# US 5,348,580 A · Stabilization of organic pigments

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- Number: US 5,348,580 A
- Document ID: US5348580A
- Status: Granted
- Kind: A
- Application number: 08/111,530
- Filed: 1993-08-25
- Granted: 1994-09-20
- Earliest claimed: 1992-09-03
- Assignees: Ciba-Geigy Corporation
- Inventors: Laurent Chassot
- Web page: https://patentgrep.com/patent/US5348580A

## CPC

- C09B 67/0063: {of organic pigments with only macromolecular substances}
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)

## Abstract

Pigment compositions comprising a) at least one organic pigment selected from the group consisting of diketopyrrolopyrroles, azo pigments quinacridones, quinophthalones, phthalocyanines, indanthrones, flavanthrones, pyranthrones, anthraquinones, perylenes, dioxazines, perinones, thioindigo, isoindolines isoindolinones and metal complexes and b) 0.01 to 100% by weight, based on the pigment, of a condensation or addition polymer, the recurring molecular unit of which contains at least one radical containing a nitroxyl or hydroxylamino group or is substituted by a side group containing a nitroxyl or hydroxylamino group, and copolymers thereof with one another or with nitroxyl- or hydroxylamine-free components. These pigment compositions are distinguished by outstanding resistance to light and weathering.

## Claims

### Claim 1

A light-stabilized pigment composition comprising
a) at least one organic pigment selected from the group consisting of diketopyrrolopyrroles, azo pigments quinacridones, quinophthalones, phthalocyanines, indanthrones, flavanthrones, pyranthrones, anthraquinones, perylenes, dioxazines, perinones, thioindigo, isoindolines, isoindolinones and metal complexes and
b) 0.01 to 100% by weight, based on the pigment, of a condensation or addition polymer, the recurring molecular unit of which contains at least one radical containing a nitroxyl or hydroxylamino group or is substituted by a side group containing a nitroxyl or hydroxylamino group, or a copolymer thereof with other such compounds or with nitroxyl- or hydroxylamine-free components.

### Claim 2 (depends on 1)

A pigment composition according to claim 1, wherein a pigment of the isoindoline, isoindolinone, metal complex or, in particular, the diketopyrrolopyrrole, azo, quinacridone, phthalocyanine, anthraquinone or perylene series is used.

### Claim 3 (depends on 1)

A pigment composition according to claim 1, wherein a diketopyrrolopyrrole pigment is used in a fine form having an average particle size of 0.005 to 0.1 .mu.m.

### Claim 4 (depends on 1)

A pigment composition according to claim 1, wherein the polymeric nitroxyl compound is employed in an amount of 0.1-10% by weight, based on the pigment.

### Claim 5 (depends on 1)

A pigment composition according to claim 1, wherein an organic or inorganic salt of the nitroxyl compound is used.

### Claim 6 (depends on 1)

A pigment composition according to claim 1, wherein a polymeric nitroxyl compound, the recurring molecular unit of which contains at least one radical of the formula ##STR65## or is substituted at least once, directly or indirectly, by one of the side groups of the formulae ##STR66## in which R is O. or OH,
R.sub.1 is hydrogen or C.sub.1 -C.sub.4 alkyl,
R.sub.2 is hydrogen or C.sub.1 -C.sub.4 alkyl,
R.sub.3 is hydrogen or a free valency and
Q is --CH.sub.2 --,--(CH.sub.2).sub.2 -- or --CH.sub.2 --CH(CH.sub.3)--,
or a copolymer with other such compounds or with nitroxyl- and hydroxylamine-free components is used.

### Claim 7 (depends on 6)

A pigment composition according to claim 6, wherein R in the formulae I-VII is O.

### Claim 8 (depends on 6)

A pigment composition according to claim 6, wherein a polymeric nitroxyl compound, the recurring molecular unit of which contains at least one radical of the formula ##STR67## or is substituted at least once, directly or indirectly, by a side group of the formula ##STR68## in which R, R.sub.2 and R.sub.3 are as defined in claim 6, is used.

### Claim 9 (depends on 8)

A pigment composition according to claim 8, wherein a polymeric nitroxyl compound, the recurring molecular unit of which contains at least one radical of the formula ##STR69## or is substituted at least once by a side group of the formula ##STR70## in which A is a group of the formula ##STR71## R and R.sub.2 are as defined in claim 8, R.sub.4 is hydrogen, methyl or ethyl,
m is zero or 1,
n is 1 if m is zero and is zero or 1 if m is 1,
X.sub.1 is a direct bond, --O-- or a group of the formula ##STR72## in which R.sub.5 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.7 cycloalkyl or C.sub.7 -C.sub.11 aralkyl and
p is a number between 1 and 6,
X.sub.2 is a direct bond or a group of the formula --(CH.sub.2).sub.p --, --CO--O--CHR.sub.5 --CH.sub.2 -- or --CO--NR.sub.4 --CHR.sub.5 --CH.sub.2 --
wherein R.sub.4, R.sub.5 and p are as defined above, and
X.sub.3 is a direct bond, --O-- or a group of the formula --CO--O--, --O--CH.sub.2 --O-- or --(CH.sub.2).sub.p --
in which p is as defined above, is used.

### Claim 10 (depends on 1, 9)

A pigment composition according to claim 1, wherein a polymer having a recurring unit of the formula ##STR73## in which Q is a radical of the formula XII in which A is a group ##STR74## R, R.sub.2, R.sub.4 and R.sub.5 are as defined in claim 9, q is a number between 10 and 50 and
r is zero or 1, and
if r is zero,
Y.sub.2 is an aliphatic, aromatic, araliphatic or alicyclic diacyl group having up to 20 carbon atoms,
if r is 1 and Q is a radical of the formula XII in which A is ##STR75## Y.sub.1 is a saturated, aliphatic diacyl group having up to 20 carbon atoms, a benzenedicarbonyl group, a cyclohexanedicarbonyl group or a group ##STR76## and if r is 1 and Q is a radical of the formula XII in which A is ##STR77## Y.sub.1 is a saturated, aliphatic diacyl group having up to 20 carbon atoms, a benzenedicarbonyl group, a cyclohexanedicarbonyl group or a group ##STR78## in which x is zero or a number from 1 to 8 and R.sub.5 is hydrogen or methyl, and
if r is 1,
Y.sub.2 is a saturated, aliphatic diacyl group having up to 20 carbon atoms, a benzenedicarbonyl group, a cyclohexanedicarbonyl group, an alkylene group having 2 to 10 carbon atoms, a xylylene group or a group ##STR79## in which Y.sub.3 is an alkylene group having 2 to 10 carbon atoms or a phenylene group, which is unsubstitutcd or substituted by methyl, is used.

### Claim 11 (depends on 1, 9)

A pigment composition according to claim 1, wherein a polymer having a recurring unit of the formula ##STR80## in which R.sub.7 is a group of the formula ##STR81## in which R and R.sub.2 are as defined in claim 9,
Y.sub.4 is --O-- or --NR.sub.5 --,
in which R.sub.5 is as defined in claim 9,
Y.sub.5 is a group --O--CH.sub.2 --CH.sub.2).sub.z or --NR.sub.5 --CH.sub.2 --CH.sub.2).sub.z
in which z is zero or 1,
R.sub.8, R.sub.9 and R.sub.10 independently of one another are hydrogen or C.sub.1 -C.sub.4 alkyl,
R.sub.9 is additionally also --COOH, and, if R.sub.8 and R.sub.10 are hydrogen,
R.sub.7 and R.sub.9 together form a group of the formula ##STR82## in which Q.sub.1 is a group ##STR83## in which R and R.sub.2 are as defined in claim 9, or a copolymer of XVII with a compound containing at least one polymerizable double bond, at least one recurring unit XVII being present per 10 co-components, is used.

### Claim 12 (depends on 1, 9)

A pigment composition according to claim 1, wherein a copolymer of
1) at least one unsaturated derivative of the formula
R.sub.12 --Y.sub.6 --CO--CH.dbd.CH--CO--Y.sub.7 --R.sub.13 (XVIII),
and
2) at least one comonomer of the formula ##STR84## in which R.sub.12 is a group of the formula XII as defined in claim 9 and
R.sub.13 is hydrogen, C.sub.1 -C.sub.12 alkyl, which can be interrupted by --O--, C.sub.3 -C.sub.5 alkenyl,
C.sub.7 -C.sub.11 aralkyl or C.sub.5 -C.sub.7 cycloalkyl or is the same as R.sub.12,
Y.sub.6 and Y.sub.7 independently of one another are --O-- or --NR.sub.5 --
in which R.sub.5 is as defined in claim 9,
R.sub.14 is hydrogen or methyl,
R.sub.15 is hydrogen, C.sub.1 -C.sub.12 alkyl, phenyl, Cl, CN, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.5 alkanoyloxy, --CONH.sub.2, --COOR.sub.16 or --CONR.sub.17 R.sub.18,
R.sub.16 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.4 hydroxyalkyl or a group of the formula XII as defined in claim 9,
R.sub.17 is C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl or a group Q.sub.2 of the formula ##STR85## in which R and R.sub.2 are as defined in claim 9,
R.sub.18 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.7 cycloalkyl or C.sub.7 -C.sub.11 aralkyl, or
R.sub.17 and R.sub.18, together with the N atom to which they are bonded, form a 5- to 7-membered heterocyclic ring selected from the group consisting of pyrrolidine, piperidine, morpholine or 4-alkylpiperazine,
or a copolymer of
1) at least one maleimide of the formula ##STR86## in which R 9 is a group Q.sub.2, and 2) at least one comonomer of the formula
CH.sub.2 .dbd.CH--R.sub.20
in which R.sub.20 is hydrogen or C.sub.1 -C.sub.12 alkyl, is used.

### Claim 13 (depends on 1, 9)

A pigment composition according to claim 1, wherein a polymer having a recurring unit of the formula ##STR87## in which Q.sub.3 is a group of the formula ##STR88## in which R and R.sub.2 are as defined in claim 9,
Y.sub.4 is --O-- or --NR.sub.5 --
in which R.sub.5 is as defined above,
Y.sub.5 is a group --O--CH.sub.2 --CH.sub.2 --CH.sub.2).sub.z or --N.sub.5 --CH.sub.2 --CH.sub.2).sub.z
in which z is zero or 1,
or a copolymer of XX with a compound containing at least one polymerizable double bond, at least one recurring unit XX being present per 10 co-components, is used.

### Claim 14 (depends on 1, 9)

A pigment composition according to claim 1, wherein a polymer obtained by condensation of a compound of the formula ##STR89## in which R and R.sub.2 are as defined in claim 9,
R.sub.21 is hydrogen,
Y.sub.8 is a group --(CH.sub.2).sub.u --NH--,
u is a number from 1 to 4,
t is zero or 1,
w is zero or 1 and
v is 1 or 2, with the proviso that if v is 2, t is zero, with a diisocyanate of the formula
O.dbd.C.dbd.N--Y.sub.9 --N.dbd.C.dbd.O (XXII)
in which
Y.sub.9 is a group ##STR90## in which Y.sub.10 is a direct bond, --(CH.sub.2).sub.b --, --NR.sub.22 --, --O--, --S-- or --SO.sub.2 --,
a is a number from 1 to 10 and
b is a number from 1 to 5 and
R.sub.22 is C.sub.1 -C.sub.4 alkyl, is used.

### Claim 15 (depends on 1, 9)

A pigment composition according to claim 1, wherein a polymer of the formula ##STR91## in which R is as defined in claim 9,
R.sub.23 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.12 alkyl, which is substituted by --OH, C.sub.1 -C.sub.4 alkyl or C.sub.2 -C.sub.8 dialkylamino, or is C.sub.3 -C.sub.5 alkenyl, C.sub.5 -C.sub.7 cycloalkyl, C.sub.6 -C.sub.18 aryl, C.sub.7 -C.sub.11 aralkyl or a group ##STR92## R.sub.24 is C.sub.5 -C.sub.7 cycloalkyl, C.sub.6 -C.sub.18 aryl, C.sub.7 -C.sub.11 aralkyl or a group of the formula ##STR93## X.sub.4 is --O--, --S-- or --NR.sub.25 --in which R.sub.25 can be the same as defined for R.sub.23,
R.sub.23 X.sub.4 --regarded as a single substituent can also be a heterocyclic radical selected from the group consisting of pyrrolidin-1-yl, piperidin-1-yl, hexahydroazepin-1-yl, morpholin-4-yl or methylpiperazin-1 -yl,
Y.sub.11 is C.sub.2 -C.sub.10 alkylene, C.sub.4 -C.sub.10 alkylene, which is interrupted by 1 or 2 oxygen or --NH-- groups, cyclohexane, phenylene, a group ##STR94## in which Y.sub.13 is a direct bond or --CH.sub.2).sub.1-10,
Y.sub.12 is C.sub.2 -C.sub.10 hydroxyalkylene, C.sub.4 -C.sub.8 alkenylene or a group --CO--, --OOC--Y.sub.11 --COO--, --COO--Y.sub.11 --OOC--, --OCNH--Y.sub.11 --NHCO--, --HNOC--Y.sub.11 --CONH-- or --OC--Y.sub.11 --CO--,
the ratio of c:d being between 4:1 and 1:4, is used.

### Claim 16 (depends on 1, 9)

A pigment composition according to claim 1, wherein a polymer having a recurring unit of the formula ##STR95## in which R and R.sub.2 are as defined in claim 9,
Y.sub.14 is --O-- or --NR.sub.18 --in which R.sub.18 is C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.7 cycloalkyl or C.sub.7 -C.sub.11 aralkyl,
g can be a number from 2 to 12,
Y.sub.15 is the group --CH.sub.2).sub.g,
in which g is as defined above,
or the group ##STR96## in which R.sub.27 and R.sub.28 independently of one another are hydrogen or methyl, or ##STR97## in which h can be 1 to 3,
R.sub.26 is hydrogen, C.sub.1 -C.sub.12 alkyl, a group of the formula ##STR98## in which R, R.sub.2 and Y.sub.14 are as defined in claim 9 and
g is as defined above,
or a group of the formula ##STR99## as defined above, e is zero or 1,
Y.sub.16, if e is zero, is as defined for Y.sub.15 or is a group ##STR100## in which R.sub.29 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.7 cycloalkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.7 C.sub.11 aralkyl, phenyl, which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, or a group ##STR101## --O--R.sub.30 or --S--R.sub.30 in which R.sub.30 and R.sub.31 independently of one another are hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.7 cycloalkyl, C.sub.7 -C.sub.11 aralkyl or phenyl, which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, or
R.sub.30 and R.sub.31, together with the N atom to which they are bonded, form piperidine or morpholine, or
R.sub.29 is a group ##STR102## as defined above, Y.sub.17 is ##STR103## in which i is a number from 1 to 8, Y.sub.18 is ##STR104## Y.sub.19 is ##STR105## in which k is a number from 2 to 18, Y.sub.20 is ##STR106## in which l is 1 or 2, and f can be a number between 2 and 2000, is used.

### Claim 17 (depends on 1, 6)

A pigment composition according to claim 1, wherein a polymer having a recurring unit of the formula ##STR107## in which R and R are as defined in claim 6 and
y can vary between 10 and 100, is used.

### Claim 18 (depends on 1)

A pigment composition according to claim 1, wherein a polymer having a recurring unit of the formula ##STR108## in which R.sub.5 and R.sub.9 independently of one another are hydrogen or methyl and Y.sub.4 is --O-- or --NH--, and in which recurring units of the formula ##STR109## in which R.sub.8 is as defined above and
R.sub.1 ' is hydrogen or methyl, can also occur, is used.

### Claim 19 (depends on 1)

A pigment composition according to claim 1, wherein a polymer having a recurring unit of the formula ##STR110## in which R.sub.8 is hydrogen or methyl and
Y.sub.4 is --O-- or --NH--, is used.

### Claim 20

A process for light-and weathering-stabilization of a pigment selected from the group consisting of diketopyrrolopyrroles, azo pigments, quinacridones, quinophthalones, phthalocyanines, indanthrones, flavanthrones, pyranthrones, anthraquinones, perylenes, dioxazines, perinones, thioindigo, isoindolines, isoindolinones and metal complexes, by mixing or coating the pigment particles with 0.01 to 100% by weight, based on the pigment, of a condensation or addition polymer, the recurring molecular unit of which contains at least one radical containing a nitroxyl or hydroxylamino group or is substituted by a side group containing a nitroxyl or hydroxylamino group, or its copolymer with other such compounds or with nitroxyl- or hydroxylamine-free components.

### Claim 21 (depends on 20)

A process according to claim 20, wherein, instead of the nitroxyl compound, a corresponding precursor containing the group N--OT, in which T is C.sub.1 -C.sub.12 alkyl, which liberates the nitroxyl compound during heat treatment, is employed.

### Claim 22 (depends on 1)

High molecular weight organic material comprising a pigment composition according to claim 1.

### Claim 23 (depends on 21)

High molecular weight organic material according to claim 21, which is a coating material.

### Claim 24 (depends on 22)

High molecular weight organic material according to claim 22, which is an automobile paint.