Note: Descriptions are shown in the official language in which they were submitted.
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NEW HETEROCYCLIC COMPOUNDS, A PROCESS FOR THEIR PREPARATION AND
THEIR USE AS DYES AND PIGMENTS
The present invention relates to new compounds, to their preparation and to
their use in the
production of coloured plastics or polymeric colour particles.
The subject of the present invention are compounds of formula (1)
O
X'
R~
Z A Z' ~ (1),
I R'~
X ~Y~)v ~
O
wherein
R~ is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, Garb~xylic
ester, sulfo, sulfo-
nic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or
aryloxy,
R', is hydrogen, Ilydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic
ester, sulfo, sulfo-
nic ester, carboxylic amide, sulfonic amide, alkyltllio, arylthio, alkoxy or
aryloxy,
X is -O-, -S-, -NH- or-N(alkyl)-,
X' is -O-, -S-, -NH- or-N(alkyl)-,
Y is hydrogen or carboxylic .ester,
Y' is hydrogen or Garb~xylic ester,
Z is =C- or =N-,
Z' is =C- or =N-,
x is 0 or 1, when Z is =N-, then x is 0,
y is 0 or 1, when Z' is =N-, then y is 0,
A is a conjugated linking bridge of the formula
Rz
T
j , ~T.~ /~ / , ~ g /TAW / or
L" JrriT I / / ' vT/
JnT/
Rz Rz
iT ~~/ G G ~ / Ti,
wherein
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n is 0, 1, 2 or 3,
m is 0, 1, 2 or 3,
B is a phenyl ring,
T is =C(R3)- or =N-, wherein R3 is hydrogen, C~-C~2alkyl or CN,
W is a heterocyclic, or linear or polycondensed aromatic group which is
unsubstituted or sub-
stituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino,
G is -CH= or-N=, and
Rz is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino.
According to the invention an alkyl is for example a straight-chain or
branched C~_$alkyl as
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
n-pentyl, 2-pentyl,
3-pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-
ethylhexyl or octyl, prefe-
rence being given to a C,_4alkyl.
According to the invention an alkylthio is for example methylthio, ethylthio,
propylthio, butyl-
tllio, lleptylthio or hexylthio.
According to the invention an alkoxy is for example a straight-chain or
branched C,_$alkoxy,
for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,
isobutoxy, tert.
butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-
hexyloxy, n-heptyloxy,
n-octyloxy, 1,1,3,3-tetramethylbutoxy or 2-ethylhexyloxy.
According to the invention an aryloxy is to be understood as being for example
a C6_~øaryl-
oxy, preferably a C6_~~arylOxy radical, for example phenoxy or 4-
methylphenoxy.
According to the invention an arylthio is for example phenylthio or
napthylthio.
G is preferred -CH=.
W as aromatic group includes, for example, phenylene, naphthalene,
acenaphthylene,
anthracene, phenanthrene, naphthacene, chrysene, pyrene or perylene. W is
preferably phe-
nylene, naphthalene, anthracene, phenanthrene, perylene or pyrene, and most
preferably
phenylene or naphthalene.
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W as heterocyclic group is, for instance, pyridine, pyrazine, pyrimidine,
pyridazine, indole iso-
indole, quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone,
benzothiazole,
pyrrolo, imidazole, pyrrolidine, piperidine, piperazine, morpholine or
pyrazole.
According to the invention an ester is for example methyl-, ethyl-, propyl- or
butylester.
If A is a single double bond / , preferred compounds of formula (1 ) are
a) compounds of phenyl-butyrolactams of formula
0 0
/ ~ EtOZC N -H / H N -H
i /
R1 \ C C/ / , R1 \ ~ / C~ / and
H- N CO Et \ R1 I R1
z H- N H \
~ O
O
R / ~ EtOZC N -nC4H9
~ \ C / Ci /
R1
H9CQn- N COzEt \
O
b) compounds of phenyl-butyrolactones of formula
O
/ H O
R1
\ ~ / O~ / ,
I R1
O H \
O
c) compounds of phenyl oxazolones of formula
O
O
R1
\ N / Ni
O \ H1
O
and
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d) compounds of phenyl imidazolones of formula
O
/ ~ N -H
R~
\ N / Ni /
R~
H- N \
O
wherein R, has the meaning given under the formula (1 ) and Et is -CH2CH3.
If A is a conjugated linking bridge, preferred compounds of formula (1 ) are
e) compounds of phenyl-carboethoxy-butyrolactams of formula
/ CO~Et RZ
R ~ ~ O H
\ N, and
N
H, ~ n C \
R~ C~~Et ~ / R1
n=0, 1 or2
/ COZEt R~
R ~ I O nBut
\ N.
N /
nBllt~~ O n ~ \
_. ~ _ _. ~ R~
f) compounds of phenyl-butyrolactones of formula
R / ~ H R~
0
~c / ~ \ o
o / r
Q n C \
I I R~
RZ H /
n=0, 1 or2
n=0, 1 or2
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~g) compounds of phenyl-butyrolactams of formula
R1 I H
\ C
N-
H O ~ J n" ~j I I ~ R1
h) compounds of phenyl-oxazolones of formula
/ R
R z O
1 \ iN / \ O
O L I / /
O ~ 'N \
R1
Rz I /
n=0, 1 or2
and
i) compounds of phenyl-imidazolones ~f formula
R
R1 \ I N z O H
/ \ N.
N I / /
H, O ~ , N I \
R1
R2 /
n=0, 1 or2
wherein R1 and R2 have the meaning given under the formula (1 ), Et is -CHzCH3
and nEut is
n-butanole.
Further preferred are compounds of formula (1 ), wherein R1 is hydrogen,
chloro, bromo,
methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro is, R~1 is hydrogen,
chloro, bromo,
methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro, RZ is hydrogen or
methoxy, X is -NH-,
-N(n-C4H9)-, or -O-, X is -NH-, -N(n-C4H9)-, or -O-, Y is hydrogen or COOCzHS,
Y is hydro-
gen or COOC2H5, Z is =C- or =N-, Z~ is =C- or =N-, A is = or -T ~ g ~ T = ,
n
T is =C(R3)-, R3 is hydrogen and n is 0, 1 or 2.
n=0, 1 or2
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The most preferred compounds of formula (1) are the compounds of the formulae
O
I o C o C~ , (100),
o H wl
0
0
0
I o C C ~~~ o (101 ),
' ' \ / H H ~
O
OCH3 O O
I o C C C~~ o (102),
~H H ~
O OCH3
O
O
O
I o N C C~~ o (103),
/ H
O- ~ w
O
O
O
I o C C Ci\C' o (104),
' \ / \ / H H
O
O
O
O
I o N C C'~N' o (105),
\ / \ / H \ I
O
OCZHS
O NHZCHZCHzCH3
0 0 0 (106),
N~O C=O I o
H3CHZCHZCHZC OC H
2 5
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CH CH CH CH
O(;ZHS O ~ 2 2 2 3
__ N
C O H
i ~ ~ \ / C ~ (107) and
~H C=O
N
H3CH~CHZCH~C O OCZHS
OCZHS O CHZCHZCHZCH3
C=O H N
i ~ \ / \ / H ~ I ~ (103).
N C=O
H3CH~CH~CH~C O OOHS
The compounds of formula (1 ) according to the invention are prepared, for
example, by
reacting 2 mol of compound of formula
~Y~x
1
~~ CHI (50) which possess an active methylene group -CHI
X --
O
or 1 mol of compound of formula (50) and 1 mol of compound of formula
R, W (Y,>v
/~~CHZ (51 ), which possess an active metllylene group -CHI
O
with 1 mol of one of the compounds of formula
O = C3 CH = CH (5~)' ~ (53), R3 R3 (54),
C3= O ~ 3 3 O=C- -
O=C \g/ C=O W G=O
n
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8
Rz Rz
i s ~ 3 (55)' O = N CH = CH N = O (56),
O=C ~' ~ CH=CH ~' ~ C=O ",
Rz
(5~), O = N - W - N = O (5$) or
O=N ~g~ N=O
n
Rz Rz
(59),
O=N ~ ~ CH=CH ~ / N=O
wherein R~, R~1, X, X~, Y, Y~, Z, Z~, x and y are as defined above for formula
(1 ), n is 0, 1, 2 or
3, m is 0, 1, 2 or 3, B is a phenyl ring, RZ is hydrogen, alkyl, halogen,
hydroxy, alkoxy, alkyl-
thio or amino and R3 is hydrogen, C~-C,zalkyl or CN,
at elevated temperature
or
by oxidation 2 mol of compound of formula (50) at elevated temperature
or
by oxidation 1 mol of compound of formula (50) and 1 mol of compound of
formula (51 ) at
elevated temperature.
The general synthesis of phenyl-butyrolactams (in this case C-substituted by
carboethoxy)
derivatives is characterized by the following reaction schema:
/ (Et0)~CO / CO~Et CICHzCOzEt / ~ COzEt
\ ~ CH3 NaOEt \ ~ K.,CO \
i ' Aceton
O O O COzEt
AcOH / O
N~ \ ~ COZEt [O~ / ~ EtOZC /N
/ \ / / /
HN -~ HN ~ COZEt
0 O
5-Phenyl-4-carboethoxy
butyrolactam type
wherein Ac means acetic acid residue and Et means ethyl.
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9
The general synthesis of phenyl-butyrolactam and phenyl-butyrolactone (N- and
C- unsubsti-
tuted) derivatives is characterized by the following reaction schema:
/
Ac20 / I
N~ / -
\ I \ C02H ~ \
O CuCI
O
O
O O
/I O /I N
\ NCH / CHJ / I ~ \ NCH / CHr / I
O \ HN \
O O
wherein Ac20 means acetic anhydride.
The general synfihesis of phenyl-oxazolone derivatives is characterized by the
following reac-
tion schema:
AczO /
1
/ N\
oN
O CO~H
O
Hippurio acid 2-Phenyl-5-oxazolone* O
Heterocycles, 19(12) 2331, 1982 / ~ O
iN / N~ /
O
O O
PhCHzNH
~oH ~ Phenyl-Oxazolone type
OH SOCIZ
PhCHZNH
O
wherein Ph means phenyl and Ac20 means acetic anhydride
The general synthesis of pheny-imidazolone derivatives is characterized by the
following re-
action schema:
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R~
OOMe
COOMe
HN NH2
phenyl-imidazolone type
wherein R~ has the meaning given under the formula (1 ) and Me is methyl.
The general synthesis based on the condensation of a dialdehyde with an active
methylene
compound is characterized by the following reaction schema:
OHC'[
/ Y l~I~~\ "cHO / Y
\ iZ / \ X
x x ~ / / ~
O p n
Active methylene compound n = o, ~ or 2 Y
wherein X, Y and ~ have the meaning given under the formula (1 ).
The compound of formula (1 ) can be symmetrical or asymmetrical and can
contain one or
more water soluble groups (sulfonic, carboxylic or cationic groups).
Water soluble derivatives of compounds of formula (1 ) can be used as
dyestuffs for textile
application, coloration of cotton, wool, polyamide and polyacrylonitrile using
all the well
known dyeing processes.
Such dyes are useful for dyeing and printing manufactured natural polymer and
especially
synthetic hydrophobic fibre materials, especially textile materials. Textile
materials composed
of blend fabrics comprising such manufactured natural polymer or synthetic
hydrophobic
textile materials are likewise dyeable or printable with the dyes of the
invention.
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11
Useful manufactured natural polymer textile materials are especially cellulose
acetate and
cellulose triacetate.
Synthetic hydrophobic textile materials are especially linear aromatic
polyesters, for example
polyesters formed from a terephthalic acid and glycols, particularly ethylene
glycol, or con-
densation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane;
polycarbo-
nates, for example those formed from a,oc-dimethyl-4,4-
dihydroxydiphenylmethane and phos-
gene; or fibres based on polyvinyl chloride or polyamide.
The above dyes are applied to the textile materials according to known dyeing
processes.
For example, polyester fibres are exhaust dyed from an aqueous dispersion in
the presence
of customary anionic or nonionic dispersants with or without customary
carriers at temperatu-
res between 80 and 140°C. Cellulose acetate is preferably dyed at
between about 65 to 85°C
and cellulose triacetate at up to 115°C.
The above dyes are also useful for dyeing by the thermosol, exhaust and
continuous proces-
ses and for printing processes. The exhaust process is preferred. The liquor
ratio depends
on the apparatus, the substrate and the make-up form. However, the liquor
ratio can be cho-
sen to be within a wide range, for example in the range from 4:1 io 100:1, but
it preferably is
between 6:1 to 25:1.
The textile material mentioned may be present in the various processing forms,
for example
as a f bre, yarn or web or as a woven or loop-formingly Knitted fabric.
It is advantageous to convert the dyes into a dye preparation before use. For
this, the dyes
are ground so that their particle size is on average between 0.1 and 10
microns. The grinding
may be effected in the presence of dispersants. For example, the dried dye is
ground with a
dispersant or kneaded in paste form with a dispersant and then dried under
reduced pressu-
re or by spray drying. The preparations thus obtained can be used to prepare
print pastes
and dyebaths by adding water.
Printing utilizes the customary thickeners, for example modified or
nonmodified natural pro-
ducts, for example alginates, British gum, gum arabic, crystal gum, carob bean
flour, traga-
canth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic
products, for
example polyacrylamides, polyacrylic acid or copolymers thereof or polyvinyl
alcohols.
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The above dyes confer on the materials mentioned, especially on polyester
material, level
shades having very good service fastnesses, such as in particular good light
fastness, espe-
cially a very good hot light fastness, fastness to dry heat setting and
pleating, chlorine fast-
ness and wet fastness such as fastness to water, perspiration and washing; the
dyeings are
further characterized by good rub fastness and heat stability.
Water insoluble derivatives of compounds of formula (1 ) can be used as
disperse dyes for
coloration of PET by exhaustion or pigments for mass coloration of plastics or
can be used
for inks and paints. These products can also be used for coloration of wood
and metals and
they are also suitable as functional dyes for special applications such as
optical information
storage, or display devices or printed circuit boards.
The present invention relates also to a process for the production of coloured
plastics or po-
lymeric colour particles, which comprises mixing together a high molecular
weight organic
material and a tinctorially effective amount of afi least one compound of
formula (1 ).
The present invention further relates to the use of the compounds of formula
(1 ) individually
as colourants, especially for colouring or pigmenting organic or inorganic,
high-molecular-
weight or low-molecular-weight material, especially high-molecular-weight
organic material. It
is also possible, however, for the compositions according to the invention
comprising com-
pounds of formula (1 ) to be used in the form of mixtures, solid solutions or
mixed crystals.
Compounds of formula (1 ) can also be combined with colourants of another
chemical class,
for example with dyes or pigments, for example those selected from the group
of the diketo-
pyrrolopyrroles, quinacridones, perylenes, dioxazines, anthraquinones,
indanthrones, fla-
vanthrones, indigos, thioindigos, quinophthalones, isoindolinones,
isoindolines, phthalocyani-
nes, metal complexes, azo pigments and azo dyes.
The high-molecular-weight material may be organic or inorganic and may be
synthetic and/or
natural material. The high-molecular-weight organic material usually has an
average molecu-
lar weight of 105-10~g/mol. It may be, for example, a natural resin or a
drying oil, rubber or
casein or a modified natural material, such as chlorinated rubber, oil-
modified alkyd resins,
viscose, or a cellulose ether or ester, such as ethylcellulose, cellulose
acetate, propionate or
butyrate, cellulose acetobutyrate or nitrocellulose, but is especially a
completely synthetic or-
ganic polymer (duroplasts and thermoplasts) as may be obtained by
polymerisation, for
example by polycondensation or polyaddition. The class of polymers includes,
for example,
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13
polyolefins, such as polyethylene, polypropylene, polyisobutylene, and
substituted polyole-
fins, such as polymerisates of monomers such as vinyl chloride, vinyl acetate,
styrene, acry-
lonitrile, acrylates, methacrylates, fluoropolymers, such as
polyfluoroethylene, polytrifluoro-
chloroethylene or tetrafluoroethylene/hexafluoropropylene mixed polymerisate,
and copoly-
merisates of the mentioned monomers, especially ABS
(acrylonitrile/butadiene/styrene) or
EVA (ethylene/vinyl acetate). From the group of polyaddition and
polycondensation resins it
is possible to use, for example, condensation products of formaldehyde with
phenols, the so-
called phenoplasts, and condensation products of formaldehyde and urea or
thiourea, also
melamine, the so-called aminoplasts, and the polyesters used as surface
coating resins,
either saturated, such as alkyd resins, or unsaturated, such as malefic
resins, and also linear
polyesters, polyamides, polyurethanes, polycarbonates, polyphenylene oxides or
silicones,
and silicone resins. The mentioned high-molecular-weight compounds may be
present indivi-
dually or in mixtures in the form of kneadable compounds, melts or in the form
of spinning
solutions. They may also be present in the form of their monomers or in the
polymerised sta-
te in dissolved form as film-formers or binders for paints or printing inks,
such as, for examp-
le, boiled linseed oil, nitrocellulose, alkyd resins, melamine resins and urea-
formaldehyde re-
sins or acrylic resins.
Low-molecular-weight materials are, for example, mineral oils, waxes or
lubricating greases.
The present invention further relates, theref~re, to the use ~f the c~mpounds
~f formula (1)
for the producti~n of inks, for printing inks in printing processes, for
flexographic printing,
screen printing, the printing of packaging, security colour printing, intaglio
printing or offset
printing, for preliminary printing stages and for textile printing, for office
and home use or for
graphics, such as, for example, for paper goods, for ball-point pens, felt-tip
pens, fibre-tip
pens, paperboard, wood, (wood) stains, metal, stamp pads or inks for impact
printing proces-
ses (with impact printing ink ribbons), for the production of colourants, for
paints, for use in
industry or advertising, for textile decoration and industrial labelling, for
roll coating or powder
coating compositions or for automobile paints, for high-solids (low-solvent),
water-containing
or metallic paints or for pigmented formulations for aqueous paints, for
mineral oils, lubrica-
ting greases or waxes, for the production of coloured plastics for coatings,
fibres, plates or
moulded substrates, for the production of non-impact printing material for
digital printing, for
the thermal wax-transfer printing process, the ink jet printing process or for
the thermal trans-
fer printing process, and also for the production of colour filters,
especially for visible light in
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14
the range of from 400 to 700 nm, for liquid crystal displays (LCDs) or charge-
coupled devices
(CCDs) or for the production of cosmetics or for the production of polymeric
colour particles,
toners, dry copy toners, liquid copy toners or electrophotographic toners.
The present invention further relates to inks comprising high-molecular-weight
organic mate-
rial and a colour-producing amount of the compound of formula (1 ).
For example, the inks can be produced by mixing the compounds according to the
invention
with polymeric dispersants.
The mixing of the compounds according to the invention with the polymeric
dispersant is pre-
ferably carried out by generally known mixing methods, such as stirring or
mixing, and the
use of an intensive mixer, such as an Ultraturax, is especially to be
recommended.
When mixing the compounds according to the invention with polymeric
dispersants, a water-
dilutable organic solvent is advantageously used.
The weight ratio of the compounds according to the invention to ink is
advantageously selec-
ted to be in the range of from 0.0001 to 75 % by weight, preferably from 0.001
to 50 % by
weight, based on the total weight of the ink.
The present inventi~n theref~re relates also to a process f~r the producti~n
~f inks which
comprises mixing high-molecular-weight organic material with a colour-
producing amount of
the compound of formula (1 ).
The present invention further relates to colourants comprising high-molecular-
weight organic
material and a compound according to the invention of formula (1 ) in a colour-
producing
amount.
The present invention relates, in addition, to a process for the preparation
of colourants
which comprises mixing a high-molecular-weight organic material and a colour-
producing
amount of the compound according to the invention of formula (1 ).
The present invention further relates to coloured or pigmented plastics or
polymeric coloured
particles comprising high-molecular-weight organic material and compound of
formula (1 ) in
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WO 2004/089941 PCT/EP2004/050276
a colour-producing amount.
The present invention relates, in addition, to a process for the preparation
of coloured or pig-
mented plastics or polymeric coloured particles which comprises mixing
together a high-mo-
lecular-weight organic material and a colour-producing amount of the compound
of formula
(1 ).
The colouring of high-molecular-weight organic substances with the colourants
of formula (1 )
is carried out, for example, by mixing such a colourant, optionally in the
form of a master
batch, into those substrates using roll mills or mixing or grinding apparatus,
whereby the co-
lourant is dissolved or finely distributed in the high-molecular-weight
material. The high-mole-
cular-weight organic material with the admixed colourant is then processed
according to pro-
cedures known per se, such as, for example, calendering, compression moulding,
extrusion
moulding, coating, spinning, casting or injection-moulding, whereby the
coloured material
acquires its final form. Admixing of the colourant can also be carried out
immediately prior to
the actual processing step, for example by continuously metering a powdered
colourant ac-
cording to the invention and a granulated high-molecular-weight organic
material, and option-
ally also additional ingredients, such as additives, directly into the inlet
gone of an extruder si-
multaneously, where mixing takes place just before the processing operation.
In general,
however, prior mixing of the colourant into the high-molecular-weight organic
material is pre-
ferred, since more uniform results can be obtained.
It is often desirable for the purpose of producing non-rigid mouldings or
reducing the brittle-
ness thereof to incorporate so-called plasticisers into the high-molecular-
weight compounds
before shaping. There may be used as plasticisers, for example, esters of
phosphoric acid,
phthalic acid or sebacic acid. In the process according to the invention, the
plasticisers can
be incorporated into the polymers before or after the incorporation of the
colourant. In order
to obtain different colour shades it is also possible to add to the high-
molecular-weight orga-
nic substances, in addition to the compounds of formula (I), any desired
amounts of consti-
tuents such as white, coloured or black pigments.
For the colouring of paints and printing inks, the high-molecular-weight
organic materials and
the compounds of formula (1 ) optionally together with additional ingredients,
such as fillers,
dyes, pigments, siccatives or plasticisers, are finely dispersed or dissolved
in a common or-
ganic solvent or solvent mixture. That procedure may comprise dispersing or
dissolving each
individual component on its own or dispersing or dissolving several components
together and
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16
only then combining all the components. Processing is carried out in
accordance with custo-
mary methods, for example by spraying, film-spreading or one of the many
printing methods,
whereupon the paint or printing ink is advantageously cured thermally or by
irradiation, optio-
nally after previous drying.
When the high-molecular-weight material to be coloured is a paint, it may be a
conventional
paint or a special paint, for example an automobile finish, preferably a metal-
effect finish con-
taining, for example, metal or mica particles.
Preference is given to the colouring of thermoplastics, especially also in the
form of fibres,
and printing inks. Preferred high-molecular-weight organic materials that can
be coloured ac-
cording to the invention are, very generally, polymers having a dielectric
constant >_ 2.5, es-
pecially polyesters, polycarbonate (PC), polystyrene (PS),
polymethylmethacrylate (PMMA),
polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or
acrylonitrile/butadie-
ne/styrene (ABS). More especially preferred are polyesters, polycarbonate,
polystyrene and
PMMA. Most especially preferred are polyesters, polycarbonate and PMMA,
especially aro-
matic polyesters that can be obfiained by polycondensation of terephthalic
acid, such as, for
example, polyethylene terephthalate (PET) or polybutylene terephthalate.
They can be used in the form of their monomers or copolymers or in the
polymerised state in
dissolved form as film formers or binders for paints that can be used for the
decoration of
metal or for decorative colour f niches, and for printing inks used, for
example, in the ink-jet
printing process, or also for wood stains.
Special preference is also given to the colouring of mineral oils, lubricating
greases and wa-
xes with the compounds according to the invention.
The present invention also relates to mineral oils, lubricating greases and
waxes comprising
high-molecular-weight organic material and a compound of formula (1 ), in a
colour-producing
amount.
The present invention also relates to a process for the preparation of mineral
oils, lubricating
greases and waxes, which comprises mixing high-molecular-weight organic
material with a
colour-producing amount of the compound of formula (1 ).
The present invention also relates to non-impact printing material comprising
high-molecular-
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17
weight organic material and a compound of formula (1 ), in a colour-producing
amount.
The present invention relates, in addition, to a process for the preparation
of non-impact prin-
ting material, which comprises mixing together a high-molecular-weight organic
material and
a colour-producing amount of the compound of formula (1 ).
The present invention further relates to a process for the production of
colour filters compri-
sing a transparent substrate and a red, a blue and a green coating applied
thereto in any de-
sired sequence, which comprises using for the production of the red, blue and
green coatings
a correspondingly coloured compound of formula (1 ).
The different-coloured coatings are preferably arranged in such a pattern that
they do not
overlap over at least 5 % of their respective surface area and, most
preferably, do not over-
lap at all.
The colour filters can be coated, for example, using inks, especially printing
inks, comprising
the compounds according to the invention, or, for example, by mixing a
compound according
to the invention witll a chemically, thermally or photolytically structurable
high-molecular-
weight material (resist). The further production can be carried out, for
example, analogously
to EP-A-654 711, by application to a substrate, such as an LCD, subsequent
photo-structu-
ring and developing.
The invention further includes a transparent substrate coated with a red, a
blue and a green
coating each of a correspondingly coloured compound of formula (1 ),
comprising pigmented
high-molecular-weight organic material.
The sequence in which coating is carried out is not important as a rule. The
different-colou-
red coatings are preferably arranged in such a pattern that they do not
overlap over at least
5% of their respective surface area and, most preferably, do not overlap at
all.
The present invention also includes colour filters comprising a transparent
substrate and,
applied thereto, a red, a blue and a green coating, each obtainable from a
correspondingly
coloured compound of formula (1 ).
The present invention also includes the use of the compounds of formula (1 )
for optical infor-
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18
mation storage applications (ois).
The present invention relates, in addition, to toners comprising high-
molecular-weight organic
material and a compound of formula (1), in a colour-producing amount.
The present invention also relates to a process for the production of toners,
which comprises
mixing together a high-molecular-weight organic material and a colour-
producing amount of
the compound of formula (1 ).
The present invention also relates to inks or colourants for paints, printing
inks, mineral oils,
lubricating greases or waxes, or coloured or pigmented plastics, non-impact
printing material,
colour filters, cosmetics or toners comprising high-molecular-weight organic
material and a
compound of formula (1 ), in a colour-producing amount.
In a special embodiment of the process according to the invention, toners,
paints, inks or co-
loured plastics are produced by processing master batches of toners, paints,
inks or coloured
plastics in roil mills or mixing or grinding apparatus.
A colour-producing amount of the compound of formula (1 ) means in the present
invention
normally from 0.0001 to 99.99 % by weight, preferably from 0.001 to 50 % by
weight and es-
pecially from 0.01 t~ 50 % by weight, based on the t~tal weight of tile
material c~loured or
pigmented therewith.
The colouredlpigmented high-molecular-weight materials obtained, such as, for
example,
plastics, fibres, paints and prints, are distinguished by very high colour
intensity, high satura-
tion, good fastness to overspraying, good migration-stability, good fastness
to heat, light and
weathering and by a high gloss and good IR reflectance behaviour.
In order to improve the light fastness properties, UV absorbers are
advantageously mixed
into the plastics or polymeric particles to be coloured with the compound of
formula (1 ) accor-
ding to the invention. The amount of UV absorber can vary within a wide range;
advanta-
geously there is used from 0.01 to 1.0 % by weight, especially from 0.05 to
0.6 % by weight,
more especially from 0.1 to 0.4 % by weight, of a UV absorber, based on the
weight of the
plastics or polymeric particles.
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19
The following Examples serve to illustrate the invention. Unless otherwise
indicated, the
parts are parts by weight and the percentages are percentages by weight. The
temperatures
are given in degrees Celsius. The relationship between parts by weight and
parts by volume
is the same as that between grams and cubic centimetres.
Example 1: (general procedure for oxidative dimerization)
A solution of 5-phenyl-4-carbethoxy-1,3-dihydro-pyrrol-2-one (10.0 g, 0.04
mol) is heated at
130° C., under stirring in dry DMF (dimethyl formamide) (100 ml). Slow
stream of oxygen gas
is bubbled through the solution and progress of the reaction is monitored by
TLC (~3 hours).
After completion of the reaction, it is poured on water (5-times). Bluish
suspension is filtered
through Buchner funnel to give dark violet colored crude product (11.0 g). The
crude product
is purified by selective precipitation from hexane-ethyl acetate solvent
mixture to give (2.0 g,
20%) of the pure product. ~H NMR (dmso): ~ 1.1 (6H, t), 4.1 (4H, q), 7.4-7.7
(10H, m), 11.2
(2H, s). All other compounds given in the Table 1 (entries 1, 3, 4, 7) are
obtained following
the same procedure.
Exa J~le 2: (general procedure for N-butylation)
Dimer obtained from process of Example1 (4..5 g, 0.009 mol) is taken in dry
DMF (70 ml)
under nitrogen atmosphere and the solution is cooled to 5° C. To this
sodium hydride 50%
(0.94 g, 0.019 mol) is added in portions. After some time n-butyl bromide
(4.65 g, 0.034 mol)
is added in cane lot. Reacti~n was monitored by TLC and after the completion,
it is poured on
brine. Aqueous part is extracted with ethyl acetate, dried over anhydrous
sodium sulfate.
Evaporation of organic layer gives the crude violet colored product. It is
purified on silica gel
column using hexane-ethyl acetate solvent mixture (10 : 90) to give (3.3 g,
58%) of the pure
product.'H NMR (dmso): g 0.6(6H, t), 0.8(10H, m), 1.2(4H, t), 3.4(4H, t),
3.9(4H, q), 7.7
(10H, s). All other compounds given in the Table 1 (entries 2, 5, 6) are
obtained following the
same procedure.
In the following Tables Et means -CH~CHs, Me means -CH3, OMe means -OCH3, t-
But
means -C(CH3)3, Ph means -Phenyl, OEt means -OCH2CHs and n-But means -
(CHZ)3CH3.
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Table 1
O
/ Et0 C X
R~ I ZI
\ C / C~ /
X COZEt \ R1
O
Example X R~ Shade (PET)
1 N-H H Violet
2 N-nC4H9 H Violet
3 N-H 4-Me Blue
4 N-H 4-OMe Blue
5 N-nC4H9 4-Me Violet
6 N-nC4H9 4-OMe Violet
7 N-H 4-CI Blue
Example 8:
Benzoylacrylic acid (10.Og, 0.056 mol), cuprous chloride (2.0 g, 0.010 mol),
ammonium chlo-
ride (2,2 g, 0.041 mol) are taken in acetic anhydride (50 ml). It is gradually
heated to refilux
under stirring for 2 hours. After the reaction is over, it is thoroughly
cooled in an ice bath.
Settled solids are filtered through Buchner funnel. Solids are washed with
acetic anhydride,
water and ethanol to give the crude product (5.2 g). The crude solids are
purifiied by soxhlet
extraction in toluene to give pure red colored s~lids (3.8 g, 42%). m.
p.315°C, Anal. Calc. For
C2oH~aOa; C. 75.94; H, 3.82; Found: C, 74.79; H, 3.82. All other compounds
given in the
Table 2 are obtained following the above same procedure.
Table 2
O
/ O
R~
i H /
CH /
O R~
O
Example R1 Shade (PET)
8 H Scarlet (fluorescent)
9 4-Me Red
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21
4-t-But Red
11 4-Ph Red
12 4-OMe Red
13 4-O Et Red
14 4-CI Red
4-Br Red
16 3-NO2 Red
Example 17:
2.0 g of the above dimmer from Example 8 is taken in acetic acid (50 ml).
Ammonia gas is
then bubbled through the solution under reflux for 2 hours. Reaction mixture
is cooled to
70° C. and filtered. Solids are washed with water, ethanol and ether.
The crude product is
purified by continuous soxhlet extraction to give (1.4 g, 70%) of violet
colored product. Anal.
Calc. For CzoH~aN~02; C, 76.42; H, 4.49; N, 8.90; Found: C, 75.84; H, 5.10 ;
N, 7.70. All other
compounds given in the Table 3 are obtained following the above same
procedure.
Table 3
~ H
N,
R~
CH / CHr /
H \ R~
H
Example R~ Shade (PET)
17 H Violet
18 4-Me Violet
19 4-t-But Violet
4-Ph Violet
21 4-OMe Grey
22 4-OEt Grey
23 4-CI Red
24 4-Br Red
3-NO2 Red
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22
Example 26:
2,3-Bis-benzoylamino-succinic acid (5.0 g, 0.014 mol) (synthesized as given in
Stachel, S. D.
et al. Arch. Pharm. 312, 968, 1979) is taken in thionyl chloride (50 ml) and
refluxed for 2
hours. Excess thionyl chloride is distilled off. Traces of thionyl chloride
are removed by tolue-
ne co-distillation. It is cooled to room temperature and water is added to it.
The crude mass is
then filtered and dried in an oven till constant weight. The red colored pure
product obtained,
weighted (3.5g, 78%). Anal. Calc. For C~$H~oN~04; C, 67.90; H, 3.17; N, 8.8;
Found: C,
67.07; H, 4.95 ; N, 8.81. All other compounds given in the Table 4 are
obtained following the
above same procedure.
Table 4
R~
\ N / Ni /
R~
Example R~ Shade (PET)
2G H Red
27 4-Me Red
28 4-CI Red
29 4~-N~2 Red
Example 30:
Benzamidine free base (6.0 g, 0.049 mol) and dimethyl acetylenedicarboxylate
(3.6 g, 0.025
mol) are taken in benzene (ca. 50 ml). The deep red colored solution obtained
is heated to
reflux for 2 hours. The cooled mixture is filtered to give (9.0 g) of the
crude. The crude pro-
duct is taken in minimum amount of warm DMF and poured on large excess of
water under
stirring. The solids separated (2.1 g) are filtered and soxhlet extracted with
methanol for 16
hours. The methanol insoluble pure red colored product obtained, weighted (0.8
g, 10%).
Anal. Calc. For C~gH~2N4O2; C, 68.37; H, 3.79; N, 17.72; Found: C, 69.33; H,
3.43 ; N, 17.47.
Methoxy derivative from Example 31 (see Table 5) is synthesized using above
same method.
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23
Table 5
O H
/ N.
\ N / N~ /
N \ R~
H~ O
Example R, Shade (PET)
30 H Yellow
31 4-OMe Orange
Example 33:
5-Phenyl-4-carbethoxy-1,3-dihydro-pyrrol-2-one (2.3 g, 0.01 mol) is dissolved
in acetic acid
(50 ml) at 60 to 70° C. To this PTSA (0.7 g) is added, followed by
addition of 2,5-dimethoxy-
terephthalaldehyde (1.0 g, 0.005 mol) and temperature is increased to
100° C. Heating is
continued for 3 hours and after cooling, solids are filtered through Buchner
funnel. The crude
product is washed with acetic said, water, DMF and methanol. Finally the crude
product is
dissolved in cone. sulphuric acid, reprecipitated from water and filtered. It
is then dried in an
oven to give red colored pure product (1.5 g, 50%). Anal. Calc. For
C36H3~N2Oa, C, 69.60; H,
5.15; N, 4.52; Found: G, 66.47; H, 4.98 ; N, 4.34. All other compounds given
in the Table 6
are obtained following the above same procedure
Table G
/ CO2Et RZ
C O H
/ \ N.
N
O ~n ' C \
I I R~
Rz COZEt /
Example n R~ Rz Shade (PET)
32 0 H H Red
33 1 H OMe Orange
34 1 H H Orange
35 2 H H Yellow
36 0 4-Me H Red
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24
37 1 4-Me H Orange
38 2 4-Me H Yellow
39 0 4-CI H Red
40 1 4-CI H Orange
41 2 4-CI H Yellow
42 0 4-OMe H Red
43 1 4-OMe H Orange
Example 44:
5-(p-Methylphenyl)-4-carbethoxy-1,3-dihydro-pyrrol-2-one (5.1 g, 0.0086 mol)
is taken in dry
DMF (70 ml) under nitrogen atmosphere and the solution is cooled to 5°
C. To this sodium
hydride 50% (1.0 g, 0.04 mol) is added in portions. After some time n-butyl
bromide (6.35 g,
0.046 mol) is added to it at ones. Reaction is monitored by TLC and after the
completion, it is
poured on brine. Aqueous part is extracted with ethylacetate, dried over
anhydrous sodium
sulfate. Evaporation of organic layer gives the crude violet colored product.
It is purified on si-
lica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give
(3.5 g,58%) of
the pure product.'H NMR (dmso): 5 0.6(6H, t), 0.8(6H, t), 1.2(4H, m), 1.4(4H,
m), 2.4(6H,
s),3.4(4H, t), 4.0(4H, q), 7.2-8.3(14H, m). All other compounds given in the
Table 7 are obtai-
ned following the same procedure.
Table 7
R / COZEt R'
O ,nBut
i / ~ N
N L I / /
nBut~ ~ .
RZ CO2Et / R~
Example n R, R~ Shade (PET)
44 1 4-Me H Gold Yellow
45 1 H H Orange
46 2 H H Yellow
47 0 4-Me H Red
48 0 H H Red
49 2 4-Me H Yellow
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50 0 4-CI H Red
51 1 4-CI H Orange
52 2 4-CI H Yellow
53 1 4-OMe H Red
Example 54:
Terephthalaldehyde (2.0 g, 0.015 mol), sodium acetate (7.5 g, 0.091 mol) and
acetic anhydri-
de (70 ml) are taken in round bottom flask and heated to 90° C under
nitrogen atmosphere.
To this is added (3-Benzoylpropionic acid (16.0 g, 0.09 mol). Temperature of
the reaction is
maintained for 3 hours and after cooling solids are filtered through Buchner
funnel, washed
with acetic acid, water and methanol. The crude product is heated in DMF at 80-
90° C for 2
hours. After filtration and washing with water, it is dried in an oven till
constant weight to give
(5.2g, 83%) of the pure product. Anal. Calc. For Cz$H,$O4; C, 78.37; H, 4.34;
Found: C,
78.87; H, 4.45. The compounds of Examples 55 and 56 (see table 8) are
synthesized using
above same method.
Table 8
/ R
R z
O
~ \ iCH / \ O
O L ~ / /
~ ~ 'CH
R~
Rz /
Example n R~ Rz Shade (PET)
54 1 H H Orange
55 1 H OMe Orange
56 2 H H Yellow
Example 57:
Above prepared lactone of Example 54 (11.5 g, 0.027 mol) is taken in acetic
acid (200 ml).
Ammonia gas is bubbled through it and the solution is refluxed for 2 hours.
After completion
of the reaction, it is cooled and filtered. The solids are washed with acetic
acid, water and
methanol. Final purification is done by stirring the solids in DMF at room
temperature for 4-5
hours. Filtered solids are then washed with water, methanol and dried in an
oven till constant
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26
weight to give (10.2 g, 89%) of the orange colored pure product. Anal. Calc.
For C~$HzoNz02;
C, 80.76; H, 4.80;N, 6.73 Found: C, 80.37; H, 4.14; N, 7.21. Example 58 (see
Table 9) is
synthesized using above same method.
Example 59:
Above lactam from Example 57 (6.5 g, 0.020 mol) is taken in dry DMF (90 ml)
under nitrogen
atmosphere and the solution is cooled to 5° C. To this sodium hydride
50% (1.8 g, 0.075 mol)
is added in portions. After some time n-butyl bromide (9.90 g, 0.075 mol) is
added to it at
ones. Reaction is monitored by TLC and after completion, it is poured on
brine. Aqueous
part is extracted with ethyl acetate, dried over anhydrous sodium sulfate.
Evaporation of or-
ganic layer gives the crude orange colored product. It is purified on silica
gel column using
hexane-ethyl acetate solvent mixture (10 : 90) to give orange colored (2.0
g,18%) of the pure
product. m. p. 160°C; ~H NMR (cdcls): ~ 0.8(6H, t), 1.2(4H, t), 1.4(4H,
m), 3.7(4H, t), 6.2(2H,
s), 7.2-7.6(16H, m).
Table 9
/ R
R
\ X
X / / ~ \
~ ~ CH
R~
R~ /
Example X n R~ Rz Shade (PET)
57 NH 1 H H Orange
58 NH 2 H H Yellow
59 N-nBut1 H H ~range
Example 60:
Terephthalaldehyde (7.0 g, 0.055 mol), sodium acetate (14 g, 0.017 mol) and
acetic anhydri-
de (150 ml) are taken in round bottom flask and heated to 90° C under
nitrogen atmosphere.
To this is added hippuric acid (30.0 g, 0.167 mol). Temperature of the
reaction is maintained
for 4 hours and after cooling yellow solids are filtered through Buchner
funnel, washed with
acetic acid, water and methanol. The crude product is heated in DMF at 80-
90° C for 2
hours. After filtration and washing with water, it is dried in an oven till
constant weight to give
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27
(14.5g, 66%) of the pure product. Anal. Calc. For C~sH~6Na04; C, 74.28; H,
3.84;N, 6.66
Found: C, 73.57; H, 3.67; N, 6.79.
Table 10
/ ~ R
R z O
1 \ ~N / \ O
O ~I / /
O )n ~ N I \
R~
R~ /
Example n R~ R2 Shade (PET)
60 1 H H Yellow (fluorescent)
61 0 H H Orange
62 2 H H Yellow
Example 63:
Above oxazoline based compound of Example 61 (1.0 g, 0.0023 mole) is taken in
acetic acid
(30 ml). The reaction mixture is refluxed while ammonia gas is bubbled through
the solution
for 2 hours. The reaction mixture is filtered after cooling and washed with
acetic acid, water
and methanol. The crude mass is stirred in DMF at room temperature for 15
hours followed
by boiling in water f~r 3 hours. Final wash is given with methanol and dried
in an oven till
constant weight. The pure product obfiained in this way gives (2.5 g, 22%)
yield of the pure
product. Anal. Calc. For G2~H,gN402; C, 74.64; H, 4.34;N, 13.79 Found: C,
72.75; H, 4.19; N,
13.60.
Table 11
/ R
R ~ O
iN / \ N -H
H- N ~ I / /
O .~ ' N I \
R~
R~ /
Example n R~ R2 Shade (PET)
63 1 H H Orange
64 2 H H Yellow
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28
Dyeing Example 1:
1200.00 g of polyester granules (PET Arnite D04-300, DSM) are pre-dried for 4
hours at
130°C and then mixed homogeneously with
2.6 g of the compound of formula
0
0
i C i ~ ~ (100)
O H
O
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per
minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from
Collin,
D-85560 Ebersberg) with 6 heating zones at a maximum temperature of
275°C, cooled with
water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001
Bern) and
then dried for 4 hours at 130°C.
The resulting greenish yellow-coloured polyester granules have good allround
fastness pro-
perties, especially good light fastness and high-temperature light fastness
properties.
Dyeing Example 2:
1200.00 g of polyamide-6 granules (lJltramid 831, BASF) are pre-dried for 4
hours at 75°C
and then mixed homogeneously with
3.5 g of the compound of formula
OC H ~ ~HaOHZCHZGH3
z s
C ~ H i /
i ~ \ / H I ~ (108)
C=O
1 O Oc2H5
H3CHzCHzCHzC
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per
minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from
Collin,
D-85560 Ebersberg) with 6 heating zones at a maximum temperature of
220°C, cooled with
water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001
Bern) and
then dried for 4 hours at 75°C.
The resulting orange-coloured polyamide granules have good allround fastness
properties,
especially good light fastness and high-temperature light fastness properties.
