Note: Descriptions are shown in the official language in which they were submitted.
- 1 -
2~160~3
HW/P-19462/A
Stabilisation of or~anic pi~nents
The present invention relates to the stabilisation of organic pigments against the influence
of light and weather by the addition of an N-hydrocarbyloxy amine.
It is known that no~ all organic pigments always have a very good fastness to light and
weathering. Nevertheless, some of them have proved to be vialuable pigments. Although
they already have a very good resistance to light and weathering, it has now been found
that, surprisingly, this can be improved further, in transparent as well as in opaque
pigment forms, if the pigments are mixed with an N-hydrocarbyloxy amine.
N~hydrocarbyloxy amines, in particular an N-hydrocarbyloxy derivatives of HALS
(Hinder~d Amine Light Stabiliser), have been disclosed e.g. in US Patents 4 921 962,
5 019 613, 5 021 483, 5 021 486, 5 021 577 and in EP-A 389 428 as light stabilisers for
polymers against the degradative effectis of actinic stimuli. They were found particularly
effoctiw in stabil~sing organic matelials such as polyolefins, elastomers, polyvinyl
chlorido, polyosters, polyurethanes, ambient cureid and acid catalysed thermoset coatings
andename1s.
13P A 309 401 discloses the use of N-hydroxy-HALS for preventing deficiencies such as
embrittlement, cracking, ca~sion, erosion, loss of gloss, chaLking and yellowing of
coatings containing some specific organic pigments such as phthalocyanine and azo
pigments.
,
, It has now been found, quite surprisingly, that e~en the already high resistance of certain
pigments to light and weathering can be improved further by mixing or coating of the
pigment par~cles with an N-hydrocarbyloxy amine.
: , .
The present invention accordingly relates to light-stabilised pigment compositions
comprising
.,
~;~ a) at least one organic pigment chosen from the group comprising azo pigments,
~: ~, `:
211fiO~3
- 2 -
quinacridones, phthalocyanines, indanthrones, flavanthrones, pyranthrones,
anthraquinones, perylenes, dioxazines, perinones, thioindigo, isoindolines, isoindolinones
and metal complexes and
b) 1 to 100% by weight, based on the pigment, of an N-hydrocarbyloxy amine consisting
of at least one unsubstituted or substituted 5-, 6- or 7-membered heterocyclic ring
containing a divalent group of the formula
\C/ \C/
N--O-R (~ or \ N--O-R aI)
/\ /~< '
R2 R1
in which
R is Cl-C18alkyl, C2-CI2alkenyl, C2-CI2alkynyl, Cs-CI2cycloa1kyl, C6-C~WI or
C7-C12aralkyl, ,
R1 and R2 independently of one another are methyl, ethyl or phenyl, or together form a 4-
to 12-membered aliphatic ring, and
L is an aromatic radical.
Particularly suitable pigments are those of the isoindoline, isoindolinone, metal complex,
monoazo and, in particular, the bisazo, quinacridone, phthalocyanine, anthraquinone and
perylene series. These are generally known and in some cases comrnercially obtainable
products.
N hydrocarbyloxy amine are likewise known compounds. Any that are still novel can be
prepared in analogy to well known methods.
The N-hydrocarbyloxy amine is preferably employed in an amount of 5-100% by weight,
based on the pigment.
Rl and R2 are preferably methyl.
Pigment compositions which are of particular interest are those in which an
2116~6~
N-hydrocarbyloxy amine of the fonnula
R3\~G /CHs
~R
H3C~
--T~X (IV),
m ~;:
?~H2~N--C~ 1 (V), ;~
H3C CH9 0
H3C CH3
; , : >~ CH2~ ~ ~ . ,
kCH2 o~ ,v
~ ~ .; H3C CHJ n
. ~
~` '''
.
~; ` .
2116063
>~ CH2f ~
kC~2\o/ _w (V~
H3C CH3 --n ~:
is used, in which
R is tcrt.-butyl, C7-C18alkyl or C5-C6cycloa1kyl,
R3 is Cl-C~8aL~cyl or Cl-CI8aL~coxy,
G is a divalent group of ~e formula -CR4=CH- or -CHR4-CH2- and ~
R4 is Cl-C~8aLkyl, '~`t ",
Q is a group of the formula
Q :
.
-CH2- lCH-, -CH=~-, -Cl H-O-, - IC=N-, -Cl =N-, -CO-~-,
*
8 ;
CO-~-CO-, -CH2 lFH CH2 ~ -CH2-l~-C- ~
.
"
; ~ ~3 8 :
CH2-CH2-~-CO-, -CH2-CH-~-C- or -CH2-CI =CH-
",
in which the bond labelled * is the bond lcading to T,
T is a direct bond or a group of the formula ~, in which Rs is hydrogen, halogen~: R5
~: or C~-C4alkyl. or -(CH2)--~
in which r is 1 or 2,
: m is the number 1, 2, 3, 4 or 6,
X, if m = 1, is hyd~ogen, Cl-CI8aL~cyl, phenyl which is unsubstltuted or subsdtuted by
Cl-C4alkyl, Cl-C4aLkoxy, phenyl or halogen, or, under the condidon that T, if bonded
21160~3
-5 -
to a nitrogen atom, is not a direct bond, is a group of the formula -OCO-NR6R7,
-OSO2-NR6R7, -OCO-R7, -COOR7, -CONR6R7, -NR6-COR7, -NR6-CONR6R7, -OE~7,
O O
-NR6R7 or--N~ 3~ or--N~ r . in which R6 is hydrogen or
~1 11
O O
Cl-CI8alkyl, R7 is Cl-ClgaLlcyl, C2-C12aL~cenyl, C5-Cl2cycloaL~yl, or phenyl or
naphthyl which is unsubsdtuted o~ subsdtuted by Cl-C4alkyl, Cl-C4aL~coxy, halogen,
phenyl or nitro, or a group -(CH2),-CHR8R9, s is zero, 1, 2 or 3, R8 is hydrogen,
methyl or phenyl and R9 is -OH, halogen or a group -COOCH3 or -COOC2Hs and,
if m = 2, is a group of the formula -(CH2)~ or, under the condidon that T, if bonded
to a nitrogen atom, is not a direct bond, is a group of dle formula -O-(CH2)p-O-,
-NR6~ I2)p-NR6-,-OCO-F-COO-,-NR6-CO-F-(~O-NR6-,-OCO-NH-F-NH-COO- ~ :
or -NR6-CONH-F-NHCO-NR6-, in which ~7 is -(CH2)p-, ~ or ~
~ ..
\J '
and p ls a number between 2 and 10, and,
if m - 3, is a group
R,N~N~NR,- OOC~COO- -HNOC~CONH-
~: ~ NR6 COO- CONH
and, if m = 4, is a group
:~ . H2C Cll- CIH--IH2 and
CO CO CO CO
O O O O
~ I I ' ' , ,.
~ if m = 6, is a group
~ . ,
211~063
- 6 -
CH3 0 -CH2 CH2--0 CH3 -
H2C~--I H--Cl H--CHz-COO--CHz--C--C~l C CH--C--CH2-
o C, O , CH3 O-CH2 CH2-- CH3 2
n isthenumber 1 or2,
V, if n = 1, is C2-C8aLlcylene or hydroxyaL~cylene or
C4-C22acyloxyaL~cylene, and, if n = 2, is the group (-CH2)2C(CH2-)2 or ~C~, and
Z is a group of the formula
. , .,:
-CHr~H- or -CHr~(C2Hs)-CHr
~H2 !H2
,
:
in which the bond labelled with ~ is the bond leading to W, and -
W, if n - 1, is a group -OCOR~o, in which Rlo is Cl-CI8alkyl, orphenyl or naphthyl
which is unsubstituted or substituted by Cl-C4alkyl, Cl-C4aL~oxy or halogen, and,
if n ~ 2, is a group of the fonnula OCO-(CH~)p-COO or
~,COO ::, ',
-OCO-(/ ~) , ,
\=~ .,,
Any Cl-C4allcyl substituent5 are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,
scc-buql or tert-butyl, and any Cl-CI8alkyl substituents are additionally, fo~ example,
n-amyl, tert-amyl, hexyl, hepql, ocql, 2-othylhexyl, decyl, dodecyl, tetradecyl, hexadecyl
or octadeicyl;
'; ; : ,',,
Cl-C4aLIcoxy is, for example, mcthoxy, ethoxy, n-propoxy, isopropoxy or butoxy, and
Cl-CI8alkoxy is additionally, for example, hexyloxy, decyloxy, dodecyloxy, hexadecyloxy
oroctadecyloxy;
~: ,
halogen is, for example, iodine, fluoqinc or, in particular, bromine, and preferably
chlorine;
any C2-CI2alkenyl subsdtucnts are, for oxample, vinyl, allyl, methallyl, 2-butenyl,
2-hexenyl, 3-hexenyl, 2-octenyl o~ 2-dodecenyl. AL~ynyl is preferably propargyl.
'
~,'`'''''.''','~','`'`'`','"'i"'"'~'`' '
21~6063
C6-CIOaryl R is, for example, phenyl, naphthyl or tolyl and C7-Cl2aralkyl R is~ for
example, benzyl, a-methylbenzyl or a,a-dimethylbenzyl.
R7 as C5-CI2cycloaL~yl is, for example, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl,
cyclododecyl and, preferably, cyclohexyl.
V as C2-C8alkylene or -hydroxyaLlcylene is, for example, ethylene, l-methyl-ethylene,
propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpq~pylene, and V as ~ .
C4-C22acyloxyaL~ylene is, fo~ exan~le, 2-ethyl-2-acetoxymethylpropylene.
Pigment compositions in which an N-hydrocarbyloxy amine of the formula IV, V or VI, as
defined above, is used are of very special interest.
Particularly suitablo N-hydrocarbyloxy amine are those of the formula
_ _ "~
H3C~ ~ H3
I ,C--CH2 T~X
~H3C CH3
m
H3C~ ~ H3 1l
C--C~ 2~C--N--X2
R O-N C~ ¦ (~) or
~C~ CH2 N--C~,
H3C CH3
: ~ '
211~63
- 8 -
H3C /CH9 : ~
C--C\H2/O~ L -. ;: ~:
/ \ ,V (X), ~ .
H3C CH3
n
in which ~ :
R is as defined in the prcfe~red meaning cited above,
T is a direct bond, ~ ~:
m is1,20~3, . ~.
~C R
Xl, if m = 1, is Cl-C~8aLlcyl, -OCO-R7, -NR6-COR7 or--N~ r . in which R6 is
~: :"''
hydrogen or Cl-C~8aL1cyl and R7 is Cl-CI8aL~cy1, or phenyl o~ naphthyl which is
unsubstituted or substituted by Cl-C4aL~yl, Cl-C4allcoxy, phenyl or halogen, and,
if m = 2, is a group OCO-(CH2)p-OCO- or -NR6CO-(CH~p-CONR~s-, in which p is
CONR6 ~OCO-
a number bctwecn 2 and g~ -NR6co~ or -CO~
.,
and,
if m - 3, is a group
~ ::
R6N~N~NR6- -OOC COO-
N~N ~
' NR~I COO- ;
,
~ X2 is Cl-Cl8a1kyl,
`` ;~ n is the number 2j and
V is the group (-CH2)2C(CH2-)2 or ,~ .
N-hydrocarbyloxy amines of the formula VIII or IX, in which R is tert-butyl, n-heptyl,
. . ,
., .
:.
211~063
g
n-octyl or cyclohexyl, T is a direct bond, X1, if m is 1, is benzoyloxy or naphthoyloxy, if
m is 2, is a group -OCO-(CH2)p-OCO- in which p is a number between 2 and 8, and X2 iS
C8-Cl8aL~yl, are prefelTed.
As already mentioned above, the pigments are stabilised against the action of light and
weather, which can lead either to fading or also to darkening of the colourations, by
admixing with an N-hydrocarbyloxy amine. The admLxing, according to the invention, of
the N-hydrocarbyloxy amine with the pigment has proved to be effective, i.e. stabilising, ~
in both cases. The invention furthermore accordingly relates to a process for light- and
weather-stabilisation of pigments chosen from the group comprising azo pigments,quinacridones, phthalocyanines, indanthrones, flavanthrones, pyranthrones, anthra-
quinones, perylenes, dioxazines, perinones, thioindigo, isoindolines, isoindolinones and
metal complexes comprising mixing or coating the pigment panicles with 1 to lOO~o by
weight, based on the pigment, of an N-hydtocarbyloxy amine consisting of at least one
unsubstituted or substituted 5-, ~ or 7-membered heterocyclic ring containing a divalent
group of the formula
R'2\C/R1 --C
N--OR (I) or N--O-R aI).
R R
in which
R is Cl-CI8alkyl, C2-CI2aU~enyl, C2-CI2alkynyl, Cs-C1*ycloalkyl, C6-CIOaryl or
C7-CI2araLlcyl,
Rl and R2 independently of one another are methyl, ethyl or phenyl, or together form a 4-
to 12-membered aliphatic ring, and
L is an aromatic radical.
This can be effected by the following va~ious methods:
- The N-hydrocarbyloxy amine is dissolved in an organic solvent in the desired
amount. The pigment is suspended in this solution by customary methods and, if
appropriate, the resulting suspension is dispersed in a conventional mill. The
2116063
- 10-
pigment mixture is isolated by distilling off the solvent and then drying;
- The required amount of N-hydrocarbyloxy amine, dissolved in an organic solvent, is
added to a pigment suspension prepared by customary methods and is then
precipitated and also suspended by the addition of a solvent in which it is not
soluble, for exarnple water. The suspension is then filtered and the pigment mixture
is isolated by customary methods;
- Preferably, however, the pigment and the N-hydrocarbyloxy amine are incorporated
in the desired amount by customary methods, either in premixed form or separately,
into the substrate to be pigmented.
Preferred N-hydrocarbyloxy amines for this process are as defined above.
The pigment compositions according to the invention are excellently suitable as pigments
for colouring high molecular weight organic material, especially if high requirements of
resistance to light and weathering are imposed.
High molecular weight organic materials which can be pigmented with the pigment
compositions according to the invention are, for example, cellulose ethers and esters, such
as ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, naturally
occurring resins or synthedc resins, such as polymerisadon resins or condensadon resins,
such as aminoplasts, in particular urea- and melamine-formaldehyde resins, alkyd resins,
phenolic resins, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides,
polyurethanes, polyesters, ABS, polyphenylene oxides, rubber, casein, silicone and
silicone resins, individually or as mixtures.
The pigment compositions according to the invendon are patdcularly suitable for
colouring polyvinyl chloride and polyolefins, such as polyethylene and polypropylene, and
for pigmendng varnishes, paints and prindng inks. Due to their high light fastness,
however, they are also pardcularly suitable for use in electrophotographic materials (for
example photocells), colour filters (for example liquid crystal displays), informadon
storage materials (opdcal discs), non-linear opdcal materials and in opdcal limiters.
However, the pigment composidons according to the invendon are preferably suitable for
colouring aqueous and/or solvent-containing varnishes, in particular automotive paints.
2~16~63
They are especially preferably used for effect finishes in which transparent organic
pigments are employed.
The high molecular weight organic compounds mentioned can be present individually or
in mixtures as plastic compositions, melts or in the form of spinning solutions, varnishes,
paints or printing inks. Depending on the intended use, it proves advantageous to employ
the pigment compositions according to the invention as toners or in tne form of
preparaffons.
The pigment compositions according to the invention can be employed in an amount of
0.01 to 40% by wdght, preferably 0.1 to 20% by weight, based on the high molecular
weight organic material to be pigmented.
The high molecular weight organic substances are pigmented with the pigment
compositions according to the invention, for example, by admixing such a pigmentcomposition, if appropriate in the form of masterbatches, or the individual components to
these substrates using roll mills or mixing or grinding apparatuses. The pigmented
material is then brought into the desired final form by processes which are known per se,
for example calendering, pressing, extrusion, brushing, casting or injection moulding. To
produce non-rigid mouldings or to reduce their brittleness, it is often desirab1e to
incorporate so-called plasticisers into the high molecular weight compounds before
shaping. Plasticisers can be, for example, esters of phosphoric acid, phthalic acid or
sebacic acid. The plasdcisers can be incorporated into the polymers before or after
incorporation of the pigment compositions according to the invention. ln order to achieve
various colour shades, it is furthermore possible also to add fillers or other chromophoric
components, such as white, coloured or black pigrnents, in any ~mounts to the high
molecular weight organic substances, in addition to the pigment compositions according
to the invention.
For pigmenting varnishes, paints and printing inks, the high molecular weight organic
materials and the pigment compositions according to the invention are finely dispersed or
dissolved in a common organic solvent or solvent mixture, if appropriate together with
additives, such as fillers, other pigments, siccatives or plasticisers. A procedure can be
followed here in which the individual components are dispersed or dissolved by
themselves, or also several of them together, and only then are all the components brought
together.
, . .. . . . ....... , ,, . .. . . , , ~ . . . . .
21i6063
-12-
,:
In colourations, for example of varnishes, polyvinyl chloride or polyolefins, the pigment
compositions according to the invention are distinguished by good general pigment
properties, such as good dispersibi1ity, high tinctorial strength and pUlity, and good
resistance to migration, heat and, in particular, light and weathering.
The following examples illustrate the invention. Parts are by weight, unless stated
otherwise.
E ample 1: 0.5 g of a scarlet red bisazo pigment (C.I. Pigment Red 166) of the formula
Cl
CON~
and 0.05 g of an N-hydrocsrbyloxy srnine of the formula
o
~N -C12H2s
~0
H3C>~ <CH3
H3C IN CH3
O-C~H~7
7.6 g of TiO2, 3 g of xylene and 30 g of stoving lacquer comprising 56 parts of aLlcyd resin
~ALPTALAT AC 451M (Hoechst AG, 60 % in xylene/Solvesso lS0~), 23 paTts of
melamine resin ~19MAPRENAL M~ 600 (Hoechst AG, 65 % in n-butanoVisobutanol), 20
parts of xylene, and 1.0 part of silicone oil (1% in xylene) are mixed by customaTy
methods. The coloured paint is applied to aluminium sheets and stoved at 130C for 30
minutes.
~ ~SOLVESSO 150, aromatic solvent from ESSO
~ .
2~6~3
- 13 -
A control coloured coating is likewise produced in the same manner, with the exception
that the pigment is employed widhout addidon of the N-hydrocarbyloxy amine.
The resistance of the resulting coloured coatings to weathering is determined inaccordance with the WOM test according to DIN 53387 after weathering for 500 hours.
The colouration obtained with addition of the N-hydrocarbyloxy amine has a significandy
better resistance to weathering than the control coloured coating.
Example 2: Example 1 is repeated, with the only excepdon that instead of the pigment of
the formula XI, the same amount by weight of the bisazo pigment (C.I. Pigment Yellow
93) of the fo~mula
_ _ Cl
N~N--CH--CONH-
~C ~ Cl C~
L~CH3
~s employed. The colouled coating shows a significandy better resistance to weathering
than the co~responding control coloured coating.
ExamPles 3-34: 0.4 g of one of the pigments shown in column 1 in the following Table 1
and 0.08 g of one of the N-hydrocarbyloxy amine shown in column 2 of Table 1 areincorporated separately, but otherwise in the same manner, into the same alk~d-melamine
sto~ring enamel (white roducdon) as described in Example 1 (method B). The resistance of
the resuldng coloured coadngs and corresponding control coloured coatings without an
N-hydrocarbyloxy amine to weathering is deterrnined as described in Example 1. In all the
examples shown, a better resistance to weathering can be detected than in the case of the
corresponding control coloured coatings.
~ ;
.,
: ., . ~ ~ : - ~ . . - . ~ - . . . - . .
~, " ,~ ",";,,",~", ,~,,,~,,, ,~ ," ;.~
211~063
- 14-
FX- I _ Il
_ _
H2 C 2~C CH3 CH3
3 C.I. Pigment 5 1 `O ~<
Orange 34 >~<-O-CaH,7
3 CH3 -
4 l ol l gm41~t~Hl R = -O-C-(CH~)8-C-O-
l H3C 3 ~2
S C.I. Pigment ~30-N>~ ll
Orange 34H3C>~H3 C (CH2)10CH3
o,~ CHa CH3
6 C.I. Pigment ~ )~<N~~CsH17
Orange 34 ~ ~CH3
_
H25C.20 ~8 ~CH3
7 CyeI1l0Piwgm95ent >~-~CaH~7
CH3 CH3
8 ~ C.I. P graPltt~ ~ ~ = -O-C-(CI~)8-C~
_ H3C CH3 H :
9 C.I. Pigment ~O-N>~
Yellow95 H3C>~CJH (CH2)~ocH3
,
2116063
Table 1: (Continuation)
_ _ _
Exnple I II
_
C.I. Pigment X~N O C8H17
Yellow 95 ~ CH3 CH3
H2sC~20~8 o ~CH3
1 1 C.I. Pigrnent ~/ \ 0-C8H
Yellow 62 /~CH3
_
12 C.I.Pigment H3C~ 3 O O
Yellow 62 Hl7C8-~ ~ R = -O-C-(CH2)8-C-O-
_
¦ 13 ¦ C Ij Pl ~ent¦ ~ H o
H3C 3 C ~CH2)10cH3
14 C.I. Pigmen H ~>
Yellow 62 ~ CH3
-- H25C,20 ~ C~CH3
CY'elilPow l7en >~CH3
. .
i~ ~ ~ ~....... L ~
21~6063
- 16- ~:
Table 1: (Continuation)
_ _
Ex- ~ H3C CH3 H
17 CeIilPiwgml7nt H3C~< C (CH2)10-CH3
_ ~ CH CH3
¦ 18 ¦CY~eliltP~ 31n7ent ~ 3 CHy
.
H25C~2 ~ C CH3~CH3
19 CI. Pigment O /~C
Red 177 >~ O,c8H17
_ r-
H3C CH3 ....
20 C Idpli7g7ment H17ca ~N~ 8 8
L H3C CH3 2 R = -O-C-(CH2)8-C-O-
_ H3C CH3 H
¦ 21 ¦ C I Pl~ nent ¦ H3C~< C CH2) jo-cH3
.,
~ 22 ~CReld li7l nent ~ ~
_ O ,,
; H25C12O ~ C ~CH3
23 CReIdPli8g8ment >~-O-C8H"
CH3 CH9
21~6063
Table 1: (Conti luation) _
ample I II
H3C CH9
24 yeIjloPig lm8e8tH~7C8 -O-N~ O O
L H3C CH3 `R R = -O-C-(CH2)8-C-O-
_ _ .
25 C.I. Pigment `C-- 0
Yellow 188 ~ \;;Z~CH3
_
H2sC12o~c CH3/ H3
26 C.I. Pigment ~/~ C H
Blue 15:4 ~ N-O- 8 17
~CH3
_ _H3C CH9
27 BiIue lgS:m4ent H17cs ~ ~ ~ R = -O-C-(CH2)8-C-O-
H3C CH3 2
_H3C CHa
28 CiIuePig5m4ent ~;~<H
H3CkCJH (CH2)10~CH3
29 C.I. Pigment ~C 0~
L Bluel5:4 ~ CH3
:
2116063
- 18 -
Table 1: (Continuation)
_ _ _.
I II
C.I. Pigment ~<N--O ~ . :
Red 170 ~ H/\~;Z<
~ 3 CH3
31 ¦C.l.P lment
Red 170 l H3C CH3 ~ ~(CH
H3C CH3
32 C.I. Pigment H~7C8 -O-N>~( 1l
Red 170 >~ O--C --- -(CH
L H3C CH3 2
33 CI Pigment `C--O>~
. Yeilow 110 Ci~ CH
:..
¦ 34 l Cl. Pil meol lo _ c~C ~ O ~3H~7
Red 170 ~ CH3
2116063
- 19-
Examples 35-37: 0.7 g of C.I. Pigment Yellow 95 and 0.35 g of one of the
N-hydrocarbyloxy amines shown in the following Table 2 are mixed in the dry state with
700 g of polyethylene VESTOLEN A 6016~' (Huls) and 1.4 g of calcium carbonate
MILICARB~, The rnixture is then extruded in a single-sclew extruder twice at 200C.
The granules thus obtained are processed to sheets on an injection moulding machine at
200C. The resistance to weathering is detern~ined by weathering the sheets as described
for the coloured coadngs in Example 1. In all the examples, a better resistance to
weathering can be determined than in the case of control sheets produced correspondingly
without N-hydrocarbyloxy amines.
Table 2:
Ex- ¦ N-hydrocarbyloxy amine
amp
H25C12 ¢~ 1~ CH3 CH3
>~H3 CH3
_
36 ~ 8 8
L H3C CH3 ~R R = -O-C-(CH2)8-C-O-
_ .,
37 ~H1~C8-o-N>~ 1l
I k-- o--c~ -(CH2~ .,
I
Examples 38-40: 0.5 g of C.I. Pigment Yellow 95, 0.1 g of one of the N-hydrocarbyloxy
amines shown in the following Table 3 and 16.2 g of a nitrocellulose printing ink
comprising 11 g of nitrocellulose A 250, 9 g of DOWANOL PM~9 (Dow Chem.), 20 g of
ethyl acetate and 60 g of ethanol are mixed by customary methods. The resulting printing
ink is spread onto paper. The resistance to weathering is determined by exposure of the
colourations to light in accordance with the fadeometer test for 500 hours. In all the
,, . . ~, ., . - . -, . ... - ,
2~i6~63
- 20 -
examples, a better resistance to weathering can be determined than in the case of control
colourations pr~duced correspondingly without N-hydrocarbyloxy amines.
Table 3:
.__
aExpl Nitroxyl compound
38 H25C120~C CH3 CH3 :
>~ N-O-C8H17
~CH3
, G~
_ , ~
H3C?~3 H ~ :
_ H3C CH3 0
Examples 41-43: Exampks 38 40 are repeated with the only exception that instead of C.I.
Pigment ~e110w 95, the same amount by wdght of C.I. Pigment Yellow 188 is used. A
better light fastness than in the case of coqresponding control colourations without a
N~hydrocarbyloxy amine can also be determined in these examples.
The classes to which the pigments used in Examples 3-43 belong are shown in the
following Table 4.
21~6~3
- 21 -
Table 4:
C.I. designation Pigrnent class
_
C.I. Pigment Yellow 17 Bisazo pigment
C.I. Pigment Yellow 62 Laked rnonoazo pigment
C.I. Pigment Yellow 95 Bisazo condensation pigment
C.I. Pigment Yellow 110 Isoindolinone pigment
C.I. Pigrnent Yellow 188 Bisazo pigment
C.I. Pigment Orange 34 Bisazo pigment
C.I. Pigment Red 170 Monoazo pigment
C.I. Pigment Red 177 Anthraquinone pigment
C.I. Pigment Blue 15:4 Copperphthalocyanine pigment
~ .
.
