Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
3~
Addition compounds suitable as dispersing agents,
processes for their preparation, their use and
solids coated therewith
The present invention relates to addition compounds
or their salts suitable as dispersing agents, obtainable
by the reaction of polyisocyanates, hydroxyl compounds,
compounds having zerewitinoff-active hydrogen and at
least one basic group containing nitro~en, and optionally
compounds containing amine hydrogen optionally in the
presence of solvents and optionally in the presence of
reaction catalysts.
The invention further relates to the preparation
of these addition compounds, their use as dispersing
agents and pulverulent or fibrous solids which are coated
with such dispersing agents and ar~ to be incorporated
in liquid systems.
Powerful mechanical forces are required for introduc-
ing solids into liquid media. This depends to a largeextent on the ease with which the solid can be wetted
by the surrounding medium and on the affinity to this
medium. To reduce these forces required for dispersion
it is customary to employ dispersing agents which facili-
tate incorporation. These are in most cases surface-
active substances, also known as tensides which have
an anion-active or cation-active or non-iollogenic structure.
These substances are added in relatively sma]l quantities
either by direct application to the solid or by introduc-
tion into the di;persing medium. The effolt requiredfor dispersion is substantially reduced by such a
tenside.
It is a]xo known that: these so]ids tend to reagglom-
erate af`t;er the dispersion procesc; ~ thus vitiatirlg the
-_
`~:
.. . .
.. . . . . . . . ... . . . ..... .
effort previously expended for dispersion and leading
to serious problems. This phenomenon is explained by
London/van der Waal's forces by which the solids attract
each other. To overcome these forces of attraction, it
S is necessary to apply adsorption layers on the solids.
This is achieved by using such tensides.
~ During and after dispersion, however, an interaction
between the solid particle and the surrounding medium
ta~es place and desorption of the tenside occurs, accom-
panied by its replacement by the surrounding medium,which is present at a higher concentration. This surround-
ing medium, however, is in most cases not capable of
building up such stable adsorption layers, and the whole
system breaks down. This manifests itself by a rise in
viscosity in liquid systems, loss of gloss and shift
in colour tone in lacquers and coatings, insufficient
development of colour power in pigmented plastics, and
loss of mechanical strength in reinforced plastics.
Dispersing agents have been proposed for solving
this problem, e.g. in US-A-4 032 698, GB-A-1 393 401
and GB-A-1 393 402. These dispersing agents, however,
provide only partial solutions, in particular with regard
to the ability of different pigments, such as organic
and inorganic pigments, to be mixed together without
flocculating-. Moreover, pigment pastes prepared by the
processës described tend to interact with the surrounding
medium, for example, when they are used in lacquers.
It may thus be assumed that the adsorption layers which
are built up have insufficient stability against desorp-
tion.
It is an object of the present invention to finddispersing agents which do not have the above disadvan-
; tages or only to a substantially less extent, and which
result in the formation of dispersions of solids which
do not tend, or only to a minor degree, to reagglomerateafter the dispersion process.
It-has now surprisingly been found that this problem
.. , . , -- .. , .. . ... .. . . .. . . . . . . . ..... ~ . .. ... ..
~ . 5~
., .
may be solved by means of the addition products defined
below.
'The invention thus relates to additiorl compolJnd~s
or their salts suitable as dispersing agents, obtainable
by the reaction of polyisocyanate's, hydroxyl compounds,
compoundshaving zerewitinoff-active hydrogen and
at least one basic group containing nitrogen, and option-
ally compounds containing amine hydrogen, optionally
in the presence of solvents and optionally in the presence
of reaction catalysts, characterised in that they are
obtainable by the reaction of polyisocyanates having
an average functionality of from 2.5 to 6
a) in such a quantity with monohydroxyl compounds of
the formula I
Y-OH
wherein Y.has the following meanings:
i.) aliphatic and/or cycloaliphatic hydrocarbon groups
with 8 to 30 carbon atoms in which the hydrogen
atoms may be partly replaced by halogens and/or
20 aryl groups,
ii) aliphati.c, cycloaliphatic and/or aromatic groups
- with molecular weights of from 350 to ~3000 which
contain at least one -O- and/or -COO- group and
in which the hydrogen atoms may be partly replaced
by halogens
that from 15 to 50%, preferably 20 to 40% and most
preferably 20 to 35% of the NCO groups are reacted,
b) reacting the resulting reaction product in such a
quantit,y wi.t,h compo~ ds of the formllla II
3 0 C - ( E, ) :[ I
wherein E stands for -Oli, -Nl12 and/or -NE~R (wherei.n
R represents an allcyl group having 1 to 4 carbon atoms)
and n stands for 2 or 3, and C represents an aliphatic,
cycloaliphat,ic ar,d/or aromatic group with molecular
weights of at the most 3000 whi.ch has at least 2 carbon
atom~ al)d rnay contain -O-, -COO-, -COiill-, -S- alld/or
-S02- gro~ s, that a further 15 to 45%, preferably 20
.. . . . . .. , . ~ . . . ~ .
to 40~ and ~ost preferably 20 to 35~ of the.NCO groups ..
of the polyisocyanates originally put into the process
are reacted but the sum of the degrees of NCO reaction
of reactions a) and b) amounts to at least 40% and
at the most 75%, preferably 45 to 65~ and most prefer-
ably 45 to 55%, and
c) reacting the resulting reaction product in such a
quantity with compounds of the general formula III
z_Q III
wherein Q stands for -OH, -NH2, -NHR.(wherein R stands
for an alkyl group having 1 to 4 carbon atoms~ or
SH, and Z is an aliphatic group with 2 to 10 carbon
atoms containing at least one tertiary amino group
or a heterocyclic group containing at least one basic
ring nitrogen atom which carries. no hydrogen atom,
which heterocyclic group may be attached to the group
Q by way of an alkylene.group having up to 10 carbon
atoms
that at least one molecule of the compound Z-Q is
available for each remaining isocyanate group which
has not been reacted in stages a) and b).
- The invention also relates to the process for the
preparation of the addition compounds as described above.
The invention further relates to the use of the addi-
tion compounds described above as dispersing agents.
The invention also relates to pulverulent or fibrous
solids which are coated with these addition compounds
as dispersing agents and are to be incorporated in liquid
systems. Pulverulent or fibrous solids are of the kind
which were coated with dispersing agents according to
the state of the art, in particular or~ai1ic and inorganic
pigments used in paints, coating compounds, moulding
compounds or other synthetic resins, and inorganic or
- organic fillers used for filling or reinforcing paints,
coating compounds, moulding cornpounds or other synthetic
resins, A sub-group of such fillers are formed by fibres
. . .
-- , .. ... _ . .. .. . ... . . . .
of an organic and/or inorganic nature which are also
used as fillers or reinforcing materials. Such pulveru-
lent or fibrous solids having a coating of dispersing
agents according to the invention are prepared in known
manner but using the dispersing agents according to the
invention instead of the dispersing agents known in the
art. In the field of fibrous materials, these dispersing
agents are frequently referred to as sizes. In this
context, the solidsmay be coated with a solution or emul-
sion of the addition compounds according to the invention,e.g. in a fluidized bed. The solvent or emulsifying agent
may subsequently be removed or it may be left in the
mixture so that pastes are obtained. Another possibility
consists, for example, of introducing the solids to be coated
into a liquid medium to form a slurry and then adding
the addition compounds according to the invention to
this slurry. Formation of this slurry may also be carried
out in such a manner that a workable paste is obtained,
the liquid medium used for forming the slurry being,
of course, adapted to the subsequent purpose of use of
this paste, e.g. the pigment paste.
The addition compounds according to the invention
may, however, also be used as dispersing agents in the
same manner as known dispersing agents are used in the
state of the art, in that they are added to the systems,
e.g. lacquers, synthetic resin mixtures or the like,
in which the solids which are to be incorporated, such
as pigments, fillers or fibres, are already contained
in a dispersed form.
The pol~isocyanates used for the preparation of the
addition compounds according to the invention are those
already used in the state of the art in this technical
field but they must have an average functionality of
from 2.5 to 6. ~xamples of such polyisocyanates include
those ~hich may be obtained by the addition of diiso-
cyanates to polyols, such as
s
NCO
CH20CONH~ ~ J ~ -CH3
/ . / NCO
CH3~CH2oC --CH OCON~ CH3
\ . ~NCO
CH20CONH ~ O ~-_.CH3
Trade product: Desmodur L (Registered Trade Mark)
or those obtainable from diisocyanates by the biuret
- --~~ reaction, such as
O
Il
.C-NH-~CH ) -NCO
OCN-(cH2)6-N~ 2 6
C-NH-(CH ) -NCO
--- 0 2 6
Trade product: Desmodur N (Registered Trade Mark)
or polyisocyanates with an isocyanurate structure obtain-
able by the cyclisatisn of diisocyanates
N ItH~)~ N ~N ~tU~ tO t~ R 7'~ to
t~' ~N ~0 0 ~N ~0 0~ \11/ ~o ~ \1(/ ~0
0 (~ htt ~ o
Trade product: Desmodur HL Trade product: Desmoclur IL
(registered Trade Mark) (registered Trade Mark)
.... . . . .. . . . .
-' -.P..~-O~D ~-c~ ?o~Y~o~ O ~CJ
~L~o ~co ; ~o
- ~ CRJ C113 CU~ -
Trade product : Polurene KC (registered Trade Mark)
~C~ol~ o~ JC
I~~ I ~~t~ ~C113
y--A~
Cl~3 ~CO
CB3 ~3
Trade product: Polurene HR (registered Trade Mark)
lC ~ 0 O ~ O ~ Cl~3
f~ ~ o ~1 ~ c~l ~ C~ O
"'
C~ CJ~,~NCO ~J~rco
C~
Tolylene diisocyanate-isophorone diisocyanate-isocyanurate
/ C4mpany: SAPICI)
~<
N--C~O
. ~ ~
O-C-N~q~h~-C~
Trimeric isophorollediisocyanate (isocyanurate T18~0 of
Chemische ~erke ~ls)
.. . . .. . . .. . . . . . .. .. .. .
s
As already mentioned above, the relevant eompounds
are trade produets whieh frequently do not eonsist of
eompounds of the above ehemieal formulae in their pure
form but are mixtures of eertain eompounds of a similar
strueture. By "average functionality" is meant that with
regard to the isoeyanate groups, the trade produets have
the given funetionality of from 2.5 to 6, preferably
3 to 6. For example, a "funetionality of 3" means that
a moleeule contains, on statistieal average, 3 free
isoc~yanate groups. The average functionality may be deter-
mined experimentally by determining the average molecular
weight Mn, In addition, the isocyanate number is determined
and the isocyanate equivalent weight is calculated from
this number. The average funetionality is th~ quotient
of the average moleeular weight and the isoeyanate equi-
valent weight.
The monohydroxyl compounds of formula I may be
aliphatie, eyeloaliphatie and/or araliphatie eompounds
having in eaeh ease 8 to 30 earbon atoms~ Mixtures of
sueh compounds may also be used.
Straight chained or branched aliphatie or araliphatie
eompounds may be used They may be satur~ted or unsaturated.
Saturated compounds are preferred. The hydrogen atoms
may be partly replaced by halogens, preferably by fluorine
and/or chlorine. When such substituted eompounds are
used, they are preferably aliphatie monohydrie aleohols.
Sueh products are available eommercially and, as is well
known to the man of the art, generally have no halogen
atoms on the carbon atoms elose to the hydroxyl group.
Examples of specially fluorinated alcohols include hepta-
deeafluorodecal1ol or C6F13Cl12C~l2O~-I. The eorresponding
products available commercially are frequently not uniform
but mixtures of different fluorinated eompounds as obtainec~
from teehnical synthesis.
3~ The monol-yclroxy] eompounds of formula I may eontain
at least one -O- and/or -COO-group, which means they
are polyethers, polyesters or mixed polyether-polyesters.
. .
~. , i
Examples of p~lyesters include those which may be
obtained by the polymerisation oE a lactone such as
propiolactone~ valerolactone, caprolactone or substi-
tuted derivatives thereof, using a monohydroxyl starting
component. The starting components used may be monohydric
alcohols, suitably with 4 to 30, preferably 4 to 14
carbon atoms, such as n-butanol, relatively long chained,
saturated and unsaturated alcohols such as propargyl
alcohol, oleyl alcohol, lineloyl alcohol, oxo alcohols,
cyclohexanol, phenyl ethanol or neopentyl alcohol or
flu~rinated alcohols of t~e kind mentione~ above. Alcohols
of the type described above and substituted and unsubsti-
tuted phenols may also be converted into polyoxyalkylene
monoalkyl-, aryl-, aralkyl- or cycloalkyl ethers by ~nown
methods of alkoxylation with ethylene oxide and/or propylene
oxide, and these monohydroxypolyethers may be used in
the manner prescribed as starting components for lactone
polymerisation. Mixtures of the above mentioned compounds
may in all cases be used.
This lactone polymerisation is carried out by known
methods at temperatures of about 100C to 180C, initiated,
for example-, by p-toluenesulphonic acid or dibutyl tin
dilaurate, and proceeds according to the following mech-
anism:
O ~ ~
2 2)4 C O + CH3-(CEI2)5-O
~ 2)5 ~Cl 1 2 ( 2)9 C 3
- These polyesters suitably have a molecular weight
in the region of about 350 to 8000, preferably 500 to
5000~ compounds obtained by lactone polymerisation carried
out as described above being preerred. The alcohols
used as starting components are preferably saturated
monohydric alcohols having 4 to 18 carbon atoms.
Other examples of polyesters include those which
,, , , ,,,, , _ , .. ,, _, . . ,, ., . . , .. .. . ... ., _, .... ..... ... ... ... ... .... .. .
1 0
may be obtained by the condensation of a glycol and a
dibasic acid in the presence of monohydroxyl compounds.
The formation of dihydroxypolyesters may be suppressed
by using the appropriate stoichiometric quantities of
monohydroxyl compounds as described above. The reaction
then proceeds according to the mechanism illustrated
by the following example:
CH H CH oH + S HOOC CH COOH H
3 ( 2)15 OH 5 ( 2)4 ( 2)4 >
H ~ (CH2)4-O-C-(CH2)4-~C~-O~ (CH2)15 3 2
L O 15
. .
These polyesters suitably have an average molecular
weight of from 400 to 2500, preferably from 800 to 1500.
A further example is provided by polyesters which
are obtainable by tlle condensation of a hydroxycarboxylic
acid in the presence of monohydroxyl compounds of the
kind described above for controlling the molecular weight.
The reaction then proceeds according to the mechanism
illustrated by the following example:
CH3-CH2-1O-CH2- CH2'-OH- + 5 HO-CH-CH2-CH=CH(CH2)7
~ 5 (CH )
CH3 OOH
E~O ~ H-CH2-CH=CH-(CH2)7-C-O~- (CH2-CEI2-0)5-CE~2-C~3+ 5 H20
l( ICH2)5 ' -!
' CH3 ~5
In this case, the average molcc~l]ar weight of the
polyester is suitably from 600 to 3000 ? preferably from
800 to 1500.
The compounds of formula I may also be monohydroxy-
polyethers of the kind obtained by the alko~ylation of
alkanols, cycloalkaJlols and phenols. These polyethers
:
1 1
suitably have a molecular weight in the region of about
~ 350 to 1500.
The reaction of the polyisocyanates with the compounds
of formula I thus results in a proportion of the free
isocyanate groups undergoing reaction with the hydroxyl
groups of the compounds of formula I. On average, at
least 0.8, preferably about 1 molecule of formula I should
react for each molecule of polyisocyanate so that about
one compound of formula I is attached to each polyisocyan-
ate molecule. When polyisocyanates having an averagefunctionality greater than 3 are used, a larger quan~ity
of compounds of formula I may be used. What is important
is that of each molecule of polyisocyanate, at least
two isocyanate groups, and in the case of polyisocyanates
having an average functionality less than 4, about 2
isocyanate groups should remain unreacted, and of these
unreacted isocyanate groups, in the simplest case about
one isocyanate group is used for cross-linking with
compounds of formula II in subsequent reactions and about
one isocyanate group is reacted with compounds of formula
III. Depending on the functionality of the polyisocyanates
used and of the compounds of formula II, the individual
quantitative proportions may be selected by suitably
applying the principles just outlined.
The reaction product obtained is then reacted with
compounds of the formula II. This reaction may be carriecl
out in the same vessel as the reaction with compounds
- of formula I. In some cases, the polyisocyanates may
be reacted with a mixture of compounds of f ormula I and
formula II. Reaction a) with compounds of formul~l I thus
resul-ts in the reaction of 15 to 50?; of tl1e NCO ~roups
of the polyisocyanates originally put into the process.
The lower limit is preferably 20%. The upper limit is
preferably-90~, most preferably 35~ and in some cases
only 30%.
When ~reaction b) takes place with compounds of the
formula II, a furtl1er 15 to 45~ of the ~CO groups of
12
the polyisocyanates originally put into the process are
reacted. The lower limit is preferably 2G%. The upper
limit is suitably 40~, preferably 35~ and in some cases
preferably 30~.
In reactions a) and b) together, however, at least
40% and not more than 75% of the NCO groups of the poly-
isocyanates originally put into the process are reacted,
the lower limit being preferably at 45%. The upper limit
is suitably at 65~, preferably at 55~ and in some cases
preferably at 50~. If, for example, according to a),
the isocyanates originally put into the process are reacted
with compounds of formula I in such quantities that 15%
of the NCO groups are reacted, the compounds of formula
II must be used in such quantities in reaction b) that
--- 15 at least 25% of the NCO groups of the polyisocyanates -
originally put into the process undergo reaction, giving
a total of 15 + 25 = 40~. -
The compounds of formula II essentially differ fromthose of formula I in that they contain two or three
functional groups which react with the isocyanate groups.
These functional groups are preferably hydroxyi groups
because compounds of this kind are readily available
and obtainable commercially and the reaction products
obtained are readily soluble in solvents which may be
used in the subsequent application of the dispersing
agents according to the invention.
Examples of compounds of formula II are: Diols and
triols, diamines, dialkanolamines, monoalkanolamines
with 2 to 12 carbon atoms, dihydroxydialkylsulphides
and dihydroxysulphones, e.g. butanediol, hexanediol,
cyclohexanedimethal1ol, neopentyl glycol, ethylene glycol,
alkyl-substituted dialkanolamines~ glycerol, trimethylol
propane,-fatty acid dialkanolamides, thiodiglycol, di-(4-
hydroxyphenyl)-sulphone. A preferred group of compounds
of formula II are the polyoxyalkylene glycols, preferably
with alkylene moieties having 2 to 4, preferably 2 carbon
atoms, and prr-~Ierably with molecular weigl1ts in the range
of from 400 to 2000, preferably from 600 to 1500.
13
Ethoxylates with 3 hydroxyl groups are obtained by poly-
merisation, using trifunctional alcohols as starting
components~ Polyethylene glycols are preferred polyoxy-
alkylene glycols.
The compounds of formula II may be compounds which
are obtainable by the polymerisation of a lactone, as
already mentioned above, using dihydroxy or trihydroxy
starting components. These polyester polyols suitably
have an average molecular weight Mn of from 800 to 2000.
sutanediol or ethylene glycol is pref~rred as starting
components but the diols or triols mentioned above may
also be used as starting components.
The compounds of formula II bring about a cross-linking
between the reaction products of polyisocyanate and
-- 15 compounds of formula I. In the simplest case, the starting
products are used in such quantities that the compounds
of formula II constitute the centre of the molecule and
the polyisocyanates are attached to the compounds of
formula II by way of the groups E while the remaining
isocyanate groups have reacted with or undergo reaction
with compounds of formula I and formula III, respectively.
A certain amount of excess cross-linking or sub-
equivalent cross-linking may, of course, occur. For this
reason, the number of molecules of polyisocyanate to
one molecule of formula II may range from 0.8 n to 1.1 n
(n has the same meaning as in formula II).
Excess cross-linking rnay be prevented to a certain
extent by operating in dilute solutions in strongly polar,
aprotic solvents such as dirnethylformamide, dimethyl
acetamide or N-methylpyrrolidon~.
The reaction products thus obtained are reacted in
such a quantity with compounds of formula III that at
least one molecule of formula III is available for each
remaining isocyanate group which has not yet reacted
in stages a) arld b~. If the compounds of formula III
contain on]y one group capable of reacting with isocyanate
groups, an excess is not required, and indeed, about
14
one molecule of formula III is used to each as yet unreact-
ed isocyanate group. If the compounds of formula III
contain more than one group capable of reacting with
isocyanates, it is sufficient to provide one molecule
of formula III to each as yet unreacted-isocyanate group
although less than the equivalent quantity should not
be used because undesirable cross-linking might then
occur. A slight excess may be advisable to prevent unwanted
cross-linking. An excess of about 10, preferably 5 mol-%
is generally sufficient. In formula III, Q preferably
stands for -NH2. Furthermore, Z in formula III is pr~f-
erably a mononuclear or dinuclear heterocyclic group
having a ring nitrogen atom which is attached to the
group Q, preferably by way of an alkylene group having
2 to 5 carbon atoms. Preferred heterocyclic groups are
triazole, pyrimidine, imidazole, pyridine, morpholine,
pyrrolidine, piperazine, benzimidazole, benzothiazole
and/or triazine. They may have substituents, such as
up to 3, preferably 1 of the following groups: ~lkyl
- 20 and/or alkoxy groups having 1 to 6, preferably 1 to 4
carbon atoms (a methoxy group being preferred), amino
groups (this leads to compounds which are polyfunctional
in their reaction with isocyanates).
- The heterocyclic groups mentioned above may be directly
attached to the group Q but they may also be attached
by one of the groups conventionally used for this purpose,
such as alkylene groups having 2 to 8, preferably 2 to
4 carbon atoms or polyether groups having the same number
of carbon atoms. The same applies to the tertiary amino
group. The compounds used as compounds oE formula III
may in princip'e be any which have already been used
in this ficld of the art for the preparation of other
dispersing agel1ts, e.g. as described in US-A-4 032 698.
Thc following are examples of co~npounds o~ formula III:
N,N-Diethyl-1,~-butanediamine, 1-(2-aminoethyl)-piperazine,
2-(1-pyrrolidyl)-et}lylamine, 4-amino-2-methoxy-pyrimidine,
2-dimethylaminoetl-anol, 1-(2-hydroxyethyl)-piperazine,
4-(2-hydroxyethyl)-morpholine, 2-mercaptopyrimidine,
2-mercaptobenzimidazole. The following are particularly
preferred: N,N-dimethyl-1,3-propanediamine, 4-~2-amino-
ethyl)-pyridine, 2-amino-6-methoxybenzothiazole, 4-(amino-
methyl)-pyridine? N,N-diallyl-melamine, 3-amino-1,2,4-
triazole, 1-(3-aminopropyl)-imidazole, 4-(2-hydroxyethyl)-
pyridine, 1-(2-hydroxyethyl)-imidazole, 3-mercapto-1,2,4-
- triazole. It is characteristic of these compounds that
they contain at least one Zerewitinoff-active hydrogen
atom per molecule, which hydrogen atom preferably reacts
with the isocyanate groups, and that they in addition
contain a basic group which contains nitrogen and which
is not capable of reacting with isocyanate groups to
form urea. These basic groups are also characterised
according to the state of the art by their pKa-value
(see US-A-3 817 944; 4 032 698 and 4 070 388). Compounds
with basic groups having a pKa-value of from 2 to 14
are preferred, especially those with pKa-values of from
5 to 14 and most especially those with pKa-values of
from 5 to 12. The pKa-value can be obtained from tables.
- The limiting values given above refer to the measurement
of the pKa-value at 25C at an 0.01 molar concentration
in water. These basic groups also impart a basicity to
the addition compounds according to the invention, as
is known in this field of the art (see the above mentioned
US Patent Specifications).Due to these basic groups,
the addition compounds are capable of salt formation.
According to the invention, they may also be used in
the form of such salts as dispersing agents.
These salts are obtained from the resulting reaction
product by neutralisation with ol-ganic or inorganic
acids or by quaternisation. Salts with organic monocar-
boxylic acids are preferred.
All the reactions may, as in the state of the art,
be carried out in the presence of suitable solvents which
do not interfe~e with the reaction, e.g. hydrocarboTIs
such as xylel1es, eLhers,including dioxane and dimethyl-
16
formamide, etc. The reactions may also be carried outin the presence of conventional catalysts such as dibutyl
tin dilaurate, iron acetyl acetonate or triethylenediamine.
Reference may be had in this connection to the Patent
Specifications cited above.
By varying the substituents of formulae I and II
and/or their quantitative proportions, the compatibility
of the addition compounds according to the invention
may be adjusted to a wide variety of polymer compounds
used in coating and moulding formulations in which the addition
compounds according to the invention are employed. If,
for example, the binder in a lacquer is a polyester,
the addition compounds according to the invention used
in such a binder should, by virtue of the groups present
in the starting compounds of formulae I and II, also
contain in their molecule polyester groups or similar
groups which are known to the man of the art to be compat-
ible with polyesters. The same applies in analogous manner,
for example, to polyethylenes or polyamides. Addition
compounds according to the invention which contain only
slightly polar groups are particularly compatible with
these compounds. The same applies analogously to substit-
uents of formula III, which have a particular influence
on the affinity of the addition compounds according to
the invention for the pigments which are to be dispersed.
The preparation of compounds of formula I is illustrated
in the examples of preparation A to G given below.
Parts are parts by weight unless otherwise stated.
In compounds such as polymers in which the moleçules
are not uniform, the molecular weights given are average
values in terms of numerical averages (Mn). l~he molecular
weights or average molecular weights Mn may be determined
by the usual methods, e.g. by determining the OH number
or the amine number or kryoscopically.
Thc NCO content of the polyisocyanates used in the
process and the course of the reaction of additiol1 are
determined by methods such as those described in
.. . . . . , . ~
17
"The Chemistry of Cyanates and their Thioderivatives"
by Paul Patai, Part 1, Chapter 5, 1977.
The heterocyclic groups of compound III, which are
represented by the symbol Z, may be attached to the group
S Q either directly or by way of an alkylene group, as
already mentioned above. These heterocyclic groups are
preferably attached to the group Q by way of a ring
nitrogen atom and an alkylene group, preferably one having
2 to 5 carbon atoms. The heterocyclic group may, of course,
contain other hetero atoms in addition to this ring
nitrogen atom, including further ring nitrogen atoms.
These additional ring nitrogen atoms may also carry a
hydrogen atom (e.g. in the case of N-alkylpiperazine).
The heterocyclic groups may, however, be attached to
the group Q by means of a ring carbon atom, as in the
case of benzimidazole, optionally by way of an alkylene
group. The nature of the linkage depends to a large
extent on the particular constitution of the heterocyclic
groups and the reactivities of the individual atoms,
as is well known to the organic che~lst.
,
.
. ,. .. .~ .. _
18
Example of preparation A
2.1 Parts of a commercial heptadecafluorodecanol
having an average molecular weight of 445 are homogen-
ised with 5.9 parts of 2-ethylhexanol and 92 parts of
valerolactone at 60C under a protective atmosphere.
0.004 parts of dibutyl tin dilaurate are added and the
reaction mixture is heated to 180C within one hour.
The reaction mixture is stirred at this temperature until
a solids content of 98~ is obtained.
The colourless to slightly yellowish product is solid
at room temperature and mel~s at 60 to 70C.
Example of preparation B -
11.1 Parts of phenyl ethyl alcohol and 88.9 parts
of caprolactone are homogenised in the reactor at room
temperature and 0.002 parts of dibutyl tin dilaurate
is added as catalyst under nitrogen. The reaction mixture
is heated to 160C within one hour and stirred at this
temperature. The reaction is terminated as soon as a
solids content of 99~ is reached.
The polyester may be handled as a 100% product with
a melting range of from 50 to 60C or, for example, as
a 50% mixture in xylene. The latter modification is solid
at room temperature with a melting range of from ~0 to
50C.
Example of preparation C
. 7o2 Parts of n-octanol, 92.8 parts of caprolactone
and 0.003 parts of dibutyl tin dilaurate are homogenised
under a protective atmosphere and heated to 160C within
one hour. The addition reaction is terminatecl as soon
as a solids cont:eilt above 99~ is reclcilecl, At this temper-
ature this solids content is reacned after 10 to 12 hours.
The product is a colourless solid at room temperature
and melts at 50 to 60C.
_.
19
Example of preparation D
2.9 Parts of isononanol, 97.1 parts of caprolactone
and 0.002 parts of dibutyl tin dilaurate are homogenised
under a protective atmosphere and heated to 170C within
one hour. The addition reaction is terminated as soon
as the solids content rises above 99.5%, which is attained
after 8 to 10 hours. The product is a colourless solid
at room temperature and melts at 60 to 70C.
Example of preparation E
10.5 Parts of n-octanol, 89.5 parts of 12-hydroxy-
stearic acid and 0.04 parts of tetrabutyltitanate are
homogenised with 100 parts of xylene with exclusion of
oxygen (12-hydroxystearic acid: OH number 160 mg KOH/g,
~'~' - acid number 182 mg KOH/g). The reaction mixture is heated
under normal pressure and the water of reaction formed
is distilled off azeotropically within 7 to 10 hours.
The product may be used for further reaction in the form
in which it is obtained. To produce the 100% product,
- the solvent is carefully drawn off under vacuum.
ExamPle of preparation F
38 Parts of adipic acid, 52.7 parts of dodecanediol, -
9.3 parts of octanol, 0.01 parts of p toluenesulphonic
acid and 30 parts of toluene are homogenised and heated.
The water of reaction formed is removed from the equilibrium
by azeotropic distillation within 5 to 6 hours, the temper-
ature reaching 140 to 150C. The solvent is then carefully
drawn off under vacuum. The polyester is solid at room
temperature and melts at 70 to 80C.
Example of pre~ra,tion G
23.4 Parts of an alkali-free and dehydrated nonyl
phenol ethoxylate having an average molecular weight
of 445 are homogenised,with 76.6 parts of caprolactone
and 0.004 parts Or dibutyl tin dilaurate under a protec-
tive atmosphere~ The reaction mixture is heated to 150C
and stirred at this temperature for 20 hours.
The colourle5s~ waxy product has a solids content of
98~.
Examples of preparation for compounds of formula II
=~ ' .
9.6 Parts of trimethylolpropane and 90.4 parts of
caprolactone are reacted at 170C for 6 to 8 hours after
the addition ofO.003 parts of dibutyl tin dilaurate as
catalyst until a polyester having an average molecular
weight of 1400 is obtained.
Example of preparation II
9 Parts of 1,4-butanediol, 91 parts of caprolactone
and 0.002 parts of dibutyl tin dilaurate are homogenised
under a protective atmosphere and heated to 160C within
one hour. The addition reaction is terminated at this
temperature as soon as the solids content rises above
99~. The resulting polyester diol has an average molecular
weight of 1000. -
., . ., ,.. . . .... ,, _.. ~ . . . . . . . . .
..s`2~ ~3
21
Example 1
7.2 Parts of Desmodur N ~75~ in ethyl glycol ace-
tate/xylene 1:1) are homogenised under a protective
atmosphere with 10 parts of ethyl glycol acetate and
16.9 parts of a caprolactone polyester haviny an average
molecular weight of 1800 (Example of preparation C)
dissolved in 20 parts of xylene, 0.004 parts of dibutyl
tin dilaurate are added and the reaction mixture is stirred
at 60C until the OH groups have completely reacted.
For the cross-linking reaction, the reaction mixture
is diluted with 10 parts of xylene, and 0.8 parts of
1,12-diaminododecane dissolved in 10 parts of N-~ethyl-
pyrrolidone are rapidly added.
When 66% of the NCO groups originally put into the
process have undergone reaction, the reaction mixture
is diluted with 13.2 parts of xylene, and 1.9 parts of
N,N-diallyl melamine dissolved in 10 parts of N-methyl-
pyrrolidone are added. The reaction mixture is heated
to 70C and stirred at this temperature for one hour.
- The end product has a medium viscosity and is a colour-
less, clear to slightly cloudy substance.
Example 2
Under a protective atmosphere, 10.4 parts of Desmodur N
(75~ in ethyl glycol acetate/xylene 1:1) are diluted
with 10 parts of ethyl glycol acetate, and 15 parts of
a caprolactone polyester having an average molecular
weight of 1100 (Example of preparation B) dissolved in
20 parts of xylene are added. After the addition of 0.004
parts of dibutyl tin dilaurate, the reaction mixture
is heated to 60C.
When 33~ of tlle NCO ~roups put into the process ha~e
undergone reaction, 0.6 parts of trimethylolpropalle dis-
solved in 30 parts of xylene are added.
As soon as 66~ of the NCO yroups have reacted, 1.6
parts of 4-(2-hydroxyethyl)-pyridi;le dissolved in 12.4
parts of ethyl ylycol acetate are aclded, and the reaction
~ixture is heated to 70C and stirred at this te~perature
... . .. .
22
for one hour. The end product is colourless and has a
medium viscosity.
Example 3
10.3 Parts of Desmodur N (75% in ethyl glycol ace-
S tate/xylene 1:1) are homogenised under a protective atmos-
phère with 20 parts of ethyl glycol acetate and 10.2
parts of a commercial methoxypolyethylene glycol having
an average molecular weight of 750 dissolved in 15 parts
of xylene, 0.004 parts of dibutyl tin dilaurate are added
and the reaction mixture is he~ted to 50C.
After one third of the NCO groups have reacted, 5.4
parts of polyethylene glycol 800 dissolved in 15 parts
of xylene are added.
When 66% of the NCO groups put into the process have
-- 15 reacted, the reaction mixture is diluted with 12.4 parts
of xylene, and 1.7 parts of 1-(2-aminoethyl)-piperazine
dissolved in 10 parts of ethyl glycol acetate are added.
The reaction mixture is stirred at 70C for 2 hours.
The product is yellowish and slightly viscous.
Example 4
9.1 Parts of Desmodur N (75% in ethyl glycol acetate/
xylene 1:1), 17.7 parts of ethyl glycol acetate, 0.003
parts of di~utyl tin dilaurate and 13 parts of a capro-
lactone polyester with an average molecular weight of
1100 (Example of preparation B) dissolved in 10 parts
of xylene are homogenised under a protective atmosphere
and heated to 50C. After chemical addition of the poly-
ester, 3.7 parts of an ethoxylated oleylamine having
an average molecular weight of 630 dissolved in 30 ~arts
of xylene are ad(1ed. As soon as 65~ oE the NCO groups
have reacted~ 1.5 parts oE ~-(2-alninoelhyl)-pyridine
dissolved in 15 parts of N-methylpyrrolidone are added
and the mixture is stirred for one hour to complete the
reaction.
Example 5
7.6 Pa~:ts of Desmodur N (75% in ethyl glycol
....
3~3~
. .
23
acetate/xylene 1:1) 18.1 parts of xylene and 13.8 parts
of a polyester of adipic acid, dodecane diol and octanol
having an average molecular weight of 1400 (~xample of
preparation F) dissolved in 10 parts of xylene are homo-
genised under a protective atmosphere, 0.003 parts ofdibutyl tin dilaurate are added and the reaction mixture
is heated to 40C. When 30% of the NCO groupshave reacted,
4;5 parts of the trimethylolpropane-caprolactone polyester
described in Example of preparation I, dissolved in 30
parts of xylene, are added.
After addition of the hydroxyl groups, 1 part of
N,N-dimethyl-1,3-propanediamine dissolved in 15 parts
- of N-methylpyrrolidone is added and the reaction mixture
is heated to 60C and stirred for one hour. The product
is highly viscous and colourless.
Example 6
12.9 Parts of Desmodur L (67% in ethyl glycol ace-
tate/xylene 1:1) are diluted with 20 parts of ethyl glycol
acetate/xylene (1:1) under a protective atmosphere. 9 Parts
of a commercial methoxy polyethylene giycol having an
average molecular weight of 750, dissolved in 10 parts
of xylene, and 0.003 parts of dibutyl tin dilaurate are
added. When 33% of the NCO groups have reacted at 50C,
6 parts of the caprolactone polyester with an average
molecular weight of 1000 described in ~xample of prepar-
ation II, dissolved in 20 parts of xylene, are added.
The reaction is terminated as soon as 66% of the NCO
groups have reacted. 1.4 Parts of 1-(2-hydroxyethyl)-
imidazole dissolved in 20.7 parts of xylene are added
for addition to the remaining NCO groups and the reaction
mixture is stirred at 70C for 2 ho~1rs.
The colourless, clear product is slightly ~iscous.
Exa~ple 7
14.3 Parts of a polyester of adipic acid, dodecar.e
diol and octanol having an average molecular weight of
1400 (Example of prepar~tion F) are dissolved at
.
24
50C in a mixture of 15 parts of ethyl glycol acetate
and 10 parts of xylene under a protective atmosphere.
The reaction mixture is cooled to 20C and 11.1 parts
of Desmodur L (67% in ethyl glycol acetate/xylene 1:1)
and 0.003 parts of dibutyl tin dilaurate are added with
stirring. The reaction mixture is slowly heated to 50C,
and the progress of the reaction is followed by NCO
determination. After one third of the NCO groups put
into the process have reacted, 2.1 parts of polyethylene
glycol having an average molecular weight of 400 dissolved
in 20 parts of xylene are added and the second third
of the NCO groups are left to react. The reaction mixture
is then diluted with 11.4 parts of xylene, and 1.1 parts of
N,N-dimethyl-1,3-diaminopropane dissolved in 15 parts
of N-methylpyrrolidone are added. The reaction mixture
is stirred at 50C for one hour.
Example 8
8.8 Parts of Desmodur L (67~ in ethyl glycol acetatej
xylene 1:1) in 15 parts of ethyl glycol acetate are homo-
genised under a protective atmosphere and 15.5 partsof a caprolactone polyester which has been started on
nonyl phenol ethyl oxylate (Example of preparation G)
dissolved in 12.2 parts of xylene as well as 0.002 parts
of dibutyl tin di]aurate are added. The reaction mixture is
25 heated to 50C and sti~d until 30g~ of the NC3 gro~lps have reacted.
It is then diluted with 20 parts of xylene, and 2.7 parts
of commercial polytetrahydrofuran diol having an average
molecular weight of 650, dissolved in 10 parts of xylene,
are added.
As soon as 66% of the NCO groups put into the process
have reacted, 0.9 parts o 4-(aminomethyl)-pyridine dis-
solved in 15 parts of xylene are added ancl the reaction
mixture is heated to 70C and stirred at this temperature
for one hour. Ti1e colourless product has a very low viscos-
ity.
.. . . .. ., . . ~ , .... . ... . . ..
a~
Example 9
12.4 Parts of ethyl glycol acetat,e, 11 parts of
Desmodur L (67% in ethyl glycol acetate/xylene 1:1) and
14.2 parts of a polyester of adipic acid, dodecane diol
and octanol having an average molecular weight of 1400
(Example of preparation F) dissolved in 20 pàrts of xylene
are homogenised under a protective atmosphere, and 0.003
parts of dibutyl tin dilaurate are added. The reaction
mixture is heated to 50C and the polyester is chemically
1~ a~ded to the Desmodur L.
After this reaction step, 2.2 parts of a commercial
coconut acid diethanolamide dissolved in 30 parts of
ethyl glycol acetate/xylene (1:1~ are added. The coconut
acid diethanolamide has an average molecular weight of
-- 15 440. As soon as two thirds of the NCO groups put into
the process have reacted, 1.3 parts of 1-(3-aminopropyl)-
imidazole dissolved in 10 parts of NMP are rapidly added
and the reaction mixture is heated to 70C and stirred
- at this temperature for one hour. The medium viscosity
product is clear to slightly cloudy.
ExamDle 10
7.9 Parts of poly-isophorone diisocyanate (70% in
ethyl glycol acetate/xylene 1:1) dissolved in 10 parts
- of ethyl glycol acetate and 15 parts of a valerolactone
polyester having an average molecular wei,ght of 2000
(Example of preparation A) dissolved in 20 parts of xylene
are homogenised under a protective atmosphere with exclu-
sion of moisture. 0.003 Parts of di~utyl tin dilaurate
are added and the reaction mixturc is heatecl to 50C.
When the OH groups have completed their reaction, 3.7'
parts of a polypropylene glycol having an average molecular
weight of 1000 dissolved in 20 parts of xylene are added.
When 66~ of t'ne NCO groups put into the process have
reacted, 7.6 parts of xylene and 0.8 parts of 3-mercapto-
1~2,~-triazole di,ssolved in 15 parts of N-methylpyrrolidone
are added,ancl the reaction mixture is stirred for one hour
26
at 60C.
The solution of product has a low viscosity and a
slightly brown colouration.
Example 11
14.1 Parts of Desmodur HL (60% in butyl acetate)
are dissolved in 20 parts of ethyl glycol acetate with
exclusion of moisture, 11.6 parts of an 1100 caprolactone
polyester (Example of preparation B) dissolved in 20
parts of xylene and 0.003 parts of dibutyl tin diiaurate
are added and the reaction mixture is slowly heated to
60C.
~ he first stage is completed as soon as 30% of the
NCO groups put into the process have reacted.
For the coupling reaction, 3.4 parts of commercial
polytetrahydrofurane diol having an average molecular
weight of 650 dissolved in 14.4 parts of xylene are added.
In the last stage, which follows the reaction of
60~ of the NCO groups put into the process, 1.5 parts
o~ 3-mercapto-1,2,4-triazole dissolved in 15 parts of
~-methylpyrrolidone are added and the reacti.on mixture
is heated to 70~C and stirred at this temperature for
one hour.
Example 12
The reaction takes place at 50C under a protective
atmosphere. 14.4 Parts of Desmodur HI. (60~ in butyl acetate)
are dissolved in 15 parts of ethyl glycol acetate, and
9.9 parts of a caprolactone polyester which has been
started-on phenyl ethyl alcohol and has an average mol-
ecular weight of 1100 (Example of preparation B) are
added. The polyester is partly dissolved in 13 parts
by weigl1t oE xylene.
When.the polyester addition reaction has been comple-ted,
which can be seen by the reduction in ~CO groups, 4.5 parts
of polyethylene glycol having an average molecular weight
of 1000 are added. To complete the reaction of the remainincJ
NCO group~s, 2.3 parts of 1-(2-aminoethyl)-pi.perazine
.
....... .. .. . .. .. , -
~3
- 27
are added and the reaction mixture is diluted with xylene
to a solids content of 30%. The product is a slightly
cloudy, viscous solution.
Example 13
10.1 Parts of Desmodur HL (60% in butyl acetate)
are diluted with 30 parts of a mixture of xylene/ethyl
glycol acetate (1:1) under protective gas and 12.7 parts
of a polyester having an average molecular weight of
2000 (Example of preparation A) are added. After the
addition of 0.003 parts of dibutyl tin dilaurate, the
addition reaction is carried out at room temperature.
When 25% of the NCO groups have reacted, 4.7 parts
of a polyethylene glycol having an average molecular
weight of 1500 are added in the second stage.
When half the NCO groups have reacted, the reac.ion
mixture is diluted with xylene to an end product solids
content of 25~, 1.5 parts of 4-(2-aminoethyl)-pyridine
are added, and the mixture is heated to 60C and stirred
at this temperature for one hour. The product has a
slightly yellow colour and is viscous.
Example 14
The reaction is carried out at 50C under a protective
gas atmosphere. 6.3 Parts of Desmodur HL (60~ in butyl
acetate) are diluted with a mixture of 15 parts of ethyl
qlycol acetate and 36 parts of xylene. 0.7 Parts of a
polyethylene glycol having an average molecular weight
of 400 and 19.6 parts of a caprolactone polyester having
an average molecular weight of 5000 (Example of preparation
D) are added in the molten state. 0.002 Parts of dibutyl
tin dilaurate are addecl to accelerate the reaction.
When all the OH groups have reacted, 0.9 parts of
4-(2-hydroxyethyl)-pyridine are added and the solids
content of.the reaction mixture is adjusted to 25~ with
xylene. ~he reaction mixture is stirred for one hour
at 60C to complete the reaction. A colourless, low viscosi-
ty product is obtained.
28
Example 15
10.7 Parts of Desmodur HL (60% in butyl acetate)
are homogeniSed under a protective atmosphere with a
solution in 15.7 parts of xylene of 16.2 parts of a
valerolactone polyester with an average molecular weight
of 2000 which was started with heptadecafluorodecanol/2-
ethylhexanol (Example of preparation A). 0.001 Parts
of dibutyl tin dilaurate are added and the addition reac-
tion of the polyester is carried out at 50C.
After termination of this reaction, the reaction
mixture is diluted with 20 parts of ethyl glycol acetate
and 0.3 parts of 1,4-butanediamine dissolved in 20 parts
of xylene are added.
As soon as 55% of the NCO groups put into the process
have reacted, the slightly exothermic reaction is stopped
by the addition of 2.1 parts of 2-amino-6-methoxybenzo-
thiazole dissolved in 15 parts of NMP. The reaction mixture
is heated to 70C and stirred for one hour.
The product is a slightly viscous, yellowish, clear
solution.
Example 16
16.1 Parts of Desmodur IL (51% in butyl acetate)
and 11 parts of a caprolactone polyester 1800 (Example
of preparation C) dissolved in 20 parts of xylene are
25 added to 20 parts of ethyl glycol acetate/xylene (1:1) -
under a protective atmosphere and the addition is carried
out at room temperature after the addition of 0.002 parts
of dibutyl tin dilaurate as catalyst.
When 20% of the NCO groups have been used up, 3.8
parts of the polycaprolactone polyester described in
Example of preparation II dissolved in 17.1 parts of
xylene are added.
After the NCO groups put into the process have been
reduced to 55~, 10 parts of xylene and 2.0 parts of
4-(2-aminoethyl)-pyridine dissolved in 10 parts of
diisobutyl ketone are added. The reaction mixture is
.... . ... . . .
~3~
29
heated to 50C and stirred for one hour. The colourless
to slightly yellowish product has a low viscosity.
Example 17
9 Parts of Desmodur IL (51% in butyl acetate) are
homogenised with a solution of 17 parts of a polyester
with an average molecular weight of S000 (Example of
preparation D) in 25 parts of xylene under a protective
atmosphere and with exclusion of moisture, and 0.003
parts of dibutyl tin dilaurate are added. The reaction
is carried out at 60C. After the polyester addition
reaction, 2 5 parts of polypropylene glycol having an
average molecular weight of 1000 dissolved in 30 parts
of xylene are added. Q.002 Parts of dibutyl tin dilaurate
are added to accelerate the reaction. When the hydroxyl
groups have reacted, the reaction mixture is diluted
with 5.6 parts of xylene, and 0.9 parts of 3-mercapto-1,2,4-
triazole dissolved in 10 parts of N-methylpyrrolidone
are added to the remaining NCO groups. The product has
a medium viscosity and is yellowish in colour.
Example 18
15.5 Parts of Desmodur IL (5l% in butyl acetate)
are homogenised under a protective atmosphere with 13.3
parts of a polyester having an average molecular weight
of 1800 (~xample of preparation C) dissolved in 15 parts
of xylene, 0.003 parts of dibutyl tin dilaurate are added
and the reaction mixture is heated to 50C. After the
addition reaction of the polyester, which is recognised
by reduction of the NCO groups by 25~, the reaction mixture
is dilutcd with 20 parts of xylene, and 0.7 parts of
1,12-diaminododecane are added.
After the exothermic reaction, 14 parts of xylene
and 1.5 parts of N,N-dimethyl-1,3-propanediamine dissolved
in 20 parts of N-methylpyrrolidone are added. Stirring
is continued for a further hour at 70C. The product
has a mediurn viscosity and is slightly cloudy.
~ Example 19
15.5 Parts of Desmodur IL (51% in butyl acetate)
are homogenised under a protective atmosphere with 30
parts of xylene/butyl acetate (4:1) and 26.6 parts of
a polyester having an average molecular weight of 1800
(Example of preparation C). When 0.003 parts of dibutyl
tin dilaurate are added and the reaction mixture is heated
to 50C, half the NCO groups undergo reaction.
0.3 Parts of 1,4-butanediol dissolved in 30 parts
of xylene are added. When,as a result,75~ of the NCO
groups have undergone reaction, 0.6 parts of 3-amino-1,2,4-
triazole dissolved in 10 parts of N-methylpyrrolidone
are added, and the solids content is adjusted to 30~
with xylene. The medium viscosity, yellowish product
.. . ..
is stirred for one hour at 60C.
Example of practical application
______ _____ ____ _ ___ _ ___
Milled material
- 25 Parts by weight of a 50~ hydroxy-acrylate resin
are mixed with 3 parts by weight of xylene and 1 part
by weight of butyl acetate in a tempered (50C) refined
steel stirrer vessel. X parts by weight of the addition
compound according to the invention or of the comparison
compound (Example 8 of US-A-4 032 698) are then added,
the mixture is homogenised, and Y parts by weight of
a pigment (Table 1) are added. The parts by weight of
the addition compound according to the invention and
of the comparison compound are calculated as 100~ solid
bodies.
The mixture is homogenised, 200% by weight of steel
beads, based 0l1 the grindin~ mixture, are added and the
substance is dispersed for 40 minutes at 50C by stirring
at the rate of about 12 m-s 1 with a polypropylene disc
adapted to the size of the vessel.
Stock lacqll~r
The làcqueL medium, which has been prepared from -
..... . .. ~
~ ~35
31
52 parts by weight of hydroxy-acrylate resin (50~), 6
parts by weight of xylene, 2 parts by weight of butyl
acetate and 0.1 part by weight of a levelling additive,
is added to the milled material. The mixture is stirred
for 2 minutes at a rate of about 2 m s 1 to homogenise
it. The steel ba~ls are filtered off. This stock lacquer
is left to stand for 12 to 15 hours before further treat-
ment. Part of the stock lacquer prepared as described
above is then processed as described below while another
part of the stock lacquer is processed by the same manner
- after 14 days' storage at 50C. The results obtained
with the immediately processed lacquer are summarized
in Table 2 while the results obtained with the lacquer
which is processed after 14 days' storage are summarized
---- 15 in Table 3.
For cross-linkln~, 30 parts by weight of a cro~s-linker cont~n-
ing 75~ of triisocyanate (Desmodur N) are added to 100
parts by weight of stock lacquer and stirred in.
The viscosity of the finished lacquer is then adjusted
20 to 16" DIN 4/23 by dilution with a mixture of xylene/alkyl
benzene (~Cg)/butyl acetate ~2:1:1). After one hour,
the adjusted lacquer is poured out on a cleaned glass
plate inclined at an angle of 80.
After complete cross-linking, the lacquer film (coloured
lacquer) is assessed for gloss and transparency and exam-
ined under a light microscope for the particle size and
for the presence of flocculation.
The assessment is carried out according to a numerical
scale of 0 to 10, where 0 = no flocculation~ high gloss
and good transparency, and 10 = complete flocculation,
no g]oss and no transparency.
The results obtained are entered in the line "Coloured
lacquer"-in Tables 2 and 3.
~ nother method of determining the pigment size distri-
bution and pigment stabilization in the lacquer consistsof mixing the lacquer with a white ]acquer and then carry-
ing out the rub-out test (white mixing). For this test,
~ ~3~5
32
the lacquer which has been poured out on a surface is
left exposed to air (about 10 minutes) and the sample
is then rubbed with a finger until the colour is constant.
For this test, the stock lacquers of coloured pigments
5 I to V entered in Table 1 are mixed with the white lacquer
VI of Table 1 in the proportions 1:4, homogenised and
adjusted to 16" DIN 4/23. The product is poured out on
a-glass plate inclined at an angle of 80 and the rub-out
test is carried out after exposure to air ~about 10
minutes).
After complete cross-linking of the film~ the lntensity
of colour both of the rubbed-out sample and of the sample
which has not been rubbed out is determined. A scale
from 0 to 10 is used for this purpose,
~-~~ -15 where O = same colour intensity, same colour shade, no flo~ding
and floatin~, ln other words no detecta~le difference
be~en the rubbed-out sample and the sample
which haS not been rubbed out, and
10 = completely altered colour intensity and .flooding
and floating of pigment.
The results obtained are shown in Tables 2 and 3
in the line "White mixture".
33
! Table 1
Pigment used Y Parts Addition compound X Parts
, by wt. according to the by wt.
invention or
_ _ comparison exatnple*
a Polycyclic 4.5 Example 14 0.67
thio-indigo
I derivative
b C.I.1 Pigment 4.5 Comparison 0.67
red 88 example
C.I.2 17712
e.g. Novo-
perm Red-
violet MRS
a 1 Polycyclic quin- ¦4.0 IExample 14 0.4
¦ acridone der-
ivative l
II b C.I.1 Pigment 4.0 !Comparison 0.4
violet 19 lexample
C.I.2 46500
e.g.Quindo
violettRV 6902
a Mono-azo-aryl- 15 Example 14 l0.5
amide deriva- I i ¦
II I tive I ' j
b ¦ C.I.1 Pigment l5 Comparison ~0.5
_ orange 3 6 ~example
C.I.2 11780
e.g. Novoperm
Orange HL 70
a Polycyclic l5 'Example 14 j0.5
perylene deri- 1,
IV vative '
b C.I.1 Pigment ,5 Comparison ,0.5
red 178 j example
C.I.2 71155
e.g. Paliogen
Red L 3910 HD
a Anthraquinone ,5 Example 14 j0.75
V derivative '
b C.I.1 Pigment 5 Comparison i0.75
red 177 example
C.I.2 65 300
e.g. Cronnoph-
tal Red A2B
a Inorganic 25 Example 14 0.75
VI white pigment
b Titanium dioxide 25 Comparison !o . 75
_ exa~e
* CGmparison example:
Example 8 of US-A-4 032 698
i5
34
Table 2
Pigments I , II III I IV ' V
la b a b L a b a b a b
Coloured
lacquer ! 0 5 ' O 6 , 0 5 1 1 7'1 9
White
mixture ,1 7 j 0 7 0 6 i O 9 1 10
a = addition compound according to the invention
b = comparison example
Table 3
Pigments ~ IV I V
! b I a b ! a b 1 a b I a b
Coloured
lacquer lo6 j 0 6 ' O 6 1 0 7 0 10
White
mixture ¦ 8 0 7 1 O 5 , 010 1 10
-- ' - _ ! . !
a = addition compound according to the invention
b = comparison example
The lacquers prepared with the addition compounds
according to ~he invention considerably improve the stab-
ilization of the pigments.
,
... . , . . . _ _ ,
