U.S. patent application number 12/511380 was filed with the patent office on 2009-11-26 for transparent polymer articles of low thickness.
Invention is credited to Michela Bonora, Francois Gugumus, DAVID GEORGE LEPPARD.
Application Number | 20090291289 12/511380 |
Document ID | / |
Family ID | 8174830 |
Filed Date | 2009-11-26 |
United States Patent
Application |
20090291289 |
Kind Code |
A1 |
LEPPARD; DAVID GEORGE ; et
al. |
November 26, 2009 |
TRANSPARENT POLYMER ARTICLES OF LOW THICKNESS
Abstract
The novel transparent polyolefin, polyester or polyamide article
disclosed is stabilized against the effects of light, oxygen, heat
and agressive chemicals by addition of 0.005-0.30% by weight the
polymeric substrate of a hydroxyphenyl triazine UV absorber, and is
characterized by its thickness between 1 and 500 .mu.m. Preferred
polyolefin articles thus stabilized are agricultural films
containing as further stabilizer a sterically hindered amine. The
novel compositions act as selective UV filter especially useful in
agriculture.
Inventors: |
LEPPARD; DAVID GEORGE;
(Marly, CH) ; Gugumus; Francois; (Allschwil,
CH) ; Bonora; Michela; (Bologna, IT) |
Correspondence
Address: |
JoAnn Villamizar;Ciba Corporation/Patent Department
540 White Plains Road, P.O. Box 2005
Tarrytown
NY
10591
US
|
Family ID: |
8174830 |
Appl. No.: |
12/511380 |
Filed: |
July 29, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12283464 |
Sep 12, 2008 |
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12511380 |
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11827210 |
Jul 11, 2007 |
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12283464 |
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11359228 |
Feb 22, 2006 |
7265171 |
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11827210 |
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10894773 |
Jul 20, 2004 |
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11359228 |
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09912139 |
Jul 24, 2001 |
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10894773 |
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Current U.S.
Class: |
428/220 |
Current CPC
Class: |
C08K 5/3492 20130101;
C08J 2323/12 20130101; C08K 5/34 20130101; C07D 251/24 20130101;
C08J 5/18 20130101; C08J 2323/06 20130101; C08L 23/02 20130101;
C08K 5/3492 20130101; Y10T 428/298 20150115; Y10T 428/24
20150115 |
Class at
Publication: |
428/220 |
International
Class: |
B32B 27/32 20060101
B32B027/32; B32B 27/34 20060101 B32B027/34; B32B 27/36 20060101
B32B027/36 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 26, 2000 |
EP |
00810666.8 |
Claims
1. Transparent polyolefin, polyester or polyamide article having a
thickness between 1 and 200 .mu.m, which is stabilized against the
effects of light, oxygen, heat and/or agressive chemicals by
addition of 0.005-0.30% by weight, based on the polyolefin,
polyester or polyamide, of a hydroxyphenyl triazine UV absorber,
and which article further contains a sterically hindered amine
stabilizer in an amount of 0.01-6% by weight of the polyolefin,
polyester or polyamide.
2. Transparent polyolefin article of claim 1.
3. Transparent polyolefin, polyester or polyamide article of claim
1 wherein the weight ratio sterically hindered amine:hydroxyphenyl
triazine UV absorber ranges from 2:1 to 20:1.
4. Transparent polyolefin, polyester or polyamide article of claim
1 wherein the sterically hindered amine belongs to the class of
hydroxylamine ethers.
5. Transparent polyolefin, polyester or polyamide article of claim
1 wherein the hydroxyphenyl triazine UV absorber conforms to the
formula I ##STR00032## wherein R.sub.1 is H or OR.sub.7; R.sub.2
and R.sub.3 independently are H, C.sub.1-C.sub.8alkyl, ##STR00033##
OR.sub.9; R.sub.4 and R.sub.5 independently are H,
C.sub.1-C.sub.8alkyl, OR.sub.10; R.sub.6 is H,
C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl, C.sub.7-C.sub.12alkylphenyl,
C.sub.3-C.sub.12alkenyl, halogen, OH, OR.sub.9; R.sub.8 is H;
halogen; C.sub.1-C.sub.12alkoxy; C.sub.1-C.sub.12alkyl;
C.sub.3-C.sub.24alkyl interrupted by oxygen and/or substituted by
OH; or is NH--CO--R.sub.14 or NH--COO--R.sub.12; R.sub.7, R.sub.9
and R.sub.10 independently are H; C.sub.1-C.sub.24alkyl;
C.sub.3-C.sub.12alkenyl; C.sub.3-C.sub.24alkyl interrupted by
oxygen and/or substituted by OH; or is C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl, C.sub.7-C.sub.12alkylphenyl;
CH.sub.2CH(OH)CH.sub.2OR.sub.11; C.sub.1-C.sub.12alkyl substituted
by COOR.sub.12, CONR.sub.13R.sub.14, OCOR.sub.15, OH or halogen; or
R.sub.7 is a polymeric hydrocarbon residue of 10 to 1000 carbon
atoms; and R.sub.7 also embraces a residue of formula II
##STR00034## wherein X is C.sub.2-C.sub.24alkylene;
--CH.sub.2CH(OH)CH.sub.2--;
--CH.sub.2CH(OH)CH.sub.2O-D-OCH.sub.2CH(OH)CH.sub.2;
(C.sub.1-C.sub.18alkylene)-CO--O-D-O--CO--(C.sub.1-C.sub.18alkylene);
CO; CO--(C.sub.2-C.sub.24alkylene)-CO; C.sub.3-C.sub.24alkylene
interrupted by oxygen; D is C.sub.2-C.sub.12alkylene;
C.sub.4-C.sub.50alkylene interrupted by O; phenylene; biphenylene
or phenylene-E-phenylene; E is O, S, SO.sub.2; CH.sub.2; CO or
--C(CH.sub.3).sub.2--; R.sub.11 is H, C.sub.1-C.sub.12alkyl;
phenyl; phenyl substituted by 1-3 C.sub.1-C.sub.4alkyl;
C.sub.5-C.sub.12cycloalkyl; C.sub.7-C.sub.12phenylalkyl;
C.sub.3-C.sub.12alkenyl; R.sub.12 is H; C.sub.1-C.sub.24alkyl;
C.sub.3-C.sub.12alkenyl; C.sub.3-C.sub.36alkyl interrupted by
oxygen and/or substituted by OH; or is C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl, C.sub.7-C.sub.12alkylphenyl; phenyl;
R.sub.13 and R.sub.14 independently are H, C.sub.1-C.sub.18alkyl;
phenyl; phenyl substituted by 1-3 C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; C.sub.5-C.sub.12cycloalkyl;
C.sub.3-C.sub.12alkenyl; R.sub.15 is C.sub.1-C.sub.12alkyl; phenyl;
phenyl substituted by 1-3 C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; C.sub.5-C.sub.12cycloalkyl;
C.sub.3-C.sub.12alkenyl; C.sub.1-C.sub.12alkoxy; or is
NR.sub.13R.sub.14.
6. Transparent polyolefin, polyester or polyamide article of claim
5, where in the hydroxyphenyl triazine UV absorber of formula I
R.sub.2 and R.sub.3 independently are H, methyl, ##STR00035##
OR.sub.9; R.sub.4 and R.sub.5 independently are H or methyl;
R.sub.6 is H; R.sub.8 is H; C.sub.1-C.sub.8alkoxy;
C.sub.1-C.sub.8alkyl; R.sub.7, R.sub.9 independently are H;
C.sub.1-C.sub.18alkyl; C.sub.3-C.sub.12alkenyl;
C.sub.3-C.sub.24alkyl interrupted by oxygen and/or substituted by
OH; or is C.sub.5-C.sub.12cycloalkyl, C.sub.7-C.sub.12phenylalkyl,
C.sub.7-C.sub.12alkylphenyl; C.sub.1-C.sub.12alkyl substituted by
COOR.sub.12, OCOR.sub.15, OH; or R.sub.7 is a polymeric hydrocarbon
residue of 20 to 500 carbon atoms; and R.sub.7 also embraces a
residue of formula II, wherein X is C.sub.2-C.sub.18alkylene;
--CH.sub.2CH(OH)CH.sub.2--;
--CH.sub.2CH(OH)CH.sub.2O-D-OCH.sub.2CH(OH)CH.sub.2;
(C.sub.1-C.sub.4alkylene)-CO--O-D-O--CO--(C.sub.1-C.sub.4alkylene);
CO; CO--(C.sub.2-C.sub.18alkylene)-CO; C.sub.3-C.sub.18alkylene
interrupted by oxygen; D is C.sub.2-C.sub.12alkylene; R.sub.12 is
H; C.sub.1-C.sub.24alkyl; C.sub.3-C.sub.12alkenyl;
C.sub.3-C.sub.24alkyl interrupted by oxygen and/or substituted by
OH; or is C.sub.5-C.sub.12cycloalkyl, C.sub.7-C.sub.12phenylalkyl,
C.sub.7-C.sub.12alkylphenyl; phenyl; R.sub.15 is
C.sub.1-C.sub.12alkyl; C.sub.5-C.sub.12cycloalkyl;
C.sub.3-C.sub.12alkenyl.
7. Transparent polyolefin, polyester or polyamide article of claim
1 which is a film, fiber, ribbon or stretched tape.
8. Transparent polyolefin article of claim 1, wherein the
polyolefin is polyethylene or polypropylene.
9. Transparent polyolefin, polyester or polyamide article of claim
1 additionally containing a further component selected from the
group consisting of processing stabilizers, fillers, clarifiers,
modifiers, acid scavengers, flame retardants and further light
stabilizers.
10. Transparent polyolefin article of claim 1 which is a polyolefin
agricultural film.
11. Transparent polyolefin, polyester or polyamide article of claim
1 wherein the sterically hindered amine is selected from
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(1,2,2,6,6-pentamethyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane, the condensate of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine; a condensate of
1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as
N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine;
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-
ethene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethy-
lenediamine, a diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,
a reaction product of maleic acid anhydride-.alpha.-olefin
copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine;
N,N',N'',N'''-Tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperid-
in-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine;
##STR00036## where n is from the range 3-5; sterically hindered
hydroxylamine ethers, and mixtures of these compounds; and
contained in an amount of 0.01 to 6% by weight of the polyolefin,
polyester or polyamide.
12. Transparent polyolefin, polyester or polyamide article of claim
1, where the article contains from 0.005 to 0.15% by weight, based
on the polyolefin, polyester or polyamide, of a hydroxyphenyl
triazine UV absorber.
13. Transparent polyolefin, polyester or polyamide article of claim
1, where the article contains from 0.005 to 0.06% by weight, based
on the polyolefin, polyester or polyamide, of a hydroxyphenyl
triazine UV absorber.
14. Transparent polyolefin, polyester or polyamide article of claim
1, where the article contains from 0.01 to 0.06% by weight, based
on the polyolefin, polyester or polyamide, of a hydroxyphenyl
triazine UV absorber.
15. Transparent polyolefin, polyester or polyamide article of claim
1, where the article contains a further component selected from the
group consisting of hindered phenolic antioxidants,
hydroxyphenylbenzotriazole or hydroxybenzophenone UV absorbers,
phosphites or phosphonites, hydroxylamines and benzofuranones.
Description
[0001] This is a continuation of application Ser. No. 12/283,464,
filed Sep. 12, 2008, pending, which is a continuation of
application Ser. No. 11/827,210, filed Jul. 11, 2007, abandoned,
which is a continuation of Ser. No. 11/359,228, filed Feb. 22,
2006, now U.S. Pat. No. 7,265,171, which is continuation of
application Ser. No.10/894,773, filed Jul. 20, 2004, abandoned,
which is a continuation of application Ser. No. 09/912,139, filed
Jul. 24, 2001, abandoned, the disclosures of which are incorporated
by reference.
[0002] The invention relates to a novel polymer article of low
thickness and good transparency having enhanced stability against
the effects of light, oxygen, heat and agressive chemicals, which
is also effective as a selective UV filter for agricultural
applications, and to some novel stabilizers suitable for this
application.
[0003] Certain polyolefin articles containing UV absorbers of the
type hydroxyphenyl triazine are known from GB-A-2319523,
EP-A-704437, EP-A-704560, WO 99/57189.
[0004] Present invention pertains to a transparent polyolefin,
polyester or polyamide article stabilized by addition of
0.005-0.30% by weight the polymer substrate of a hydroxyphenyl
triazine UV absorber, characterized in that the article has a
thickness between 1 and 500 .mu.m.
[0005] Preferred articles contain as a hydroxyphenyl triazine UV
absorber a compound of the formula I
##STR00001##
wherein [0006] R.sub.1 is H or OR.sub.7; [0007] R.sub.2 and R.sub.3
independently are H, C.sub.1-C.sub.8alkyl,
##STR00002##
[0007] OR.sub.9;
[0008] R.sub.4 and R.sub.5 independently are H,
C.sub.1-C.sub.8alkyl, OR.sub.10; [0009] R.sub.6 is H,
C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl, C.sub.7-C.sub.12alkylphenyl,
C.sub.3-C.sub.12alkenyl, halogen, OH, OR.sub.9; [0010] R.sub.8 is
H; halogen; C.sub.1-C.sub.12alkoxy; C.sub.1-C.sub.12alkyl;
C.sub.3-C.sub.24alkyl interrupted by oxygen and/or substituted by
OH; or is NH--CO--R.sub.14 or NH--COO--R.sub.12; [0011] R.sub.7,
R.sub.9 and R.sub.10 independently are H; C.sub.1-C.sub.24alkyl;
C.sub.3-C.sub.12alkenyl; C.sub.3-C.sub.24alkyl interrupted by
oxygen and/or substituted by OH; or is C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl, C.sub.7-C.sub.12alkylphenyl;
CH.sub.2CH(OH)CH.sub.2OR.sub.11; C.sub.1-C.sub.12alkyl substituted
by COOR.sub.12, CONR.sub.13R.sub.14, OCOR.sub.15, OH or halogen; or
R.sub.7 is a polymeric hydrocarbon residue of 10 to 1000 carbon
atoms, preferably 20 to 500 carbon atoms; [0012] and R.sub.7 also
embraces a residue of formula II
##STR00003##
[0012] wherein X is C.sub.2-C.sub.24alkylene;
--CH.sub.2CH(OH)CH.sub.2--;
--CH.sub.2CH(OH)CH.sub.2O-D-OCH.sub.2CH(OH)CH.sub.2; [0013]
(C.sub.1-C.sub.18alkylene)-CO--O-D-O--CO--(C.sub.1-C.sub.18alkylene);
CO; CO--(C.sub.2-C.sub.24alkylene)-CO; [0014]
C.sub.3-C.sub.24alkylene interrupted by oxygen; [0015] D is
C.sub.2-C.sub.12alkylene; C.sub.4-C.sub.50alkylene interrupted by
O; phenylene; biphenylene or phenylene-E-phenylene; [0016] E is O,
S, SO.sub.2; CH.sub.2; CO or --C(CH.sub.3).sub.2--; [0017] R.sub.11
is H, C.sub.1-C.sub.12alkyl; phenyl; phenyl substituted by 1-3
C.sub.1-C.sub.4alkyl; C.sub.5-C.sub.12cycloalkyl;
C.sub.7-C.sub.12phenylalkyl; C.sub.3-C.sub.12alkenyl; [0018]
R.sub.12 is H; C.sub.1-C.sub.24alkyl; C.sub.3-C.sub.12alkenyl;
C.sub.3-C.sub.36alkyl interrupted by oxygen and/or substituted by
OH; or is C.sub.5-C.sub.12cycloalkyl, C.sub.7-C.sub.12phenylalkyl,
C.sub.7-C.sub.12alkylphenyl; phenyl; [0019] R.sub.13 and R.sub.14
independently are H, C.sub.1-C.sub.18alkyl; phenyl; phenyl
substituted by 1-3 C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; C.sub.5-C.sub.12cycloalkyl;
C.sub.3-C.sub.12alkenyl; [0020] R.sub.15 is C.sub.1-C.sub.12alkyl;
phenyl; phenyl substituted by 1-3 C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; C.sub.5-C.sub.12cycloalkyl;
C.sub.3-C.sub.12alkenyl; C.sub.1-C.sub.12alkoxy; or is
NR.sub.13R.sub.14.
[0021] More preferably, in the hydroxyphenyl triazine UV absorber
of the formula I [0022] R.sub.4 and R.sub.5 independently are H or
methyl; [0023] R.sub.6 is H; [0024] R.sub.8 is H;
C.sub.1-C.sub.8alkoxy; C.sub.1-C.sub.8alkyl; [0025] R.sub.7,
R.sub.9 independently are H; C.sub.1-C.sub.18alkyl;
C.sub.3-C.sub.12alkenyl; C.sub.3-C.sub.24alkyl interrupted by
oxygen and/or substituted by OH; or is C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl, C.sub.7-C.sub.12alkylphenyl;
C.sub.1-C.sub.12alkyl substituted by COOR.sub.12, OCOR.sub.15, OH;
or R.sub.7 is a polymeric hydrocarbon residue of 20 to 500 carbon
atoms; [0026] and R.sub.7 also embraces a residue of formula II,
wherein X is C.sub.2-C.sub.18alkylene; --CH.sub.2CH(OH)CH.sub.2--;
--CH.sub.2CH(OH)CH.sub.2O-D-OCH.sub.2CH(OH)CH.sub.2; [0027]
(C.sub.1-C.sub.4alkylene)-CO--O-D-O--CO--(C.sub.1-C.sub.4alkylene);
CO; CO--(C.sub.2-C.sub.18alkylene)-CO; [0028]
C.sub.3-C.sub.18alkylene interrupted by oxygen; D is
C.sub.2-C.sub.12alkylene; [0029] R.sub.12 is H;
C.sub.1-C.sub.24alkyl; C.sub.3-C.sub.12alkenyl;
C.sub.3-C.sub.24alkyl interrupted by oxygen and/or substituted by
OH; or is C.sub.5-C.sub.12cycloalkyl, C.sub.7-C.sub.12phenylalkyl,
C.sub.7-C.sub.12alkylphenyl; phenyl; [0030] R.sub.15 is
C.sub.1-C.sub.12alkyl; C.sub.5-C.sub.12cycloalkyl;
C.sub.3-C.sub.12alkenyl; especially [0031] R.sub.1 is OR.sub.7;
[0032] R.sub.2 and R.sub.3 independently are H, methyl,
##STR00004##
[0032] OR.sub.9;
[0033] R.sub.4 and R.sub.5 and R.sub.6 are H; [0034] R.sub.8 is H;
C.sub.1-C.sub.8alkoxy; C.sub.1-C.sub.4alkyl; [0035] R.sub.7,
R.sub.9 independently are C.sub.4-C.sub.18alkyl or
C.sub.5-C.sub.12cycloalkyl; [0036] and R.sub.7 also embraces a
residue of formula II, wherein X is C.sub.4-C.sub.18alkylene.
[0037] Of utmost importance are compounds of the formula I, wherein
R.sub.1 is OR.sub.7; R.sub.2 and R.sub.3 each are phenyl; R.sub.4,
R.sub.5 and R.sub.6 are hydrogen; and R.sub.7 is
C.sub.4-C.sub.18alkyl or C.sub.5-C.sub.12cycloalkyl or a residue of
formula II, wherein X is C.sub.4-C.sub.12alkylene.
[0038] A halogen substitutent is --F, --Cl, --Br or --I, preferably
--F, --Cl or --Br and, in particular, --Cl.
[0039] Alkylphenyl is alkyl-substituted phenyl;
C.sub.7-C.sub.14alkylphenyl embraces examples such as methylphenyl
(tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl),
ethylphenyl, propylphenyl, butylphenyl, dibutylphenyl,
pentylphenyl, hexylphenyl, heptylphenyl and octylphenyl.
[0040] Phenylalkyl is phenyl-substituted alkyl;
C.sub.7-C.sub.11phenylalkyl embraces examples such as benzyl,
.alpha.-methylbenzyl, .alpha.-ethylbenzyl,
.alpha.,.alpha.-dimethylbenzyl, phenylethyl, phenylpropyl,
phenylbutyl and phenylpentyl.
[0041] n-alkyl or alkyl-n is an unbranched alkyl radical.
[0042] Alkyl interrupted by O, NH, NR.sub.13, etc., can generally
comprise one or more nonadjacent heteroatoms. Preferably, a carbon
atom of the alkyl chain bonds to not more than 1 heteroatom.
R.sub.7, R.sub.9 and R.sub.10, especially R.sub.7, as alkyl
substituted by COOR.sub.12 is most preferably
CH.sub.2--COOR.sub.12. R.sub.12 is most preferably
C.sub.1-C.sub.18alkyl, or C.sub.6-C.sub.12cycloalkyl; cycloalkyl is
most preferably cyclohexyl or cyclododecyl.
[0043] Within the scope of the stated definitions, the radicals
R.sub.4, R.sub.5, R.sub.6, R.sub.8, R.sub.9, R.sub.11, R.sub.12,
R.sub.13, R.sub.14, R.sub.15 as alkyl are branched or unbranched
alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl,
1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl,
n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl,
3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl,
1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,
dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl and octadecyl.
[0044] C.sub.1-C.sub.4alkyl is especially methyl, ethyl, isopropyl,
n-butyl, 2-butyl, 2-methylpropyl or tert-butyl.
[0045] Within the scope of the stated definitions, R.sub.4,
R.sub.5, R.sub.6, R.sub.8, R.sub.9, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, R.sub.15 as alkenyl include allyl, isopropenyl,
2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,
3-methyl-but-2-enyl.
[0046] R.sub.4, R.sub.5 and R.sub.6 are most preferably hydrogen.
R.sub.2 and R.sub.3 are most preferably phenyl or OR.sub.9,
especially phenyl. R.sub.9 is most preferably
C.sub.1-C.sub.4alkyl.
[0047] Examples for highly effective compounds of the formula I are
as listed below or in the following tables:
[0048] 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-di-
methyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethy-
l)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2-
,4-dimethylphenyl) 1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethy-
lphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine.
TABLE-US-00001 TABLE 1 Compounds of the formula ##STR00005##
compound R.sub.7 a)
CH.sub.2CH(C.sub.2H.sub.5)--(CH.sub.2).sub.3--CH.sub.3 b)
CH(CH.sub.3)--(CH.sub.2).sub.9--CH.sub.3 c) n-C.sub.6H.sub.13 d)
n-C.sub.8H.sub.17 e) n-C.sub.12H.sub.25
[0049] In the above definitions, n denotes a straight alkyl
chain.
TABLE-US-00002 TABLE 2 Compounds of the formula (k) ##STR00006##
compound X f) --(CH.sub.2).sub.12-- g) --(CH.sub.2).sub.10--
or corresponding compounds wherein X is C.sub.13-C.sub.24alkylene;
(C.sub.1-C.sub.18alkylene)-CO--O-D-O--CO--(C.sub.1-C.sub.18alkylene);
CO--(C.sub.13-C.sub.24alkylene)-CO; C.sub.3-C.sub.24alkylene
interrupted by oxygen, especially
(C.sub.1-C.sub.3alkylene)-O--(C.sub.1-C.sub.3alkylene).
[0050] Further examples for highly effective compounds of the
formula I are the compounds
##STR00007##
[0051] Some compounds of formula I are known, e.g. from WO
96/28431, U.S. Pat. No. 5,591,850, EP-A-434608; others, e.g. the
compounds
##STR00008##
as well as (b), (f), (g) and (h) are novel compounds. They are
conveniently prepared in analogy to procedures described in these
references, especially to the method given in example 18 of WO
96/28431.
[0052] A particular useful application of polymer films, especially
polyolefin films of present invention is their use as greenhouse
films. Some types of crops are degraded by the UV-components of
solar radiation which must be filtered off to obtain high quality
and productivity of the crops. Additionally, some microorganisms
such as fungi, e.g. Botrytis cinerea, Botryosporium, Cladosporium
cucumerium, Endomyces geotrichium, Endomyces fibulinger,
Sphaerotheca pannosa, Erysiphe polygoni, Gonatobotrys,
Cylindrocapron, Fusarium, Thielaviopsis, Verticillium, and virus,
e.g Cucumo-virus, Tombus-virus, etc. as well as some harmful
insects, e.g. white flies, aphides, thrips or leafminers,
proliferate under preferred specific UV-irradiation. These pests
can be significantly reduced when UV light does not or to less
extent reach the plants. [R. Reuveni et al., Development of
photoselective PE films for control of foliar pathogens in
greenhouse-grown crops, Plasticulture No. 102, p. 7 (1994); Y.
Antignus et al., The use of UV absorbing plastic sheets to protect
crops against insects and spread of virus diseases, CIPA Congress
March 1997, pp. 23-33]. On the other hand, bee activity, requiring
a certain band of UV radiation, needs to be retained in greenhouses
in order to ensure fructification on flowering plants, e.g. tomato,
cucumber, pumpkin, melon, lemon, rose, strawberry, lettuce, grape,
pepper etc.
[0053] Present hydroxyphenyl triazine UV absorbers show excellent
compatibility and persistence in the polyolefin, polyester or
polyamide. The same time, these UV absorbers provide efficient and
selective UV shielding for suppressing microbial proliferation in a
protected environment, especially a plant cultivation, while
retaining the UV irradiation necessary for bee, bumblebee activity.
Thus, present invention also pertains to the use of a transparent
polyolefin film as described above for suppressing microbial
proliferation in a protected cultivation.
[0054] Examples for polyolefines to be used for manufacturing the
articles of present invention include the following polymers:
[0055] 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), high density and high
molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), (VLDPE) and (ULDPE).
[0056] 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: [0057] a) radical polymerisation (normally under high
pressure and at elevated temperature). [0058] b) catalytic
polymerisation using a catalyst that normally contains one or more
than one metal of groups IVb, Vb, VIb or VIII of the Periodic
Table. These metals usually have one or more than one ligand,
typically oxides, halides, alcoholates, esters, ethers, amines,
alkyls, alkenyls and/or aryls that may be either .pi.- or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC).
[0059] 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).
[0060] 3. Polyolefin copolymers: 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.
[0061] Polyesters to be used for manufacturing the articles of
present invention are mainly those derived from dicarboxylic acids
and diols and/or from hydroxycarboxylic acids or the corresponding
lactones, for example polyethylene terephthalate, polybutylene
terephthalate, poly-1,4-dimethylolcyclohexane terephthalate,
polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as
block copolyether esters derived from hydroxyl-terminated
polyethers; and also polyesters modified with polycarbonates or
MBS. Preferred is polyethylene terephthalate (PET).
[0062] Polyamides are usually those 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,-trimethylhexamethylene
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).
[0063] Most preferred are polyolefines such as polyethylene,
especially LDPE or LLDPE, or polypropylene.
[0064] Preferably, the amount of hydroxyphenyl triazine UV absorber
in the transparent polymer article of the invention is from 0.005
to 0.15%, more preferably from 0.005 to 0.06%, especially from 0.01
to 0.06% by weight the polymer substrate.
[0065] The transparent polyolefin, polyester or polyamide article
of the invention usually is a film, fiber, ribbon or stretched
tape, especially an agricultural film. Its thickness preferably
ranges between 1 and 300 .mu.m, especially between 1 and 200 .mu.m.
Films, ribbons or tapes of the invention usually are not biaxially
oriented. The transparent polyolefin, polyester or polyamide
article of the invention often contains one or more further
components, e.g. selected from further light stabilizers,
processing stabilizers, fillers, clarifiers, modifiers, acid
scavengers, pigments, flame retardants or other additives known in
the art. These components usually do not effectively block light
transmission through the present polymer articles, which is usually
more than 20%, often more than 50%, and preferably more than 80% of
white incoming light. For sufficient transparency, present articles
preferably do not contain crystalline components in an amount that
would significantly impair this property; preferably they contain
no pigments and no or merely minor amounts, e.g. 0-5% by weight of
the polymer, of fillers or crystalline inorganic components having
lower opaquing effect than pigments (e.g. hydrotalcites). Examples
for additional components which may be contained in the polymer
articles of the invention include the following:
1. Antioxidants
[0066] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-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'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0067] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol.
[0068] 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.
[0069] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (vitamin E).
[0070] 1.5. Hydroxylated thiodiphenyl ethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.
[0071] 1.6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-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-methylphe-
nyl]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-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0072] 1.7. O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0073] 1.8. Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,
di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat-
e,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hyd-
roxybenzyl)malonate.
[0074] 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.
[0075] 1.10. Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-
azine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-t-
riazine,
2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0076] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
[0077] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0078] 1.13. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,
i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0079] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
[0080] 1.15. Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxvphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0081] 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.
[0082] 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).
[0083] 1.18. Ascorbic acid (vitamin C)
[0084] 1.19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyidiphenylamine, 4-isopropoxy-diphenylamine,
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'-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-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octylphenothiazines, N-allylphenothiazine,
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-tetramethylpiperidin-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
2. UV Absorbers and Light Stabilisers
[0085] 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlo-
robenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)--
5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobe-
nzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotr-
iazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyp-
henyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-yl-
phenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--COO--CH.sub.2CH.sub.2 .sub.2, where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)phenyl]-benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)phenyl]benzotriazole.
[0086] 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.
[0087] 2.3. Esters of substituted and unsubstituted benzoic acids,
for example 4-tert-butylphenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-d
i-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
[0088] 2.4. Acrylates, for example ethyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline.
[0089] 2.5. Nickel compounds, for example nickel complexes of
2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1
or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.
the methyl or ethyl ester, of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands.
[0090] 2.6. Sterically hindered amines, for example
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)-malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or
cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)-ethane, the condensate of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]); a condensate of 1,6-hexanediamine and
2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[192268-64-7]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro-[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-
ethene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethy-
lenediamine, a diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,
a reaction product of maleic acid anhydride-.alpha.-olefin
copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine.
[0091] 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide,
2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and
p-methoxy-disubstituted oxanilides and mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0092] 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.
[0093] 4. Phosphites and phosphonites, for example triphenyl
phosphite, diphenylalkyl phosphites, phenyidialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearylpentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,
bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite,
tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)
4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosph-
ocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosp-
hocin,
2,2',2''-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biph-
enyl-2,2'-diyl)phosphite],
2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite-
,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
[0094] The following phosphites are especially preferred:
[0095] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos.RTM. 168,
Ciba-Geigy), tris(nonylphenyl) phosphite,
##STR00009## ##STR00010##
[0096] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0097] 6. Nitrones, for example N-benzyl-alpha-phenylnitrone,
N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,
N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecyinitrone,
N-hexadecyl-alpha-pentadecylnitrone,
N-octadecyl-alpha-heptadecylnitrone,
N-hexadecyl-alpha-heptadecylnitrone,
N-ocatadecyl-alpha-pentadecylnitrone,
N-heptadecyl-alpha-heptadecylnitrone,
N-octadecyl-alpha-hexadecylnitrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0098] 7. Thiosynergists, for example dilauryl thiodipropionate or
distearyl thiodipropionate.
[0099] 8. 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 dibutyidithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0100] 9. Polyamide stabilisers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0101] 10. Basic co-stabilisers, 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.
[0102] 11. Nucleating agents, for example inorganic substances,
such as talcum, metal oxides, such as titanium dioxide or magnesium
oxide, phosphates, carbonates or sulfates of, preferably, alkaline
earth metals; organic compounds, such as mono- or polycarboxylic
acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic
acid, diphenylacetic acid, sodium succinate or sodium benzoate;
polymeric compounds, such as ionic copolymers (ionomers).
Especially preferred are
1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol,
1,3:2,4-di(paramethyldibenzylidene)sorbitol, and
1,3:2,4-di(benzylidene)sorbitol.
[0103] 12. 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.
[0104] 13. Other additives, for example plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0105] 14. Benzofuranones and indolinones, for example those
disclosed in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S.
Pat. No. 5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No.
5,252,643; DE-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,
3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
[0106] Where appropriate, the conventional additives are
judiciously employed in amounts up to 10% by weight, e.g. 0.1-10%
by weight, especially 0.2-5% by weight, based on the material to be
stabilized.
[0107] Acid scavengers may be added, especially in order to improve
the lifetime of agricultural materials which come in contact with
pesticides, e.g. greenhouse films. Components active as acid
scavengers include metal oxides and/or hydroxides, e.g. oxides or
hydroxides of zinc, magnesium, aluminum, calcium, mixed salts
thereof, as well as hydrotalcites or zeolithes as described, for
example, in GB-A-2300192, from page 2, line 2, until page 4, line
22.
[0108] Thin-walled articles of the invention, especially
transparent polyolefin agricultural films, act as a selective UV
filter enhancing plant growth and crop while suppressing the
undesired proliferation of microorganisms. Light of the medium or
far UV region (e.g. 200-360 nm, especially 300-340 nm) required by
these microorganisms is effectively blocked. The same time, the
activity of useful insects such as bees and bumblebees is not
affected.
[0109] Preferably, the transparent polyolefin, polyester or
polyamide article of the invention also contains a sterically
hindered amine as further stabilizer in order to obtain optimum
light stability of the substrate. The sterically hindered amine is
usually contained in an amount of 0.01-6% by weight the polyolefin,
polyester or polyamide, the weight ratio sterically hindered
amine:hydroxyphenyl triazine UV absorber preferably ranging from
2:1 to 20:1.
[0110] Examples for sterically hindered amines preferably contained
in the polyolefin, polyester or polyamide articles of the invention
are given in the above list (item 2.6).
[0111] More preferred sterically hindered amines include the
following compounds: [0112]
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate; [0113]
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; [0114] the
condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid (CAS-No. 65447-77-0); [0115]
N,N',N'',N'''-Tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperid-
in-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine (CAS-No.
106990-43-6);
##STR00011##
[0115] (Chimassorb.RTM. 2020, CAS No. 192268-64-7),
[0116] where n is mainly from the range 3-5; or mixtures of these
compounds.
[0117] Best results are obtained with a sterically hindered amine
from the class of the hydroxylamine ethers. Sterically hindered
hydroxylamine ethers are mainly piperidine derivatives containing
one or more functional groups of the formula
##STR00012##
wherein R and R' independently are hydrogen or methyl, and at least
the chemical bond of the oxygen atom and optionally a further
chemical bond is linked to an organic residue while the remaining
is/are saturated with hydrogen; or all 3 chemical bonds are linked
to an organic residue. Examples for such compounds are described
inter alia in U.S. Pat. Nos. 5,204,473, 5,216,156, or in
GB-A-2347928.
[0118] Examples for the most preferred hydroxylamine ethers are
compounds of the formula (1g-1)
##STR00013##
in which the index n ranges from 1 to 15, being especially from the
range 3-9; [0119] R.sub.12 is C.sub.2-C.sub.12alkylene,
C.sub.4-C.sub.12alkenylene, C.sub.5-C.sub.7cycloalkylene,
C.sub.5-C.sub.7cycloalkylene-di(C.sub.1-C.sub.4alkylene),
C.sub.1-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylene),
phenylenedi(C.sub.1-C.sub.4alkylene) or [0120]
C.sub.4-C.sub.12alkylene interrupted by 1,4-piperazinediyl, --O--
or >N--X.sub.1 with X.sub.1 being C.sub.1-C.sub.12acyl or [0121]
(C.sub.1-C.sub.12alkoxy)carbonyl or having one of the definitions
of R.sub.14 given below except hydrogen; [0122] or R.sub.12 is a
group of the formula (Ib') or (Ic');
##STR00014##
[0122] with m being 2 or 3, [0123] X.sub.2 being
C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or substituted by 1, 2 or 3 [0124]
C.sub.1-C.sub.4alkyl; phenyl which is unsubstituted or substituted
by 1, 2 or 3 C.sub.1-C.sub.4alkyl or [0125] C.sub.1-C.sub.4alkoxy;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; and [0126] the
radicals X.sub.3 being independently of one another
C.sub.2-C.sub.12alkylene; [0127] the radicals B are independently
of one another Cl, --OR.sub.13, --N(R.sub.14)(R.sub.15) or a group
of the formula (IIId);
##STR00015##
[0127] R.sub.13, R.sub.14 and R.sub.15, which are identical or
different, are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
1, 2 or 3 C.sub.1-C.sub.4alkyl; C.sub.3-C.sub.18alkenyl, phenyl
which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl or
C.sub.2-C.sub.4alkyl which is substituted in the 2, 3 or 4 position
by --OH, C.sub.1-C.sub.8alkoxy, [0128]
di(C.sub.1-C.sub.4alkyl)amino or a group of the formula (Ie');
##STR00016##
[0128] with Y being --O--, --CH.sub.2--, --CH.sub.2CH.sub.2-- or
>N--CH.sub.3, [0129] or --N(R.sub.14)(R.sub.15) is additionally
a group of the formula (Ie'); [0130] X is --O-- or >N--R.sub.16;
[0131] R.sub.16 is hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or [0132] substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl; C.sub.7-C.sub.9phenylalkyl which is
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl, a group of the formula
(IIIf),
##STR00017##
[0132] or C.sub.2-C.sub.4alkyl which is substituted in the 2, 3 or
4 position by --OH, C.sub.1-C.sub.8alkoxy, [0133]
di(C.sub.1-C.sub.4alkyl)amino or a group of the formula (Ie');
[0134] R.sub.11 has one of the definitions given for R.sub.16.
[0135] In these compounds, the end group bonded to the triazine
residue can be, for example, a group B or
--N(R.sub.11)--R.sub.12--B, such as chlorine or a group
##STR00018##
and the end group bonded to the diamino group can be, for example,
hydrogen or a di-B-substituted triazinyl group, such as a group
##STR00019##
[0136] It may be convenient to replace the chlorine attached to the
triazine by e.g. --OH or an amino group. Suitable amino groups are
typically: pyrrolidin-1-yl, morpholino, --NH.sub.2,
--N(C.sub.1-C.sub.8alkyl).sub.2 and --NY'(C.sub.1-C.sub.8alkyl)
wherein Y' is hydrogen or a group of the formula
##STR00020##
[0137] In the above shown oligomeric and polymeric compounds,
[0138] examples of alkyl are methyl, ethyl, propyl, isopropyl,
n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,
isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,
1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,
1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,
1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl,
undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
eicosyl and docosyl; [0139] examples of cycloalkyl are cyclopentyl,
cyclohexyl, cycloheptyl and cyclooctyl; [0140] an example of
C.sub.7-C.sub.9phenylalkyl is benzyl; and [0141] examples of
alkylene are ethylene, propylene, trimethylene, tetramethylene,
pentamethylene, 2,2-dimethyltrimethylene, hexamethylene,
trimethylhexamethylene, octamethylene and decamethylene.
[0142] Another example for a sterically hindered amine ether
advantageously to be used within present polymer articles is the
compound of the formula
##STR00021##
[0143] An example for a highly effective compound of formula (1g-1)
is the compound of the formula (1g-2)
##STR00022##
wherein n' is approximately 3 (example 2 of GB-A-2334717, CAS
#247243-62-5, which is the NO-n-propyl derivative of the block
oligomer Chimassorb.RTM. 2020 CAS #192268-64-7, Ciba Specialty
Chemicals Corp.).
[0144] The additives of the invention and optional further
components may be added to the polymer material individually or
mixed with one another. If desired, the individual components can
be mixed with one another for example in the melt (melt blending)
before incorporation into the polymer.
[0145] The incorporation of the additives of the invention and
optional further components into the polymer 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. The additives of
the invention and optional further additives may be incorporated,
for example, before or after molding or also by applying the
dissolved or dispersed addtitve or additive mixture to the polymer
material, with or without subsequent evaporation of the solvent.
They may be added direct into the processing apparatus (e.g.
extruders, internal mixers, etc), e.g. as a dry mixture or powder
or as solution or melt.
[0146] The incorporation can be carried out in any heatable
container equipped with a stirrer, e.g. in a closed apparatus such
as a kneader, mixer or stirred vessel. The incorporation is
preferably carried out in an extruder or in a kneader. It is
immaterial whether processing takes place in an inert atmosphere or
in the presence of oxygen.
[0147] The additives of the invention and optional further
additives can also be added to the polymer in the form of a
masterbatch which contains the components in a concentration of,
for example, about 2.5% to about 25% by weight; in such operations,
the polymer can be used in the form of powder, granules, solutions,
suspensions or in the form of latices.
[0148] The examples which follow describe the invention further
without constituting any restriction. Parts and percentages therein
are by weight; an example which mentions room temperature means
thereby a temperature in the range 20-25.degree. C. In the case of
solvent mixtures such as those for chromatography the parts
indicated are by volume. These definitions apply unless specified
otherwise.
[0149] The following abbreviations are used: [0150] m.p. melting
point or melting range [0151] NMR nuclear magnetic resonance [0152]
T.sub.g glass transition temperature; [0153] h: hours.
Preparation of Hydroxyphenyl Triazine UV Absorbers
##STR00023##
[0154] Synthesis of
2,4-bis-biphenyl-6-[2-hydroxy-4-(2-ethyl-hexyloxy)phenyl]-1,3,5-triazine
[0155] A yellow suspension of
2,4-bis-biphenyl-6-[2,4-dihydroxyphenyl]-1,3,5-triazine (11.2 g,
0.0227 mole) in dimethylformamide (30 ml) is heated under nitrogen
at 70.degree. until a clear brown solution is formed. Anhydrous
potassium carbonate (3.77 g, 0.0227 mole) is added and the brown
suspension heated at 80.degree. C. for 30 minutes.
2-Ethylhexylbromide (5.70 g, 0.0295 mole) is added dropwise over 30
minutes, after which the suspension is heated at 110.degree. C. for
a further 3 hours. Precipitated salts are filtered off and the
filtrate cooled to 0.degree. C. Methanol (20 ml) is added and the
precipitated product removed by filtration. After drying under
vacuum,
2,4-bis-biphenyl-6-[2-hydroxy-4-(2-ethylhexyloxy-phenyl]-1,3,5-tr-
iazine (12.8 g) is obtained with mp 70.degree..
[0156] h) When in the above preparation the educt
2,4-bis-biphenyl-6-[2,4-dihydroxyphenyl]-1,3,5-triazine is replaced
by the equivalent amount of
2,4-bis(4-methoxyphenyl)-6-[2,4-dihydroxyphenyl]-1,3,5-triazine,
compound (h) of the formula
##STR00024##
is obtained with mp 105.degree. C.,
[0157] The compounds shown in the following table are obtained when
the above reaction (a) is repeated using corresponding amounts of
other alkylbromides or alkylene-dibromides.
TABLE-US-00003 ##STR00025## Example R-1 Mp: .degree. C. b)
CH(CH.sub.3)--(CH.sub.2).sub.9--CH.sub.3 OIL c) n-C.sub.6H.sub.13
178 d) n-C.sub.8H.sub.17 160 e) n-C.sub.12H.sub.25 146
TABLE-US-00004 ##STR00026## Example X Mp: .degree. C. f)
--(CH.sub.2).sub.10-- >250 g) --(CH.sub.2).sub.12-- >250
[0158] Corresponding compounds wherein X is
C.sub.13-C.sub.24alkylene;
(C.sub.1-C.sub.18alkylene)-CO--O-D-O--CO--(C.sub.1-C.sub.18alkylene);
CO--(C.sub.13-C.sub.24alkylene)-CO; C.sub.3-C.sub.24alkylene
interrupted by oxygen, especially
(C.sub.1-C.sub.3alkylene)-O--(C.sub.1-C.sub.3alkylene) are obtained
using the appropriate alkylene-dibromides or alkylene-dibromides
interrupted by --CO--O-D-O--CO-- or oxygen, or dichlorides or
dibromides of aliphatic C.sub.15-C.sub.26diacids.
l) Preparation of the Compound of the Formula:
##STR00027##
[0160] In a manner analogous to Example 16 of WO 96/28431, a white
powder is obtained from the starting material:
4-(4,6-bis-biphenyl-4-yl-(1,3,5)triazin-2-yI)-benzene-1,3-diol and
allyl bromide.
[0161] .sup.1H NMR (300 MHz, CDCl.sub.3): .delta.=13.3 (s, 1H),
8.7-6.2 (aromatic signals, 21H), 6.1 (m, 1H), 5.3 (m, 2H), 4.3 (m,
2H).
m) Preparation of the Oligomer of the Formula:
##STR00028##
[0163] 30 g (0.056 mol) of the compound from Example (l) and 30.2 9
(0.320 mol) of norbornylene and 42.3 g (0.320 mol) of
dicyclopentadiene and 0.49 g (0.6 mmol) of the catalyst
bis(tricyclopentylphosphine)dichloro(3-methyl-2-butenylidene)ruthenium
(APT Cat ASMC 716) are added to 300 ml of toluene. The mixture is
left to react for 24 hours at 30.degree.. The solution is then
concentrated under vacuum and a pale brown solid is obtained.
[0164] Visual melting range: 168-180.degree. C.; M.sub.n2216;
M.sub.w: 4663; PDI: 2.10;
[0165] Elemental analysis:
TABLE-US-00005 % C % H % N theory 87.5 8.4 2.3 found 85.8 8.6
2.1
n) Preparation of the Hydrogenated Oligomer of the Formula:
##STR00029##
[0167] To a solution of 92 g (0.050 mol) of the oligomer of Example
(m) in 300 ml of xylene, 1.0 g of platinum on carbon (10% w/w) is
added. The mixture is poured into an autoclave and hydrogenated for
24 hours at 65 bar (p.sub.H2) and 105.degree. C. The hydrogenated
mixture is purified from the catalyst by adding 10 g of
Tonsyll.COPYRGT. 414 FF at 80-90.degree. C. and left under vigorous
stirring for 2 hours. After filtering off over a pad of 10 g of
Tonsil the filtrated yellow solution is concentrated under vacuum
and a pale yellow solid is obtained.
[0168] Visual melting range: 55-68.degree. C.; M.sub.n: 2197;
M.sub.w: 4347; PDI: 1.98;
[0169] .epsilon.(290 nm, toluene): 34574;
[0170] Elemental analysis:
TABLE-US-00006 % C % H % N theory 85.8 10.2 2.2 found 84.7 10.2
2.0
APPLICATION EXAMPLES
[0171] In some of the application examples, the following
sterically hindered amines (HALS) are employed:
TABLE-US-00007 com- pound formula/chemical name (1g-2) H-2
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate) H-3 condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- hydroxypiperidine and
succinic acid (CAS-No. 65447-77-0) H-4 ##STR00030## H-5
N,N',N'',N'''-Tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-
tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-
1,10-diamine (CAS-No. 106990-43-6). indicates data missing or
illegible when filed
Example 1
[0172] Combination Hydroxyphenyl Triazine Compound (a) with
Compound (1g-2)
[0173] In order to evaluate the UV-absorber characteristics of
hydroxyphenyl triazine compound (a), when mixed with a commercial
thermoplastic material, thin low density polyethylene (LDPE) films
are prepared, containing, as a typical formulation, 0.15% by weight
of the above compound (a) and 0.70% of the sterically hindered
amine ether (1g-2), used as light stabilizer of the polymeric
system in highly demanding environments for agriculture
applications. To do so, properly weighted amounts of the compounds
are mixed with ground LDPE (Polimeri Europa, supplied by Enichem,
Milano, Italy), characterized by a density of 0.921 g/cm.sup.3 and
a melt flow index (190.degree. C./2.16 kg) of 0.6 in a turbo mixer.
The mixture is extruded at a maximum temperature of 200.degree. C.
in a OMC.RTM. twin-screw extruder. The granules so obtained are
blown in a lab scale Formac.RTM. blow-extruder at a maximum
temperature of 210.degree. C. to give a film of 150 .mu.m
thickness.
[0174] UV-Vis spectrum of the film as-obtained is recorded in the
range 200-800 nm by means of a Perkin-Elmer lambda.RTM. 20
spectrophotometer, equipped with a RSA-PE-20 Labsphere.RTM.
integrating sphere. At 0.15% loading, compound (a) imparts to the
film a strong UV absorption feature, with a transmittance value
less than 10% between 290 and 360 nm and less than 1% between 300
and 340 nm. The photostability of compound (a) is demonstrated by
exposing the film sample to UV light in an Atlas Ci 65 Xenon Arc
Weather-O-meter.RTM. (WOM, 63.degree. C. black panel temperature,
continuos dry cycle, according to ASTM G 26-96). After 1500 hours
of WOM exposure the minimum transmittance displayed by the film is
still around 1% at 320 nm.
[0175] Compound (a) is fully compatible in LDPE film; no blooming
is observed after storage of the film for 6000 hours at room
temperature. Same behavior is observed keeping the film for the
same amount of time in oven at 60.degree. C. After the same time of
exposure in oven, no significant change in the UV-Vis absorption
spectrum is observed, meaning there is no loss of additive, because
of the high temperature.
[0176] WOM exposure of the formulation reported in this example is
continuing, in order to evaluate the light stability performance of
the polymer containing compound (a). Samples are also being exposed
to natural weathering and are subdued to treatments with
pesticides, in order to evaluate the resistance to chemicals that
can be employed in agriculture.
Example 2
Hydroxyphenyl Triazine Compound (c) as a UV Filter in a
Polyethylene Agrofilm
[0177] In order to prepare thin LDPE films and to evaluate the
spectral features imparted by the additive and its persistency,
compound (c) is mixed with LDPE pellets (Riblene FF 29, supplied by
Polimeri Europa, Milano, Italy), characterized by a density of
0.921 g/cm.sup.3 and a melt flow index (190.degree. C./2.16 Kg) of
0.6) in a turbo mixer in order to give a formulation containing
0.15% by weight of the additive. The mixture is extruded at a
maximum temperature of 200.degree. C. in a OMC twin-screw extruder.
The granules so obtained are blown in a lab scale Formac
blow-extruder at a maximum temperature of 210.degree. C. to give a
film 150 .mu.m thick. UV-Vis spectra are recorded in the range
200-800 nm by means of a Perkin-Elmer Lambda 20 spectrophotometer,
equipped with a RSA-PE-20 Labsphere integrating sphere.
[0178] Results: The film displays a strong absorption band in the
range 280-360 nm. In particular, transmittance is below 20% in the
above mentioned range and below 5% in the range 295-345 nm.
[0179] In order to test the photostability of the additive upon
exposure to light, a portion of the film is exposed in an Atlas
Weather-o-Meter (WOM), model Ci65A (as per ASTM G26-96, irradiance
0.35 W/m.sup.2, black panel temperature 63.+-.3.degree. C.). After
1000 hours of exposure the film still displays a transmittance
below 40% between 280 and 360 nm and below 25% between 295 and 345
nm.
Example 3
[0180] A film containing 0.15% by weight of compound (d) is
prepared as described in example 2. The film displays a strong
absorption band in the range 280-360 nm. In particular,
transmittance is below 20% in the above mentioned range and below
5% in the range 295-345 nm.
[0181] After 1000 hours of exposure in the WOM (see example 2 for
details), the film still retains the spectral features described
above.
[0182] Another portion of the film is also exposed in a forced
circulating air oven at 60.degree. C., in order to evaluate the
thermal persistency of the additive in the film. After 1000 hours
of exposure the film still retains the initial spectral
features.
Example 4
[0183] A film containing 0.15% by weight of compound (b)is prepared
as described in example 2. The film displays a strong absorption
band in the range 280-360 nm. In particular, transmittance is below
20% in the above mentioned range and below 5% in the range 295-345
nm.
[0184] After 1000 hours of exposure in the WOM (see example 2 for
details), the film still retains the spectral features described
above.
Example 5
[0185] A film containing 0.15% by weight of compound (g) is
prepared as described in example 2. The film displays a strong
absorption band in the range 280-360 nm. In particular,
transmittance is below 20% in the above mentioned range and below
5% in the range 295-345 nm.
[0186] After 1000 hours of exposure in the WOM (see example 2 for
details), the film still displays a transmittance below 25% between
280 and 360 nm and below 10% between 295 and 345 nm.
[0187] Another portion of the film is also exposed in oven at
60.degree. C. After 1000 hours of exposure the film retains about
75% of the initial absorption.
Example 6
[0188] A film containing 0.15% by weight of compound (f) is
prepared as described in example 2. The film displays a strong
absorption band in the range 280-360 nm. In particular,
transmittance is below 20% in the above mentioned range and below
5% in the range 295-345 nm.
[0189] After 1000 hours of exposure in the WOM (see example 2 for
details), the film still displays a transmittance below 25% between
280 and 360 nm and below 15% between 295 and 345 nm.
Example 7
Light Stabilization of Polypropylene (PP) Cast Films
[0190] 100 parts of polypropylene powder (melt flow index 3.8 g/10
minutes, 230.degree. C./2160 g) are blended in a barrel mixer with
0.05 parts of
pentaerythrityl-tetrakis-3-(3,5-ditert.butyl-4-hydroxyphenyl)-pr-
opionate, 0.05 parts of tris-(2,4-di-tert.butylphenyl)-phosphite,
0.1 parts of Ca stearate, 0.1 part HALS and the amount of UV
absorber (compound j) indicated in the figures below. Then the
blend is compounded in an extruder at temperatures of
180-220.degree. C. The granules obtained on extrusion and
granulation are transformed into films at 220-260.degree. C. in a
second extruder equipped with a flat sheet die. Samples of
60.times.25 mm are cut out of these 0.11 mm films and exposed in a
WEATHER-OMETER Ci 65 (black panel temperature 63.+-.2.degree. C.,
without water-spraying).
[0191] Periodically, these samples are removed from the exposure
apparatus and their carbonyl content is measured with an infrared
spectrophotometer. The exposure time corresponding to formation of
a carbonyl absorbance of 0.1 is a measure for the stabilizing
efficiency of the light stabilizer. The values obtained are plotted
in FIGS. 1, 2 and 3. The following HALS are used (0.1 part of each
per 100 parts PP):
[0192] FIG. 1: Low molecular mass HALS H-2
(bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate);
[0193] FIG. 2: Polymeric HALS H-3 (CAS-No. 65447-77-0, white
circles); [0194] polymeric HALS H-4 (white squares); and [0195]
blend of 1 part H-3 with 1 part H-4 (filled circles);
[0196] FIG. 3: non-polymeric high molecular mass HALS H-5.
[0197] The plots show that already small amounts of the
hydroxyphenyl triazine UV absorber give considerable improvement of
the UV stability conferred by HALS.
Example 8
Light Stabilization of Polypropylene Tapes
[0198] 100 parts of polypropylene powder (melt flow index 3.5 g/10
minutes, 230.degree. C./2160 g) are blended in a barrel mixer with
0.05 parts of
pentaerythrityl-tetrakis-3-(3,5-ditert.butyl-4-hydroxyphenyl)-pr-
opionate, 0.05 parts of tris-(2,4-di-tert.butylphenyl)-phosphite,
0.1 parts of Ca stearate, 0.1% polymeric HALS H-3 (condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid (CAS-No. 65447-77-0)) and the amount of light
stabilizer compound (j) indicated in the figure. Then the blend is
compounded in an extruder at temperatures of 180-220.degree. C. The
granules obtained on extrusion and granulation are transformed into
films at 220-260.degree. C. in a second extruder equipped with a
flat sheet die. The films are cut into ribbons, which are drawn to
achieve a stretch ratio of 1:6. The tapes obtained with this
procedure are finally 50 .mu.m thick and 2.5 mm wide.
[0199] The tapes are mounted without tension on sample holders and
subjected to natural weathering in Florida (45.degree. South,
direct, approximately 140 kLy/year). Periodically, the tensile
strength of the exposed tapes is measured. The received energy (in
kLy) corresponding to a loss of 50% of the initial tensile strength
is a measure for the stabilizing efficiency of the light
stabilizer. The values obtained with a polymeric HALS and the
hydroxyphenyl triazine UV absorber are plotted in FIG. 4.
[0200] The results show that the contribution of the UV absorber to
light stability is also marked in PP tapes that are less than half
as thick as the PP films used in Example 7.
Example 9
Light Stabilization of Polypropylene Tapes
[0201] 100 parts of polypropylene powder (melt flow index 3.5 g/10
minutes, 230.degree. C./2160 g) are blended in a barrel mixer with
0.05 parts of
pentaerythrityl-tetrakis-3-(3,5-ditert.butyl-4hydroxyphenyl)-pro-
pionate, 0.05 parts of tris-(2,4-di-tert.butyl-phenyl) phosphite,
0.1 parts of Ca stearate and the amount of light stabilizers
indicated in the below table. Then the blend is compounded in an
extruder at temperatures of 180-220.degree. C. The granules
obtained on extrusion and granulation are transformed into films at
220-260.degree. C. in a second extruder equipped with a flat sheet
die. The films are cut into ribbons, which are drawn to achieve a
stretch ratio of 1:6. The tapes obtained with this procedure are
finally 50 .mu.m thick and 2.5 mm wide.
[0202] The tapes are mounted without tension on sample holders and
exposed in a WEATHER-O-METER Ci 65 (black panel temperature
63.+-.2.degree. C., without water-spraying). Periodically, the
tensile strength of the exposed tapes is measured. The exposure
time corresponding to a loss of 50% of the initial tensile strength
(T50) is a measure for the stabilizing efficiency of the light
stabilizer.
[0203] The values obtained are summarized in the below table.
TABLE-US-00008 TABLE Effect of various UV absorber types on the
performance of HALS in PP tapes. HALS UV Absorber T50 (h) none none
530 0.1% H-3 none 2150 0.1% H-3 0.1% V-1 2500 0.1% H-3 0.1% V-2
2700 0.1% H-3 0.1% compound j 3800 0.1% H-4 none 3000 0.1% H-4 0.1%
V-2 2900 0.1% H-4 0.1% compound j 4150
[0204] Compound V-1 is
2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole.
[0205] Compound V-2 is of the formula
##STR00031##
[0206] The data show that the contribution of the hydroxyphenyl
triazine UV absorber (compound j) to the light stability of the
tapes is significant while the contribution of the benzotriazole or
the benzophenone UV absorber (V-1 and V-2) remains small or not
detectable.
Example 10
Absorption Band and Persistency in LDPE of Compound (m)
[0207] Thin low density polyethylene (LDPE) films are prepared as
described in example 2 but without addition of HALS. They are 150
.mu.m thick and contain 0.5% of the compound (m). UV-Vis spectra
are recorded as described in example 2. The film displays a strong
absorption in the range 280-360 nm. Transmittance values below 3%
are detected in the range 290-350 nm.
[0208] The persistency of the polymer in LDPE films is determined
after exposure of the films at 60.degree. C. in a forced
circulating air oven and evaluated as described in example 3. No
decrease of the absorbance value at the maximum is observed after
3000 hours at 60.degree. C.
BRIEF DESCRIPTION OF THE FIGURES
[0209] FIG. 1: Effect of the addition of hydroxyphenyl-triazine UV
absorber compound (j) in presence of a low molecular mass HALS H-2
in PP cast films (0.1 mm thick). T.sub.0.1=exposure time to 0.1
carbonyl absorbance. Example 7.
[0210] FIG. 2: Effect of the addition of a hydroxyphenyl-triazine
UV absorber compound (j) in presence of a polymeric HALS H-3 (white
circles), H-4 (white squares) and blend of 1 part H-3 with 1 part
H-4 (filled circles) in PP cast films (0.1 mm thick).
T.sub.0.1=exposure time to 0.1 carbonyl absorbance. Example 7.
[0211] FIG. 3: Effect of the addition of a hydroxyphenyltriazine UV
absorber compound j in presence of high molecular mass HALS H-5 in
PP cast films (0.1 mm thick). T.sub.0.1=exposure time to 0.1
carbonyl absorbance. Example 7.
[0212] FIG. 4: Effect of the addition of hydroxylphenyl triazine UV
absorber (compound j) in presence of 0.1% polymeric HALS H-3 in PP
tapes (50 .mu.m thick). E50=energy to 50% retained tensile
strength. Example 8.
* * * * *