U.S. patent application number 09/974382 was filed with the patent office on 2002-09-12 for inhibition of pulp and paper yellowing using nitroxides, hydroxylamines and other coadditives.
Invention is credited to Cunkle, Glen T., Heitner, Cyril, McGarry, Peter F., Nelson, Randall B., Schmidt, John A., Seltzer, Raymond R., Wolf, Jean-Pierre.
Application Number | 20020124980 09/974382 |
Document ID | / |
Family ID | 27489566 |
Filed Date | 2002-09-12 |
United States Patent
Application |
20020124980 |
Kind Code |
A1 |
Seltzer, Raymond R. ; et
al. |
September 12, 2002 |
Inhibition of pulp and paper yellowing using nitroxides,
hydroxylamines and other coadditives
Abstract
Pulps or papers, especially chemimechanical or thermomechanical
pulps or papers, which still contain lignin, have enhanced
resistance to yellowing when they contain an effective stabilizing
amount of a hindered amine compound which preferably is a
nitroxide, a hydroxylamine or an ammonium salt thereof. This
performance is often further enhanced by the presence of one or
more coadditives selected from the group consisting of the UV
absorbers, the polymeric inhibitors, the nitrones, the fluorescent
whitening agents, metal chelating agents, sulfur containing
stabilizers, metal salts and diene compounds. Combinations of
nitroxides, hydroxylamines or their salts, benzotriazole or
benzophenone UV absorbers and a metal chelating agent are
particularly effective. Selected derivatives of
1-oxyl-2,2,6,6-tetramethyl-piperidin-4-ol and selected
hydroxylamine salts are novel compounds and are surprisingly
effective for this purpose.
Inventors: |
Seltzer, Raymond R.; (New
City, NY) ; Wolf, Jean-Pierre; (Courtaman, CH)
; Heitner, Cyril; (Pierrefonds, CA) ; Schmidt,
John A.; (L'ile Bizard, CA) ; McGarry, Peter F.;
(L'ile Bizard, CA) ; Cunkle, Glen T.; (Stamford,
CT) ; Nelson, Randall B.; (Seattle, WA) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
27489566 |
Appl. No.: |
09/974382 |
Filed: |
October 10, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09974382 |
Oct 10, 2001 |
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09573401 |
May 18, 2000 |
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09573401 |
May 18, 2000 |
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09119567 |
Jul 20, 1998 |
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60053489 |
Jul 23, 1997 |
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60054968 |
Aug 7, 1997 |
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Current U.S.
Class: |
162/158 ;
162/160; 162/166 |
Current CPC
Class: |
D21H 21/143 20130101;
C07D 211/94 20130101; C08L 97/00 20130101; C08K 5/3435 20130101;
C07D 405/12 20130101; C08K 5/3435 20130101; D21C 9/005
20130101 |
Class at
Publication: |
162/158 ;
162/160; 162/166 |
International
Class: |
D21H 021/00; D21H
017/07; D21H 021/38 |
Claims
What is claimed is:
1. A composition having reduced loss of brightness and enhanced
resistance to yellowing which comprises (a) a pulp or paper which
still contains lignin, and (b) and effective stabilizing amount of
a hindered amine compound of formula I or II 5where G.sub.1 G.sub.2
are independently alkyl of 1 to 4 carbon atoms or are together
pentamethylene, Z.sub.1 and Z.sub.2 are each methyl, or Z.sub.1 and
Z.sub.2 together form a linking moiety which may additionally be
substituted by an ester, ether, hydroxy, oxo, cyanohydrin, amide,
amino, carboxy or urethane group, E is oxyl, hydroxyl, hydrogen,
alkyl, alkyl substituted by hydroxyl, oxo or carboxy or interrupted
by oxygen or carboxy; alkenyl, alkynyl, cycloalkyl, cycloalkenyl,
bicycloalkyl, alkoxy, alkoxy substituted by hydroxyl, oxo or
carboxy or interrupted by oxygen or carboxy, cycloalkoxy,
alkenyloxy, cycloalkenyloxy, aralkyl, aralkoxy, acyl,
R(C.dbd.O)O--, RO(C.dbd.O)O--, RN(C.dbd.O)O-- or chloro, where R is
an aliphatic or aromatic moiety, X is an inorganic or organic
anion, and where the total charge of cations h is equal to the
total charge of anions j, and with the proviso that the compound of
formula I is not bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate or
the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-te-
tramethyl4-hydroxypiperidine and succinic acid.
2. A composition according to claim 1 where in the compound of
component (b), E is oxyl, hydroxyl, alkenyloxy, aralkoxy, alkyloxy
substituted by oxo or interrupted by carboxy.
3. A composition according to claim 1 where in the compound of
component (b), E is oxyl, hydroxy or alkenyloxy.
4. A composition according to claim 1 where in the compound of
component (b), E is oxyl or hydroxy.
5. A composition according to claim 1 where in the compound of
component (b), E is hydroxy.
6. A composition according to claim 1 where in the compound of
component (b), X is phosphate, phosphonate, carbonate, bicarbonate,
nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate,
borate, formate, acetate, benzoate, citrate, oxalate, tartrate,
acrylate, gluconate, polyacrylate, fumarate, maleate, itaconate,
glycolate, malate, mandelate, tiglate, ascorbate, polymethacrylate,
a carboxylate of nitrilotriacetic acid,
hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentamethylenephosphonate, an
alkylsulfonate or an arylsulfonate.
7. A composition according to claim 1 where in the compound of
component (b), E is hydroxyl, alkenyloxy, aralkoxy, alkyloxy
substituted by oxo or interrupted by carboxy and X is chloride,
bisulfate, sulfate, formate, acetate, benzoate, oxalate, citrate,
ascorbate, a carboxylate of ethylenediaminetetraacetic acid or of
diethylenetriaminepentaacetic acid or polyacrylate.
8. A composition according to claim 1 where in the compound of
component (b), E is hydroxyl or alkenyloxy and X is chloride,
bisulfate, sulfate, citrate or a carboxylate of
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid.
9. A composition according to claim 1 where in the compound of
component (b), E is hydroxyl and X.sup.- is citrate.
10. A composition according to claim 1 wherein the hindered amine
compound of component (b) is selected from the compounds of
formulas A to EE and A* to EE* 6wherein E is oxyl, hydroxyl,
hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of 2 to 12 carbon
atoms substituted by one to three hydroxyl or said alkyl
interrupted by one to four oxygen atoms, or said alkyl both
substituted by said hydroxyl groups and interrupted by said oxygen
atoms, alkenyl of 2 to 18 carbon atoms, alkynyl of 2 to 12 carbon
atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12
carbon atoms, bicycloalkyl of 6 to 10 carbon atoms, alkoxy of 1 to
18 carbon atoms, alkoxy of 2 to 12 carbon atoms substituted by one
to three hydroxyl groups or said alkoxy interrupted by one to four
oxygen atoms or said alkoxy substituted by --COOZ where Z is
hydrogen or alkyl of 1 to 4 carbon atoms, cycloalkoxy of 5 to 12
carbon atoms, cycloalkenyloxy of 5 to 12 carbon atoms, alkenyloxy
of 2 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aralkoxy
of 7 to 15 carbon atoms, alkanoyl of 2 to 12 carbon atoms, alkenoyl
of 2 to 12 carbon atoms, benzoyl, or R(C.dbd.O)O--, RO(C.dbd.O)O--,
RN(C.dbd.O)O--, where R is alkyl of 1 to 6 carbon atoms or phenyl,
R is hydrogen or methyl, in formula A and A*, n is 1 or 2, when n
is 1, R.sub.1 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl
of 2-18 carbon atoms, propargyl, glycidyl, alkyl of 2 to 50 carbon
atoms interrupted by one to twenty oxygen atoms, said alkyl
substituted by one to ten hydroxyl groups or both interrupted by
said oxygen atoms and substituted by said hydroxyl groups, or
R.sub.1 is alkyl of 1 to 4 carbon atoms substituted by a carboxy
group or by --COOZ where Z is hydrogen, alkyl of 1 to 4 carbon
atoms or phenyl, or where Z is said alkyl substituted by
--(COO.sup.-).sub.nM.sup.n+ where n is 1-3 and M is a metal ion
from the 1st, 2nd or 3rd group of the periodic table or is Zn, Cu,
Ni or Co, or M is a group N.sup.n+(R.sub.2).sub.4 where R.sub.2 is
alkyl of 1 to 8 carbon atoms or benzyl, when n is 2, R.sub.1 is
alkylene of 1 to 12 carbon atoms, alkenylene of 4 to 12 carbon
atoms, xylylene or alkylene of 1 to 50 carbon atoms interrupted by
one to twenty oxygen atoms, substituted by one to ten hydroxyl
groups or both interrupted by said oxygen atoms and substituted by
said hydroxyl groups, in formula B and B*, m is 1 to 4, when m is
1, R.sub.2 is alkyl of 1 to 18 carbon atoms, alkyl of 3 to 18
carbon atoms interrupted by --COO--, or R.sub.2 is
--CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.3 where n is 1 to 12, or
R.sub.2 is cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 12
carbon atoms, or said aryl substituted by one to four alkyl groups
of 1 to 4 carbon atoms, or R.sub.2 is --NHR.sub.3 where R.sub.3 is
alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,
aryl of 6 to 12 carbon atoms, or said aryl substituted by one to
four alkyl of 1 to 4 carbon atoms, or R.sub.2 is --N(R.sub.3).sub.2
where R.sub.3 is as defined above, when m is 2, R.sub.2 is alkylene
of 1 to 12 carbon atoms, alkenylene of 4 to 12 carbon atoms,
xylylene, alkylene of 2 to 12 carbon atoms interrupted by --COO--,
or R.sub.2 is --CH.sub.2(OCH.sub.2CH.sub.2)- .sub.nOCH.sub.2--
where n is 1 to 12, or R.sub.2 is cycloalkylene of 5 to 12 carbon
atoms, aralkylene of 7 to 15 carbon atoms or arylene of 6 to 12
carbon atoms, or R.sub.2 is --NHR.sub.4NH-- where R.sub.4 is
alkylene of 2 to 18 carbon atoms, cycloalkylene of 5 to 12 carbon
atoms, aralkylene of 8 to 15 carbon atoms or arylene of 6 to 12
carbon atoms, or R.sub.2 is --N(R.sub.3)R.sub.4N(R.sub.3)-- where
R.sub.3 and R.sub.4 are as defined above, or R.sub.2 is --CO-- or
--NH--CO--NH--, when m is 3, R.sub.2 is alkanetriyl of 3 to 8
carbon atoms or benzenetriyl, or when m is 4, R.sub.2 is
alkanetetrayl of 5 to 8 carbon atoms or benzenetetrayl, in formula
C and C*, R.sub.10 is hydrogen, alkyl of 1 to 18 carbon atoms,
cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15 carbon
atoms, alkanoyl of 2 to 18 carbon atoms, alkenoyl of 3 to 5 carbon
atoms or benzoyl, x is 1 or 2, when x is 1, R.sub.11 is hydrogen,
alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms,
propargyl, glycidyl, alkyl of 2 to 50 carbon atoms interrupted by
one to twenty oxygen atoms, said alkyl substituted by one to ten
hydroxyl groups or both interrupted by said oxygen atoms and
substituted by said hydroxyl groups, or R.sub.11 is alkyl of 1 to 4
carbon atoms substituted by a carboxy group or by --COOZ where Z is
hydrogen, alkyl of 1 to 4 carbon atoms or phenyl, or where Z is
said alkyl substituted by --(COO.sup.-).sub.nM.sup.n+ where n is
1-3 and M is a metal ion from the 1st, 2nd or 3rd group of the
periodic table or is Zn, Cu, Ni or Co, or M is a group
N.sup.n+(R.sub.2).sub.4 where R.sub.2 is hydrogen, alkyl of 1 to 8
carbon atoms or benzyl, or when x is 2, R.sub.11 is alkylene of 1
to 12 carbon atoms, alkenylene of 4 to 12 carbon atoms, xylylene or
alkylene of 1 to 50 carbon atoms interrupted by one to twenty
oxygen atoms, substituted by one to ten hydroxyl groups or both
interrupted by said oxygen atoms and substituted by said hydroxyl
groups, in formula D and D*, R.sub.10 is as defined above, y is 1
to 4, and R.sub.12 is defined as R.sub.2 above, in formula E and
E*, k is 1 or 2, when k is 1, R.sub.20 and R.sub.21 are
independently alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12
carbon atoms or aralkyl of 7 to 15 carbon atoms, or R.sub.20 is
also hydrogen, or R.sub.20 and R.sub.21 together are alkylene of 2
to 8 carbon atoms or said alkylene substituted by hydroxyl, or are
acyloxy-alkylene of 4 to 22 carbon atoms, or when k is 2, R.sub.20
and R.sub.21 are together (--CH.sub.2).sub.2C(CH.sub.2--).- sub.2,
in formula F and F*, R.sub.30 is hydrogen, alkyl of 1 to 18 carbon
atoms, benzyl, glycidyl, or alkoxyalkyl of 2 to 6 carbon atoms, g
is 1 or 2, when g is 1, R.sub.31 is defined as R.sub.1 above when n
is 1, when g is 2, R.sub.31 is defined as R.sub.1 above when n is
2, in formula G and G*, Q.sub.1 is --NR.sub.41-- or --O--, E.sub.1
is alkylene of 1 to 3 carbon atoms, or E.sub.1 is
--CH.sub.2--CH(R.sub.42)--O-- where R.sub.42 is hydrogen, methyl or
phenyl, or E.sub.1 is --(CH.sub.2).sub.3--NH-- or E.sub.1 is a
direct bond, R.sub.40 is hydrogen or alkyl of 1 to 18 carbon atoms,
R.sub.41 is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of
5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to
10 carbon atoms, or R.sub.41 is --CH.sub.2--CH(R.sub.42)--OH where
R.sub.42 is as defined above, in formula H and H*, p is 1 or 2,
T.sub.4 is as defined for R.sub.11 when x is 1 or 2, M and Y are
independently methylene or carbonyl, preferably M is methylene and
Y is carbonyl, in formula I and I*, this formula denotes a
recurring structural unit of a polymer where T.sub.1 is ethylene or
1,2-propylene or is the repeating structural unit derived from an
alpha-olefin copolymer with an alkyl acrylate or methacrylate, and
where q is 2to 100, Q.sub.1 is --N(R.sub.41)-- or --O-- where
R.sub.41 is as defined above, in formula J and J*, r is 1 or 2,
T.sub.7 is as defined for R.sub.1 when n is 1 or 2 in formula A,
preferably T.sub.7 is octamethylene when r is 2, in formula L and
L*, u is 1 or 2, T.sub.13 is as defined for R.sub.1 when n is 1 or
2 in formula A, with the proviso that T.sub.13 is not hydrogen when
u is 1, in formula M and M*, E.sub.1 and E.sub.2, being different,
each are --CO-- or --N(E.sub.5)-- where E.sub.5 is hydrogen, alkyl
of 1 to 12 carbon atoms or alkoxycarbonylalkyl of 4 to 22 carbon
atoms, preferably E.sub.1 is --CO-- and E.sub.2 is --N(E.sub.5)--,
E.sub.3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl,
naphthyl, said phenyl or said naphthyl substituted by chlorine or
by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon
atoms, or said phenylalkyl substituted by alkyl of 1 to 4 carbon
atoms, E.sub.4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl,
naphthyl or phenylalkyl of 7 to 12 carbon atoms, or E.sub.3 and
E.sub.4 together are polymethylene of 4 to 17 carbon atoms, or said
polymethylene substituted by one to four alkyl of 1 to 4 carbon
atoms, preferably methyl, in formula N, R.sub.1 is as defined for
R.sub.1 in formula A when n is 1, G.sub.3 is a direct bond,
alkylene of 1 to 12 carbon atoms, phenylene or --NH--G.sub.1--NH--
where G.sub.1 is alkylene of 1 to 12 carbon atoms, in formula O and
O*, R.sub.10 is as defined for R.sub.10 in formula C, in formula P
and P*, E.sub.6 is an aliphtic or aromatic tetravalent radical,
preferably neopentanetetrayl or benzenetetrayl, in formula T and
T*, R.sub.51 is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl
of 5 to 12 carbon atoms, or aryl of 6 to 10 carbon atoms, R.sub.52
is hydrogen or alkyl of 1 to 18 carbon atoms, or R.sub.51 and
R.sub.52 together of alkylene of 4 to 8 carbon atoms, f is 1 or 2,
when f is 1, R.sub.50 is as defined for R.sub.11 in formula C when
x is 1, or R.sub.50 is --(CH.sub.2).sub.zCOOR.sub.54 where z is 1
to 4 and R.sub.54 is hydrogen or alkyl of 1 to 18 carbon atoms, or
R.sub.54 is a metal ion from the 1st, 2nd or 3rd group of the
periodic table or a group --N(R.sub.55).sub.4 where R.sub.55 is
hydrogen, alkyl of 1 to 12 carbon atoms or benzyl, when f is 2,
R.sub.50 is as defined for R.sub.11 in formula C when x is 2, in
formula U and U*, R.sub.53, R.sub.54, R.sub.55 and R.sub.56 are
independently alkyl of 1 to 4 carbon atoms or are together
pentamethylene. in formula V and V*, R.sub.57, R.sub.58, R.sub.59
and R.sub.60 are independently alkyl of 1 to 4 carbon atoms or are
together pentamethylene. in formula W and W*, R.sub.61, R.sub.62,
R.sub.63 and R.sub.64 are independently alkyl of 1 to 4 carbon
atoms or are together pentamethylene, R.sub.65 is alkyl of 1 to 5
carbon atoms, M is hydrogen or oxygen, wherein in formulas X to CC
and X* to CC* n is 2to 3, G.sub.1 is hydrogen, methyl, ethyl, butyl
or benzyl, m is 1 to 4, x is 1 to 4, when x is 1, R.sub.1 and
R.sub.2 are independently alkyl of 1 to 18 carbon atoms, said alkyl
interrupted by one to five oxygen atoms, said alkyl substituted by
1 to 5 hydroxyl groups or said alkyl both interrupted by said
oxygen atoms and substituted by said hydroxyl groups; cycloalkyl of
5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to
10 carbon atoms or said aryl substituted by one to three alkyl of 1
to 8 carbon atoms, or R.sub.1 is also hydrogen, or R.sub.1 and
R.sub.2 are together tetramethyl, pentamethylene, hexamethylene or
3-oxapentamethylene, when x is 2, R.sub.1 is hydrogen, alkyl of 1
to 8 carbon atoms, said alkyl interrupted by one or two oxygen
atoms, said alkyl substituted by a hydroxyl group, or said alkyl
both interrupted by one or two oxygen atoms and substituted by a
hydroxyl group, R.sub.2 is alkylene of 2 to 18 carbon atoms, said
alkylene interrupted by one to five oxygen atoms, said alkylene
substituted by 1 to 5 hydroxyl groups or said alkylene both
interrupted by said oxygen atoms and substituted by said hydroxyl
groups; o-, m- or p-phenylene or said phenylene substituted by one
or two alkyl of 1 to 4 carbon atoms, or R.sub.2 is
--(CH.sub.2).sub.kO[(CH.sub.2).sub.kO].sub.h(CH.sub.2).sub.k--
where k is 2 to 4 and h is 1 to 40, or R.sub.1 and R.sub.2 together
with the two N atoms to which they are attached are
piperazin-1,4-diyl, when x is 3, R.sub.1 is hydrogen, R.sub.2 is
alkylene of 4 to 8 carbon atoms interrupted by one nitrogen atom,
when x is 4, R.sub.1 is hydrogen, R.sub.2 is alkylene of 6 to 12
carbon atoms interrupted by two nitrogen atoms, R.sub.3 is
hydrogen, alkyl of 1 to 8 carbon atoms, said alkyl interrupted by
one or two oxygen atoms, said alkyl substituted by a hydroxyl
group, or both interrupted by one or two oxygen atoms and
substituted by a hydroxyl group, p is 2 or 3, and Q is an alkali
metal salt, ammonium or N.sup.+(G.sub.1).sub.4, and in formula DD
and DD* m is 2 or 3, when m is 2, G is
--(CH.sub.2CHR--O).sub.rCH.sub.2CHR--, where r is 0 to 3, and R is
hydrogen or methyl, and when m is 3, G is glyceryl, in formula EE
and EE* G.sub.2 is --CN, --CONH.sub.2 or --COOG.sub.3 where G.sub.3
is hydrogen, alkyl of 1 to 18 carbon atoms or phenyl, X is an
inorganic or organic anion, where the total charge of cations h is
equal to the total charge of anions j, and with the proviso that
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate or the
polycondensation product of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid are excluded.
11. A composition according to claim 10 where in the compounds of
component (b), X is phosphate, phosphonate, carbonate, bicarbonate,
nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate,
borate, formate, acetate, benzoate, citrate, oxalate, tartrate,
acrylate, gluconate, polyacrylate, fumarate, maleate, itaconate,
glycolate, malate, mandelate, tiglate, ascorbate, polymethacrylate,
a carboxylate of nitrilotriacetic acid,
hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentamethylenephosphonate, an
alkylsulfonate or an arylsulfonate.
12. A composition according to claim 10 wherein the compound of
component (b) is selected from the compounds of formulas A, A*, B,
B*, C, C*, D, D*, Q, Q*, R, R*, S, S*, X, X*, Y, Y*, Z and Z* where
E is oxyl or hydroxyl, R is hydrogen, in formula A and A* n is 1 or
2, when n is 1, R.sub.1 is hydrogen, alkyl of 1 to 6 carbon atoms,
alkenyl of 2-6 carbon atoms, propargyl, glycidyl, alkyl of 2 to 20
carbon atoms interrupted by one to ten oxygen atoms, said alkyl
substituted by one to five hydroxyl groups or both interrupted by
said oxygen atoms and substituted by said hydroxyl groups, or
R.sub.1 is alkyl of 1 to 4 carbon atoms substituted by a carboxy
group or by --COOZ where Z is hydrogen or alkyl of 1 to 4 carbon
atoms, when n is 2, R.sub.1 is alkylene of 1 to 8 carbon atoms,
alkenylene of 4 to 8 carbon atoms, alkylene of 1 to 20 carbon atoms
interrupted by one to ten oxygen atoms, substituted by one to five
hydroxyl groups or both interrupted by said oxygen atoms and
substituted by said hydroxyl groups, in formula B and B* m is 1 or
2 when m is 1, R.sub.2 is alkyl of 1 to 4 carbon atoms or R.sub.2
is CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.3 where n is 1 to 12,
or R.sub.2 is phenyl, or said phenyl substituted by one to three
methyl groups, R.sub.2 is --NHR.sub.3 where R.sub.3 is alkyl of 1
to 4 carbon atoms or phenyl, or said phenyl substituted by one or
two methyl groups, when m is 2, R is alkyl of 1 to 8 carbon atoms,
alkenyl of 4 to 8 carbon atoms, or R.sub.2 is
--CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.2-- where n is 1 to 12,
R.sub.2 is NHR.sub.4NH where R.sub.4 is of 2 to 6 carbon atoms,
aralkylene of 8 to 15 carbon atoms or arylene of 6 to 12 carbon
atoms, R.sub.2 is --CO-- or --NHCONH, in formula C and C*, R.sub.10
is hydrogen or, alkanoyl of 1 to 3 carbon atoms, x is 1 or 2, when
x is 1, R.sub.11 is hydrogen, alkyl of 1 to 6 carbon atoms or
glycidyl, R.sub.11 is alkyl of 1 to 4 carbon atoms substituted by a
carboxy group or by COOZ where Z is hydrogen or alkyl of 1 to 4
carbon atoms, when x is 2, R.sub.11 is alkylene of 1 to 6 carbon
atoms, in formula D and D*, R.sub.10 is hydrogen, y is 1 or 2,
R.sub.12 is defined as R.sub.2 above, in formula Y, Y*, Z and Z*, x
is 1 or 2, when x is 1, R.sub.1 and R.sub.2 are independently alkyl
of 1 to 4 carbon atoms, or R.sub.1 and R.sub.2 are together
tetramethylene, or pentamethylene, R.sub.2 is hydrogen or alkyl of
1 to 4 carbon atoms, said alkyl group substituted by a hydroxyl
group, when x is 2, R.sub.1 is hydrogen, alkyl of 1 to 4 carbon
atoms, said alkyl substituted by a hydroxyl group, R.sub.2 is
alkylene of 2 to 6 carbon atoms, R.sub.3 is as defined above.
13. A composition according to claim 12 wherein the compound of
component (b) is selected from the compounds of formulas A, A*, B,
B*, C, C*, D, D*, Q, Q*, R and R* where E is oxyl or hydroxyl, R is
hydrogen, in formula A and A*, h is 1, R.sub.1 is hydrogen, alkyl
of 1 to 4 carbon atoms, glycidyl, alkyl of 2 to 4 carbon atoms
interrupted by one or two oxygen atoms, said alkyl substituted by
one or two hydroxyl groups or both interrupted by said oxygen atoms
and substituted by said hydroxyl groups, or R.sub.1 is alkyl of 1
to 4 carbon atoms substituted by --COOZ where Z is hydrogen or
alkyl of 1 to 4 carbon atoms, in formula B and B*, m is 1 or 2,
R.sub.2 is alkyl of 1 to 4 carbon atoms or R.sub.2 is
CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.3 where n is 1 to 4, when
m is 2, R is alkyl of 1 to 8 carbon atoms, in formula C and C*,
R.sub.10 is hydrogen or alkanoyl of 1 or 2 carbon atoms, x is 1 or
2, when x is 1, R.sub.11 is hydrogen, alkyl of 1 to 4 carbon atoms
or glycidyl, R.sub.11 is alkyl of 1 to 4 carbon atoms substituted
by COOZ where Z is hydrogen or alkyl of 1 to 4 carbon atoms, when x
is 2, R.sub.11 is alkylene of 1 to 6 carbon atoms, in formula D and
D*, R.sub.10 is hydrogen, y is 1 or 2, R.sub.12 is defined as
R.sub.2 above.
14. A composition according to claim 10 wherein the compound of
component (b) is (a)
bis(1-oxyl-2,2-6-6-tetramethylpiperidin-4-yl)sebacate; (b)
bis(1-hydroxy-2,2-6-6-tetramethylpiperidin-4-yl)sebacate; (c)
1-hydroxy-2,2-6-6-tetramethyl-4-acetoxypiperidinium citrate; (d)
1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine; (e)
1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidine; (f)
1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate;
(g) 1-oxyl-2,2,6,6-tetramethyl-4-oxo-piperidine; (h) 1-hydroxy
-2,2,6,6-tetramethyl-4-oxo-piperidine; (i) 1-hydroxy
-2,2,6,6-tetramethyl-4-oxo-piperidinium acetate; (j)
1-oxyl-2,2,6,6-tetramethyl-4-methoxy-piperidine; (k)
1-hydroxy-2,2,6,6-tetramethyl-4-methoxy-piperidine; (l)
1-hydroxyl-2,2,6,6-tetramethyl-4-methoxy-piperidinium acetate; (m)
1-oxyl-2,2,6,6-tetramethyl-4-acetoxypiperidine; (n)
1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidine; (o)
1-oxyl-2,2,6,6-tetramethyl-4-propoxy-piperidine; (p)
1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium acetate; (q)
1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidine; (r)
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidine;
(s)
1-hydroxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidinium
acetate; (t) 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine; (u)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine; (v)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride; (w)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate; (x)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate; (y)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate; (z)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;
(aa)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate.
(bb)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediamine-
tetraacetate; (cc)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidi- nium)
ethylenediaminetetraacetate; (dd)
tetra(1-hydroxy-2,2,6,6-tetramethy- l-4-oxopiperidinium)
ethylenediaminetetraacetate; (ee)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriam-
inepentaacetate; (ff)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiper-
idinium)diethylenetriaminepentaacetate; (gg)
penta(1-hydroxy-2,2,6,6-tetra-
methyl-4-oxopiperidinium)diethylenetriaminepentaacetate; (hh)
tri(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)nitrilotriacetate-
; (ii)
tri(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)nitrilotr-
iacetate; (jj)
tri(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)nitrilo-
triacetate; (kk)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium-
)diethylenetriaminepentamethylenephosphonate; (ll)
penta(1-hydroxy-2,2,6,6- -tetramethyl-4-acetamidopiperidinium)
diethylenetriaminepentamethylenephos- phonate; or (mm)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)die-
thylenetriaminepentamethylenephosphonate.
15. A composition according to claim 14 wherein the compound of
component (b) is (a)
1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine; (b)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine; (c)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride; (d)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate; (e)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate; (f)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate; (g)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) citrate;
(h) tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate; (i)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediamine-
tetraacetate; (j)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidin-
ium)ethylenediaminetetraacetate; (k)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-
-oxopiperidinium)ethylenediaminetetraacetate; (l)
penta(1-hydroxy-2,2,6,6--
tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentaacetate;
(m)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetri-
aminepentaacetate; or (n)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperid-
inium)diethylenetriaminepentaacetate.
16. A composition according to claim 1 wherein the effective amount
of the hindered amine compound of component (b) is 0.001 to 5% by
weight based on the pulp or paper.
17. A composition according to claim 16 wherein the effective
amount of the hindered amine compound of component (b) is 0.005 to
2% by weight based on the pulp or paper.
18. A composition according to claim 17 wherein the effective
amount of the hindered amine compound of component (b) is 0.01 to
1% by weight based on the pulp or paper.
19. A composition according to claim 1 which additionally includes
an effective amount of at least one coadditive selected from the
group consisting of the UV absorbers, the polymeric inhibitors, the
fluorescent whitening agents and metal chelating agents and
mixtures thereof.
20. A composition according to claim 19 wherein the effective
amount of the coadditive is 0.001 to 5% by weight based on the pulp
or paper.
21. A composition according to claim 20 wherein the effective
amount of the coadditive is 0.005 to 2% by weight based on the pulp
or paper.
22. A composition according to claim 21 wherein the effective
amount of the coadditive is 0.01 to 2% by weight based on the pulp
or paper.
23. A composition according to claim 19 wherein the additional
coadditive is a UV absorber.
24. A composition according to claim 19 wherein the UV absorber is
selected from group consisting of the benzotriazoles, the
s-triazines, the benzophenones, the .beta.-cyanoacrylates, the
oxanilides, the benzoxazinones, the benzoates and the .beta.-alkyl
cinnamates.
25. A composition according to claim 24 wherein the UV absorber is
a benzotriazole, an s-triazine or a benzophenone.
26. A composition according to claim 19 wherein the additional
coadditive is a polymeric inhibitor.
27. A composition according to claim 19 wherein the polymeric
inhibitor is poly(ethylene glycol), poly(propylene glycol),
poly(butylene glycol), poly(vinyl pyrrolidone or
poly(ethylene/propylene glycol).
28. A composition according to claim 19 wherein the additional
coadditive is a fluorescent whitening agent.
29. A composition according to claim 28 wherein the flouorescent
whitening agent is selected from the group consisting of the
4,4'-bis-(triazinylamino)-stilbene-2,2'-disulfonic acids,
4,4'-bis-(triazol-2-yl)stilbene-2,2'-disulfonic acids,
4,4'-dibenzofuranyl-biphenyls, 4,4'-(diphenyl)-stilbenes,
4,4'-distyryl-biphenyls, 4-phenyl-4'-benzoxazolyl-stilbenes,
stilbenyl-naphthotriazoles, 4-styryl-stilbenes,
bis-(benzoxazol-2-yl) derivatives, bis-(benzimidazol-2-yl)
derivatives, coumarins, pyrazolines, naphthalimides,
triazinyl-pyrenes, 2-styryl-benzoxazole or -naphthoxazoles,
benzimidazole-benzofurans and oxanilides.
30. A composition according to claim 19 wherein the additional
coadditive is a metal chelating agent.
31. A composition according to claim 30 wherein the chelating agent
is ethylenediaminetetraacetic acid (EDTA),
diethylenetriaminepentaacetic acid (DTPA),
hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic
acid (NTA) or diethylenetriaminepentamethylenephosphonic acid
(DTPMPA).
32. A composition according to claim 19 wherein the additional
coadditive is a mixture of a UV absorber and polymeric
inhibitor.
33. A composition according to claim 19 wherein the additional
coadditive is a mixture of a UV absorber and a fluorescent
whitening agent.
34. A composition according to claim 19 wherein the additional
coadditive is a mixture of a UV absorber and metal chelating
agent.
35. A composition according to claim 19 wherein the additional
coadditive is a mixture of a polymeric inhibitor and a fluorescent
whitening agent.
36. A composition according to claim 19 wherein the additional
coadditive is a mixture of a polymeric inhibitor and a metal
chelating agent.
37. A composition according to claim 19 wherein the additional
coadditive is a mixture of a fluorescent whitening agent and a
metal chelating agent.
38. A composition according to claim 19 wherein the additional
coadditive is a mixture of a UV absorber, a polymeric inhibitor and
a metal chelating agent.
39. A composition according to claim 19 wherein the additional
coadditive is a mixture of a fluorescent whitening agent, a
polymeric inhibitor and a metal chelating agent.
40. A compound of formula IV, V, VI, VII or VIII 7wherein n is 2 to
3, G.sub.1 is hydrogen, methyl, ethyl, butyl or benzyl, X is
inorganic or organic anion, m is 1 to 4, x is 1 to 4, when x is 1,
R.sub.1 and R.sub.2 are independently alkyl of 1 to 18 carbon
atoms, said alkyl interrupted by one to five oxygen atoms, said
alkyl substituted by 1 to 5 hydroxyl groups or said alkyl both
interrupted by said oxygen atoms and substituted by said hydroxyl
groups; cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15
carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted
by one to three alkyl of 1 to 8 carbon atoms, or R.sub.1 is also
hydrogen, or R.sub.1 and R.sub.2 are together tetramethyl,
pentamethylene, hexamethylene or 3-oxapentamethylene, when x is 2,
R.sub.1 is hydrogen, alkyl of 1 to 8 carbon atoms, said alkyl
interrupted by one or two oxygen atoms, said alkyl substituted by a
hydroxyl group, or said alkyl both interrupted by one or two oxygen
atoms and substituted by a hydroxyl group, R.sub.2 is alkylene of 2
to 18 carbon atoms, said alkylene interrupted by one to five oxygen
atoms, said alkylene substituted by 1 to 5 hydroxyl groups or said
alkylene both interrupted by said oxygen atoms and substituted by
said hydroxyl groups; o-, m- or p-phenylene or said phenylene
substituted by one or two alkyl of 1 to 4 carbon atoms, or R.sub.2
is --(CH.sub.2).sub.kO[(CH.sub.2).sub.kO].sub.h(- CH.sub.2).sub.k--
where k is 2 to 4 and h is 1 to 40, or R.sub.1 and R.sub.2 together
with the two N atoms to which they are attached are
piperazin-1,4-diyl, when x is 3, R.sub.1 is hydrogen, R.sub.2 is
alkylene of 4 to 8 carbon atoms interrupted by one nitrogen atom,
when x is 4, R.sub.1 is hydrogen, R.sub.2 is alkylene of 6 to 12
carbon atoms interrupted by two nitrogen atoms, R.sub.3 is
hydrogen, alkyl of 1 to 8 carbon atoms, said alkyl interrupted by
one or two oxygen atoms, said alkyl substituted by a hydroxyl
group, or both interrupted by one or two oxygen atoms and
substituted by a hydroxyl group, p is 2 or 3, and Q is an alkali
metal salt, ammonium or N.sup.+(G.sub.1).sub.4.
41. A compound according to claim 40 wherein X is phosphate,
phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide,
bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate,
gluconate, benzoate, citrate, oxalate, tartrate, acrylate,
polyacrylate, fumarate, maleate, itaconate, glycolate, malate,
mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of
nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentam- ethylenephosphonate, an
alkylsulfonate or an arylsulfonate.
42. A compound according to claim 40 where in the compounds of
formulas IV to VIII n is 2; G.sub.1 is hydrogen or methyl; X is
chloro or bromo; x is 1 or 2, R.sub.1 and R.sub.2 are independently
alkyl of 1 to 8 carbon atoms, said alkyl interrupted by one or two
oxygen atoms, said alkyl substituted by a hydroxyl group, or said
alkyl both interrupted by one or two oxygen atoms and substituted
by a hydroxyl group, or R.sub.1 is hydrogen; or R.sub.1 and R.sub.2
together are 3-oxa-pentamethylene; R.sub.3 is hydrogen or alkyl of
1 to 2 carbon atoms, or said alkyl substituted by a hydroxyl group,
p is 2, m is 1, and Q is Na.sup.+, NH.sub.4.sup.+ or
N(CH.sub.3).sub.4.sup.+.
43. A compound according to claim 40 which is (a)
1-oxyl-2,2,6,6-tetrameth-
yl-4-(2-hydroxy-4-oxa-6-trimethylammmoniumhexyloxy)-piperidine
chloride; (b)
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-3-trimethylammoniumpropoxy)pi-
peridine chloride; (c)
1-oxyl-2,2,6,6-tetramethyl-4-{2-hydroxy-3-[di(2-hyd-
roxyethyl)amino]propoxy}-piperidine; (d)
1-oxyl-2,2,6,6-tetramethyl-4-(2-h-
ydroxy-3-dimethylaminopropoxy)piperidine; (e)
1-oxyl-2,2,6,6-tetramethyl-4-
-(2-hydroxy-3-diethylaminopropoxy)piperidine; (f)
N,N'-dimethyl-N,N'-bis-[-
3-(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yloxy)-2-hydroxy
propyl]hexamethylenediamine; (g)
N,N,N',N'-tetramethyl-N,N'-bis-[3-(1-oxy-
l-2,2,6,6-tetramethylpiperidin-4-yloxy)-2-hydroxypropyl]-hexamethylenediam-
monium dibromide; (h)
1-oxyl-2,2,6,6-tetramethyl-4-[2-hydroxy-3-(N,N-dimet-
hyl-N-propylammonium)-propoxy]piperidine chloride; (i) sodium
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yloxyacetate; or (j)
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yloxyacetic acid, choline
ester.
44. A hydroxylamine salt of formula A*, D*, X*, Y*, Z*, AA*, BB*,
CC* or DD* 8wherein R is hydrogen, in formula A* n is 1, R.sub.1 is
hydrogen or alkyl of 1 to 4 carbon atoms, in formula D* y is 1,
R.sub.10 is hydrogen or methyl, preferably hydrogen, R.sub.12 is
alkyl of 1 to 4 carbon atoms, preferably methyl, X is phosphate,
phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide,
bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate,
benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate,
fumarate, maleate, itaconate, glycolate, malate, mandelate,
tiglate, gluconate, ascorbate, polymethacrylate, a carboxylate of
nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentamethylenephosphonate, an
alkylsulfonate or an arylsulfonate, where the total charge of
cations h is equal to the total charge of anions j, wherein in
formulas X* to DD* n is 2 to 3, G.sub.1 is hydrogen, methyl, ethyl,
butyl or benzyl, m is 1 to 4, x is 1 to 4, when x is 1, R.sub.1 and
R.sub.2 are independently alkyl of 1 to 18 carbon atoms, said alkyl
interrupted by one to five oxygen atoms, said alkyl substituted by
1 to 5 hydroxyl groups or said alkyl both interrupted by said
oxygen atoms and substituted by said hydroxyl groups; cycloalkyl of
5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to
10 carbon atoms or said aryl substituted by one to three alkyl of 1
to 8 carbon atoms, or R.sub.1 is also hydrogen, or R.sub.1 and
R.sub.2 are together tetramethylene, pentamethylene, hexamethylene
or 3-oxapentamethylene, when x is 2, R.sub.1 is hydrogen, alkyl of
1 to 8 carbon atoms, said alkyl interrupted by one or two oxygen
atoms, said alkyl substituted by a hydroxyl group, or said alkyl
both interrupted by one or two oxygen atoms and substituted by a
hydroxyl group, R.sub.2 is alkylene of 2 to 18 carbon atoms, said
alkylene interrupted by one to five oxygen atoms, said alkylene
substituted by 1 to 5 hydroxyl groups or said alkylene both
interrupted by said oxygen atoms and substituted by said hydroxyl
groups; o-, m- or p-phenylene or said phenylene substituted by one
or two alkyl of 1 to 4 carbon atoms, or R.sub.2 is
--(CH.sub.2).sub.kO[(CH.sub.2).sub.kO].sub.h(CH.sub.2).sub.k--
where k is 2 to 4 and h is 1 to 40, or R.sub.1 and R.sub.2 together
with the two N atoms to which they are attached are
piperazin-1,4-diyl, when x is 3, R.sub.1 is hydrogen, R.sub.2 is
alkylene of 4 to 8 carbon atoms interrupted by one nitrogen atom,
when x is 4, R.sub.1 is hydrogen, R.sub.2 is alkylene of 6 to 12
carbon atoms interrupted by two nitrogen atoms, R.sub.3 is
hydrogen, alkyl of 1 to 8 carbon atoms, said alkyl interrupted by
one or two oxygen atoms, said alkyl substituted by a hydroxyl
group, or both interrupted by one or two oxygen atoms and
substituted by a hydroxyl group, p is 2 or 3, and Q is an alkali
metal salt, ammonium or N.sup.+(G.sub.1).sub.4, in formula DD and
DD* m is 2 or 3, when m is 2, G is
--(CH.sub.2CHR--O).sub.rCH.sub.2CHR--, where r is 0 to 3, and R is
hydrogen or methyl, and when m is 3, G is glyceryl, with the
proviso that in formula A* when R.sub.1 is hydrogen, X is not
chloride or bisulfate, and when in formula D* when R.sub.10 is
hydrogen and R.sub.12 is methyl, X is not chloride or
bisulfate.
45. A hydroxylamine salt according to claim 44 wherein X is
chloride, bisulfate, ascorbate, bisulfite, sulfate, nitrate,
acetate, citrate or a carboxylate of ethylenediaminetetraacetic
acid or diethylenetriaminepenta- acetic acid.
46. A hydroxylamine salt according to claim 45 wherein X is
bisulfate or citrate.
47. A hydroxylamine salt according to claim 44 which is (a)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate; (b)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) citrate;
(c) tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate; (d) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
DTPA; (e) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
DTPA; (f) tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
DTPA; (g)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) DTPA;
(h) pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
DTPA; (i) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium EDTA;
(j) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) EDTA;
(k) tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) EDTA;
(l) tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
EDTA; (m) 1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium citrate;
(n) bis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) citrate;
(o) tris(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) citrate;
(p) 1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium DTPA; (q)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) DTPA; (r)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) DTPA; (s)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) DTPA;
(t) pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium)
DTPA; (u) 1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium EDTA;
(v) bis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) EDTA; (w)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) EDTA; (x)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium) EDTA;
(y) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium citrate;
(z) bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
citrate; (aa)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
citrate; (bb) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium
DTPA; (cc)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) DTPA;
(dd) tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
DTPA; (ee)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
DTPA; (ff)
pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
DTPA; (gg) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium
EDTA; (hh)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) EDTA;
(ii) tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
EDTA; (jj)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) EDTA;
(kk) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium citrate;
(ll) bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
citrate; (mm)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) citrate;
(nn) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium DTPA; (oo)
bis((1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) DTPA;
(pp) tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
DTPA; (qq)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) DTPA;
(rr) pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
DTPA; (ss) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium
EDTA; (tt) bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
EDTA; (uu)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) EDTA or
(vv) tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
EDTA.
48. A process for preventing the loss of brightness and for
enhancing resistance to yellowing of chemimechanical or
thermomechanical pulp or paper which still contains lignin, which
comprises treating said pulp or paper with an effective stabilizing
amount of a compound of formula I or II according to claim 1.
49. A process according to claim 46 where in the compound of
formula I, E ix oxyl or hydroxyl.
50. A process according to claim 49 wherein E is hydroxyl.
51. A process for preventing the loss of brightness and for
enhancing resistance to yellowing of chemimechanical or
thermomechanical pulp or paper which still contains lignin, which
comprises treating said pulp or paper with an effective stabilizing
amount of a compound of formula A to EE or A* to EE* according to
claim 10.
52. A process according to claim 51 where in the compound of
formula A to EE, E is oxyl or hydroxyl.
53. A process according to claim 52 wherein E is hydroxyl.
Description
[0001] This application claims the benefit under 35 USC 119(e) of
U.S. Provisional Application Nos. 60/053,489 and 60/054,968, filed
on Jul. 23, 1997 and on Aug. 7, 1997 respectively.
[0002] The instant invention pertains to a method for preventing
the loss of brightness and for enhancing resistance to yellowing in
pulp or paper which still contains lignin by the addition of
nitroxides, hydroxylamines or their salts and other coadditives.
The instant invention also pertains to novel compounds which are
selected derivatives of 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-ol
or which are their hydroxylamine salts.
BACKGROUND OF THE INVENTION
[0003] High-yield and ultra-high yield wood pulps undergo rapid
light-induced discoloration, particularly when they are exposed to
near ultraviolet light (wave lengths 300-400 nm) in indoor
fluorescent light and daylight. This characteristic restricts their
use to short-life, low-value paper products. High-yield and
ultra-high yield wood pulps can be bleached to a high level of
whiteness. If this whiteness could be stabilized against
discoloration, these bleached high-yield pulps could displace
significant amounts of more expensive fully-bleached, low-yield
chemical pulps.
[0004] This discoloration is ascribed to the substantial lignin
content of high-yield pulps totaling about 20-45% by mass. Phenoxy
radicals are the key intermediates in the reaction mechanism.
Several light-induced reactions have been proposed to account for
their formation such as abstraction of a hydrogen atom from
phenolic groups, cleavage of the aryl ether bond of phenacyl aryl
ether groups, or breakdown of ketyl radicals formed from saturated
aryl-glycerol .beta.-aryl ether structures in lignin. The phenoxy
radicals are oxidized by other oxygen-centered radicals (alkoxy,
peroxy, hydroxy and perhydroxy) to form yellow chromophores. (C.
Heitner in "Photochemistry of Lignocellulosic Materials", C.
Heitner, J. C. Scaiano, eds,: ACS Sym. Ser. 531, 1-25 (1993).)
[0005] I. E. Arakin et al., Khymiya drevesiny (Chemistry of Wood),
1982, No. 2, 114 and A. D. Sergeev et al., ibid, 1984, No. 5, 20
disclosed that the use of iminoxyl radicals such as TEMPO
(1-oxyl-2,2,6,6-tetramethylpip- eridine) is useful in the
delignification of wood using the one-stage oxygen-soda (alkaline)
process, but made no mention or suggestion of any activity provided
by TEMPO on preventing light-induced discoloration of paper or pulp
made from such treated wood.
[0006] EP 717,143 and WO 97/36041 describe a multicomponent system
for changing, reducing or bleaching lignin and lignin-containing
materials which comprise a oxidation catalyst, and a N-hydroxyl
mediator compound such as a N-hydroxyphthalimide or a
dialkylhydroxylamine. These references are aimed at the
delignification of wood. There is no mention or suggestion of any
activity provided by the N-hydroxyl compounds in preventing the
light-induced discoloration of paper or pulp made from such treated
wood.
[0007] V. I. Khodyrev et al., Vysokomol soyed, A29, No. 3, 616
(1987) [Polymer Sci. U.S.S.R., 29, No. 3, 688 (1987)] show that the
photoinitiated oxidation by oxygen causes weathering of cellulosic
textile materials such as flax or cotton. The UV absorbers offer no
protection, and are actually detrimental. The authors noted that
the stable nitroxyl radical
1-oxyl-2,2,6,6-tetra-methyl-4-hydroxypiperidine interacts with
alkyl radicals in the cellulose to afford its salubrious
stabilizing activity. There is no suggestion by the authors that
this stabilizing activity could be applied successfully in
lignin-containing pulp and/or paper made therefrom.
[0008] M-K. Syker et al., J. Assn. Paper Pulp Tech, 29, 135 (1990)
show that selected metal salts such as magnesium sulfate and lower
alkanoic acids inhibit color reversion in bleached pulp.
[0009] P. Fornier de Violet et al., Cellulose Chem. Tech., 24, 225
(1990) show that the use of UV absorbers and hydrogen donor agents
such as thiols, ascorbic acid, etc. help prevent the photoinduced
discoloration of hydrogen peroxide bleached wood pulp, but that
chain breakers such as hindered phenols and hindered amines (having
>N--H or >N--CH.sub.2-- moieties) had no or even a
detrimental effect on preventing photoinduced discoloration.
[0010] R. Agnemo et al., Holzforschung (1991), 45 (Suppl), 101,
confirmed that free hydroxyl radicals plus lignin lead to
undesirable photoyellowing in pulp and paper.
[0011] S. Omori et al., J. Assn. Paper Pulp Tech, 48, 1388 (1993)
describes the effect of antioxidants and UV absorbers on light
reversion and concludes that the combination of an antioxidant and
UV absorber prevents color reversion and has a synergistic effect
in that activity.
[0012] M. Paulsson et al., Nordic Pulp Pap. Res. J., (1995), 10
(1), 62-67, show that efficient photostabilization of unbleached
paper or hydrogen peroxide bleached TMP pulp can be achieved by
acetylation.
[0013] There have been a number of different approaches proposed to
inhibiting the yellowing of mechanical pulps. These include:
radical scavengers and antioxidants; UV screens; elimination of
chromophores after their formation; chemical modification of lignin
by alkylation or acetylation; polymeric inhibitors; and two types
of coadditives used in combination Z-H. Wu et al., Holzforschung,
48, (1994), 400 discuss the use of radical scavengers like
phenyl-N-tert-butylnitrone to reduce the formation of chromophores
during mechanical pulping and give a more light-stable pulp.
[0014] C. Heitner, "Chemistry of Brightness Reversion and It
Control, Chapter 5", in Pulp Bleaching-Principles and Practice, C.
W. Dence, D. W. Reeve, eds., TAPPI Press, Atlanta, 1996, pp
183-211, summarizes the state of the art in the thermal and
light-induced yellowing of lignin-containing pulps such as
thermomechanical (TMP) and chemithermomechical (CTMP) pulps,
showing the seriousness of these undesirable effects discusses
generally the then current prior art methods used to attack this
problem. These include bleaching, the use of phosphites, UV
absorbers, polyalkylene glycols and free radical scavengers such as
ascorbic acid, thiols, thioethers, dienes and aliphatic aldehydes
and chelating agents such as ethylene-diaminetetraace- tic acid
(EDTA). The author concluded that, although much progress had been
made, much still remains to be done before a successful and
practical solution to this loss of brightness and undesirable
yellowing of lignin-containing pulp and/or paper is found.
[0015] The instant invention described in detail below provides
such a solution where the use of selected hindered amine
nitroxides, hindered amine hydroxylamines or their salts in
combination with selected UV absorbers and metal chelating agents
is seen to prevent loss of brightness and to enhance resistance to
yellowing in pulp or paper still containing lignin.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The addition of hydroxylamines or nitroxide free radicals to
high-yield pulp paper either alone or in combinations with UV
absorbers, metal chelating agents, fluorescent whitening agents
and/or stabilizing polymers effectively achieves light and thermal
stability which is similar to that found in papers made from kraft
pulps.
[0017] Hydroxylamines and nitroxides are known to be efficient free
radical traps and may limit the production of o-quinones; UV
absorbers limit photochemistry in the underlying substrate to which
they are applied, and ultimately reduce the production of free
radicals. UV absorbers and nitroxides are each effective at
stemming some of the free radical chemistry leading to paper
yellowing when used singly. However, when they are used together,
hydroxylamines or nitroxides and UV absorbers can effectively stop
photochemical yellowing of lignin containing papers which are
exposed 24 hours a day under ambient fluorecent lighting conditions
for at least 200 days. Both of these types of stabilizers show
enhanced inhibiting activity when combined with a metal chelating
agent such diethylenetriaminepentaacetic acid, or polymeric
inhibitors such as polyethylene glycol.
[0018] More particularly the instant invention pertains to a
composition having reduced loss of brightness and enhanced
resistance to yellowing which comprises
[0019] (a) a pulp or paper which still contains lignin, and
[0020] (b) an effective stabilizing amount of a hindered amine
compound of formula I or II 1
[0021] where
[0022] G.sub.1 and G.sub.2 are independently alkyl of 1 to 4 carbon
atoms or are together pentamethylene,
[0023] Z.sub.1 and Z.sub.2 are each methyl, or Z.sub.1 and Z.sub.2
together form a linking moiety which may additionally be
substituted by an ester, ether, hydroxy, oxo, cyanohydrin, amide,
amino, carboxy or urethane group,
[0024] E is oxyl, hydroxyl, hydrogen, alkyl, alkyl substituted by
hydroxyl, oxo or carboxy or interrupted by oxygen or carboxy;
alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, alkoxy,
alkoxy substituted by hydroxyl, oxo or carboxy or interrupted by
oxygen or carboxy, cycloalkoxy, alkenyloxy, cycloalkenyloxy,
aralkyl, aralkoxy, acyl, R(C.dbd.O)O--, RO(C.dbd.O)O--,
RN(C.dbd.O)O-- or chloro, where R is an aliphatic or aromatic
moiety,
[0025] X is an inorganic or organic anion, such as phosphate,
phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide,
bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate,
benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate,
fumarate, maleate, itaconate, glycolate, gluconate, malate,
mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of
nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentam- ethylenephosphonate, an
alkylsulfonate or an arylsulfonate, and
[0026] where the total charge of cations h is equal to the total
charge of anions j, and with the proviso that the compound of
formula I is not bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate or
the polycondensation product of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid.
[0027] Preferably, the compositions are those where in the compound
of component (b), E is oxyl, hydroxyl, alkenyloxy, aralkoxy,
alkyloxy or alkyl substituted by oxo or interrupted by carboxy,
especially wherein E is oxyl or hydroxy; most especially wherein E
is hydroxy.
[0028] Most preferably, X is chloride, bisulfite, bisulfate,
sulfate, phosphate, nitrate, ascorbate, acetate, citrate or
carboxylate of ethylenediaminetetraacetic acid or of
diethylenetriaminepentaacetic acid; most especially wherein X is
bisulfate or citrate.
[0029] Preferably, the hindered amine compounds of component (b)
are those of formulas A to EE and A* to EE* 2
[0030] wherein
[0031] E is oxyl, hydroxyl, hydrogen, alkyl of 1 to 18 carbon
atoms, alkyl of 2 to 12 carbon atoms substituted by one to three
hydroxyl or said alkyl interrupted by one to four oxygen atoms, or
said alkyl both substituted by said hydroxyl groups and interrupted
by said oxygen atoms, alkenyl of 2 to 18 carbon atoms, alkynyl of 2
to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,
cycloalkenyl of 5 to 12 carbon atoms, bicycloalkyl of 6 to 10
carbon atoms, alkoxy of 1 to 18 carbon atoms, alkoxy of 2 to 12
carbon atoms substituted by one to three hydroxyl groups or said
alkoxy interrupted by one to four oxygen atoms or said alkoxy
substituted by --COOZ where Z is hydrogen or alkyl of 1 to 4 carbon
atoms, cycloalkoxy of 5 to 12 carbon atoms, cycloalkenyloxy of 5 to
12 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, aralkyl of 7
to 15 carbon atoms, aralkoxy of 7 to 15 carbon atoms, alkanoyl of 2
to 12 carbon atoms, alkenoyl of 2 to 12 carbon atoms, benzoyl, or
R(C.dbd.O)O--, RO(C.dbd.O)O--, RN(C.dbd.O)O--, where R is alkyl of
1 to 6 carbon atoms or phenyl,
[0032] R is hydrogen or methyl,
[0033] in formula A and A*,
[0034] n is 1 or 2,
[0035] when n is 1,
[0036] R.sub.1 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl
of 2-18 carbon atoms, propargyl, glycidyl, alkyl of 2 to 50 carbon
atoms interrupted by one to twenty oxygen atoms, said alkyl
substituted by one to ten hydroxyl groups or both interrupted by
said oxygen atoms and substituted by said hydroxyl groups, or
[0037] R.sub.1 is alkyl of 1 to 4 carbon atoms substituted by a
carboxy group or by --COOZ where Z is hydrogen, alkyl of 1 to 4
carbon atoms or phenyl, or where Z is said alkyl substituted by
--(COO.sup.-).sub.nM.sup.- n+ where n is 1-3 and M is a metal ion
from the 1st, 2nd or 3rd group of the periodic table or is Zn, Cu,
Ni or Co, or M is a group N.sup.n+(R.sub.2).sub.4 where R.sub.2 is
alkyl of 1 to 8 carbon atoms or benzyl,
[0038] when n is 2,
[0039] R.sub.1 is alkylene of 1 to 12 carbon atoms, alkenylene of 4
to 12 carbon atoms, xylylene or alkylene of 1 to 50 carbon atoms
interrupted by one to twenty oxygen atoms, substituted by one to
ten hydroxyl groups or both interrupted by said oxygen atoms and
substituted by said hydroxyl groups,
[0040] in formula B and B*,
[0041] m is 1 to 4,
[0042] when m is 1,
[0043] R.sub.2 is alkyl of 1 to 18 carbon atoms, alkyl of 3 to 18
carbon atoms interrupted by --COO--, or R.sub.2 is
--CH.sub.2(OCH.sub.2CH.sub.2)- .sub.nOCH.sub.3 where n is 1 to 12,
or
[0044] R.sub.2 is cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to
12 carbon atoms, or said aryl substituted by one to four alkyl
groups of 1 to 4 carbon atoms, or
[0045] R.sub.2 is --NHR.sub.3 where R.sub.3 is alkyl of 1 to 18
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 12
carbon atoms, or said aryl substituted by one to four alkyl of 1 to
4 carbon atoms, or
[0046] R.sub.2 is --NHR.sub.3 where R.sub.3 is alkyl of 1 to 18
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 12
carbon atoms, or said aryl substituted by one to four alkyl of 1 to
4 carbon atoms, or
[0047] R.sub.2 is --N(R.sub.3).sub.2 where R.sub.3 is as defined
above,
[0048] when m is 2,
[0049] R.sub.2 is alkylene of 1 to 12 carbon atoms, alkenylene of 4
to 12 carbon atoms, xylylene, alkylene of 2 to 12 carbon atoms
interrupted by --COO--, or R.sub.2 is
--CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.2-- where n is 1 to 12,
or
[0050] R.sub.2 is cycloalkylene of 5 to 12 carbon atoms, aralkylene
of 7 to 15 carbon atoms or arylene of 6 to 12 carbon atoms, or
[0051] R.sub.2 is --NHR.sub.4NH-- where R.sub.4 is alkylene of 2 to
18 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, aralkylene
of 8 to 15 carbon atoms or arylene of 6 to 12 carbon atoms, or
[0052] R.sub.2 is --N(R.sub.3)R.sub.4N(R.sub.3)-- where R.sub.3 and
R.sub.4 are as defined above, or
[0053] R.sub.2 is --CO-- or --NH--CO--NH--,
[0054] when m is 3,
[0055] R.sub.2 is alkanetriyl of 3 to 8 carbon atoms or
benzenetriyl, or
[0056] when m is 4,
[0057] R.sub.2 is alkanetetrayl of 5 to 8 carbon atoms or
benzenetetrayl,
[0058] in formula C and C*,
[0059] R.sub.10 is hydrogen, alkyl of 1 to 18 carbon atoms,
cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15 carbon
atoms, alkanoyl of 2 to 18 carbon atoms, alkenoyl of 3 to 5 carbon
atoms or benzoyl,
[0060] x is 1 or 2,
[0061] when x is 1,
[0062] R.sub.11 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl
of 2 to 18 carbon atoms, propargyl, glycidyl, alkyl of 2 to 50
carbon atoms interrupted by one to twenty oxygen atoms, said alkyl
substituted by one to ten hydroxyl groups or both interrupted by
said oxygen atoms and substituted by said hydroxyl groups, or
[0063] R.sub.11 is alkyl of 1 to 4 carbon atoms substituted by a
carboxy group or by --COOZ where Z is hydrogen, alkyl of 1 to 4
carbon atoms or phenyl, or where Z is said alkyl substituted by
--(COO.sup.-).sub.nM.sup.- n+ where n is 1-3 and M is a metal ion
from the 1st, 2nd or 3rd group of the periodic table or is Zn, Cu,
Ni or Co, or M is a group N.sup.n+(R.sub.2).sub.4 where R.sub.2 is
hydrogen, alkyl of 1 to 8 carbon atoms or benzyl, or
[0064] when x is 2,
[0065] R.sub.11 is alkylene of 1 to 12 carbon atoms, alkenylene of
4 to 12 carbon atoms, xylylene or alkylene of 1 to 50 carbon atoms
interrupted by one to twenty oxygen atoms, substituted by one to
ten hydroxyl groups or both interrupted by said oxygen atoms and
substituted by said hydroxyl groups,
[0066] in formula D and D*,
[0067] R.sub.10 is as defined above,
[0068] y is 1 to 4, and
[0069] R.sub.12 is defined as R.sub.2 above,
[0070] in formula E and E*,
[0071] k is 1 or 2,
[0072] when k is 1,
[0073] R.sub.20 and R.sub.21 are independently alkyl of 1 to 12
carbon atoms, alkenyl of 2 to 12 carbon atoms or aralkyl of 7 to 15
carbon atoms, or R.sub.20 is also hydrogen, or
[0074] R.sub.20 and R.sub.21 together are alkylene of 2 to 8 carbon
atoms or said alkylene substituted by hydroxyl, or are
acyloxy-alkylene of 4 to 22 carbon atoms, or
[0075] when k is 2,
[0076] R.sub.20 and R.sub.21 are together
(--CH.sub.2).sub.2C(CH.sub.2--).- sub.2,
[0077] in formula F and F*,
[0078] R.sub.30 is hydrogen, alkyl of 1 to 18 carbon atoms, benzyl,
glycidyl, or alkoxyalkyl of 2 to 6 carbon atoms,
[0079] g is 1 or 2,
[0080] when g is 1, R.sub.31 is defined as R.sub.1 above when n is
1,
[0081] when g is 2, R.sub.31 is defined as R.sub.1 above when n is
2,
[0082] in formula G and G*,
[0083] Q.sub.1 is --NR.sub.41-- or --O--,
[0084] E.sub.1 is alkylene of 1 to 3 carbon atoms, or E.sub.1 is
--CH.sub.2--CH(R.sub.42)--O-- where R.sub.42 is hydrogen, methyl or
phenyl, or E.sub.1 is --(CH.sub.2).sub.3--NH-- or E.sub.1 is a
direct bond,
[0085] R.sub.40 is hydrogen or alkyl of 1 to 18 carbon atoms,
[0086] R.sub.41 is hydrogen, alkyl of 1 to 18 carbon atoms,
cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15 carbon
atoms, aryl of 6 to 10 carbon atoms, or R.sub.41 is
--CH.sub.2--CH(R.sub.42) --OH where R.sub.42 is as defined
above,
[0087] in formula H and H*,
[0088] p is 1 or2,
[0089] T.sub.4 is as defined for R.sub.11 when x is 1 or 2,
[0090] M and Y are independently methylene or carbonyl, preferably
M is methylene and Y is carbonyl,
[0091] in formula I and I*,
[0092] this formula denotes a recurring structural unit of a
polymer where T.sub.1 is ethylene or 1,2-propylene or is the
repeating structural unit derived from an alpha-olefin copolymer
with an alkyl acrylate or methacrylate, and where
[0093] q is 2 to 100,
[0094] Q.sub.1 is --N(R.sub.41)-- or --O-- where R.sub.41 is as
defined above,
[0095] in formula J and J*,
[0096] r is 1 or 2,
[0097] T.sub.7 is as defined for R.sub.1 when n is 1 or 2 in
formula A,
[0098] preferably T.sub.7 is octamethylene when r is 2,
[0099] in formula L and L*,
[0100] u is 1 or 2,
[0101] T.sub.13 is as defined for R.sub.1 when n is 1 or 2 in
formula A, with the proviso that T.sub.13 is not hydrogen when u is
1,
[0102] in formula M and M*,
[0103] E.sub.1 and E.sub.2, being different, each are --CO-- or
--N(E.sub.5)-- where E.sub.5 is hydrogen, alkyl of 1 to 12 carbon
atoms or alkoxycarbonylalkyl of 4 to 22 carbon atoms, preferably
E.sub.1 is --CO-- and E.sub.2 is --N(E.sub.5)--,
[0104] E.sub.3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl,
naphthyl, said phenyl or said naphthyl substituted by chlorine or
by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon
atoms, or said phenylalkyl substituted by alkyl of 1 to 4 carbon
atoms,
[0105] E.sub.4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl,
naphthyl or phenylalkyl of 7 to 12 carbon atoms, or
[0106] E.sub.3 and E.sub.4 together are polymethylene of 4 to 17
carbon atoms, or said polymethylene substituted by one to four
alkyl of 1 to 4 carbon atoms, preferably methyl,
[0107] in formula N,
[0108] R.sub.1 is as defined for R.sub.1 in formula A when n is
1,
[0109] G.sub.3 is a direct bond, alkylene of 1 to 12 carbon atoms,
phenylene or --NH--G.sub.1--NH-- where G.sub.1 is alkylene of 1 to
12 carbon atoms,
[0110] in formula O and O*,
[0111] R.sub.10 is as defined for R.sub.10 in formula C,
[0112] in formula P and P*,
[0113] E.sub.6 is an aliphtic or aromatic tetravalent radical,
preferably neopentanetetrayl or benzenetetrayl,
[0114] in formula T and T*,
[0115] R.sub.51 is hydrogen, alkyl of 1 to 18 carbon atoms,
cycloalkyl of 5 to 12 carbon atoms, or aryl of 6 to 10 carbon
atoms,
[0116] R.sub.52 is hydrogen or alkyl of 1 to 18 carbon atoms,
or
[0117] R.sub.51 and R.sub.52 together of alkylene of 4 to 8 carbon
atoms,
[0118] f is 1 or 2,
[0119] when f is 1,
[0120] R.sub.50 is as defined for R.sub.11 in formula C when x is
1, or R.sub.50 is --(CH.sub.2).sub.zCOOR.sub.54 where z is 1 to 4
and R.sub.54 is hydrogen or alkyl of 1 to 18 carbon atoms, or
R.sub.54 is a metal ion from the 1st, 2nd or 3rd group of the
periodic table or a group --N(R.sub.55).sub.4 where R.sub.55 is
hydrogen, alkyl of 1 to 12 carbon atoms or benzyl,
[0121] when f is 2, R.sub.50 is as defined for R.sub.11 in formula
C when x is 2,
[0122] in formula U and U*,
[0123] R.sub.53, R.sub.54, R.sub.55 and R.sub.56 are independently
alkyl of 1 to 4 carbon atoms or are together pentamethylene.
[0124] in formula V and V*,
[0125] R.sub.57, R.sub.58, R.sub.59 and R.sub.60 are independently
alkyl of 1 to 4 carbon atoms or are together pentamethylene.
[0126] in formula W and W*,
[0127] R.sub.61, R.sub.62, R.sub.63 and R.sub.64 are independently
alkyl of 1 to 4 carbon atoms or are together pentamethylene,
[0128] R.sub.65 is alkyl of 1 to 5 carbon atoms,
[0129] M is hydrogen or oxygen,
[0130] wherein in formulas X to CC and X* to CC*
[0131] n is 2 to 3,
[0132] G.sub.1 is hydrogen, methyl, ethyl, butyl or benzyl,
[0133] m is 1 to 4,
[0134] x is 1 to 4,
[0135] when x is 1, R.sub.1 and R.sub.2 are independently alkyl of
1 to 18 carbon atoms, said alkyl interrupted by one to five oxygen
atoms, said alkyl substituted by 1 to 5 hydroxyl groups or said
alkyl both interrupted by said oxygen atoms and substituted by said
hydroxyl groups; cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7
to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl
substituted by one to three alkyl of 1 to 8 carbon atoms, or
R.sub.1 is also hydrogen,
[0136] or R.sub.1 and R.sub.2 are together tetramethylene,
pentamethylene, hexamethylene or 3-oxapentamethylene,
[0137] when x is 2,
[0138] R.sub.1 is hydrogen, alkyl of 1 to 8 carbon atoms, said
alkyl interrupted by one or two oxygen atoms, said alkyl
substituted by a hydroxyl group, or said alkyl both interrupted by
one or two oxygen atoms and substituted by a hydroxyl group,
[0139] R.sub.2 is alkylene of 2 to 18 carbon atoms, said alkylene
interrupted by one to five oxygen atoms, said alkylene substituted
by 1 to 5 hydroxyl groups or said alkylene both interrupted by said
oxygen atoms and substituted by said hydroxyl groups; o-, m- or
p-phenylene or said phenylene substituted by one or two alkyl of 1
to 4 carbon atoms, or
[0140] R.sub.2 is
--(CH.sub.2).sub.kO[(CH.sub.2).sub.kO].sub.h(CH.sub.2).s- ub.k--
where k is 2 to 4 and h is 1 to 40, or
[0141] R.sub.1 and R.sub.2 together with the two N atoms to which
they are attached are piperazin-1,4-diyl,
[0142] when x is 3,
[0143] R.sub.1 is hydrogen,
[0144] R.sub.2 is alkylene of 4 to 8 carbon atoms interrupted by
one nitrogen atom,
[0145] when x is 4,
[0146] R.sub.1 is hydrogen,
[0147] R.sub.2 is alkylene of 6 to 12 carbon atoms interrupted by
two nitrogen atoms,
[0148] R.sub.3 is hydrogen, alkyl of 1 to 8 carbon atoms, said
alkyl interrupted by one or two oxygen atoms, said alkyl
substituted by a hydroxyl group, or both interrupted by one or two
oxygen atoms and substituted by a hydroxyl group,
[0149] p is 2 or 3, and
[0150] Q is an alkali metal salt, ammonium or
N.sup.+(G.sub.1).sub.4,
[0151] in formula DD and DD*
[0152] m is 2or 3,
[0153] when m is 2, G is --(CH.sub.2CHR--O).sub.rCH.sub.2CHR--,
where r is 0 to 3, and R is hydrogen or methyl, and
[0154] when m is 3, G is glyceryl,
[0155] in formula EE and EE*
[0156] G.sub.2 is --CN, --CONH.sub.2 or --COOG.sub.3 where G.sub.3
is hydrogen, alkyl of 1 to 18 carbon atoms or phenyl,
[0157] X is an inorganic or organic anion, such as phosphate,
phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide,
bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate,
benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate,
fumarate, maleate, itaconate, glycolate, gluconate, malate,
mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of
nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentam- ethylenephosphonate, an
alkylsulfonate or an arylsulfonate, and where the total charge of
cations h is equal to the total charge of anions j, and with the
proviso that bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate or the
polycondensation product of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-- hydroxypiperidine and
succinic acid are excluded.
[0158] Most preferably, the compounds of component (b) are those of
formulas A, A*, B, B*, C, C*, D, D*, Q, Q*, R, R*, S, S*, X, X*, Y,
Y*, Z and Z*,
[0159] where E is oxyl or hydroxyl,
[0160] R is hydrogen,
[0161] in formula A and A*
[0162] n is 1 or 2,
[0163] when n is 1,
[0164] R.sub.1 is hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl
of 2-6 carbon atoms, propargyl, glycidyl, alkyl of 2 to 20 carbon
atoms interrupted by one to ten oxygen atoms, said alkyl
substituted by one to five hydroxyl groups or both interrupted by
said oxygen atoms and substituted by said hydroxyl groups, or
[0165] R.sub.1 is alkyl of 1 to 4 carbon atoms substituted by a
carboxy group or by --COOZ where Z is hydrogen or alkyl of 1 to 4
carbon atoms,
[0166] when n is 2,
[0167] R.sub.1 is alkylene of 1 to 8 carbon atoms, alkenylene of 4
to 8 carbon atoms, alkylene of 1 to 20 carbon atoms interrupted by
one to ten oxygen atoms, substituted by one to five hydroxyl groups
or both interrupted by said oxygen atoms and substituted by said
hydroxyl groups,
[0168] in formula B and B*
[0169] m is 1 or 2
[0170] when m is 1,
[0171] R.sub.2 is alkyl of 1 to 4 carbon atoms or R.sub.2 is
CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.3 where n is 1 to 12,
or
[0172] R.sub.2 is phenyl, or said phenyl substituted by one to
three methyl groups,
[0173] R.sub.2 is --NHR.sub.3 where R.sub.3 is alkyl of 1 to 4
carbon atoms or phenyl, or said phenyl substituted by one or two
methyl groups,
[0174] when m is 2,
[0175] R.sub.2 is alkylene of 1 to 8 carbon atoms, alkenylene of 4
to 8 carbon atoms, or R.sub.2 is
--CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.2-- - where n is 1 to
12,
[0176] R.sub.2 is NHR.sub.4NH where R.sub.4 is of 2 to 6 carbon
atoms, aralkylene of 8 to 15 carbon atoms or arylene of 6 to 12
carbon atoms,
[0177] R.sub.2 is --CO-- or --NHCONH,
[0178] in formula C and C*,
[0179] R.sub.10 is hydrogen or, alkanoyl of 1 to 3 carbon
atoms,
[0180] x is 1 or 2,
[0181] when x is 1,
[0182] R.sub.11 is hydrogen, alkyl of 1 to 6 carbon atoms or
glycidyl,
[0183] R.sub.11, is alkyl of 1 to 4 carbon atoms substituted by a
carboxy group or by COOZ where Z is hydrogen or alkyl of 1 to 4
carbon atoms,
[0184] when x is 2,
[0185] R.sub.11 is alkylene of 1 to 6 carbon atoms,
[0186] in formula D and D*,
[0187] R.sub.10 is hydrogen,
[0188] y is 1 or 2,
[0189] R.sub.12 is defined as R.sub.2 above,
[0190] in formula Y, Y*, Z and Z*,
[0191] x is 1 or 2,
[0192] when x is 1,
[0193] R.sub.1 and R.sub.2 are independently alkyl of 1 to 4 carbon
atoms,
[0194] or R.sub.1 and R.sub.2 are together tetramethylene, or
pentamethylene,
[0195] R.sub.2 is hydrogen or alkyl of 1 to 4 carbon atoms, said
alkyl group substituted by a hydroxyl group,
[0196] when x is 2,
[0197] R.sub.1 is hydrogen, alkyl of 1 to 4 carbon atoms, said
alkyl substituted by a hydroxyl group,
[0198] R.sub.2 is alkylene of 2 to 6 carbon atoms,
[0199] R.sub.3 is as defined above.
[0200] Especially preferred, the compounds of component (b) are
those of formulas A, A*, B, B*, C, C*, D, D*, Q, Q*, R and R*,
[0201] where E is oxyl or hydroxyl,
[0202] R is hydrogen,
[0203] in formula A and A*,
[0204] h is 1,
[0205] R.sub.1 is hydrogen, alkyl of 1 to 4 carbon atoms, glycidyl,
alkyl of 2 to 4 carbon atoms interrupted by one or two oxygen
atoms, said alkyl substituted by one or two hydroxyl groups or both
interrupted by said oxygen atoms and substituted by said hydroxyl
groups, or
[0206] R.sub.1 is alkyl of 1 to 4 carbon atoms substituted by
--COOZ where Z is hydrogen or alkyl of 1 to 4 carbon atoms,
[0207] in formula B and B*,
[0208] m is 1 or 2,
[0209] R.sub.2 is alkyl of 1 to 4 carbon atoms or R.sub.2 is
CH.sub.2(OCH.sub.2CH.sub.2).sub.nOCH.sub.3 where n is 1 to 4,
[0210] when m is 2,
[0211] R.sub.2 is alkylene of 1 to 8 carbon atoms,
[0212] in formula C and C*,
[0213] R.sub.10 is hydrogen or alkanoyl of 1 or 2 carbon atoms,
[0214] x is 1 or 2,
[0215] when x is 1,
[0216] R.sub.11 is hydrogen, alkyl of 1 to 4 carbon atoms or
glycidyl,
[0217] R.sub.11 is alkyl of 1 to 4 carbon atoms substituted by COOZ
where Z is hydrogen or alkyl of 1 to 4 carbon atoms,
[0218] when x is 2,
[0219] R.sub.11 is alkylene of 1 to 6 carbon atoms,
[0220] in formula D and D*,
[0221] R.sub.10 is hydrogen,
[0222] y is 1 or 2,
[0223] R.sub.12 is defined as R.sub.2 above.
[0224] More particularly, the hindered amine compound is
[0225] (a) bis(1-oxyl-2,2-6-6-tetramethylpiperidin-4-yl)
sebacate;
[0226] (b) bis(1-hydroxy-2,2-6-6-tetramethylpiperidin-4-yl)
sebacate;
[0227] (c) 1-hydroxy-2,2-6-6-tetramethyl-4-acetoxypiperidinium
citrate;
[0228] (d) 1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine;
[0229] (e) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidine;
[0230] (f) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium
bisulfate;
[0231] (g) 1-oxyl-2,2,6,6-tetramethyl-4-oxo-piperidine;
[0232] (h) 1-hydroxy -2,2,6,6-tetramethyl-4-oxo-piperidine;
[0233] (i) 1-hydroxy -2,2,6,6-tetramethyl-4-oxo-piperidinium
acetate;
[0234] (j) 1-oxyl-2,2,6,6-tetramethyl-4-methoxy-piperidine;
[0235] (k) 1-hydroxy-2,2,6,6-tetramethyl-4-methoxy-piperidine;
[0236] (l) 1-hydroxyl-2,2,6,6-tetramethyl-4-methoxy-piperidinium
acetate;
[0237] (m) 1-oxyl-2,2,6,6-tetramethyl-4-acetoxypiperidine;
[0238] (n) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidine;
[0239] (o) 1-oxyl-2,2,6,6-tetramethyl-4-propoxy-piperidine;
[0240] (p) 1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium
acetate;
[0241] (q) 1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidine;
[0242] (r)
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidine-
;
[0243] (s)
1-hydroxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperid-
inium acetate;
[0244] (t) 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine;
[0245] (u) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine;
[0246] (v) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
chloride;
[0247] (w) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
acetate;
[0248] (x) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperdinium
bisulfate;
[0249] (y) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
citrate;
[0250] (z) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate;
[0251] (aa)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate.
[0252] (bb)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
ethylenediaminetetraacetate;
[0253] (cc)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
ethylenediaminetetraacetate;
[0254] (dd) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)
ethylenediaminetetraacetate;
[0255] (ee)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
diethylenetriaminepentaacetate;
[0256] (ff)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
diethylenetriaminepentaacetate;
[0257] (gg) penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)
diethylenetriaminepentaacetate;
[0258] (hh)
tri(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
nitrilotriacetate;
[0259] (ii)
tri(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
nitrilotriacetate;
[0260] (jj) tri(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)
nitrilotriacetate;
[0261] (kk)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
diethylenetriaminepentamethylenephosphonate;
[0262] (ll)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
diethylenetriaminepentamethylenephosphonate;
[0263] (mm) penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)
diethylenetriaminepentamethylenephosphonate.
[0264] Most especially, the hindered amine compound is
[0265] (a) 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine;
[0266] (b) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine;
[0267] (c) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
chloride;
[0268] (d) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
acetate;
[0269] (e) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
bisulfate;
[0270] (f) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
citrate;
[0271] (g) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate;
[0272] (h)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate;
[0273] (i)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
ethylenediaminetetraacetate;
[0274] (j)
tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
ethylenediaminetetraacetate;
[0275] (k) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)
ethylenediaminetetraacetate;
[0276] (l)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
diethylenetriaminepentaacetate;
[0277] (m)
penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
diethylenetriaminepentaacetate;
[0278] (n) penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)
diethylenetriaminepentaacetate.
[0279] The instant compositions may additionally include an
effective amount of at least one coadditive selected from the group
consisting of the UV absorbers, the polymeric inhibitors, the
sulfur containing inhibitors, the phosphorus containing compounds,
the nitrones, the benzofuran-2-ones and the hydroxylamines and
mixtures thereof.
[0280] The compositions which also include a UV absorber are
especially preferred. The UV absorber is selected from group
consisting of the benzotriazoles, the s-triazines, the
benzophenones, the .alpha.-cyanoacrylates, the oxanilides, the
benzoxazinones, the benzoates and the .alpha.-alkyl cinnamates.
[0281] Preferably, the UV absorber is a benzotriazole, an
s-triazine or a benzophenone, most especially a benzotriazole UV
absorber or benzophenone UV absorber.
[0282] Typical and useful UV absorbers are, for example,
[0283] (a)
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole-
;
[0284] (b)
2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
[0285] (c)
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
[0286] (d)
2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole;
[0287] (e)
2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazo-
le;
[0288] (f) 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;
[0289] (g)
3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesu-
lfonic acid monosodium salt;
[0290] (h)
3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamic acid
and sodium salt;
[0291] (i) 12-hydroxy-3,6,9-trioxadodecyl
3-tert-butyl-4-hydroxy-5-(2H-ben-
zotriazol-2-yl)-hydrocinnamate;
[0292] (j) octyl
3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinn-
amate;
[0293] (k)
4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropox-
y)-2-hydroxy phenyl)-s-triazine (*is mixture of C.sub.12-14oxy
isomers);
[0294] (l)
4,6-bis(2,4-dimethylphenyl)-2-(4-octyloxy-2-hydroxyphenyl)-s-tr-
iazine;
[0295] (m) 2,4-dihydroxybenzophenone;
[0296] (n) 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone,
disodium salt;
[0297] (o) 2-hydroxy-4-octyloxybenzophenone;
[0298] (p) 2-hydroxy-4-dodecyloxybenzophenone;
[0299] (q) 2,4-dihydroxybenzophenone;
[0300] (r) 2,2',4,4'-tetrahydroxybenzophenone;
[0301] (s) 4-aminobenzoic acid;
[0302] (t) 2,3-dihydroxypropyl-4-aminobenzoic acid;
[0303] (u) 3-(4-imidazolyl)acrylic acid;
[0304] (v) 2-phenyl-5-benzimidazole sulfonic acid;
[0305] (w)
N,N,N-trimethyl-.alpha.-(2-oxo-3-bornylidene)-p-toluidinium methyl
sulfate;
[0306] (x) 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid,
sodium salt;
[0307] (y)
3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxy-N,N,N-trimethyl-1-prop-
anaminium chloride;
[0308] (z)
3-[4-(2H-benzotriazol-2-yl)-3-hydroxyphenoxy]-2-hydroxy-N,N,N-t-
rimethyl-1-propanaminium, chloride;
[0309] (aa) 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; and
[0310] (bb) 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinul.RTM.
3049).
[0311] Preferred UV absorbers are
[0312] (a)
3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesu-
lfonic acid monosodium salt;
[0313] (b)
3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamic acid
and sodium salt;
[0314] (c
)2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
[0315] (d)
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
[0316] (e)
4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropox-
y)-2-hydroxy phenyl)-s-triazine (*is mixture of C.sub.12-14oxy
isomers);
[0317] (f) 12-hydroxy-3,6,9-trioxadodecyl
3-tert-butyl-4-hydroxy-5-(2H-ben-
zotriazol-2-yl)-hydrocinnamate;
[0318] (g) 2,4-dihydroxybenzophenone;
[0319] (h) 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone,
disodium salt;
[0320] (i) 2,2',4,4'-tetrahydroxybenzophenone;
[0321]
(j)3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxy-N,N,N-trimethyl-1-propa-
naminium chloride;
[0322] (k)
3-[4-(2H-benzotriazol-2-yl)-3-hydroxyphenoxy]-2-hydroxy-N,N,N-t-
rimethyl-1-propanaminium, hloride;
[0323] (l) 5-benzoyl-4-hydroxy-2-methoxy-benzenesulfonic acid,
sodium salt
[0324] (m)
2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazo-
le.
[0325] Other preferred compositions are those which additionally
contain a metal chelating agent, i.e. those that offer
thermodynamic or kinetic control of metal ions. Examples kinetic
controlling chelating agents are citrates, keto acids, gluconates,
heptagluconates, phosphates, and phosphonates. Examples of
chelating agents that offer thermodynamic control are the
aminocarboxylic acid chelates. Well known and commercially
available members of this class include ethylenediaminetetraacetic
acid (EDTA), diethylenetriaminepentaacetic acid (DTPA),
hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic
acid (NTA) and diethylenetriaminepentamethylenephosphoni- c acid
(DTPMPA).
[0326] Still other preferred compositions are those which contain
mixtures of thermodynamic and kinetic controlling chelating agents
are also preferred.
[0327] Still other preferred compositions are those which
additionally contain a polymeric inhibitor; preferably
poly(ethylene glycol) (PEO), poly(propylene glycol) (PPO),
poly(butylene glycol) (PTHF), poly(vinyl pyrrolidone) (PVP) or
thiol-capped poly(ethylene glycol) as well as copolymers such as
poly(ethylene/propylene glycol).
[0328] Still other preferred compositions are those which
additional contain a fluorescent whitening agent selected from a
wide range of chemical types such as
4,4'-bis-(triazinylamino)-stilbene-2,2'-disulfonic acids,
4,4'-bis-(triazol-2-yl)stilbene-2,2'-disulfonic acids,
4,4'-dibenzofuranyl-biphenyls, 4,4'-(diphenyl)-stilbenes,
4,4'-distyryl-biphenyls, 4-phenyl-4'-benzoxazolyl-stilbenes,
stilbenyl-naphthotriazoles, 4-styryl-stilbenes,
bis-(benzoxazol-2-yl) derivatives, bis-(benzimidazol-2-yl)
derivatives, coumarins, pyrazolines, naphthalimides,
triazinyl-pyrenes, 2-styryl-benzoxazole or -naphthoxazoles,
benzimidazole-benzofurans or oxanilides.
[0329] Some preferred compositions contain a mixture of additional
stabilizers such as a mixture of a UV absorber and polymeric
inhibitor; or a mixture of a UV absorber and a metal chelating
agent; or a mixture of a polymeric inhibitor and a metal chelating
agent; or a mixture of a polymeric inhibitor and a fluorescent
whitening agent; or a mixture of a fluorescent whitening agent and
a metal chelating agent; or a mixture of a UV absorber, metal
chelating agent and a polymeric inhibitor; or a mixture of
fluorescent whitening agent, metal chelating agent and polymeric
inhibitor.
[0330] Preferably the compositions are those wherein the compound
of formula I or II is of low molecular weight or contains
hydrophilic moieties especially cationic groups, is both of low
molecular weight and contains hydrophilic moieties.
[0331] The instant invention also pertains to a process for
preventing the loss of brightness and for enhancing resistance to
yellowing of chemimechanical or thermomechanical pulp or paper
which still contains lignin, which comprises
[0332] treating said pulp or paper with an effective stabilizing
amount of a compound of formula I or II, preferably a compound of
formula A to EE or A* to EE* as described above.
[0333] Preferably the process is that where in the compound of
formula A to EE or A* to EE*, E is oxyl or hydroxyl and most
preferably E is hydroxyl.
[0334] The instant invention also pertains to new compounds of
formula IV, V, VI, VII or VIII 3
[0335] wherein
[0336] n is 2 to 3,
[0337] G.sub.1 is hydrogen, methyl, ethyl, butyl or benzyl,
[0338] X is an inorganic or organic anion, such as phosphate,
phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide,
bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate,
benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate,
fumarate, maleate, itaconate, glycolate, gluconate, malate,
mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of
nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentam- ethylenephosphonate, an
alkylsulfonate or an arylsulfonate,
[0339] m is 1 to 4,
[0340] x is 1 to 4,
[0341] when x is 1, R.sub.1 and R.sub.2 are independently alkyl of
1 to 18 carbon atoms, said alkyl interrupted by one to five oxygen
atoms, said alkyl substituted by 1 to 5 hydroxyl groups or said
alkyl both interrupted by said oxygen atoms and substituted by said
hydroxyl groups; cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7
to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl
substituted by one to three alkyl of 1 to 8 carbon atoms, or
R.sub.1 is also hydrogen,
[0342] or R.sub.1 and R.sub.2 are together tetramethylene,
pentamethylene, hexamethylene or 3-oxapentamethylene,
[0343] when x is 2,
[0344] R.sub.1 is hydrogen, alkyl of 1 to 8 carbon atoms, said
alkyl interrupted by one or two oxygen atoms, said alkyl
substituted by a hydroxyl group, or said alkyl both interrupted by
one or two oxygen atoms and substituted by a hydroxyl group,
[0345] R.sub.2 is alkylene of 2 to 18 carbon atoms, said alkylene
interrupted by one to five oxygen atoms, said alkylene substituted
by 1 to 5 hydroxyl groups or said alkylene both interrupted by said
oxygen atoms and substituted by said hydroxyl groups; o-, m- or
p-phenylene or said phenylene substituted by one or two alkyl of 1
to 4 carbon atoms, or
[0346] R.sub.2 is
--(CH.sub.2).sub.kO[(CH.sub.2).sub.kO].sub.h(CH.sub.2).s- ub.k--
where k is 2 to 4 and h is 1 to 40, or
[0347] R.sub.1 and R.sub.2 together with the two N atoms to which
they are attached are piperazin-1,4-diyl,
[0348] when x is 3,
[0349] R.sub.1 is hydrogen,
[0350] R.sub.2 is alkylene of 4 to 8 carbon atoms interrupted by
one nitrogen atom,
[0351] when x is 4,
[0352] R.sub.1 is hydrogen,
[0353] R.sub.2 is alkylene of 6 to 12 carbon atoms interrupted by
two nitrogen atoms,
[0354] R.sub.3 is hydrogen, alkyl of 1 to 8 carbon atoms, said
alkyl interrupted by one or two oxygen atoms, said alkyl
substituted by a hydroxyl group, or both interrupted by one or two
oxygen atoms and substituted by a hydroxyl group,
[0355] p is 2 or 3, and
[0356] Q is an alkali metal salt, ammonium or
N.sup.+(G.sub.1).sub.4.
[0357] Preferably, in the compounds of formulas IV to VIII
[0358] n is 2; G.sub.1 is hydrogen or methyl; X is chloro or bromo;
x is 1 or 2, R.sub.1 and R.sub.2 are independently alkyl of 1 to 8
carbon atoms, said alkyl interrupted by one or two oxygen atoms,
said alkyl substituted by a hydroxyl group, or said alkyl both
interrupted by one or two oxygen atoms and substituted by a
hydroxyl group, or R.sub.1 is hydrogen; or R.sub.1 and R.sub.2
together are 3-oxa-pentamethylene; R.sub.3 is hydrogen or alkyl of
1 to 2 carbon atoms, or said alkyl substituted by a hydroxyl group,
p is 2, m is 1, and Q is Na.sup.+, NH.sub.4.sup.+ or
N(CH.sub.3).sub.4.sup.+.
[0359] Typical compounds falling within the structures of formulas
IV to VIII and which are useful in this invention are:
[0360] (a)
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxa-6-trimethylammmon-
iumhexyloxy) piperidine chloride;
[0361] (b)
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-3-trimethylammoniumprop-
oxy)piperidine chloride;
[0362] (c)
1-oxyl-2,2,6,6-tetramethyl-4-{2-hydroxy-3-[di(2-hydroxyethyl)am-
ino]propoxy}piperidine;
[0363] (d)
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-3-dimethylaminopropoxy)-
piperidine;
[0364] (e)
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-3-diethylaminopropoxy)p-
iperidine;
[0365] (f)
N,N'-dimethyl-N,N'-bis-[3-(1-oxyl-2,2,6,6-tetramethyl-piperidin-
-4-yloxy)-2-hydroxy propyl]hexamethylenediamine;
[0366] (g)
N,N,N',N'-tetramethyl-N,N'-bis-[3-(1-oxyl-2,2,6,6-tetramethylpi-
peridin-4-yloxy)-2-hydroxypropyl]-hexamethylenediammonium
dibromide;
[0367] (h)
1-oxyl-2,2,6,6-tetramethyl-4-[2-hydroxy-3-(N,N-dimethyl-N-propy-
lammonium) propoxy]piperidine chloride;
[0368] (i) sodium
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yloxyacetate; or
[0369] (j) 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yloxyacetic acid,
choline ester.
[0370] The instant invention also pertains to novel hydroxylamine
salts of formulae A*, D*, X*, Y*, Z*, M*, BB*, CC* and DD*, 4
[0371] wherein
[0372] R is hydrogen,
[0373] in formula A*
[0374] n is 1,
[0375] R.sub.1 is hydrogen or alkyl of 1 to 4 carbon atoms,
preferably hydrogen,
[0376] in formula D*
[0377] y is 1,
[0378] R.sub.10 is hydrogen or methyl, preferably hydrogen,
[0379] R.sub.12 is alkyl of 1 to 4 carbon atoms, preferably
methyl,
[0380] X is phosphate, phosphonate, carbonate, bicarbonate,
nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate,
borate, formate, acetate, benzoate, citrate, oxalate, tartrate,
acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate,
gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate,
a carboxylate of nitrilotriacetic acid,
hydroxyethylethylenediaminetriacetic acid,
ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic
acid, a diethylenetriaminepentamethylenephosphonate, an
alkylsulfonate or an arylsulfonate,
[0381] where the total charge of cations h is equal to the total
charge of anions j,
[0382] wherein in formulas X* to DD*
[0383] n is 2 to 3,
[0384] G.sub.1 is hydrogen, methyl, ethyl, butyl or benzyl,
[0385] m is 1 to 4,
[0386] x is 1 to 4,
[0387] when x is 1, R.sub.1 and R.sub.2 are independently alkyl of
1 to 18 carbon atoms, said alkyl interrupted by one to five oxygen
atoms, said alkyl substituted by 1 to 5 hydroxyl groups or said
alkyl both interrupted by said oxygen atoms and substituted by said
hydroxyl groups; cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7
to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl
substituted by one to three alkyl of 1 to 8 carbon atoms, or
R.sub.1 is also hydrogen,
[0388] or R.sub.1 and R.sub.2 are together tetramethylene,
pentamethylene, hexamethylene or 3-oxapentamethylene,
[0389] when x is 2,
[0390] R.sub.1 is hydrogen, alkyl of 1 to 8 carbon atoms, said
alkyl interrupted by one or two oxygen atoms, said alkyl
substituted by a hydroxyl group, or said alkyl both interrupted by
one or two oxygen atoms and substituted by a hydroxyl group,
[0391] R.sub.2 is alkylene of 2 to 18 carbon atoms, said alkylene
interrupted by one to five oxygen atoms, said alkylene substituted
by 1 to 5 hydroxyl groups or said alkylene both interrupted by said
oxygen atoms and substituted by said hydroxyl groups; o-, m- or
p-phenylene or said phenylene substituted by one or two alkyl of 1
to 4 carbon atoms, or
[0392] R.sub.2 is
--(CH.sub.2).sub.kO[(CH.sub.2).sub.kO].sub.h(CH.sub.2).s- ub.k--
where k is 2 to 4 and h is 1 to 40, or
[0393] R.sub.1 and R.sub.2 together with the two N atoms to which
they are attached are piperazin-1,4-diyl,
[0394] when x is 3,
[0395] R.sub.1 is hydrogen,
[0396] R.sub.2 is alkylene of 4 to 8 carbon atoms interrupted by
one nitrogen atom,
[0397] when x is 4,
[0398] R.sub.1 is hydrogen,
[0399] R.sub.2 is alkylene of 6 to 12 carbon atoms interrupted by
two nitrogen atoms,
[0400] R.sub.3 is hydrogen, alkyl of 1 to 8 carbon atoms, said
alkyl interrupted by one or two oxygen atoms, said alkyl
substituted by a hydroxyl group, or both interrupted by one or two
oxygen atoms and substituted by a hydroxyl group,
[0401] p is 2 or 3, and
[0402] Q is an alkali metal salt, ammonium or
N.sup.+(G.sub.1).sub.4,
[0403] in formula DD and DD*
[0404] m is 2 or 3,
[0405] when m is 2, G is --(CH.sub.2CHR--O).sub.rCH.sub.2CHR--,
where r is 0 to 3, and R is hydrogen or methyl, and
[0406] when m is 3, G is glyceryl,
[0407] with the proviso that in formula A* when R.sub.1 is
hydrogen, X is not chloride or bisulfate, and when in formula D*
when R.sub.10 is hydrogen and R.sub.12 is methyl, X is not chloride
or bisulfate.
[0408] Preferably, X is chloride, bisulfate, bisulfite, sulfate,
nitrate, acetate, citrate or carboxylate of
ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic
acid; most preferably, X is bisulfate or citrate.
[0409] Hydroxylamine salts of particular interest are
[0410] (a) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
citrate;
[0411] (b) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate;
[0412] (c)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
citrate;
[0413] (d) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
DTPA;
[0414] (e) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
DTPA;
[0415] (f)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) DTPA;
[0416] (g)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
DTPA;
[0417] (h)
pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
DTPA;
[0418] (i) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium
EDTA;
[0419] (j) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
EDTA;
[0420] (k)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium) EDTA;
[0421] (l)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
EDTA;
[0422] (m) 1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium
citrate;
[0423] (n) bis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium)
citrate;
[0424] (o) tris(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium)
citrate;
[0425] (p) 1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium
DTPA;
[0426] (q) bis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium)
DTPA;
[0427] (r) tris(1-hydroxy-2,2,6,6-tetramethyl--oxo-piperdinium)
DTPA;
[0428] (s)
tetrakis(1-hydroxy-2,2,6,6-tetramethy-4-oxo-piperidinium) DTPA;
[0429] (t)
pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium)
DTPA;
[0430] (u) 1b-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium
EDTA;
[0431] (v) bis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium)
EDTA;
[0432] (w) tris(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperdinium)
EDTA;
[0433] (x)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-oxo-piperidinium)
EDTA;
[0434] (y) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium
citrate;
[0435] (z)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
citrate;
[0436] (aa)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
citrate;
[0437] (bb) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium
DTPA;
[0438] (cc)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
DTPA;
[0439] (dd)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
DTPA;
[0440] (ee)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium- )
DTPA;
[0441] (ff)
pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium- )
DTPA;
[0442] (gg) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium
EDTA;
[0443] (hh)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)
EDTA;
[0444] (ii) tris(
1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium) EDTA;
[0445] (jj)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
EDTA;
[0446] (kk) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium
citrate;
[0447] (ll)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
citrate;
[0448] (mm)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
citrate;
[0449] (nn) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium
DTPA;
[0450] (oo)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) DTPA;
[0451] (pp)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) DTPA;
[0452] (qq)
tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
DTPA;
[0453] (rr)
pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
DTPA;
[0454] (ss) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium
EDTA;
[0455] (tt)
bis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) EDTA;
[0456] (uu)
tris(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium) EDTA or
(vv) tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium)
EDTA.
[0457] Nitroxides, hydroxylamines and their salts alone or in
combination with UV absorbers are also effective in improving the
resistance to yellowing of mechanical pulps which have been
modified by acylation, alkylation, treatment with sodium
borohydride or hydrogenated.
[0458] The intermediates needed to make the instant compounds are
largely items of commerce.
[0459] The effective stabilizing amounts of the hindered amine is
0.001 to 5% by weight based on the pulp or paper. Preferably, the
effective stabilizing amount is 0.005 to 2% by weight; preferably
0.01 to 1% by weight.
[0460] When a coadditive is also present, the effective amount of
the coadditives is also 0.001 to 5% by weight based on the pulp or
paper; preferably 0.005 to 2% by weight; most preferably 0.01 to 2%
by weight.
[0461] The instant inhibitor additive system can be added to pulp
or paper at a number of places during the manufacturing or
processing operations. These include
[0462] a. on a pulp slurry in the latency chest;
[0463] b. on a pulp slurry in or after the bleaching stage in a
storage, blending or transfer chest;
[0464] c. on pulp during or after bleaching, washing and dewatering
followed by cylinder or flash drying;
[0465] d. before or after the cleaners;
[0466] e. before or after the fan pump to the paper machine
headbox;
[0467] f. to the paper machine white water;
[0468] g. to the silo or save all;
[0469] h. in the press section using a size press, coater or spray
bar;
[0470] i. in the drying section using a size press, coater or spray
bar;
[0471] j. on the calender using a wafer box;
[0472] k. on paper in an off-machine coater or size press;
and/or
[0473] l. in the curl control unit.
[0474] Clearly, the precise location where the stabilizer additives
should be added will depend on the specific equipment involved, the
exact process conditions being used and the like. In some cases,
the additives may be added at one or more locations for most
effectiveness.
[0475] At these various locations, the instant inhibitor additive
system can also be added with a carrier or additive typically used
in paper making, such as retention aids, sizing aids and solutions,
starches, precipitated calcium carbonate, ground calcium carbonate,
or other clays or fillers, and brightening additives.
[0476] The following examples are for illustrative purposes only
and are not to be construed to limit the instant invention in any
manner whatsoever.
[0477] Handsheet Treatment
[0478] All additives are applied by syringe-injecting the
appropriate weight % of additive combination in either an aqueous
solution when the additive is water soluble, or a solution in 1:1
(ethanol/dioxane) onto bleached thermomechanical pulp (BTMP)
brightness squares (4 cm.times.4 cm). The clamped sheets are
allowed to air dry for one day.
[0479] The brightness of the handsheets is recorded before and
after treatment by light exposure.
[0480] Accelerated testing is carried out by subjecting the treated
sheets to accelerated light induced yellowing in a fan-cooled light
box containing eight fluorescent lamps with a spectral maximum
output at 5700 .ANG. with a total output approximately 43 times
greater than normal office fluorescent lamps. The lamps are only
about ten inches away from the handsheets being illuminated.
[0481] Ambient testing is carried out by placing the treated
handsheets on a desk under normal cool-white fluorescent office
lights at a nominal distance of six feet.
[0482] In both case ISO brightness is tracked as a function of
photolysis time and converted to post color number (PC number) in
the usual manner. (Giertz, Svensk Papperstidn, (1945) 48 (13),
317)
[0483] Post color (PC) number is defined as follows:
PC=[(k/s).sub.after-(k/s).sub.before].times.100
k/s=(1-R.sub.inf).sup.2/2R.sub.inf
[0484] where k and s are the absorption and scattering
coefficients, respectively, and R.sub.inf is the value of ISO
brightness.
[0485] The relationship between R.sub.inf and the chromophore
concentration is non-linear, whereas, the PC number is roughly
linearly related to the concentration of the chromophore in the
sample.
[0486] Low PC numbers are desired as they indicate less
yellowing.
[0487] When using the ambient test conditions untreated BTMP
handsheets are compared to Kraft handsheets, after 60 days the BTMP
handsheets have a PC number which is about 10 while the Kraft paper
has a PC number which is 0.388742. The Kraft handsheets are clearly
less yellow than untreated BTMP handsheets after exposure to
ambient light.
[0488] The incident light flux for the accelerated yellowing
experiments (Examples 1-4) is 43 times greater than normal office
fluorescent lamps as measured by the A. W. Speery SLM-110 digital
light power meter. The brightness of the handsheets is tracked and
compared to that of untreated sheets exposed in the same manner.
The treated sheets exhibit significant resistance to yellowing as
seen below.
[0489] Materials Used in the Examples
[0490] Compound A is
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine;
[0491] Compound B is
1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine;
[0492] Compound C is
1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine;
[0493] Compound D is 1-oxyl-2,2,6,6-tetramethylpiperidine
TEMPO;
[0494] Compound E is bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate;
[0495] Compound F is
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride;
[0496] Compound G is
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate;
[0497] Compound H is
bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidini- um)
sulfate;
[0498] Compound I is
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate;
[0499] Compound J is
pentakis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiper- idinium)
diethylenetriaminepentaacetic acid;
[0500] Compound K is
3-(4-benzyloxy-2,2,6,6-tetramethyl-piperidin-1-yloxy)- -propionic
acid methyl ester;
[0501] Compound L is
3-(4-{4-[1-(2-methoxycarbonyl-ethoxy)-2,2,6,6-tetrame-
thyl-piperidin-4-yloxymethyl]-benzyloxy}-2,2,6,6-tetramethyl-piperidin-1-y-
loxy)-propionic acid methyl ester;
[0502] Compound M is 2,2-diethyl-malonic acid
bis-(1-butylcarbamoyloxy-2,2- ,6,6-tetramethyl-piperidin-4-yl)
ester;
[0503] Compound N is acetic acid
4-hydroxy-2,2,6,6-tetramethyl-piperidin-1- -yl ester;
[0504] Compound O is benzoic acid
1-butoxycarbonyloxy-2,2,6,6-tetramethyl-- piperidin-4-yl ester;
[0505] Compound P is
2,2,6,6-tetramethyl-1-(1-phenyl-ethoxy)-piperidin-4-o- l;
[0506] Compound Q is 2,4-dihydroxybenzophenone;
[0507] Compound R is
12-hydroxy-3,6,9-trioxadodecyl-3-tert-butyl-4-hydroxy-
-5-(2H-benzotriazol-2-yl)-hydrocinnamate (Tinuvin.RTM. 1130);
[0508] Compound S is,
3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl-
)-benzenesulfonic acid monosodium salt (Cibafast.RTM. W);
[0509] Compound T is
1-oxyl-2,2,6,6-tetramethyl-4-(2,3-dihydroxypropoxy) piperidine;
[0510] Compound U is
1-oxyl-2,2,6,6-tetramethyl-4-(carboxymethoxy)piperidi- ne;
[0511] Compound V is
3-oxyl-1,2,2,4,4-pentamethyl-3,4-dihydro-2.H.-imidazo- l-1-ium
methylsulfate;
[0512] Compound W is
3-(3-benzotriazol-2-yl-5-.tert.-butyl-4-hydroxy-pheny- l)-propionic
acid;
[0513] Compound X is polyethylene glycol of molecular weight 300
(PEO);
[0514] Compound Y is
4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hyd-
roxypropoxy)-2-hydroxyphenyl)-s-triazine (* is mixture of
C.sub.12-14oxy isomers) (Tinuvin.RTM. 400);
[0515] Compound Z is
2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenon- e, disodium
salt (Uvinul.RTM. 3048);
[0516] Compound M is 2,2'-dihydroxy-4,4'-dimethoxybenzophenone
(Uvinul.RTM. 3049);
[0517] Compound BB is diethylenetriamine tetraacidic acid
(DTPA);
[0518] Compound CC is 5,5-dimethyl-1-pyrroline N-oxide;
[0519] Compound DD is N-tert-butyl-.alpha.-phenyinitrone;
[0520] Compound EE is
1-oxyl-2,2,6,6-tetramethyl-4-oxo-piperidine;
[0521] Compound FF is
tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidi- nium)
citrate;
[0522] Compound GG is dithiothreitol;
[0523] Compound HH is 1-thioglycerol;
[0524] Compound II is 2,2'-oxydiethanethiol;
[0525] Compound JJ is
2,2,6,6-tetramethyl-4-acetamidopiperidine;
[0526] Compound KK is UVINUL.RTM. 3000,
2,4-dihydroxybenzophenone;
[0527] Compound LL is Brightener 28;
4,4'-bis[4-anilino-6-(bis(2-hydroxyet-
hyl)amino-s-triazin-2-yl]amino-2,2'-stilbenedisulfonic acid,
disodium salt;
[0528] TMHP is 2,2,6,6-tetramethyl-4-hydroxypiperidine.
EXAMPLE 1
[0529] Accelerated Yellowing with High Intensity Lamps
[0530] A BTMP sheet is treated with 0.5%-0.1% by weight of Compound
A. The sheets treated with Compound A exhibit substantial
inhibition to yellowing compared to the untreated control sheet as
seen by the PC numbers.
1 PC Number Time in Concentration Days 0.5% 0.4% 0.3% 0.2% 0.1%
Blank 1.0 1.63 1.51 1.56 1.67 2.13 5.51 2.1 3.05 2.94 3.12 3.35 4.2
9.97 3.0 4.17 4.09 4.37 4.76 5.92 13.14 4.0 5.35 5.26 5.56 6.01
6.82 15.85 5.0 6.28 6.35 6.76 7.24 8.97 18.07 6.1 7.43 7.52 7.87
8.54 10.42 20.4 7.0 8.46 8.66 9.10 9.88 12.09 23.63
[0531] Even levels as low as 0.1% by weight of Compound A show
effective stabilization effects.
EXAMPLE 2
[0532] Accelerated Yellowing with High Intensity Lamps
[0533] BTMP sheets are treated with 0.50% by weight of various
hydroxylamine compounds by the procedure of Example 1.
[0534]
1-hydroxy-2,2,6,6-tetramethyl-1,2,3,6-tetrahydro-pyridine;
[0535] 1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidine;
[0536] 1-hydroxy-2,2,6,6-tetramethyl-4-ethoxypiperidine;
[0537] 1-hydroxy-2,2,6,6-tetramethyl-4-propoxypiperidine;
[0538] 1-hydroxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)
piperidine;
[0539]
4,4'-[1,6-hexanediylbis(formylimino)]bis[2,2,6,6-tetramethyl-1-hydr-
oxypiperdine;
[0540]
2-(8-carboxyoctyl)-4,4-dimethyl-2-octyl-3-hydroxy-oxazolidine;
[0541] 3,3-dimethyl-4-hydroxy-1-oxa-4-azaspiro[4.5]decane;
[0542] 3-aminomethyl-2,2,5,5-tetramethyl-1-hydroxy-pyrrolidine;
[0543] 3-carboxy-2,2,5,5-tetramethyl-1-hydroxypyrrolidine;
[0544] 4-phenyl-2,2,5,5-tetramethyl-1-hydroxy-3-imidazoline;
[0545]
4-phenyl-2,2,5,5-tetramethyl-1-hydroxy-3-imidazoline-3-oxide;
[0546] di-tert-butyl hydroxylamine.
[0547] The sheets treated with hydroxylamines exhibit substantial
inhibition to yellowing compared to the untreated control
sheet.
EXAMPLE 3
[0548] Accelerated Yellowing with High Intensity Lamps
[0549] BTMP sheets are treated with 0.25% by weight of Compounds B,
C, D and E. The sheets treated with nitroxides exhibit substantial
inhibition to yellowing compared to the untreated control
sheet.
2 PC Number Compounds Time in Days Blank B C D E 0 0 0 0 0 0 0.93
2.49 0.88 1.6 2.01 1.28 1.9 5.27 1.89 3.24 4.06 2.49 2.94 8.46 3.41
5.52 6.73 4.28 3.93 10.54 4.36 6.89 8.57 5.4 4.98 12.34 5.36 8.31
10.5 6.53 5.88 13.81 6.11 9.45 11.62 7.74 6.91 15.55 7.17 11.05
13.17 8.81 7.98 17.34 8.18 12.5 14.57 10.12 8.97 19.44 9.33 13.72
16.28 11.32 10.01 20.98 10.1 15.07 17.75 12.21 10.94 22.35 11.01
16.3 19.1 13.16
EXAMPLE 4
[0550] Accelerated Yellowing with High Intensity Lamps
[0551] BTMP sheets are treated with 0.25% by weight of Compound EE.
The sheets treated with nitroxides exhibit substantial inhibition
to yellowing compared to the untreated control sheet.
3 Compound Time in Days EE Blank PC Number 0 0 0 1.04 1.77 4.53
2.02 3.77 7.91 3.06 5.97 11.16 4.02 7.76 13.72 5.02 9.28 15.47 6.23
10.49 17.61 6.98 11.88 18.78 7.98 13.06 20.09 10.96 16.92 25.25
EXAMPLE 5
[0552] Accelerated Yellowing with High Intensity Lamps
[0553] BTMP sheets are treated with 0.25% by weight of each of the
following compounds:
[0554] 1-oxyl-2,2,6,6-tetramethyl-1,2,3,6-tetrahydro-pyridine;
[0555] 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate;
[0556]
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate;
[0557] 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-stearate;
[0558] 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-benzoate;
[0559]
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-(4-tert-butyl)benzoate;
[0560] bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-succinate;
[0561] bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-adipate;
[0562]
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylmalonate;
[0563] bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-phthalate;
[0564]
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-isophthalate;
[0565]
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-terephthalate;
[0566]
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-hexahydroterephthalat-
e;
[0567]
N,N'-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-adipinamide;
[0568]
N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-caprolactam;
[0569]
N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-dodecylsuccinimide;
[0570]
2,4,6-tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]-s--
triazine;
[0571]
4,4'-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one;
[0572]
tris-(2,2,6,6-tetramethyl-1-oxyl-piperidin-4-yl)-phosphite;
[0573] 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine;
[0574] 1-oxyl-2,2,6,6-tetramethyl-4-ethoxypiperidine;
[0575] 1-oxyl-2,2,6,6-tetramethyl-4-propoxypiperidine;
[0576] 1-oxyl-2,2,6,6-tetramethyl-4-carboxypiperidine;
[0577]
1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidine;
[0578]
4,4'-[1,6-hexanediylbis(formylimino)]bis[2,2,6,6-tetramethyl-1-pipe-
rdinyloxy;
[0579]
2-(8-carboxyoctyl)-4,4-dimethyl-2-octyl-3-oxazolidinyloxy;
[0580] 3,3-dimethyl-1-oxa-4-azaspiro[4.5]dec-4-yloxy;
[0581] 3-aminomethyl-2,2,5,5-tetramethyl-1-pyrrolidinyloxy;
[0582] 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy;
[0583] 4-phenyl-2,2,5,5-tetramethyl-3-imidazolin-1-yloxy;
[0584]
4-phenyl-2,2,5,5-tetramethyl-3-imidazolin-1-yloxy-3-oxide;
[0585] di-tert-butyl nitroxide.
[0586] The sheets treated with nitroxides exhibit substantial
inhibition to yellowing compared to the untreated control
sheet.
EXAMPLE 6
[0587] Accelerated Yellowing with High Intensity Lamps
[0588] BTMP sheets are treated with 0.50% by weight of Compounds A,
F,G, H, I and J. The sheets treated with hydroxylamine salts
exhibit substantial inhibition to yellowing compared to the
untreated control sheet.
4 PC Numbers Time in Compounds Days Blank A F G H I J 0 0 0 0 0 0 0
0 0.77 3.62 0.90 1.26 1.42 1.23 1.02 1.08 1.74 6.27 1.69 2.29 2.60
2.08 1.97 1.98 2.81 8.82 2.50 3.23 3.54 2.92 2.8 2.84 3.8 10.97
3.25 4.20 5.0 3.85 3.65 3.66 4.75 12.86 4.08 5.01 5.52 4.60 4.3
4.44 5.81 14.68 4.88 5.95 6.6 5.5 5.08 5.36 6.79 16.24 5.62 6.81
7.51 6.27 5.85 6.0 7.8 17.36 6.09 7.40 8.42 6.97 6.36 6.56 8.76
18.44 6.71 8.13 9.24 7.7 7.02 7.13 9.75 19.41 7.33 8.76 9.95 8.3
7.62 7.72 10.8 20.35 7.85 9.43 10.68 8.92 8.26 8.2 11.87 21.13 8.34
9.98 11.36 9.46 8.68 8.6 12.81 21.98 8.77 10.52 12.12 9.98 9.10
9.06
EXAMPLE 7
[0589] Accelerated Yellowing with High Intensity Lamps
[0590] BTMP sheets are treated with 0.50% by weight of Compounds K
and L. The sheets treated with hindered amine hydroxylamine
Compounds K and L exhibit substantial inhibition to yellowing
compared to the untreated control sheet.
5 Compounds Time in Days Blank K L PC Number 0 0 0 0 .81 3.19 1.42
1.59 1.82 5.85 2.62 3.02 2.8 8.06 3.93 4.41 3.75 10.02 4.79 5.42
4.83 12.08 5.85 6.61 5.8 13.81 7.35 7.52 6.76 15.49 7.73 8.40 7.77
16.98 8.39 9.2 8.74 18.54 9.34 10.36 9.76 20.06 10.02 11.18 10.74
21.56 11.06 12.24
EXAMPLE 8
[0591] Accelerated Yellowing with High Intensity Lamps
[0592] BTMP sheets are treated with 0.50% by weight of Compounds M,
N and O. The sheets treated with selected hydroxylamine derivatives
exhibit substantial inhibition to yellowing compared to the
untreated control sheet.
6 Compounds Time in Days Blank M N O PC Number 0 0 0 0 0 .82 3.87
2.06 2.02 2.05 2.72 8.9 5.28 4.87 5.13 3.76 10.88 6.53 6.03 6.42
4.76 15.59 7.72 7.17 7.62 5.76 14.32 8.92 8.28 8.77 6.77 16.36
10.42 9.61 10.24 7.81 18.47 11.97 10.94 11.7 8.79 20.15 13.14 12.01
12.86 10 21.9 14.31 13.08 13.96 10.77 23.5 15.51 14.02 15.16
EXAMPLE 9
[0593] Accelerated Yellowing with High Intensity Lamps
[0594] BTMP sheets are treated with 0.5% by weight of each of the
following:
[0595] 1-acetyl-4-hydroxy-2,2,6,6-tetramethyl-piperidine;
[0596] 1-acetyl-2,2,6,6-tetramethyl-piperidin-4-one;
[0597] bis(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate.
[0598] The sheets treated with acylated hindered amine derivatives
exhibit substantial inhibition to yellowing compared to the
untreated control sheet.
EXAMPLE 10
[0599] Accelerated Yellowing with High Intensity Lamps
[0600] BTMP sheets are treated with 0.50% by weight of Compound P.
The sheets treated with Compound P exhibit substantial inhibition
to yellowing compared to the untreated control sheet.
7 Compound Time in Days Blank P PC Number 0 0 0 .81 3.19 1.66 1.82
5.85 2.68 2.8 8.06 3.76 3.75 10.02 4.64 4.83 12.08 5.50 5.8 13.81
6.28 6.76 15.49 7.21 7.77 16.98 7.90 8.74 18.54 8.9 9.76 20.06 9.63
10.74 21.56 10.47
EXAMPLE 11
[0601] Accelerated Yellowing with High Intensity Lamps
[0602] BTMP sheets are treated with 0.5%-0.1% by weight of Compound
A and 0.5% by weight of Compound Q. The sheets treated with a
combination of hydroxylamine and benzophenone UVA exhibit
substantial inhibition to yellowing compared to the untreated
control sheet.
8 PC Number Time in Concentration of Compound A Days 0.50 0.40 0.30
0.20 0.10 Blank 0 0 0 0 0 0 0 1 1.05 0.73 0.71 0.93 0.86 5.74 2.1
2.17 1.63 1.6 2.11 2.02 10.51 2.98 3.05 2.48 2.43 3.12 3.09 13.75
3.98 4.12 3.41 3.39 4.37 4.2 16.67 4.97 4.95 4.22 4.16 5.39 5.15
18.96 6.05 5.95 5.18 5.18 6.59 6.36 21.42
EXAMPLE 12
[0603] Accelerated Yellowing with High Intensity Lamps
[0604] BTMP sheets are treated with 0.25% by weight of Compound A
and 0.5% by weight of the UVA compounds R and S. The sheets treated
with a combination of hydroxyamine and benzotriazole UVA exhibit
substantial inhibition to yellowing compared to the untreated
control sheet and illustrate the performance enhancement when
combinations of hydroxylamine and UVA are used.
9 Compound 0.25% A 0.25% A Time in Days 0.25% A 0.5% R 0.5% S Blank
PC Number 0 0 0 0 0 0.77 0.97 0.21 0.21 3.74 1.85 1.86 0.48 0.54
7.25 2.78 2.85 0.8 0.83 10.43 5.84 6.42 2.23 2.38 19.5 6.93 7.85
2.93 3.05 21.69 8 8.82 3.32 3.38 23.25
EXAMPLE 13
[0605] Accelerated Yellowing with High Intensity Lamps
[0606] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the UVA compound S. The sheets
treated with a combination of nitroxide and UVA exhibit substantial
inhibition to yellowing compared to the untreated control sheet and
illustrate the performance enhancement when combinations of
nitroxide and UVA are used.
10 PC Number Time in 0.25% B 0.25% T 0.25% U 0.25% V Days 0.5% S
0.5% S 0.5% S 0.5% S 0.5% S Blank 0 0 0 0 0 0 0 0.9 0.54 1.02 1.01
0.29 3.37 4.24 1.9 1.12 2.06 2 2.12 6.49 7.81 2.9 1.86 3.19 3.11
4.17 9.38 10.91 3.96 2.5 4.52 4.29 6.44 12.31 14.04 7.16 5.03 8.63
8.41 12.92 19.98 22.31 7.89 5.6 9.58 9.44 14.43 21.54 24.13
EXAMPLE 14
[0607] Accelerated Yellowing with High Intensity Lamps
[0608] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the benzophenone UVA
compounds:
[0609] (2-hydroxy-4-octyloxy-phenyl)-phenyl-methanone;
[0610] (2-hydroxy-4-methoxy-phenyl)-phenyl-methanone;
[0611] (4-dodecyloxy-2-hydroxy-phenyl)-phenyl-methanone;
[0612]
(2-hydroxy-4-methoxy-phenyl)-(2-hydroxy-phenyl)-methanone;
[0613] bis-(2-hydroxy-4-methoxy-phenyl)-methanone;
[0614] bis-(2,4-dihydroxy-phenyl)-methanone;
[0615]
[3-(3-benzoyl-2-hydroxy-6-methoxy-benzyl)-2-hydroxy-4-methoxy-pheny-
l]-phenyl-methanone;
[0616] 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid;
[0617] 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disodium
sulfonate.
[0618] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 15
[0619] Accelerated Yellowing with High Intensity Lamps
[0620] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the UVA compounds:
[0621] (a)
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole-
;
[0622] (b)
2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;
[0623] (c)
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
[0624] (d)
2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole;
[0625] (e)
2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazo-
le;
[0626] (f) 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;
[0627] (g)
3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesu-
lfonic acid monosodium salt;
[0628] (h)
3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamic acid
and sodium salt;
[0629] (i) 12-hydroxy-3,6,9-trioxadodecyl
3-tert-butyl-4-hydroxy-5-(2H-ben-
zotriazol-2-yl)-hydrocinnamate;
[0630] (j) octyl
3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinn-
amate;
[0631] (k)
4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropox-
y)-2-hydroxy phenyl)-s-triazine (*is mixture of C.sub.12-14oxy
isomers);
[0632] (l)
4,6-bis(2,4-dimethylphenyl)-2-(4-octyloxy-2-hydroxyphenyl)-s-tr-
iazine;
[0633] (m) 2,4-dihydroxybenzophenone;
[0634] (n) 2,2',4,4'-tetrahydroxy-5,5'-disulfobenzophenone,
disodium salt;
[0635] (o) 2-hydroxy-4-octyloxybenzophenone;
[0636] (p) 2-hydroxy-4-dodecyloxybenzophenone;
[0637] (q) 2,4-dihydroxybenzophenone;
[0638] (r) 2,2',4,4'-tetrahydroxybenzophenone;
[0639] (s) 4-aminobenzoic acid;
[0640] (t) 2,3-dihydroxypropyl-4-aminobenzoic acid;
[0641] (u) 3-(4-imidazolyl)acrylic acid;
[0642] (v) 2-phenyl-5-benzimidazole sulfonic acid;
[0643] (w)
N,N,N-trimethyl-.alpha.-(2-oxo-3-bornylidene)-p-toluidinium methyl
sulfate;
[0644] (x) 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid,
sodium salt;
[0645] (y)
3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxy-N,N,N-trimethyl-1-prop-
anaminium chloride;
[0646] (z)
3-[4-(2H-benzotriazol-2-yl)-3-hydroxyphenoxy]-2-hydroxy-N,N,N-t-
rimethyl-1-propanaminium, chloride;
[0647] (aa) 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole.
[0648] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 16
[0649] Accelerated Yellowing with High Intensity Lamps
[0650] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the triazine UVA compounds:
[0651]
4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropoxy)-2-
-hydroxyphenyl)-s-triazine (*mixture of C.sub.12-14oxy isomers)
(Tinuvin 400);
[0652]
4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazi-
ne;
[0653]
2,4,6-tris(4-(3-dodecyloxy*-2-hydroxypropoxy)-2-hydroxyphenyl)-s-tr-
iazine (*mixture of C.sub.12-14oxy isomers);
[0654]
2,4-bis(4-(3-dodecyloxy*-2-hydroxypropoxy)-2-hydroxyphenyl)-6-(2,4--
dimethylphenyl)-s-triazine (*mixture of C.sub.12-14oxy
isomers).
[0655] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 17
[0656] Accelerated Yellowing with High Intensity Lamps
[0657] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the cinnamate UVA compounds:
[0658] 2-cyano-3,3-diphenyl-2-propenoic acid ethyl ester;
[0659] 2-cyano-3,3-diphenyl-2-propenoic acid 2-ethylhexyl
ester;
[0660] 3-(4-methoxyphenyl)-2-propenoic acid 2-ethylhexyl ester.
[0661] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used
EXAMPLE 18
[0662] Accelerated Yellowing with High Intensity Lamps
[0663] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the oxalanilide UVA compounds:
[0664]
N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl)-ethanediamide;
[0665] N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)-ethanediamide.
[0666] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 19
[0667] Accelerated Yellowing with High Intensity Lamps
[0668] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the salicylate UVA compounds:
[0669] 2-hydroxy-benzoic acid phenyl ester;
[0670] 2-hydroxy-benzoic acid 4-(1,1-dimethylethyl)phenyl
ester;
[0671] 2-hydroxy-benzoic acid 2-ethylhexyl ester;
[0672] 2-hydroxy-benzoic acid 4-isopropylbenzyl ester;
[0673] 2-hydroxy-benzoic acid 3,3,5-trimethylcyclohexyl ester.
[0674] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 20
[0675] Accelerated Yellowing with High Intensity Lamps
[0676] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the formamidine UVA compounds:
[0677] 4-[[(methylphenylamino)methylene]amino]-benzoic acid, ethyl
ester;
[0678] 4-[[(ethylphenylamino)methylene]amino]-benzoic acid, ethyl
ester.
[0679] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 21
[0680] Accelerated Yellowing with High Intensity Lamps
[0681] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the 4-hydroxybenzoate UVA
compounds:
[0682] 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzoic acid hexadecyl
ester;
[0683] 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzoic acid
2,4-bis(1,1-dimethylethyl)phenyl ester.
[0684] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 22
[0685] Accelerated Yellowing with High Intensity Lamps
[0686] BTMP sheets are treated with 0.25% by weight of Compounds B,
T, U and V and 0.5% by weight of the 4-aminobenzoate UVA
compounds:
[0687] 4-aminobenzoic acid;
[0688] 2,3-dihydroxypropyl-4-aminobenzoate;
[0689] 2-ethylhexyl 4-dimethylaminobenzoate;
[0690] ethyl 4-[bis(2-hydroxypropyl)amino]benzoate.
[0691] The sheets treated with a combination of nitroxide and UVA
exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and UVA are used.
EXAMPLE 23
[0692] Accelerated Yellowing with High Intensity Lamps
[0693] BTMP sheets are treated with 0.50% by weight of Compounds A,
F, G, H, I and J and 0.5% of Compound R. The sheets treated with
hydroxylamine salts and UVA exhibit substantial inhibition to
yellowing compared to the untreated control sheet.
11 PC Number Time in 0.5% G 0.5% H 0.5% F 0.5% I 0.5% J 0.5% A Days
0.5% R 0.5% R 0.5% R 0.5% R 0.5% R 0.5% R Blank 0 0 0 0 0 0 0 0
0.76 0.57 -0.14 0.06 0.16 -0.18 -0.55 3.51 1.85 0.96 0.02 0.32 0.33
0 -0.49 6.43 2.81 1.55 0.17 0.63 0.57 0.25 -0.33 8.77 3.76 1.94
0.38 0.9 0.81 0.48 -0.21 10.89 4.82 2.52 0.57 1.24 1.01 0.66 -0.06
12.99 5.8 2.89 0.68 1.49 1.17 0.87 0.05 14.7 6.82 3.27 0.81 1.64
1.38 1.06 0.14 16.03 7.77 3.84 1.05 2 1.59 1.29 0.3 17.33 8.76 4.05
1.16 2.17 1.75 1.42 0.43 18.22 9.81 4.77 1.38 2.46 1.98 1.67 0.57
19.27 10.88 5.11 1.53 2.69 2.27 1.86 0.69 20.18 11.82 5.51 1.7 2.97
2.45 2.08 0.84 21.03 12.78 5.77 1.89 3.13 2.7 2.25 0.92 22.03
EXAMPLE 24
[0694] Accelerated Yellowing with High Intensity Lamps
[0695] BTMP sheets are treated with 0.50% by weight of Compounds K
and L and 0.5% by weight of Compound S. The sheets treated with
Compounds K and L and a UVA exhibit substantial inhibition to
yellowing compared to the untreated control sheet.
12 0.5% K 0.5% L Time in Days 0.5% S 0.5% S 0.5% S Blank PC Number
0 0 0 0 0 0.81 0 0.04 0.29 3.03 1.82 0.51 0.87 0.89 5.78 2.8 1.08
1.1 1.47 8.11 3.75 1.56 1.65 2.14 10.21 4.83 2.04 2.25 2.83 12.33
5.8 2.64 2.76 3.56 14.13 6.76 2.98 3.23 4.18 15.6 7.77 3.54 3.82
4.93 17.45 8.74 3.97 4.45 5.7 18.98 9.75 4.6 5.18 6.5 30.34 10.74
5.07 5.85 7.39 21.91
EXAMPLE 25
[0696] Accelerated Yellowing with High Intensity Lamps
[0697] BTMP sheets are treated with 0.50% by weight of Compounds M,
N and O and 0.5% by weight of the UVA Compound W. The sheets
treated with selected hydroxylamine derivatives and the UVA exhibit
substantial inhibition to yellowing compared to the untreated
control sheet.
13 PC Number Time in 0.5% M 0.5% N 0.5% O Days 0.5% W 0.5% W 0.5% W
0.5% W Blank 0 0 0 0 0 0 .82 0.59 0.46 0.51 .79 3.87 2.72 1.84 1.46
1.77 2.25 8.9 3.76 2.43 1.91 2.46 2.90 10.88 4.76 3.09 2.34 3.12
3.52 12.59 5.76 3.84 2.9 3.87 4.32 14.32 6.77 4.75 3.59 4.72 5.12
16.36 7.81 5.7 4.37 5.68 6.09 18.47 8.79 6.55 4.98 6.46 6.86 20.15
10.0 7.43 5.45 7.37 7.7 21.9 10.77 8.28 6.19 8.28 8.64 23.5
EXAMPLE 26
[0698] Accelerated Yellowing with High Intensity Lamps
[0699] BTMP sheets are treated with 0.50% by weight of Compound P
and 0.5% Compound S. The sheets treated with Compound P in
combination with a UVA exhibit substantial inhibition to yellowing
compared to the untreated control sheet.
14 0.5% P Time in Days 0.5% S 0.5% S Blank PC Number 0 0 0 0 0.81
0.06 0.29 3.03 1.82 0.46 0.89 5.78 2.8 0.95 1.47 8.11 3.75 1.37
2.14 10.21 4.83 1.74 2.83 12.33 5.8 2.13 3.56 14.13 6.76 2.5 4.18
15.6 7.77 2.95 4.93 17.45 8.74 3.42 5.7 18.98
EXAMPLE 27
[0700] Accelerated Yellowing with High Intensity Lamps
[0701] BTMP sheets are treated with and 0.5% Compound S and 0.5% by
weight of:
[0702] 1-acetyl-4-hydroxy-2,2,6,6-tetramethyl-piperidine;
[0703] 1-acetyl-2,2,6,6-tetramethyl-piperidin-4-one;
[0704] bis(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate.
[0705] The sheets treated with acylated hindered amine derivatives
in combination with a UVA exhibit substantial inhibition to
yellowing compared to the untreated control sheet.
EXAMPLE 28
[0706] Accelerated Yellowing with High Intensity Lamps
[0707] BTMP sheets are treated with 0.25% by weight of Compound A,
0.5% Compound W and 0.5% of Compound X. The sheets treated with
hydroxylamine, UVA and PEO exhibit substantial inhibition to
yellowing compared to the untreated control sheet.
15 0.25% A 0.25% A 0.5% W Time in Days 0.25% A 0.5% W 0.5% X Blank
PC Number 0 0 0 0 0 0.77 0.97 0.06 0.03 3.74 1.85 1.86 0.28 0.27
7.25 2.78 2.85 0.49 0.46 10.43 5.84 6.42 1.54 1.48 19.5 6.93 7.85 2
1.98 21.69 8 8.82 2.34 2.26 23.25
EXAMPLE 29
[0708] Accelerated Yellowing with High Intensity Lamps
[0709] BTMP sheets are treated with 0.25% by weight of Compound A,
0.5% Compound Y, Z and M and 0.5% of Compound X. The sheets treated
with hydroxylamine, UVA and PEO exhibit substantial inhibition to
yellowing compared to the untreated control sheet.
16 PC Number 0.25% 0.25% 0.25% 0.25% A 0.25% A 0.25% A A 0.5% A
0.25% A 0.5% Y A 0.5% Z 0.5% A A Time in Days A 0.5% Y 0.5% X 0.5%
Z 0.5% X A 0.5% X Blank 0 0 0 0 0 0 0 0 0 0.84 1.22 0.34 0.27 1.11
1.09 0.33 0.22 4 1.77 1.94 0.64 0.45 1.32 1.54 0.53 0.43 7.73 4.88
5.48 2.41 1.86 3.87 4.9 2.39 1.67 18.19 5.92 6.9 3.11 2.46 4.82
5.82 3.01 2.09 21.03 6.99 7.64 3.64 2.81 5.34 6.51 3.48 2.41
22.93
EXAMPLE 30
[0710] Accelerated Yellowing with High Intensity Lamps
[0711] BTMP sheets are treated with 0.5% by weight of Compound G,
0.25% by weight of Compound W and 0.25% by weight of Compound BB.
The sheets treated with hydroxylamine, UVA and metal chelating
agent exhibit substantial inhibition to yellowing compared to the
untreated control sheet.
17 PC Number 0.5% G Time in 0.25% W 0.5% G 0.5% G Days 0.25% BB
0.25% BB 0.25% W 0.5% G 0.25% BB Blank 0 0 0 0 0 0 0 0.83 0.13 0.69
0.23 0.76 3.6 3.68 1.79 0.37 1.26 0.48 1.33 6.17 6.19 2.77 0.58
1.82 0.72 1.87 8.41 8.45 3.81 0.84 2.44 1.01 2.46 10.48 10.49 4.9
1.14 3.02 1.35 2.99 12.36 12.19 5.83 1.37 3.53 1.62 3.51 14.05
13.82 6.8 1.62 4.1 1.87 4.07 15.82 15.39 7.77 1.93 4.67 2.23 4.69
17.31 16.59
EXAMPLE 31
[0712] Accelerated Yellowing with High Intensity Lamps
[0713] BTMP sheets are treated with 0.25% by weight of Compound B,
0.5% by weight of Compound Q and 1.0% by weight of Compound CC or
DD. The results show the effectiveness of nitrones alone, nitrones
with a UVA, nitrones with a nitroxide and especially nitrone with a
UVA and a nitroxide in inhibition to yellowing compared to the
untreated control sheet.
18 PC Number 0.5% Q 0.5% Q 0.25% 0.25% 0.25% Time in 0.25% B B 0.5%
Q 0.5% Q B B Days 1% CC 1% DD 1% CC 1% DD 0.5% Q 1% CC 1% DD 1% CC
1% DD Blank 0 0 0 0 0 0 0 0 0 0 0 0.74 -1.25 0.13 -0.43 0.25 0.55
-0.43 0.85 0.28 2.14 3.22 1.74 -0.92 0.45 -0.16 0.72 1.19 0.28 2.49
1.82 4.78 7.24 2.82 -0.59 0.84 0.25 1.26 1.82 0.83 3.83 3.69 6.68
9.77 3.83 -0.41 1.33 0.93 1.88 2.63 1.63 5.09 5.88 8.34 12.42 4.76
-0.19 1.75 1.7 2.56 3.53 2.53 6.13 7.8 9.8 14.78 5.75 -0.01 2.08
2.54 3.13 4.41 3.3 6.87 9.63 11.14 16.89 6.77 0.19 2.51 3.35 3.77
5.36 3.96 7.67 11.25 12.33 19.13 7.75 0.44 2.91 4.14 4.36 6.13 4.56
8.23 12.39 13.16 20.09 8.77 0.63 3.22 5.07 4.87 6.94 5.27 8.84
13.87 14 21.84
EXAMPLE 32
[0714] Accelerated Yellowing with High Intensity Lamps
[0715] BTMP sheets are treated with 0.5% by weight of Compound Q
and 0.25% by weight of Compounds D, B, C, E and A. The results show
the superiority of hydroxylamines over nitroxides in maintaining a
high brightness of the paper upon application and during
exposure.
19 ISO Brightness Time in 0.5% Q 0.5% Q 0.5% Q 0.5% Q 0.5% Q 0.5% Q
Blank Days 0.25% D 0.25% B 0.25% C 0.25% E 0.25% A 0 78.83 76.96
76.75 78.24 79.85 79.75 78.6 0.75 77.45 77.53 77.15 76.21 78.91
75.36 68.43 1.74 75.77 77.16 76.66 74.36 78.48 72.22 62.89 2.74
73.61 76.59 75.89 72.1 77.7 68.93 58.54 3.75 71.95 75.96 75.21
70.14 77.12 66.09 55.41 6.81 65.96 72.86 72.02 64.11 74.09 58.58
49.29
EXAMPLE 33
[0716] Accelerated Yellowing with High Intensity Lamps
[0717] Additives are added with a sizing treatment on 100% BTMP
paper coated with 2 g/m.sup.2/side using a Pilot Liquid Application
System from Bonnier Technology Group Inc. (LAS System). It consists
of a hydrophilic roll, soft metering roll, soft backing roll, and
sizing pan. A film of sizing solution is drawn through the metering
nip onto the hydrophilic roll. The paper gets sized when it runs
between the hydrophilic roll and the A backing roll.
[0718] Starch based coating formulation:
20 Commercial name Chemical Nature Parts Penford .RTM. Gum 280
Hydroxyethylated starch 80 Acronal .RTM. S728 N-Butylacrylate &
styrene copolymer 20 dispersion Total solids content of 20%, pH
around 7.0
[0719]
21 Sizing Sizing 0.36% G 0.24% G Time in Days Blank Sizing only
0.84% S 0.55% S PC Number 0 0 0 0 0 1.01 4.69 4.45 0.59 0.95 1.85
6.78 6.51 0.79 1.53 2.9 8.95 8.98 1.04 1.91 4.1 11.61 10.68 1.41
2.51 4.8 13.29 12.12 1.66 2.84 5.81 14.75 13.98 1.89 3.23 6.77
16.15 15.26 2.04 3.66 7.82 17.16 16.27 2.42 3.85 8.78 18.17 17.19
2.45 4.22 9.89 19.28 18.19 2.66 4.42 10.92 21.11 19.45 3.02 4.97
11.81 20.8 20.31 3.18 5.37 12.81 21.98 21.18 3.55 5.58 13.79 22.68
22.16 3.65 5.99
EXAMPLE 34
[0720] Accelerated Yellowing with High Intensity Lamps
[0721] Additives are added with a pigmented sizing treatment on
100% BTMP paper coated with 2 g/m.sup.2/side using a Pilot Liquid
Application System from Bonnier Technology Group Inc. (LAS System).
It consists of a hydrophilic roll, soft metering roll, soft backing
roll, and sizing pan. A film of sizing solution is drawn through
the metering nip onto the hydrophilic roll. The paper gets sized
when it runs between the hydrophilic roll and the backing roll.
[0722] 100% BTMP paper coated with 4 g/m.sup.2/side pigments based
coating formulation:
22 Commercial name Chemical Nature Parts Covercarb .RTM. Ultrafine
ground calcium carbonate 80 Astraplate .RTM. Delaminated clay 20
Penford .RTM. Gum 280 Hydroxyethylated starch 6 Acronal .RTM. S728
N-Butylacrylate & styrene copolymer 12 dispersion Sterocoll
.RTM. AL Anionic water-in-oil emulsion of an 0.1 acrylamide-acrylic
copolymer AZCOTE .RTM. 5800 M Ammonium zirconium carbonate solution
0.5 Total solids content of 57%, pH around 8.0
[0723]
23 PC Number Blank Coating only Coating Coating Coating Time in
0.13% G 0.4% G 0.19% G Days 0.4% S 0.74% S 0.48% S 0 0 0 0 0 0 1
4.46 3.66 0.65 0.16 0.7 1.83 7.16 5.15 1.03 0.31 1.15 2.91 8.54 6.7
1.21 0.43 1.41 4.11 11.04 8.47 1.53 0.59 1.61 4.8 13.08 10.55 2.1
0.59 1.96 5.82 14.25 11.19 2.02 0.8 2.16 6.78 16.01 12.44 2.39 0.92
2.54 7.83 17.45 13.67 2.61 1.02 2.7 8.8 18.09 14.08 2.68 0.98 2.86
9.9 18.9 14.88 2.95 1.09 3.02 10.94 20.19 15.67 3.12 1.21 3.28
11.81 21.38 16.68 3.59 1.31 3.57 12.82 22.25 17.57 3.58 1.46 3.75
13.8 23.26 18.21 3.83 1.59 4.27
EXAMPLE 35
[0724] Using the accelerated test method, BTMP handsheets
containing various combinations of 0.25% by weight of a hindered
amine, 0.5% by weight of an s-triazine UV absorber and/or 0.5% by
weight of a polymeric additives are compared for efficacy in
preventing yellowing. The data are presented on the table
below.
24 Table for Example 35 Days PC Numbers Square Names A B C D E F G
H I J K 1.14 2.56 1.937 2.557 .1627 .2688 .6753 2.754 1.833 2.188
1.927 5.319 1.97 4.40 3.214 4.042 .4481 .5323 1.249 4.484 2.987
3.643 3.219 8.064 2.98 6.20 4.546 5.752 .7997 .9261 1.873 6.326
4.360 5.338 4.778 10.99 4.06 9.04 6.210 7.590 1.287 1.460 2.742
8.403 5.855 6.964 6.352 13.95 5.03 11.50 8.252 9.841 2.087 2.228
3.957 10.64 7.498 9.008 8.229 17.20 5.98 12.74 9.404 11.19 2.466
2.582 4.593 12.16 8.572 10.13 9.295 19.28 6.96 14.25 10.54 12.58
2.747 2.889 5.203 13.25 9.360 11.04 10.18 21.01 7.98 16.48 12.23
14.65 3.541 3.792 6.425 15.24 11.07 12.66 11.74 23.52 A contains
the UV absorber TINUVIN .RTM. 400; Compound Y. B contains the UV
absorber TINUVIN .RTM. 400 and the polymer PEO. C contains the UV
absorber TINUVIN .RTM. 400 and the polymer PTHF. D contains the
hindered amine nitroxide Compound B, the UV absorber TINUVIN .RTM.
400 and the polymer PEO. E contains the hindered amine nitroxide
Compound B, the UV absorber TINUVIN .RTM. 400 and the polymer PTHF.
F contains the hindered amine nitroxide Compound B and the UV
absorber TINUVIN .RTM. 400. G contains the hindered amine nitroxide
Compound JJ and the UV absorber TINUVIN .RTM. 400. H contains the
hindered amine nitroxide Compound B. I contains the hindered amine
TEMPO. J contains the hindered amine TEMPO. K is the control
containing no stabilizer additives.
[0725] As inspection of the data on the table attests, in best to
poorest order
D.congruent.E>F>H>J>B>I>C>G>A>>K.
These data show that the combination of a nitroxide, a UV absorber
and a polymer coadditive provides the best protection against
yellowing after 8 days exposure.
EXAMPLE 36
[0726] Using the accelerated test method, BTMP handsheets
containing various combinations of 0.25% by weight of a hindered
amine, 0.5% by weight of a benzophenone UV absorber and/or 0.5% by
weight of a polymeric additives are compared for efficacy in
preventing yellowing. The data are presented on the table
below.
25 Table for Example 36 Days PC Numbers Square Names A B C D E F G
H I .822 1.89 1.545 1.784 .0633 .0881 .0211 1.574 .9791 3.826 1.87
3.41 2.733 3.241 .3018 .2650 .1786 2.911 2.048 6.978 2.91 5.00
4.254 4.939 .6705 .5656 .4648 4.489 3.249 10.19 3.87 6.96 6.038
6.875 1.371 1.183 1.100 6.319 4.770 13.68 4.83 8.59 7.534 8.702
1.808 1.484 1.334 7.759 5.903 16.43 5.81 9.93 8.690 9.944 2.031
1.658 1.483 8.810 6.785 18.26 6.83 11.80 10.37 11.67 2.704 2.217
2.079 10.34 7.968 21.39 7.82 13.59 11.99 13.49 3.288 2.653 2.559
11.53 9.169 23.91 A contains the UV absorber UVINUL .RTM. 3000. B
contains the UV absorber UVINUL .RTM. 3000 and the polymer PEO. C
contains the UV absorber UVINUL .RTM. 3000 and the polymer PTHF. D
contains the hindered amine nitroxide Compound B, the UV absorber
UVINUL .RTM. 3000 and the polymer PEO. E contains the hindered
amine nitroxide Compound B, the UV absorber UVINUL .RTM. 3000 and
the polymer PTHF. F contains the hindered amine nitroxide Compound
B and the UV absorber UVINUL .RTM. 3000. G contains the hindered
amine Compound JJ and the UV absorber UVINUL .RTM. 3000. H contains
the hindered amine nitroxide Compound B. I is the control
containing no stabilizer additives.
[0727] As inspection of the data on the table attests, in best to
poorest order F>E>D>H>G>B>C.congruent.A>>I.
These data show that the combination of a nitroxide and a
benzophenone UV absorber coadditive provides the best protection
against yellowing after 8 days exposure.
EXAMPLE 37
[0728] Using the accelerated test method, BTMP handsheets
containing various combinations of 0.25% by weight of a hindered
amine, 0.5% by weight of a benzophenone UV absorber and/or 0.5% by
weight of a polymeric additives are compared for efficacy in
preventing yellowing. The data are presented on the table
below.
26 Table for Example 37 Days PC Numbers Square Names A B C D E F G
1.01 3.60 3.621 1.383 1.764 3.454 1.221 5.048 2.09 6.42 6.027 2.412
3.200 5.842 2.501 8.506 3.05 9.03 8.646 3.845 5.012 8.433 4.123
12.04 4.01 11.60 11.21 4.957 6.360 10.54 5.245 15.26 4.98 13.19
13.01 4.412 7.396 11.92 6.115 17.50 6.01 15.49 15.26 6.252 9.151
14.34 7.611 20.59 7.00 17.75 17.67 7.653 10.83 16.64 8.926 23.32 A
contains the UV absorber UVINUL .RTM. 3048; Compound Z. B contains
the UV absorber UVINUL .RTM. 3048 and the polymer PEO. C contains
the hindered amine nitroxide Compound F, the UV absorber UVINUL
.RTM. 3048 and the polymer PEO. D contains the hindered amine
nitroxide Compound B and the UV absorber UVINUL .RTM. 3048. E
contains the hindered amine Compound JJ and the UV absorber UVINUL
.RTM. 3048. F contains the hindered amine nitroxide Compound B. G
is the control containing no stabilizer additives.
[0729] As inspection of the data on the table attests, in best to
poorest order C>F>D>E>B.congruent.A>>G. These
data show that the combination of a nitroxide, a benzophenone UV
absorber and polymer coadditive provides the best protection
against yellowing after 7 days exposure.
[0730] The tables in Examples 38 to 48 all show PC Numbers.
EXAMPLE 38
[0731] Using the accelerated test method, BTMP handsheets
containing various combinations of 1% by weight of a hindered
amine, 0.5% by weight of a benzotriazole UV absorber and/or 0.5% by
weight of a polymeric additives are compared for efficacy in
preventing yellowing. The data are presented on the table
below.
27 Table for Example 38 Days A B C D E F G H 0 0 0 0 0 0 0 0 0 1.17
1.62 0.91 1.13 1.4 2.26 2.85 3.35 3.42 2 3 1.81 2.18 2.24 3.69 4.42
5.07 5.26 2.98 4.23 2.62 3.15 3.14 5.21 5.9 6.75 7.22 4 5.67 3.58
4.32 4.44 7.26 7.81 9.09 9.87 5.01 6.73 4.28 5.2 5.13 8.84 9.08
10.48 11.72 5.99 7.73 5.01 5.98 6.08 10.64 10.49 12.11 13.69 6.94
8.75 5.74 6.79 6.75 11.91 11.42 13.29 14.95 7.98 9.62 6.46 7.55
7.48 13.25 12.44 14.36 16.48 8.99 10.27 6.99 8.14 8.2 14.63 13.54
15.66 18.25 9.98 10.6 7.36 8.56 9.03 16.1 14.56 16.81 19.97 11.01
11.34 7.96 9.27 9.93 17.85 15.9 18.37 21.84 12.01 13.48 9.17 10.27
10.57 19.04 16.65 19.19 23.03 A contains the hindered amine TMHP,
the UV absorber TINUVIN .RTM. 1130 and the polymer PEO. B contains
the hindered amine TMHP, the UV absorber TINUVIN .RTM. 1130 and the
polymer PTHF. C contains the hindered amine TMHP and the UV
absorber TINUVIN .RTM. 1130. D contains the hindered amine Compound
G and the UV absorber TINUVIN .RTM. 1130. E contains the UV
absorber TINUVIN .RTM. 1130. F contains the hindered amine TMHP. G
contains the hindered amine Compound JJ. H is the control
containing no stabilizer additives.
[0732] As inspection of the data on the table attests, in best to
poorest order D>B>C>F>A>E>G>H. These data show
that the combination of a hindered amine and a benzotriazole UV
absorber coadditive provides the best protection against yellowing
after 12 days exposure.
EXAMPLE 39
[0733] Using the ambient test method, BTMP handsheets containing
1%, 0.6% or 0.1% by weight of the hindered amine nitroxide Compound
F, 2% by weight of the benzotriazole UV absorber TlNUVIN.RTM. 328
and 1% by weight of the polymer PEO are compared for efficacy in
yellowing. The data are presented on the table below.
28 Table for Example 39 Days p51a p51b p51c p51d p51e 0 0.00 0.00
0.00 0.00 0.00 1 0.10 -0.08 -0.37 -0.24 -0.21 5 0.54 -0.18 -0.84
-0.64 -0.54 7 1.07 -0.04 -0.67 -0.47 -0.30 8 1.00 -0.12 -0.83 -0.63
-0.42 9 1.37 -0.04 -0.73 -0.50 -0.32 11 1.70 -0.10 -0.97 -0.67
-0.44 13 2.05 -0.08 -0.93 -0.61 -0.40 15 2.33 -0.13 -1.09 -0.73
-0.46 29 4.29 -0.02 -1.12 -0.67 -0.20 40 5.86 0.00 -1.16 -0.69
-0.13 55 7.52 0.03 -1.12 -0.60 0.18 59 7.88 0.02 -1.16 -0.60 0.22
66 8.83 0.05 -1.12 -0.55 0.39 69 9.05 0.01 -1.21 -0.67 0.35 73 9.56
0.09 -1.10 -0.53 0.49 80 10.48 0.14 -1.01 -0.44 0.64 87 10.91 0.10
-1.12 -0.56 0.55 94 12.11 0.28 -0.91 -0.37 0.83 111 13.38 0.32
-0.86 -0.29 1.01 122 14.71 0.52 -0.67 -0.10 1.32 129 14.60 0.37
-0.79 -0.19 1.38 136 15.92 0.50 -0.60 0.17 1.77 143 16.20 0.58
-0.47 0.28 1.99 150 16.68 0.52 -0.52 0.26 2.06 157 17.40 0.61 -0.40
0.34 2.16 164 18.08 0.67 -0.31 0.40 2.41 171 19.54 0.75 -0.13 0.58
2.82 178 19.98 0.89 -0.09 0.63 3.01 185 20.39 0.90 -0.07 0.69 3.23
188 20.70 0.83 -0.02 0.70 3.39 191 21.64 0.92 -0.12 0.66 3.41 199
22.11 0.85 -0.10 0.70 3.52 206 22.94 0.97 -0.02 0.75 3.71 213 23.59
0.91 0.03 0.82 3.82 220 24.34 0.95 -0.02 0.81 3.90 A is the control
containing no stabilizer additives. B is a control which is a Kraft
handsheet. C contains 1% of the nitroxide. D contains 0.6% of the
nitroxide. E contains 0.1% of the nitroxide.
[0734] As inspection of the data on the table attests, in best to
poorest order C.congruent.D.congruent.B>E>>>A. These
data show that the nitroxide provides resistance to yellowing
particularly at the 0.6 and 1% by weight levels that makes the
color after 220 days of exposure essentially equal to that obtained
with Kraft paper. Even at the 0.1% level, the nitroxide provides
very good resistance to yellowing.
EXAMPLE 40
[0735] Using the accelerated test method; the ambient test method;
and dark aging, BTMP handsheets containing 0.25%, 0.2%, 0.15%, 0.1%
or 0.05% by weight of the hindered amine nitroxide Compound F are
compared for efficacy in preventing yellowing. The data are
presented on the three tables below respectively.
29 Time a b c d e f Accelerated Test Method 0.00 0.00 0.00 0.00
0.00 0.00 0.00 24.33 2.27 2.55 3.16 3.46 3.68 5.18 48.50 4.17 4.52
5.46 6.05 6.29 8.60 73.25 5.71 6.18 7.46 8.05 8.62 11.65 97.00 7.42
7.94 9.39 10.34 10.97 14.68 121.50 9.00 9.57 11.42 12.57 13.17
17.34 144.50 10.56 11.28 13.32 14.53 15.36 20.05 168.25 12.04 12.84
15.08 16.52 17.39 22.57 Ambient Test Method 0.00 0.00 0.00 0.00
0.00 0.00 0.00 3.02 0.39 0.21 0.39 0.49 0.44 0.80 10.01 1.00 0.63
1.01 1.23 1.27 2.04 17.00 1.33 0.90 1.44 1.78 1.82 3.01 31.03 1.97
1.44 2.43 2.88 3.09 5.04 38.06 2.71 1.98 3.18 3.73 4.04 6.34 4.5.15
3.24 2.50 3.84 4.48 4.80 7.33 52.15 3.59 2.77 4.22 4.94 5.37 8.00
55.02 3.60 2.72 4.22 4.99 5.49 8.21 62.02 4.31 3.28 5.04 5.91 6.36
9.28 66.00 4.49 3.38 5.27 6.03 6.63 9.78 Dark Aging Test Method
0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.06 0.18 0.12 0.16 0.19 0.17
0.18 10.04 0.23 0.18 0.21 0.23 0.22 21.02 0.16 0.13 0.16 0.19 0.19
0.31 24.17 0.23 0.18 0.21 0.26 0.25 0.41 38.16 0.16 0.12 0.15 0.21
0.23 0.48 45.15 0.21 0.17 0.21 0.27 0.28 0.57 52.01 0.20 0.15 0.19
0.25 0.26 0.58 62.96 0.20 0.15 0.21 0.27 0.28 0.67 A contains 0.25%
of the nitroxide. B contains 0.2% of the nitroxide. C contains
0.15% of the nitroxide. D contains 0.1% of the nitroxide. E
contains 0.05% of the nitroxide. F is a control containing no
stabilizer additive.
[0736] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order A>B>C>D>E>F.
These data show that the nitroxide provides resistance to yellowing
after 168 hours of accelerated photoaging.
[0737] During ambient photoaging, inspection of the data on the
table shows in best to poorest order
B>A>C>D>E>>F. These data show that the nitroxide
provides resistance to yellowing after 66 days of ambient
photoaging.
[0738] During dark aging, inspection of the data on the table shows
in best to poorest order B>C>A>D>E>>F. These data
show that the nitroxide provides resistance to yellowing after 63
days of dark aging.
EXAMPLE 41
[0739] Using the accelerated test method; the ambient test method;
and dark aging, BTMP handsheets containing 0.25% by weight of the
hindered amine nitroxide Compound F and 1%, 0.5%, 0.25%, 0.2% or
0.1% by weight of the benzotriazole UV absorber TINUVIN.RTM. 1130
are compared for efficacy in preventing yellowing. The data are
presented on the three tables below respectively.
30 Time a b c d e f 0.00 0.00 0.00 0.00 0.00 0.00 0.00 24.50 0.28
0.53 1.14 1.30 1.88 5.39 49.25 0.57 0.93 1.96 2.35 3.38 8.92 72.55
0.86 1.46 2.84 3.44 4.83 12.23 97.50 1.20 1.92 3.66 4.57 6.35 15.14
120.50 1.66 2.54 4.72 5.87 7.97 18.18 144.25 2.02 3.06 5.56 6.98
9.39 20.82 168.50 2.57 3.73 6.71 8.34 11.05 23.47 Ambient Test
Method 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.02 0.09 -0.03 0.03
-0.02 0.00 0.41 9.01 0.42 0.26 0.42 0.36 0.49 1.75 16.00 0.48 0.22
0.45 0.51 0.72 2.75 23.02 0.58 0.38 0.73 0.79 1.05 3.90 30.05 0.64
0.43 0.95 0.99 1.31 4.79 37.07 0.94 0.71 1.34 1.41 1.84 6.17 44.15
1.11 0.96 1.72 1.76 2.27 7.26 51.15 1.20 1.04 1.87 1.94 2.55 7.98
54.03 1.31 1.09 1.95 1.96 2.54 8.27 61.02 1.49 1.29 2.35 2.35 3.04
9.29 64.98 1.44 1.33 2.43 2.38 3.14 9.73 Dark Aging Test Method
0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.06 0.05 0.02 -0.01 -0.01 0.00
0.02 9.04 0.12 0.10 0.05 0.06 0.08 0.15 20.02 0.05 0.01 -0.03 -0.03
0.00 0.13 23.17 0.15 0.07 0.03 0.06 0.05 0.21 30-17 0.06 0.00 -0.04
-0.05 -0.03 0.20 37.17 0.10 0.00 -0.02 -0.04 0.00 0.26 44.15 0.13
0.08 0.00 0.03 0.06 0.33 51.06 0.15 0.03 -0.01 0.00 0.04 0.37 61.96
0.14 0.01 -0.01 -0.01 0.05 0.43 79.06 0.30 0.07 0.08 0.01 0.13 0.51
A contains 1% of the UV absorber. B contains 0.5% of the UV
absorber. C contains 0.25% of the UV absorber. D contains 0.2% of
the UV absorber. E contains 0.1% of the UV absorber. F is a control
containing no stabilizer additive.
[0740] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order
A>B>C>D>E>>F. These data show that the nitroxide
plus UV absorber provides resistance to yellowing after 168 hours
of accelerated photoaging.
[0741] During ambient photoaging, inspection of the data on the
table shows in best to poorest order
B>A>C>D>E>>F. These data show that the nitroxide
plus UV absorber provides resistance to yellowing after 65 days of
ambient photoaging.
[0742] During dark aging, inspection of the data on the table shows
in best to poorest order D>B>C>E>A>F. These data
show that the nitroxide plus UV absorber provides resistance to
yellowing after 79 days of dark aging, but that in the dark the UV
absorber is much less critical for efficacy.
EXAMPLE 42
[0743] Using the accelerated test method; the ambient test method;
and dark aging, BTMP handsheets containing 0.25% by weight of the
hindered amine nitroxide Compound B and 1%, 0.75%, 0.5%, 0.25% or
0.1% by weight of the polymer PTHF are compared for efficacy in
preventing yellowing. The data are presented on the three tables
below respectively.
31 Time a b c d e f Accelerated Test Method 0.00 0.00 0.00 0.00
0.00 0.00 0.00 25.00 1.42 1.08 1.50 1.58 1.57 4.56 48.75 2.41 1.98
2.64 2.82 2.86 7.58 73.25 3.63 3.07 4.04 4.37 4.46 11.08 96.25 4.88
4.12 5.38 5.78 5.95 14.07 120.00 5.90 5.14 6.62 7.20 7.41 16.88
144.25 7.20 6.22 8.14 8.64 8.84 19.74 Ambient Test Method 0.00 0.00
0.00 0.00 0.00 0.00 0.00 8.00 0.37 0.24 0.17 0.41 0.45 1.66 14.99
0.39 0.32 0.38 0.56 0.73 2.74 22.01 0.59 0.55 0.66 0.96 1.10 3.90
29.02 0.78 0.74 0.85 1.25 1.42 4.88 36.07 1.21 1.13 1.24 1.50 2.06
6.21 50.14 1.59 1.44 1.66 2.33 2.57 7.93 53.01 1.66 1.51 1.73 2.37
2.65 8.16 60.01 2.06 1.76 2.13 2.90 3.16 9.22 63.97 2.03 1.81 2.16
3.05 3.36 9.73 70.99 2.29 2.07 2.60 3.55 3.89 10.75 77.97 2.55 2.27
2.81 3.85 4.31 11.64 Dark Aging Test Method 0.00 0.00 0.00 0.00
0.00 0.00 0.00 1.05 -0.12 -0.13 -0.10 -0.09 -0.08 -0.06 8.03 -0.12
-0.10 -0.07 -0.09 -0.08 0.05 19.01 -0.19 -0.18 -0.15 -0.18 -0.17
0.02 22.16 -0.13 -0.12 -0.10 -0.10 -0.10 0.10 29.16 -0.23 -0.21
-0.22 -0.19 -0.21 0.08 36.16 -0.21 -0.17 -0.16 -0.17 -0.19 0.17
50.05 -0.21 -0.16 -0.15 -0.17 -0.19 0.28 A contains 1% of the
polymer PTHF. B contains 0.75% of the polymer PTHF. C contains 0.5%
of the polymer PTHF. D contains 0.25% of the polymer PTHF. E
contains 0.1% of the polymer PTHF F is a control containing no
stabilizer additive.
[0744] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order
B>A>C>D>E>>F. These data show that the nitroxide
plus polymer provides resistance to yellowing after 144 hours of
accelerated photoaging.
[0745] During ambient photoaging, inspection of the data on the
table shows in best to poorest order
B>A>C>D>E>>F. These data show that the nitroxide
plus polymer provides resistance to yellowing after 78 days of
ambient photoaging.
[0746] During dark aging, inspection of the data on the table shows
in best to poorest order A>E>D>B>C>>>F. These
data show that the nitroxide plus polymer provides resistance to
yellowing after 50 days of dark aging.
EXAMPLE 43
[0747] Using the accelerated test method; the ambient test method;
and dark aging, BTMP handsheets containing 0.25% by weight of the
hindered amine nitroxide Compound B, 1%, 0.5%, 0.25%, 0.2% or 0.1%
by weight of the benzotriazole UV absorber TINUVIN.RTM. 1130 and
0.5% by weight of polymer PTHF are compared for efficacy in
preventing yellowing. The data are presented on the three tables
below respectively.
32 Time a b c d e f Accelerated Test Method 0.00 0.00 0.00 0.00
0.00 0.00 0.00 23.42 -0.01 0.48 0.60 0.47 1.34 4.52 47.25 0.34 1.22
1.32 1.18 2.65 8.11 71.75 0.71 1.91 2.00 1.80 3.81 11.04 96.17 1.04
2.62 2.72 2.49 4.90 13.60 119.75 1.64 3.42 3.51 3.28 6.40 16.52
145.75 2.30 5.05 5.11 4.65 8.26 20.82 168.08 2.73 5.60 5.59 5.22
9.24 22.57 Ambient Test Method 0.00 0.00 0.00 0.00 0.00 0.00 0.00
6.98 -0.14 0.20 -0.01 0.07 0.48 1.79 13.97 -0.11 0.35 0.04 0.21
0.48 2.63 20.99 -0.04 0.58 0.25 0.44 0.74 3.73 28.01 0.02 0.71 0.37
0.63 1.01 4.73 35.04 0.24 1.06 0.64 0.98 1.41 6.01 42.11 0.47 1.28
0.91 1.26 1.79 7.02 49.11 0.55 1.29 0.88 1.36 1.87 7.78 51.99 0.61
1.33 0.95 1.45 1.91 8.07 59.11 0.79 1.70 1.24 1.72 2.40 9.32 62.97
0.76 1.78 1.25 1.77 2.52 9.70 69.97 1.16 2.09 1.59 2.14 3.00 10.88
77.01 1.25 2.27 1.64 2.30 3.27 11.75 Dark Aging Test Method 0.00
0.00 0.00 0.00 0.00 0.00 0.00 6.97 0.00 0.04 0.03 0.04 0.10 0.17
17.95 -0.09 -0.03 -0.05 -0.01 0.01 0.16 21.09 -0.04 -0.03 -0.01
0.02 0.06 0.23 28.10 -0.12 -0.16 -0.10 -0.07 -0.04 0.19 35.10 -0.07
-0.10 -0.07 -0.02 -0.02 0.28 48.99 -0.05 -0.08 -0.05 -0.02 0.00
0.36 59.89 -0.07 -0.11 -0.06 -0.04 -0.01 0.45 A contains 1% of the
UV absorber. B contains 0.5% of the UV absorber. C contains 0.25%
of the UV absorber. D contains 0.2% of the UV absorber. E contains
0.1% of the UV absorber. F is a control containing no stabilizer
additive.
[0748] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order
A>D>B>C>E>>F. These data show that the nitroxide
plus UV absorber plus polymer provides resistance to yellowing
after 168 hours of accelerated photoaging.
[0749] During ambient photoaging, inspection of the data on the
table shows in best to poorest order A>C>D=B>E>>F.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 77 days of ambient
photoaging.
[0750] During dark aging, inspection of the data on the table shows
in best to poorest order B>A>C>D>E>F. These data
show that the nitroxide plus UV absorber plus polymer provides
resistance to yellowing after 60 days of dark aging.
EXAMPLE 44
[0751] Using the accelerated test method; the ambient test method;
and dark aging, BTMP handsheets containing 0.25%, 0.2%, 0.15%, 0.1%
and 0.05% by weight of the hindered amine nitroxide Compound B,
0.5% by weight of the benzotriazole UV absorber TINUVIN.RTM. 1130
and 0.5% by weight of polymer PTHF are compared for efficacy in
preventing yellowing. The data are presented on the three tables
below respectively.
33 Time a b c d e f Accelerated Test Method 0.00 0.00 0.00 0.00
0.00 0.00 0.00 26.00 0.49 0.41 1.12 1.93 2.02 6.01 48.33 1.10 0.91
1.95 3.21 3.33 9.20 73.50 1.63 1.39 2.73 4.47 4.55 11.87 96.00 2.23
1.80 3.32 5.44 5.59 14.00 119.83 2.64 2.31 4.13 6.63 6.65 15.98
144.83 3.16 2.76 4.81 7.70 7.64 17.94 167.67 3.76 3.36 5.63 8.85
8.82 19.87 191.00 4.25 3.73 6.15 9.86 9.64 21.07 216.42 5.20 4.73
7.58 11.69 11.18 23.66 Ambient Test Method 0.00 0.00 0.00 0.00 0.00
0.00 0.00 1.99 -0.19 -0.10 -0.12 0.10 0.20 0.76 8.98 -0.17 0.06
0.01 0.37 0.61 1.98 16.00 -0.08 0.17 0.22 0.70 1.09 3.14 23.03 0.09
0.28 0.31 0.93 1.45 3.98 30.07 0.31 0.58 0.65 1.39 2.03 5.30 37.13
0.56 0.80 0.99 1.85 2.47 6.30 44.04 0.61 0.86 1.00 1.96 2.83 7.10
47.00 0.71 0.94 1.02 2.02 2.94 7.26 54.00 0.93 1.18 1.35 2.36 3.47
8.36 57.96 0.93 1.20 1.46 2.48 3.63 8.86 64.98 1.14 1.43 1.79 2.76
4.03 9.95 72.00 1.27 1.75 2.04 3.21 4.61 11.01 Dark Aging Test
Method 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.02 0.03 0.03 0.06 0.04
0.07 0.11 12.98 -0.06 -0.06 0.00 -0.01 0.02 0.21 16.15 -0.01 -0.01
0.03 0.03 0.07 0.28 23.15 -0.09 -0.12 -0.05 -0.07 0.02 0.25 30.15
-0.10 -0.08 -0.03 -0.07 0.05 0.34 37.13 -0.06 -0.06 -0.01 -0.01
0.08 0.38 44.04 -0.09 -0.06 -0.03 -0.02 0.07 0.42 54.94 -0.11 -0.07
-0.03 -0.05 0.08 0.47 72.03 0.00 -0.04 0.00 -0.03 0.11 0.56 A
contains 0.25% of the nitroxide. B contains 0.2% of the nitroxide.
C contains 0.15% of the nitroxide. D contains 0.1% of the
nitroxide. E contains 0.05% of the nitroxide. F is a control
containing no stabilizer additive.
[0752] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order
B>A>C>D>E>>F. These data show that the nitroxide
plus UV absorber plus polymer provides resistance to yellowing
after 216 hours of accelerated photoaging.
[0753] During ambient photoaging, inspection of the data on the
table shows in best to poorest order A>B>C>D>E>EF.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 72 days of ambient
photoaging.
[0754] During dark aging, inspection of the data on the table shows
in best to poorest order B>D>C>A>E>>F. These data
show that the nitroxide plus UV absorber plus polymer provides
resistance to yellowing after 72 days of dark aging.
EXAMPLE 45
[0755] Using the accelerated test method; the ambient test method;
and dark aging, BTMP handsheets containing 0.25% by weight of the
hindered amine nitroxide Compound B, 0.5% by weight of the
benzotriazole UV absorber TINUVIN.RTM. 1130 and 1%, 0.75%, 0.25% or
0.1% by weight of the polymer PTHF are compared for efficacy in
preventing yellowing. The data are presented on the three tables
below respectively.
34 Time a b c d e Accelerated Test Method 0.00 0.00 0.00 0.00 0.00
0.00 22.33 0.49 0.86 0.31 0.45 4.68 47.50 1.11 1.76 0.77 1.04 7.82
70.00 1.61 2.53 1.20 1.49 10.05 93.00 2.26 3.36 1.73 2.08 12.46
118.83 2.70 4.10 2.16 2.67 14.44 141.67 3.41 5.04 2.80 3.39 16.69
165.00 3.95 5.74 3.20 3.90 18.16 189.42 4.97 7.28 4.18 5.52 21.00
214.00 6.32 9.24 5.37 6.86 24.13 Ambient Test Method 0.00 0.00 0.00
0.00 0.00 0.00 7.90 -0.21 0.13 -0.20 -0.07 1.75 14.92 -0.10 0.32
-0.08 0.12 2.96 21.92 -0.05 0.43 -0.06 0.21 3.87 28.98 0.24 0.74
0.19 0.52 5.15 43.04 0.59 1.03 0.29 1.08 6.97 45.91 0.69 1.08 0.35
0.99 7.13 52.88 0.90 1.40 0.55 1.26 8.23 56.92 0.90 1.46 0.59 1.34
8.74 63.90 1.12 1.78 0.85 1.71 9.77 Dark Aging Test Method 0.00
0.00 0.00 0.00 0.00 0.00 0.94 0.04 0.03 0.02 0.02 0.04 11.92 -0.03
-0.04 -0.06 -0.04 0.23 15.06 0.03 0.00 -0.01 0.01 0.33 22.07 -0.07
-0.07 -0.09 -0.09 0.31 29.07 -0.04 -0.04 -0.08 -0.04 0.42 42.96
-0.03 -0.04 -0.06 -0.05 0.49 53.85 -0.01 -0.04 -0.07 -0.05 0.61
70.96 0.06 0.01 -0.03 -0.04 0.70 A contains 1% of the polymer PTHF.
B contains 0.75% of the polymer PTHF. C contains 0.25% of the
polymer PTHF. D contains 0.1% of the polymer PTHF. E is a control
containing no stabilizer additive.
[0756] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order C>A>D>B>>>E.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 214 hours of accelerated
photoaging.
[0757] During ambient photoaging, inspection of the data on the
table shows in best to poorest order C>A>D>B>>>E.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 64 days of ambient
photoaging.
[0758] During dark aging, inspection of the data on the table shows
in best to poorest order D>C>B>A>>>E. These data
show that the nitroxide plus UV absprber plus polymer provides
resistance to yellowing after 71 days of dark aging.
EXAMPLE 46
[0759] Using the accelerated test method; the ambient test method;
and dark aging, BCTMP Aspen handsheets containing 0.25% by weight
of the hindered amine nitroxide Compound B, 1%, 0.5% or 0% by
weight of the benzotriazole UV absorber TINUVIN.RTM. 1130 and 1%,
0.5% or 0% by weight of the polymer PTHF are compared for efficacy
in preventing yellowing. The data are presented on the three tables
below respectively.
35 Time a b c d e Accelerated Test Method 0.00 0.00 0.00 0.00 0.00
0.00 1.00 3.50 2.59 0.77 1.02 5.81 2.02 5.57 3.81 1.16 1.51 8.77
3.03 7.49 5.05 1.71 2.02 11.62 4.01 9.04 5.82 2.06 2.46 13.93 4.98
10.54 6.76 2.56 2.95 16.26 6.14 12.04 7.67 2.82 3.21 18.49 7.64
13.90 8.61 3.37 3.81 21.64 8.24 14.60 8.76 3.54 3.95 22.42 Ambient
Test Method 0.00 0.00 0.00 0.00 0.00 0.00 1.99 0.76 0.49 0.07 0.26
1.51 3.06 1.27 0.84 0.28 0.48 2.44 24.13 1.80 1.22 0.52 0.73 3.25
31.13 2.00 1.34 0.61 0.76 3.85 34.02 1.94 1.33 0.61 0.79 3.93 41.00
2.16 1.63 0.84 0.95 4.63 45.00 2.39 1.66 0.84 0.96 4.91 52.14 2.81
1.66 1.04 1.13 5.57 59.02 3.15 1.84 1.23 1.22 6.10 Dark Aging Test
Method 0.00 0.00 0.00 0.00 0.00 0.00 9.17 -0.04 -0.03 0.01 -0.02
0.01 16.16 0.03 0.01 0.07 0.04 0.03 23.13 0.09 0.08 0.12 0.08 0.10
30.06 0.07 0.03 0.10 0.03 0.05 40.94 0.06 0.04 0.11 0.05 0.05 58.04
0.11 0.28 0.32 0.28 0.29 A contains no UV absorber or no polymer
PTHF. B contains no UV absorber and 1% of the polymer PTHF. C
contains of 1% of the UV absorber and no polymer PTHF. D contains
0.5% of the UV absorber and 0.5% of polymer PTHF. E is a control
containing no stabilizer additive.
[0760] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order C>D>B>A>>E.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 8 days of accelerated
photoaging.
[0761] During ambient photoaging, inspection of the data on the
table shows in best to poorest order C>D>B>A>>E.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 59 days of ambient
photoaging.
[0762] During dark aging, inspection of the data on the table shows
in best to poorest order A>B>D>E>C. These data show
that the nitroxide plus UV absorber plus polymer provides
resistance to yellowing after 71 days of dark aging.
EXAMPLE 47
[0763] Using the accelerated test method; the ambient test method;
and dark aging, stone-ground wood (SGW) handsheets containing 0.25%
by weight of the hindered amine nitroxide Compound B, 1%, 0.5% or
0% by weight of the benzotriazole UV absorber TINUVIN.RTM. 1130 and
1%, 0.5% or 0% by weight of the polymer PTHF are compared for
efficacy in preventing yellowing. The data are presented on the
three tables below respectively.
36 Time a b c d e Accelerated Test Method 0.00 0.00 0.00 0.00 0.00
0.00 0.99 3.94 3.28 0.82 1.51 8.19 1.97 6.95 5.11 1.69 2.70 12.54
2.94 9.75 6.84 2.48 3.81 16.70 4.09 12.18 8.83 3.34 5.09 20.41 5.60
15.07 10.72 4.42 6.39 25.36 6.20 15.74 11.24 4.83 6.90 26.84
Ambient Test Method 0.00 0.00 0.00 0.00 0.00 0.00 6.95 0.44 0.15
-0.25 -0.24 1.80 14.01 1.19 0.63 0.08 0.03 3.22 28.08 2.27 1.28
0.51 0.36 5.25 30.98 2.26 1.32 0.57 0.38 5.30 37.96 2.91 1.74 0.82
0.63 6.55 41.94 3.03 1.86 0.89 0.70 7.13 48.99 3.64 2.12 1.21 0.83
8.30 55.98 4.12 2.40 1.44 1.01 9.15 Dark Aging Test Method 0.00
0.00 0.00 0.00 0.00 0.00 7.13 -0.08 -0.17 -0.06 -0.13 -0.10 14.12
-0.01 -0.15 -0.01 -0.14 -0.02 21.08 0.16 0.02 0.10 0.00 0.18 28.02
0.13 -0.02 0.09 -0.03 0.13 38.90 0.18 0.00 -0.03 -0.09 0.13 56.00
0.88 0.13 0.31 0.05 0.28 A contains no UV absorber or no polymer
PTHF. B contains no UV absorber and 1% of the polymer PTHF. C
contains of 1% of the UV absorber and no polymer PTHF. D contains
0.5% of the UV absorber and 0.5% of polymer PTHF. E is a control
containing no stabilizer additive.
[0764] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order C>D>B>A>>E.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 6 days of accelerated
photoaging.
[0765] During ambient photoaging, inspection of the data on the
table shows in best to poorest order D>C>B>A>>E.
These data show that the nitroxide plus UV absorber plus polymer
provides resistance to yellowing after 56 days of ambient
photoaging.
[0766] During dark aging, inspection of the data on the table shows
in best to poorest order D>B>E>C>A. These data show
that the nitroxide plus UV absorber plus polymer provides
resistance to yellowing after 56 days of dark aging.
EXAMPLE 48
[0767] Using the accelerated test method; the ambient test method;
and dark aging, BTMP paper loadings with 0.25%, 0.2%, 0.15%, 0.1%
amd 0.05% by weight of hindered amine nitroxide Compound B and 0.5%
by weight of Compound LL are compared for efficacy in preventing
yellowing on aging. The data are presented on the three tables
below respectively.
37 Time a b c d e f g h Accelerated Test Method 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 0.00 24.67 2.94 2.72 3.19 3.46 4.29 4.76 6.70
6.48 48.25 5.79 5.16 5.68 6.06 7.46 8.16 10.98 10.98 71.75 7.60
7.25 7.93 8.31 10.03 11.02 14.43 14.37 97.08 9.13 8.83 9.60 10.13
11.85 13.14 16.98 17.00 120.25 10.76 10.55 11.21 11.72 13.58 15.01
19.31 19.34 168.25 14.63 14.71 15.17 15.52 18.08 19.76 25.10 25.36
Ambient Test Method 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
8.01 0.39 0.21 0.54 0.50 0.68 1.13 1.91 2.05 15.03 0.62 0.41 0.81
0.80 1.05 1.67 2.80 3.02 22.05 1.19 0.89 1.30 1.28 1.62 2.44 3.92
4.31 29.14 1.74 1.25 1.74 1.78 2.13 3.17 4.88 5.38 36.14 2.07 1.45
2.00 2.00 2.48 3.56 5.65 6.25 39.01 2.03 1.47 2.01 2.06 2.50 3.60
5.75 6.46 46.01 2.46 1.98 2.53 2.53 3.11 4.42 6.82 7.62 50.01 2.62
2.04 2.67 2.71 3.31 4.74 7.28 8.10 56.99 3.06 2.40 3.09 3.11 3.71
5.33 8.24 9.17 64.01 3.36 2.80 3.46 3.42 4.25 5.94 9.19 10.03 Dark
Aging Test Method 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.16
0.09 -0.06 0.02 0.08 0.02 0.05 0.13 0.17 15.17 -0.08 -0.21 -0.11
-0.05 -0.07 -0.05 0.10 0.18 22.18 -0.13 -0.22 -0.17 -0.11 -0.09
-0.07 0.13 0.30 29.14 0.01 -0.16 0.01 0.06 0.01 0.06 0.29 0.40
36.07 0.00 -0.22 -0.05 0.02 -0.02 0.03 0.27 0.40 46.95 -0.07 -0.21
-0.05 0.01 -0.03 0.04 0.32 0.49 A contains 0.25% nitroxide and 0.5%
brightner. B contains 0.25% nitroxide and no brightner. C contains
0.2% nitroxide and 0.5% brightner. D contains 0.15% nitroxide and
0.5% brightner. E contains 0.1% nitroxide and 0.5% brightner. F
contains 0.05% nitroxide and 0.5% brightner. G is a control
containing no nitroxide and 0.5% brightner. H is a control
containing no stabilizer additive.
[0768] During accelerated photoaging, inspection of the data on the
table shows in best to poorest order
A>B>C>D>E>F>>G=H. These data show that the
nitroxide plus brightner provides resistance to yellowing after 168
hours of accelerated photoaging.
[0769] During ambient photoaging, inspection of the data on the
table shows in best to poorest order
B>A=C=D>E>F>G>H. These data show that the nitroxide
plus brightner provides resistance to yellowing after 64 days of
ambient photoaging.
[0770] During dark aging, inspection of the data on the table shows
in best to poorest order B>C>A>E>D>F>G>H.
These data show that the nitroxide plus brightner provides
resistance to yellowing after 47 days of dark aging.
EXAMPLE 49
[0771] Using the dark aging method, BTMP handsheets are allowed to
sit in the dark for 10 days before treatment with 0.05% by weight
of nitroxide Compound B. The sheets are then dark aged for a period
of 72 days. The ISO brightness data are given on the table
below.
38 Days e f -10 78.11 78.22 0 77.94 77.48 2.02 77.71 77.14 12.98
77.89 76.85 16.15 77.72 76.65 23.15 77.87 76.75 30.15 77.8 76.48
37.13 77.68 76.37 44.04 77.74 76.28 54.94 77.7 76.13 72.03 77.6
75.89 E contains 0.05% nitroxide. F is a control containing no
stabilizer additive.
[0772] The nitroxide provides the good ISO brightness values after
the 72 day period of dark aging.
EXAMPLE 50
[0773] Accelerated Yellowing with High Intensity Lamps
[0774] BTMP sheets are treated with 0.5% by weight of Compound S
and 0.5% by weight of Compound A and Compound FF
39 PC Number Time in days S, A S, FF S A FF Control 0 0 0 0 0 0 0
0.78 0.14 -0.23 1.93 0.7 0.67 3.26 1.75 0.38 -0.32 3.77 1.12 1.09
6.19 2.75 0.85 -0.19 5.8 1.93 1.86 9.16 3.77 1.25 -0.14 7.62 2.51
2.45 11.6 4.77 1.54 -0.22 9.48 3.19 3.07 13.8 5.75 1.87 -0.07 10.9
3.74 3.59 15.83 6.78 2.16 -0.13 11.87 4.22 4.07 16.97
[0775] Inspection of the data reveals that hydroxylamine citrate
salt are more effective in inhibiting yellowing than the
hydroxylamine and in combination with a UVA superior results are
achieved with the citrate salt.
EXAMPLE 51
[0776] Accelerated Yellowing with High Intensity Lamps
[0777] BTMP sheets are treated with 0.25% by weight of Compound A
and with 1% by weight of the sulfur containing inhibitors:
[0778] 2-(2'-methoxyethoxy)-ethanethiol;
[0779] 2,2'-oxydiethanethiol;
[0780] 1-thioglycerol;
[0781] sodium thioglycolate;
[0782] thiolactic acid;
[0783] sodium thiolactate;
[0784] .beta.-mercaptopropionic acid;
[0785] sodium .beta.-mercaptopropionate;
[0786] glycol dimercaptoacetate;
[0787] glycol dimercaptopropionate;
[0788] polyethylene glycol dimercaptoacetate;
[0789] polyethylene glycol dimercaptopropionate;
[0790] pentaerythritol tetrathioglycolate;
[0791] trimethylol propane tri-(3-mercaptopropionate);
[0792] polymethylene sulfide;
[0793] disodium methylene bis thiopropionate;
[0794] 3,3'-thiodipropionic acid;
[0795] dithiothreitol.
[0796] The sheets treated with a combination of hydroxylamine and
sulfur containing compounds exhibit substantial inhibition to
yellowing compared to the untreated control sheet and illustrate
the performance enhancement when combinations of hydroxylamine and
sulfur containing compounds are used.
EXAMPLE 52
[0797] Accelerated Yellowing with High Intensity Lamps
[0798] BTMP sheets are treated with 0.25% by weight of Compound FF
and with 1% by weight of the sulfur containing inhibitors:
[0799] 2-(2'-methoxyethoxy)-ethanethiol;
[0800] 2,2'-oxydiethanethiol;
[0801] 1-thioglycerol;
[0802] sodium thioglycolate;
[0803] thiolactic acid;
[0804] sodium thiolactate;
[0805] .beta.-mercaptopropionic acid;
[0806] sodium .beta.-mercaptopropionate;
[0807] glycol dimercaptoacetate;
[0808] glycol dimercaptopropionate;
[0809] polyethylene glycol dimercaptoacetate;
[0810] polyethylene glycol dimercaptopropionate;
[0811] pentaerythritol tetrathioglycolate;
[0812] trimethylol propane tri-(3-mercaptopropionate);
[0813] polymethylene sulfide;
[0814] disodium methylene bis thiopropionate;
[0815] 3,3'-thiodipropionic acid;
[0816] dithiothreitol.
[0817] The sheets treated with a combination of hydroxylamine salt
and sulfur containing compounds exhibit substantial inhibition to
yellowing compared to the untreated control sheet and illustrate
the performance enhancement when combinations of hydroxylamine salt
and sulfur containing compounds are used.
EXAMPLE 53
[0818] Accelerated Yellowing with High Intensity Lamps
[0819] BTMP sheets are treated with 0.25% by weight of Compound B
and with 1% by weight of the sulfur containing inhibitors Compounds
GG, HH and II
40 PC Number Time in Days B,GG B,HH B,II GG HH II control 0 0 0 0 0
0 0 0 0.92 1.1 1.25 1.1 2.92 3.65 2.55 3.94 1.88 2.4 2.32 2.09 5.9
6.45 4.93 6.91 3.9 5.33 4.36 3.98 11.88 11.48 9.81 12.15 5 7.31
5.59 5.13 15.56 14.26 12.86 14.84 5.98 9.37 6.88 6.32 18.55 16.58
15.5 17.13 6.95 11.32 8.06 7.37 21.3 18.51 17.75 18.93 7.92 13.34
9.17 8.55 24.39 20.74 20.43 21.43 8.88 15.1 10.34 9.72 27.33 22.74
22.9 23.55
[0820] The sheets treated with a combination of nitroxide and
sulfur containing compounds exhibit substantial inhibition to
yellowing compared to the untreated control sheet and illustrate
the performance enhancement when combinations of nitroxides and
sulfur containing compounds are used. Inspection of the data
reveals that Compound HH and II are particularly effective when
combined with a nitroxide.
EXAMPLE 54
[0821] Accelerated Yellowing with High Intensity Lamps
[0822] BTMP sheets are treated with 0.25% by weight of Compound A,
0.5% of Compound R and with 1% by weight of the sulfur containing
inhibitors:
[0823] 2-(2'-methoxyethoxy)-ethanethiol;
[0824] 2,2'-oxydiethanethiol;
[0825] 1-thioglycerol;
[0826] sodium thioglycolate;
[0827] thiolactic acid;
[0828] sodium thiolactate;
[0829] .beta.-mercaptopropionic acid;
[0830] sodium .beta.-mercaptopropionate;
[0831] glycol dimercaptoacetate;
[0832] glycol dimercaptopropionate;
[0833] polyethylene glycol dimercaptoacetate;
[0834] polyethylene glycol dimercaptopropionate;
[0835] pentaerythritol tetrathioglycolate;
[0836] trimethylol propane tri-(3-mercaptopropionate);
[0837] polymethylene sulfide;
[0838] disodium methylene bis thiopropionate;
[0839] 3,3'-thiodipropionic acid;
[0840] dithiothreitol.
[0841] The sheets treated with a combination of hydroxylamine, UVA
and sulfur containing compounds exhibit substantial inhibition to
yellowing compared to the untreated control sheet and illustrate
the performance enhancement when combinations of hydroxylamine, UVA
and sulfur containing compounds are used.
EXAMPLE 56
[0842] Accelerated Yellowing with High Intensity Lamps
[0843] BTMP sheets are treated with 0.25% by weight of Compound FF,
0.5% of Compound R and with 1% by weight of the sulfur containing
inhibitors:
[0844] 2-(2'-methoxyethoxy)-ethanethiol;
[0845] 2,2'-oxydiethanethiol;
[0846] 1-thioglycerol;
[0847] sodium thioglycolate;
[0848] thiolactic acid;
[0849] sodium thiolactate;
[0850] .beta.-mercaptopropionic acid;
[0851] sodium .beta.-mercaptopropionate;
[0852] glycol dimercaptoacetate;
[0853] glycol dimercaptopropionate;
[0854] polyethylene glycol dimercaptoacetate;
[0855] polyethylene glycol dimercaptopropionate;
[0856] pentaerythritol tetrathioglycolate;
[0857] trimethylol propane tri-(3-mercaptopropionate);
[0858] polymethylene sulfide;
[0859] disodium methylene bis thiopropionate;
[0860] 3,3'-thiodipropionic acid;
[0861] dithiothreitol.
[0862] The sheets treated with a combination of hydroxylamine salt,
UVA and sulfur containing compounds exhibit substantial inhibition
to yellowing compared to the untreated control sheet and illustrate
the performance enhancement when combinations of hydroxylamine
salt, UVA and sulfur containing compounds are used.
EXAMPLE 57
[0863] Accelerated Yellowing with High Intensity Lamps
[0864] BTMP sheets are treated with 0.25% by weight of Compound B,
0.5% of Compound R and with 1% by weight of the sulfur containing
inhibitors Compounds GG, HH and II
41 PC Number Time in R,B, R,B, R,B, Days R B GG HH II R,GG R,HH
R,II control 0 0 0 0 0 0 0 0 0 0 0.92 1.62 1.52 0.97 0.48 0.5 1.58
1.92 1.51 3.94 1.88 3.05 3 2.08 1.1 1.2 3.23 3.56 3.08 6.91 3.9 5.8
5.99 4.33 2.14 2.55 6.65 6.75 6.35 12.15 5 7.47 7.58 5.82 2.99 3.65
9.12 8.93 8.63 14.84 5.98 9.07 9 7.26 3.82 4.7 11.17 10.65 10.59
17.13 6.95 10.28 10.35 8.43 4.58 5.78 12.99 12.25 12.36 18.93 7.92
11.58 11.72 10.03 5.38 6.77 14.95 14.05 14.36 21.43 8.88 12.9 12.88
11.21 6.13 7.89 17.25 15.97 16.12 23.55
[0865] The sheets treated with a combination of nitroxide, UVA and
sulfur containing compounds exhibit substantial inhibition to
yellowing compared to the untreated control sheet and illustrate
the performance enhancement when combinations of nitroxides, UVA
and sulfur containing compounds are used. Inspection of the data
reveals that Compound HH and II are particularly effective when
combined with a nitroxide and UVA.
EXAMPLE 58
[0866] Accelerated Yellowing with High Intensity Lamps
[0867] BTMP sheets are treated with 0.25% by weight of Compound A
and with 1% by weight of the following metal salts:
[0868] MgSO.sub.4
[0869] MnSO.sub.4
[0870] ZnSO.sub.4
[0871] The sheets treated with a combination of hydroxylamine and
metal salt exhibit substantial inhibition to yellowing compared to
the untreated control sheet and illustrate the performance
enhancement when combinations of hydroxylamine and metal salt are
used.
EXAMPLE 59
[0872] Accelerated Yellowing with High Intensity Lamps
[0873] BTMP sheets are treated with 0.25% by weight of Compound B
and with 1% by weight of the following metal salts:
[0874] MgSO.sub.4
[0875] MnSO.sub.4
[0876] ZnSO.sub.4
[0877] The sheets treated with a combination of nitroxide and metal
salt exhibit substantial inhibition to yellowing compared to the
untreated control sheet and illustrate the performance enhancement
when combinations of nitroxide and metal salt are used.
EXAMPLE 60
[0878] Accelerated Yellowing with High Intensity Lamps
[0879] BTMP sheets are treated with 0.25% by weight of Compound A
and with 1% by weight of the diene compounds:
[0880] 1-methoxy-1,3-cyclohexadiene;
[0881] 1-methoxy-1,4-cyclohexadiene;
[0882] 2,4-hexadienoic acid;
[0883] trans, trans-2,4-hexadien-1-ol.
[0884] The sheets treated with a combination of hydroxylamine and
diene compound exhibit substantial inhibition to yellowing compared
to the untreated control sheet and illustrate the performance
enhancement when combinations of hydroxylamine and diene compound
are used.
EXAMPLE 61
[0885] Accelerated Yellowing with High Intensity Lamps
[0886] BTMP sheets are treated with 0.25% by weight of Compound B
and with 1% by weight of the following diene compounds:
[0887] 1-methoxy-1,3-cyclohexadiene;
[0888] 1-methoxy-1,4-cyclohexadiene;
[0889] 2,4-hexadienoic acid;
[0890] trans, trans-2,4-hexadien-1-ol.
[0891] The sheets treated with a combination of nitroxide and diene
compound exhibit substantial inhibition to yellowing compared to
the untreated control sheet and illustrate the performance
enhancement when combinations of nitroxide and compounds are
used.
EXAMPLE 62
[0892] Accelerated Yellowing with High Intensity Lamps
[0893] BTMP sheets are treated with 0.25% by weight of Compound FF
and with 1% by weight of the following diene compounds:
[0894] 1-methoxy-1,3-cyclohexadiene;
[0895] 1-methoxy-1,4-cyclohexadiene;
[0896] 2,4-hexadienoic acid;
[0897] trans, trans-2,4-hexadien-1-ol.
[0898] The sheets treated with a combination of hydroxylamine salt
and diene compound exhibit substantial inhibition to yellowing
compared to the untreated control sheet and illustrate the
performance enhancement when combinations of hydroxylamine salt and
compounds are used.
EXAMPLE 63
1-Oxyl-2,2,6,6-tetramethyl-4-glycidyloxypiperidine
[0899] A vigorously stirred two phase solution of
1-oxyl-2,2,6,6-tetrameth- yl4-hydroxypiperidine, epichlorohydrin,
tetrabutylammonium bromide in 50% aqueous sodium hydroxide and
toluene is reacted together. The organic phase is dried over
anhydrous magnesium sulfate and concentrated to yield the title
compound as a low melting red solid after column
chromatography.
EXAMPLE 64
1-Oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxa-6-trimethylammmoniumhexyloxy-
)piperidine Chloride
[0900] The title compound is prepared by reacting the glycidyloxy
compound of Example 63 with choline chloride
[(2-hydroxyethyl)trimethylammonium chloride].
EXAMPLE 65
1-Oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-3-trimethylammoniumpropoxy)piperid-
ine Chloride
[0901] To 25 mL of 0.4 molar aqueous trimethylammonium hydroxide
(0.01 mol) is added 2.28 g (0.01 mol) of
1-oxyl-2,2,6,6-tetramethyl4-glycidylox- ypiperidine. The mixture is
stirred at ambient temperature for 16 hours. The solution is then
neutralized with one equivalent of hydrochloric acid, washed twice
with 50 mL of ethyl acetate and concentrated under reduced
pressure. The resulting red oil is purified by column
chromatography yielding 1.0 g of the title compound as a red
oil.
EXAMPLE 66
1-Oxyl-2,2,6,6-tetramethyl-4-{2-hydroxy-3-[di(2-hydroxyethyl)amino]propoxy-
}piperidine
[0902] A solution of 2.28 g (0.01 mol) of
1-oxyl-2,2,6,6-tetramethyl-4-gly- cidyloxypiperidine and 1.05 g
(0.01 mol) of diethanolamine in 25 mL of water is stirred at
ambient temperature for 16 hours. The solution is then extracted
with methylene chloride. The methylene chloride extract is dried
over anhydrous magnesium sulfate, filter and concentrated. The
crude reaction product is purified by column chromatography to
afford 1.0 g of the title compound as a red oil.
EXAMPLE 67
1-Oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-3-dimethylaminopropoxy)piperidine
[0903] A mixture of 10.0 g (0.044 mol) of
1-oxyl-2,2,6,6-tetramethyl-4-gly- cidyloxypiperidine and 10 mL of
40% (ca. 0.091 mol) of dimethylamine (w/w) is dissolved in 100 mL
of water and then stirred for 16 hours at ambient temperature.
Water is then removed by vacuum distillation to leave 10 g of the
title compound as a red oil.
EXAMPLE 68
1-Oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-3-diethylaminopropoxy)piperidine
[0904] The title compound is prepared according to the procedure of
Example 67 when the dimethylamine is replaced with an equivalent
amount of diethylamine. The product is purified by column
chromatography and is isolated as a red oil.
EXAMPLE 69
N,N'-Dimethyl-N,N'-bis-[3-(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yloxy)-2-
-hydroxypropyl]hexamethylenediamine
[0905] The title compound is prepared according to the procedure of
Example 66 replacing diethanolamine with an equivalent amount of
N,N'dimethylhexamethylenediamine. The product is purified by column
chromatography and is isolated as a red oil.
EXAMPLE 70
N,N,N',N'-Tetramethyl-N,N'-bis-[3-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-y-
loxy)-2-hydroxypropyl]-hexamethylenediammonium Dibromide
[0906] A solution of 3.0 g (0.011 mol) of the compound of Example
67 and 0.89 g (0.0036 mol) of dibromohexane om 25 mL of absolute
ethanol is refluxed for 16 hours. The resultant solution is
concentrated under reduced pressure and the residue is washed
thrice with 20 mL of ethyl acetate and then dried under vacuum. The
title compound is obtained in a yield of 3.0 g as a red solid.
EXAMPLE 71
1-Oxyl-2,2,6,6-tetramethyl-4-[2-hydroxy-3-(N,N-dimethyl-N-propylammonium)p-
ropoxy]piperidine Chloride
[0907] The title compound is prepared according to the procedure of
Example 70 by replacing 1,6-dibromohexane with an equivalent amount
of 1-bromopropane. The title compound is isolated as a red oil.
EXAMPLE 72
Ethyl 1-Oxyl-2,2,6,6-tetramethyl-piperidin-4-yloxyacetate
[0908] To a solution of 3.0 g (17 mmol) of
1-oxyl-2,2,6,6-tetramethyl-4-hy- droxypiperidine in 25 mL of
anhydrous tetrahydrofuran is added 0.48 g (20 mmol) of sodium
hydride. The reaction mixture is stirred under a blanket of
nitrogen for one hour. The mixture is then chilled to 0.degree. C.
amd 2.9 g (17 mmol) of ethyl bromoacetate is added dropwise. After
the addition, the reaction mixture is stirred for an additional 30
minutes during which time a precipitate forms. The mixture is
filtered and the solvent is removed under reduced pressure. The
title compound is isolated after column chromatography as an orange
solid melting at 41-43.degree. C.
EXAMPLE 73
1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yloxyacetic Acid
[0909] To a solution of 0.2 g of sodium hydroxide in 20 mL of 1:1
water:methanol is added 1.0 g (39 mmol) of the compound of Example
72. The mixture is stirred for one hour and then carefully
acidified with 1% aqueous hydrochloric acid. The resultant mixture
is extracted with ethyl acetate. The organic extract is dried over
anhydrous magnesium sulfate and concentrated under reduced pressure
to afford the title compound as an orange solid.
EXAMPLE 74
Sodium 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yloxyacetate
[0910] To a solution of 1.0 g (4.3 mmol) of the compound of Example
73 dissolved in 20 mL of water is added 0.17 g (4.3 mmol) of sodium
hydroxide. The solution is stirred for one hour and the water is
then removed by vacuum distillation to afford the title compound as
an orange solid.
EXAMPLE 75
1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yloxyacetic Acid Choline
Ester
[0911] The title compound is prepared by reacting the acid of
Example 73 with choline chloride [(2-hydroxyethyl)trimethyl
ammonium chloride].
EXAMPLE 76
1-Hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium Chloride
[0912] 67 mL of isopropanol is cooled to 0.degree. C. and saturated
with HCl gas. This solution is added dropwise to a mechanically
stirred solution of 50 g (0.29 mol)
1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidin- e in 130 mL of
isopropanol, maintaining a reaction temperature of about 20.degree.
C. by occasionally cooling with an ice bath. The HCl salt is vacuum
filtered and washed with isopropanol, giving a pale yellow solid.
5.0 g of this crude product is recrystallized from 100 mL
isopropanol affording 3 g of a white crystalline solid,
mp>260.degree. C.
[0913] Elemental Analysis:
42 Calc. Found % C 51.55 51.30 % H 9.61 9.70 % N 6.68 6.42 % Cl
16.91 16.83
EXAMPLE 77
1-Hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium Acetate
[0914] 5.0 g (0.029 mol)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine and 2.0 g (0.033
mol) acetic acid are recrystallized from 50 mL of isopropanol,
yielding 4.0 g of the desired hydroxylamine salt as a white
crystalline solid, mp 140-143.degree. C.
[0915] Elemental Analysis:
43 Calc. Found % C 56.63 56.78 % H 9.94 10.13 % N 6.00 6.07
EXAMPLE 78
1-Hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium Bisulfate
[0916] 5.0 g (0.029 mol)
1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine and 3.0 g (0.031
mol) sulfuric acid are recrystallized from 50 mL of isopropanol,
yielding 3.0 g of the desired hydroxylamine salt as a white
crystalline solid, mp 238-241.degree. C.
[0917] Elemental Analysis:
44 Calc. Found % C 39.99 40.06 % H 7.46 8.06 % N 5.18 5.11 % S
11.86 11.87
EXAMPLE 79
1-Hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium Bisulfate
[0918] 2.6 ml of concentrated sulfuric acid is added dropwise to a
solution of 10.0 g (46.9 mmol)
1-oxyl-2,2,6,6-tetramethyl-4-acetamidopipe- ridine in 50 ml
isopropanol. After 48 hrs the resulting white solid is collected by
filtration, washed with isopropanol and dried under vacuum, mp
198.degree. C.
[0919] Elemental Analysis:
45 Calc. Found % C 42.28 42.23 % H 7.76 7.76 % N 8.97 8.85
EXAMPLE 80
Bis-(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
Oxalate
[0920] To a glass 0.5 L reaction bottle are added 10.0 g (58 mmol)
of C, 5.22 g (58 mmol) oxalic acid, 200 mg 5% Pt on C and 100 mL
water. Catalytic hydrogenation is carried out at 50 psi for 30
minutes at room temperature. Catalyst is removed by vacuum
filtration with Celite. Water is removed by distillation under
reduced pressure, giving a colorless solid. The crude product is
recrystallized from 100 mL isopropanol affording 3.5 g of the
product as a white crystalline solid, mp 244.degree. C.
[0921] Elemental Analysis:
46 Calc. Found % C 55.03 54.69 % H 9.24 9.49 % N 6.42 6.32
EXAMPLE 81
Tris-(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
Citrate
[0922] To a glass 0.5 L reaction bottle are added 20.0 g (116 mmol)
of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 7.39 g (38.5
mmol) citric acid, 200 mg 5% Pt on C and 100 mL water. Catalytic
hydrogenation is carried out at 50 psi for 30 minutes at room
temperature. Catalyst is removed by filtration through a pad of
Celite. The aqueous salt solution has a pH of 5.56. Removal of
water yields the product as a hygroscopic glassy solid.
EXAMPLE 82
Bis-(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
Citrate
[0923] To a glass 0.5 L reaction bottle are added 20.0 g (116 mmol)
of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 11.12 g (58
mmol) citric acid, 200 mg 5% Pt on C and 100 mL water. Catalytic
hydrogenation is carried out at 50 psi for 30 minutes at room
temperature. Catalyst is removed by filtration through a pad of
Celite. The aqueous salt solution has a pH of 4.39. Removal of
water yields the product as a hygroscopic glassy solid.
EXAMPLE 83
1-Hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium Citrate
[0924] To a glass 0.5 L reaction bottle are added 20.0 g (116 mmol)
of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 22.2 g (116
mmol) citric acid, 200 mg 5% Pt on C and 100 mL water. Catalytic
hydrogenation is carried out at 50 psi for 30 minutes at room
temperature. Catalyst is removed by filtration through a pad of
Celite. The aqueous salt solution has a pH of 3.30. Removal of
water yields the product as a hygroscopic glassy solid.
EXAMPLE 84
Bis-(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)
Sulfate
[0925] To a glass 0.5 L reaction bottle are added 10.0 g (58 mmol)
of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2.85 g (29 mmol)
sulfuric acid, 200 mg 5% Pt on C and 100 mL water. Catalytic
hydrogenation is carried out at 50 psi for 30 minutes at room
temperature. Catalyst is removed by filtration through a pad of
Celite. Removal of water yields the product as an pale yellow
solid.
* * * * *