US006054534A

United States Patent (19) 11 Patent Number: 6,054,534

JOsten et al. (45) Date of Patent: Apr. 25, 2000

54 SILICONE POLY(METH) ACRYLATES, 56) References Cited

THER PREPARATION AND THEIR USE IN U.S. PATENT DOCUMENTS
COATINGS
4,929,666 5/1990 Schmidt et al..
75 Inventors: Wolfgang Josten, Essen; Gerhard 5,006,624 4/1991 Schmidt et al..
Reusmann, Minster; Stefan Silber, FOREIGN PATENT DOCUMENTS
Krefeld, all of Germany
0117311 9/1984 European Pat. Off. .
73 Assignee: R Th. Goldschmidt AG, Essen, 0205827 12/1986 European Pat. Off..
Germany 0368320 5/1990 European Pat. Off..
0603561 6/1994 European Pat. Off..
3535283 4/1987 Germany.
21 Appl. No.: 08/944,847 4414465 5/1995 Germany.
Primary Examiner Bernard Lipman
22 Filed: Oct. 6, 1997 Attorney, Agent, or Firm-Frommer Lawrence & Haug
30 Foreign Application Priority Data 57 ABSTRACT
Oct. 11, 1996 DEI Germany ........................... 196 42 269 The present invention relates to Silicone poly(meth)
(51) Int. Cl. .................................................. C08F 8/00 acrylates, to a process for their preparation from alkoxySi
loxanes and hydroxy-functional poly(meth)acrylates and to
52 U.S. Cl. ................... 525/100; 525/329.7; 525/330.3; their use as an additive in coatings, especially as an anti
525/342 graffiti additive.
58 Field of Search ..................................... 525/100, 342,
525/329.7, 330.3 19 Claims, No Drawings
 6,054,534
1 2
SILICONE POLY (METH) ACRYLATES, One subject of the invention is, therefore, modified
THER PREPARATION AND THEIR USE IN polysiloxanes which are Suitable as an additive for coating
COATINGS compositions.
The compounds according to the invention can be used,
The present invention relates to Silicone poly(meth) for example, as additives in water-based, Solvent-based or
acrylates, to a process for their preparation from alkoxySi pulverulent coatings or printing inks, including use as deaer
loxanes and hydroxy-functional poly(meth)acrylates and to ating agents, lubricants and leveling agents, etc. Typical use
their use as an additive in coatings, especially as an anti concentrations are between 0.01 and 15% by weight.
graffiti additive. The compounds according to the invention correspond to
In recent years there has been a continual increase in the the general formula
frequency of unwanted graffiti produced in public. In many
cases it is public buildings and means of transport that are
affected. Since in the majority of cases removal by Simple
Washing off is not possible, labor- and cost-intensive recoat
ing of the graffiti-Soiled Surfaces is generally necessary.
| i
Consequently, possibilities have for Some time now been 15 R-i- o--
R1 R3 al
o-i-
Sought for removing unwanted graffiti in a simple and
cost-effective manner.
For instance, protective coatings have been developed
which comprise fluorine-containing polymers, as described
R-i-R al
for example in U.S. Pat. No. 4,929,666 and U.S. Pat. No. R-Si-R1
5,006,624. In this case dirt-repelling properties are achieved
by the reduction in Surface tension of the coating. One of the
disadvantages of fluorine-containing products, however, is
k b
the high price. R1 R1
DE-A-3535 283 describes polysiloxanes which contain
polyester groupS and are intended for coating materials and
molding compounds. The polysiloxane imparts an antiad
hesive property to the coating materials or molding com
25

o-- o--
R3 al R1
pounds. However, a very high concentration is necessary in
order to achieve an adequate effect, with the result that other in which the radials
properties of the coating material may be adversely affected.
The transesterification of poly(meth)acrylates with R" are identical or different aliphatic or aromatic hydrocar
hydroxy-functional siloxanes is described in DE-A-44 14 bon radicals, at least 90% of the groups R' being methyl
465. This transesterification takes place selectively at the grOupS,
chain ends of the polymer framework and permits likewise Rare identical or different alkoxy radicals or are identical
only a limited degree of modification. 35 or different poly(meth)acrylate radicals, at least 20% of
Hydroxy-functional (meth)acrylates are linked with the groups R being poly(meth)acrylate radicals,
hydroxy-functional siloxanes, according to EP-A-0368 320, R is R' or R,
by way of at least difunctional isocyanates to form urethane a is 1 to 100 and
linkages. Polyfunctional, hydroxy-functional (meth) b is 0 to 20.
acrylates tend under these conditions, however, to gel easily. 40 The skilled worker is well aware that the compounds are
By copolymerizing C,c)-unsaturated Siloxane monomers in the form of a mixture with a distribution determined
with (meth)acrylate monomers, according to EP-A-0 117 essentially by Statistical laws. The values for the indices a
311 or EP-A-0205827, siloxane-modified (meth)acrylates and b are therefore mean values.
are prepared. The Silicone poly(meth)acrylates according to the inven
EP-A-0 603 561 describes polydimethylsiloxane 45 tion are obtainable by metal-catalyzed nucleophilic Substi
containing binders which are obtained by free-radically tution of, for example, customary commercial hydroxy
initiated polymerization of (meth)acrylate monomers or functional poly(meth)acrylates with organoalkoxysiloxanes.
Vinylaromatic monomers in the presence of C,C)-functional In this case the linking of the polymer Segments takes
polysiloxanes. In this reaction the functional groups of the place by way of an Si-O-C bond, at least 20% of the
polysiloxanes employed are largely retained. Since the fiX 50 groups R being hydroxy-functional poly(meth)acrylate
ing of the polysiloxanes in the binder matrix formed by the radicals. Particular preference, moreover, is given to copoly
polymerization of the monomerS is very largely only physi mers in which not more than 70% of the groups R are
cal (interlooped polymer networks) there are incompatibili hydroxy-functional poly(meth)acrylate radicals.
ties with coating Systems. Moreover, the Systems exhibit For the purposes of this application hydroxy-functional
inadequate resistance to Soiling, for example to felt pens. 55 poly(meth)acrylates are products of the addition polymer
It is an object of the invention, therefore, to provide ization of acrylates and/or methacrylates, and also corre
coating components which are Suitable for dirt-repelling sponding products of copolymerization with other unsatur
coatings and which retain their dirt-repelling action over a ated compounds, which possess at least one reactive
long period of time, for example Several years. This includes hydroxyl group attached to carbon.
the permanence of the dirt-repelling effect over a number of 60 The synthesis of these hydroxy-functional poly(meth)
cleaning cycles as well. acrylates takes place by processes of free-radical polymer
It has Surprisingly been found that this object can be ization which correspond to the prior art. Preferred hydroxy
achieved by coating compositions which comprise as the functional acrylate monomers are hydroxyethyl acrylate,
coating constituent, in concentrations of from 0.01 to 15%, hydroxypropyl acrylate, hydroxyethyl methacrylate and
preferably from 1 to 10%, the silicone poly(meth)acrylates 65 hydroxypropyl methacrylate.
obtained by condensation reactions from alkoxysiloxane For the purpose of this invention the hydroxy-functional
intermediates. poly(meth)acrylates feature a weight-average molecular
 6,054,534
3 4
weight (Mw) of from 2000 to 30,000 and an OH content of The compounds according to the invention can be incor
from 1 to 10%. porated by Simple Stirring into the coating compositions
Examples of hydroxy-functional poly(meth)acrylates of which are intended to exhibit a dirt-repelling effect. These
this kind which are customary commercially include JagoteX coating compositions can be coating Systems which are
F 237 (from Ernst Jager, Dusseldorf), Kacryl Al 190 (from customary in the paints Sector. Surprisingly, the compounds
Kapol-Chemie, Hamburg), Synthalat A 191 (from Synthopol according to the invention are Suitable both for Solvent
Chemie, Buxtehude), Joncryl 500 (from SC Johnson based and for water-based coating Systems.
Polymer, Mijdrecht) and Desmophen A 66S BW (from The liquid phase can also be in the form of monomers for
Bayer AG, Leverkusen). low molecular mass compounds which react with other
The siloxanes employed for the reactions with hydroxy- 10 binder components to form the coatings. The coating mate
functional poly(meth)acrylates can have, for example, the rials according to the invention can also be So-called powder
following Structure coatings, which thus comprise no liquid phase and are

R1 R1 R1 R1

R-i- o--
R1 R3 3.
o-i- o-- R3

-- O

R-Si-R1
3.

k b

Compound a b= R = R2 = R3

1. 6 O Me OEt
2 12 O Me OEt
3 19 O Me OMe
4 8 2 Me OEt

35
By condensation of these siloxanes with hydroxy applied in the form of powders to the Substrates that are to
functional poly(meth)acrylates preferably Some, but at least be coated, where they are reacted.
20%, of the groups R are replaced by hydroxy-functional The coating compositions can be prepared by adding
poly(meth)acrylate radicals. additives as are customary in the paints Sector, for example.
The particular degree of conversion can be determined by 40 Examples of Such additives are pigments, for example
means of 'Si NMR spectroscopy. hiding, color-imparting pigments, Such as titanium dioxides
Examples of Silicone poly(meth)acrylates according to or carbon black, and Special-effect pigments, Such as metal
the invention, then, are: flake pigments and/or pearl luster pigments or transparent
pigments.
45
Other examples of additives are fillers, for example talc
and Silicates, plasticizers, Stabilizers, including light
Compound a= b= R= R= R= Stabilizers, and leveling agents, Such as Silicone oils.
5 6 O Me 50% OEt, 50% OR Me The desired application Viscosity of the coating compo
6 12 O Me 30% OEt, 70% OR Me Sitions prepared with the compounds according to the inven
7 19 O Me 55% OMe, 45% OR Me tion can be established by appropriately regulating the
8 8 2 Me 75% OEt, 25% OR Me 50 addition of Solvents and/or water and/or additives.
The curing of coatings produced from the coating com
R" in these cases is a copolymer comprising 5 parts by positions is dependent on the respective nature of the
weight hydroxypropyl methacrylate, 20 parts by weight crosslinking reaction and can take place within a wide
butyl acrylate, 4 parts by weight acrylic acid and 19 parts by temperature range of, for example, from -10° C. to 200 C.
weight methyl methacrylate, obtained by Solution 55 Surprisingly, the compounds according to the invention
polymerization-in accordance with the prior art-in exhibit a good antigraffiti effect even on curing at room
Solves.so 150 with regulation by dodecyl mercaptan. The temperature.
weight-average molecular weight in this case is 8000 g/mol. The coating compositions prepared from the compounds
The skilled worker is well aware that the reaction of oligo according to the invention are Suitable for coatings which
and/or polyfunctional molecules with one another leads to a 60 adhere to a large number of Substrates, for example wood,
mixture of Substances which also includes corresponding plastic, glass, ceramic, textiles, plaster, cement and, in
oligomers and polymers of the co-reactants. These are particular, metal. The coating compositions can also be
likewise claimed. employed in a multicoat process. They can be applied, for
Surprisingly, the use of the compounds according to the example, to customary primers, basecoats, fillers or existing
invention is particularly Suitable for producing dirt-repelling 65 topcoats.
coatings. They can be used, for example, to produce anti The compounds according to the invention are especially
graffiti coatings. Suitable for coating compositions which are to have a
 6,054,534
S 6
dirt-repelling action. The present invention therefore also added. The mixture is heated slowly to 155 to 160° C. and
relates to the use of the compounds according to the inven the distillate which forms is removed continuously. After
tion in topcoats or clearcoats. about 1 h, 45g of Solves.so 150 are added and the conditions
With the compounds according to the invention a high are held for a further 2 h. Under these conditions the reaction
dirt-repelling action (e.g. antigraffiti effect) is obtained and mixture is clear and homogeneous at room temperature
is retained over long periods of time even under unfavorable (tested by applying a quantity of Sample to a glass plate).
weather conditions. The dirt-repelling action is retained The mixture is cooled, and 10% of methoxybutyl acetate is
even after repeated cleaning of the Surface of the coating added. The resulting product is clear, yellowish and has a
composition, for example by Solvents, customary commer solids content of 34%. At least 50% of the ethoxy groups
cial graffiti removers or ScraperS. have reacted (conversion check by way of gas
When the dirt-repelling coating according to the invention chromatographic analysis of the distillate); the number
is Soiled by graffiti, the disruptive effect on wetting means average molecular weight M, is about 5000 g/mol. NMR
that the development of an uninterrupted graffiti paint film is Spectroscopic analyses show the expected Signals of the
impossible. Silicone poly(meth)acrylate.
Especially in connection with clearcoats where clouding 15
EXAMPLE 3
of the dried coating film causes adverse effects with respect Preparing a silicone poly(meth)acrylate according to the
to the optical quality of the coating as a result of incompat invention
ibility of the antigraffiti compound with the coating
components, the Outstanding compatibility of Silicone poly 192.9 g of Joncry1500 (80% solid content in 2-heptanone,
(meth)acrylates according to the invention with the coating from Speciality Chemicals, Mijdrecht), 88.4 g of methox
System, and the associated development of clear, transparent ypropyl acetate and 38.7 g of siloxane 4 (ethoxy content
films, show particular advantages. 6.4%) are placed in a reaction vessel with Stirrer, thermom
The invention is particularly Surprising because of the fact eter and distillation device, the mixture is heated to 120° C.,
that the quality of the antigraffiti effect and the ability of the and 2.8 ml of a 33% solid content solution of butyl titanate
antigraffiti compounds to form clear films in the coating 25 in butyl acetate are added. The mixture is heated slowly to
formulation often run counter to one another. Surprisingly, 150 C., the distillate which forms is removed continuously,
when using the Silicone poly(meth)acrylates according to the and the conditions are held for about 1 h. The mixture is
invention, a combination of excellent antigraffiti effect and cooled and filtered through a T 750 filter (from Seitz). The
outstanding compatibility with the coating compounds, and resulting product is almost clear and yellowish. At least 70%
the consequential formation of cloudleSS transparent films, of the ethoxy groups have reacted (conversion check by
has been found. gas-chromatographic analysis of the distillate); the number
The coating composition according to the invention can average molecular weight M, is about 2500 g/mol. NMR
be applied in a customary manner, for example dipping, Spectroscopic analyses show the expected Signals of the
Spraying, spreading or by an electrostatic method. Silicone poly(meth)acrylate.
The examples which follow serve to illustrate the inven 35
Preparing coating materials
tion.
EXAMPLE 1. Coating Example Ia
Preparing a silicone poly(meth)acrylate according to the 50p of Macrynal VSM 1565 (70%)
invention
40 1 p of methoxypropyl acetate
466.0 g of Joncryl 500 (80% strength in 2-heptanone, 1.5 p of Solves.so 100
from Speciality Chemicals, Mijdrecht), 149.8g of Solves.so 5 p of butyl acetate
150, 84.2 g of siloxane 1 (ethoxy content 6.6%) and 2.75g 0.6 p of dibutyltin dilaurate (1% in Xylene)
of aluminum acetylacetonate are placed in a reaction vessel 2. p of compound according to the invention from Example
with stirrer, thermometer and distillation device. The mix 45 1 or 2
ture is heated slowly to 155 to 160° C. and the distillate 4 p of butyl acetate
which forms is removed continuously. After about 30 min 1 p of customary commercial isocyanate hardener
utes at 155 to 160° C. the reaction mixture is clear and
homogeneous at room temperature (tested by applying a are mixed homogeneously with one another in Succession.
quantity of Sample to a glass plate). The mixture is cooled, The mixture is then applied with a dry film thickness of from
50 30 to 100 um to a customary commercial primer. The coating
4 g of Celite J 10 are added, and the mixture is filtered is cured at room temperature for 7 dayS. Alternatively, curing
through a T1000 filter (from Seitz). The resulting product is can be carried out at 60° C. for 16 hours.
clear, yellowish and has a viscosity of about 340 mPas at 25
C. At least 65% of the ethoxy groups have reacted Comparison Experiment A
(conversion check by way of gas-chromatographic analysis 55 The procedure of Example Ia is repeated, the compound
of the distillate); the number-average molecular weight M, according to the invention from Preparation Example 1
is about 2400 g/mol. NMR-spectroscopic analyses show the being replaced by the C,c)-hydroxy-functional polydimeth
expected Signals of the Silicone poly(meth)acrylate. ylsiloxane Tegopren H-Si 2111 (Th. Goldschmidt AG).
EXAMPLE 2
Preparing a silicone poly(meth)acrylate according to the 60
Comparison Experiment B
invention The procedure of Example Ia is repeated, the compound
158.0 g of Synthalat A 191 (from Synthopol Chemie, according to the invention from Preparation Example 1
Buxtehude) (63.3% strength in Shellsol A.butyl acetate being replaced by silicone caprolactone Byk 370 (BYK).
1.35:1), 62.9 g of Solves.so 150 and 22.3 g of siloxane 1 The following analyses are carried out:
(ethoxy content 6.3%) are placed in a reaction vessel with 65 Abhesion
Stirrer, thermometer and distillation device, the mixture is After the coating material is cured, the Bonder metal
heated to 65 C., and 0.72 g of aluminum acetylacetonate is panel is sprayed with customary commercial spray-can
 6,054,534
7 8
paints. After this coat of paint has dried, this area is covered are processed as for Coating Example Ia.
with adhesive tape. By tearing off the tape the Spray-can coat
is removed. Coating Example Ic
1=Very good spray-can paint adhesion 50 p of Bayhydrol VPLS 2139
2=good spray-can paint adhesion 1 p of Surfinol 104E (50%)
3=no Spray-can paint adhesion 5.5 p of Acrysol RM8 (18% in ethanol)
Felt-tip pen resistance 24 p of Bayertitan RKB-4
After the paint is cured, the object is written on with 2. p of compound from Example 2
customary commercial felt-tip pen. After drying, the felt-tip pH 7.5 with DMEA
is removed by rubbing with a dry paper handkerchief. 35 p of fully deionized water
1=felt-tip impossible to remove are mixed homogeneously with one another using a bead
mill and the mixture is adjusted with fully deionized water
2=felt-tip difficult to remove to a flow time of 85" DIN 4 cup. It is then applied with a dry
3=felt-tip easy to remove film thickness of from 30 to 100 um to a customary
Chemical resistance 15 commercial primer. The coating material is cured at room
The chemical tests were carried out with the solvent temperature for 7 days. Alternatively, curing can be carried
Xylene, ethyl glycol and methoxypropyl acetate in accor out at 60° C. for 16 hours.
dance with DIN 53 168. The coatings of Coating Example Ib and Ic give an
After 100 WOM: outstanding antigraffiti effect against Spray paints and felt-tip
The abhesion test and the felt-tippen resistance are tested pens. The effect is retained even after weathering or after
after 100 h of Weatherometer (WOM) Sunshine testing. chemical treatment with, for example, customary commer
Clouding of the clearcoat film: cial graffiti removers.
The coating film is applied to a transparent sheet and the The abovementioned examples readily demonstrate the
clouding is assessed Visually after the clearcoat film has Superiority of the compounds according to the invention in
dried. 25 terms of obtaining a permanent antigraffiti effect.
After drying for 2 days at room temperature: We claim:
1. A silicone poly(meth)acrylate of the general formula
Felt-tip
resistance Abhesion
Trans
parency in i i
Coating example
48 h after 100 h 48 h after 100 h the clear
Rt WOM RT WOM coat film
R-i- o--
R1 R al
o-i-
Ia (Example 1)
Ia (Example 2)
3
3
3
3
3
3
3
3
transparent
transparent 35
R-i-R
Comparison Ex. A
Comparison Ex. B
1.
1.
1.
1.
1.
1.
1.
1.
clouding
transparent
R-Si-R1
J.
The chemical resistance is very good for all the coating 40
k b
examples.
After drying for 7 days at room temperature: R1 R1
-:
o-- o--
R3 al R1
Felt-tip Trans 45
resistance Abhesion parency in
48 h after 100 h 48 h after 100 h the clear in which the groups
Coating example Rt WOM RT WOM coat film R" are identical or different aliphatic or aromatic hydro
Ia (Example 1) 3+ 3+ 3+ 3+ transparent 50
carbon radicals, at least 90% of the groups R' being
Ia (Example 2) 3 3 3 3 transparent methyl groups,
Comparison Ex. A 2 2 2 2 clouding Rare identical or different alkoxy groups or are identical
Comparison Ex. B 1. 1. 1. 1. transparent
or different poly(meth)acrylate at least 20% of the
groups R being hydroxy-functional poly(meth)
The chemical resistance is very good for all the coating 55
acrylate groups,
examples. R is R' or R,
a is 1 to 100 and
Coating Example Ib b is 0 to 20 for use in dirt-repelling compositions.
50p of Macrynal VSM 1565 (70%) 2. The Silicone poly(meth)acrylate as claimed in claim 1,
1 p of methoxypropyl acetate 60 wherein R' is methyl.
1.5 p of Solves.so 100 3. The Silicone poly(meth)acrylate as claimed in claim 1
5 p of butyl acetate or 2, wherein a is 5 to 30.
0.6 p of dibutyltin dilaurate (1% in xylene) 4. The Silicone poly(meth)acrylate as claimed in claim 1
36 p of Kronos RW 59 or 2, wherein b is 0 to 3.
2. p of compound from Example 2 65 5. The silicone poly(meth)acrylate as claimed in claim 1
4 p of butyl acetate wherein R are identical or different alkoxy groups or iden
1 p of customary commercial isocyanate hardener tical or different poly(meth)acrylate groups at least 20% of
 6,054,534
10
the groups R being poly(meth)acrylate groups and these 13. The silicone poly(meth)acrylate as claimed in claim 5
hydroxy-functional poly(meth) acrylates featuring, wherein b is 0.
moreover, a weight-average molecular weight of from 2000 14. A coating composition for producing dirt-repelling
to 30,000 g/mol and an OH content of from 1 to 10%. coatings, comprising one or more compounds as claimed in
6. The Silicone poly(meth)acrylate as claimed in claims 1 claim 5.
wherein b is 0. 15. A coating composition for producing dirt-repelling
7. A coating composition for producing dirt-repelling coatings, comprising one or more compounds as claimed in
coatings, comprising one or more compounds as claimed in claim 6.
claim 1.
8. The coating composition as claimed in claim 7, which 16. The coating composition as claimed in claim 14 or 15,
comprises one or more customary paint Solvents. which comprises one or more customary paint Solvents.
9. The coating composition as claimed in claim 7, which 17. The coating composition as claimed in claim 14 or 15,
is an aqueous coating composition which can comprise one which is an aqueous coating composition which can com
or more organic Solvents. prise one or more organic Solvents.
10. The coating composition as claimed in claim 7, 15 18. The coating composition as claimed in claim 14 or 15,
wherein the liquid phase is in the form of monomers or low wherein the liquid phase is in the form of monomers or low
molecular mass compounds. molecular mass compounds.
11. The coating composition as claimed in claim 7, which 19. The coating composition as claimed in claim 14 or 15,
is a powder coating. which is a powder coating.
12. The Silicone poly(meth)acrylate as claimed in claim 3,
wherein b is 0 to 3. k k k k k