U.S. patent application number 10/495519 was filed with the patent office on 2005-01-06 for pigment compositions with modified atrp copolymer dispersants.
Invention is credited to Auschra, Clemens, Eckstein, Ernst, Muhlebach, Andreas, Zink, Marie-Odile.
Application Number | 20050004317 10/495519 |
Document ID | / |
Family ID | 8184277 |
Filed Date | 2005-01-06 |
United States Patent
Application |
20050004317 |
Kind Code |
A1 |
Auschra, Clemens ; et
al. |
January 6, 2005 |
Pigment compositions with modified atrp copolymer dispersants
Abstract
The present invention relates to a composition containing
modified block copolymer dispersants and dispersible inorganic or
organic pigment. The block copolymers are prepared by atom transfer
radical polymerization (ATRP) and modified with a salt forming
group. The pigment composition is useful for preparing coating
compositions, prints, images, inks or lacquers and other disperse
systems.
Inventors: |
Auschra, Clemens; (Freiburg,
DE) ; Eckstein, Ernst; (Rheinfelden, DE) ;
Zink, Marie-Odile; (Mulhouse, FR) ; Muhlebach,
Andreas; (Frick, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8184277 |
Appl. No.: |
10/495519 |
Filed: |
May 14, 2004 |
PCT Filed: |
November 21, 2002 |
PCT NO: |
PCT/EP02/13064 |
Current U.S.
Class: |
525/244 ;
524/401; 524/505 |
Current CPC
Class: |
C08F 293/005 20130101;
C08K 5/0041 20130101; C08L 53/00 20130101; C08F 2438/01 20130101;
C08K 5/0041 20130101; C09D 153/00 20130101; C09D 11/03 20130101;
C08F 293/00 20130101; C08L 53/00 20130101 |
Class at
Publication: |
525/244 ;
524/401; 524/505 |
International
Class: |
C08L 053/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 29, 2001 |
EP |
01811158.3 |
Claims
1. A composition comprising a) 0.1-99.9% by weight dispersible
inorganic or organic pigment particles; and b) 0.1-99.9% by weight
dispersing agents that essentially consist of a combination of (i)
a copolymer of the formula {X-[(A.sub.x-B.sub.y)}.sub.pY].sub.q
(I), wherein X represents the fragment of a polymerisation
initiator capable of initiating polymerisation of ethylenically
unsaturated monomers by atom transfer radical polymerisation (ATRP)
in the presence of a catalyst capable of activating controlled
radical polymerisation by ATRP; Y represents a polymer chain
terminal group; A and B represent polymer blocks composed of
non-ionic repeating units of ethylenically unsaturated monomers;
and wherein at least one of the polymer blocks A or B or the chain
terminal group Y additionally contains repeating units of
ethylenically unsaturated monomers substituted with basic residues;
one of x and y represents zero, one or a numeral greater than one
and the other one represents a numeral greater than one; and
wherein x and y defines the number of monomer repeating units in
the polymer blocks A and B; one of p and q represents one and the
other one represents one or a numeral greater than one; and wherein
p defines the number of groups of the partial formula
X-(A.sub.x-B.sub.y)-- (A), attached to the polymer chain terminal
group Y; and q defines the number of groups of the partial formula
-(A.sub.x-B.sub.y)--Y (B), per initiator fragment X; and (ii) a
salt forming compound selected from the group consisting of an
organic acid, an alkylhalide group and a sulphonic acid ester or,
in the alternative, (i') a copolymer (I), wherein X, Y, A, B, x, y,
p, and q are as defined above; and wherein at least one of the
polymer blocks A or B or the chain terminal group Y additionally
contains repeating units of ethylenically unsaturated monomers
substituted with acidic residues; and (ii') a salt forming compound
substituted with basic residues; with the proviso that
p-toluenesulphonic acid is excluded as salt-forming component
(ii).
2. A composition according to claim 1, wherein the dispersible
organic pigments or pearlescent flakes of component a) are selected
from the azo pigment group consisting of azo, disazo, naphthol,
benzimidazolone, azocondensation, metal complex, isoindolinone, and
isoindoline pigments, the chinophthalon pigment, dioxazine pigment
and the polycyclic pigment group consisting of indigo, thioindigo,
quinacridones, phthalocyanines, perylenes, perionones,
anthraquinones, anthrapyrimidines, indanthrones, flavanthrones,
pyranthrones, anthantrones, isoviolanthrones,
diketoypyrrolopyrrole, and carbazoles.-.
3. A composition according to claim 1, wherein the dispersible
inorganic pigment particles of component a) are selected from the
group consisting of aluminum, aluminum oxide, silicon oxide and
silicates, iron(III)oxide, chromium(III)oxide, titanium(IV)oxide,
zirconium(IV)oxide, zinc oxide, zinc sulphide, zinc phosphate,
mixed metal oxide phosphates, molybdenum sulphide, cadmium
sulphide, carbon black or graphite, vanadates, chromates, and
molybdates, and mixtures, crystal forms or modifications
thereof.
4. A composition according to claim 1, wherein X represents a
polymer chain terminal group from a polymerisation initiator which
is selected from the group consisting of C.sub.1-C.sub.8alkyl
halides, C.sub.6-C.sub.15aralkyl halides, C.sub.2-C.sub.8haloalkyl
esters, arene sulphonyl halides, .alpha.-haloalkanenitriles,
.alpha.-haloacrylates and halolactones; Y represents a radically
transferable group, hydrogen or a polymerisable chain terminal
group and p and q represent one.
5. A composition according to claim 1, wherein X represents a
polymer chain terminal group from a polymerisation initiator which
is selected from the group consisting of C.sub.1-C.sub.8alkyl
halides, C.sub.6-C.sub.15aralkyl halides, C.sub.2-C.sub.8haloalkyl
esters, arene sulphonyl halides, .alpha.-haloalkane nitriles and
halolactones; Y represents a saturated polymer chain terminal
group; p represents a numeral greater than one; and q represents
one.
6. A composition according to claim 1, wherein one of the polymer
blocks A and B is essentially composed of repeating units of
ethylenically unsaturated monomers selected from the group
consisting of styrenes, acrylic and C.sub.1-C.sub.4alkylacrylic
acid-C.sub.1-C.sub.24alkyl esters, acrylic and
C.sub.1-C.sub.4alkylacrylic acid-C.sub.6-C.sub.11aryl-
-C.sub.1-C.sub.4alkyl esters, acrylic and
C.sub.1-C.sub.4alkylacrylic
acid-C.sub.6-C.sub.11aryloxy-C.sub.1-C.sub.4alkyl esters, acrylic
and C.sub.1-C.sub.4alkylacrylic acid-hydroxy-C.sub.2-C.sub.6alkyl
esters, acrylic and C.sub.1-C.sub.4alkylacrylic
acid-polyhydroxy-C.sub.3-C.sub.6a- lkyl esters, acrylic and
C.sub.1-C.sub.4alkylacrylic
acid-(C.sub.1-C.sub.4alkyl).sub.3silyloxy-C.sub.2-C.sub.4alkyl
esters; acrylic and C.sub.1-C.sub.4alkylacrylic
acid-(C.sub.1-C.sub.4alkyl).sub.3- silyl-C.sub.1-C.sub.4alkyl
esters, acrylic and C.sub.1-C.sub.4alkylacrylic
acid-heterocyclyl-C.sub.2-C.sub.4alkyl esters; acrylic and
C.sub.1-C.sub.4alkylacrylic acid esters having
poly-C.sub.2-C.sub.4alkyle- neglycol ester groups, wherein the
ester groups may be substituted with C.sub.1-C.sub.24alkoxy groups,
acrylic and methacrylic acid amides, acrylic and
C.sub.1-C.sub.4alkylacrylic acid-(C.sub.1-C.sub.4alkyl).sub.1-
-2amide, acrylonitrile, esters of maleic acid or fumaric acid,
maleinimide and N-substituted maleinimides.
7. A composition according to claim 1, wherein one of the polymer
blocks A and B is essentially composed of repeating units of
ethylenically unsaturated monomers selected from the group
consisting of styrenes, acrylic and methacrylic
acid-C.sub.1-C.sub.24alkyl esters, acrylic and methacrylic
acid-hydroxy-C.sub.2-C.sub.6alkyl esters, acrylic and methacrylic
acid-dihydroxy-C.sub.3-C.sub.4alkyl esters and acrylic and
methacrylic acid esters having poly-C.sub.2-C.sub.4alkyleneglycol
ester groups, wherein the ester groups may be substituted with
C.sub.1-C.sub.24alkoxy groups.
8. A composition according to claim 1, wherein the repeating unit
of an ethylenically unsaturated monomer substituted with basic
residues present in at least one of the polymer blocks A and B or
the chain terminal group Y is represented by a compound of the
formula CH.sub.2.dbd.C(--R.sup.1)--- C(.dbd.O)--R.sup.2 (III),
wherein R.sup.1 represents hydrogen or C.sub.1-C.sub.4alkyl; and
R.sup.2 represents a basic substituent selected from the group
consisting of amino-C.sub.2-C.sub.18alkoxy,
C.sub.1-C.sub.4alkylamino-C.sub.2-C.sub.18alkoxy,
di-C.sub.1-C.sub.4alkyl- amino-C.sub.2-C.sub.18alkoxy,
hydroxy-C.sub.2-C.sub.4alkylamino-C.sub.2-C.- sub.18alkoxy and
C.sub.1-C.sub.4alkyl-(hydroxy-C.sub.2-C.sub.4alkyl)amino--
C.sub.2-C.sub.18alkoxy; or wherein the ethylenically unsaturated
monomer substituted with a basic group present in one of the
polymer blocks A and B or the chain terminal group Y is an amino
monomer selected from the group consisting of amino substituted
styrene, (C.sub.1-C.sub.4alkyl).sub- .1 2amino substituted styrene,
N-mono-(C.sub.1-C.sub.4alkyl).sub.1-2amino--
C.sub.2-C.sub.4alkyl(meth)acrylamide and
N,N-di-(C.sub.1-C.sub.4alkyl).sub-
.1-2amino-C.sub.2-C.sub.4alkyl(meth)acrylamide, vinylpyridine or
C.sub.1-C.sub.4alkyl substituted vinylpyridine, vinylimidazole and
C.sub.1-C.sub.4alkyl substituted vinylimidazole.
9. A composition according to claim 8, wherein the repeating unit
of an ethylenically unsaturated monomer substituted with a basic
group present in one of the polymer blocks A and B is represented
by a compound of the formula (III), wherein R.sup.1 represents
hydrogen or methyl; and R.sup.2 represents amino substituted
C.sub.2-C.sub.18alkoxy selected from the group consisting of
amino-C.sub.2-C.sub.4alkoxy, C.sub.1-C.sub.4alkylamin-
o-C.sub.2-C.sub.4alkoxy,
di-C.sub.1-C.sub.4alkylamino-C.sub.2-C.sub.4alkox- y,
hydroxyC.sub.2-C.sub.4alkylamino-C.sub.2-C.sub.18alkoxy and
C.sub.1-C.sub.4alkyl-(hydroxy-C.sub.2-C.sub.4alkyl)amino-C.sub.2-C.sub.4a-
lkoxy; or is amino substituted styrene,
(C.sub.1-C.sub.4alkyl).sub.1-2amin- o substituted styrene, and
N,N-di-(C.sub.1-C.sub.4alkyl).sub.2amino-C.sub.-
2-C.sub.4alkyl(meth)acrylamide.
10. A composition according to claim 1, wherein the repeating unit
of an ethylenically unsaturated monomer substituted with basic
residues present in at least one of the polymer blocks A and B or
the chain terminal group Y is selected from the group consisting of
4-aminostyrene, 4-dimethylaminostyrene,
2-dimethylaminoethylacrylate (DMAEA), 2-dimethylaminoethyl
methacrylate (DMAEMA), 2-diethylaminoethyl acrylate (DEAEA),
2-diethylaminoethyl methacrylate (DEAEMA), 2-t-butylamino
ethylacrylate (t-BAEA), 2-t-butylaminoethyl methacrylate (t-BAEMA),
3-dimethylaminopropylmethacrylamide
3-dimethylaminopropylmethacrylamide, 4-vinylpyridine,
2-vinylpyridine and 1-vinylimidazole.
11. A composition according to claim 1, wherein the polymer chain
terminal group Y represents a radically transferable group,
hydrogen, a polymerisable chain terminal group or a saturated
polymer chain terminal group, which is formed by polymerisation or
copolymerisation of a polymerisable chain terminal group.
12. A composition according to claim 1, wherein the component (ii)
forms a salt with the copolymer (I) by acid-base reaction, acid
addition or quaternisation reaction.
13. A composition according to claim 12, wherein a sulpho, carboxy
or phosphono group, a sulphonic acid-C.sub.1-C.sub.4alkyl ester
group or an C.sub.1-C.sub.8alkyl halide group, which is present in
the salt forming compound (ii), forms a salt by reaction with a
free amino group or a primary, secondary or tertiary amino group
which is present in at least one of the polymer blocks A and B or
the chain terminal group Y of the copolymer component (i).
14. A composition according to claim 12, wherein the salt forming
compound (ii) is selected from the group consisting of monocyclic
or polycyclic sulphonic, mono- or polycyclic carboxylic or
phosphonic acids, aliphatic sulphonic, carboxylic or phosphonic
acids substituted with mono- or polycyclic groups,
C.sub.1-C.sub.8alkyl halides substituted with mono- or polycyclic
groups and C.sub.1-C.sub.4alkyl esters of mono- or polycyclic
sulphonic acids, with the proviso that p-toluenesulphonic acid is
excluded.
15. A composition according to claim 12, wherein the salt forming
compound (ii) is selected from the group consisting of polycyclic
sulphonic, mono- or polycyclic carboxylic or phosphonic acids,
aliphatic sulphonic, carboxylic or phosphonic acids substituted
with mono- or polycyclic groups, C.sub.1-C.sub.8alkyl halides
substituted with mono- or polycyclic groups and
C.sub.1-C.sub.4alkyl esters of mono- or polycyclic sulphonic
acids.
16. A composition according to claim 1, which additionally contains
binding agents and conventional additives selected from the group
consisting of surfactants, light stabilisers, UV-absorbers,
anti-foaming agents, antioxidants, dyes, plasticisers, thixotropic
agents, drying catalysts, anti-skinning agents and levelling
agents.
17. A pigment dispersion comprising a') dispersed pigment
particles; and b') a combination of a copolymer (I) wherein X, A,
B, Y, x, y, p and q are as defined in claim 1; and a salt forming
compound (ii) or (ii') as defined in claim 1; and a carrier
liquid.
18. A process for preparing the pigment dispersion according to
claim 17, which comprises preparing the copolymer (I) by
copolymerising the fragments A and B by ATRP and optionally
replacing or polymerising the chain terminal group Y; and .alpha.)
modifying the copolymer with the salt forming compound, isolating
and adding the modified block copolymer to dispersible pigment
particles and optionally binder materials, fillers or other
conventional additives; or .beta.) modifying the copolymer with the
salt forming compound in the presence of dispersible pigment
particles and optionally binder materials, fillers or other
conventional additives.
19. A process according claim 18 comprising the additional step of
isolating the pigment and the modified copolymer and optionally
other conventional additives in a solid product form essentially
free from liquid carrier medium.
20. A method of preparing coating compositions, prints, images,
inks, lacquers, pigmented plastics, adhesives, casting resins,
filled composites, glass fibre reinforced composites, laminates,
cement based construction materials like plaster and tile adhesives
which comprises adding the pigment dispersion according to claim 17
thereto.
Description
[0001] The present invention relates to a composition containing
dispersible inorganic or organic pigment particles and modified
ATRP block copolymer or comb type dispersants, a process for
preparing the composition, a pigment dispersion containing
dispersible inorganic or organic pigment particles and modified
ATRP block- or comb-type copolymer dispersants, a process for
preparing the pigment dispersion and to the use of the pigment
dispersion for preparing coatings, images, lacquers and others.
[0002] Dispersions containing pigments and polymer additives are
used in an almost unlimited number of different technical
applications, e.g. as coating materials, for printing inks,
colouring plastic materials, including fibres, glasses, or ceramic
products, for formulations in cosmetics, or for the preparation of
paint systems, in particular automotive, industrial and decorative
paints.
[0003] The function of polymers in pigment dispersions is manifold.
They may act as solubilisers in the given carrier liquid, e.g.
water or organic solvents. Suitable polymers are also needed as
stabilisers to prevent precipitation or flocculation. Polymers may
also improve the gloss of the pigment dispersion or enhance its
rheology. Depending on the type and polarity of the dispersing
agent, e.g. water, organic solvents or mixtures thereof, polymers
of variable structure are chosen. In view of ecological
requirements, the use of aqueous pigment dispersions is
particularly preferred, as well as dispersions based on organic
solvents with high solids content. In aqueous systems, mixtures of
hydrophobic and hydrophilic polymers or block copolymers, so-called
A-B block copolymers, containing hydrophilic and hydrophobic
polymer blocks can be used. The hydrophobic "A" blocks (homo- or
copolymers of methacrylate monomers) associate with either pigment
or emulsion polymer surfaces or both. With hydrophilic "B" blocks
(neutralised acid or amine containing polymers), these copolymers
are useful for preparing water based pigment dispersions, cf. H. J.
Spinelli, Progress in Organic Coatings 27 (1996), 255-260.
[0004] Many different well-established methods are available for
preparing the polymers used in pigment dispersions. Most methods
have the disadvantage that uncontrollable recombination reactions
of initiator radicals may occur immediately after their formation
with the effect that variable ratios between initiator radicals and
stable free radicals are produced. Consequently, in some cases
there is an inefficient control of the polymerisation process.
[0005] Group transfer polymerisation (GTP) is a well-established
method for producing A-B block copolymers of defined structure from
methacrylate monomers. Despite its wide applicability and
usefulness the GTP method still has several drawbacks. The
polymerisation initiators used in this method, such as the silyl
ketene acetals disclosed in U.S. Pat. No. 4,656,226, e.g.
1-trimethylsilyloxy-1-isobutoxy-2-methylpropene, are highly
reactive and difficult to prepare in a multi-step synthesis. This
necessitates the use of carefully dried and purified reactants,
which limits this method in industrial applications operating on a
large scale.
[0006] In view of the almost unlimited range of different technical
applications, there remains a growing need for pigment dispersions
of improved pigment affinity and rheology, as expressed by the
viscosity of the mill base at a given shear rate and improved gloss
of surface coatings.
[0007] WO 96/30421 discloses a controlled or "living"
polymerisation process of ethylenically unsaturated polymers, such
as styrene or (meth) acrylates, by employing the Atom Transfer
Radical Polymerisation (ATRP) method. This method produces defined
oligomeric homo-polymers and copolymers, including block
copolymers. Initiators are employed which generate radical atoms,
such as .Cl, in the presence of a redox system of transition metals
of different oxidation states, e.g. Cu(I) and Cu(II), providing
"living" or controlled radical polymerisation.
[0008] WO 00/40630 discloses pigment dispersions containing block
copolymers as dispersants prepared by the ATRP method. The block
copolymers consist of defined hydrophobic and hydrophilic polymer
blocks. The difference in polarity is obtained by copolymerising
polymer blocks A and B wherein different amounts of monomer units
with hydrophilic functional groups are present, such as amino or
alkylated amino groups. This changes the hydrophilic/hydrophobic
character of the block copolymer dispersant. In one embodiment, the
individual hydrophobic "A" blocks based on uncharged homo- or
copolymers of methacrylate or acrylate monomers form steric
stabiliser blocks In solvent based coating formulations. The
presence of more hydrophilic "B" blocks (e.g. amino functional
acrylates or methacrylates) is the basis for pigment affinity to
certain organic or inorganic pigments. Various additives, such
p-toluenesulphonic acid are also disclosed.
[0009] WO 01/51534 discloses comb polymer dispersants prepared via
macromonomers made by ATRP. Certain additives like
p-toluenesulphonic acid are disclosed.
[0010] It has surprisingly been found that the addition of specific
salt forming compounds, such as specific monocyclic sulphonic acids
or polycyclic sulphonic acids or mono- or polycyclic carboxylic and
phosphonic acids, or alkyl halogenide containing monocyclic or
polycyclic groups or esters of monocyclic or polycyclic sulphonic
acids in the event that monomer units containing amino groups are
present in one block of the co polymer, produces pigment
dispersions having improved properties for the above-mentioned
technical applications.
[0011] The present invention relates to a composition
comprising
[0012] a) 0.1-99.9% by weight dispersible inorganic or organic
pigment particles; and
[0013] b) 0.1-99.9% by weight dispersing agents that essentially
consist of a combination of
[0014] (i) a copolymer of the formula
{X-[(A.sub.x-B.sub.y)}.sub.p--Y].sub.q (I),
[0015] wherein
[0016] X represents the fragment of a polymerisation initiator
capable of initiating polymerisation of ethylenically unsaturated
monomers by atom transfer radical polymerisation (ATRP) in the
presence of a catalyst capable of activating controlled radical
polymerisation by ATRP;
[0017] Y represents a polymer chain terminal group;
[0018] A and B represent polymer blocks composed of non-ionic
repeating units of ethylenically unsaturated monomers; and
wherein
[0019] at least one of the polymer blocks A or B or the chain
terminal group Y additionally contains repeating units of
ethylenically unsaturated monomers substituted with basic
residues;
[0020] one of x and y represents zero, one or a numeral greater
than one and the other one represents a numeral greater than one;
and wherein
[0021] x and y defines a the number of monomer repeating units in
the polymer blocks A and B;
[0022] one of p and q represents one and the other one represents
one or a numeral greater than one; and wherein
[0023] p defines the number of groups of the partial formula
X-(A.sub.x-B.sub.y)-- (A),
[0024] attached to the polymer chain terminal group Y; and
[0025] q defines the number of groups of the partial formula
--(A.sub.x-B.sub.y)--Y (B),
[0026] per initiator fragment X; and
[0027] (ii) a salt forming compound selected from the group
consisting of an organic acid, an alkyl halide group and a
sulphonic acid ester, or, in the alternative,
[0028] (i') a copolymer (I), wherein
[0029] X, Y, A, B, x, y, p, and q are as defined above; and
wherein
[0030] at least one of the polymer blocks A or B or the chain
terminal group Y additionally contains repeating units of
ethylenically unsaturated monomers substituted with acidic
residues; and
[0031] (ii') a salt forming compound substituted with basic
residues;
[0032] provided that p-toluenesulphonic acid is excluded as
salt-forming compound (ii).
[0033] The present invention also relates to a pigment dispersion
comprising
[0034] a') dispersed pigment particles; and
[0035] b') a combination of a copolymer (I) wherein X, A, B, Y, x,
y, p and q are as defined above; and a salt forming compound (ii)
or (ii') as defined above;
[0036] and a carrier liquid comprising water, organic solvents and
mixtures thereof.
[0037] The pigment dispersions are useful for a large variety of
technical applications, e.g. for the preparation of inks or
printing inks in printing processes, such as flexographics, screen,
packaging, security ink, intaglio or offset printing, for pre-press
stages and textile printing, for office, home or graphic
applications, for paper goods, pens, felt tips, fibres tips, card,
wood, (wood) stains, metal, inking pads, or inks for impact
printing, (with impact-pressure ink ribbons), or for the
preparation of colorants, for coatings, e.g. paints, for textile
decoration and industrial marking, for roller coatings or powder
coatings or for automotive finishes for high-solids, for
low-solvent, water containing or metallic coating materials or for
water-containing formulations, water-containing paints, or for the
preparation of pigmented plastics, fibres, platters or mold
carriers, or for pigmented radiation curable coatings, or for
pigmented gel coats, laminates, composites, adhesives and casting
resins, or for non-impact printing material, for digital printing,
thermal wax transfer printing, inkjet printing or thermal transfer
printing, or for the preparation of colour filters, especially for
visible light in the range from 400 to 700 nm, which can be used
for the production of liquid crystal displays (LCD) or charge
combined devices (CCD), for the preparation of cosmetics, toners,
or polymeric ink particles for the preparation of toners, such as
dry or liquid copy toners or electro photographic toners. The
toners can be prepared in master batches and be used in turn in
master batches for the preparation of coloured plastics.
[0038] The terms and definitions used in the specification of the
present invention preferably have the following meanings:
[0039] Component a)
[0040] Suitable dispersible organic pigments are pigments or
pearlescent flakes selected from the group consisting of azo,
disazo, naphthol, benzimidazolone, azocondensation, metal complex,
isoindolinone, and isoindoline pigments, the chinophthalon pigment,
dioxazine pigment and the polycyclic pigment group consisting of
indigo, thioindigo, quinacridones, phthalocyanines, perylenes,
perionones, anthraquinones, such as aminoanthraquinones or
hydroxyanthraquinones, anthrapyrimidines, indanthrones,
flavanthrones, pyranthrones, anthantrones, isoviolanthrones,
diketopyrrolopyrrole, and carbazoles, e.g. carbazole violet, and
the like. Further examples of organic pigments can be found in the
monograph: W. Herbst, K. Hunger "Industrielle Organische Pigmente"
2d Edition, 1995, VCH Verlagsgesellschaft, ISBN: 3-527-28744-2.
[0041] Suitable dispersible inorganic pigments are selected from
the group consisting of metallic flakes, such aluminium, aluminium
oxide, calcium carbonate, silicon oxide and silicates,
iron(III)oxide, chromium(III)oxide, titanium(IV)oxide,
zirconium(IV)oxide, zinc oxide, zinc sulphide, zinc phosphate,
mixed metal oxide phosphates, molybdenum sulphide, cadmium
sulphide, carbon black or graphite, vanadates, such as bismuth
vanadate, chromates, such as lead(IV)chromate, and molybdates, such
as lead(IV)molybdate, and mixtures, crystal forms or modifications
thereof, such as rutil, anatas, mica, talcum or kaolin.
[0042] The composition may contain in addition to component
a)--pigments--and component b)--dispersing agents--conventional
binder materials for preparing coating compositions, e.g. paints,
fillers, and other conventional additives, in particular
conventional additives selected from the group consisting of
surfactants, light stabilisers, UV-absorbers, anti-foaming agents,
dyes, plasticisers, thixotropic agents, drying catalysts,
anti-skinning agents and levelling agents. The composition may also
contain conventional additives, such as antioxidants, flow control
agents, rheology control agents such as fumed silica, micro gels,
screeners, quenchers or absorbers. These additives can be added
individually or in mixtures, with or without so-called sterically
hindered amines (HALS).
[0043] The composition may contain the above-mentioned pigment
component a) in an amount of 0.1 to 99.9% by weight, preferably 0.1
to 50.0% by weight, and particularly preferably 1.0 to 30.0% by
weight.
[0044] Component b)
[0045] The term dispersing agent is defined within the limits of a
so-called solid/liquid dispersion, as opposed to other types of
dispersions, such as liquid/liquid (e.g. emulsions) or solid/gas
(e.g. fumes) dispersions. Solid/liquid dispersions that apply here
consist of a two-phase system containing insoluble solid particles
or solid particles of low solubility within a liquid. The
dispersing agent enables solid particles, in the instant case
pigment particles, to be distributed homogeneously within a liquid
phase, e.g. water or organic solvent, or mixtures of both, or a
polymer melt. Homogeneous distribution means that the concentration
of the solid particles within the liquid phase in any volume
fraction of the liquid phase is identical or approximately
identical (even distribution of the solid particles).
[0046] The term copolymer comprises block or comb copolymers
obtainable by methods wherein at least one polymerisation step
consists of ATRP.
[0047] The term block copolymer comprises random block,
multi-block, star-block or gradient co-polymers. The polymer blocks
A and B consist of at least two repeating units of polymerisable
ethylenically unsaturated monomers.
[0048] The term comb copolymer comprises comb type and graft
copolymers prepared from macromonomers obtainable by methods
wherein at least one polymerisation step consists of ATRP. The term
macromonomer comprises homopolymers, random copolymers, AB-type
block copolymers, gradient or tapered copolymers. Comb polymers are
obtainable by co-polymerisation of macromonomers with other
monomers by any of the known polymerisation methods like
conventional or controlled or "living" radical polymerisation, e.g.
ATRP.
[0049] The term polymerisable ethylenically unsaturated monomers
applies to monomeric compounds characterised by the presence of the
group >C.dbd.C< which are polymerisable in the known methods,
such as conventional or controlled or "living" polymerisation.
Controlled or "living" polymerisation is defined as a process
wherein the polymerisation is initiated from an initiating fragment
which adds monomers by radical poly-addition reactions under
conditions which suppress undesirable side reactions, such as
radical transfer to solvent, bimolecular termination or so-called
disproportionation. The suppression of these side reactions is
effected to such a degree that enables the formation of a block
copolymer by subsequent addition of different monomers or the
functionalisation of a terminal group to form a macromonomer. The
method of living polymerisation is described in U.S. Pat. No.
4,581,429.
[0050] At least three different types of copolymers (I) are present
in the compositions defined above, wherein
[0051] 1 ) One group A.sub.x-B.sub.y is attached to one polymer
chain terminal group Y. In this case there is one radically
transferable group, such as chlorine or bromine, per initiator
fragment X. Each of p and q is one. Block copolymers wherein each
of p and q is one and wherein the transferable group has been
replaced with a polymerisable chain terminal group, are known as
macromonomers;
[0052] 2) More than one of the groups A.sub.x-B.sub.y is attached
to one polymer chain terminal group Y. In that embodiment p is a
numeral greater than one, whereas q is one. Copolymers of this type
are known as comb polymers or graft copolymers. They are obtained
by further polymerising or copolymerising the polymerisable chain
terminal group Y in the macromonomers by any known method of
polymerisation;
[0053] 3) More than one of the groups A.sub.x-B.sub.y is attached
to one initiator fragment X. The index p is one and the index q is
a numeral greater than one. In this case up to six, preferably up
to four, transferable groups are attached to the initiator fragment
X. This type of copolymer comprises so-called star type or branched
copolymers. In the event that p represents 1 and q represents 2
tri-block copolymers of the type
Y(A.sub.x-B.sub.y)X(A.sub.x-B.sub.y)Y are comprised. In the case
that the chain terminal group Y is an unsaturated group, telechelic
or multifunctional star type macromonomers are comprised, wherein
the individual polymer "branches" are linked together at one
initiator fragment X. Branched comb polymers (I) are obtainable
from these macromonomers.
[0054] In copolymers (I) the group X represents the polymerisation
initiator fragment of a polymerisation initiator of the formula
X--Y'.sub.q (II),
[0055] wherein
[0056] X represents the fragment of a polymerisation initiator
capable of initiating polymerisation of ethylenically unsaturated
monomers by atom transfer radical polymerisation (ATRP) in the
presence of a catalyst capable of activating controlled radical
polymerisation by ATRP;
[0057] Y' represents a radically transferable atom or group;
and
[0058] q represents one or a numeral greater than one.
[0059] A suitable polymerisation initiator is capable of initiating
atom transfer radical polymerisation of the fragments A and B. The
polymerisation subsequently proceeds by a reaction mechanism known
under the term ATRP or related methods. A suitable polymerisation
initiator, which contains a radically transferable atom or group
.Y', is described in WO 96/30421 and WO 98101480. A preferred
radically transferable atom or group .Y' is .Cl or .Br, which is
cleaved as a radical from the initiator molecule and may
subsequently be replaced after polymerisation as a leaving group
with a polymerisable chain terminal group. The index q is one if
one group Y, e.g. chlorine or bromine, is present in the initiator
molecule (II). A representative initiator molecule (II) wherein q
is one, is a compound of the formula 1
[0060] wherein Hal represents chlorine or bromine.
[0061] A representative initiator molecule, wherein q is the
numeral three, is a "star-shaped" or "bird type" compound of the
formula 2
[0062] and a representative initiator molecule wherein q is the
numeral up to four, is a "star-shaped" compound of the formula
3
[0063] In the formulae above Hal represents chlorine or bromine.
These initiator molecules are prepared by the reaction of a
reactive functional derivative of .alpha.-halogen carboxylic acid
of the formula 4
[0064] e.g. the acid chloride or bromide of this compound, with an
alcohol of the formula
HO--R.sub.2,
[0065] wherein R.sub.2 together with the HO-group represents a
branched trihydroxy alcohol, e.g. 1,1,1-(tris-hydroxymethyl)propane
or represents a branched tetrahydroxy alcohol, e.g.
pentaerythritol.
[0066] The use of initiators (II) wherein q represents one and one
transferable group Y' is present per initiator fragment X and
subsequent replacement of Y' with a polymerisable chain terminal
group Y, generates linear macromonomers (I). Polymerisation
initiators wherein q is greater than one, generate branched
macromonomers (I), wherein the individual polymer "branches" are
linked together at the initiator fragment X. Branched comb polymers
(I) are obtainable from these macromonomers, particularly branched
comb polymers from the "star-shaped" initiators of the formulae
above.
[0067] A preferred polymerisation initiator (II), which generates
linear polymers, block copolymers or macromonomers, is selected
from the group consisting of C.sub.1-C.sub.8alkyl halides,
C.sub.6-C.sub.15aralkyl-halid- es, C.sub.2-C.sub.8haloalkyl esters,
arene sulphonyl chlorides, .alpha.-haloalkane nitriles,
.alpha.-haloacrylates and halolactones.
[0068] Specific initiators (II) are selected from the group
consisting of .alpha.,.alpha.'-dichloro- or
.alpha.,.alpha.'-dibromoxylene, p-toluenesulphonylchloride (PTS),
hexakis-(.alpha.-chloro- or .alpha.-bromomethyl)-benzene,
1-phenethyl chloride or bromide, methyl or ethyl 2-chloro- or
2-bromopropionate, methyl or ethyl-2-bromo- or
2-chlorooisobutyrate, and the corresponding 2-chloro- or
2-bromopropionic acid, 2-chloro- or 2-bromoisobutyric acid, chloro-
or bromoacetonitrile, 2-chloro- or 2-bromopropionitrile,
.alpha.-bromobenzacetonitrile, .alpha.-bromo-.gamma.-butyrolactone
(=2-bromo-dihydro-2(3H)-furanone) and the initiators derived from
1,1,1-(tris-hydroxymethyl)propane and pentaerythritol of the
formulae of above.
[0069] In the copolymer (I) one of the polymer blocks A and B is
composed of non-ionic repeating units of ethylenically unsaturated
monomers suitable for the method of controlled or living
polymerisation. Representative monomers are selected from the group
consisting of styrenes, acrylic and C.sub.1-C.sub.4alkylacrylic
acid-C.sub.1-C.sub.24al- kyl esters, acrylic and
C.sub.1-C.sub.4alkylacrylic
acid-C.sub.6-C.sub.11aryl-C.sub.1-C.sub.4alkyl esters, acrylic and
C.sub.1-C.sub.4alkylacrylic
acid-C.sub.6-C.sub.11aryloxy-C.sub.1-C.sub.4a- lkyl esters, acrylic
and C.sub.1-C.sub.4alkylacrylic acid-hydroxy-C.sub.2-C.sub.6alkyl
esters, acrylic and C.sub.1-C.sub.4alkyl-acrylic
acid-polyhydroxy-C.sub.3-C.sub.6alkyl esters, acrylic and
C.sub.1-C.sub.4alkylacrylic acid-(C.sub.1-C.sub.4alky-
l).sub.3silyloxy-C.sub.2-C.sub.4alkyl esters; acrylic and
C.sub.1-C.sub.4alkylacrylic
acid-(C.sub.1-C.sub.4alkyl).sub.3silyl-C.sub.- 1-C.sub.4alkyl
esters, acrylic and C.sub.1-C.sub.4alkylacrylic
acid-heterocyclyl-C.sub.2-C.sub.4alkyl esters; acrylic and
C.sub.1-C.sub.4alkylacrylic acid esters having
poly-C.sub.2-C.sub.4alkyle- neglycol ester groups, wherein the
ester groups may be substituted with C.sub.1-C.sub.24alkoxy groups,
acrylic and methacrylic acid amides, acrylic and
C.sub.1-C.sub.4alkylacrylic acid-(C.sub.1-C.sub.4alkyl).sub.1-
-2amide, acrylonitrile, esters of maleic acid or fumaric acid,
maleinimide and N-substituted maleinimides.
[0070] In a preferred embodiment of the invention one of the
polymer blocks A and B is essentially composed of repeating units
of ethylenically unsaturated monomers selected from the group
consisting of styrenes, acrylic and methacrylic
acid-C.sub.1-C.sub.2.sub.4alkyl esters, acrylic and methacrylic
acid-hydroxy-C.sub.2-C.sub.6alkyl esters, acrylic and methacrylic
acid-dihydroxy-C.sub.3-C.sub.4alkyl esters and acrylic and
methacrylic acid esters having poly-C.sub.2-C.sub.4alkyleneglycol
ester groups, wherein the ester groups may be substituted with
C.sub.1-C.sub.24alkoxy groups.
[0071] Suitable styrenes may be substituted at the phenyl group by
one to three additional substituents selected from the group
consisting of hydroxy, C.sub.1-C.sub.4alkoxy, e.g. methoxy or
ethoxy, halogen, e.g. chloro, and C.sub.1-C.sub.4alkyl, e.g.
methyl.
[0072] Suitable acrylic acid or methacrylic
acid-C.sub.1-C.sub.24alkyl esters are acrylic acid or methacrylic
acid esters esterified by methyl, ethyl, n-butyl, isobutyl,
tert-butyl, neopentyl, 2-ethylhexyl, isobornyl, isodecyl,
n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
[0073] Representative acrylic and C.sub.1-C.sub.4alkylacrylic
acid-C.sub.6-C.sub.11aryl-C.sub.1-C.sub.4alkyl esters are acrylic
acid or methacrylic acid esters esterified by benzyl,
2-phenylethyl, 1- or 2-naphthylmethyl or 2-(1- or
2-naphthyl)-ethyl. The phenyl or naphthyl groups may be
additionally substituted with one to three additional substituents
selected from the group consisting of hydroxy,
C.sub.1-C.sub.4alkoxy, e.g. methoxy or ethoxy, halogen, e.g.
chloro, and C.sub.1-C.sub.4alkyl, e.g. methyl or methyl.
[0074] Representative acrylic and C.sub.1-C.sub.4alkylacrylic
acid-C.sub.6-C.sub.11aryloxy-C.sub.1-C.sub.4alkyl esters are
acrylic acid or methacrylic acid esters esterified by
2-phenoxyethyl or 2-benzyloxyethyl.
[0075] Representative acrylic acid and C.sub.1-C.sub.4alkylacrylic
acid-hydroxy-C.sub.2-C.sub.4alkyl esters are acrylic acid- or
methacrylic acid-2-hydroxyethyl esters (HEA, HEMA) or acrylic acid-
or methacrylic acid-2-hydroxypropyl ester (HPA, HPMA).
[0076] Representative acrylic and C.sub.1-C.sub.4alkylacrylic
acid-polyhydroxy-C.sub.3-C.sub.6alkyl esters are acrylic acid- or
methacrylic acid esterified by ethylene glycol or glycerol.
[0077] Representative acrylic acid- and C.sub.1-C.sub.4alkylacrylic
acid-silyloxy-C.sub.2-C.sub.4alkyl esters are acrylic acid- or
methacrylic acid-2-trimethylsilyloxyethyl esters TMS-HEA,
TMS-HEMA).
[0078] Representative acrylic acid- or C.sub.1-C.sub.4alkylacrylic
acid-(C.sub.1-C.sub.4alkyl).sub.3silyl-C.sub.2-C.sub.4alkyl esters
are acrylic acid- or methacrylic acid-2-trimethylsilylethyl esters
or acrylic acid- or methacrylic acid-3-trimethylsilyl-n-propyl
esters.
[0079] Representative acrylic and C.sub.1-C.sub.4alkylacrylic acid
esters having poly-C.sub.2-C.sub.4alkyleneglycol ester groups,
wherein the ester groups may be substituted with
C.sub.1-C.sub.24alkoxy groups are illustrated by the formula given
below: 5
[0080] wherein
[0081] n represents a numeral from one to 100;
[0082] R.sub.1 and R.sub.2 independently of one another represent
hydrogen or methyl; and
[0083] R.sub.3 represents C.sub.1-C.sub.24alkyl, e.g. methyl,
ethyl, n- or isopropyl, n-, iso-, or tert-butyl, n- or neo-pentyl,
n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, or represents
aryl-C.sub.1-C.sub.24alkyl, e.g. benzyl or phenyl-n-nonyl, as well
as C.sub.1-C.sub.24alkylaryl or
C.sub.1-C.sub.24alkylaryl-C.sub.1-C.sub.24al- kyl.
[0084] Representative acrylic acid- and C.sub.1-C.sub.4alkylacrylic
acid-heterocyclyl-C.sub.2-C.sub.4alkyl esters are acrylic acid- or
methacrylic acid-2-(N-morpholinyl, 2-pyridyl, 1-imidazolyl,
2-oxo-1-pyrrolidinyl, 4-methylpiperidin-1-yl or
2-oxoimidazolidin-1-yl)-e- thyl esters.
[0085] Representative C.sub.1-C.sub.4alkylacrylic acid esters
having poly-C.sub.2-C.sub.4alkyleneglycol ester groups, wherein the
ester groups may be substituted with C.sub.1-C.sub.24alkoxy groups
are acrylic acid- or methacrylic acid esters of ethoxylated decanol
or ethoxylated lauryl or stearyl alcohol, wherein the degree of
ethoxylation, as expressed by the index n in the formula above, is
typically in the range from 5 to 30.
[0086] Representative acrylic and C.sub.1-C.sub.4alkylacrylic
acid-(C.sub.1-C.sub.4alkyl).sub.1-2amide are acrylic acid- or
methacrylic acid N-methyl, N,N-dimethyl, N-ethyl or N,N-diethyl
amide.
[0087] Representative esters of maleic acid or fumaric acid are the
C.sub.1-C.sub.24alkyl esters, e.g. the methyl, ethyl, n-butyl,
isobutyl, tert-butyl, neopentyl, 2-ethylhexyl, isobornyl, isodecyl,
n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl esters, the
C.sub.6-C.sub.11aryl, e.g. phenyl or naphthyl, esters or the
C.sub.6-C.sub.11aryl-C.sub.1-C.sub.4alkyl esters, e.g. benzyl or
2-phenethyl esters. The phenyl or naphthyl groups may be
additionally substituted with one to three additional substituents
selected from the group consisting of hydroxy,
C.sub.1-C.sub.4alkoxy, e.g. methoxy or ethoxy, halogen, e.g.
chloro, and C.sub.1-C.sub.4alkyl, e.g. methyl.
[0088] Representative N-substituted maleinimides are the
N--C.sub.1-C.sub.4alkyl, e.g. N-methyl or N-ethyl, or N-aryl, e.g.
N-phenyl substituted maleinimides.
[0089] According to the embodiment (i) one of the polymer blocks A
or B or the chain terminal group Y additionally in the copolymer
(I) contains repeating units of ethylenically unsaturated monomers
substituted with basic groups. A suitable ethylenically unsaturated
monomer substituted with a basic group present in one of the
polymer blocks A and B or the chain terminal group Y is represented
by a compound of the formula
CH.sub.2.dbd.C(--R.sup.1)--C(.dbd.O)--R.sup.2 (III),
[0090] wherein
[0091] R.sup.1 represents hydrogen or C.sub.1-C.sub.4alkyl; and
[0092] R.sup.2 represents a basic substituent selected from the
group consisting of amino-C.sub.2-C.sub.18alkoxy,
C.sub.1-C.sub.4alkylamino-C.s- ub.2-C.sub.18alkoxy,
di-C.sub.1-C.sub.4alkylamino-C.sub.2-C.sub.18alkoxy,
hydroxy-C.sub.2-C.sub.4alkylamino-C.sub.2-C.sub.18alkoxy and
C.sub.1-C.sub.4alkyl-(hydroxy-C.sub.2-C.sub.4alkyl)amino-C.sub.2-C.sub.18-
alkoxy; or wherein
[0093] the ethylenically unsaturated monomer substituted with a
basic group present in one of the polymer blocks A and B or the
chain terminal group Y is an amino monomer selected from the group
consisting of amino substituted styrene,
(C.sub.1-C.sub.4alkyl).sub.1-2amino substituted styrene,
N-mono-(C.sub.1-C.sub.4alkyl).sub.1-2amino-C.sub.2-C.sub.4alkyl(-
meth)acryl amide and
N,N-di-(C.sub.1-C.sub.4alkyl).sub.1-2amino-C.sub.2-C.-
sub.4alkyl(meth)acryl amide, vinyl pyridine or C.sub.1-C.sub.4alkyl
substituted vinyl pyridine, vinyl imidazole and
C.sub.1-C.sub.4alkyl substituted vinyl imidazole.
[0094] According to the alternate embodiment (i') one of the
polymer blocks A or B or the chain terminal group Y in the
copolymer (I) additionally contains repeating units of
ethylenically unsaturated monomers substituted with acidic groups.
A suitable ethylenically unsaturated monomer substituted with an
acidic group present in one of the polymer blocks A and B or the
chain terminal group Y is represented by a compound of the formula
(III), wherein R.sup.1 represents hydrogen or C.sub.1-C.sub.4alkyl;
and R.sup.2 represents C.sub.1-C.sub.4alkyl substituted by carboxy,
sulpho or phosphono.
[0095] Representative styrenes are substituted at the phenyl group
with one or two amino groups or one or two
(C.sub.1-C.sub.4alkyl).sub.1-2amino groups, particularly one amino
group in 4-position. Additional substituents are selected from the
group consisting of hydroxy, C.sub.1-C.sub.4alkoxy, e.g. methoxy or
ethoxy, halogen, e.g. chloro, or C.sub.1-C.sub.4alkyl, e.g. methyl
or ethyl.
[0096] Representative
N-mono-(C.sub.1-C.sub.4alkyl).sub.1-2amino-C.sub.2-C-
.sub.4alkyl(meth)acryl amide and
N,N-di-(C.sub.1-C.sub.4alkyl).sub.1-2amin-
o-C.sub.2-C.sub.4alkyl(meth)acryl amide are 2-N-tert-butylamino- or
2-N,N-dimethyl-aminoethylacrylamide or 2-N-tert-butylamino- or
2-N,N-dimethylaminopropylmethacrylamide.
[0097] In a particularly preferred embodiment of the invention the
repeating unit of an ethylenically unsaturated monomer substituted
with a basic group present in one of the polymer blocks A and B is
represented by a compound of the formula (III), wherein
[0098] R.sup.1 represents hydrogen or methyl; and
[0099] R.sup.2 represents amino substituted C.sub.2-C.sub.18alkoxy
selected from the group consisting of amino-C.sub.2-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylamino-C.sub.2-C.sub.4alkoxy,
di-C.sub.1-C.sub.4alkyla- mino-C.sub.2-C.sub.4alkoxy,
hydroxy-C.sub.2-C.sub.4alkylamino-C.sub.2-C.su- b.18alkoxy and
C.sub.1-C.sub.4alkyl-(hydroxy-C.sub.2-C.sub.4alkyl)amino-C.-
sub.2-C.sub.4alkoxy;
[0100] or is amino substituted styrene,
(C.sub.1-C.sub.4alkyl).sub.1-2amin- o substituted styrene, and
N,N-di-(C.sub.1-C.sub.4alkyl).sub.2amino-C.sub.-
2-C.sub.4alkyl(meth)acryl amide.
[0101] The repeating unit of an ethylenically unsaturated monomer
substituted with a basic group present in one of the polymer blocks
A or B as described above forms a salt with the salt forming
compound (ii) by acid-base reaction, acid addition or quatemisation
reaction.
[0102] In a particularly preferred embodiment of the invention the
unsaturated monomer substituted with a basic group present in one
of the polymer blocks A and B is represented by an 2-ammoniumethyl
ester group of the formula 6
[0103] wherein
[0104] R.sup.a, R.sup.b and R.sup.c independently of one another
represent hydrogen or a substituent selected from the group
consisting of C.sub.1-C.sub.4alkyl, aryl-C.sub.1-C.sub.4alkyl and
(C.sub.1-C.sub.4alkyl).sub.1-3aryl.
[0105] In an especially preferred embodiment of the invention the
repeating unit of an ethylenically unsaturated monomer substituted
with a basic group is represented by an amino monomer selected from
the group consisting of 4-aminostyrene, 4-dimethylaminostyrene, an
amino alkyl(meth)acrylate selected from the group consisting of
2-dimethylaminoethyl acrylate (DMAEA), 2-dimethylaminoethyl
methacrylate (DMAEMA), 2-diethylaminoethyl acrylate (DEAEA),
2-diethylaminoethyl methacrylate (DEAEMA), 2-t-butylaminoethyl
acrylate (t-BAEA), 2-t-butylaminoethyl methacrylate (t-BAEMA) and
3-dimethylaminopropylmetha- cryl-amide, 4-vinylpyridine,
2-vinylpyridine and 1-vinylimidazole.
[0106] The index numbers x and y independently of one another
define the number of monomer units present in the polymer blocks A
and B. One of x and y represents zero, one or a numeral greater
than one and the other one represents a numeral greater than one.
At least one of the index numbers x and y represents a numeral
greater than one. In the event that one of the index numbers x and
y is zero, the copolymer (I) is a macromonomer which may be
converted to a comb polymer. A range from two to 1000 is preferred
for the sum of x and y. The preferred molecular weight range of
both polymer blocks A and B is from about 1 000 to 100 000,
preferably about 1 000 to 50 000. A particularly preferred
molecular weight range is from about 1 000 to 15 000.
[0107] The polymerisation process may be carried out in the
presence of water or an organic solvent or mixtures thereof.
Additional co-solvents or surfactants, such as glycols or ammonium
salts of fatty acids, may be added to the reaction mixture. The
amount of solvent should be kept as low as possible. The reaction
mixture may contain the above-mentioned monomers or oligomers in an
amount of 1.0 to 99.9% by weight, preferably 5.0 to 99.9% by
weight, and especially preferably 50.0 to 99.9% by weight, based on
the monomers present in the polymerisate.
[0108] If organic solvents are used, suitable solvents or mixtures
of solvents are typically pure alkanes (hexane, heptane, octane,
isooctane), hydrocarbons (benzene, toluene, xylene), alkanols
(methanol, ethanol, ethylene glycol, ethylene glycol monomethyl
ether), esters (ethyl n-propyl, n-butyl or n-hexyl acetate) and
ethers (diethyl or dibutyl ether, ethylene glycol dimethyl ether,
tetrahydrofuran), or mixtures thereof.
[0109] If water is used as a solvent the reaction mixture can be
supplemented with a water-miscible or hydrophilic co-solvent. The
reaction mixture will then remain in a homogeneous single phase
throughout the monomer conversion. Any water-soluble or
water-miscible co-solvent may be used, as long as the aqueous
solvent medium is effective in providing a solvent system, which
prevents precipitation or phase separation of the reactants or
polymer products until full completion of the polymerisation.
Exemplary co-solvents useful in the process may be selected from
the group consisting of aliphatic alcohols, glycols, ethers, glycol
ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkylpyrrolidones,
polyethylene glycols, polypropylene glycols, amides, carboxylic
acids and salts thereof, esters, organosulphides, sulphoxides,
sulphones, alcohol derivatives, hydroxyether derivatives such as
butyl carbitol or cellosolve, amino alcohols, ketones, and the
like, as well as derivatives and mixtures thereof. Specific
examples include methanol, ethanol, propanol, dioxan, ethylene
glycol, propylene glycol, diethylene glycol, glycerol, dipropylene
glycol, tetrahydrofuran, and other water-soluble or water-miscible
materials, and mixtures thereof. When mixtures of water and
water-soluble or water-miscible organic solvents are selected for
the process, the water to co-solvent weight ratio is typically in
the range of about 99:1 to about 10:90.
[0110] When monomer mixtures or monomer/oligomer mixtures are used,
the calculation of mol % is based on an average molecular weight of
the mixture.
[0111] The polymerisation temperature may range from about
50.degree. C. to about 180.degree. C., preferably from about
80.degree. C. to about 150.degree. C. At temperatures above about
180.degree. C., the controlled conversion of the monomers into
polymers may decrease, and undesirable by-products like thermally
initiated polymers are formed or decomposition of the components
may occur.
[0112] A suitable catalyst capable of activating ATRP is a
transition metal complex catalyst salt present as an oxidisable
complex ion in the lower oxidation state of a redox system.
Preferred examples of such redox systems are selected from the
group consisting of Group V(B), VI(B), VII(B), VIII, IB and IIB
elements, such as Cu.sup.+/Cu.sup.2+, Cu.sup.0/Cu.sup.+,
Fe.sup.0/Fe.sup.2+, Fe.sup.2+/Fe.sup.3+, Cr.sup.2+/Cr.sup.3+,
Co.sup.+/Co.sup.2+, Co.sup.2+/Co.sup.3+, Ni.sup.0/Ni.sup.+,
Ni.sup.+/Ni.sup.2+, Ni.sup.2+/Ni.sup.3+, Mn.sup.0/Mn.sup.2+,
Mn.sup.2+/Mn.sup.3+, Mn.sup.3+/Mn.sup.4+ or Zn.sup.+/Zn.sup.2+.
[0113] The ionic charges are counterbalanced by anionic ligands
commonly known in complex chemistry of transition metals, such
hydride ions (H.sup.-) or anions derived from inorganic or organic
acids, examples being halides, e.g. F.sup.-, Cl.sup.-, Br.sup.- or
I.sup.-, halogen complexes with transition metals, such as
Cu.sup.IBr.sub.2.sup.-, halogen complex ions of the type
BF.sub.4.sup.-, PF.sub.6.sup.-, SbF.sub.6.sup.- or AsF.sub.6.sup.-,
anions of oxygen acids, alcoholates or acetylides or the anion of
cyclopentadiene.
[0114] Anions of oxygen acids are, for example, sulphate,
phosphate, perchlorate, perbromate, periodate, antimonate,
arsenate, nitrate, carbonate, the anion of a
C.sub.1-C.sub.8carboxylic acid, such as formate, acetate,
propionate, butyrate, benzoate, phenylacetate, mono-, di- or
trichloro- or -fluoroacetate, sulphonates, for example methyl-,
ethyl-, n-propyl- or n-butylsulphonate, trifluoromethylsulphonate
(triflate), unsubstituted or C.sub.1-C.sub.4alkyl-,
C.sub.1-C.sub.4alkoxy- or halo-, especially fluoro-, chloro- or
bromo-substituted phenylsulphonate or benzylsulphonate, for example
tosylate, mesylate, brosylate, p-methoxy- or
p-ethoxyphenylsulphonate, pentafluorophen-ylsulphonate or
2,4,6-triisopropylsulphonate, phosphonates, for example
methylphosphonate, ethylphosphonate, propylphosphonate,
butylphosphonate, phenylphosphonate, p-methylphenylphosphonate or
benzylphosphonate, carboxylates derived from a
C.sub.1-C.sub.8carboxylic acid, for example formate, acetate,
propionate, butyrate, benzoate, phenylacetate, mono-, di- or
trichloro- or -fluoroacetate, and also C.sub.1-C.sub.12alcoholates,
such as straight chain or branched C.sub.1-C.sub.12alcoholates,
e.g. methanolate or ethanolate.
[0115] Anionic ligands and neutral may also be present up to the
preferred coordination number of the complex cation, especially
four, five or six. Additional negative charges are counterbalanced
by cations, especially monovalent cations such as Na.sup.+,
K.sup.+, NH.sub.4.sup.+ or (C.sub.1-C.sub.4alkyl).sub.4N.sup.+.
[0116] Suitable neutral ligands are inorganic or organic neutral
ligands commonly known in complex chemistry of transition metals.
They coordinate to the metal ion through a .sigma.-, .pi.-, .mu.-
or .eta.-type bonding or any combinations thereof up to the
preferred coordination number of the complex cation. Suitable
inorganic ligands are selected from the group consisting of aquo
(H.sub.2O), amino, nitrogen, carbon monoxide and nitrosyl. Suitable
organic ligands are selected from the group consisting of
phosphines, e.g. (C.sub.6H.sub.5).sub.3P,
(i-C.sub.3H.sub.7).sub.3P, (C.sub.5H.sub.9).sub.3P or
(C.sub.6H.sub.11).sub.3P, di-, tri-, tetra- and hydroxyamines, such
as ethylenediamine, ethylenediaminotetraacetate (EDTA),
N,N-Dimethyl-N',N'-bis(2-dimethylaminoethyl)-ethylenediamine
(Me.sub.6TREN), catechol, N,N'-dimethyl-1,2-benzenediamine,
2-(methylamino)phenol, 3-(methylamino)-2-butanol or
N,N'-bis(1,1-dimethylethyl)-1,2-ethanediamine,
N,N,N',N",N"-pentamethyidi- ethylenetriamine (PMDETA),
C.sub.1-C.sub.8-glycols or glycerides, e.g. ethylene or propylene
glycol or derivatives thereof, e.g. di-, tri- or tetraglyme, and
mono- or bidentate heterocyclic e.sup.- donor ligands. Heterocyclic
e.sup.- donor ligands are derived, for example, from unsubstituted
or substituted heteroarenes from the group consisting of furan,
thiophene, pyrrole, pyridine, bis-pyridine, pi-colylimine,
.gamma.-pyran, .gamma.-thiopyran, phenanthroline, pyrimidine,
bis-pyrimidine, pyrazine, indole, coumarone, thionaphthene,
carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole,
benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole,
isothiazole, quinoline, bis-quinoline, isoquinoline,
bis-isoquinoline, acridine, chromene, phenazine, phenoxazine,
phenothiazine, triazine, thianthrene, purine, bis-imidazole and
bis-oxazole.
[0117] The oxidisable transition metal complex catalyst can be
formed in a separate preliminary reaction step from its ligands or
is preferably formed in-situ from its transition metal salt, e.g.
Cu(I)Cl, which is then converted to the complex compound by
addition of compounds corresponding to the ligands present in the
complex catalyst, e.g. by addition of ethylenediamine, EDTA,
Me.sub.6TREN or PMDETA.
[0118] The transition metal in the oxidisable transition metal
complex catalyst salt is converted from its lower oxidation state
in the above-mentioned redox systems to its higher oxidation state.
In a preferred embodiment of the process a Cu(I) complex catalyst
salt is converted to the corresponding Cu(II) oxidation state.
[0119] Because the present polymerisation by ATRP is a "living"
polymerisation, it can be started and terminated practically at
will. The copolymers (I) as obtained by the process have a low
polydispersity. Preferably the polydispersity is from 1.01 to 2.20,
more preferably from 1.01 to 1.90, and most preferably from 1.01 to
1.50.
[0120] The various advantages of the process of this type that
allow a large range of polymerisation reactions are described by K.
Maiyjaszewski in ACS Symp. Ser. Vol. 685 (1998), pg. 2-30.
[0121] In a block copolymer (I) Y represents a polymer chain
terminal group. A suitable chain terminal group is a radically
transferable group, hydrogen, a polymerisable chain terminal group
or a saturated polymer chain terminal group, which is formed by
polymerisation or copolymerisation of a polymerisable chain
terminal group.
[0122] A radically transferable group is a group that results from
ATRP with suitable initiators of the formula II described above,
such as chlorine or bromine.
[0123] An alternative embodiment relates to compositions comprising
copolymers (I), e.g. macromonomers, wherein Y is a polymerisable
chain terminal group. Such group contains at least one
polymerisable, ethylenically unsaturated monomer unit that has the
same preferred meanings in respect of the polymerised saturated
monomer units present in a linear chain terminal group Y.
[0124] A preferred polymerisable chain terminal group is an
ethylenically unsaturated group corresponding to monomers selected
from the group consisting of styrenes, acrylic acid,
C.sub.1-C.sub.4alkylacrylic acid, amides, anhydrides and salts of
acrylic acid or C.sub.1-C.sub.4alkylacryl- ic acid, acrylic
acid-C.sub.1-C.sub.24alkyl esters and C.sub.1-C.sub.4alkylacrylic
acid-C.sub.1-C.sub.24alkyl esters, acrylonitrile,
methacrylonitrile, vinyl substituted heterocycles, styrene
sulphonic acid and salts, vinyl benzoic acid and salts, vinyl
formamide and amidosulphonic acid derivatives.
[0125] The macromonomers are prepared by known methods such as the
ones described WO 01/51534, e.g. by reacting a copolymer (I)
obtainable by ATRP, wherein Y is a radically transferable atom or
group, e.g. halogen, with ethylenically unsaturated monomers as
defined above.
[0126] The elimination of the transfer group Y, e.g. halogen, with
the polymerisable chain terminal group X is advantageously
performed in such a way that the polymerisate is dissolved in a
solvent and the monomeric compound corresponding to X is added in
the presence of a non-nucleophilic base such as
diazabicycloundecene (DBU) or other bases at higher temperatures.
The reaction, which is a conventional esterification reaction,
takes place under the conditions of a regular esterification
reaction within a temperature range from room temperature to the
boiling temperature of the reaction mixture, preferably from room
temperature to 100.degree. C.
[0127] Copolymers (I) wherein Y is saturated polymer chain terminal
group Y, e.g. comb polymers, are obtained by further polymerising
the macromonomers of above with ethylenically unsaturated monomers
by any known method of polymerisation, such as radical
polymerisation with initiators of the nitrile type, e.g. AIBN, or
peroxides, e.g. benzoyl peroxide or di-tert-butyl peroxide. In the
alternative the copolymerisation of the macromonomer with
co-monomers can also be conducted by ATRP or any other method of
controlled radical polymerisation, such as like nitroxyl mediated
controlled free radical polymerisation.
[0128] A preferred embodiment relates to a composition, which
comprises a copolymer of the formula I, wherein
[0129] X represents a polymer chain terminal group from a
polymerisation initiator which is selected from the group
consisting of C.sub.1-C.sub.8alkyl halides, C.sub.6-C.sub.15aralkyl
halides, C.sub.2-C.sub.8haloalkyl esters, arene sulphonyl halides,
.alpha.-haloalkane nitrites and halolactones;
[0130] Y represents a radically transferable group, hydrogen or a
polymerisable chain terminal group; and
[0131] p and q represent one.
[0132] Another preferred embodiment relates to a composition, which
comprises a copolymer of the formula (I), wherein
[0133] X represents a polymer chain terminal group from a
polymerisation initiator which is selected from the group
consisting of C.sub.1-C.sub.8alkyl halides, C.sub.6-C.sub.15aralkyl
halides, C.sub.2-C.sub.8haloalkyl esters, arene sulphonyl halides,
.alpha.-haloalkane nitriles and halolactones;
[0134] Y represents a saturated polymer chain terminal group;
[0135] p represents a numeral greater than one; and
[0136] q represents one.
[0137] In the composition according to the present invention the
salt forming compound (ii) or (ii') forms a salt with the copolymer
(I) by acid-base reaction, acid addition or quatemisation
reaction.
[0138] In particular, the acidic group, such as the sulpho, carboxy
or phosphono group, the sulphonic acid-C.sub.1-C.sub.4alkylester
group or the C.sub.1-C.sub.8alkyl halide group, which is present in
the salt forming compound (ii), forms a salt by reaction with a
basic group, such as the free amino group or a primary, secondary
or tertiary amino group, which is present in one of the polymer
blocks A and B or the chain terminal group Y of the copolymer
component (I). In an alternative embodiment of the invention the
acidic group, such as the sulpho, carboxy or phosphono group is
present in one of the polymer blocks A and B or the chain terminal
group Y of the copolymer component (I). The salt forming compound
(ii') then contains the free amino group or a primary, secondary or
tertiary amino group.
[0139] A suitable salt forming compound (ii) is an organic acid
selected from the group consisting of monocyclic or polycyclic
sulphonic, mono- or polycyclic carboxylic or phosphonic acids,
aliphatic sulphonic, carboxylic or phosphonic acids substituted
with mono- or polycyclic groups, C.sub.1-C.sub.8alkyl halides
substituted with mono- or polycyclic groups and
C.sub.1-C.sub.4alkyl esters of mono- or polycyclic sulphonic acids,
provided that p-toluenesulphonic acid is excluded as salt-forming
component (ii).
[0140] In a preferred embodiment of the invention the salt forming
compound (ii) is an organic acid selected from the group consisting
polycyclic sulphonic, mono- or polycyclic carboxylic or phosphonic
acids, aliphatic sulphonic, carboxylic or phosphonic acids
substituted with mono- or polycyclic groups, C.sub.1-C.sub.8alkyl
halides substituted with mono- or polycyclic groups and
C.sub.1-C.sub.4alkyl esters of mono- or polycyclic sulphonic
acids.
[0141] The term monocyclic defines the presence of a carbo- or
heterocycloaliphatic, e.g. C.sub.3-C.sub.8cycloalkyl, or an
aromatic carbocyclic or heterocyclic group, e.g. phenyl.
[0142] The term polycyclic defines the presence of more than one
cyclic group in a given molecular structure, especially two or
three cyclic groups. The cyclic groups may be saturated or
unsaturated, carbocyclic or heterocyclic. Polycyclic sulphonic
acids have at least two cyclic groups, e.g. two aromatic, e.g. two
condensed aromatic groups, or condensed bicycloaliphatic or
bicycloaliphatic aromatic groups.
[0143] Mono- or polycyclic sulphonic, carboxylic or phosphonic
acids comprise within their given molecular structure at least one
cyclic group, e.g. one or two aromatic, e.g. two condensed aromatic
groups, or one or two cycloaliphatic groups, condensed
bicycloaliphatic or cycloaliphatic aromatic groups.
[0144] In a preferred embodiment the mono- or polycyclic groups
present in the sulphonic, carboxylic and phosphonic acids or the
mono- or polycyclic substituents of the aliphatic sulphonic,
carboxylic or phosphonic acids are selected from the group
consisting of saturated or unsaturated mono- or bicycloaliphatic,
heteromonocycloliphatic or heterobicycloaliphatic, carbomonocyclic
or carbobicyclic aromatic, partially saturated carbobicyclic
aromatic, heteromonocyclic or heterobicyclic aromatic and partially
saturated heterobicyclic aromatic groups. A preferred group of
substituted mono- or polycyclic sulphonic, carboxylic and
phosphonic acids is represented by the general formula: 7
[0145] wherein
[0146] X represents sulpho, carboxy or P(.dbd.O)(OH).sub.2; and
[0147] R.sub.1, R.sub.2 or R.sub.3 independently of one another
represent hydrogen or a substituent selected from the group
consisting of functional groups or derivatised functional groups
selected from the group consisting of amino,
C.sub.1-C.sub.4alkylamino, C.sub.1-C.sub.4-dialkylamino, hydroxy,
oxo, thio, --NO.sub.2, carboxy, carbamoyl, sulpho, sulphamoyl,
ammonio, amidino, cyano, formylamino, formamido and halogen; or
[0148] R.sub.1, R.sub.2 or R.sub.3 independently of one another
represent saturated or unsaturated aliphatic, cycloaliphatic or
heterocycloaliphatic groups, carbocyclic or heterocyclic aryl
groups, condensed carbocyclic, heterocyclic or
carbocyclic-heterocyclic groups, which may additionally be combined
with one of these groups or which may additionally be substituted
with one of the functional groups or derivatised functional groups
mentioned above.
[0149] The substituent groups may additionally be interrupted with
one or more bivalent groups selected from the group consisting of
--O--, --S--, --C(.dbd.O)--O--, --O--C(.dbd.O)--,
--C(.dbd.O)--N(C.sub.1-C.sub.4alkyl)-- ,
--N(C.sub.1-C.sub.4alkyl)-C(.dbd.O)--, --S(.dbd.O)--,
--S(.dbd.O).sub.2--, --S(.dbd.O)--O--, --S(.dbd.O).sub.2--,
--O--S(.dbd.O)--, --O--S(.dbd.O).sub.2--,
--S(.dbd.O)--N(C.sub.1-C.sub.4a- lkyl)-,
--S(.dbd.O).sub.2--N(C.sub.1-C.sub.4alkyl)-,
--(C.sub.1-C.sub.4alkyl)N--S(.dbd.O)--,
--(C.sub.1-C.sub.4alkyl)N--S(.dbd- .O).sub.2--, --P(.dbd.O)--,
--P(.dbd.O)--O--, --O--P(.dbd.O)-- and --O--P(.dbd.O)--O--.
[0150] Two substituents from the group R.sub.1 and R.sub.2 may also
represent bivalent, bridge-type C.sub.2-C.sub.6alkylen-,
C.sub.4-C.sub.8alkyldiyliden- or C.sub.4-C.sub.8alkenyldiyliden
groups which are connected with one of the above-mentioned cyclic
or bicyclic groups.
[0151] p-Toluenesulphonic acid (PTSA) is excluded from the
definitions above.
[0152] Specific salt forming compounds (ii), which are selected
from the group consisting of mono- or polycyclic sulphonic acids,
are illustrated by their structural formulae given below: 89
[0153] Specific salt forming compounds (ii) that are selected from
the group consisting of mono- or polycyclic carboxylic acids are
illustrated by their structural formulae given below:
1011121314
[0154] Further specific salt forming compounds (ii), which are
selected from the group consisting of mono- or polycyclic
carboxylic acids and phosphonic acids are illustrated by their
structural formulae given below: 1516
[0155] Preferred sulphonic acid-C.sub.1-C.sub.4alkyl esters
suitable as a salt forming compounds (ii) are the methyl or ethyl
esters of p-toluenesulphonic acid or the methyl or ethyl esters of
the sulphonic acids mentioned above and illustrated by their
structural formulae.
[0156] Preferred C.sub.1-C.sub.8alkyl halides substituted with the
above-mentioned mono-, bi- or tricyclic groups are benzyl chloride,
2-chlorobenzylchloride, 4-chlorobenzylchloride,
2,4-dichlorobenzylchlorid- e.
[0157] In another preferred embodiment, the salt groups on the
copolymer are derived from an aminic structure of a compound (III)
by quaternisation with active aryl-C.sub.1-C.sub.4alkyl halides or
C.sub.1-C.sub.4alkyl esters of organic sulphonic acids. In this
case examples of preferred salt forming compounds (II) are benzyl
chloride, 2-chlorobenzylchloride, 4-chlorobenzylchloride,
2,4-di-chlorobenzylchlori- de, p-toluenesulphonic acid methyl
ester, p-toluenesulphonic acid ethyl ester and the methyl- or ethyl
esters of the polycyclic sulphonic acids described above.
[0158] According to another embodiment of the invention the acidic
group present in the salt forming compounds (ii), particularly the
sulpho, carboxy or phosphono group, may be attached directly or
with a bivalent bridge group to any aliphatic, cycloaliphatic,
aliphatic cycloaliphatic, aromatic or aromatic aliphatic
hydrocarbon backbone from a UV-absorber moiety.
[0159] Preferred bivalent groups are selected from the group
consisting of --O--, --O--C(.dbd.O)--, --C(.dbd.O)--O--,
--O(C.sub.1-C.sub.8alkylene)- and C.sub.1-C.sub.8alkylene.
[0160] The term UV-light absorber moiety comprises any structural
moiety effective as a photostable UV-filter which is derived from
UV-light absorber compounds present in cosmetic and pharmaceutical
preparations for protecting the human epidermis or human hair from
UV-radiation, particularly in the range from 290 to 400 nm.
Examples of suitable UV-light absorber moieties are described in
U.S. Pat. No. 6,132,703. A preferred UV-light absorber moiety is a
substituent selected from the group consisting of
2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic
acid esters, oxanilides and
2-(2-hydroxyphenyl)-1,3,5-triazines.
[0161] Specific 2-(2'-hydroxyphenyl)benzotriazoles are
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(2',4'-dihydroxyphenyl)-b- enzotriazole,
2-[3'-tert-butyl-2'-hydroxy-5-(1-hydroxycarbonyl-2-ethyl)-ph-
enyl]-benzotriazole,
2-[3'-tert-butyl-2'-hydroxy-5-(1-hydroxycarbonyl-2-et-
hyl)-phenyl]-5-chlorobenzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxypheny- l)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)-phenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-h- ydroxyphenyl)benzotriazole,
2-(3',5'-bis(.alpha., .alpha.-di
methylbenzyl)-2'-hydroxyphenyl)-benzotriazole,
2-(3'-tert-butyl-2'-hydrox-
y-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)--
5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylet-
hyl)phenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-metho-
xycarbonylethyl)phenyl)-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-o-
ctyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethyl-
hexyl-oxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-
phenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxy-
carbonylethyl)-2'-hydroxyphenyl]-benzotriazole with polyethylene
glycol 300; [R--CH.sub.2CH.sub.2--COO--CH.sub.2CH.sub.2.sub.2,
wherein R represents
3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl;
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)phenyl]benzotriazole and
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-
-5'-(.alpha.,.alpha.-dimethylbenzyl)phenyl]benzotriazole.
[0162] Specific 2-hydroxybenzophenones are, for example, the
4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy,
4-benzyloxy, 2,4-dihydroxy, 4,2',4'-trihydroxy and
2'-hydroxy-4,4'-dimethoxy derivatives.
[0163] Specific benzoic acid esters are, for example,
4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl
salicylate, dibenzoylresorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxyben- zoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0164] Specific oxanilides are, for example,
2-ethyl-2'-hydroxyoxanilide, 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-
-tert-butyloxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide,
2-ethoxy-2'-ethyloxanilide,
N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o-
and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.
[0165] Specific 2-(2-hydroxyphenyl)-1,3,5-triazines are, for
example, 2,4-bis(biphenyl-4-yl)-6-(2,6-dihydroxy)-1,3,5-triazine,
2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-n-butoxypropoxy)phenyl]-4,6-bis(2,4-di-
methylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)-
-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2-
,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy--
propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine-
, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropoxy]phenyl}-4,6-bis(2,-
4-dimethylphenyl)-1,3,5-triazine.
[0166] Particularly preferred are UV-light absorbers selected from
the group consisting of (2,4-di-hydroxyphenyl)-phenylmethanone,
2-benzotriazol-2-yl-4-methylphenol,
4-benzotriazol-2-ylbenzene-1,3-diol,
3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propionic
acid, 3-[5-(benzotriazol-2-yl)-3tertbutyl-4-hydroxyphenyl]propionic
acid; 4-(4,6-diphenyl)-1,3,5-triazin-2-yl-benzene1,3-diol,
4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-benzene-1,3-diol,
4-[4,6-di-(2,4-di-hydroxyphenyl)1,3,5-triazin2-yl]benzene-1,3-diol
and N'-2-ethylphenyl-N'-2-hydroxyphenyloxalamide.
[0167] The composition may contain the above-mentioned polymer
component b) in an amount of 0.1 to 99.9% by weight, preferably 0.1
to 50.0% by weight, and particularly preferably 1.0 to 30.0% by
weight.
[0168] A preferred embodiment of the invention relates to a
composition comprising
[0169] a) 0.1-99.9% by weight dispersible inorganic or organic
pigment particles; and
[0170] b) 0.1-99.9% by weight dispersing agents that essentially
consist of a combination of
[0171] (i) a block copolymer (I), wherein
[0172] X represents the fragment of a polymerisation initiator
capable of initiating polymerisation of ethylenically unsaturated
monomers by atom transfer radical polymerisation (ATRP) in the
presence of a catalyst capable of activating controlled radical
polymerisation by ATRP;
[0173] Y represents a radically transferable group, a polymerisable
chain terminal group or a saturated polymer chain terminal
group;
[0174] A and B represent polymer blocks composed of repeating units
of ethylenically unsaturated monomers selected from the group
consisting of styrenes, acrylic and methacrylic
acid-C.sub.1-C.sub.24alkyl esters, acrylic and methacrylic
acid-hydroxy-C.sub.2-C.sub.6alkyl esters, acrylic and methacrylic
acid-dihydroxy-C.sub.3-C.sub.4alkyl esters and acrylic and
methacrylic acid esters having poly-C.sub.2-C.sub.4alkyleneglycol
ester groups, wherein the ester groups may be substituted with
C.sub.1-C.sub.24alkoxy groups;
[0175] and wherein at least one of the polymer blocks A or B or the
chain terminal group Y additionally contains repeating units of
ethylenically unsaturated monomers substituted with basic residues
which are represented by a compound of the formula
CH.sub.2.dbd.C(--R.sup.1)--C(.dbd.O)--R.sup.2 (III),
[0176] wherein
[0177] R.sup.1 represents hydrogen or methyl; and
[0178] R.sup.2 represents a basic residue selected from the group
consisting of amino-C.sub.2-C.sub.4alkoxy,
C.sub.1-C.sub.4alkylamino-C.su- b.2-C.sub.4alkoxy,
di-C.sub.1-C.sub.4alkylamino-C.sub.2-C.sub.4alkoxy,
hydroxy-C.sub.2-C.sub.4alkylamino-C.sub.2-C.sub.18alkoxy and
C.sub.1-C.sub.4alkyl-(hydroxy-C.sub.2-C.sub.4alkyl)-amino-C.sub.2-C.sub.4-
alkoxy;
[0179] one of x and y represents zero, one or a numeral greater
than one and the other one represents a numeral greater than
one;
[0180] p and q represent one; and
[0181] (ii) a salt forming compound (II) selected from the group
consisting of mono- or polycyclic sulphonic, mono- or polycyclic
carboxylic or phosphonic acids, aliphatic sulphonic, carboxylic or
phosphonic acids substituted with mono- or polycyclic groups,
C.sub.1-C.sub.8alkyl halides substituted with mono- or polycyclic
groups and C.sub.1-C.sub.4alkyl esters of mono- or polycyclic
sulphonic acids;
[0182] provided that
[0183] p-toluenesulphonic acid is excluded.
[0184] Another embodiment of the invention relates to A pigment
dispersion comprising
[0185] a') dispersed pigment particles; and
[0186] b') a combination of a copolymer (I) wherein X, A, B, Y, x,
y, p and q are as defined above; and a salt forming compound (ii)
or (ii') as defined above;
[0187] and a carrier liquid, particularly water.
[0188] Another embodiment of the invention relates to the process
for preparing the above-mentioned pigment dispersion, which
comprises preparing the copolymer (I) by copolymerising the
fragments A and B by ATRP and optionally replacing or polymerising
further the chain terminal group Y; and
[0189] .alpha.) modifying the copolymer with the salt forming
compound, isolating and adding the modified block copolymer to
dispersible pigment particles and optionally binder materials,
fillers or other conventional additives; or
[0190] .beta.) modifying the copolymer with the salt forming
compound in the presence of dispersible pigment particles and
optionally binder materials, fillers or other conventional
additives.
[0191] According to a preferred embodiment the process comprises
the additional step of isolating the pigment and the modified
copolymer and optional other conventional additives in a solid
product form essentially free from liquid carrier medium.
[0192] According to the process variant .alpha.) the copolymer (I)
is modified by addition of the salt forming compound (ii) or (ii')
defined above, and isolating the modified block copolymer (I) in
pure form or as a solution or dispersion in water or an organic
solvent or a mixture of both. The modified block copolymer is then
added in pure form or as a solution or dispersion to dispersible
pigment particles and optionally binder materials, fillers or other
conventional additives.
[0193] In an alternative embodiment of the process the polymers or
copolymers can be further processed and used in most cases without
any further purification step. This is an important advantage when
industrial scale-up is intended. According to the process variant
.beta.) the copolymer (I) is modified with the salt forming
compound (ii) or (ii') in the presence of dispersible pigment
particles and optionally binder materials, fillers or other
conventional additives. A separate mixture of the salt forming
compound (ii), dispersible pigment particles and the optional
components, such as binder materials, fillers or other conventional
additives, e.g. solvent, is prepared to which the copolymer (I) is
added.
[0194] The sequential order of performing the individual mixing
steps comprising the copolymer (I), the salt forming compound (ii)
or (ii') and the optional components of the composition is
non-critical according to the process of above.
[0195] The pigments are dispersed in the presence of the modified
copolymer dispersant by using conventional techniques, such as high
speed mixing, ball milling, sand grinding, attritor grinding or two
or three roll milling. The resulting pigment dispersion may have a
pigment to dispersant binder weight ratio of about 0.1:100 to
1500:100.
[0196] The organic solvents present in the dispersion are mentioned
above, cf. process, and preferably are commonly used solvents in
coatings technology. For water based coatings applications, aside
from water, preferably polar, water-miscible solvents such as
C.sub.1-C.sub.4alkohols- , e.g. methanol, ethanol, or isopropanol,
glycol ethers like butyl glycol, or methoxypropylene glycol,
polyols, e.g. glycerol, or ethylene, diethylene, triethylene,
triethylene or propylene glycol are used. For solvent based coating
systems, preferably less polar solvents like aliphatic
hydrocarbons, esters like butyl acetate, or glycol ethers like
methoxypropylene glycol or glycol ether esters like
methoxypropylene glycol acetate are used.
[0197] In another preferred embodiment of the process variants
.alpha.) or .beta.) fine pigment dispersions are prepared by mixing
the pigments with a solution of the modified copolymers or an
aqueous emulsion of the modified copolymers, concentrating the
resulting mixture by distilling off the solvents and/or water,
preferably to dryness, and optionally further subjecting the
resulting concentrate to thermal and/or mechanical treatment to
prepare a mixture comprising pigments and modified copolymers which
may then be subsequently dispersed in aqueous and/or organic
solvents. According to this process, the solid composition of
pigment and modified copolymer is easy to disperse and does not
require time and energy intensive grinding to be incorporated into
e.g. a paint formulation.
[0198] The above-mentioned methods for preparing the composition,
such as high speed mixing, ball milling, sand grinding, attritor
grinding or two or three roll milling may in the alternative be
employed when preparing the dispersion.
[0199] The present invention also relates to the use of the pigment
dispersion described above for preparing coating compositions,
prints, images, inks, lacquers, pigmented plastics, adhesives,
casting resins, filled composites, glass fibre reinforced
composites, laminates, cement based construction materials like
plaster and tile adhesives.
[0200] Likewise of particular interest is a specific embodiment of
the above-mentioned process for preparing the dispersion, wherein
coating compositions, for example paints, are prepared. The
invention therefore also relates to compositions, wherein
film-forming binders for coatings are added to the composition
comprising components a) and b) described above.
[0201] The novel coating composition preferably comprises
0.01-100.0 parts by weight of the combined components a) and b) in
the composition, in particular 0.05-50.0 parts, especially 0.1-20.0
parts, per 100 parts by weight of solid binder.
[0202] Suitable binders are the ones customarily used, for example
the ones described in Ullmann's Encyclopedia of Industrial
Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991,
Germany. In general, the film-forming binder is based on a
thermoplastic or thermosetting resin, predominantly on a
thermosetting resin. Examples thereof are alkyd, acrylic,
polyester, phenolic, melamine, epoxy and polyurethane resins and
mixtures thereof. Also resins curable by radiation or air-drying
resins can be used.
[0203] Binders that may be used are any cold- or hot-curable
binders; the addition of a curing catalyst may be advantageous.
Suitable catalysts that accelerate the curing of binders are
described, for example, in Ullmann's, Vol. A18, loc. cit., p.
469.
[0204] Preference is given to coating compositions comprising a
functional acrylate resin and a cross linking agent. Examples of
coating compositions containing specific binders are:
[0205] Paints based on cold- or hot-cross linkable alkyd, acrylate,
polyester, epoxy or melamine resins or mixtures of such resins, if
desired with addition of a curing catalyst;
[0206] Two-component polyurethane paints based on
hydroxyl-containing acrylate, polyester or polyether resins and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0207] One-component polyurethane paints based on blocked
isocyanates, isocyanurates or polyisocyanates which are deblocked
during baking, if desired with addition of a melamine resin;
[0208] One-component polyurethane paints based on a
trisalkoxycarbonyl triazine cross linker and a hydroxyl group
containing resin such as acrylate, polyester or polyether
resins;
[0209] One-component polyurethane paints based on aliphatic or
aromatic urethane acrylates or polyurethane acrylates having free
amino groups within the urethane structure and melamine resins or
polyether resins, if necessary with curing catalyst;
[0210] Two-component paints based on (poly)ketimines and aliphatic
or aromatic isocyanates, isocyanurates or polyisocyanates;
[0211] Two-component paints based on (poly)ketimines and an
unsaturated acrylate resin or a polyacetoacetate resin or a
methacrylamidoglycolate methyl ester;
[0212] Two-component paints based on carboxyl- or amino-containing
polyacrylates and polyepoxides;
[0213] Two-component paints based on acrylate resins containing
anhydride groups and on a polyhydroxy or polyamino component;
[0214] Two-component paints based on acrylate-containing anhydrides
and polyepoxides;
[0215] Two-component paints based on (poly) oxazolines and acrylate
resins containing anhydride groups, or unsaturated acrylate resins,
or aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0216] Two-component paints based on unsaturated polyacrylates and
polymalonates;
[0217] Thermoplastic polyacrylate paints based on thermoplastic
acrylate resins or externally cross linking acrylate resins in
combination with etherified melamine resins; and
[0218] Paint systems based on siloxane-modified or
fluorine-modified acrylate resins.
[0219] In addition to the components mentioned above, the coating
composition according to the invention preferably comprises a light
stabiliser of the sterically hindered amine type, the
2-(2-hydroxyphenyl)-1,3,5-triazine and/or the
2-hydroxyphenyl-2H-benzotri- azole types. Further examples for
light stabilisers of the 2-(2-hydroxyphenyl)-1,3,5-triazine type
advantageously to be added can be found e.g. in the published
patent literature, e.g. U.S. Pat. No. 4,619,956, EP-A-434 608, U.S.
Pat. No. 5,198,498, U.S. Pat. No. 5,322,868, U.S. Pat. No.
5,369,140, U.S. Pat. No. 5,298,067, WO-94/18278, EP-A-704 437,
GB-A-2 297 091, WO-96/28431. Of special technical interest is the
addition of the 2-(2-hydroxyphenyl)-1,3,5-triazines and/or
2-hydroxyphenyl-2H-benzotriazoles, especially the
2-(2-hydroxyphenyl)-1,3- ,5-triazines.
[0220] Apart from the components mentioned above, the coating
composition can also comprise further components, examples being
solvents, pigments, dyes, plasticisers, stabilisers, thixotropic
agents, drying catalysts and/or levelling agents. Examples of
possible components are those described in Ullmann's, Vol. A 18,
pp. 429-471.
[0221] Possible drying catalysts or curing catalysts are, for
example, organometallic compounds, amines, amino-containing resins
and/or phosphines. Examples of organometallic compounds are metal
carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or
Cu, or metal chelates, especially those of the metals Al, Ti or Zr,
or organometallic compounds, such as organotin compounds.
[0222] Examples of metal carboxylates are stearates of Pb, Mn or
Zn, octanoates of Co, Zn or Cu, naphthenoates of Mn and Co or the
corresponding linoleates, resinates or tallates.
[0223] Examples of metal chelates are aluminium, titanium or
zirconium chelates of acetylacetone, ethyl acetylacetate,
salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl
trifluoroacetylacetate, and the alkoxides of these metals.
[0224] Examples of organotin compounds are dibutyltin oxide,
dibutyltin dilaurate or dibutyltin dioctoate.
[0225] Examples of amines are, in particular, tertiary amines, for
example tri-n-butylamine, triethanolamine, N-methyldiethanolamine,
N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or
diazabicyclooctane (triethylenediamine) and salts thereof. Further
examples are quaternary ammonium salts, for example trimethylbenzyl
ammonium chloride.
[0226] Amino-containing resins function simultaneously as binder
and curing catalyst. Examples thereof are amino-containing acrylate
copolymers.
[0227] The curing catalyst used can also be a phosphine, for
example triphenylphosphine.
[0228] The novel coating compositions include radiation-curable
coating compositions. In this case, the binder essentially
comprises monomeric or oligomeric compounds containing
ethylenically unsaturated bonds, which after application are cured
by actinic radiation, i.e. converted into a crosslinked, high
molecular weight form. Where the system is UV-curing, it generally
contains a photoinitiator as well. Corresponding systems are
described in the above-mentioned publication Ullmann's, Vol. A18,
pp. 451-453. In radiation-curable coating compositions, the novel
stabilisers can also be employed without the addition of sterically
hindered amines.
[0229] The coating compositions according to the invention can be
applied to any desired substrates, for example to metal, wood,
plastic or ceramic materials. They are preferably used as base
coats in the finishing of automobiles. If the topcoat comprises two
layers, of which the lower layer is pigmented and the upper layer
is not pigmented, the novel compositions can be used preferably for
the lower layer.
[0230] The novel coating compositions can be applied to the
substrates by the customary methods, for example by brushing,
spraying, pouring, dipping or electrophoresis; see also Ullmann's,
Vol. A18, pp. 491-500.
[0231] Depending on the binder system, the coatings can be cured at
room temperature or by heating. The coatings are preferably cured
at 50-150.degree. C., and in the case of powder coatings or coil
coatings even at higher temperatures.
[0232] The coating compositions can comprise an organic solvent or
solvent mixture in which the binder is soluble. The coating
composition can otherwise be an aqueous solution or dispersion. The
vehicle can also be a mixture of organic solvent and water. The
coating composition may be high-solids paint or can be solvent-free
(e.g. a powder coating material). Powder coatings are, for example,
those described in Ullmann's, A18, pp. 438-444. The powder coating
material may also have the form of a powder-slurry (dispersion of
the powder preferably in water).
[0233] The above-mentioned coating compositions or disperse systems
may additionally contain fillers, such as calcium carbonate,
silicates, glass fibers, glass beads, talc, kaolin, mica, barium
sulphate, metal oxides and hydroxides, carbon black, graphite, wood
powders, powders and fibres of other natural products, synthetic
fibres, plasticisers, lubricants, emulsifiers, pigments, rheology
additives, catalysts, flow auxiliaries, optical brighteners, flame
retardants, or antistatic or blowing agents.
[0234] The following examples illustrate the invention.
EXAMPLES
[0235]
1 Abbreviations: PMDETA N,N,N',N",N"- TREN tris(2-Aminoethyl)-amine
Pentamethyldiethylenetriamine RT Room temperature MBP
Methyl-2-bromopropionate h Hour(s) GPC Gel permeation
chromatography BA n-Butyl acrylate Calc calculated DMAEA
2-Dimethylaminoethyl acrylate PDI Polydispersity index DMAEMA
2-Dimethylaminoethyl M Monomer methacrylate MI Macroinitiator DBU
1,8-Diazabicyclo[2.2.2]undec- L Ligand former 7-ene Me.sub.6TREN
N,N-Dimethyl-N',N'- PTSA p-Toluenesulphonic acid
bis(2-dimethylaminoethyl)- AIBN Azoisobutyronitrile
ethylenediamine.sup.1) CAB Cetyl ammonium bromide
.sup.1)Synthesised by methylation of TREN with formaldehyde
according to Beilstein E IV, Vol. 4, p. 1251; El. anal. calc C:
62.55%, H: 13.12%, N: 24.32%; found C: 62.22%, H: 13.29%, N:
24.54%.
1 Dispersions and Pigmented Coatings Containing Block Copolymers or
Comb Polymers Prepared By ATRP
1.1 Preparation of Polymers
1.1.1 Poly-n-butylacrylate with Terminal Br-Groups By the ATRP
Method without the Addition of Solvent
([M]:[I]:[CuBr]:[L]=110:1:0.6:0.6)
[0236] 600.00 g (4.68 mol) BA (BASF, techn. quality) and 3.65 g
(25.5 mmol) CuBr (Fluka, purified by treatment with acetic acid)
are added to a 1500 ml round flask equipped with a mechanical
stirrer. The air is removed from the flask by stirring and
evacuating and rinsing with nitrogen 3 times. 4.42 g (5.3 ml, 25.5
mmol) PMDETA are added through the rubber sealing with a syringe.
The mixture is homogenised by stirring, evacuated again and rinsed
with nitrogen 3 times. After addition of 7.10 g (4.7 ml, 42.5 mmol)
MBP (initiator) with a syringe and heating up to 90.degree. C. in
the oil bath the exothermal polymerisation reaction is started. The
temperature rises quickly and is controlled at a level of
100-105.degree. C. (ice bath). The mixture is polymerised for 2 h.
After this time the conversion of the monomer reaches 90%, as
determined by .sup.1H-NMR-analysis (CDCl.sub.3). The reaction
mixture is cooled to room temperature and 500 ml ethyl acetate and
440 g neutral aluminum oxide (Aloxo for chromatography, Merck) are
added in 2 portions. After stirring the mixture for 1 h at room
temperature, filtration and drying in the rotary evaporator at
80.degree. C. and additional drying with a vacuum pump, 489.9 g
(90%) of a viscous polymer is obtained.
[0237] GPC (THF, PS-standards): M.sub.n: 13780, M.sub.w: 15640,
PDI: 1.13 (M.sub.n(calc): 12670);
[0238] Elementary analysis:
2 C H Br Calc 65.11 9.98 0.62 Found 65.14 9.39 0.48
1.1.2 Block Copolymer of n-butyl Acrylate and DMAEA by ATRP
([M]:[I]:[CuBr]:[L]=14.4:1:0.5:0.5)
[0239] 120.00 g poly-n-butyl acrylate, prepared as described above
(1.1.1) and 0.62 g (4.35 mmol) CuBr (Fluka, purified by treatment
with acetic acid) are added to a 350 ml round flask equipped with a
mechanical stirrer. The air is removed from the flask by stirring,
evacuating and rinsing 3 times with nitrogen. The mixture is
stirred and 17.95 g (19.2 ml, 125 mmol) DMAEA (BASF, technical
quality) and 1.0 g (1.18 ml, 4.35 mmol) Me.sub.6TREN are added
through the rubber sealing with a syringe. The mixture is made
homogeneous by stirring, and the slightly exothermal polymerisation
reaction is started at RT. The mixture is subjected to
polymerisation for 4 h and the conversion is determined by
.sup.1H-NMR-analysis in CDCl.sub.3 (90%). After cooling to room
temperature, 120 ml ethyl acetate and 25 g ALOX are added. The
purified polymer is obtained after stirring for 1 h at room
temperature, filtration and drying in the rotary evaporator at
80.degree. C., followed by drying in the vacuum pump. 139.8 g (98%)
of a viscous polymer are obtained.
[0240] GPC (THF/PS standards): M.sub.n: 15480 (calc: 15640),
M.sub.w: 18700; PDI: 1.21;
[0241] Elementary Analysis
3 C H N Br Calc 64.31 9.34 1.24 0.54 Found 65.14 9.52 1.16 0.18
[0242] The pure viscous block copolymer 1.1.2 is dissolved in butyl
acetate at 80% solids to give a clear solution and is used in the
preparation of pigment dispersions.
1.1.3 Block Copolymer P(BA-b-DMAEA) Which is Modified with PTSA
[0243] Analogous to 1.1.2 a block copolymer of BA and DMAEA is
prepared by ATRP.
[0244] GPC (THF, PS-standards): M.sub.n: 7050, M.sub.w: 8670, PDI:
1.23 (M.sub.n(calc): 7340);
[0245] .sup.1H-NMR (CDCl.sub.3): 80 mol % BA, 20 mol % DMAEA
(taking into account the GPC results of the PBA-precursor):
.about.42.5 units of BA and 12 units of DMAEA).
[0246] Elementary Analysis:
4 C H N Br Calc 63.31 9.28 2.44 1.14 Found 63.63 9.31 2.07 0.49
[0247] 80 g of the above-mentioned block-copolymer (containing 118
mmol N) is diluted with 39.1 ml butyl acetate solution and stirred
at room temperature in a 350 ml round flask equipped with a
mechanical stirrer. 11.26 g (59.2 mmol, corresponding to 50%
neutralisation of the amines) PTSA (Fluka, purum), dissolved in 30
ml hot n-butyl acetate (Fluka, purum) is slowly added and the
reaction mixture stirred during 1 h. 144 g of a slightly
yellow-orange viscous solution is obtained. The solution of the
modified copoymer 1.1.3 with solids content of 60% is used without
further purification.
[0248] Analysis of the modified copolymer:
[0249] GPC (DMF, PS-standards): M.sub.n: 9590, M.sub.w: 11500, PDI:
1.20 (M.sub.n(calc): 8200).
1.1.4 Poly-n-butylacrylate Macromonomer(M.sub.n: 13530) with
Terminal Methacrylate Group
[0250] 1282 g (10.0 mol) n-butylacrylate (BASF, techn.) and 9.7 g
(68 mmol) CuBr (Fluka, purified by treatment with acetic acid) are
added to a 2500 ml round flask equipped with a mechanical stirrer.
The air is removed from the flask by stirring and evacuating and
rinsing with nitrogen 3 times. 21.4 g (137 mmol) of the ligand
precursor 2,2'-Bipyridyl (Fluka, puriss p.a.), dissolved in 143 ml
DMF (Fluka, puriss p.a.) are added under nitrogen. The mixture is
evacuated and rinsed with nitrogen 3 times and homogenised by
stirring at 50.degree. C. After the addition of 15.2 g (10.1 ml, 91
mmol) MBP (initiator, Fluka purum) with a syringe and heating up to
110.degree. C. in the oil bath the exothermal polymerisation
reaction is started. The temperature rises quickly and is
controlled at a level of 110-116.degree. C. (ice bath). The mixture
is polymerised for 4 h. After this time the conversion of the
monomer reaches 90%, determined by .sup.1H-NMR-analysis in
CDCl.sub.3. The mixture is cooled to 80.degree. C. and 400 ml ethyl
acetate is added. After cooling to room temperature and stirring
for 1 h the mixture is filtered to remove the Cu-complex. The
filtered solution is directly used for the methacrylate
functionalisation: 9.38 g (9.24 ml, 109 mmol) methacrylic acid
(Fluka, purum) is added, followed by 16.59 g (109 mmol) DBU (Fluka,
purum) and the mixture stirred for 20 h at room temperature. The
mixture is filtered, stirred with 200 g silicagel and filtered
again to remove all of the DBU-hydrobromide formed. The final
macromonomer is obtained after drying in the rotary evaporator at
100.degree. C. with a vacuum pump. 1130.3 g of a yellow, viscous
polymer is obtained (97%, taking into account the 90% polymer
conversion).
[0251] GPC (THF, PS-standards): M.sub.n: 13530, M.sub.w: 16900,
PDI: 1.25;
[0252] Elementary analysis:
5 C H Br Calc 65.47 9.41 0.0 Found 65.73 9.04 <0.3
[0253] Titration of double bonds: Calculated: 0.074 meq/g, found:
0.086 meq/g.
1.1.5 Comb Copolymer by Copolymerisation of Poly-n-butylacrylate
Macromonomer of Example 1.1.4 with DMAEMA
[0254] 230 g (17 mmol) of the macromonomer 1.1.4, 64.87 g (413
mmol) DMAEMA (Aldrich, 98%), 220.3 ml butyl acetate (Fluka, purum)
and 5.90 g (35.9 mmol) AIBN (Fluka, purum) are mixed in a 1500 ml
round flask equipped with a mechanical stirrer. The air is removed
from the flask by stirring, evacuating and rinsing with nitrogen 3
times. The mixture is heated on an oil bath to 80.degree. C. and
polymerised for 4 h. The conversion of monomers, determined by
.sup.1H-NMR-analysis in CDCl.sub.3, is almost quantitative. After
cooling to room temperature 484.2 g of a transparent, slightly
yellow, viscous polymer solution is obtained with 63.6% solid
content. This solution of the copolymer 1.1.5 is used without
further purification.
[0255] GPC (THF, PS-standards): M.sub.n: 21600, M.sub.w: 46600,
PDI: 2.16;
6 C H N Calc 64.52 9.45 2.07 Found 64.26 9.03 2.14
[0256] Elementary analysis:
1.1.6 Comb Copolymer Modified by Neutralisation of 50 mol % of the
Amino Groups in the Copolymer 1.1.5 with PTSA
[0257] 78.65 g of the copolymer solution according to 1.1.5
(corresponding to 50 g pure graft copolymer) is stirred at
80.degree. C. in a 350 ml round flask equipped with a mechanical
stirrer. 7.28 g (38.3 mmol, 0.5 equ.) PTSA (Fluka, purum),
dissolved in 32.5 ml hot butyl acetate (Fluka, purum), is slowly
added. The reaction mixture is stirred for 2 h. After cooling to
room temperature, the yellow viscous solution of the comb copolymer
1.1.6 with a solids content of 50% is used without further
purification.
1.1.7 Poly-n-butylacrylate Macromonomer of Molecular Weight
M.sub.n: 6930 with Terminal Methacrylate Group
[0258] 1000 g (7.8 mol) BA (BASF, techn.), 6.71 g (46.8 mmol)
Cu(I)Br (Fluka, purified by treatment with acetic acid), 1.16 g
(5.2 mmol) Cu(II)Br.sub.2 (Fluka, puriss p.a.) and 275 ml acetone
(Fluka puriss p.a.) are added to a 2500 ml round flask equipped
with a mechanical stirrer. The air is removed from the flask by
stirring, evacuating and rinsing with nitrogen 3 times. 9.01 g
(10.9 ml, 52 mmol) PMDETA (Fluka, purum) are added through the
rubber sealing with a syringe. The mixture is homogenised by
stirring, evacuated and rinsed again with nitrogen 3 times. After
the addition of 21.71 g (14.5 ml, 130 mmol) MBP (initiator) with a
syringe and heating up to 60.degree. C. in the oil bath the
slightly exothermal polymerisation reaction is started. The
temperature rises to 65.degree. C. and is controlled at a level of
60-65.degree. C. (ice bath). The mixture is polymerised for 6 h.
After this time the conversion of the monomer reaches 75%, as
determined by .sup.1H-NMR-analysis in CDCl.sub.3. The mixture is
cooled to room temperature and 200 ml ethyl acetate and 200 g
neutral ALOX (for chromatography, Merck) are added. The mixture is
stirred for 1 h at room temperature and filtrated. The filtered
solution is directly used for the methacrylate functionalisation:
13.43 g (13.2 ml, 156 mmol) Methacrylic acid (Fluka, purum) is
added followed by 23.75 g (156 mmol) DBU (Fluka, purum). The
mixture is stirred for 20 h at room temperature, filtered, stirred
with 200 g silicagel and filtered again to remove all of the
DBU-hydrobromide formed. The macromonomer is obtained after drying
for 1 h in the rotary evaporator at 90.degree. C. 763 g (99%,
taking into account the 90% polymer conversion) of a yellow,
viscous polymer is obtained.
[0259] GPC (THF, PS-standards): M.sub.n: 6930, M.sub.w: 7650, PDI:
1.10;
[0260] Elementary analysis:
7 C H Br Calc 65.35 9.38 0.0 Found 64.91 9.31 <0.3
[0261] Titration of double bonds: calc: 0.140 meq./g, found: 0.144
meq./g.
1.1.8 Comb Copolymer By Copolymerisation of Poly-n-butylacrylate
Macromonomer 1.1.7 with DMAEMA
[0262] 230 g (33.2 mmol) macromonomer 1.1.7, 68.7 g (437 mmol)
DMAEMA (Aldrich, 98%), 230 ml butyl acetate (Fluka, purum) and 5.97
g (36.4 mmol) AIBN (Fluka, purum) are mixed in a 1500 ml round
flask equipped with a mechanical stirrer. The air is removed from
the flask by stirring, evacuating and rinsing with nitrogen 3
times. The mixture is heated on an oil bath to 80.degree. C. and
polymerised for 4 h. The conversion of monomers, determined by
.sup.1H-NMR-analysis in CDCl.sub.3, is almost quantitative. After
cooling to room temperature, 494 g of a transparent, slightly
yellow, viscous polymer solution is obtained with 62.5% solid
content. This solution of copolymer 1.1.8 is used without further
purification.
[0263] GPC (THF, PS-standards): M.sub.n: 18000, M.sub.w: 52700,
PDI: 2.92;
[0264] Elementary analysis:
8 C H N Calc 64.42 9.43 2.20 Found 63.55 9.04 2.09
1.2 Modifying Agents Used as Salt Forming Compounds According to
the Process Variants .alpha.) or .beta.)
1.2.1
3-(2H-Benzotriazol-2-yl)-5-sec-butyl-4-hydroxybenzenesulphonic
acid
[0265] 17
1.2.2 Uvinul.RTM. MS40:
[0266] 18
1.2.3 1-(Benzothiazol-2-ylthio)-succinic acid
[0267] 19
1.3 Preparation and Testing of Pigment Dispersions Containing
Modified Block Copolymers or Modified Comb Polymers
[0268] The performance of the different ATRP copolymers modified
with the different salt forming compounds is evaluated in millbase
preparations and corresponding coating formulations made
therefrom.
1.3.1 Preparation and Testing of the Millbase
[0269] A polyester millbase formulation is prepared according to
the following prescripition:
9 Dynapol .RTM. H700-08 11.99 g Pigment 9.60 g Dispersant (60%
active) 3.20 g Xylene/Butylacetate 40/60 55.21 g Total 80.00 g
[0270] Dependent on the active content of the different dispersants
used and the optional addition of acids, the formulation is
slightly adjusted by solvents and DYNAPOL resin in order to adjust
a pigment binder ratio of about 1. The components are ground for 4
h with glass beads on a shaking machine (DIN 5323B-13). The
viscosity of the millbase after grinding is measured at different
shear rates with a cone-plate rheometer (Paar Physica UDS 200).
Good dispersant efficiency can be seen by lowering of the millbase
viscosity especially at mid to low shear rates, e.g. at a shear
rate of 16. Two different processes for the preparation of the
millbase may be used:
[0271] Process .alpha.)
[0272] The modified copolymer dispersant is prepared separately in
the form of a concentrate additive solution. The additive solution
is added together with the other components of the millbase and
then ground for 4 hours.
[0273] Process .beta.)
[0274] The aminic block copolymer or comb polymer and the
corresponding salt forming compound are added separately to the
other components of the millbase and then ground for 4 h. In this
case, the modified copolymer is formed in-situ during the grinding
of the millbase.
1.3.2 Preparation and Testing of a Full Shade Coating of Type
Polyester/Melamine/CAB
[0275] Full shade formulations with a pigment content of 5% are
prepared from the polyester-millbase according to the following
general prescription:
10 Millbase 30.00 g Dynapol .RTM. H700-08 12.42 g CAB 531.1 18.97 g
Maprenal .RTM. MF650 2.12 g O/S Zirkonium 6 0.36 g
Xylene/Butylacetate 40/60 8.13 g Total 72.00 g
[0276] The fullshade formulation is drawn down on a glass plate,
dried at room temperature and cured at 130.degree. C. for 30 min.
Gloss measurements are made on the cured coatings. High gloss
indicates a good dispersion of the pigment in the final
coating.
[0277] 2 Results
[0278] The following Table shows the composition of the dispersants
and the results of application tests in a typical millbase
formulation and a fullshade coating formulation made therefrom. The
formulations containing modified copolymers of the invention are
compared to reference formulations containing other pigment
dispersants made by controlled free radical polymerisation.
Application results are based on the commercial pigment
Iragazin.RTM. DPP Rubine TR in a coating system
polyester/melamine/CAB. The results demonstrate that the
dispersants modified with the different salt forming compounds of
the invention possess superior rheology of the millbase and/or
improved gloss of the full shade coating.
11TABLE Application Results with IRGAZINE RUBINE TR in Coating
System Polyester/Melamine/CAB Dispersant Molecular Modi- Process
Type/ Millbase Viscosity Millbase at Full Shade Dispersant Polymer
Weight fying theor. Degree % % Shear Rate: Coating No.
Composition.sup.1) Tested GPC.sup.2) Agent of Neutralisation
Copolymer.sup.3) Modifier.sup.4) 1 16 128 1024 Gloss 20.degree.
1.sup.5) P(BA-b-DMAEMA) Polymer Mw = 18700 -- .alpha. 20.0 -- 13000
4170 698 116 37 87-13 1.1.2 Mn = 15480 PD = 1.21 2.sup.5)
P(BA-b-DMAEA) Polymer Mw = 8670 pTSA 17.7 2.3 23100 3540 547 96 55
78-22 1.1.3 Mn = 7050 PD = 1.23 3.sup.6) P(BA-b-DMAEMA) Polymer Mw
= 18700 Acid 1 .beta. .apprxeq. 34% 16.0 4.0 6340 764 141 36 67
87-13 1.1.2 Mn = 15480 PD = 1.21 4.sup.6) P(BA-b-DMAEA) Polymer Mw
= 18700 Acid 1 .beta. .apprxeq. 76% 13.0 7.0 7650 815 159 38 76
87-3 1.1.2 Mn = 15480 PD = 1.21 5.sup.6) P(BA-b-DMAEA) Polymer Mw =
18700 Acid 2 .beta. .apprxeq. 40% 16.0 4.0 17800 3040 468 85 74
87-13 1.1.2 Mn = 15480 PD = 1.21 6.sup.6) P(BA-b-DMAEA) Polymer Mw
= 18700 Acid 2 .beta. .apprxeq. 89% 13.0 7.0 18600 2180 337 64 70
87-13 1.1.2 Mn = 15480 PD = 1.21 7.sup.6) P(BA-b-DMAEA) Polymer Mw
= 18700 Acid 3 .beta. .apprxeq. 50% 18.8 1.2 16700 2220 353 69 78
87-13 1.1.2 Mn = 15480 PD = 1.21 8.sup.6) P(BA-b-DMAEA) Polymer Mw
= 18700 Acid 3 .beta. .apprxeq. 100% 17.7 2.3 14500 1850 309 64 79
87-13 1.1.2 Mn = 15480 PD = 1.21 9.sup.5) P(BA-g-DMAEMA) Polymer Mw
= 46600 PTSA .alpha. 17.5 2.5 33200 4020 607 111 59 78-22 1.1.6 Mn
= 21600 PD = 2.16 10.sup.6) P(BA-g-DMAEMA) Polymer Mw = 46600 Acid
3 .beta. .apprxeq. 100% 16.6 3.4 25800 2970 455 87 66 78-22 1.1.5
Mn = 21600 PD = 2.16 11.sup.6) P(BA-g-DMAEMA) Polymer Mw = 52700
Acid 3 .beta. .apprxeq. 100% 16.5 3.5 20200 2710 420 77 69 77-23
1.1.8 Mn = 18000 PD = 2.92 .sup.1)Monomer composition given in wt
%; BA = butyl acrylate, DMAEMA = dimethylaminoethyl methacrylate,
DMAEA = dimethylaminoethyl acrylate; .sup.2)Molecular weights
determined with the non-modified block copolymers;
.sup.3)Concentration of block copolymer is relative to the pigment;
.sup.4)Concentration of modifier is relative to the pigment;
.sup.5)Comparative Examples; .sup.6)Modified Block Copolymers
* * * * *