| United States Patent Application |
20030125413
|
| Kind Code
|
A1
|
|
Herbst, Heinz
; et al.
|
July 3, 2003
|
Mixtures of phenolic and inorganic materials with antimicrobial activity
Abstract
Plastic films, fibers and articles are provided long-term antimicrobial
activity with a combination of certain phenolic and inorganic
antimicrobial agents. The plastic films, fibers and articles with
antimicrobial activity exhibit superior resistance to discoloration, may
be processed at high temperature, and maintain physical properties upon
weathering, especially upon exposure to ultraviolet radiation.
| Inventors: |
Herbst, Heinz; (Loerrach, DE)
; Stadler, Urs; (Madison, NJ)
|
| Correspondence Name and Address:
|
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
| Serial No.:
|
323239 |
| Series Code:
|
10
|
| Filed:
|
December 18, 2002 |
| U.S. Current Class: |
523/122; 442/123 |
| U.S. Class at Publication: |
523/122; 442/123 |
| Intern'l Class: |
C08K 003/00; B32B 027/04; B32B 027/12 |
Claims
What is claimed is:
1. A mixture of antimicrobial agents for plastics applications which
comprises a) at least one phenolic antimicrobial compound, and b) at
least one inorganic antimicrobial compound, wherein the phenolic
antimicrobial compound is of the formula (I) 4wherein n is 0or 1,
R.sub.1 and R.sub.2 are hydrogen or chlorine, R.sub.3 is hydrogen or
hydroxyl, R.sub.4, R.sub.5 and R.sub.6 are hydrogen or chlorine, R.sub.7
is hydroxyl, and X is --O-- or --CH.sub.2-, and wherein the inorganic
antimicrobial compound is selected from the group consisting of zinc
oxide, copper and copper compounds, silver,
colloidal silver, silver
nitrate, silver sulphate, silver chloride, silver complexes,
metal-containing zeolites and surface-modified metal-containing zeolites,
wherein the ratio of components a):b) is from about 1:9 to about 9:1.
2. A mixture of antimicrobial agents according to claim 1 wherein the
phenolic antimicrobial compound is selected from the group consisting of
o-benzyl-phenol, 2-benzyl-4-chloro-phenol, 2,4,4'-trichloro-2'-hydroxydip-
henyl ether, 4,4'-dichloro-2-hydroxydiphenyl ether,
5-chloro-2-hydroxy-diphenyl-methane, mono-chloro-o-benzyl-phenol,
2,2'-methylenbis-(4-chloro-phenol) and 2,4,6-trichlorophenol.
3. A mixture of antimicrobial agents according to claim 2 wherein the
phenolic antimicrobial compound is selected from the group consisting of
2,4,4'-trichloro-2'-hydroxydiphenyl ether and 4,4'-dichloro-2-hydroxydiph-
enyl ether.
4. A mixture of antimicrobial agents according to claim 1 wherein the
inorganic antimicrobial agent is a metal-containing zeolite or a
surface-modified metal-containing zeolite.
5. A mixture of antimicrobial agents according to claim 4 wherein the
metal is selected from the group consisting of silver, copper, zinc,
zirconium and combinations thereof.
6. A mixture of antimicrobial agents according to claim 5 wherein the
metal is selected from the group consisting of silver and combinations of
silver with copper, zinc or zirconium.
7. A mixture of antimicrobial agents according to claim 4 wherein the
inorganic antimicrobial agent is a metal-containing surface-modified
zeolite wherein the metal is selected from the group consisting of silver
and combinations of silver with copper, zinc or zirconium.
8. A mixture of antimicrobial agents according to claim 7 wherein
component a) is 2,4,4'-trichloro-2'-hydroxydiphenyl ether and wherein
component b) is a surface-modified metal-containing zeolite.
9. An antimicrobial plastic film, fiber or article which has incorporated
therein a mixture of antimicrobial agents according to claim 1.
10. An antimicrobial plastic film, fiber or article according to claim 9
in which the plastic is selected from the group consisting of
polyethylene, polypropylene, acrylonitrile-butadiene-styrene terpolymer
(ABS), styrene-acrylonitrile copolymer (SAN), polystyrene (PS),
polymethyl methacrylate (PMMA), polyester, polyamide, polyvinyl chloride
(PVC), polymer latex, polyurethane (PUR), thermoplastic urethane (TPU),
urea formaldehyde resin (UF) and unsaturated polyester (UP).
11. An antimicrobial plastic film, fiber or article according to claim 10
in which the plastic is selected from low-density polyethylene (LDPE),
high-density polyethylene (HDPE), polypropylene (PP), polyester and
polyamide.
12. An antimicrobial plastic film, fiber or article according to claim 9
in which the mixture of components a) and b) is present from about 0.005
to about 10% by weight based on the plastic film, fiber or article.
13. An antimicrobial plastic film, fiber or article according to claim 12
in which the mixture of components a) and b) is present from about 0.01
to about 5% by weight based on the plastic film, fiber or article.
14. An antimicrobial plastic film, fiber or article according to claim 13
in which the mixture of components a) and b) is present from about 0.05
to about 3% by weight based on the plastic film, fiber or article.
15. An antimicrobial plastic film, fiber or article according to claim 9
which additionally comprises at least one co-additive selected from the
group consisting of antioxidants, ultraviolet light absorbers, hindered
amines, phosphites or phosphonites, hydroxylamines, nitrones,
benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal
stearates, nucleating agents, fillers, reinforcing agents, lubricants,
emulsifiers, dyes, pigments, optical brighteners, flame retardants,
antistatic agents and blowing agents.
16. A masterbatch or concentrate of a mixture of antimicrobial agents
according to claim 1 wherein the components a) and b) are present at a
total concentration of about 2.5% to about 70% by weight based on the
weight of the carrier, and wherein the carrier is selected from the group
consisting of polyethylene, polypropylene (PP), acrylonitrile-butadiene-s-
tyrene terpolymer (ABS), styrene-acrylonitrile copolymer (SAN),
polystyrene (PS), acrylates, polymethyl methacrylate (PMMA), polyamide,
polyesters, polyvinyl chloride (PVC), polymer latex, styrene, polyol,
thermoplastic urethane (TPU), unsaturated esters, urea, paraformaldehyde
and water emulsion.
Description
[0001] This application claims the benefit under 35 USC 119(e) of U.S.
Provisional Application Serial No. 60/234,433, filed Sep. 21, 2000.
[0002] The present invention relates to combinations of phenolic and
inorganic compounds which exhibit excellent antimicrobial activity when
incorporated into a substrate resin, which mixtures do not exhibit the
negative effects associated with the use of either alone. Plastic
articles manufactured via a variety of processes from such resins are
provided long term antimicrobial activity and exhibit superior resistance
to discoloration and maintenance of physical properties, especially upon
exposure to ultraviolet radiation.
[0003] Triclosan, or Irgaguard.RTM., Ciba Specialty Chemicals,
2,4,4'-trichloro-2'-hydroxydiphenyl ether, is a known antimicrobial for
plastics applications. It is known to have high activity against numerous
gram-positive and gram-negative bacterial. It can be incorporated as a
neat material or via a masterbatch into a variety of polymer substrates,
for example, polyethylenes such as LDPE, HDPE, MDPE, polypropylene (PP),
acrylonitrile-butadiene-styrene terpolymer (ABS), styrene-acrylonitrile
copolymer (SAN), polystyrene (PS), polyacrylates, polymethyl methacrylate
(PMMA), polyamide, polyesters, polyvinyl chloride (PVC), polymer latex,
polyurethane (PUR), thermoplastic polyurethane (TPU), unsaturated
polyester (UP), urea formaldehyde resin (UF), etc. Irgaguard.RTM.
exhibits high activity at the surface of plastic articles and the
activity remains after repeated washing of plastic articles. Further,
Irgaguard.RTM. has a good toxicological profile.
[0004] Disadvantages of Irgaguard.RTM. are that plastic articles
formulated with it exhibit strong discloloration upon weathering. For
example, polypropylene samples containing Irgaguard.RTM. exposed in a
Xenon Arc Weather-Ometer at 035 W/m.sup.2, 63.degree. C. discolor within
hours. Further, processing at temperatures greater than 250.degree. C. is
poblematic due to the volatility of Irgaguard.RTM..
[0005] Silver based materials, such as
colloidal silver, silver nitrate,
silver sulfate, silver chloride, silver complexes and silver ion
containing zeolites are known antimicrobial agents for plastic articles.
Silver compounds exhibit high activity against microorganisms and they
have a good toxicological profile. High processing temperatures are
possible with silver compounds (greater than 300.degree. C.).
[0006] Disadvantages of silver based antimicrobials are that plastic
articles containing them often exhibit discloloration upon weathering,
and the activity on the surface of the articles is often lost after
repeated washing.
[0007] It has been found, surprisingly, that a combination of certain
phenolic compounds with certain inorganic compounds avoids the
disadvantages of using either Irgaguard.RTM. or silver based
antimicrobials alone in plastic articles while providing excellent
long-term antimicrobial activity to the articles.
OBJECTS OF THE INVENTION
[0008] An object of the present invention is to provide a novel mixture of
antimicrobial agents for plastics applications.
[0009] Another object of the invention is to provide plastic articles or
films with antimicrobial activity which also exhibit superior resistance
to discoloration, may be processed at high temperatures, and which
maintain physical properties upon weathering, especially upon exposure to
UV radiation.
DETAILED DESCRIPTION
[0010] The instant invention pertains to a novel mixture of antimicrobial
agents for plastics applications which comprises
[0011] a) at least one phenolic antimicrobial compound, and
[0012] b) at least one inorganic antimicrobial compound,
[0013] wherein
[0014] the phenolic antimicrobial compound is of the formula (I) 1
[0015] wherein
[0016] n is 0 or 1,
[0017] R.sub.1 and R.sub.2 are hydrogen or chlorine,
[0018] R.sub.3 is hydrogen or hydroxyl,
[0019] R.sub.4, R.sub.5 and R.sub.6 are hydrogen or chlorine,
[0020] R.sub.7 is hydroxyl, and
[0021] X is --O-- or --CH.sub.2--,
[0022] and wherein the inorganic antimicrobial compound is selected from
the group consisting of zinc oxide, copper and copper compounds,
colloidal silver, silver nitrate, silver sulphate, silver chloride,
silver complexes, metal-containing zeolites and surface-modified
metal-containing zeolites,
[0023] and wherein the ratio of components a):b) is from about 1:9 to
about 9:1.
[0024] Preferred phenolic antimicrobial compounds of component a) are
o-benzyl-phenol, 2-benzyl-4-chloro-phenol, 2,4,4'-trichloro-2'-hydroxydip-
henyl ether, 4,4'-dichloro-2-hydroxydiphenyl ether,
5-chloro-2-hydroxy-diphenyl-methane, mono-chloro-o-benzyl-phenol,
2,2'-methylenbis-(4-chloro-phenol) and 2,4,6-trichlorophenol.
[0025] Most preferred phenolic antimicrobial compounds of component a) are
2,4,4'-trichloro-2'-hydroxydiphenyl ether and 4,4'-dichloro-2-hydroxydiph-
enyl ether.
[0026] The metal-containing zeolites of component b) are those such as
described in U.S. Pat. Nos. 4,775,585, 4,911,898, 4,911,899 and
6,071,542, the disclosures of which are hereby incorporated by reference.
A zeolite is generally aluminosilicate having a three dimensionally grown
skeleton structure and is generally represented by
xM.sub.2/nO.Al.sub.2O.sub.3.ySiO.sub.2.zH.sub.2O, written with
Al.sub.2O.sub.3 as a basis, wherein M represents an ion-exchangeable
metal ion, which is usually the ion of a monovalent or divalent metal; n
corresponds to the valence of the metal; x is a coefficient of the metal
oxide; y is a coefficient of silica; and z is the number of water of
crystallization. The zeolites of the present invention have a specific
surface area of at least 150 m.sup.2/g.
[0027] Antibacterial metals for use in metal-containing zeolites include
silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium,
cobalt, nickel, zirconium, or a combination of two or more of these
metals. Preference is given to silver, copper, zinc and zirconium, or a
combination of these. Especially preferred metals are silver alone or a
combination of silver with copper, zinc or zirconium.
[0028] Particularly preferred inorganic antimicrobial compounds of
component b) are surface-modified metal-containing zeolites according to
U.S. Pat. No. 6,071,542.
[0029] Especially preferred is the antimicrobial mixture wherein component
a) is 2,4,4'-trichloro-2'-hydroxydiphenyl ether and wherein the inorganic
antimicrobial compound of component b) is a surface-modified
silver-containing zeolite. The term "silver-containing" includes the
combination of silver with other metals such as zinc, copper and
zirconium. BACTEKILLER BM-102GA (Kanebo) is an example of a
surface-modified silver-containing zeolite according to U.S. Pat. No.
6,071,542.
[0030] In addition to zeolites, it is also contemplated that antibacterial
metals such as silver, silver compounds and silver complexes may be
supported on other inert materials, for example SiO.sub.2, TiO.sub.2 and
glass.
[0031] The instant invention also pertains to plastic films, fibers or
articles that comprise the novel mixture of components a) and b).
[0032] The novel antimicrobial mixture of components a) and b) may be
incorporated into the plastic resin prior to its being subjected to such
manufacturing processes as blown film, rotational molding fiber spinning,
etc. The mixture of components a) and b) is able to withstand demanding
processing conditions such as high temperature, e.g. temperatures greater
than 200.degree. C.
[0033] The plastic films, fibers and articles comprising the present
antimicrobial mixture of components a) and b) is suitable for outdoor
exposure; they are resistant to weathering and UV light degradation.
[0034] The antimicrobial mixture of components a) and b) exhibit good
long-term activity and a good toxicological profile.
[0035] Triclosan containing plastic samples lead to a strong discoloration
within a very short time when exposed to weathering. Plastic samples
containing the present combination of components a) and b) exhibit only
minimal color changes.
[0036] Triclosan containing plastic samples exhibit a reduced light
stability. Plastic samples containing the present combination of
components a) and b) exhibit physical properties that are comparable to a
control formulation without antimicrobial agents.
[0037] The plastic films, fibers and articles of the present invention are
advantageously employed for applications that require long-term hygienic
activity on the surface, e.g., medical devices, hand rails, door handles,
etc. The antimicrobial plastic films, fibers and articles of the present
invention are used for example in hospitals, households, public
institutions, ventilation systems, air cleaning and air conditioning
systems and waste disposal systems. Plastic articles exposed to outdoor
weathering that may have incorporated therein the antimicrobial mixture
of the present invention are for example waste containers, swimming pool
equipment, outdoor swing set equipment, slides and the like, and stadium
seats.
[0038] The plastic films, fibers and articles of the present invention
exhibit high antimicrobial activity at the surface. The antimicrobial
activity remains after repeated washings.
[0039] The plastic films, fibers and articles of the present invention,
that is to say, the plastic materials, may also have incorporated therein
one or more of the following known additives:
[0040] 1. Antioxidants
[0041] 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.
[0042] 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-te-
rt-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphen-
ol.
[0043] 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.
[0044] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and mixtures
thereof (Vitamin E).
[0045] 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.
[0046] 1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-but-
yl-4-methylphenol), 2,2'-methylenebis(6tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methly-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)-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.
[0047] 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-mercapto-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.
[0048] 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.
[0049] 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.
[0050] 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-hydroxy-benzyl)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.
[0051] 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.
[0052] 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.
[0053] 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.
[0054] 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-hexane-diol, 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.
[0055] 1.15. Esters of .beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic
acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,
octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene
glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)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.
[0056] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene
glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,
3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0057] 1.17. Amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic
acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethyle-
nediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylen-
ediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami-
de (Naugard.RTM.XL-1 supplied by Uniroyal).
[0058] 1.18. Ascorbic acid (vitamin C)
[0059] 1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylen-
ediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpenty-
l)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine-
, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenyle-
nediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenyl-
enediamine, N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-
-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine-
, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine,
octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine,
4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyl-diphenylamines, a mixture of mono- and
dialkylated nonyidiphenylamines, a mixture of mono-and dialkylated
dodecyldiphenylamines, a mixture of mono- and dialkylated
isopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylated
tert-butyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,
phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-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-tetramethylpiperid-
in-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
[0060] 2. UV Absorbers and Light Stabilizers
[0061] 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 and
5,977,219, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,
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.-cumyl-phenyl)-2H-benzotriazole,
5-chloro-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole,
5-chloro-2-(2-hydroxy-3-.alpha.-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-(5trifluoromethyl-2H-benzotriazol-2-yl)-5-butyl-4-hyd-
roxyhydrocinnamate, 5-butylsulfonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-t-octyl-
phenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-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-.alph-
a.-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-bu-
tylphenyl)-2H-benzotriazole and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-but-
ylphenyl)-2H-benzotriazole.
[0062] 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.
[0063] 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.
[0064] 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-p-methoxy-cinnamic acid methyl ester or butyl ester,
.alpha.-carbomethoxy-p-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).
[0065] 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.
[0066] 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-amino-propylamino)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-oxo-spiro[4,5]decane, a
reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4--
oxospiro [4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4--
piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(-
2,2,6,6-tetramethyl-4-piperidyl)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.
[0067] 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.
[0068] 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.
[0069] 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)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine, 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylp-
iperidine, the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpip-
eridine with a carbon radical from t-amylalcohol, 1-(2-hydroxy-2-methylpro-
poxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropox-
y)-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-methylprop-
oxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-(2-hydroxy-2-methyl-
propoxy)-2,2,6,6-tetramethylpiperidin-4-yl) succinate,
bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)
glutarate and 2,4-bis{(N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetrameth-
ylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine.
[0070] 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.
[0071] 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, for example 4,6-bis-(2,4-dimethylphenyl)-2-(2-hy-
droxy-4-octyloxyphenyl)-s-triazine, 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-chlorophenyl)-s-triazine,
2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazi-
ne, 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dime-
thylphenyl)-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-dimethylphe-
nyl)-s-triazine, 2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethy-
lideneoxyphenyl)-s-triazine, 2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hyd-
roxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)-ph-
enyl]-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy--
2-hydroxy-propyloxy)phenyl]-s-triazine, 2,4-bis(2-hydroxy-4-n-butyloxyphen-
yl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6--
[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-.alpha.-cumylphenyl]-s-tri-
azine (*denotes a mixture of octyloxy, nonyloxy and decyloxy groups),
methylenebis{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hyd-
roxypropoxy)-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-isooctyloxycarbonylisopropylideneoxyphenyl)-s-tria-
zine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-.alpha.-cumylp-
henyl)-s-triazine, 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butylo-
xy-2-hydroxypropyloxy)phenyl]-s-triazine, 2,4,6-tris[2-hydroxy-4-(3-sec-bu-
tyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, mixture of
4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropox-
y)-phenyl)-s-triazine and 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-t-
ridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine, Tinuvin.RTM. 400, Ciba
Specialty Chemicals Corp., 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-
-hydroxyphenyl)-s-triazine.
[0072] 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.
[0073] 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.
[0074] Especially preferred are the following phosphites:
[0075] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos.RTM.168, Ciba
Specialty Chemicals Corp.), tris(nonylphenyl) phosphate, 2
[0076] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecylhydroxylam-
ine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
[0077] 6. Nitrones, for example N-benzyl-alpha-phenyl-nitrone,
N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,
N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,
N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitron-
e, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nit-
rone, N-heptadecyl-alpha-hep-tadecyl-nitrone, N-octadecyl-alpha-hexadecyl--
nitrone, nitrone derived from N,N-dialkylhydro-xylamine derived from
hydrogenated tallow amine.
[0078] 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.
[0079] 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.
[0080] 9. Thiosynergists, for example dilauryl thiodipropionate or
distearyl thiodipropionate.
[0081] 10. Peroxide scavengers, for example esters of
.beta.-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.
[0082] 11. Polyamide stabilizers, for example copper salts in combination
with iodides and/or phosphorus compounds and salts of divalent manganese.
[0083] 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 rate, zinc stearate, magnesium behenate,
magnesium stearate, sodium ricinoleate and potassium palmitate, antimony
pyrocatecholate or zinc pyrocatecholate.
[0084] 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; polymeric compounds such as ionic
copolymers (ionomers).
[0085] 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.
[0086] 15. 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# 18600-59-4), and blowing agents.
[0087] 16. Other biocides, for example fungicides such as
3,5-dimethyl-tetrahydro-1,3,5-2H-thiodiazin-2-thione,
Bis-tributyltinoxide, 4.5-dichlor-2-n-octyl-4-isothiazolin-3-one,
N-butyl-benzisothiazoline, 10.10'-oxybisphenoxyarsine,
zinc-2-pyridinthiol-1-oxide, etc., and algicides such as
2-methylthio-4-cyclopropylamino-6-(.alpha.,.beta.-dimethylpropylamino)-s--
triazine, 2-methylthio-4-cyclopropylamino-6-tert-butylamino-s-triazine,
2-methylthio-4-ethylamino-6-(.alpha.,.beta.-dimethylpropylamino)-s-triazi-
ne, etc.
[0088] In general the plastic resins with antimicrobial activity according
to the present invention may be selected from:
[0089] 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).
[0090] 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:
[0091] a) radical polymerization (normally under high pressure and at
elevated temperature).
[0092] 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).
[0093] 2. Mixtures of the polymers mentioned under 1), for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene (for example PP/HDPE, PP/LDPF) and mixtures of different
types of polyethylene (for example LDPE/HDPE).
[0094] 3. Copolymers of monoolefins and diolefins with each other or with
other vinyl monomers, for example ethylene/propylene copolymers, linear
low density polyethylene (LLDPE) and mixtures thereof with low density
polyethylene (LDPE), propylene/but-1-ene copolymers,
propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,
ethylene/hexene copolymers, ethylene/methylpentene copolymers,
ethylene/heptene copolymers, ethylene/octene copolymers,
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/EAA and alternating or random
polyalkylene/carbon monoxide copolymers and mixtures thereof with other
polymers, for example polyamides.
[0095] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9) including
hydrogenated modifications thereof (e.g. tackifiers) and mixtures of
polyalkylenes and starch.
[0096] 5. Polystyrene, poly(p-methylstyrene), poly(.alpha.-methylstyrene).
[0097] 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/butadiene/alkyl methacrylate,
styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures
of high impact strength of styrene copolymers and another polymer, for
example a polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.
[0098] 7. Graft copolymers of styrene or a-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 AES polymers.
[0099] 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.
[0100] 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.
[0101] 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.
[0102] 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.
[0103] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bis-glycidyl ethers.
[0104] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
[0105] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0106] 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.
[0107] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the corresponding
lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9,
6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides
starting from m-xylene diamine and adipic acid; polyamides prepared from
hexamethylenediamine and isophthalic or/and terephthalic acid and with or
without an elastomer as modifier, for example poly-2,4,4,-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).
[0108] 17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
[0109] 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.
[0110] 19. Polycarbonates and polyester carbonates.
[0111] 20. Polysulfones, polyether sulfones and polyether ketones.
[0112] 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.
[0113] 22. Drying and non-drying alkyd resins.
[0114] 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.
[0115] 24. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or polyester
acrylates.
[0116] 25. Alkyd resins, polyester resins and acrylate resins crosslinked
with melamine resins, urea resins, polyisocyanates or epoxy resins.
[0117] 26. Crosslinked epoxy resins derived from polyepoxides, for example
from bis glycidyl ethers or from cycloaliphatic diepoxides.
[0118] 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.
[0119] 28. Blends of the aforementioned polymers (polyblends), for example
PP/EPDM, Polyamide/-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.
[0120] 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, oils 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.
[0121] 30. Aqueous emulsions of natural or synthetic rubber, e.g. natural
latex or latices of carboxylated styrene/butadiene copolymers.
[0122] 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.
[0123] 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.
[0124] 33. Radiation curable compositions containing ethylenically
unsaturated monomers or oligomers and a polyunsaturated aliphatic
oligomer.
[0125] 34. Epoxymelamine resins such as light-stable epoxy resins
crosslinked by an epoxy functional coetherified high solids melamine
resin such as LSE-4103 (Monsanto).
[0126] Preferably, the plastic resin is selected from the group consisting
of LDPE, HDPE, MDPE, PP, ABS, SAN, PS, PMMA, PET, polyamide, PVC, polymer
latex, PUR, TPU, UF and UP.
[0127] The mixture of components a) and b) is preferably present in the
antimicrobial plastic film, fiber or article in an amount of about 0.005
to about 10% by weight, relative to the plastic material. An amount of
from about 0.01 to about 5% by weight or about 0.05 to about 3% by weight
of the mixture of components a) and b) relative to the plastic material
is especially preferred
[0128] The mixture of components a) and b) and optional further additives
may be added to the plastic resin, e.g. the polyolefin, individually or
mixed with one another. If desired, the individual components of an
additive mixture can be mixed with one another in the melt (melt
blending) before incorporation into the plastic material.
[0129] The incorporation of the mixture of components a) and b) and
optional further additives into the plastic material is carried out by
known methods such as dry mixing in the form of a powder, or wet mixing
in the form of solutions or suspensions. Components a) and b) and
optional further additives may be incorporated, for example, before or
after molding or also by applying the dissolved or dispersed stabilizer
mixture to the plastic material, with or without subsequent evaporation
of the solvent. The mixture of components a) and b) and optional further
additives can also be added to the plastic material in the form of a
masterbatch which contains these components in a concentration of, for
example, about 2.5% to about 70% by weight; in such operations, the
polymer can be used in the form of powder, granules, solutions,
suspensions or in the form of latices.
[0130] If added to a plastic resin in the form of a masterbatch or
concentrate, the novel antimicrobial mixture of components a) and b) is
added via carriers such as LDPE, HDPE, MDPE, PP, ABS, SAN, PS, acrylates,
PMMA, polyamide, polyesters, PVC, polymer latex, styrene, polyol, TPU,
unsaturated esters, urea, paraformaldehyde, water emulsion, etc. The
total concentration of a)+b) in the carriers is from about 2.5% to about
70% by weight based on the weight of the carrier.
[0131] Components a) and b) and optional further additives can also be
added before, during or after polymerization or crosslinking.
[0132] Components a) and b) and optional further additives can be
incorporated into the plastic material in pure form or encapsulated in
waxes, oils or polymers.
[0133] Components a) and b) and optional further additives can also be
sprayed onto the plastic material. They are able to dilute other
additives (for example the conventional additives indicated above) or
monomers or their melts so that they can be sprayed also together with
these additives onto the plastic material. 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.
[0134] In the case of spherically polymerized polyolefins it may, for
example, be advantageous to apply components a) and b) and optionally
together with other additives, by spraying.
[0135] 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. Parts and percentages are by
weight.
EXAMPLE 1
[0136] High density polyethylene, Borealis MS 6591, is dry blended with
the antimicrobial agents set forth in Table 1. The levels are percent by
weight based on the HDPE. The mixtures are compounded with a twin screw
at a maximum temperature of 220.degree. C. The samples are injection
molded into 2 mm plaques at a maximum temperature of 220.degree. C. The
plaques are subjected to accelerated weathering in a Ci65 Xenon Arc
Weather-Ometer at 63.degree. C., 0.35 W/m.sup.2 with a spray cycle.
Yellowness Index results are found in Table 1.
1TABLE I
Antimicrobial
Agents 0 h 24 h
48 h 96 h 500 h
none 1.9 2.7 1.9 0.3 -0.8
0.2% Irgaguard .RTM. B1000 4.0 57.1 60.8 62.5 66.9
0.2% Irgaguard
.RTM. B1000 + 1.1 38.9 42.5 45.4 49.9
0.1% BM-102GA 1.1
0.5% Irgaguard .RTM. B1000 + 2.2 21.2 27.9 33.1 33.4
0.1% BM-102GA
Irgaguard .RTM. B1000 is 2,4,4'-trichloro-2'-hydroxydiphen-
yl ether, Ciba Specialty Chemicals. BM-102GA (Kanebo) is a
surface-modified silver-containing zeolite.
[0137] It can be seen that the formulations of the present invention,
using a combination of antimicrobial agents of components a) and b),
provide superior resistance to yellowing upon accelerated weathering.
EXAMPLE 2
[0138] Polypropylene homopolymer, Montell Pro-fax 6301, is dry blended
with the antimicrobial agents set forth in Table 2. The levels are
percent by weight based on the polypropylene. The mixtures are
additionally formulated with 0.06% Irgastab.RTM. FS-301, 0.06%
Tinuvin.RTM. 783 and 0.05% calcium stearate. The polypropylene samples
are spun into fibers at 260.degree. C. The fibers are subjected to
accelerated weathering in a Ci65 Xenon Arc Weather-Ometer at 63.degree.
C., 0.35 W/m.sup.2 with a spray cycle. Yellowness Index results are found
in Table 2.
2TABLE 2
Antimicrobial
Agents 0 h 12 h
68 h 157 h 392 h
none 1.7 1.8 1.5 1.1 1.4
0.5% Irgaguard .RTM. B1000 2.0 24.1 16.9 9.5 failure
0.25%
Irgaguard .RTM. B1000 + 1.9 9.3 7.3 4.9 2.8
0.25% BM-102GA
[0139] It can be seen that the formulations of the present invention,
using a combination of antimicrobial agents of components a) and b),
provide superior resistance to yellowing upon accelerated weathering.
[0140] Irgaguard.RTM. B1000 is 2,4,4'-trichloro-2'-hydroxydiphenyl ether,
Ciba Specialty Chemicals. BM-102GA (Kanebo) is a surface-modified
silver-containing zeolite.
[0141] Tinuvin.RTM.783 is a combination of sterically hindered amine light
stabilizers available from Ciba Specialty Chemicals, Tinuvin.RTM.622 and
Chimassorbe.RTM.944: 3
[0142] Irgastab.RTM. FS-301, Ciba Specialty Chemicals, is a combination of
Irgafos.RTM. 168 and Irgastab.RTM. FS-042. Irgafos.RTM. 168 is
tris-(2,4-di-tert-butylphenyl)phosphite. Irgastab.RTM. FS-042 is the
N,N-di(alkyl)hydroxylamine produced by the direct oxidation of
N,N-di(hydrogenated tallow)amine.
