US 20070293692A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2007/0293692 A1
Pirrung et al. (43) Pub. Date: Dec. 20, 2007
(54) PHOSPHORIC ACID ESTERS AND THEIR Publication Classification
USE AS WETTING AND DISPERSING
AGENT (51) Int. Cl.
C07F 9/09 (2006.01)
(52) U.S. Cl. ................................................................ 558770
(76) Inventors: Frank Oliver Heinrich Pirrung, Weil
am Rhein (DE); Arend Noordam, (57) ABSTRACT
Oranjewoud (NL); Petrus Johannes The invention relates to a phosphoric acid ester and salts
Harbers, Sintojohannesga (NL); thereof of the general formula (I), wherein A is a monohy
Elizabeth Maaike Loen, Leeuwarden droxyl residue derived from C-Co-alkyl-(AO)x-OH or
(NL); Aron Eliane Munneke, Acyl-(AO)x-OH, or C-Co-alkyl-(AO)x-(HA)y-OH or
Heerhugowaard (NL) Acyl-(AO)x-(HA)y-OH, or C-Co-alkyl-(AO)x-(AA
AO)y-OH or Acyl-(AO)x-(AA-AO)y-OH; or MO-(HA)y-
Correspondence Address: OH or MO-(AA-AO)y-OH; wherein Acyl is an aromatic
JoAnn Villamizar carboxylic acid residue or a saturated or unsaturated fatty
Patent Department acid residue, AO is a polyC-C alkyleneglycol residue, HA
540 White Plains Road is a hydroxycarboxylic acid or a lactone thereof, AA is a
P.O.BOX 2005 dicarboxylic acid, MO is a monoalcohol. X is 1 to 250, y is
Tarrytown, NY 10591-9005 (US) 1 to 250, B is a mono-, di-, or tri- or polyhydroxy di-, tri or
multi-carboxylic acid residue which is linked via the
(21) Appl. No.: 10/590,467 hydroxy group to the phosphoric acid and via one of the
carboxylic acid groups to the monohydroxyl residue A, the
(22) PCT Filed: Feb. 28, 2005 remaining carboxyl acid group(s) is/are free or is/are esteri
fied with a further monohydroxyl residue A, resulting in
(86). PCT No.: PCT/EP05/50830 branched esters; n is 1-2; m is 1-4. The phosphoric acid
esters are used as wetting agent or dispersants.
S 371(c)(1),
(2), (4) Date: May 15, 2007 (I)
O

(30) Foreign Application Priority Data

Mar. 8, 2004 (EP)........................................ O4100927.5
US 2007/0293692 A1 Dec. 20, 2007

PHOSPHORIC ACID ESTERS AND THEIR USE AS organic and inorganic pigments, as well as for fillers and
WETTING AND DISPERSINGAGENT extenders in aqueous and non-aqueous systems.
0001. This invention relates to phosphoric acid esters and 0009. The invention relates to a phosphoric acid ester and
their salts and to the use of these phosphoric acid esters and salts thereof of the general formula I,
salts as dispersants.
0002 To introduce solid substances, such as pigments, O
into liquid media, high mechanical forces are necessary.
This depends to a large extent on the Solid Substance's wet
ability by the surrounding medium, as well as on the affinity
for this medium. In order to reduce these dispersing forces,
it is conventional to use dispersing agents, which facilitate wherein
incorporating the Substances. This mostly concerns Surface
active agents or Surfactants, of anionic or cationic or non A is a monohydroxyl residue;
ionic structure. In relatively low amounts of addition, these
agents are either applied directly to the Solid Substance or B is a mono-, di-, tri- or polyhydroxy di-, tri- or multi
added to the dispersing medium. Through Such a surfactant, carboxylic acid residue which is linked via the hydroxy
the energy required for the dispersion is considerably group to the phosphoric acid and via one of the carboxylic
reduced. acid groups to the monohydroxyl residue A, the remaining
carboxylic acid group(s) is/are free or is/are esterified with
0003. Further, it is known that such solid substances, after a further monohydroxyl residue A, resulting in branched
dispersion, tend to reagglomerate, which nullifies the ini esters;
tially induced dispersing energy and leads to serious prob
lems. This phenomenon can be explained by inter alia n is 1-2;
London/van der Waals forces, by which the solid sub m is 1-4.
stances are mutually attracted. In order to nullify these
attractive forces, adsorption layers should be provided on 0010. An essential feature of the inventive phosphoric
the Solid Substances. This occurs through the use of Such acid esters is the presence of a mono-, di-, tri- or polyhy
surfactants or polymers. droxy di-, tri- or multi-carboxylic acid residue B).
0004. During and after the dispersion, however, there 0011. With regard to B it is important that either at least
arises an interaction of the Surrounding medium with the one free carboxylic acid group is present or that at least one
Solid particle, so that desorption of the Surfactant can arise branching center results by esterifying the free carboxylic
in exchange for the Surrounding medium present in a higher acid.
concentration. However, in most cases this Surrounding 0012. If a tri- or multi-carboxylic acid is chosen, two or
medium is incapable of building up Such stable adsorption more free carboxylic acid groups are present. It is possible
layers, so that the entire system flocculates. This is evi that the free carboxylic acid groups remain free, are fully
denced by inter alia an increase of the Viscosity in liquid esterified resulting in branched compounds or are partly
systems, loss of gloss, color shifts in paints and coatings, esterified resulting in branched compounds having a free
insufficient development of coloring power in pigmented carboxylic acid group. The free carboxylic groups can be
plastics and lacquers, as well as a decrease of the mechanical transformed into a salt in all cases.
strength in reinforced plastics.
0005. The European Patent EP 0417 490 B1 (Byk-Che 0013 The mono-, di-, tri- or polyhydroxy di-, tri- or
mie) describes phosphoric acid esters and their salts corre
multi-carboxylic acid B to be used may, for example, be
sponding to the formula (HO). PO—(OR), wherein R is tartaric acid, malic acid, citromalic acid (2-methylmalic
acid), 3-hydroxy-3-methylglutaric acid, 5-hydroxyisoph
an aliphatic, cycloaliphatic and/or aromatic residue contain thalic acid, ascorbic acid or citric acid, preferably malic acid
ing at least one ether oxygen (-O ) and at least one (hydroxybutane dicarboxylic acid) or citric acid.
carboxylic acid ester group (-COO-) and/or urethane
group (-NHCOO ) without Zerewitinoff hydrogen. As an 0014) A multi-carboxylic acid is any acid that comprises
example a compound of the following formula: Alkyl more than three carboxylic acid groups, e.g. hydroxyben
(O(CH),), O C=O(CH.),), O P=O(OH), is dis Zene-1,2,4,5-tetracarboxylic acid.
closed.
0015 The monohydroxyl residue A may comprise a
0006. The European Patent EP765356 B1 (Zeneca) polyether chain, a polyester chain or a mixed polyether
describes a dispersant obtainable by reacting a polyethylene polyester chain, whereby the respective groups can be
glycol with a hydroxycarboxylic acid and/or with an alky arranged in blocks or randomly.
lene oxide to form a polymeric diol and phosphating the
diol. 0016 Preferably Acomprises a polyC-C alkylene gly
colmonoether and/or a poly C-C alkylene glycol monoester
0007 Phosphoric acid esters having a free carboxyl of a carboxylic acid.
group, or phosphoric acid esters which are branched via the 0017 Suitable polyC-C alkylene glycolmonoethers are
free carboxylic acid group are not described. C-Coalkylethers, preferably methylethers (MePEG),
0008. It is an object of the present invention to provide a (MePPG), butylethers (BuPPG), alkylphenol ethers (APE),
dispersant having improved dispersing properties for C-C fatty alcohol ethers or Co-Cs oxoalcohol ethers.
US 2007/0293692 A1 Dec. 20, 2007

0018 PolyC-Calkylene glycol esters of carboxylic wherein

acids are, for example, polyC-C alkylene glycol monolau
rate, polyC-C alkylene glycol monostearate, polyC MO is a monoalcohol as described above,
Calkylene glycol monooleate, and polyC-Calkylene gly HA is a hydroxycarboxylic acid or a lactone thereof as
col benzoate.
described above,
0019. The polyC-Calkylene glycolmonoether and/or AA is a dicarboxylic acid as described above,
the polyC-C alkylene glycol monoester may be esterified
with B or may be linked to B via polyester units derived AO is a polyC-C alkyleneglycol residue as described
from a hydroxy-carboxylic acid or a lactone thereof HA above.
and/or via units derived from a dicarboxylic acid AA
which is linked to a diol with a C-C-alkylene oxide AO 0027) Further units may be included in the monohydroxyl
Structure. compound A Such as urethane or amide units/functional
groups.
0020 Thus, the following monohydroxyl compounds A
may be obtained 0028. The ratio of the molecular weight of unit A to B
is 1.5:1 to 8:1, preferably 2:1 to 5:1.
0029. The preferred phosphoric acid esters are those
derived from Me-PEG-OH having a molecular weight from
250 to 750. It is also preferred that e-caprolactone is present
as hydroxy carboxylic acid. The preferred hydroxy-dicar
boxylic acid is malic acid.
0030 The phosphoric acid ester of the formula I can be
wherein made by known esterification reactions. A polyalkylene
C-Co-alkyl is a straight chain or branched hydrocarbon glycolether, preferably Me-PEG-OH is reacted at elevated
residue, temperatures, for example at 100-250° C., with a mono-, di-,
tri- or polyhydroxy di-, tri- or multicarboxylic acid in the
acyl is an aromatic carboxylic acid residue Such as, for presence of an esterification catalyst Such as, for example,
example, a benzoic acid residue or a saturated or dibutyl tin dilaurate, tetra-alkyltitanate, p-toluene sulfonic
unsaturated fatty acid residue such as, for example, acid or ferrous acetylacetonate.
lauric acid, myristic acid, Stearic acid, arachic acid, 0031) If a hydroxycarboxylic acid unit is present, such as,
oleic acid, linoleic acid and the like, for example, caprolactone, polyalkylene glycolether is first
AO is a polyC-Calkyleneglycol residue such as, for esterified with the hydroxycarboxylic acid and then with the
example, polyethylene glycol (PEG), polypropylene mono-, di-, tri- or polyhydroxy di-, tri- or multi-carboxylic
glycol (PPG), polybutylene glycol, including a block acid.
copolymer of ethylene oxide and propylene oxide, 0032. The catalyst is generally used in an amount of
HA is a hydroxycarboxylic acid or a lactone thereof such 0.005-0.5 mole per 100 moles of the hydroxy di- or tricar
as, for example, lactic acid, glycolic acid, 6-hydroxy boxylic acid. An inert solvent may be added, however, the
hexanoic acid, 12-hydroxy Stearic acid, 12-hydroxy esterification takes place preferably in the absence of a
solvent.
dodecanoic acid, 5-hydroxydodecanoic acid, 5-hy
droxydecanoic acid, 4-hydroxy decanoic acid, or 0033 Phosphoric acid esters of the formula I are obtained
lactones such as B-propiolactone, Y-butyrolactone, by reaction of one of the hydroxyl groups of the mono-, di-,
8-valerolactone or e-caprolactone, including a block tri- or polyhydroxy di-, tri- or multi carboxylic acid residue
copolymer Such as, for example, of e-caprolactone/8- of the block copolymer obtained above with a phosphorus
Valerolactone, compound which forms phosphoric esters, in a manner
known per se. The phosphorus compound is preferably a
AA is a dicarboxylic acid Such as, for example Succinic polyphosphoric acid or P-Os. If POs is used as phosphoric
acid, maleic acid, malonic acid, glutaric acid, adipic acid a mixture of the mono- and di-ester is obtained.
acid, phthalic acid, sebacic acid, oxalic acid, diglycolic
acid and acid anhydrides thereof, 0034 Salts of the phosphoric acid ester can be obtained
by neutralisation with an alkali hydroxide, with ammonia,
X is 1 to 250, preferably 2 to 50, more preferably 5 to 15, with an amine, an alkanolamine or a quaternary ammonium
compound.
y is 1 to 250, preferably 2 to 50, more preferably 2 to 15.
0035) It is another aspect of the invention to provide
0024. It is also possible to start the polyester unit with a mixtures of the phosphoric acid esters of the formula I with
monoalcohol suitably with 4 to 30, preferably with 4 to 20 phosphoric acid esters of polyC-C alkylene glycolmonoet
carbon atoms, such as n-butanol and 2-ethyl-1-hexanol, hers and/or a polyC-Calkylene glycol monoester of a
cetylalcohol, oleyl alcohol, linoloyl alcohol, oxo alcohols, carboxylic acid or with other commercially available wet
cyclohexanol, phenol, phenyl ethanol and benzylalcohol. ting and dispersing agents such as for example with EFKA
0.025 Thus, the following monohydroxyl compounds A 5066, EFKA-5070, EFKA-5207, EFKA-5244, EFKA-6220,
may be obtained EFKA-6225, EFKA-6230, EFKA-8503, EFKA-8510,
EFKA-8511, EFKA-8530, EFKA-8531, EFKA-8532 and
the like.
US 2007/0293692 A1 Dec. 20, 2007

0.036 Preferred are mixtures of the phosphoric acid esters During several hours, reaction water was removed from the
of the formula I with phosphoric esters of polyC reactor until an acid value of 105-115 mg KOH/g was
Calkylene glycolmonoethers in wt ratio of 0.01 to 99.99; reached. Subsequent cooling of the light yellow liquid to 60°
preferably 10 to 90, more preferably 50 to 50. C. was followed by slow addition of polyphosphoric acid
0037. The invention also relates to the use of the phos (tetraphosphoric acid (PPA 116), 20.8 g., 0.33 equivalents)
phoric acid esters of the formula I as dispersants and as under vigorous stirring. This mixture was stirred at 100° C.
dispersion stabilizers. The dispersants according to the for one hour. No solvent was added during the whole
invention can be used for the production of water- and process. Phosphoric ester A was obtained as a clear, viscous,
Solvent-based coatings and printing inks. Those dispersants, yellowish liquid at room temperature.
which are not water-soluble, may have a self-emulsifying Example 2
effect in water, so that these are suitable for use in water- and Procedure B, Phosphoric Ester B-1
Solvent-based coatings and printing inks as well. Alterna
tively, they can be made fully water-soluble by neutralising Me-(EO), CL-MA-P
the phosphoric and carboxylic ester groups by alkali hydrox 0042. Under a nitrogen atmosphere, polyethyleneglycol
ides, like potassium hydroxide Solution, or amines like monomethylether (MW 350, 44.4 g, 1 equivalent) and
ammonia, dimethylethanolamine and the like. The neutrali caprolactone (28.3 g, 2 equivalents) were placed in a reactor
sation degree is 0.5 to 2 equivalents of neutralising agent per at room temperature and heated to 180° C. Two drops of
dispersant, preferably 0.8 to 1.5 equivalents of neutralising dibutyl tin dilaurate were added as esterification catalyst.
agent. In this connection water- and solvent-based coatings The reaction mixture was stirred for a few hours until a solid
and printing inks, as used herein, also refer to those prod content of >98% was reached.
ucts, which partially comprise organic cosolvents. Pigments
used in this field are the organic and inorganic pigments 0043. The reaction mixture was cooled to 140°C., and
insoluble in the employed liquid, e.g., soot, polycyclic malic acid (16.6 g. 1 equivalent) was added. Subsequently,
pigments, iron oxides, etc. the reaction mixture was heated to 180° C. and during
0038. The dispersants according to the invention can also several hours, reaction water was removed from the equip
be employed in the production of resins comprising Solids ment until an acid value of 60-70 mg KOH/g was reached.
Subsequent cooling of the light yellow liquid to 60° C. was
Such as pigments, fillers and fibres. Such systems are known followed by slow addition of polyphosphoric acid (tetra
as sheet moulding compounds (SMC) or bulk moulding phosphoric acid, 13.8 g., 0.33 equivalents) under vigorous
compounds (BMC) and are based on unsaturated polyester stirring. This mixture was stirred at 100° C. for one hour. No
resins. In the state of the art, these systems must contain a solvent was added during the whole process. Phosphoric
high loading of such solids (typically >250 phr) in order to ester B was obtained as a clear, Viscous, orange liquid, which
achieve the desired physical properties of the final product. slowly solidified at room temperature.
Due to the high viscosity caused by the high solids load,
insufficient wetting of the reinforcing fibres and air entrap Example 3
ment is observed. The use of the dispersants, according to Procedure B, Phosphoric Ester B-2
the invention, lead to a Sufficient reduction in Viscosity to
enhance wetting of the fibres at Such high filler grades. Me-(EO), CL-MA-P
0.039 Examples of extenders and fillers which can be 0044) Under a nitrogen atmosphere, polyethyleneglycol
dispersed are, for example, calcium carbonate, alumina, monomethylether (MW 350, 44.4 g, 1 equivalent) and
aluminium trihydroxide (ATH), sand, china clay, talc, caprolactone (56.6.3 g, 4 equivalents) were placed in a
kaolin, silica, barytes and chalk, glass fibers, glass beads or reactor at room temperature and heated to 180°C. Two drops
metal powders. of dibutyl tin dilaurate were added as esterification catalyst.
The reaction mixture was stirred for a few hours until a solid
0040. It is obvious and conventional to the skilled worker content of >98% was reached.
that these examples represent merely a selection of the
possibilities, which exist and are in no way to be regarded 0045. The reaction mixture was cooled to 140°C., and
as a limitation. malic acid (16.6 g. 1 equivalent) was added. Subsequently,
the reaction mixture was heated to 180° C. and during
EXPERIMENTAL several hours, reaction water was removed from the equip
ment until an acid value of 50-60 mg KOH/g was reached.
General Procedure for Phosphoric Ester Preparation Subsequent cooling of the light yellow liquid to 60° C. was
and Examples followed by slow addition of polyphosphoric acid (tetra
phosphoric acid, 13.8 g., 0.33 equivalents) under vigorous
Example 1 stirring. This mixture was stirred at 100° C. for one hour. No
solvent was added during the whole process. Phosphoric
Procedure A, Phosphoric Ester A ester B was obtained as a clear, Viscous, orange liquid, which
slowly solidified at room temperature.
Example 4
0041 Under a nitrogen atmosphere, polyethyleneglycol Procedure C, Phosphoric Ester C
monomethylether (MPEG 350, MW 350, 65.3 g, 1 equiva
lent) and malic acid (25.0 g, 1 equivalent) were placed in a Me-(EO), CL-CA-P
reactor at room temperature and heated to 180°C. Two drops 0046 Under a nitrogen atmosphere, polyethyleneglycol
of dibutyl tin dilaurate were added as esterification catalyst. monomethylether (MW 350, 43.3 g, 1 equivalent) and
US 2007/0293692 A1 Dec. 20, 2007

caprolactone (28.3 g, 2 equivalents) were placed in a reactor Example 9

at room temperature and heated to 180° C. Two drops of
dibutyl tin dilaurate were added as esterification catalyst. Phosphoric Ester J-3
The reaction mixture was stirred for a few hours until a solid
content of >98% was reached. (Me-(EO),), CA-P
0047 The reaction mixture was cooled to 140°C., and 0052 As procedure C, but with a ratio of 2 equiv of
citric acid (23.8 g. 1 equivalent) was added. Subsequently, MPEG 350 to 1 equiv of citric acid, fully esterified in the
the reaction mixture was heated to 180° C. and during first step.
several hours, reaction water was removed from the reactor Example 10
until an acid value of 130-140 mg KOH/g was reached.
Subsequent cooling of the light yellow liquid to 60° C. was Phosphoric Ester J-4
followed by slow addition of polyphosphoric acid (tetra
phosphoric acid, 13.8 g., 0.33 equivalents) under vigorous (Me-(EO),), CA-P
stirring. This mixture was stirred at 100° C. for one hour. No
solvent was added during the whole process. Phosphoric 0053 As procedure C, but with a ratio of 3 equiv of
ester C was obtained as a clear, Viscous, brownish liquid at MPEG 350 to 1 equiv of citric acid, fully esterified in the
room temperature. first step.
Example 5 Example 11
Procedure D
Procedure K. Phosphoric Ester K
(Me-(EO))-2-MA-P 0054 Under a nitrogen atmosphere, polyethyleneglycol
0.048. As procedure A or B, but with a ratio of 2 equiv of monomethylether (MW 350, 35 g, 1 equivalent), adipic acid
polymeric monoalcohol to 1 equiv of malic acid, fully (36.5g, 2.5 equivalents) and dipropyleneglycol (33.5g, 2.5
esterified in the first step. equiv) were placed in a reactor at room temperature and
Example 6 heated to 190° C. Two drops of dibutyl tin dilaurate were
0049. In a similar way the following products were added as esterification catalyst. Reaction water was removed
prepared: from this mixture during 6 hours. The resulting yellowish
liquid was cooled to 140° C. and further reacted with malic
acid (13.4g, 1 equiv) and polyphosphoric acid (11.0 g, 0.33
equiv) as indicated in procedure B. Phosphoric ester K was
P-ester Procedure Raw materials* (MW) Equivalents a dark yellow liquid at room temperature.
D (yellow liq) D Me-PEG-OH 500 2 Example 12
E (yellow liq) A. Me-PPG-OH 200 1
F (yellow liq) A B-PPG-OH 1100 1
G (orange liq) B 2-Ethyl-1-hexanol 130 1 Procedure L. Phosphoric Ester L
Caprolactone? 2:3
Valerolactone Mixture of Phosphoric Acid Esters
H (white solid) B Cetyl alcohol 242 1 0055 Under a nitrogen atmosphere, polyethyleneglycol
Caprolactone 7
-1 C Me-PEG-OH 350 2 monolaurate (MW 600, 24 g, 1 equiv) and caprolactone
(off-white paste) Caprolactone 6 (13.7 g., 3 equiv) were placed in a reactor at room tempera
-2 C Me-PEG-OH 350 3
(yellowish paste) Caprolactone 9 ture and heated to 180°C. Two drops of dibutyl tin dilaurate
-3 C Me-PEG-OH 350 2 were added as esterification catalyst. The reaction mixture
(yellowish liq) was stirred for a few hours until a solid content of >98% was
4 C Me-PEG-OH 350 3 reached. The reaction mixture was cooled to 140° C., and
(brownish liq) malic acid (5.36 g. 1 equiv) was added. Subsequently, all
*PEG: polyethylene glycol was heated to 180°C. and during several hours, and reaction
*PPG: polypropylene glycol water was removed from the reactor until an acid value of
50-60 mg KOH/g was reached. The contents of the reactor
Example 7 were cooled down to 60° C., and polyethylene glycol
monoalkyl ether (Lutensol TO 8TM (BASF) MW ca. 540,
Phosphoric Ester J-1 21.6 g. 1 equiv) was added. After homogeneous stirring, this
(Me-(EO), CL)-CA-P was followed by slow addition of polyphosphoric acid
0050. As procedure C, but with a ratio of 2 equiv of (Tetraphosphoric acid, 9.05 g, 0.66 equivalents) under vig
polymeric monoalcohol to 1 equiv of citric acid, fully orous stirring. The resulting mixture was stirred at 100° C.
esterified in the first step. for one hour. Phosphoric ester L was obtained as a clear,
viscous, yellowish liquid that solidified to a slightly yellow
Example 8 paste at room temperature.
Phosphoric Ester J-2 Example 13
(Me-(EO), CL)--CA-P
Procedure M
0051. As procedure C, but with a ratio of 3 equiv of
polymeric monoalcohol to 1 equiv of citric acid, fully 0056. As procedure A or B. Instead of polyphosphoric
esterified in the first step. acid, phosphorous pentoxide was used in the last step of the
US 2007/0293692 A1 Dec. 20, 2007

synthesis (1 equiv on 3 equiv of polymeric monoalcohol) to

obtain the 1:1 mixture of the mono and the diphosphoric
esters. Reaction conditions: addition of POs at 50° C. to the Formulation 2
monoalcohol under vigorous stirring, followed by slow
increase of temperature to 80° C. and stirring for 1 hour. MEG 04.75 wt % (Mono ethylene glycol)
Dem. Water 16.88 wt %
Bentone EW 00.20 wt % antisettling agent, Rheox Inc..)
AMP 90 00.15 wt % (amine neutralisation, Angus Chemie)
P-ester Procedure Raw materials* (MW) Equivalents EFKA-2SSO 00.20 wt % (defoamer, EFKA Additives)
Parmetol A28 S 00.20 wt % (fungicide, Schulke & Mayr GmbH)
M (light brown liq) M Me-PEG-OH 500 1 Kulubrite 5 76.19 wt % (CaCO, Idwala Ind. Holdings (Pty)
N (white paste) M Me-PEG-OH 350 1 Ltd.)
Caprolactone 2 Phosphoric ester O1.43 wt %
O (yellowish solid) M 1-Dodecanol 186 1
Caprolactone 3
*PEG: polyethylene glycol 0061 Preparation: the samples according to above for
mulation were dispersed with a dissolver at 4000 rpm for 2
minutes. Subsequently the samples were cooled to room
Example 14 temperature for 24 h and measured on a Haake Rheometer
RS 600.
Phosphoric Ester P 0062) The viscosity measurements are performed at a
0057 Phosphoric ester B (100 g, MW ca. 775, 1 equiv) shear rate between 5 and 50.1/s)
was dispersed in 125 ml of demineralized water alt room
temperature. To this mixture, a KOH solution (25% in water,
26g, 0.9 equiv) was slowly added during 30 minutes, while Formulation 1
the temperature rose to 40°C. The resulting clear solution
was stirred for another 30 minutes at 40° C. This yielded Viscosity InPas
phosphoric ester P (potassium salt of B) as a slightly shear rate 5 sec 10sec 20sec 50sec
yellowish liquid with 41% of solid content (Mettler Halogen
dryer, 150° C., 0.5 g). Example 5 5560 2954 1672 843
Example 10 S169 2734 1566 791
Example 15 BYKW 9010 6869 442O 2313 1223
Example 1 10731 663.O 3701 1767
Example 2 17510 8640 4831 2122
Phosphoric Ester Q Example 9 8883 4901 2767 1327
Disperbyk 110 21947 10520 5743 2629
0.058 Under a nitrogen atmosphere, phosphoric ester B
(80 g, MW ca. 775, 1 equiv) was dispersed in 100 ml of BYK-W 9010 is a cdispersant according to EP 417 490
Disperbyk 110 is a dispersant according to EP 417 490
demineralized water at room temperature. To this mixture,
N,N-di-methyl ethanolamine (8.3 g, 0.9 equiv) was slowly
added during 1 hour, while the temperature rose to 35° C. 0063
The resulting clear solution was stirred for 30 minutes at 40°
C. This yielded phosphoric ester Q (ammonium salt of B) as
a yellowish liquid with 42% of solid content (Mettler Formulation 2
Halogen dryer, 150° C., 0.5 g).
Viscosity InPas
Application Example shear rate 5 sec 10sec 20sec 50sec
0059. The following formulations were prepared: Example 2 2875 1270 96.O 850
Example 3 1522 910 668 523
Example 4 4426 2910 1930 1340
BYKW 9010 16390 92.70 5350 2910
Formulation 1
BYK W 9010 is a dispersant according to EP 417 490
Laropal A81 60%. 19.41 wt % (grinding resin BASF)
Solves.so 100 05.15 wt % (aromatic hydrocarbon solvent Exxon)
MPA 05.15 wt % (methoxypropylacetate, solvent, Kluthe)
Saci 300 A 01.00 wt % (antisettling agent, Stoney Creek
Technologies, LLC)
Kronos 2310 67.93 wt % (titanium dioxide, Kronos) 1. A phosphoric acid ester and salts thereof of the general
Glassbeads 3 mm 100.0 wt % (grinding aid) formula I,
Phosphoric ester O1.36 wt %

0060 Preparation: the samples according to above for O

mulation were shaken in a glass bottle for 1 hour on a
Skandex of Fluid Management. The samples were then
cooled down to room temperature for 24 h, before the
rheology was measured on a Haake RS 600 Rheometer.
US 2007/0293692 A1 Dec. 20, 2007

wherein 5. A phosphoric acid ester according to claim 1, wherein

B is malic acid or citric acid.
A is a monohydroxyl residue derived from 6. A phosphoric acid ester according to claim 1, wherein
C-C-alkyl-(AO)x-OH or Acyl-(AO)x-OH; or
Acyl is a saturated or unsaturated fatty acid residue;
AO is a polyC-Calkyleneglycol residue,
HA is e-caprolactone or Ö-Valerolactone;
AA is a dicarboxylic acid;
MO-(HA)y-OH or MO-(AA-AO)y-OH: wherein
MO is a monoalcohol having 4 to 30 carbon atoms in the
Acyl is an aromatic carboxylic acid residue or a alkyl chain,
Saturated or unsaturated fatty acid residue,
X is 2 to 50,
AO is a polyC-Calkyleneglycol residue,
y is 2 to 50.
HA is a hydroxycarboxylic acid or a lactone thereof, 7. A mixture of a phosphoric acid ester according claim 1
AA is a dicarboxylic acid, with a phosphoric acid ester of polyC-C alkylene glycol
MO is a monoalcohol, monoethers in weight ratio of 0.01 to 99.99.
8. A dispersant comprising a phosphoric acid ester of the
X is 1 to 250, formula I or salts thereof according to claim 1.
y is 1 to 250, 9. A sheet moulding compound (SMC) system or bulk
moulding compound (BMC) System comprising a phospho
B is a mono-, di-, tri- or polyhydroxy di-, tri- or multi ric acid ester of the formula I or salts thereof according to
carboxylic acid residue which is linked via the hydroxy claim 1.
group to the phosphoric acid and via one of the car 10. A water- or solvent-based coating or printing ink
boxylic acid groups to the monohydroxyl residue A. comprising a phosphoric acid ester of the formula I or salts
the remaining carboxylic acid group(s) is/are free or thereof according to claim 1
is/are esterified with a further monohydroxyl residue 11. A mixture of a phosphoric acid esters according claim
A resulting in branched esters; 7, wherein the weight ratio of phosphoric acid ester of
n is 1-2; formula 1 according to claim 1 to a phosphoric acid ester of
m is 1-4. polyC-C alkylene glycolmonoethers is 10 to 90.
2. A phosphoric acid ester according to claim 1, wherein 12. A mixture of a phosphoric acid esters according claim
B has at least one free carboxylic acid group and a non 7, wherein the weight ratio of phosphoric acid ester of
branching center. formula 1 according to claim 1 to a phosphoric acid ester of
3. A phosphoric acid ester according to claim 1, wherein polyC-Calkylene glycolmonoethers is 50 to 50.
the free carboxylic acid group(s) of B is/are fully esterified. 13. A dispersant comprising a mixture according to claim
4. A phosphoric acid ester according to claim 1, wherein 7.
B has at least one free carboxylic acid group and at least one
free carboxylic acid group is esterified.