U.S. patent application number 10/477363 was filed with the patent office on 2004-08-12 for polymer additives with improved permanence and surface affinity.
Invention is credited to Dong, Ying, McNamara, John James, Wood, Mervin Gale.
Application Number | 20040156933 10/477363 |
Document ID | / |
Family ID | 23119936 |
Filed Date | 2004-08-12 |
United States Patent
Application |
20040156933 |
Kind Code |
A1 |
McNamara, John James ; et
al. |
August 12, 2004 |
Polymer additives with improved permanence and surface affinity
Abstract
Novel stabilizers that are comprised of known polymer additive
moieties chemically bound to hyperbranched and/or dendritic
polymers or copolymers, and novel stabilizers comprised of known
polymer additive moieties chemically bound to amphiphilic
copolymers exhibit superior permanence in an organic substrate as
well as high surface affinity.
Inventors: |
McNamara, John James;
(Putnam Valley, NY) ; Wood, Mervin Gale; (Mobile,
AL) ; Dong, Ying; (Tarrytown, NY) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
23119936 |
Appl. No.: |
10/477363 |
Filed: |
November 12, 2003 |
PCT Filed: |
May 10, 2002 |
PCT NO: |
PCT/EP02/05195 |
Current U.S.
Class: |
424/59 ;
424/DIG.16; 524/90; 525/403 |
Current CPC
Class: |
C08G 83/002 20130101;
C08L 101/005 20130101; C08G 83/005 20130101 |
Class at
Publication: |
424/DIG.016 ;
525/403 |
International
Class: |
C08G 065/32 |
Claims
What is claimed is:
1. A permanent or surface-active hyperbranched or dendritic
stabilizer comprised of at least one polymer additive moiety and at
least one hyperbranched or dendritic polymer moiety.
2. A stabilizer according to claim 1 which is a hyperbranched or
dendritic polymer or copolymer of the formula (I) 4 ( additive
moiety ) x -- ( L ) y -- ( hyperbranched or dendritic polymer or
copolymer moiety ) z ( I ) where x and y are each independently
greater than or equal to 1, z is 1 to 5, and L is independently of
each other a direct bond or a chemical linking group, with the
proviso that the reaction product of the self-condensation product
of 3,5-dihydroxybenzoic acid and 4-hydroxyphenylmethyl carbinol
benzotriazole is excluded.
3. A stabilizer according to claim 2 in which the additive moiety
is selected from the group consisting of antioxidant, ultraviolet
light absorber, hindered amine light stabilizer, hydroxylamine
stabilizer, nitrone stabilizer, amine oxide stabilizer,
benzofuranone stabilizer and organic phosphorus stabilizer
moieties.
4. A stabilizer according to claim 2 in which x is greater than one
and comprising two different additive moieties.
5. A stabilizer according to claim 4 in which the two different
additive moieties are the ultraviolet light absorber and hindered
amine light stabilizer moieties.
6. A stabilizer according to claim 2 in which the hyperbranched or
dendritic moiety comprises a multi-functional monomer selected from
dimethylolpropionic acid and
.alpha.,.alpha.-bis(hydroxymethyl)butyric acid.
7. A stabilizer according to claim 2 in which the linking group L
is --OCO-- or --COO-- or is a hydrocarbylene comprising the groups
--OCO-- or --COO--.
8. A process for the preparation of a compound of formula (I) 5 (
additive moiety ) x -- ( L ) y -- ( hyperbranched or dendritic
polymer or copolymer moiety ) z ( I ) which comprises reacting an
additive compound of formula (a) (additive moiety).sub.p-(G).sub.q
(a) with a fully formed hyperbranched or dendritic polymer or
copolymer, with a partially formed hyperbranched or dendritic
polymer or copolymer, or with components of a hyperbranched or
dendritic polymer or copolymer, where x and y are each
independently greater than or equal to 1, z is 1 to 5, and L is
independently of each other a direct bond or a chemical linking
group, p and q are independently greater than or equal to 1, and G
is independently a reactive functional group (RFG) or a
hydrocarbylene comprising at least one reactive functional
group.
9. A process according to claim 8 which comprises reacting a
carboxy-functional additive with poly(ethylene glycol)monomethyl
ether and dimethylolpropionic acid.
10. A stabilized composition comprising (i) an organic material
subject to the deleterious effects of heat, light or oxidation, and
(ii) an effective stabilizing amount of a stabilizer according to
claim 1.
11. A process for stabilizing an organic material against the
deleterious effect of heat, light or oxidation, which comprises
incorporating therein or applying thereto at least one permanent or
surface-active hyperbranched or dendritic stabilizer according to
claim 1.
12. A permanent or surface active amphiphilic polymer stabilizer
comprised of at least one polymer additive moiety and at least one
amphiphilic copolymer moiety.
13. A stabilizer according to claim 12 of the formula (II) 6 (
additive moiety ) t -- ( L ) u -- ( diblock amphiphilic moiety ) v
( II ) where t, u and v are independently greater than or equal to
1, and L is independently of each other a direct bond or a chemical
linking group.
14. A stabilizer according to claim 13 in which t, u and v are each
1 and the amphiphilic copolymer moiety is selected from
C.sub.18H.sub.37(OCH.su- b.2CH.sub.2).sub.2-- and
CH.sub.3CH.sub.2(CH.sub.2CH.sub.2).sub.13CH.sub.2-
CH.sub.2(OCH.sub.2CH.sub.2).sub.2.5-- and the linking group L
comprises an ester group.
15. A stabilized composition comprising (i) an organic material
subject to the deleterious effects of heat, light or oxidation, and
(ii) an effective stabilizing amount of a stabilizer compound of
formula (II) according to claim 12.
16. A process for stabilizing an organic material against the
deleterious effect of heat, light or oxidation, which comprises
incorporating therein or applying thereto at least one permanent or
surface active amphiphilic polymer stabilizer according to claim
12.
Description
[0001] The present invention relates to novel additives that are
comprised of known polymer additive moieties chemically bound to
hyperbranched or dendritic polymers or copolymers. The present
invention also relates to novel additives that are comprised of
known polymer additive moieties chemically bound to amphiphilic
copolymers. The novel additives exhibit superior permanence in
organic substrates and high surface affinity and are useful in for
example natural or synthetic polymers, recording media and
inks.
[0002] Random hyperbranched polymers are known. Hyperbranched
polymers are obtained from the random polymerization of monomers in
the presence of at least one polyfunctional monomer capable of
introducing branching. Such a synthetic scheme is shown by Hawker
and Devonport in "Step-Growth Polymers for High-Performance
Materials: New Synthetic Methods," Hedrick, J. L. and Labadie, J.
W., Eds., Am. Chem. Soc., Washington, D. C., 1996, pp. 191-193.
Hult, et al., in "Advances in Polymer Science," Vol. 143 (1999),
Roovers, J., Ed., Springer, New York, pp. 1-34, present a review of
hyperbranched polymers.
[0003] U.S. Pat. No. 3,441,953 teaches that discrete esters of
certain hindered dihydroxycarboxylic acids possess desirable
properties and which may be used as textile softeners, lubricants,
wetting and rewetting agents and textile assistants and which
impart properties such as improved softness, scorch resistance,
wettability and rewettability, static control, lubricity, tensile
and tear strengths and sewability to textile materials. An example
is given where polyethylene glycol (PEG) is reacted with
dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid or
BMPA) to form a PEG monoester of BMPA. This diol-ester is
subsequently reacted with a tallow fatty acid to form the tallow
fatty acid diester. In fact, it is believed that in the first step
that a discrete PEG-BMPA monoester is not formed but that some
hyperbranching must have occurred, resulting in a hyperbranched
polyester.
[0004] Functionalization or end-capping of hyperbranched polymers
with various groups is known.
[0005] WO 97/23538 and U.S. Pat. No. 5,990,260 disclose highly
branched epoxide functional and alkenyl functional polyesters
respectively. The polyester is prepared by self-condensing a di,
tri, or polyhydroxy functional monocarboxylic acid monomer and
which polyester contains at least one carboxyl group and multi
hydroxyl groups. The polyester is reacted with an epoxide
containing compound such as epichlorohydrin or a compound
containing an oxidizable unsaturation to introduce the epoxide
functionality. Likewise, it is reacted with a compound containing
allylic or acrylic groups to introduce the alkenyl
functionality.
[0006] U.S. Pat. No. 3,669,939 discloses highly branched
self-condensates of polyhydroxymonocarboxylic acids, for example
dimethylolpropionic acid. Monocarboxylic acids may be present in
the condensation reaction. The resulting resins are useful in
coating compositions.
[0007] U.S. Pat. No. 5,136,014 discloses hyperbranched polyester
polymers and copolymers that may be chemically capped, crosslinked,
or copolymerized with diols or dicarboxylic acids. Suitable capping
agents include anhydrides, acyl chlorides, isocyanates and
benzylisothiocyanate.
[0008] Schmaljohann, et al., Polymeric Materials Science and
Engineering, 77 (1997), p. 173, discloses that hyperbranched
aromatic polyesters and a hyperbranched polyester based on
self-condensation of 2,2-bis(hydroxymethyl)propionic acid may be
functionalized with alkyl acid chlorides of 2 to 18 carbon atoms,
resulting in hyperbranched polyesters with an amphiphilic
character.
[0009] Highly branched dendritic polymers are well known, as
discussed for example in "Polymeric Materials Encyclopedia," Vol. 5
(1996), J. C. Salamone, Ed., CRC Press, New York, pp. 3049-3053.
Dendritic polymers have a non-linear architecture and are
intrinsically globular in shape. Discrete, stepwise synthetic
methods are used to prepare highly branched pure compounds, or
dendrimers. As discussed by Hawker and Devonport in "Step-Growth
Polymers for High-Performance Materials: New Synthetic Methods,"
Hedrick, J. L. and Labadie, J. W., Eds., Am. Chem. Soc.,
Washington, D.C., 1996, pp. 186-196, if the macromolecule has
highly regular branching which follows a strict geometric pattern,
it is a dendrimer. Dendrimers are typically monodisperse and are
prepared in a multi-step approach with purifications at each
stage.
[0010] The architecture of dendrimers is also discussed by Roovers
and Comanita in "Advances in Polymer Science," Vol. 142 (1999),
Roovers, J., Ed., Springer, New York, pp. 179-228. Dendrimers
consist of a core molecule which defines the center of symmetry of
the molecule, and branching layers. Tomalia, et al., in Angew.
Chem. Int. Ed. Eng., 29 (1990), 138-175 disclose "starburst"
dendrimers which consist of an initiator core and branching
groups.
[0011] Hyperbranched macromolecules result if the branching is
random and irregular and are therefore not monodisperse. There are
significant amounts of failure sequences present in such
hyperbranched macromolecules. As discussed by Malmstroem, et al.,
in Macromolecules, 28 (1995), 1698-1703, a hyperbranched material
contains a mixture of linear and fully branched ABx repeating units
and has a degree of branching of less than unity. An ideal
dendritic substance has a degree of branching of unity.
[0012] It is taught in WO 99/00439 and WO 99/00440 that dendrimers
are highly symmetric, while similar macromolecules designated as
hyperbranched and/or dendritic may to a certain degree hold an
asymmetry, yet maintaining the highly branched tree-like
structure.
[0013] U.S. Pat. No. 5,418,301 teaches polyester-based dendritic
macromolecules and their use as an alternative to conventional
polyester alkyd resins. The dendritic macromolecules are built from
a symmetric central initiator molecule or initiator polymer and a
monomeric chain extender having one carboxyl and two hydroxyl
groups and is optionally capped with a chain stopper. The
macromolecules described therein are prepared in a stepwise
fashion. The exemplified central initiator molecules are
ditrimethylolpropane, trimethylolpropane and ethoxylated
pentaerythritol. It is taught that the central initiator compound
may be an alkoxylate polymer such as polyethylene glycol or
polypropylene glycol as well as polytetrahydrofuran.
[0014] U.S. Pat. No. 5,663,247 discloses dendritic or near
dendritic hyperbranched polyester-based macromolecules that
comprise a central nucleus, a monomeric or polymeric chain extender
with at least three reactive sites and optionally a chain stopper.
The central nucleus is an epoxide compound with at least one
reactive epoxide group. The chain extender has at least one
hydroxyl group and at least carboxyl or epoxy group. The chain
extender may be for example dimethylolpropionic acid. The examples
given employ a stepwise preparation and employ as the nucleus a
bisphenol A-diglycidyl ether and triglycidyl isocyanurate.
[0015] WO 96/13558 discloses a binder composition comprised of at
least one unsaturated monomer and at least one unsaturated
polyester. The unsaturated polyester is a dendritic or
hyperbranched macromolecule comprising a nucleus, a chain extender,
and a chain stopper. The nucleus has at least one reactive hydroxyl
or epoxide group. The chain extender has at least two reactive
hydroxyl groups and at least one reactive carboxyl group. The
unsaturation in the polyester is introduced through the chain
stopper. Stepwise methods are disclosed for the preparation of the
polyesters. The exemplified polyesters are prepared from a nucleus
of ethoxylated pentaerythritol.
[0016] WO 96/19537 discloses thermosetting materials such as
composites with increased toughness with the incorporation of
functionalized polyester dendritic or hyperbranched macromolecules
in the thermosetting resin. The polyester macromolecules contain at
least one primary or secondary reactive site. The macromolecules
are built from a nucleus having at least one reactive epoxide or
hydroxyl group, a chain extender with at least two reactive
hydroxyl groups and at least one reactive carboxyl group and a
chain stopper. The reactive sites are introduced through the chain
termination. The disclosed polyesters are prepared in a stepwise
fashion. The exemplified polyesters are prepared from a nucleus of
pentaerythritol pentaethoxylate.
[0017] WO 97/49781 discloses a refrigeration working fluid
comprising a lubricant comprising at least one chain terminated
dendritic or hyperbranched polyester macromolecule and a
refrigerant. The polyesters are composed of a nucleus, a chain
extender and a chain terminator. The nucleus is a mono, di, tri, or
polyfunctional alcohol or epoxide. The chain extender is an hydroxy
functional carboxylic acid and the chain terminator is a aliphatic
carboxylic acid. The exemplified end-capped hyperbranched
polyesters are prepared in a stepwise fashion with a nucleus of
either neopentyl glycol or trimethylolpropane.
[0018] WO 97/45474 discloses thermoplastic polymers grafted with
hyperbranched dendritic polyester macromolecules. The polyester
macromolecules consist of a nucleus, a chain extender and an
optional chain stopper. The nucleus has at least one reactive
epoxide, hydroxyl, carboxyl or anhydride group. The chain extender
has at least three reactive groups of which at least one is a
hydroxyl group and at least one is a carboxyl or anhydride group.
The optional chain stopper may be for example an aliphatic
carboxylic acid. The exemplified hyperbranched dendritic polyesters
are prepared according to a stepwise method with pentaerythritol
pentaethoxylate as the nucleus.
[0019] WO 99/00439 discloses a process for the preparation of
hyperbranched dendritic polyester alcohols. The polyester alcohols
(polymeric polyalcohols or polyols) have a symmetrical or near
symmetrical highly branched structure. The polymeric polyalcohols
are composed of an initiator molecule with one or more reactive
groups and branching chain extender molecules with three functional
groups of which two are hydroxyl groups and one is a group reactive
to the initiator molecule and/or hydroxyl groups. The two hydroxyl
groups of the branching chain extender are acetal protected during
the addition. Deprotection and subsequent addition of another
generation of acetal protected chain extenders, etc., yields highly
branched symmetrical dendrimers. WO 99/00440 discloses a similar
process towards the preparation of the same polymeric polyalcohols.
A double stage convergent synthesis is taught wherein the nucleus
(initiator molecule) has one or more hydroxyl or epoxide groups.
The branching chain extender molecules have three functional groups
of which two are hydroxyl groups and one is a carboxyl group. The
branching generations are prepared first from ketal protected chain
extenders and a carboxylprotected chain extender and
deprotection/subsequent reaction steps. After deprotecting the
carboxyl group, the prepared branches are then coupled to the
nucleus molecule. U.S. Pat. No. 5,041,516 discloses a stepwise
"convergent" process for the preparation of polyaromatic ether and
polyamide dendrimers.
[0020] Linear polymer-dendrimer hybrids are known.
[0021] WO 93/21259 discloses dendritic macromolecules of specific
shapes such as barbells, kites, triblocks and knot shaped molecules
and a stepwise method for their preparation. Several of these
specially shaped macromolecules may be prepared by stepwise methods
with the incorporation of a linear polymer such as a polyalkyl
ether or a polystyrene. The dendritic polymer groups with unique
reactive sites are preferable prepared by the convergent growth
method as disclosed in U.S. Pat. No. 5,041,516. All of the examples
are performed with polyaromatic ethers which are true dendrimers
prepared by a convergent method as disclosed in U.S. Pat. No.
5,041,516, J. Am. Chem. Soc. 112 (1990), 7638-7647 and J. Chem.
Soc. Perkin Trans. I (1991), 1059-1076. A broad range of possible
uses for the specially shaped compounds is envisioned, including
surface modification and compatibilization. Roovers and Comanita in
"Advances in Polymer Science," Vol. 142 (1999), Roovers, J., Ed.,
Springer, New York, pp. 211-216 disclose similar hybrid
macromolecules. The functional dendrimers are reacted with a linear
polymer to form the hybrids.
[0022] The use of polyalkylene oxide polymers towards effecting the
surface properties of a polymer is known.
[0023] Bergbreiter and Srinivas in Macromolecules 25 (1992),
636-643, disclose an "entrapment functionalization" approach
towards modifying the surface of high-density polyethylene. Block
cooligomers of polyethylene and poly(ethylene glycol) are prepared
and intimately mixed with virgin polyethylene. Analysis of polymer
films prepared from this mixture showed that the poly(ethylene
glycol) units ended up primarily at the outermost layers of the
film.
[0024] U.S. Pat. No. 5,217,573 teaches a method for removing laser
printer and xerographic toner, ink or the like from paper by
alkaline washing and flotation in the presence of a surfactant
which has two lipophilic groups and one hydrophilic group. The
lipophilic groups are derived from rosin acids and the hydrophilic
group is derived from polyethylene glycol.
[0025] U.S. Pat. No. 5,464,691 discloses the use of an amphiphilic
resin towards modifying the surface energy of a polyolefin. The
amphiphilic resins are composed of hydrocarbon sections and a polar
section. The hydrocarbon sections are derived from, for example,
long-chain aliphatic carboxylic acids and the polar section is
derived from a telechelic diol, for example polyethylene
glycol.
[0026] U.S. Pat. No. 5,721,322 discloses a method for increasing
the surface activity of non-polar polymeric materials, in
particular polyolefins and polystyrenes, with the incorporation of
a triblock copolymer. The triblock copolymer has two sections
compatible with the host polymer, for example long-chain aliphatic
groups. The center section is derived from a polyepichlorohydrin
telomer.
[0027] U.S. Pat. Nos. 5,240,985, 5,272,196, 5,281,438, 5,328,951
disclose the use of an amphiphile towards increasing the surface
energy of polyolefins. The amphiphile consists of a central
hydrophilic component and two lipophilic components. The
hydrophilic component is derived from, for example, polyglycols and
the lipophilic components are derived from, for example fatty
acids.
[0028] WO 97/12882 discloses polymeric benzotriazoles including the
reaction product of the self-condensation product of
3,5-dihydroxybenzoic acid and 4-hydroxyphenylmethyl carbinol
benzotriazole. U.S. Pat. No. 6,114,489 discusses hyperbranched
polymers with functional moieties. WO 98/44024 discusses the use of
certain hyperbranched polymers as antioxidants.
[0029] U.S. Pat. No. 5,777,129 discloses hyperbranched polymers. WO
01/74946 discloses dendrimer additives.
[0030] Polymer additives are known to those skilled in the art.
They are for example antioxidants such as hindered phenolic
antioxidants, ultraviolet light absorbers (UVA's) such as
hydroxyphenylbenzotriazoles, hydroxyphenyltriazines and
hydroxybenzophenones, hindered amine light stabilizers (HALS),
hydroxylamine stabilizers, amine oxide stabilizers, benzofuranone
stabilizers and organic phosphorus stabilizers.
[0031] A subject of the present invention are polymer stabilizers
with improved permanence and/or surface affinity by virtue of being
chemically bound to hyperbranched or dendritic polymers or
copolymers. Another subject of the present invention are polymer
stabilizers with improved permanence and/or surface affinity by
virtue of being chemically bound to amphiphilic copolymers.
Compounds containing known polymer additive moieties and
appropriate reactive sites are bound to hyperbranched or dendritic
polymers or copolymers or to amphiphilic copolymers through
condensation or other chemical reactions.
[0032] A further subject of the present invention is a process for
preparing the novel plastic additives herein disclosed.
[0033] A further subject of the present invention are stabilized
compositions subject to degradation by the deleterious effects of
heat, light or oxidation, which compositions comprise an effective
stabilizing amount of the novel polymeric stabilizers herein
disclosed.
[0034] Disclosed are permanent and/or surface-active hyperbranched
or dendritic polymer stabilizers comprised of at least one polymer
additive moiety and at least one hyperbranched or dendritic polymer
moiety.
[0035] Also disclosed are permanent and/or surface active
amphiphilic polymer stabilizers comprised of at least one polymer
additive moiety and at least one amphiphilic copolymer moiety.
[0036] Specifically, the present invention discloses novel
hyperbranched or dendritic stabilizers of the formula (I) 1 (
additive moiety ) x -- ( L ) y -- ( hyperbranched or dendritic
polymer or copolymer moiety ) z ( I )
[0037] where
[0038] x and y are each independently greater than or equal to
1,
[0039] z is 1 to 5,
[0040] L is independently of each other a direct bond or a chemical
linking group,
[0041] with the proviso that the reaction product of the
self-condensation product of 3,5-dihydroxybenzoic acid and
4-hydroxyphenylmethyl carbinol benzotriazole is excluded.
[0042] The present invention also discloses novel amphiphilic
stabilizers of the formula (II) 2 ( additive moiety ) t -- ( L ) u
-- ( diblock amphiphilic moiety ) v ( II )
[0043] where t, u and v are independently greater than or equal to
1, and
[0044] L is independently of each other a direct bond or a chemical
linking group.
[0045] The variables t, u and v are for example independently 1, 2,
3 or 4.
[0046] The additive moiety is for example independently selected
from the group consisting of antioxidant, ultraviolet light
absorber, hindered amine light stabilizer, hydroxylamine
stabilizer, nitrone stabilizer, amine oxide stabilizer,
benzofuranone stabilizer and organic phosphorus stabilizer
moieties.
[0047] The terms x, y independently may be for example 1 to 200, 1
to 100, 1 to 50, for instance 1 to 25, 1 to 10 or 1 to 5.
[0048] The term z is for example 1, 2, 3 or 4. Particularly, z is 1
or 2.
[0049] For the purposes of this invention, and as is understood in
the art, the term "moiety" means a chemical functional group when
it is part of a larger compound, for example when part of a
compound of formula (I). For example, the term "hyperbranched or
dendritic polymer or copolymer moiety" refers to the hyperbranched
or dendritic portion(s) of formula (I). Likewise the term "additive
moiety" refers to the portion of formula (I) with polymer additive
functionality. Polymer additive functionality means for example
antioxidant, ultraviolet light absorber, light stabilizer, process
stabilizer, etc., functionality.
[0050] The chemical linking group L may for example be any divalent
linking group. Linking groups are for example esters, amides, and
other common divalent groups, for example --OCO--, --COO--, --O--,
--CONH--, --CONR--, --NHCO--, --NRCO--, --CO--, --NH--, --NR--,
--S--, --SO--, SO.sub.2--, --CSO--, --COS--, --CSS--, where R is a
hydrocarbyl group. Of special interest is the linking group L
--OCO-- or --COO-- or is a hydrocarbylene comprising the groups
--OCO-- or --COO--.
[0051] Linking groups L may also be a divalent hydrocarbylene group
that comprises one of the above ester, amide, etc., groups.
[0052] The term "hydrocarbyl group" broadly refers to a monovalent
hydrocarbon group in which the valency is derived by abstraction of
a hydrogen from a carbon atom. Hydrocarbyl includes for example
aliphatics (straight and branched chain), cycloaliphatics,
aromatics and mixed groups such as aralkyl, alkylaryl, alkynyl,
cycloalkynyl. Hydrocarbyl includes such groups as alkyl,
cycloalkyl, aryl, aralkyl, alkylaryl, alkenyl, and cycloalkenyl. A
hydrocarbyl may optionally be interrupted by carbonyl, carboxyl,
amino, amido, thio, sulfoxide, sulfonyl and ether groups and/or may
optionally be substituted by hydroxy, amino, amido, carboxyl and
thio groups.
[0053] The term "hydrocarbylene" broadly refers to any divalent
hydrocarbon in which both valencies derive by abstraction of
hydrogens from carbon atoms. Included within the definition of
hydrocarbylene are the same groups as indicated herein for
hydrocarbyl, with of course, the extra valency, for example
alkylene, alkenylene, arylene, alkylaryl, etc.
[0054] A hydrocarbylene as defined herein may also be any polymeric
or oligomeric backbone (non-hyperbranched and non-dendritic) known
in the art as part of polymeric or oligomeric polymer additives.
For example triazine-containing polymeric backbones that are part
of commercial hindered amine compounds, for example Chimassorb.RTM.
944.
[0055] The instant invention relates also to a process for the
preparation of a compound of formula (I) 3 ( additive moiety ) x --
( L ) y -- ( hyperbranched or dendritic polymer or copolymer moiety
) z ( I )
[0056] which comprises
[0057] reacting an additive compound of formula (a)
(additive moiety).sub.p-(G).sub.q (a)
[0058] with a fully formed hyperbranched or dendritic polymer or
copolymer, with a partially formed hyperbranched or dendritic
polymer or copolymer, or with components of a hyperbranched or
dendritic polymer or copolymer,
[0059] where
[0060] x and y are each independently greater than or equal to
1,
[0061] z is 1 to 5, and
[0062] L is independently of each other a direct bond or a chemical
linking group,
[0063] p and q are independently greater than or equal to 1,
and
[0064] G is independently a reactive functional group (RFG) or a
hydrocarbylene comprising
[0065] at least one reactive functional group.
[0066] The polymer additive compounds of formula (a) contain
additive functional moieties selected for example from the group
consisting of antioxidant, ultraviolet light absorber, hindered
amine light stabilizer, hydroxylamine stabilizer, nitrone
stabilizer, amine oxide stabilizer, benzofuranone stabilizer and
organic phosphorus stabilizer moieties.
[0067] The reactive functional group (RFG) may be, for example,
--OH, --NHR, --NH.sub.2, --SH, --SO.sub.2H, --CO.sub.2H,
--CO.sub.2R, --COX, --CSOH, --COSH, --CS.sub.2H, --NCO, epoxy,
epoxy ether, epoxy ester or X,
[0068] wherein X is Cl, Br or I and R is a hydrocarbyl group.
[0069] Preferably, in the stabilizers of formula (I) x is greater
than one and comprising two different additive moieties.
[0070] Of interest are stabilizers of formula (I) or (II) in which
the two different additive moieties are the ultraviolet light
absorber and hindered amine light stabilizer moieties.
[0071] Of special interest are stabilizers of formula (I) or (II)
in which the hyperbranched or dendritic moiety comprises a
multi-functional monomer selected from dimethylolpropionic acid and
.alpha.,.alpha.-bis(hydroxymethyl)butyric acid.
[0072] Especially preferred stabilizers of formula (I) or (II) are
those in which the hyper-branched or dendritic moiety comprises a
multi-functional monomer selected from dimethylolpropionic acid and
.alpha.,.alpha.-bis(hydroxymethyl)butyric acid and the additive
moiety is selected from the group consisting of the
hydroxyphenylbenzotrizole, hydroxyphenyltriazine,
hydroxybenzophenone, and hindered amine moieties.
[0073] The additive moieties are for example chemical structural
groups comprising additive functional structural groups selected
from the group consisting of 12
[0074] wherein at least one of the open bonds of the moieties is
bound directly to a group G,
[0075] R.sub.1 is a sterically bulky group, for example a group
selected from the group consisting of tert-butyl,
.alpha.-methylbenzyl, .alpha.,.alpha.-dimethyl-benzyl (cumyl),
.alpha.-methylcyclohexyl, cyclopentyl, benzyl and tert-octyl,
and
[0076] R.sub.x is hydrogen or methyl.
[0077] The remaining open bonds are bound to groups known to those
skilled in the art so that the additive moiety has its known
additive function, for example hydrogen or a hydro-carbyl group or
a hydrocarbylene group. It is possible for more than one
hydrocarbylene to be bound to another to form a cyclic
structure.
[0078] The reactive functional group, RFG, of the group G of the
compound of formula (a) reacts with a reactive site on a
hyperbranched or dendritic polymer or copolymer, a partially formed
hyperbranched or dendritic polymer or copolymer, or a component
thereof. The linking group L of formula (I) is formed by this
reaction.
[0079] In many instances the present compounds of the formula (a)
are disclosed and known to those skilled in the art of polymer
stabilization. Known compounds without any reactive functional
group may also be modified to have a reactive functional group; or
a known compound with a reactive functional group may be modified
to have a reactive functional group of a different reactive
functionality. For example, a compound of formula (a) where a
polymer additive moiety is attached to a group G comprising a
reactive functional group such as an electrophilic ester, the ester
may be reduced to be a nucleophilic alcohol.
[0080] That is, the polymer additives of formula (a) of the present
invention are known in the art or are known compounds that may be
modified by known methods to be of formula (a).
[0081] Of interest are stabilizers of formula (I) or (II) in which
the additive moiety is selected from the group consisting of the
hydroxyphenylbenzotrizole, hydroxyphenyltriazine,
hydroxybenzophenone, and hindered amine moieties.
[0082] Specific examples of polymer additives of formula (a) are
3
[0083] Chimassorb.RTM. 944, Ciba Specialty Chemicals 4
[0084] Tinuvin.RTM. 622, Ciba Specialty Chemicals and other
hindered amines or modifiable hindered amines, 5
[0085] and other hydroxyphenylbenzotriazoles or modifiable
hydroxyphenylbenzotriazoles, 6
[0086] and other hydroxyphenyltriazines or modifiable
triazines.
[0087] It can seen from the above structures of formulae 1)-11),
that the present variables p and q may truly be independent of each
other. Therefore, variables x and y in present compounds of formula
(I) are also truly independent of each other.
[0088] For example, in the compound of formula 1), with a reactive
hydroxyl, p is 1 and q is 2. In the compound of formula 1), the
additive moiety is 7
[0089] and the group G is a hydrocarbyl group comprising the
reactive functional group hydroxyl: 8
[0090] In formula 2), p is 1 and q is 2. The additive moiety is
9
[0091] and there are two different hydrocarbyl groups G comprising
reactive functional groups (hydroxyls): 10
[0092] In oligomeric formula 3), with a reactive amine end group,
p=2 times m, the group G may be considered the oligomeric backbone
comprising the hindered amine moieties and therefore q is 1.
[0093] In tris-resorcinol triazine 10), with 1, 2, 3, 4 or 5
reactive hydroxyl groups, p is 1 and q is 5, and each G is
hydroxyl. It can be seen that if a tris-resorcinol triazine of
formula 10) is attached to a hyperbranched moiety 1, 2, 3, 4 or 5
times, that x and y are independent of each other in compounds of
formula (I).
[0094] Of special interest are stabilizers of formula (I) or (II)
in which the additive moiety is derived from one or more compounds
selected from the group consisting of 111213
[0095] The additive functional structural groups that are
sub-structures (a part thereof) of the polymer additive moieties of
the present invention are disclosed in many U.S. Patents and are
known to those skilled in the art. They are the functional portions
of the additives disclosed and known in the art. For example, the
chromophore of a known ultraviolet light absorber (UVA) is the
primary functional portion (functional structural group) of the UVA
molecule.
[0096] For example, the hydroxyphenylbenzotriazole functional
structural groups are disclosed for example in U.S. Pat. Nos.
3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332;
3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589; 4,315,848;
4,347,180; 4,383,863; 4,675,352; 4,681,905, 4,853,471; 5,268,450;
5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349; 5,516,914;
5,554,760; 5,563,242; 5,574,166; 5,607,987, 5,977,219 and
6,166,218, the relevant parts of which are hereby incorporated by
reference.
[0097] The hydroxyphenyltriazine functional structural groups are
disclosed for example in U.S. Pat. Nos. 3,843,371; 4,619,956;
4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414; 5,354,794;
5,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854;
5,681,955; 5,726,309; 5,942,626; 5,959,008; 5,998,116 and
6,013,704, and U.S. application Ser. No. 09/383,163, the relevant
parts of which are hereby incorporated by reference.
[0098] The hindered amine functional structural groups are
disclosed for example in U.S. application Ser. Nos. 09/257,711,
09/505,529 and 09/794,710, and U.S. Pat. Nos. 5,204,473, 5,096,950,
5,004,770, 5,844,026, 6,046,304, 6,166,212, 6,117,995 and
6,221,937, the relevant parts of which are hereby incorporated by
reference. The amine of the hindered amine may be substituted by
groups known in the art, for example methyl, hydrogen, acyl, or
alkoxy or cycloalkoxy.
[0099] Hydroxylamine functional structural groups are disclosed for
example in U.S. Pat. Nos. 4,590,231, 4,668,721, 4,782,105 and
4,876,300, 4,649,221, 4,691,015, 4,703,073, 4,612,393, 4,696,964,
4,720,517 and 4,757,102, 4,831,134, 5,006,577, 5,019,285,
5,064,883, 5,185,448 and 5,235,056, 4,666,962, 4,666,963,
4,678,826, 4,753,972, 4,757,102, 4,760,179, 4,929,657, 5,057,563,
5,021,479, 5,045,583 and 5,185,448, the relevant parts of which are
hereby incorporated by reference.
[0100] Amine oxide functional structural groups are disclosed for
example in U.S. Pat. Nos. 5,081,300, 5,162,408, 5,844,029,
5,880,191 and 5,922,794, the relevant parts of which are hereby
incorporated by reference.
[0101] Nitrone functional structural groups are disclosed for
example in U.S. Pat. No. 4,898,901, the relevant parts of which are
hereby incorporated by reference.
[0102] Benzofuranone functional structural groups are disclosed for
example in U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312;
5,216,052; 5,252,643; 5,369,159; 5,488,117; 5,356,966; 5,367,008;
5,428,162; 5,428,177; 5,614,572; 5,883,165 or 5,516,920, all
incorporated herein by reference.
[0103] Phosphite and phosphonite functional structural groups are
disclosed for example in co-pending U.S. application Ser. No.
09/783,256, the relevant parts of which are hereby incorporated by
reference.
[0104] Hyperbranched or Dendritic Polymers or Copolymers
[0105] The hyperbranched or dendritic moieties are comprised of
multi-functional monomers known to those skilled in the art and are
described for example in U.S. Pat. Nos. 5,418,301 and 5,990,260 and
U.S. application Ser. No. 09/778,194. An example are monomers
containing one carboxyl group and two hydroxyl groups.
[0106] The hyperbranched or dendritic polymer or copolymer moieties
of present compounds of formula (I) may be formed in situ during
the preparation of a compound of formula (I), or may be prepared
independently and reacted with a polymer additive compound of
formula (a) to form a compound of formula (I), or a section of a
hyperbranched or dendritic polymer or copolymer moiety may be
prepared and used in a stepwise preparation of a compound of
formula (I). Preferably, the stabilizers of formula (I) are
prepared in a one-pot, one-step process.
[0107] The reactive functional group of the hyperbranched or
dendritic polymer or copolymer or sections or individual components
thereof are selected from the same group as the reactive functional
groups of the polymer additives of formula (a), with the proviso
that the reactive group of the additive is reactive with the
reactive functional group of the hyperbranched or dendritic polymer
or copolymer or sections or components thereof.
[0108] Of interest is a process which comprises reacting a
carboxy-functional additive with poly(ethylene glycol)monomethyl
ether and dimethylolpropionic acid.
[0109] Of special interest is a process which comprises reacting a
carboxy-functional additive with poly(ethylene glycol) and
dimethylolpropionic acid.
[0110] Preferred is a process for the preparation of a stabilizer
of formula (I) in which the additive is a
hydroxyphenylbenzotriazole.
[0111] Hyperbranched or dendritic polymers or copolymers are known
in the art, and are disclosed for example in U.S. Pat. Nos.
5,418,301, 5,990,260 and U.S. application Ser. No. 09/778,194,
filed Feb. 7, 2001, the disclosures of which are incorporated
herein by reference. The hyperbranched or dendritic moieties of the
compound of formula (I) of the present invention may comprise
complete compounds as described in U.S. Pat. Nos. 5,418,301,
5,990,260 and U.S. application Ser. No. 09/778,194, or they may
comprise only the hyperbranched portions thereof. For example, a
hyperbranched moiety of present formula (I) may simply be a
polyester formed from dimethylolpropionic acid or other
multi-functional monomer suitable for formation of a hyperbranched
or dendritc polymer.
[0112] For example, the disclosure of U.S. Pat. No. 5,418,301
describes a dendritic macromolecule prepared from a central
initiator molecule with at least one reactive hydroxyl group, a
hyperbranched section attached to the initiator molecule, and
optional chain stoppers. According to the present invention,
compounds of the formula (a) may be employed as either monomeric
chain extenders having two reactive groups, chain stoppers and/or
as initiator molecules according to U.S. Pat. No. 5,418,301.
Present compounds of formula (a) may also be bound to finished
macromolecules as disclosed in this reference.
[0113] The hyperbranched copolymers of U.S. application Ser. No.
09/778,194 are amphiphilic and designed for surface activity when
employed as polymer additives. The copolymers are described as
(A)(B) or (B)(A)(B) copolymers where (A) is a linear hydrophilic
polymer or oligomer and (B) is a random hyperbranched polymer or
oligomer; which copolymers are fully or partially terminated with
lipophilic groups. According to the present invention, polymer
additive compounds of present formula (a) may also be bound to or
incorporated into the hyperbranched copolymers of this
reference.
[0114] Compounds of Formula (I) of the Present Invention
[0115] For example, a present reactive additive compound of formula
(a), such as a hydroxyphenylbenzotriazole of formula 9), may act as
the initiator, and/or a reactive additive compound such as a
hydroxyphenylbenzotriazole of formula 6), 7) or 8) may act as the
chain stopper according to U.S. Pat. No. 5,418,301. If the
hyperbranched section is prepared from dimethylolpropionic acid,
the following compounds of present formula (I) may be prepared:
14
[0116] The designation BZT is the corresponding
hydroxyphenylbenzotriazole moiety. The hydroxyphenylbenzotriazole
moiety is attached to the hyperbranched polymer through a propanol
or propanoyl group. The linking group L formed then is
--CH.sub.2CH.sub.2CH.sub.2OCO-- or --CH.sub.2CH.sub.2COO--
respectively (linking group between the hydroxyphenylbenzotriazole
chromophore and the hyperbranched moiety).
[0117] The group "initiator" is a suitable initiator as described
in U.S. Pat. No. 5,418,301, for example ditrimethylolpropane or
ethoxylated pentaerythritol. The group "R" is a suitable chain
stopper according to this reference, for example a long-chain alkyl
such as lauryl.
[0118] It is contemplated that such compounds of formula (I) may
have a mixture of additive moieties and chain stopper groups R. It
is contemplated that compounds of formula (I) may have a mixture of
different additive moieties, such as hindered amines and UVA's.
[0119] In the present invention, the hyperbranched copolymers of
U.S. application Ser. No. 09/778,194 may be fully or partially
terminated with present polymer additives of formula (a), or may
have an additive moiety attached to the hydrophilic polymer. For
example, where the hydrophilic polymer is polyethylene glycol (PEG)
or poly(ethylene glycol) monomethyl ether (MPEG), the
hyperbranching monomer is dimethylolpropionic acid, and present
polymer additives of formulae 6)-8) are employed, the following
structures may be obtained: 15
[0120] Again, the designation BZT is the corresponding
hydroxyphenylbenzotriazole moiety. The hydroxyphenylbenzotriazole
moiety is attached to the hyperbranched polymer through a propanol
or propanoyl group. The linking group L formed then is
--CH.sub.2CH.sub.2CH.sub.2OCO-- or --CH.sub.2CH.sub.2COO--. In the
structure directly above, of present formula (I), the two
hyper-branched sections attached through a PEG group together is
the hyperbranched or dendritic polymer or copolymer moiety.
[0121] In any of the above specific formulae, other additive
moieties such as the herein described hindered phenolic, hindered
amine, hydroxyphenyltriazine, hydroxybenzophenone, hydroxylamine,
nitrone, amine oxide, benzofuranone, phosphite or phosphonite
moieties, may replace the hydroxyphenylbenzotriazole moieties. It
is contemplated that the hyperbranched or dendritic compounds of
formula (I) of the present invention may comprise more than one
type of additive moiety.
[0122] For example a present compound of formula (I) may have a
mixture of hindered amine (HALS) and ultraviolet light absorbing
(UVA) moieties, such as described below: 16
[0123] The UVA moieties may be selected from, for example,
hydroxyphenylbenzotriazole, hydroxyphenyltriazine and
hydroxyphenylbenzophenone moieties.
[0124] It is also contemplated that the polymer additive moieties
of the present invention may be incorporated into hyperbranched or
dendritic polymers or copolymers that are otherwise composed of
only multifunctional monomers that make up the hyperbranched
structure; that is with no other initiator or terminating (chain
stopper) group. For example, an additive moiety attached to a
hyperbranched polyester polymer.
[0125] It is also contemplated that a polymer additive of formula
(a) may itself be a suitable multi-functional monomer for
incorporation as part of a hyperbranching structure.
[0126] It is also contemplated that a polymer additive of formula
(a) may itself be a suitable multi-functional monomer used to
prepare a hyperbranching structure or to be part of a
hyperbranching structure.
[0127] An example of a compound of formula (a) that is itself a
multi-functional monomer for use as part of a hyperbranching
structure or for use to prepare a hyperbranching structure is:
17
[0128] It is contemplated that an additive of formula (a) may be
bound to a dendritic macromolecule and/or may be an initiator
molecule and/or may be a monomeric chain extender and/or may be a
chain stopper in the dendritc macromolecules disclosed in U.S. Pat.
No. 5,418,301.
[0129] It is contemplated than an additive of formula (a) may be
bound to the amphiphilic block copolymers and/or may be employed in
place of the lipophilic terminating groups and/or may be employed
in place of the linear hydrophilic polymer or oligomer component
and/or may perform as a multi-functional monomer of the
hyperbranched polymers as described in U.S. application Ser. No.
09/778,194.
[0130] It is contemplated that different additives of formula (a)
of the same class (e.g. hydroxyphenylbenzotriazoles) or of
different classes (e.g. UVA's and HALS) may be bound to the same
hyperbranched moiety.
[0131] It is contemplated that additives with more than one
reactive functional group may act as both a chain stopper and an
initiator as per U.S. Pat. No. 5,418,301.
[0132] It is contemplated that in place of the hyperbranched or
dendritic polymer or copolymer moieties of the present invention,
that in their place true dendrimers may be used. True dendrimers
are typically monodisperse and are prepared in a multi-step
approach with purifications at each stage. True dendrimers are
disclosed for example in U.S. Pat. No. 5,041,516, which discloses a
stepwise "convergent" process for the preparation of polyaromatic
ether and polyamide dendrimers. The disclosure of U.S. Pat. No.
5,041,516 is hereby incorporated by reference.
[0133] The disclosures of U.S. Pat. Nos. 3,669,939, 5,136,014,
5,041,516, 5,663,247 and 5,990,260 are also hereby incorporated by
reference. The present additives of formula (I) may be comprised of
hyperbranched or dendritic polymer or copolymer moieties as
disclosed in these references.
[0134] Process
[0135] It can be seen that an additive of formula (a) may be
reacted onto a finished hyperbranched or dendritic polymer or
copolymer according to U.S. Pat. No. 5,418,301 or U.S. application
Ser. No. 09/778,194, or may be reacted onto a partially finished
hyperbranched or dendritic polymer or copolymer according to these
references, or may be reacted onto a specific component prior to
building up the hyperbranched or dendritic polymer or
copolymer.
[0136] These processes are also a subject of the present
invention.
[0137] Particularly, a one pot, one step process where all
ingredients are reacted together at one time provide effective
conditions for the preparation of the present compounds of formula
(I).
[0138] For example, a one pot reaction of an additive compound of
formula (a), a di-functional hydrophilic polymer or oligomer, a
multi-functional monomer and a lipophilic terminating group will
result in a hyperbranched copolymer of formula (I).
[0139] A one pot reaction of an additive compound of formula (a), a
multi-functional monomer and a lipophilic terminating group will
result in a hyperbranched polymer of formula A one pot reaction of
an additive compound of formula (a) and a multi-functional monomer
will result in a hyperbranched polymer of formula (I).
[0140] The present additive moieties of the compounds of formula
(I) are "derived" from the compounds of formula (a).
[0141] Compounds of Formula (II) of the Present Invention
[0142] Also disclosed are permanent and/or surface active
amphiphilic polymer stabilizers comprised of at least one polymer
additive moiety and at least one amphiphilic copolymer moiety.
[0143] The amphiphilic copolymers are diblock copolymers that
contain both a hydrophilic and a hydrophobic section.
[0144] Diblock amphiphilic copolymers are for example poly(alkylene
oxide) adducts of long chain alcohols or poly(alkylene oxide
adducts) of fatty acid esters. Poly(alkylene oxide) is for example
poly(ethylene oxide), poly(propylene oxide), poly(ethylene glycol)
or poly(propylene glycol).
[0145] A diblock amphiphilic copolymer is for example
CH.sub.3CH.sub.2(CH.sub.2CH.sub.2).sub.a
CH.sub.2CH.sub.2(OCH.sub.2CH.sub- .2).sub.bOH, where a is 9 to 25
and b is 1 to 10.
[0146] Some diblock amphiphilic copolymers are commercially
available, for example Atmer.RTM. 502, a 2 mole ethoxylated stearyl
alcohol, C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.2OH. Atmer.RTM. is
a trademark of Uniqema. Also commercially available are the
Unithox.RTM. ethoxylated alcohols, for example Unithox.RTM. 420,
CH.sub.3CH.sub.2(CH.sub.2CH.sub.2-
).sub.13CH.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.2.5OH. Unithox.RTM.
is a trademark of Petrolite Corp.
[0147] The present compounds of the formula (II) may be prepared
from above compounds such as Atmer.RTM. 502 or Unithox.RTM. 420 and
a polymer additive compound of present formula (a) that has an
electrophilic reactive group suitable for reacting with an alcohol.
For example the condensation reaction of Unithox.RTM. 420 and the
benzotriazole of formula 8) will form:
CH.sub.3CH.sub.2(CH.sub.2CH.sub.2).sub.13CH.sub.2CH.sub.2(OCH.sub.2CH.sub.-
2).sub.2.5O-BZT.
[0148] The group BZT is the hydroxyphenylbenzotriazole moiety, and
in this case the linking group L is the group
--OCOCH.sub.2CH.sub.2--. The diblock amphiphilic moiety is
CH.sub.3CH.sub.2(CH.sub.2CH.sub.2).sub.13CH-
.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.2.5--.
[0149] In the above specific formula, other additive moieties such
as the herein described hindered phenolic, hindered amine,
hydroxyphenyltriazine, hydroxybenzophenone, hydroxylamine, nitrone,
amine oxide, benzofuranone, phosphite or phosphonite moieties, may
replace the hydroxyphenylbenzotriazole moiety.
[0150] Stabilized Compositions
[0151] Another subject of the present invention are stabilized
polymeric compositions comprising the present compounds of formula
(I) or (II).
[0152] Accordingly, a subject of the present invention are
stabilized compositions comprising
[0153] (i) an organic material subject to the deleterious effects
of heat, light or oxidation, and
[0154] (ii) an effective stabilizing amount of a compound of
formula (I) or (II).
[0155] The stabilized compositions of the present invention
comprise the present compounds of formula (I) or (II) from 0.1 to
20 percent by weight, based on the weight of component (i). For
example, component (i) may be present from 0.5 to 5 percent by
weight, based on the weight of component (ii).
[0156] It is contemplated however, that in the stabilized
compositions of the present invention, that the compounds of
formula (I) may be employed at levels above 20 percent by weight;
for example the compounds of formula (I) may themselves act as
resins in a stabilized composition. That is, it is contemplated
that present compounds of formula (I) themselves may form a
stabilized resin composition, for example a stabilized polyester
resin.
[0157] A portion of the additives of component (ii) may migrate to
the surface of the organic substrate thereby modifying the surface
properties thereof. Having light stabilizers, for example UVA's or
HALS, primarily located on the surface of an article to be
stabilized is especially advantageous. The additives of component
(ii) may also be highly persistent in the organic substrate. The
stabilizers of formula (I) or (II) of the present invention exhibit
excellent surface affinity or are highly persistent, or both.
[0158] In addition to advantageously positioning additive moieties
on the surface of an organic article to be stabilized, the surface
properties of the article may be modified with the present
compounds of formula (I) or (II).
[0159] The organic materials of the present compositions are for
example natural or synthetic polymers and copolymers and may be
selected from 1.)-34.) below:
[0160] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, 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), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), branched low
density polyethylene (BLDPE) and medium density polyethylene
(MDPE).
[0161] 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:
[0162] a) radical polymerization (normally under high pressure and
at elevated temperature).
[0163] b) catalytic polymerization 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 p- or
s-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 polymerization medium. The
catalysts can be used by themselves in the polymerization 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).
[0164] 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).
[0165] 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, ethylenelbut-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethyleneloctene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers and
their copolymers with carbon monoxide 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/EM and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0166] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9)
including hydrogenated modifications thereof (e.g. tackifiers) and
mixtures of polyalkylenes and starch.
[0167] 5. Polystyrene, poly(p-methylstyrene),
poly(.alpha.-methylstyrene).
[0168] 6. Copolymers of styrene or .alpha.-methylstyrene with
dienes or acrylic derivatives, for example styrene/butadiene,
styrene/unsaturated ester, styrene/acrylonitrile, styrene/alkyl
methacrylate, styrene/butadiene/alkyl acrylate,
styrene/butadienelalkyl 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
styrenelbutadiene/styrene, styrene/isoprenelstyrene,
styrene/ethylene/butylene/styrene or styrene/ethylene/propylenel
styrene.
[0169] 7. Graft copolymers of 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 anhydride or maleimide on polybutadiene; styrene and
maleimide on polybutadiene; styrene and alkyl acrylates or
methacrylates on polybutadiene; styrene and acrylonitrile on
ethylene/propylene/diene terpolymers; styrene and acrylonitrile on
polyalkyl acrylates or polyalkyl methacrylates, styrene and
acrylonitrile on acrylate/butadiene copolymers, as well as mixtures
thereof with the copolymers listed under 6), for example the
copolymer mixtures known as ABS, SAN, MBS, ASA or .DELTA.ES
polymers. 8. Halogen-containing polymers such as polychloroprene,
chlorinated rubbers, chlorinated or sulfochlorinated polyethylene,
copolymers of ethylene and chlorinated ethylene, epichlorohydrin
homo- and copolymers, especially polymers of halogen-containing
vinyl compounds, for example polyvinyl chloride, polyvinylidene
chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as
copolymers thereof such as vinyl chloride/vinylidene chloride,
vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate
copolymers.
[0170] 9. Polymers derived from .alpha.,.beta.-unsaturated acids
and derivatives thereof such as polyacrylates and
polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacrylonitriles, impact-modified with butyl acrylate.
[0171] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl
methacrylate/butadiene terpolymers.
[0172] 11. Polymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals thereof, for example polyvinyl
alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as well as their copolymers with olefins
mentioned in 1) above.
[0173] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bis-glycidyl ethers.
[0174] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0175] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0176] 15. Polyurethanes derived from hydroxyl-terminated
polyethers, polyesters or polybutadienes on the one hand and
aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
[0177] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 416, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexame- thylene
terephthalamide or poly-m-phenylene isophthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0178] 17. Polyureas, polyimides, polyamide-imides and
polybenzimidazoles.
[0179] 18. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polytrimethylene
terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate and
polyhydroxybenzoates, as well as block copolyether esters derived
from hydroxyl-terminated polyethers; and also polyesters modified
with polycarbonates or MBS. Polyesters and polyester copolymers as
defined in U.S. Pat. No. 5,807,932 (column 2, line 53),
incorporated herein by reference.
[0180] 19. Polycarbonates and polyester carbonates.
[0181] 20. Polysulfones, polyether sulfones and polyether
ketones.
[0182] 21. 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.
[0183] 22. Drying and non-drying alkyd resins.
[0184] 23. 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.
[0185] 24. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0186] 25. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, polyisocyanates or
epoxy resins.
[0187] 26. Crosslinked epoxy resins derived from polyepoxides, for
example from bis glycidyl ethers or from cycloaliphatic
diepoxides.
[0188] 27. Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, for example
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers such as methyl cellulose; as well as rosins
and their derivatives.
[0189] 28. Blends of the aforementioned polymers (polyblends), for
example PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,
PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,
POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
[0190] 29. Naturally occurring and synthetic organic materials
which are pure monomeric compounds or mixtures of such compounds,
for example mineral oils, animal and vegetable fats, oil and waxes,
or oils, fats and waxes based on synthetic esters (e.g. phthalates,
adipates, phosphates or trimellitates) and also mixtures of
synthetic esters with mineral oils in any weight ratios, typically
those used as spinning compositions, as well as aqueous emulsions
of such materials.
[0191] 30. Aqueous emulsions of natural or synthetic rubber, e.g.
natural latex or latices of carboxylated styrene/butadiene
copolymers.
[0192] 31. Polysiloxanes such as the soft, hydrophilic
polysiloxanes described, for example, in U.S. Pat. No. 4,259,467;
and the hard polyorganosiloxanes described, for example, in U.S.
Pat. No. 4,355,147.
[0193] 32. Polyketimines in combination with unsaturated acrylic
polyacetoacetate resins or with unsaturated acrylic resins. The
unsaturated acrylic resins include the urethane acrylates,
polyether acrylates, vinyl or acryl copolymers with pendant
unsaturated groups and the acrylated melamines. The polyketimines
are prepared from polyamines and ketones in the presence of an acid
catalyst.
[0194] 33. Radiation curable compositions containing ethylenically
unsaturated monomers or oligomers and a polyunsaturated aliphatic
oligomer.
[0195] 34. Epoxymelamine resins such as light-stable epoxy resins
crosslinked by an epoxy functional coetherified high solids
melamine resin such as LSE-4103 (Monsanto).
[0196] Preferred organic materials are synthetic polymers, most
preferably thermoplastic polymers. Especially preferred organic
materials are polyolefins such as polypropylene or
polyethylene.
[0197] The stabilized compositions of the present invention are
effective as coatings, for example automotive coatings. They are
effective as coatings over plastic. They are effective in coatings
that are water-borne paints.
[0198] The organic material of the present compositions may also be
a recording material.
[0199] The recording materials according to the invention are
suitable for pressure-sensitive copying systems, photocopying
systems using microcapsules, heat-sensitive copying systems,
photographic materials and ink jet printing.
[0200] The recording materials according to the invention are
distinguished by an unexpected improvement in quality, especially
with regard to the fastness to light.
[0201] The recording materials according to the invention have the
construction known for the particular use. They consist of a
customary carrier, for example, paper or plastic film, which has
been coated with one or more layers. Depending on the type of
material, these layers contain the appropriate necessary
components, in the case of photographic materials, for example,
silver halide emulsions, dye couplers, dyes and the like. Material
particularly suitable for ink jet printing has a layer particularly
absorptive for ink on a customary carrier. Uncoated paper can also
be employed for ink jet printing. In this case the paper acts at
the same time as the carrier material and as the ink-absorbent
layer. Suitable material for ink jet printing is, for example,
described in U.S. Pat. No. 5,073,448, which is incorporated herein
by reference.
[0202] The recording material can also be transparent as, for
example, in the case of projection films.
[0203] The organic materials of the present compositions may also
be ink jet inks.
[0204] In addition to component (ii), the stabilized compositions
may comprise further traditional additives selected from, for
example,
[0205] 1. Antioxidants
[0206] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylp- henol,
2-tert-butyl-4,6-dimethylphenol, 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-dimeth- ylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
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-methylheptad- ec-1-yl)phenol,
2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures
thereof.
[0207] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-te- rt-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylpheno- l.
[0208] 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 octadecyloxyphenol,
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.
[0209] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (Vitamin E).
[0210] 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-me- thylphenol),
4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-
-hydroxyphenyl)disulfide.
[0211] 1.6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-but- yl-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-bu- tyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylp- henol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol-
], 4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-bu- tyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl).sub.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-methylphenyl-
]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.
[0212] 1.7. Benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-- dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoace- tate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
1,3,5-tri-(3,5-di-tert-buty-
l-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
di-(3,5-di-tert-butyl-4-hydroxy- benzyl) sulfide,
3,5-di-tert-butyl-4-hydroxybenzyl-mercaptb-acetic acid isooctyl
ester, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol
terephthalate, 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, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid
dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric
acid monoethyl ester, calcium-salt.
[0213] 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)malona-
te,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hy-
droxybenzyl)malonate.
[0214] 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.
[0215] 1.10. Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-
-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3-
,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis-
(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris-(3,5-di-tert-butyl-4-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.
[0216] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-- hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphospho- nate,
dioctadecyl-3,5-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-hydroxybenzylphosphoni- c acid.
[0217] 1.12. Acylaminophenols, for example 4-hydroxy-lauric acid
anilide, 4-hydroxy-stearic acid anilide,
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-
-hydroxyanilino)-s-triazine and
octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl- )-carbamate.
[0218] 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]o- ctane.
[0219] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propi- onic 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]o- ctane.
[0220] 1.15. Esters of
.beta.-(3.5-dicyclohexvl-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)isocyanura- te, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7--
trioxabicyclo[2.2.2]octane.
[0221] 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)isocyanura- te, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7--
trioxabicyclo[2.2.2]octane.
[0222] 1.17. Amides of
.beta.-(3.5-di-tert-butyl-4-hydroxyphenyl)pronionic 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).
[0223] 1.18. Ascorbic acid (vitamin C)
[0224] 1.19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylen- ediamine,
N,N'-di-sec-butyl-.beta.-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methy- lpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-.beta.-phenylenediamine,
N,N'-diphenyl-.beta.-phenylene- diamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-.b-
eta.-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-.beta.-phenylenedia- mine,
N-(1-methylheptyl)-N'-phenyl-.beta.-phenylenediamine,
N-cyclohexyl-N'-phenyl-.beta.-phenlenediamine,
4-(p-toluenesulfamoyl)diph- enylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-.beta.-phenylenediamine,
diphenylamine, N-allyidiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyidiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethan- e, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenyl- methane,
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-octyl-diphenylamines, a mixture of
mono- and dialkylated nonyidiphenylamines, a mixture of mono- and
dialkylated dodecyidiphenylamines, 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-butylltert-octylph-
enothiazines, a mixture of mono- and dialkylated
tert-octyl-phenothiazines- , N-allylphenothiazin,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidi- n-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0225] 2. UV absorbers and light stabilizers
[0226] 2.1. 2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example
known commercial hydroxyphenyl-2H-benzotriazoles and benzotriazoles
as disclosed in, U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585;
3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763;
4,275,004; 4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352;
4,681,905, 4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091;
5,410,071; 5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166;
5,607,987, 5,977,219 and 6,166,218 such as
2-(2-hydroxy-5-methylphenyl)-2H-benzotria- zole,
2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,
2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,
2-(2-hydroxy-5-t-octylphe- nyl)-2H-benzotriazole,
5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benz- otriazole,
5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazol- e,
2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,
2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,
2-(3,5-di-t-amyl-2-hydro- xyphenyl)-2H-benzotriazole,
2-(3,5-bis-.alpha.-cumyl-2-hydroxyphenyl)-2H-b- enzotriazole,
2-(3-t-butyl-2-hydroxy-5-(2-(.omega.-hydroxy-octa-(ethyleneo-
xy)carbonyl-ethyl)-, phenyl)-2H-benzotriazole,
2-(3-dodecyl-2-hydroxy-5-me- thylphenyl)-2H-benzotriazole,
2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl-
)ethylphenyl)-2H-benzotriazole, dodecylated
2-(2-hydroxy-5-methylphenyl)-2- H-benzotriazole,
2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-
-5-chloro-2H-benzotriazole,
2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbony-
lethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,
2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benz-
otriazole,
2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-ben-
zotriazole,
2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphe-
nyl)-2H-benzotriazole,
2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethy-
l)phenyl-2H-benzotriazole,
2,2'-methylene-bis(4-t-octyl-(6-2H-benzotriazol- -2-yl)phenol),
2-(2-hydroxy-3-.alpha.-cumyl-5-t-octylphenyl)-2H-benzotriaz- ole,
2-(2-hydroxy-3-t-octyl-5-.alpha.-cumylphenyl)-2H-benzotriazole,
5-fluoro-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole,
5-chloro-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole,
5-chloro-2-(2-hydroxy-3-o-cumyl-5-t-octylphenyl)-2H-benzotriazole,
2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H--
benzotriazole,
5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-5-t-octylphe-
nyl)-2H-benzotriazole,
5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-- benzotriazole,
5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-ben-
zotriazole, methyl
3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4--
hydroxyhydrocinnamate,
5-butylsulfonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-t-oc-
tylphenyl)-2H-benzotriazole,
5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumy-
l-5-t-butylphenyl)-2H-benzotriazole,
5-trifluoromethyl-2-(2-hydroxy-3,5-di-
-t-butylphenyl)-2H-benzotriazole,
5-trifluoromethyl-2-(2-hydroxy-3,5-di-.a-
lpha.-cumylphenyl)-2H-benzotriazole,
5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-
-butylphenyl)-2H-benzotriazole and
5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t--
butylphenyl)-2H-benzotriazole.
[0227] 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.
[0228] 2.3. Esters of substituted and unsubstituted benzoic acids,
as for example 4-tertbutyl-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-hydroxybe- nzoate,
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.
[0229] 2.4. Acrylates and malonates, for example,
.alpha.-cyano-.beta.,.be- ta.-diphenylacrylic acid ethyl ester or
isooctyl ester, .alpha.-carbomethoxy-cinnamic acid methyl ester,
.alpha.-cyano-.beta.-met- hyl-.beta.-methoxy-cinnamic acid methyl
ester or butyl ester, .alpha.-carbomethoxy-.beta.-methoxy-cinnamic
acid methyl ester,
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methyl-indoline,
Sanduvor.RTM. PR25, dimethyl p-methoxybenzylidenemalonate (CAS#
7443-25-6), and Sanduvor.RTM. PR31,
di-(1,2,2,6,6-pentamethylpiperidin-4-- yl)
p-methoxybenzylidenemalonate (CAS #147783-69-5).
[0230] 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-methylphenyl undecylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole- , with or
without additional ligands.
[0231] 2.6. Sterically hindered amine stabilizers, for example
4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-allyl-4-hydroxy-2,2,6,6-tetram- ethylpiperidine,
1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,
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-hydrox- ybenzylmalonate, 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-butane-tetracarboxylate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramet- hylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl) malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate, linear or
cyclic condensates of
N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenedi- amine
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-t-
etramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
3-dodecyl-1-(2,2,6,6-te-
tramethyl-4-piperidyl)pyrrolidin-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentame-
thyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of
4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a
condensation product of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation
product 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]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[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)hexamethylenediamine, diester of
4-methoxy-methylene-malonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypipe- ridine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxa-
ne, 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-ami- nopiperidine.
[0232] The sterically hindered amine may also be one of the
compounds described in GB-A-2301106 as component I-a), I-b), I-c),
I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-l), in
particular the light stabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2,
1-d-1, 1-d-2, 1-d-3, 1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed on
pages 68 to 73 of said GB-A-2301106.
[0233] The sterically hindered amine may also be one of the
compounds described in EP 782994, for example compounds as
described in claims 10 or 38 or in Examples 1-12 or D-1 to D-5
therein.
[0234] 2.7. Sterically hindered amines substituted on the N-atom by
a hydroxy-substituted alkoxy group, for example compounds such as
1-(2-hydroxy-2-methylpropoxy).sub.4-octadecanoyloxy-2,2,6,6-tetramethylpi-
peridine,
1-(2-hydroxy-2-methylpropoxy).sub.4-hexadecanoyloxy-2,2,6,6-tetr-
amethylpiperidine, the reaction product of
1-oxyl-4-hydroxy-2,2,6,6-tetram- ethylpiperidine with a carbon
radical from t-amylalcohol,
1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin--
4-yl) adipate,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperi-
din-4-yl) succinate,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-
piperidin-4-yl) glutarate and
2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2-
,6,6-tetramethylpiperidin-4-yl]-N-butylamino)-6-(2-hydroxyethylamino)-s-tr-
iazine.
[0235] 2.8. 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'-ethoxani- lide 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.
[0236] 2.9. Tris-aryl-o-hydroxyphenyl-s-triazines, for example
known commercial tris-aryl-o-hydroxyphenyl-s-triazines and
triazines as disclosed in, WO 96/28431, EP 434608, EP 941989, GB
2,317,893, U.S. Pat. Nos. 3,843,371; 4,619,956; 4,740,542;
5,096,489; 5,106,891; 5,298,067; 5,300,414; 5,354,794; 5,461,151;
5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955;
5,726,309; 5,942,626; 5,959,008; 5,998,116 and 6,013,704, and U.S.
application Ser. No. 09/383,163, for example
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-tri-
azine, Cyasorb.RTM. 1164, Cytec Corp,
4,6-bis-(2,4-dimethylphenyl)-2-(2,4-- dihydroxyphenyl)-s-triazine,
2,4-bis(2,4-dihydroxyphenyl)-6-(4-chloropheny- l)-s-triazine,
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophe-
nyl)-s-triazine,
2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-
-6-(2,4-dimethylphenyl)-s-triazine,
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)--
phenyl]-6-(4-bromophenyl)-s-triazine,
2,4-bis[2-hydroxy-4-(2-acetoxyethoxy-
)phenyl]-6-(4-chlorophenyl)-s-triazine,
2,4-bis(2,4-dihydroxyphenyl)-6-(2,- 4-dimethylphenyl)-s-triazine,
2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octylox-
ycarbonylethylideneoxyphenyl)-s-triazine,
2-phenyl-4-[2-hydroxy-4-(3-sec-b-
utyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxy-
propyloxy)phenyl]-s-triazine,
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(-
3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,
2,4-bis(2-hydroxy-4-n-b-
utyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropylox-
y)-5-.alpha.-cumylphenyl]-s-triazine (* denotes a mixture of
octyloxy, nonyloxy and decyloxy groups),
methylenebis-2,4-bis(2,4-dimethylphenyl)-6-
-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine},
methylene bridged dimer mixture bridged in the 3:5', 5:5' and 3:3'
positions in a 5:4:1 ratio,
2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyp-
henyl)-s-triazine,
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-.-
alpha.-cumylphenyl)-s-triazine,
2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydrox-
y-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,
2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)-phenyl]-s-tria-
zine, mixture of
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-
-2-hydroxypropoxy)-phenyl)-s-triazine and
4,6-bis-(2,4-dimethylphenyl)-2-(-
2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,
Tinuvin.RTM. 400, Ciba Specialty Chemicals Corp.,
4,6-bis-(2,4-dimethylph-
enyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-tria-
zine and
4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.
[0237] 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.
[0238] 4. Phosphites and phosphonites, for example triphenyl
phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearyl pentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol
diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentae-
rythritol 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-dibenzo[d,f][1,3,2-
]dioxaphosphepin,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g-
][1,3,2]dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)
methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl
phosphite,
2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2-
'-diyl)phosphite],
2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2-
,2'-diyl)phosphite.
[0239] Especially preferred are the following phosphites:
[0240] Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos@168, Ciba
Specialty Chemicals Corp.), tris(nonylphenyl)phosphite, 18
[0241] 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-octadecylhydroxylami- ne,
N-methyl-N-octadecylhydroxylamine and the N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0242] 6. Nitrones, for example N-benzyl-.alpha.-phenylnitrone,
N-ethyl-.alpha.-methylnitrone, N-octyl-.alpha.-heptylnitrone,
N-lauryl-.alpha.-undecyInitrone,
N-tetradecyl-.alpha.-tridcyinitrone,
N-hexadecyl-.alpha.-pentadecyInitrone,
N-octadecyl-.alpha.-heptadecyinitr- one,
N-hexadecyl-.alpha.-heptadecyInitrone,
N-ocatadecyl-.alpha.-pentadecy- Lnitrone,
N-heptadecyl-.alpha.-heptadecyInitrone, N-octadecyl-.alpha.-hexa-
decyInitrone, N-methyl-.alpha.-heptadecyInitrone and the nitrone
derived from N,N-dialkylhydroxylamine derived from hydrogenated
tallow amine.
[0243] 7. Amine oxides, for example amine oxide derivatives as
disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl
amine oxide, tridecyl amine oxide, tridodecyl amine oxide and
trihexadecyl amine oxide.
[0244] 8. Benzofuranones and indolinones, for example those
disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312,
5,216,052, 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876;
EP-A-0589839 or EP-A-0591102 or
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)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-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
Irganox.RTM. HP-136, Ciba Specialty Chemicals Corp., and
3-(2,3-dimethylphenyl)-5,7-di- -tert-butyl-benzofuran-2-one.
[0245] 9. Thiosynergists, for example dilauryl thiodipropionate or
distearyl thiodipropionate.
[0246] 10. Peroxide scavengers, for example esters of
.beta.3-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.
[0247] 11. Polyamide stabilizers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0248] 12. 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.
[0249] 13. 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;
polyhieric compounds such as ionic copolymers (ionomers).
[0250] 14. Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass bulbs, 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.
[0251] 15. Dispersing Agents, such as polyethylene oxide waxes or
mineral oil.
[0252] 16. Other additives, for example plasticizers, lubricants,
emulsifiers, pigments, dyes, optical brighteners, rheology
additives, catalysts, flow-control agents, slip agents,
crosslinking agents, crosslinking boosters, halogen scavengers,
smoke inhibitors, flameproofing agents, antistatic agents,
clarifiers such as substituted and unsubstituted bisbenzylidene
sorbitols, benzoxazinone UV absorbers such as
2,2'-p-phenylene-bis(3, 1-benzoxazin-4-one), Cyasorb.RTM. 3638
(CAS# 18600-594), and blowing agents.
[0253] The additive functional parts of the above traditional
additives are suitable additive moieties of compounds of formula
(I) or (II) according to the present invention.
[0254] The present stabilizers of formula (I) or (II) of this
invention and optional further additives may be applied to or
incorporated in the polymeric substrate by any known methods, e.g.
by melt blending, solution blending, solution casting and
adsorption from solution.
[0255] For example, component (ii) and optional further additives
may be incorporated in the polymeric substrate before or after
molding or also by applying the dissolved or dispersed additive
mixture to the polymeric substrate, with or without subsequent
evaporation of the solvent. Component (ii) and optional further
additives can also be added to the polymeric substrate in the form
of a masterbatch which contains these components in a concentration
of, for example, about 2.5% to about 25% by weight.
[0256] For example, component (ii), optional further additives and
the polymeric substrate may all be dissolved in a mutually
compatible solvent wherein the concentration of polymer in the
solvent ranges from about 5 to about 50% by weight of the solvent.
The solution may then be dried at an appropriate temperature to
produce a cast film containing a blend of polymer and the
additive(s).
[0257] Alternatively, additive compounds of component (ii) and
optional further additives are blended into a polymeric substrate
by dissolving the additive(s) in a volatile solvent to provide a
solution with an additive concentration of about 5 to about 50% by
weight. The solution is then mixed with the polymer and the mixture
is dried thereby providing polymer particles which are
substantially evenly coated with additive(s). The coated polymer
particles may then be fed to an extruder wherein the mixture is
melt blended and extruded to produce an extrudate containing the
polymeric substrate and additive(s).
[0258] If in a liquid form, the stabilizers of component (ii) may
be applied directly to polymer particles by stirring the polymer
particles in the liquid additive mixture until the additive mixture
is evenly dispersed on the surface of the polymer particles. The
polymer may then be fed to an extruder to produce an extrudate of
polymer substrate containing the additives.
[0259] The compositions of this invention may also be prepared by
submitting the stabilizers of component (ii), optional further
additives and solid polymeric material to an extruder followed by
melt blending and extruding the molten mixture. Alternatively, the
polymeric material and additives may be melt blended in a
thermostatted vessel where the components are in molten form,
followed by cooling of the mixture.
[0260] Component (ii) and optional further additives can also be
added before or during the polymerization or before
crosslinking.
[0261] Component (ii) and optional further additives can be
incorporated into the polymeric substrate in pure form or
encapsulated in waxes, oils or polymers.
[0262] Component (ii) and optional further additives can also be
sprayed or coated onto the polymeric substrate. It may be used to
dilute other additives (for example the conventional additives
indicated above) or their melts so that it can be sprayed or coated
together with these additives onto the polymeric substrate.
Addition by spraying during the deactivation of the polymerization
catalysts is particularly advantageous, it being possible to carry
out spraying using, for example, the steam used for
deactivation.
[0263] In the case of spherically polymerized polyolefins it may,
for example, be advantageous to apply component (ii) optionally
together with other additives, by spraying.
[0264] Preferably, component (ii) and optional further additives
are incorporated into the polymeric substrate of component (i) by
melt blending.
[0265] The polymeric compositions of this invention, which have
modified surface properties, may exhibit improved properties in the
areas of, for example, anti-fog, dissipation of static electricity,
paintability, dyeability, printability, wicking of moisture,
adhesion, compatibility with immiscible polymers, biocompatibility
and biodegradibility.
[0266] The polymeric articles or constructions, which comprise
components (i) and (ii), and which benefit from the application or
incorporation of the compounds of formula (I) or (II) of this
invention include carpet fibers, composite fibers, agricultural
films, nonwoven coverstock, exterior automotive bumper fascia,
packaging, hygienic products, membranes such as semipermeable,
dialysis and reverse osmosis membranes, incompatible polymer
blends, laminated articles and eyewear.
[0267] Preferred articles which comprise components (i) and (ii)
are agricultural or packaging films, exterior automotive parts,
nonwoven fabrics or filtration medium, semipermeable membranes,
implantable medical devices or textile fibers.
[0268] The present compounds of formula (I) or (II) may also act as
polymer compatiblizers. That is, they may help to form compatible
blends of inherently incompatible polymers. It is also contemplated
that the compounds of formula (I) or (II) may be employed to
"place" additive functional moieties in specific locations in
polymer blends (in one polymer only, not homogeneously throughout
the blend). The polymer blends that may be compatibilized with the
incorporation of the compounds of formula (I) or (II) of this
invention include blends of polystyrene with polyesters,
polystyrene with polyamides, polyolefins with polyesters and
polyolefins with polyamides.
[0269] The compounds of formula (I) or (II) of this invention may
also be effective as rheology modifiers and dispersants for
pigments and fillers. Articles that would benefit include solvent
and water borne paints.
[0270] The additives of this invention are advantageously employed
in ink jet media and ink jet ink, for example as disclosed in EP
1120279 and EP 1031431 and U.S. Pat. Nos. 5,855,655, 5,782,963,
5,165,973, 5,215,577 and 5,670,249, the relevant disclosures of
which are hereby incorporated by reference.
[0271] Anti-fog properties are important in greenhouse
applications. A greenhouse is required to be closed during cold
periods to contain heat to maintain a growing environment. With
high humidity inside the greenhouse, this creates a situation where
water condenses on the inside of greenhouse roof or cover when the
temperature of the roof or cover is reduced to the dew point or
lower. A greenhouse film made from an olefinic polymer is
hydrophobic and has low surface tension, which causes condensed
water to coalesce into droplets. This unwanted condition, where
water condensate forms on the surface of the film as free droplets,
is known as "fogging." Fogging prevents the transmission of
sunlight and may fall onto and damage the crop below. Compositions
of the present invention have superior anti-fog properties.
Anti-fogging properties are also important in food overwrap (meat,
vegetables, etc.) or other applications where a clear film with
wettability or non-fogging is needed.
[0272] Hyperbranched polymers known in the art for example as
described in U.S. Pat. No. 5,418,301 and U.S. application Ser. No.
09/778,194, without any additive functional moieties, are also
useful in the compositions of this invention. That is to say, the
co-use of compounds of present formula (I) or (II) with known
hyperbranched or dendritic polymers or copolymers. The co-use of
known amphiphilic copolymer additives without any additive
functional moieties, such as herein described, is also
contemplated.
[0273] The invention also relates to a process for stabilizing an
organic material against the deleterious effect of heat, light or
oxidation, which comprises incorporating therein or applying
thereto at least one permanent or surface-active hyperbranched or
dendritic stabilizer or permanent or surface active amphiphilic
polymer stabilizer.
[0274] The following Examples illustrate the invention in more
detail. They are not to be construed as limiting the instant
invention in any manner whatsoever. The invention is declared to
cover all changes and modifications of the specific examples which
do not constitute departure from the spirit and scope of the
invention.
EXAMPLE 1
[0275] 19
[0276] 1,2,2,6,6-Pentamethyl-piperidin-4-ol (25.5 g, 0.15 mol),
2,2-bis(hydroxymethyl)propionic acid (40.2 g, 0.30 mol), dibutyltin
oxide (0.40 g, 0.0015 mol), and tetraglyme (60.5 g, 0.27 mol) are
added to a reaction flask equipped with a Dean Stark trap. The
reaction mixture is heated to 205.degree. C. and held at this
temperature for 4 hours. The reaction mass is cooled down and a
copious amount of heptane is added to remove a majority of the
polymerization solvent. The resins is dissolved in a mixture of 300
g of methanol and 400 g of toluene. The methanol is distilled off
under vacuum and toluene and tetraglyme are decanted off. The resin
is extracted twice with 400 g of hot toluene (80.degree. C.) with
decantation of the toluene. The resin is dried under vacuum to
constant weight. The title compound is received (60.4 g) as a light
yellow resinous solid having a molecular weight of 1240 as
determined by Gel Permeation Chromatography (GPC).
EXAMPLE 2
[0277] 20
[0278] Following the conditions of Example 1,
2,2,6,6-tetramethyl-piperidi- n-4-ol (47.1 g, 0.30 mol),
2,2-bis(hydroxymethyl)propionic acid (80.5 g, 0.60 mol), dibutyltin
oxide (2.27 g, 0.009 mol), and tetraglyme (100.9 g, 0.45 mol) are
added to a reaction flask. The title compound is obtained (115 g)
as an off-white resinous solid having a molecular weight of 2066 as
determined by GPC.
EXAMPLE 3
[0279] 21
[0280] The resin obtained in Example 2 (5 g, 0.0012 mole based on
amine), acetonitrile (50 g, 1.21 mole) and ferrous chloride (0.4 g,
0.002 mol) are added to a reaction flask. To this stirred solution,
hydrogen peroxide (3.2 g, 0.047 mole) is added drop wise over two
hours. This solution is stirred overnight at ambient temperature
after which the solvent is distilled under vacuum. The solid is
dried under vacuum to constant weight. The title compound is
obtained (5 g) as a light orange resinous solid having a molecular
weight of 1096 as determined by GPC.
EXAMPLE 4
[0281] 22
[0282] Following the conditions of Example
1,2,6-di-tert-butyl-4-(3-hydrox- ypropyl)-phenol (43.5 g, 0.165
mol), 2,2-bis(hydroxymethyl)propionic acid (44.2 g, 0.33 mol),
dibutyltin oxide (1.23 g, 0.005 mol), and tetraglyme (100.9 g, 0.45
mol) are added to a reaction flask. The title compound is obtained
(75 g) as an off-white viscous liquid having a molecular weight of
1467 as determined by GPC.
EXAMPLE 5
[0283] 23
[0284] Following the conditions of Example
1,2-benzotriazol-2-yl-4-(2-hydr- oxyethyl)-phenol (BZT, 10 g, 0.039
mol), 2,2-bis(hydroxymethyl)propionic acid (10.5 g, 0.078 mol),
dibutyltin oxide (0.40 g, 0.0016 mol), and tetraglyme (21 g, 0.093
mol) are added to a reaction flask.
[0285] The title compound is obtained (6.1 g) as a light-yellow
resinous solid having a molecular weight of 1496 as determined by
GPC.
COMPARATIVE EXAMPLE 1
[0286] 24
[0287] Following the conditions of Example
1,2,2-bis(hydroxymethyl)propion- ic acid (120.7 g, 0.90 mol),
dibutyltin oxide (2.50 g, 0.01 mol), and tetraglyme (100.9 g, 0.45
mol) are added to a reaction flask. The title compound is obtained
(110 g) as a white resinous solid having a molecular weight of 3254
as determined by GPC.
EXAMPLE 6
Ink Jet Media
[0288] A resin-coated paper impregnated with inorganic adsorbent
particles (Konica QP Photoglossy ink jet paper, Konica Corp.) is
purchased. On the ink-receiving layer, a 0.8 wt % methanol solution
of each of the compounds obtained in Examples 1-5 and Comparative
Example 1 is applied in an amount to achieve 650-700 mg/m.sup.2.
The paper is allowed to dry under ambient temperature and pressure
for 24 hours.
EXAMPLE 7
Ink Jet Media
[0289] A resin-coated paper impregnated with inorganic adsorbent
particles (Konica QP Photoglossy ink jet paper, Konica Corp.) is
purchased. On the ink-receiving layer, 0.8 wt % methanol solution
of each of the compounds obtained in Examples 1-5 and Comparative
Example 1 is applied in an amount to achieve 1300-1400 mg/m.sup.2.
The paper is allowed to dry under ambient temperature and pressure
for 24 hours.
EXAMPLE 8
Ink
[0290] The compounds of Examples 4 and 5 are added to an ink
composition, for example as disclosed in U.S. Pat. Nos. 5,855,655
or 5,782,963, at a concentration of 2 wt % and 0.5 wt %
respectively. The images printed from these stabilized inks show
reduced dye fading and better image permanence.
EXAMPLE 9
Ink Jet Media
[0291] A commercial white polyethylene terephthalate sheet is
coated with silica and polyvinylalcohol according to EP 1031431 A2
Example 1. A methanol solution of the compound of Example 1 is
applied to this sheet in an amount equivalent to 400 mg/m.sup.2.
The image printed on this receiving layer shows reduced dye fading
and better image permanence.
EXAMPLE 10
[0292] A commercial white polyethylene terephthalate sheet is
coated with alumina hydrate and polyvinylalcohol according to EP
1031431 A2 Example 5. A methanol solution of the compound of
Example 2 is applied to this sheet in an amount equivalent to 400
mg/m.sup.2. The image printed on this receiving layer shows reduced
dye fading and better image permanence.
EXAMPLE 11
[0293] A paper sheet containing alumina is prepared according to
EP1031431 A2 Example 8. A methanol solution of the compound of
Example 3 is applied to this sheet in an amount equivalent to 600
mg/m2. The image printed on this receiving layer shows reduced dye
fading and better image permanence.
EXAMPLE 12
[0294] A paper sheet containing silica is prepared according to
U.S. Pat. No. 5,165,973. A methanol solution of the compound of
Example 4 is applied to this sheet in an amount equivalent to 700
mg/m-2. The image printed on this receiving layer shows reduced dye
fading and better image permanence.
EXAMPLE 13
[0295] Separately, test patterns (cyan, magenta and yellow) are
printed on the sheets prepared in Examples 6 and 7 using a Hewlett
Packard DeskJet 970 Cxi printer. The obtained prints are left to
dry at ambient temperature and pressure for 24 hours. Color
densities and CIEL*a*b coordinates before and after exposure are
measured using X-Rite 938 Spectrodensitometer. Exposures are
carried out using normal office fluorescent lighting.
EXAMPLE 14
[0296] A mixture of dimethylolpropionic acid and a
hydroxyphenylbenzotriaz- ole of formula 8) 25
[0297] are reacted to form a hyperbranched polyester terminated
with the benzotriazole moiety.
EXAMPLE 15
[0298] Example 14 is repeated, replacing the benzotriazole of
formula 8) with the following additive compounds 1), 2), 4), 6),
7), 9), 10) and 11): 2627
[0299] The compounds of formulae 1) and 2) act as an initiators
from two different reactive sites as defined in U.S. Pat. No.
5,418,301. The compounds of formulae 4), 9), 10) and 11) act as
initiators. The compounds of formulae 6) and 7) act as chain
stoppers. The additive moieties are bound to the hyperbranched
polyester.
EXAMPLE 16
[0300] Example 14 is repeated, replacing the compound of formula 8)
with a mixture of compounds of formula 8) and the formula: 28
[0301] The compound of formula 8) is a chain stopper and the
compound of formula 12) is an initiator as defined in U.S. Pat. No.
5,418,301 in the formed hyperbranched polyester.
EXAMPLE 17
[0302] Examples 14-16 are repeated, with an additional lipophilic
component selected from stearic acid, isostearic acid, myristic
acid and behenic acid being added. These lipophilic components
additionally are part of the hyperbranched polyester as lipophilic
terminating groups as defined in U.S. application Ser. No.
09/778,194 (or chain stoppers as defined in U.S. Pat. No.
5,418,301).
EXAMPLE 18
[0303] Examples 14-17 are repeated, with an additional hydrophilic
component selected from poly(ethylene glycol) (PEG) and
poly(ethylene glycol) monomethyl ether (MPEG). These hydrophilic
components additionally are part of the hyperbranched polyester as
defined in U.S. application Ser. No. 09/778,194. When using PEG,
the additives employed are of formula 6), 7) and/or 8).
EXAMPLE 19
[0304] Atmer.RTM. 502 is reacted with a benzotriazole of formula 8)
to form the product: 29
EXAMPLE 20
[0305] Example 19 is repeated, replacing Atmer.RTM. 502 with
Unithox.RTM. 420.
EXAMPLE 21
[0306] Examples 19 and 20 are repeated, replacing the benzotriazole
of formula 8) with benzotriazoles of formuae 6) and 7).
EXAMPLE 22
Contact Angle Measurements in Compression Molded LDPE Plaques
[0307] Compression molded 10 mil plaques of copolymer additives of
the preceding Examples in low density polyethylene (Dow Chemical
LDPE 6401) are prepared as follows. The additives and substrate are
initially blended by melt compounding in a twin-screw extruder.
Plaques of the blends are made by compression molding against steel
at 400.degree. F.
[0308] Receding water contact angles of the compression molded
plaques are measured using a Kruss K12 dynamic contact angle
tensiometer. This method, often referred to as the Wilhelmy plat
technique, measures the force of wetting of a solid by a liquid
(usually water) as it is initially immersed and subsequently
withdrawn. This wetting force is then translated into receding
(withdrawn) contact angles. It is generally accepted by those
skilled in the art that receding contact angles are a measure of a
materials' hydrophilic character.
[0309] The receding angles of the plaques are measured immediately
after compression molding. They are rubbed five times with a water
moistened paper towel and the receding angle is measured again. The
plaques are stored at 70.degree. F. with a relative humidity of
30-40%. The receding angles of the plaques are monitored over the
course of 30 days. Comparison of the receding angles before and
after rubbing gives a qualitative measure of the immediate
persistence and relative modifying strength of the additive, while
the 30 day monitoring study provides insight as to the additive's
relative long-term persistence. The smaller the value of the
receding angle, the greater the surface energy of the LDPE
plaque.
[0310] The additives of this invention are effective towards
increasing the surface energy of polyethylene. The compounds of the
instant invention increase the surface energy of LDPE to a greater
degree than compounds representative of the state of the art and/or
they are more persistent in the substrate. The plaques also exhibit
excellent stability towards heat, moisture and light.
EXAMPLE 23
Contact Angle Measurements in LDPE Blown Films
[0311] When Example 22 is repeated in LDPE Blown Films, the
compounds of the instant invention increase the surface energy of
LDPE to a greater degree than compounds representative of the state
of the art and/or they are more persistent in the substrate as
measured by receding, static or advancing contact angles. The films
also exhibit excellent stability to heat, moisture and light.
EXAMPLE 24
Polypropylene Fiber Dyeability
[0312] Fiber grade polypropylene, Montell PROFAX 6301, and the
appropriate amount of a present additive of the preceding Examples
are mixed on a TURBULA mixer for 15 minutes. The blended mix is
added to a SUPERIOR MPM single screw lab extruder at 218, 232, 246
and 246.degree. C., screw speed is 80 rpm. The molten polypropylene
with additive exits a round die, is cooled in a water trough and is
fed into a CONAIR JETRO pelletizer. The compounded pellets are fed
into a HILLS LAB FIBER EXTRUDER with a 41 hole delta spinneret at
232, 246, 260 and 274.degree. C. A constant pressure of 750 psi
controls the screw speed via a feed back loop. The feed, draw, and
relax rolls are at 80 and 100.degree. C., and are rotating at 120,
400 and 383 meters per minute. The fiber comes in contact with a 6%
aqueous fiber finish solution just before the feed roll. This
solution is LUROL PP-4521 from Goulston Indstries. A LEESONA winder
at the end of the line collects the fiber onto a spool. The final
denier per filament is 15. The collected fiber is removed from the
spool and is knitted into a sock with a LAWSON HEMPHILL FAK sampler
knitter.
[0313] Solutions of dyes are prepared at 1.0 g/L in distilled water
in separate containers. For disperse dyes this is done by heating
water to 63-85.degree. C., then adding water to the dye. The
solutions of the acid dyes are made by heating water to
85-100.degree. C. The solutions of the leveler, lubricant and pH
control chemicals are made at room temperature at a 10% w/w
level.
[0314] A ROACHES programmable dye bath is set to the following
conditions:
[0315] Disperse dye for PP: Temperature rise of 3.5.degree. C. per
minute to 98.degree. C. with a hold time of 60 minutes at
98.degree. C. then a cool down at maximum cooling of 5.5.degree. C.
per minute.
[0316] Acid dye for PP: Temperature rise of 3.5.degree. C. per
minute to 98.degree. C. with a hold time of 30 minutes at
98.degree. C. then a cool down at maximum cooling of 5.5.degree. C.
per minute.
[0317] The appropriate amounts of the solutions (see Dye Solutions
Table) are added to a steel 500 mL cylinder based on a 5.0 g weight
of sock. The sock is identified with a laundry tag and is placed in
the cylinder. The cylinder is filled with distilled water. The pH
is checked and should be 4-5 for disperse dyeing and 6-6.5 for acid
dyeing. Finally the cylinders are sealed and placed into the dye
bath and the cycle is started. After the dye cycle is completed,
the socks are removed from the cylinders and are rinsed with tap
water. The excess water is removed from the socks via a centrifuge
and are dried in a forced air oven at 100.degree. C. for 15
minutes.
[0318] Lightness and darkness (L) of the socks are measured on a
Datacolor Spectrophotometer SF600. L is a measure of light and dark
on a scale of 0 (dark) to 100 (light). Instrument conditions are
CIE lab, D65, 10 deg, SCI, SAV, UV400-700. A lower L value
indicates improved dyeability.
Dye Solutions
[0319]
1 Disperse Dye % Weight on Fiber Yellow K-GL 0.5 Red K-BB 0.5 Blue
K-RB 1.0 UNIVADINE DIF 2.0 CIBAFLUID UA 1.0 Acetic Acid 0.5
[0320] The formulations contain 5% by weight of the present
additives based on the weight of polypropylene.
[0321] Formulations containing additives of the present invention
impart improved dyeability to polypropylene socks compared to socks
containing no additive. The socks also exhibit excellent stability
to the effects of heat, moisture and light.
[0322] The crocking test method determines the degree of color
which may be transferred from the surface of a dyed article to
other surfaces by rubbing. Such dye transfer is undesirable. The
test requires specific rubbing, via a crockmeter, with both a dry
and a wet white test cloth across the dyed article. The cloths are
then evaluated via the gray scale. The gray scale is a 5 unit scale
(1-5@ 0.5 divisions), with 5 representing negligible dye
transfer.
[0323] To qualify as a successful additive to promote polypropylene
(PP) dyeability, the sock containing the additive will dye to a
dark shade as would be expected of a polyester (PET) control, there
should be no or negligible dye transfer when being evaluated by the
crocking test, and there should be no loss of physical
properties.
[0324] The socks containing the amphiphilic block copolymers of the
present invention show excellent dyeability as evidenced by low L
values and acceptable wet and dry crock values.
EXAMPLE 25
Anti-Fog Properties of LDPE Blown Films
[0325] Additives of the preceding Examples are added to low density
polyethylene having a melt index of 2.0 dg/min. and a density of
0.922 g/mL at 10% by weight, based on the weight of polymer, and
the mixture is blended in a Brabender. The polymer melt temperature
is 150.degree. to 170.degree. C. The polymer mixtures are
pelletized to give a masterbatch. Granules of the masterbatch are
tumble-blended with granules of low density polyethylene at the
weight ratio of 1 to 9 (the resulting concentration of the
anti-fogging agent in the low density polyethylene polymer is
10,000 ppm). A film with a thickness of about 75 micro-meters is
produced on a tubular blown film line at a melt temperature of
about 210.degree. C.
[0326] The anti-fogging test method tests the ability of the film
surface to retain its anti-fogging property after exposure to
moisture under cold (4.degree. C.) and hot (60.degree. C.)
temperature conditions.
[0327] For the cold-fog test, 200 mL of water is put in a 250 mL
beaker and the test film is placed on the beaker so as to cover the
entire opening. The beaker is then placed in a temperature
controlled cabinet at 4.degree. C. Anti-fog evaluations are done in
predetermined time intervals up to 7 days
[0328] For the hot-fog test, 50 mL of water is put in a 250 mL
beaker and the test film is placed on the beaker so as to cover the
entire opening. The beaker is then placed in a bath containing
water at 60.degree. C. Anti-fog evaluations are done in
predetermined time intervals up to 3 hours.
[0329] Anti-fogging ratings are as follows:
[0330] High fogging: 1
[0331] Moderate fogging: 2
[0332] Fogged in patches: 3
[0333] Few large drops: 4
[0334] Clear, no drops: 5
[0335] Polyethylene film containing the additives of the present
invention have superior anti-fogging properties relative to films
with no surfactant additive and with state-of-the-art additives
such as Atmer.RTM. 103. The films also exhibit excellent stability
to heat, moisture and light.
EXAMPLE 26
[0336] 30
[0337] Following the conditions of Example 1, Tinuvin.RTM. 328
(70.3 g, 0.20 mol), 2,2-bis-(hydroxymethyl)propionic acid (53.7 g,
0.40 mol), dibutyltin oxide (1.50 g, 0.006 mol), and tetraglyme
(100.9 g, 0.45 mol) are added to a reaction flask. The
benzotriazole-functionalized hyperbranched polymer is obtained (115
g) as a light-yellow resinous solid having a molecular weight of
1332 as determined by GPC.
EXAMPLE 27
Solubility in Polar Media
[0338] The solubility of the compound of Example 26 versus
Tinuvin.RTM. 328 is determined in methanol at ambient temperature.
From the data below, compositions containing this type of
hydrophilic dendrimer have improved solubility in polar media.
2 Solubility in Compound methanol (wt %) Tinuvin .RTM. 328 0.6
Example 26 57
EXAMPLE 28
Color Change of Printed Articles
[0339] The change in color (.DELTA.E) for the printed articles of
Examples 6 & 13 is measured accordingly. The data below
demonstrate that the instant compounds are useful in reducing dye
fade when incorporated into recording media.
[0340] .DELTA.E for Cyan at 100% print density after two weeks of
fluorescent light exposure:
3 Compound .DELTA.E Blank 3.63 (no additive) Example 3 2.51 Example
4 2.17 Example 2 2.12 Example 1 1.94
[0341] .DELTA.E for Magenta at 100% print density after two weeks
of fluorescent light exposure:
4 Compound .DELTA.E Blank 7.10 (no additive) Example 2 4.52 Example
3 4.42 Example 4 4.14
[0342] .DELTA.E for Yellow at 100% print density after two weeks of
fluorescent light exposure:
5 Compound .DELTA.E Blank 1.79 (no additive) Example 1 1.32
[0343] .DELTA.E for Cyan at 50% print density after two weeks of
fluorescent light exposure:
6 Compound .DELTA.E Blank 2.76 (no additive) Example 3 2.40 Example
2 2.19 Example 1 1.92
[0344] .DELTA.E for Magenta at 50% print density after two weeks of
fluorescent light exposure:
7 Compound .DELTA.E Blank 6.94 (methanol only) Comparative 5.73
Example 1 Example 4 4.44 Example 3 4.37 Example 2 4.05
[0345] .DELTA.E for Yellow at 50% print density after two weeks of
fluorescent light exposure:
8 Compound .DELTA.E Blank 3.02 (no additive) Example 3 2.46 Example
2 2.38 Example 1 2.14 Example 4 1.95
[0346] .DELTA.E for Cyan at 100% print density after two weeks in
the dark:
9 Compound .DELTA.E Blank 2.35 (no additive) Example 1 1.73 Example
2 1.33 Example 3 1.05
EXAMPLE 29
Color Change of Printed Article
[0347] The change in color (.DELTA.E) for the printed articles of
Examples 7 & 13 is measured accordingly. The data below
demonstrate that the instant compounds are useful in reducing dye
fade when incorporated into recording media.
[0348] .DELTA.E for Cyan at 100% print density after two weeks of
fluorescent light exposure:
10 Compound .DELTA.E Blank 3.31 (methanol only) Example 4 2.82
Example 3 2.02 Example 25 1.72 Example 2 1.42 Example 1 1.14
[0349] .DELTA.E for Yellow at 100% print density after two weeks of
fluorescent light exposure:
11 Compound .DELTA.E Blank (methanol only) 2.33 Example 3 1.71
Example 2 1.58 Example 1 0.76 Example 4 0.58
[0350] .DELTA.E for Cyan at 50% print density after two weeks of
fluorescent light exposure:
12 Compound .DELTA.E Blank (methanol only) 2.65 Example 3 1.39
Example 2 1.33 Example 1 1.04
[0351] .DELTA.E for Magenta at 50% print density after two weeks of
fluorescent light exposure:
13 Compound .DELTA.E Blank (no additive) 7.50 Example 4 3.75
Example 1 2.63 Example 2 2.44
[0352] .DELTA.E for Yellow at 50% print density after two weeks of
fluorescent light exposure:
14 Compound .DELTA.E Blank (methanol only) 2.75 Comparative Example
1 2.06 Example 25 1.59 Example 1 1.42 Example 4 1.00
[0353] .DELTA.E for Magenta at 100% print density after two weeks
in the dark:
15 Compound .DELTA.E Blank (methanol only) 1.20 Example 1 0.79
Example 2 0.62 Example 3 0.42
[0354] .DELTA.E of the blank article (no print) after two weeks of
fluorescent light exposure:
16 Compound .DELTA.E Blank (no additive) 0.95 Example 1 0.21
EXAMPLE 30
Color Change of Printed Article
[0355] The change in color (.DELTA.E) for the printed articles of
Examples 6, 7, & 13 is measured accordingly. The data below
demonstrate that the instant compounds are useful in reducing dye
fade when incorporated into recording media.
[0356] .DELTA.E for Magenta at 100% print density after two weeks
of fluorescent light exposure:
17 Compound .DELTA.E Blank (methanol only) 6.60 Example 1 (650-700
mg additive/m.sup.2) 4.81 Example 1 (1300-1400 mg additive/m.sup.2)
2.53
* * * * *