadium, niobium,
tantalum, chromium, molybdenum and wolfram; and where the doping
elements are selected from boron, aluminum gallium, indium
thallium, carbon, silicon, germanium, tin and lead.
12. A composition according to claim 5 containing as further
component tin oxide doped with antimony (ATO), tin oxide doped with
indium (ITO), zinc oxide doped with aluminum (AZO), zinc oxide
doped with indium (IZO), zinc oxide doped with gallium (GaZO),
LaB.sub.6, doped tungsten oxides (YWO.sub.x), silver or gold
nanoparticles, nanoprisms or nanorods or carbon nanotubes.
13. Architectural or automotive glazing in form of a solid plate or
sheet, a monolithic sheet, a twin-wall sheet, a multi-wall sheet, a
flat sheet or a corrugated sheet; or an agricultural film in form
of a mono- or biaxially oriented film, a laminated film or a
capstock film, comprising a composition according to claim 5.
14. Process for the preparation of a transparent or translucent
heat shielding material, which process comprises the addition of a
compound of formula (I) ##STR00028## wherein R is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkyl interrupted by one or
more O atoms, benzyl or cyclohexyl; R' is hydrogen or
C.sub.1-C.sub.18alkyl; or R and R' together with the nitrogen atom
to which they are bonded form a morpholine group; and R' is
hydrogen or C.sub.1-C.sub.18alkyl and M is Mn, Zn, V(O), Ti(O), Si,
Al, Sn, Cu or Co; to a thermoplastic or crosslinkable polymer.
15-17. (canceled)
18. A composition according to claim 10 wherein the particles
consist of aluminum doped zinc oxide, indium doped zinc oxide,
gallium doped zinc oxide, aluminum doped titanium nitride, indium
doped titanium nitride, gallium doped titanium nitride, aluminum
doped vanadium nitride, indium doped vanadium nitride, gallium
doped vanadium nitride, vanadium nitride, aluminum doped scandium
nitride, indium doped scandium nitride, gallium doped scandium
nitride or scandium nitride.
Description
[0001] The instant invention relates to novel phthalocyanines and
their use as IR-absorbers, in particular in transparent
thermoplastic or crosslinkable polymers. A further aspect of the
invention is a composition of these phthalocyanines and
thermoplastic or crosslinkable polymers and an architectural or
automotive glazing containing these phthalocyanines.
[0002] The absorption of near infrared radiation (NIR) is an
important technical issue in various fields. A significant
reduction of the heat transfer into buildings and cars is possible
by blocking or filtering the near infrared part of the solar
spectrum. This allows a considerable energy saving, mainly due to a
smaller demand for air conditioning.
[0003] Up to now several solutions have been proposed and more and
more have been applied on glazing surfaces of many buildings, such
as interference reflective films, semi-conducting or conducting
films: they are all able to reflect, with good selectivity, NIR
radiation. The so-called "low-e" windows are for example reflective
coated mineral or polymeric glasses. However the production of such
coatings is an extremely time consuming step, specially considering
that almost all solutions need several layers, and that the
durability may be also quite limited due to a generally low scratch
resistance. This is, for example, described in WO 2005/072947.
[0004] Another approach is the use of bulk additives that absorb
the NIR radiation. This approach is less expensive, not time
consuming, long lasting and particularly needed for thermoplastic
polymers used in glazing. Some examples for polymers used in
glazing applications are polycarbonates (PC), polyesters like
PET-G, polymethylmethacrylate (PMMA), polyvinylbutyral (PVB) and
others. Mainly used for agricultural applications are polyolefin
films.
[0005] For this purpose several NIR absorbing dyes and pigments
have been proposed and are commercially available, such as
phthalocyanines and quaterrylenes (i.e.: LUMOGEN (RTM) 788 or 765
from BASF).
[0006] However these NIR-absorbers do not fully satisfy all
technological and market requirements.
[0007] It is therefore the object of the instant invention to
provide new phthalocyanines, which overcome the deficiencies of the
prior art NIR-absorbers.
[0008] The present invention provides NIR absorbing phthalocyanines
with strong absorption in the NIR region whilest showing low or
very low absorption in the visible region Furthermore they combine
a high compatibility with a high thermal stability and weather
resistance in the most common plastic matrices.
[0009] One aspect of the invention is a compound of formula
(Ia)
##STR00001##
R is hydrogen, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkyl
interrupted by one or more O atoms, benzyl, cyclohexyl or R and R'
together with the nitrogen atom to which they are bonded form a
morpholine group; R' is hydrogen or C.sub.1-C.sub.18alkyl;
M is Mn, Zn, V(O), Ti(O), Si, Al, Sn, Cu and Co
[0010] with the proviso that if R is methyl and R' is hydrogen, M
is not Zn if R and R' are butyl or octyl M is not Sn and if R and
R' are methyl M is not Zn, Ti(O), V(O), Cu and Co.
[0011] The alkyl radicals may be linear or branched. Examples of
alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl,
isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl,
hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
[0012] C.sub.3-C.sub.18alkyl interrupted by O are for example
derived from ethylene glycol or propylene glycol. For example M is
Mn, Cu, V(O), Co or Al.
[0013] For instance R is C.sub.1-C.sub.18alkyl; R' is H and M is
Mn, Cu, V(O), Co or Al.
[0014] In a specific embodiment of the invention R is CH.sub.3, R'
is hydrogen and M is Mn, V(O), Cu or Co.
[0015] The preparation of the instant phthalocyanines is carried
out in analogy to known synthetic routes.
[0016] One possibility is, for example,
##STR00002##
[0017] For some metals a second strategy is more useful:
##STR00003##
[0018] The compounds of formula (Ia) are ideally suitable as
IR-absorbers. The great advantage is that these phthalocyanines
lead to plastic articles which are highly transparent and
essentially colorless.
[0019] Consequently another aspect of the invention is a
transparent or translucent composition comprising
a) a compound of formula (I)
##STR00004##
R is hydrogen, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkyl
interrupted by one or more O atoms, benzyl, cyclohexyl or R and R'
together with the nitrogen atom to which they are bonded form a
morpholine group; R' is hydrogen or C.sub.1-C.sub.18alkyl;
M is Mn, Zn, V(O), Ti(O), Si, Al, Sn, Cu and Co.
[0020] which is dispersed in b) a thermoplastic or crosslinkable
polymer.
[0021] The amount of light transmitted through the present
materials, i.e. degree of translucency or transparency, mainly
depends on well known parameters such as the particle loading,
further additives used, haze level of the polymer matrix and
thickness of the material. The present materials usually are at
least 80%, or rather more than 90% translucent in each part of the
visible range (400-800 nm); preferred materials have good
transparency, and especially are selected from clear-transparent
sheets and films of thickness less than 10 mm (e.g. 0.01 to 5 mm).
Preferred materials further share one or more of the following
advantageous properties:
a full solar radiation transmittance (340-1800 nm) of less than
60%, a haze of less than 1%, and a full visible light transmittance
(400-800 nm) of more than 75%.
[0022] A wide variety of polymers may be used. Examples are given
below. [0023] Polycarbonate (PC) or a coating or coextruded layer
on polycarbonate, polyesters, acrylics, halogenated polymers such
as polyvinylchloride (PVC), polyolefins, aromatic homopolymers and
copolymers derived from vinyl aromatic monomers and graft
copolymers thereof such as acrylnitril-butadiene-styrene terpolymer
(ABS), containing these polymers as major component or in
essentially pure form (e.g. 50-100% b.w.), especially: [0024] a
polymer selected from PC, polymethylmethacrylate (PMMA),
polyethyleneterephthalate (PET, PET-G), PVC, transparent ABS,
polyvinylidene fluoride (PVDF), styrene-acrylnitril copolymer
(SAN), polypropylene (PP), polyethylene (PE) including blends,
alloys, co-polymers.
[0025] Also suitable are polyvinylacetales such as polyvinylbutyral
(PVB).
[0026] Polymers useful within the present invention include the
following ones:
1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or
polybutadiene, as well as polymers of cycloolefins, for instance of
cyclopentene or norbornene, polyethylene (which optionally can be
crosslinked), for example high density polyethylene (HDPE), high
density and high molecular weight polyethylene (HDPE-HMW), high
density and ultrahigh molecular weight polyethylene (HDPE-UHMW),
medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), (VLDPE) and
(ULDPE).
[0027] 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:
[0028] radical polymerisation (normally under high pressure and at
elevated temperature). [0029] b) catalytic polymerisation using a
catalyst that normally contains one or more than one metal of
groups IVb, Vb, VIb or VIII of the Periodic Table. These metals
usually have one or more than one ligand, typically oxides,
halides, alcoholates, esters, ethers, amines, alkyls, alkenyls
and/or aryls that may be either .pi.- or .sigma.-coordinated. These
metal complexes may be in the free form or fixed on substrates,
typically on activated magnesium chloride, titanium(III) chloride,
alumina or silicon oxide. These catalysts may be soluble or
insoluble in the polymerisation medium. The catalysts can be used
by themselves in the polymerisation or further activators may be
used, typically metal alkyls, metal hydrides, metal alkyl halides,
metal alkyl oxides or metal alkyloxanes, said metals being elements
of groups Ia, IIa and/or IIIa of the Periodic Table. The activators
may be modified conveniently with further ester, ether, amine or
silyl ether groups. These catalyst systems are usually termed
Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),
metallocene or single site catalysts (SSC). 2. Mixtures of the
polymers mentioned under 1), for example mixtures of polypropylene
with polyisobutylene, polypropylene with polyethylene (for example
PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene
(for example LDPE/HDPE). 3. Copolymers of monoolefins and diolefins
with each other or with other vinyl monomers, for example
ethylene/propylene copolymers, linear low density polyethylene
(LLDPE) and mixtures thereof with low density polyethylene (LDPE),
propylene/but-1-ene copolymers, propylene/isobutylene copolymers,
ethylene/but-1-ene copolymers, ethylene/hexene copolymers,
ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers,
ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like
COC), ethylene/1-olefins copolymers, where the 1-olefin is
generated in-situ; propylene/butadiene copolymers,
isobutylene/isoprene copolymers, ethylene/vinylcyclohexene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers or
ethylene/acrylic acid copolymers and their salts (ionomers) as well
as terpolymers of ethylene with propylene and a diene such as
hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures
of such copolymers with one another and with polymers mentioned in
1) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides. 4. Aromatic
homopolymers and copolymers derived from vinyl aromatic monomers
including styrene, .alpha.-methylstyrene, all isomers of vinyl
toluene, especially p-vinyltoluene, all isomers of ethyl styrene,
propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl
anthracene, and mixtures thereof. Homopolymers and copolymers may
have any stereostructure including syndiotactic, isotactic,
hemi-isotactic or atactic; where atactic polymers are preferred.
Stereoblock polymers are also included. 5. Copolymers including
aforementioned vinyl aromatic monomers and comonomers selected from
ethylene, propylene, dienes, nitriles, acids, maleic anhydrides,
maleimides, vinyl acetate and vinyl chloride or acrylic derivatives
and mixtures thereof, for example styrene/butadiene,
styrene/acrylonitrile (SAN), styrene/ethylene (interpolymers),
styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,
styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene. 6. Graft copolymers of vinyl
aromatic monomers such as styrene or .alpha.-methylstyrene, for
example styrene on polybutadiene, styrene on polybutadiene-styrene
or polybutadiene-acrylonitrile copolymers; styrene and
acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,
acrylonitrile and methyl methacrylate on polybutadiene; styrene and
maleic anhydride on polybutadiene; styrene, acrylonitrile and
maleic an hydride or maleimide on polybutadiene; styrene and
maleimide on polybutadiene; styrene and alkyl acrylates or
methacrylates on polybutadiene; styrene and acrylonitrile on
ethylene/propylene/diene terpolymers; styrene and acrylonitrile on
polyalkyl acrylates or polyalkyl methacrylates, styrene and
acrylonitrile on acrylate/butadiene copolymers, as well as mixtures
thereof with the copolymers listed under 4), for example the
copolymer mixtures known as ABS, MBS, ASA or AES polymers. 7.
Halogen-containing polymers such as polychloroprene, chlorinated
rubbers, chlorinated and brominated copolymer of
isobutylene-isoprene (halobutyl rubber), chlorinated or
sulfo-chlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for
example polyvinyl chloride (PVC), polyvinylidene chloride,
polyvinyl fluoride, polyvinylidene fluoride (PVDF), as well as
copolymers thereof such as vinyl chloride/vinylidene chloride,
vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate
copolymers. 8. Polymers derived from .alpha.,.beta.-unsaturated
acids and derivatives thereof such as polyacrylates and
polymethacrylates; polymethyl methacrylates (PMMA), polyacrylamides
and polyacrylonitriles, impact-modified with butyl acrylate. 9.
Polyesters derived from dicarboxylic acids and diols and/or from
hydroxycarboxylic acids or the corresponding lactones, for example
polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene
naphthalate (PAN) and polyhydroxybenzoates, as well as block
copolyether esters derived from hydroxyl-terminated polyethers; and
also polyesters modified with polycarbonates or MBS. 10.
Polycarbonates and polyester carbonates, examples have been already
given above.
[0030] Suitable polyvinylacetales include polymers derived from
unsaturated alcohols and amines (i.e. acyl derivatives or acetals
thereof), for example polyvinyl acetate, polyvinyl stearate,
polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl
phthalate or polyallyl melamine; as well as their copolymers with
olefins mentioned in 1) above.
[0031] Incorporation of the compounds of formula (I) into the
polymer matrix leads to plastic articles which are highly
transparent; they may be colorless (e.g. for clear glazings or
films) or colored, e.g. by addition of a pigment or mixture of
pigments, e.g. for applications wherein suitable light filtering or
sun screening is desired. The present compounds of formula (I)
allow high loading, giving access to high heat shielding
effects.
[0032] Preferable loadings are from 0.01 to 10%, especially 0.1 to
5% by weight of the final polymer composition.
[0033] The above polymers are all thermoplastic polymers. It is
however also possible to incorporate the instant phthalocyanines
into a curable/crosslinkable coating, which is applied to a
transparent substrate, such as glass or one of the polymers
mentioned above. Examples for curable/crosslinkable coatings are
given below.
[0034] 1. Crosslinked polymers derived from aldehydes on the one
hand and phenols, ureas and melamines on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0035] 2. Drying and non-drying alkyd resins.
[0036] 3. Unsaturated polyester resins derived from copolyesters of
saturated and unsaturated dicarboxylic acids with polyhydric
alcohols and vinyl compounds as crosslinking agents, and also
halogen-containing modifications thereof of low flammability.
[0037] 4. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0038] 5. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0039] 6. Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.
products of diglycidyl ethers of bisphenol A and bisphenol F, which
are crosslinked with customary hardeners such as anhydrides or
amines, with or without accelerators.
[0040] In general thermoplastic polymers are preferred.
[0041] Preferably the thermoplastic or crosslinkable polymer
comprises polycarbonate, a coating or coextruded layer on
polycarbonate, polyesters, acrylics, halogenated polymers, such as
polyvinylchloride, polyolefins, aromatic homopolymers and
copolymers derived from vinyl aromatic monomers and graft
copolymers thereof such as acrylnitril-butadiene-styrene
terpolymer, and polyvinylacetales; as well as blends, alloys and
co-polymers thereof.
[0042] In a specific embodiment of the invention the thermoplastic
or crosslinkable polymer comprises polycarbonate,
polymethylmethacrylate, polyethyleneterephthalate,
polyvinylchloride, transparent ABS, polyvinylidene fluoride,
styrene-acrylnitril copolymer, polypropylene, polyethylene, or
mixtures thereof.
[0043] The composition described above may contain as further
component a conventional additive selected from processing
additives, antioxidants, flame retardants, clarifiers, UV absorbers
and/or sterically hindered amines. Examples are given below.
[0044] 1. Antioxidants
[0045] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl phenol,
2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are
linear or branched in the side chains, for example,
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0046] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol.
[0047] 1.3. Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[0048] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (vitamin E).
[0049] 1.5. Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.
[0050] 1.6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-.alpha.-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane-
, ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl
6-tert-butyl-4-methyl phenyl]terephthalate,
1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl-4-n-dodecylmercaptobutane,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0051] 1.7. O-, N- and S-benzyl compounds, for example 3,
5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0052] 1.8. Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,
di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat-
e,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hyd-
roxybenzyl)malonate.
[0053] 1.9. Aromatic hydroxybenzyl compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0054] 1.10. Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-
azine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-t-
riazine,
2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0055] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
[0056] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0057] 1.13. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,
i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0058] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}1,1-dime-
thylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
[0059] 1.15. Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0060] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic
acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0061] 1.17. Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethyle-
nediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylen-
ediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami-
de (Naugard.RTM.XL-1, supplied by Uniroyal).
[0062] 1.18. Ascorbic acid (vitamin C)
[0063] 1.19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenyl-amine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butyl-aminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylamino-methylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetra-methyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octyl-phenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.
[0064] 2. UV Absorbers and Light Stabilizers
[0065] 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,
2-(3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriaz-
ole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chl-
oro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotr-
iazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyp-
henyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-y-
lphenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300;
##STR00005##
where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetra
methylbutyl)-phenyl]-benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetra
methylbutyl)-5'-(.alpha.,.alpha.-dimethylbenzyl)-phenyl]benzotriazole.
[0066] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[0067] 2.3. Esters of substituted and unsubstituted benzoic acids,
for example 4-tert-butyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0068] 2.4. Acrylates, for example ethyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxy-cinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate,
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline,
neopentyl tetra(.alpha.-cyano-.beta.,.beta.-diphenylacrylate.
[0069] 2.5. Nickel compounds, for example nickel complexes of
2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1
or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.
the methyl or ethyl ester, of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
with out additional ligands.
[0070] 2.6. Sterically hindered amines, for example
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or
cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane, the condensate of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]); a condensate of 1,6-hexanediamine and
2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[192268-64-7]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro-[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-
ethene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexa
methylenediamine, a diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetra
methyl-4-piperidyl)]siloxane, a reaction product of maleic acid
anhydride-.alpha.-olefin copolymer with
2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine,
2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylami-
no]-6-(2-hydroxyethyl)amino-1,3,5-triazine,
1-(2-hydrooxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiper-
idine,
5-(2-ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone,
Sanduvor (Clariant; CAS Reg. No. 106917-31-1],
5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, the
reaction product of
2,4-bis-[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s--
triazine with N,N'-bis(3-aminopropyl)ethylenediamine),
1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino-
)-s-triazine,
1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazine-3-one-4-yl)-am-
ino)-s-triazine.
[0071] 2.7. Oxamides, for example 4, 4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide,
2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and
p-methoxy-disubstituted oxanilides and mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0072] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,
4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-di-
methyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethy-
l)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2-
,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethy-
lphenyl-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
2-(2-hydrooxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
2-(2-hydroxyphenyl-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-tr-
iazine.
[0073] 3. Metal deactivators, for example N,N'-diphenyloxamide,
N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl
dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl
bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyloyl)oxalyl dihydrazide,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0074] 4. Phosphites and phosphonites, for example triphenyl
phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearylpentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,
bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite,
tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)
4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosph-
ocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosp-
hocin,
2,2',2''-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biph-
enyl-2,2'-diyl)phosphite],
2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite-
,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
[0075] The following phosphites are especially preferred:
Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos.RTM.168, Ciba
Specialty Chemicals Inc.), tris(nonylphenyl) phosphite,
##STR00006## ##STR00007##
[0076] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0077] 6. Nitrones, for example, N-benzyl-alpha-phenylnitrone,
N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,
N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone,
N-hexadecyl-alpha-pentadecylnitrone,
N-octadecyl-alpha-heptadecylnitrone,
N-hexadecyl-alpha-heptadecylnitrone,
N-ocatadecyl-alpha-pentadecylnitrone,
N-heptadecyl-alpha-heptadecylnitrone,
N-octadecyl-alpha-hexadecylnitrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0078] 7. Thiosynergists, for example dilauryl thiodipropionate,
dimistryl thiodipropionate, distearyl thiodipropionate or distearyl
disulfide.
[0079] 8. Peroxide scavengers, for example esters of
p-thiodipropionic acid, for example the lauryl, stearyl, myristyl
or tridecyl esters, mercaptobenzimidazole or the zinc salt of
2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl
disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0080] 9. Polyamide stabilizers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0081] 10. Basic co-stabilizers, for example melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids, for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate.
[0082] 11. Nucleating agents, for example inorganic substances,
such as talcum, metal oxides, such as titanium dioxide or magnesium
oxide, phosphates, carbonates or sulfates of, preferably, alkaline
earth metals; organic compounds, such as mono- or polycarboxylic
acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic
acid, diphenylacetic acid, sodium succinate or sodium benzoate;
polymeric compounds, such as ionic copolymers (ionomers).
Especially preferred are
1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol,
1,3:2,4-di(paramethyl-dibenzylidene)sorbitol, and
1,3:2,4-di(benzylidene)sorbitol.
[0083] 12. Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass beads, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon
black, graphite, wood flour and flours or fibers of other natural
products, synthetic fibers.
[0084] 13. Other additives, for example plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0085] 14. Benzofuranones and indolinones, for example those
disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S.
Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No.
5,252,643; DE-A4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839,
EP-A-0591102; EP-A-1291384 or
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxy-ethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]-
, 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(2-acetyl-5-isooctylphenyl)-5-isooctyl-benzofuran-2-one.
[0086] Specific UV-absorbers to be mentioned in the present
invention are the following:
##STR00008## ##STR00009## ##STR00010##
[0087] The hydroxyphenyl triazine UV-absorbers are known and are
partially items of commerce.
[0088] The most suitable benzotriazole UV-absorbers are
commercially available under the Trade Names TINUVIN 213 (RTM),
TINUVIN 326 (RTM), TINUVIN 900 (RTM), TINUVIN 328 (RTM) and TINUVIN
350 (RTM) TINUVIN 360 (RTM), TINUVIN 571 (RTM).
[0089] One or more of these further additives are usually contained
in an amount of 0.01 to about 10% of the composition, often in a
concentration level of about 0.1 to 5% by weight of the final
composition. Important are, for example, antioxidants (e.g.
phenolic antioxidants and/or phosph(on)ites listed above) and, for
many applications, flame retardants. Clarifiers/nucleating agents
may be added to provide or improve transparency, especially in
polyolefin compositions. Especially preferred is the combination of
the present phthalocyanines with light stabilizers such as UV
absorbers and/or sterically hindered amines (HALS).
[0090] In another embodiment of the invention further to the
phthalocyanines of formula (I) there may be present in the
composition as further component solid nano-scaled particles of a
thickness of less than 200 nm, which consist of an oxide of zinc
and/or a nitride of a transition metal of group III, IV, V, VI of
the periodic system, each of which is doped with one or more of the
elements belonging to main groups III and IV of the periodic
system, or consist of undoped vanadium nitride or scandium
nitride.
[0091] In particular the nitride is selected from nitrides of
scandium, yttrium, lanthanum including the lanthanides, titanium,
zirconium, hafnium, vanadium, niobium, tantalum, chromium,
molybdenum, wolfram; the doping elements are selected from boron,
aluminum, gallium, indium, thallium, carbon, silicon, germanium,
tin, lead; the particle preferably consisting of aluminum doped
zinc oxide, indium doped zinc oxide, gallium doped zinc oxide,
aluminum doped titanium nitride, indium doped titanium nitride,
gallium doped titanium nitride, aluminum doped vanadium nitride,
indium doped vanadium nitride, gallium doped vanadium nitride,
vanadium nitride, aluminum doped scandium nitride, indium doped
scandium nitride, gallium doped scandium nitride, scandium
nitride.
[0092] Useful oxides are, for example, doped zinc oxides such
as
AZO (Aluminum Zinc Oxide)
IZO (Indium Zinc Oxide)
GaZO (Gallium Zinc Oxide)
[0093] Examples of nitride and doped nitride materials useful as
further components in the invention are the following ones:
AlTiN (titanium nitride doped with Aluminium) InTiN (titanium
nitride doped with Indium) GaTiN (titanium nitride doped with
Gallium) VN (vanadium nitride) AlVN (vanadium nitride doped with
Aluminium) InVN (vanadium nitride doped with Indium) GaVN (vanadium
nitride doped with Gallium) ScN (scandium nitride) AlScN (scandium
nitride doped with Aluminium) InScN (scandium nitride doped with
Indium) GaScN (scandium nitride doped with Gallium)
[0094] Normal Zinc Oxide shows no absorption in the NIR region:
doping transforms the not conducting in a conducting material which
shows absorption in the NIR region.
[0095] Regarding the doping level, the present oxides and nitrides
may be represented by the formulae:
X.sub.aZn.sub.bO.sub.c (II)
X.sub.aY.sub.dN.sub.e (III)
where X is one or more of the elements belonging to main group III
and/or IV of the periodic system, Y is a transition metal belonging
to group III, IV, V and/or VI (see above for more details of
elements belonging to these groups); indices a-e indicate the
abundance of the components, with formula (II) obeying to the
condition a<b<c, and formula (III) obeying to the condition
a<d less or equal to e. Doping levels, for example of Al, Ga
and/or In in ZnO or TiN, often are in the range 0.01 to about 20,
especially 0.1 to 10% by weight of the final particle material. The
nanoparticles are solid and often, but not necessarily,
cristalline. They may be prepared according to methods known in the
art, e.g. using sputtering, thermal evaporation, chemical vapor
deposition (CVD), spray pyrolysis and sol-gel processes; the
materials often are commercially available.
[0096] Preferred materials are zinc oxide doped with Al, Ga, In;
titanium nitride doped with Al; vanadium nitride or especially
scandium nitride; or vanadium nitride or especially scandium
nitride doped with Al, Ga, In. Of special importance are Ga or
especially Al as doping elements.
[0097] Also of special interest are the following materials: ATO
(Tin oxide doped with Antimony), ITO (Tin oxide doped with Indium),
AZO (Zinc oxide doped with Aluminum), IZO (Zinc oxide doped with
Indium), GaZO (Zinc oxide doped with Gallium), LaB.sub.6 and doped
tungsten oxides (YWO.sub.x). Silver or gold nanoparticles,
nanoprisms or nanorods, carbon nanotubes.
[0098] Such doped oxides and their use in IR shielding applications
are for example described in US 2003/0122114 and U.S. Pat. No.
7,074,351.
[0099] One or more of these materials may be used.
[0100] The nanoparticles of the oxides or nitrides used as further
components within the present invention are found not to interact
with light as reflectors but as absorbers (scattering is present
but gives only a small contribution).
[0101] Plastic materials, especially films of the present
invention, containing polymers and nanoparticles as described
above, advantageously may be used in technical application fields
such as architectural glazing, glazing in building and
construction, automotive glazing, transportation glazing,
agricultural films and structures. The materials may be solid
sheets, monolithic sheets, twin-wall sheets, multi-wall sheets,
flat sheets, corrugated sheets, films, oriented or mono- or
biaxially oriented films, lamination films, capstock films.
[0102] Specific application fields include wintergarden and veranda
buildings, facades, skylights, pool covers and enclosures, roof
structures, vaults, walkways, shelters, signage, interior and
exterior design elements, sun shades, side window, rear window,
panorama roof, greenhouses.
[0103] Main applications are heat-shielding, light management, heat
management, energy management, solar control; also of importance
are laser welding, security features, marking, tracers, heat
transfer.
[0104] Compositions of the invention preferably are unplasticized.
Compositions of the invention do not require metals or metallic
particles and usually do not contain such components. Of special
technical interest are rigid, transparent compositions, such as
plates or sheets, for automotive or architectural glazings, or
translucent or transparent polyolefin or polyolefin copolymer
films, especially for agricultural applications.
[0105] The additives 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.
[0106] The incorporation of the additives 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
or dispersed additive 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.
[0107] The incorporation can be carried out in any heatable
container equipped with a stirrer, e.g. in a closed apparatus such
as a kneader, mixer or stirred vessel. The incorporation is
preferably carried out in an extruder or in a kneader. It is
immaterial whether processing takes place in an inert atmosphere or
in the presence of oxygen.
[0108] The addition of the additive or additive blend to the
thermoplastic 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.
[0109] The process is preferably carried out in an extruder by
introducing the additive during processing.
[0110] Particularly preferred processing machines are single-screw
extruders, contrarotating and corotating twin-screw extruders,
planetary-gear extruders, ring extruders or cokneaders. It is also
possible to use processing machines provided with at least one gas
removal compartment to which a vacuum can be applied.
[0111] Suitable extruders and kneaders are described, for example,
in Handbuch der Kunststoffex-trusion, Vol. 1 Grundlagen, Editors F.
Hensen, W Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-143394
(Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
[0112] For example, the screw length is 1-60 screw diameters,
preferably 20-48 screw diameters. The rotational speed of the screw
is preferably 1-800 rotations per minute (rpm), very particularly
preferably 25-400 rpm.
[0113] 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.
[0114] If a plurality of components is added, these can be premixed
or added individually.
[0115] The additives of the invention and optional further
additives can also be added to the polymer in the form of a
masterbatch ("concentrate") which contains the components in a
concentration of, for example, about 1% to about 40% and preferably
2% to about 20% by weight incorporated in a polymer. The polymer
must not be necessarily of identical structure than the polymer
where the additives are added finally. In such operations, the
polymer can be used in the form of powder, granules, solutions,
suspensions or in the form of latices.
[0116] Incorporation can take place prior to or during the shaping
operation, or by applying the dissolved or dispersed compound to
the polymer, with or without subsequent evaporation of the solvent.
A further possibility for incorporating the additives of the
invention into polymers is to add them before, during or directly
after the polymerization of the corresponding monomers or prior to
crosslinking. In this context the additive of the invention can be
added as it is or else in encapsulated form (for example in waxes,
oils or polymers).
[0117] The materials containing the additives 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.
[0118] A further aspect of the invention is a process for the
preparation of a transparent or translucent heat shielding
material, which process comprises the addition of a compound of
formula (I) as described above to a thermoplastic or crosslinkable
polymer.
[0119] Yet other aspects of the invention are the use of a compound
as described above as a heat shielding additive in a thermoplastic
or crosslinkable polymer matrix and the use of the transparent or
translucent composition as described above as a heat shielding
architectural or automotive glazing or agricultural film.
[0120] In another aspect, the invention relates also to the use of
compounds of formula (I) for laser welding, paper printing and
security printing.
[0121] The definitions and preferences given above apply also for
the other aspects of the invention.
[0122] The following examples illustrate the invention.
A) PREPARATION EXAMPLES
Intermediate Compound 1
##STR00011##
[0124] 3-nitro-aminophthalonitrile (100 g), and triethylamine
(116.3 g) are dissolved in N,N-dimethylacetamide (200 ml). The
mixture is stirred. An aqueous solution of methylamine (40%) is
heated and the gaseous solution is bubbled into the reaction
mixture at 30-35.degree. C. until the starting material has
disappeared. The reaction is followed via thin layer chromatography
(TLC), (toluene:THF 1:1). The mixture is then transferred into 600
ml of water and let stirring for 1 h at 25.degree. C. The
precipitate is filtered and washed with water. It is then
re-dispersed in xylene and heated so that the water is distilled
off. Once cooled down, the product precipitates. The crude product
is filtered and washed with xylene and n-hexane, then dried under
vacuum overnight at 60.degree. C. 74 g of a yellow solid are
obtained (yield: 82%). mp: 177-179.degree. C.
[0125] .sup.1H NMR (CDCl.sub.3, 300 MHz):) .delta. 6.77-7.56 (m,
3H); 5.0 (br s, 1H); 2.9 (d, 3H).
[0126] The following intermediate compounds are prepared in analogy
to the above example.
TABLE-US-00001 Inter- mediate compound Structure Yield number Amine
used obtained (%) m.p. (.degree. C.) 2 NH.sub.2Et aq ##STR00012##
67 120-122 3 NH.sub.2-n-Bu ##STR00013## 93 92-94 4 NH.sub.2-n-octyl
##STR00014## 70 63-66 5 NH.sub.2-Cy ##STR00015## 34 106-108 6
Morpholine ##STR00016## 64 168-170 7 EtO(CH.sub.2).sub.3NH.sub.2
##STR00017## 71 67-70 8 PhCH.sub.2NH.sub.2 ##STR00018## 48 159-162
9 Me.sub.2NH ##STR00019## 84 119-121
Intermediate Compound 10;
##STR00020##
[0128] In a 500 ml reaction flask, 130 g of the intermediate
compound 1 (0.47 mol) are dissolved in THF (150 ml) and methanol
(50 ml) under stirring. After a few minutes, a solution 30% w/w in
methanol of sodium methylate (0.28 mol) is added and ammonia is
bubbled into the mixture for 8 hours. The reaction progress is
followed by TLC until the complete conversion of the reactant.
(Eluent: 48:16:32=toluene:methanol:THF and 4% of ammonia hydroxide
concentrated).
[0129] When the reaction is completed, the solvent is removed using
a rotary evaporator. The crude product is purified by
crystallization from ethyl acetate and dried overnight at
50.degree. C. under reduced pressure (yield 44%) obtaining an
orange solid.
[0130] Anal. Calcd. For C.sub.9H.sub.10N.sub.4: C, 62.05%; H,
5.79%; N, 32.16%; Found: C %=61.52%; H %=5.59%; N %=32.89%;
m.p.>300.degree. C.
Intermediate Compound 11
##STR00021##
[0132] In a 500 ml reaction flask, 124 g of the intermediate
compound 3 (0.62 mol) are dissolved in THF (150 ml) and methanol
(50 ml) under stirring. After a few minutes, a solution at 30% w/w
in methanol of sodium methylate (0.25 mol) is added and ammonia is
bubbled into the mixture for 12 hours. The reaction progress is
followed by TLC until the complete conversion of the reactant
(eluent: 48:16:32=toluene:methanol:THF and 4% of ammonia hydroxide
concentrated). When the reaction is completed, the solvent is
removed using a rotary evaporator. The crude product is purified by
crystallization from ethyl acetate and dried overnight at
50.degree. C. under reduced pressure, obtaining a yellow solid.
[0133] Anal. Calcd. For C.sub.12H.sub.16N.sub.4: C %=66.64%; H
%=7.46%; N %=25.90%, Found: C %=65.97%; H %=7.42%; N %=26.61%;
m.p.: 146-147.degree. C.
A1) Preparation of Compound 101:
1,8(11),15(18),22(25)-Tetramethylamino Manganese Phthalocyanine
##STR00022##
[0135] 3-N-methyl-aminophthalonitrile intermediate compound 1 (16
g), magnesium chloride (3 g), 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU, 3.8 g) are stirred together under nitrogen atmosphere for 16
h (T: 155.degree. C.). Solvent used is n-hexanol (80 ml). After
reaction time, the mixture is allowed to cool to room temperature
and then filtered. Several washing cycles are performed (n-hexanol,
methanol, water) with the crude material. The filtered product is
dried under vacuum at 160.degree. C. overnight and 16.4 g of a
black powder are obtained (yield: 96%).
[0136] Anal. Calcd. For C.sub.36H.sub.28ClMnN.sub.12: C, 60.13%; H,
3.92%; Cl, 4.93%; Mn, 7.64%; N, 23.37% Found: C, 59.80%; H, 3.96%;
N, 21.62%; Mn (ICP):7.73%; Cl: 4.79%.
[0137] HPLC APCI-MS (negative polarization): m/z 718;
mp>300.degree. C.; UV-VIS (DMSO): A.sub.max: 897 nm (.epsilon.:
82150).
A2) Preparation of Compound 102:
1,8(11),15(18),22(25)-Tetramethylamino Vanadyl Phthalocyanine
##STR00023##
[0139] 3-N-methyl-aminophthalonitrile (17 g), intermediate compound
1, vanadium chloride (4 g), 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU, 12 g) are stirred together under nitrogen atmosphere for 16 h
(T: 155.degree. C.). Solvent used is n-hexanol (100 ml). After
reaction time, the mixture is allowed to cool to room temperature
and then filtered. Several washing cycles are performed (n-hexanol,
methanol, water) with the crude material. The filtered product is
dried under vacuum at 170.degree. C. overnight and 6.0 g of a black
powder are obtained (yield: 34%).
[0140] Anal. Calcd. For C.sub.36H.sub.28N.sub.12OV: C, 62.16%; H,
4.06%; N, 24.16%; O: 2.30%; V: 7.32% Found: C, 61.79%; H, 4.32%; N,
24.25%; V (ICP): 4.75%. HPLC APCI-MS (positive polarization): m/z
(M.sup.++1) 696.3. mp>300.degree. C. UV-VIS (CHCl.sub.3):
A.sub.max: 824 nm (.epsilon.: 97881).
[0141] The following phthalocyanine compounds are prepared in
analogy.
TABLE-US-00002 Compound Intermediate number number Metal UV-VIS
(solv): A.sub.max .epsilon..sub..lamda.max 103 2 Mn (CHCl.sub.3)
876 nm 58469 104 3 Mn (CHCl.sub.3) 881 nm 54202 105 4 Mn
(CHCl.sub.3) 882 nm 60532 106 5 Mn (CHCl.sub.3) 890 nm 68446 107 6
Mn (CHCl.sub.3) 826 nm 51171 108 7 Mn (CHCl.sub.3) 879 nm 57255 109
1 Cu (DMSO) 782 nm 4100 110 3 Cu (CHCl.sub.3) 789 nm 44731 111 1 Al
(DMSO) 822 nm 110354 112 1 Co (DMSO) 758 nm 64052 113 1 Sn
(CHCl.sub.3) 865 nm 32806 114 7 Sn (CHCl.sub.3) 878 nm 26265 115 1
Zn (CHCl.sub.3) 772 nm 19414 116 2 Zn (CHCl.sub.3) 775 nm 38776 117
3 Zn (CHCl.sub.3) 778 nm 91818 118 5 Zn (CHCl.sub.3) 782 nm 110932
119 6 Zn (CHCl.sub.3) 741 nm 68794 120 8 Zn (CHCl.sub.3) 767 nm
73040 121 1 Ti.dbd.O (CHCl.sub.3) 834 nm 43544 122 3 Ti.dbd.O
(CHCl.sub.3) 842 nm 40691 123 4 Ti.dbd.O (CHCl.sub.3) 814 nm
76646
A3) Preparation of Compound 124:
1,8(11),15(18),22(25)-Tetramethylamino Copper Phthalocyanine
##STR00024##
[0143] In a 250 ml reaction flask, 15 g of the intermediate
compound 10 (0.086 mol) are dissolved in n-hexanol (150 ml) under
stirring and after a few minutes, 3.4 g of CuCl.sub.2 (0.02 mol)
and 6.1 g of DBU (0.04 mol) are added. The reaction is then heated,
refluxed for 16 h and filtered when cooled to room temperature. The
solid is washed on the filter with 50 ml of methanol for two times.
The solid product is finally dried overnight at 140.degree. C.
under reduced pressure, providing 13.8 g of a black powder.
[0144] Anal. Calcd. For C.sub.36H.sub.28CuN.sub.12: C, 62.46%; H,
4.08%; N, 24.28%; Cu, 9.18%, Found: C, 61.73%; H, 4.10%; N, 23.63%;
Cu, 8.32%; HPLC APCI-MS (positive polarization) m/z=692.1; m.p.:
>300.degree. C.; UV-Vis (DMSO): A.sub.max: 781 nm (.epsilon.:
3777).
A4) Preparation of Compound 125:
1,8(11),15(18),22(25)-Tetrabuthylamino Copper Phthalocyanine
##STR00025##
[0146] In a 250 ml reaction flask, 15.0 g of the intermediate
compound 11 (0.07 mol) are dissolved in n-hexanol (100 ml) under
stirring and after few minutes, 3.4 g of CuCl.sub.2 (0.02 mol) and
3.2 g of DBU (0.02 mol) are added. The reaction is then heated at
reflux for 16 h. When cooled to room temperature 50 ml of
isopropanol are added, the crude is filtered and the solid obtained
is washed twice with 20 ml of isopropanol. The solid product is
finally dried overnight at 140.degree. C. under reduced pressure,
providing 8.9 g of a black powder.
[0147] Anal. Calcd. For C.sub.48H.sub.52CuN.sub.12: C, 66.69%; H,
6.09%; N, 19.53%; Cu 7.38%; Found: C, 63.84%; H, 6.01%; N, 20.07%;
Cu, 6.88%. HPLC APCI-MS (positive polarization) m/z=860; m.p.:
250.degree. C. (R) 280.degree.-290.degree. C.; UV-Vis (CHCl.sub.3):
A.sub.max: 789 nm (.epsilon.: 44731).
B) APPLICATION EXAMPLES
B1) Examples of PC Injection Molding/PC Film Extrusion
Mixing and Compounding
[0148] 3.0 kg of milled polycarbonate (Makrolon 3103) are dried in
a vacuum oven at 120.degree. C. for 8 hours. The powder is mixed
with the additives listed in Table B1 for 3 minutes at 80.degree.
C. in a 51 Henschel Turbomixer and afterwards compounded on a
Berstorff ZE 25.times.32D at 280.degree. C. The polymer strand is
granulated.
Sheet Extrusion
[0149] The pellets are used to produce a 100 .mu.m thick cast film
(platte) on a Collin CR-136/350 sheet extrusion line at a maximum
temperature of 280.degree. C.
Artificial Weathering
[0150] The samples are irradiated in a Weather-Ometer Ci65 from
ATLAS in accordance with ASTM G 155/ASTM G 151, Xenon lamp with 2
borosilicate filters, 0.35 W/m2 at 340 nm, 63.+-.3.degree. C. black
panel temperature, 102 min dry and light, 18 min water spray and
light.
Evaluation
[0151] The .DELTA.E values are measured in accordance with DIN
6174.
[0152] The UV-VIS-NIR Spectrum is recorded on a Shimadzu UV 3101 UV
with ISR3100 integrating sphere: Parameter: Slit width 20,
wavelength 250-1800 nm, Scan speed fast, Light Source change at 360
nm and Detector change at 830 nm.
[0153] The relative absorption is calculated by the absorption at
the maximum divided by the initial absorption at the same
wavelength.
[0154] Haze is measured on a Haze-gard plus from Byk Gardner in
accordance with ASTM D-1003. the results are presented in Table
B2.
PC Film sample, Thickness 100 .mu.m: Initial values
TABLE-US-00003 TABLE B1 Initial Absorption Max. TINUVIN Structure
Conc. [%] Haze [%] at max. [nm] 360 [%] 101 0.03 1.3 0.158 867 5
101 0.05 1.9 0.241 867 5 101 0.1 4.6 0.358 867 5 102 0.1 0.6 0.862
828 5 103 0.05 0.4 0.350 870 5 103 0.1 2.0 0.703 870 5 104 0.1 0.6
0.689 878 5 105 0.1 0 0.534 873 5 107 0.05 0.4 0.200 830 5 107 0.1
0.5 0.404 830 5 108 0.1 2.2 0.527 871 5
PC Film sample, Thickness 100 .mu.m: aged samples
TABLE-US-00004 TABLE B2 Haze after .DELTA.E after Rel. Absorption
after Conc. 500 hours 500 hours 500 hours Structure [%] WOM wet WOM
wet WOM wet 101 0.03 0 0.3 94% 101 0.05 2 0.6 96% 101 0.1 4.5 0.7
90% 102 0.1 1.5 1.6 93% 103 0.05 1.1 1.7 83% 103 0.1 1.7 2.2 99%
104 0.1 0.2 3.1 93% 105 0.1 0.5 3.5 92% 107 0.05 1.0 4.1 77% 107
0.1 1.0 6.0 73% 108 0.1 0.3 3.0 86%
B2) Examples of MMA Polymerization
Sheet Preparation
[0155] 70 g freshly distilled methylmethacrylate is polymerized
with 0.1% lauroylperoxide, 0.15% TINUVIN P, 0.15% TINUVIN 770 and
0.01% Compound 102. after degassing. Firstly the mixture is
prepolymerized at 60.degree. C. in a twist-off glass for ca. 2
hours and then in a second step the syrup is polymerized between
glass plates at 60.degree. C. in a water bath followed 15 hours in
oven followed by the final polymerization: 3 hours oven 120.degree.
C., resulting in a final thickness of ca. 1.8 mm.
Artificial Weathering
[0156] The samples were then irradiated in a Weather-Ometer Ci65
from ATLAS in accordance to ASTM G 155/ASTM G 151, Xenon lamp with
2 borosilicate filter, 0.35 W/m2 at 340 nm, 63.+-.3.degree. C.
black panel temperature, dry cycle with relative humidity of ca.
50-60%)
Evaluation
[0157] The .DELTA.E value was measured in accordance to DIN
6174
[0158] The UV-VIS-NIR Spectrum was recorded on a Shimadzu UV 3101
UV with ISR3100 integrating sphere: Parameter: Slit width 20,
wavelength 250-1800 nm, Scan speed fast, Light Source change at 360
nm and Detector change at 830 nm.
TABLE-US-00005 TABLE B3 .DELTA.E after Rel. Absorption Conc.
Absorption Max. TINUVIN 360 [%] 500 hours % after 500 hrs Structure
[%] at max. [nm] TINUVIN 770 [%] WOM wet WOM wet 102 0.01 0.141 800
0.15/0.15 6.3 89
B3) Examples of Pet-G Film Extrusion
[0159] PET-G powder (Eastar 6763 from Eastman), 1% Tinuvin 1577,
0.1% of 1,8(11),15(18),22(25)-Tetramethylamino manganese
phthalocyanine (compound 101) are turbo-mixed, dried at 70.degree.
C. for 12 hours, then compounded in a twin screw Collin
Extruder.
[0160] The obtained pellets are dried again and extruded in a
Collin cast line to get a 300 micron PET-G film.
C) EVALUATION OF HEAT SHEALDING
[0161] Samples containing solar controlling additives were
evaluated using an internal equipment (see FIG. 1). This instrument
compares the temperature build up of a black aluminum panel behind
two plastic samples (A4 size), one sample containing the solar
controlling additive the other being a reference without any
additive. The two samples are mounted on the front side of two
different chambers that are exposed to light of a 500 W halogen
lamp with color temperature of 5000 K. To have the best accuracy
two probes PT100 connected to a PC data logger are used.
* * * * *