DE102004034740A1 - New organopolysiloxane compounds comprising silicon oxide (SiOC) groups bounded in end or centre with (meth) acrylic acid ester group and (per)fluorinated residues useful in the preparation of hardenable adhesive coating mass - Google Patents

Abstract

Organopolysiloxane compounds (I) comprising silicon oxide (SiOC) groups bounded in end or centre with (meth) acrylic acid ester group and fluorinated or perfluorinated residues (I) are new. Organopolysiloxane compounds of formula (I) comprising SiOC groups bounded in end or centre with (meth) acrylic acid ester group and fluorinated or perfluorinated residues are new. R1>1-20C alkyl, 1-20C aryl, 1-20C alkaryl or 1-20C aralkyl (all optionally saturated); R2>R1>, R3> or R4>; R3>(meth)acrylated mono and/or polyalkoxylate or its mixture, mixture of ((meth)acrylated (optionally saturated), aromatic, aliphatic/aromatic mono- or polyalcohol, polyether monoalcohol, polyether polyalcohol, polyester monoalcohols, polyester polyalcohol or aminoalcohol (preferably N-alkyl, arylamino ethylenoxy, propylenoxy of alcohols, N-alkyl and/or arylaminoalkoxylate)); R4>fluorinated or by fluorinated monoalkoxylate and/or polyalkoxylate; a,d : 0-1000; b : 0-5; c : 1-200; and e : 1-200. Provided that one of R2> or R3> is (meth)acrylated monoalkoxylate or polyalkoxylate residue and one of R2> or R4> is fluorinated or by-fluorinated monoalkoxylate or polyalkoxylate residue. Independent claims are also included for: (1) the preparation of (I); (2) hardenable adhesive coating mass (III) comprising (I); and (3) an adhesive coating obtained by hardening of (III). [Image].

Description

The The invention relates to novel polysiloxanes having SiOC groups bonded acrylsäureestergruppen (meth) and fluorinated radicals and the use of these new organopolysiloxanes as radiation-curable Coating compositions for the production of abhesive coatings.

Abhesive coating compounds (Release agents) are on a larger scale used for coating in particular flat materials, about the adhesion tendency of adherents Products these surfaces to reduce. This prior art is described, for example in US Pat. No. 6,268,404, US Pat. No. 6,548,568.

Abhesive coating compounds, which are based exclusively on modified organopolysiloxanes however for some special applications have an insufficient release effect on. For example, the release effect against so-called silicone adhesive tapes, Bitumendichtungsmassen, Butyl rubber compounds and adhesives or other highly sticky Masses are not enough. About that In addition to a very good long-term stability and very uniform separation behavior without increased Cut-off peak when starting the separation process and little variation of the cut-off value during the separation process (also called Zipp) with said adhesive masses be achieved.

It There was therefore a need to further improve the release effect, especially in the case of radiation-curing abhesive coating compositions.

Radiation-curing abhesive coating compositions are described in US Pat. Nos. 4,421,904, 4,547,431, 4,952,657, 5,217,805, 5,279,860, 5,340,898, 5,360,833, 5,650,453, 5,866,261 and 5,973,020 and US Pat US 4,201,808 , 4,678,846, 5,494,979, 5,510,190, 5,552,506, 5,804,301, 5,891,530 and 5,977,282.

Mixtures of several such coating materials having different chain lengths and / or types of modification are in US-B-6548568, 6268404, Goldschmidt publication "TEGO ^® RC Silicones, Application Guide," Goldschmidt product data sheets for the products TEGO ^® RC 902, RC 726 , RC 711, RC 708, RC 709, RC 715, RC 706 mentioned.

Of Further can (meth) acrylated polysiloxanes with different, purely organic (meth) acrylated Monomers or oligomers UV-curable Products are mixed. This can, for example, the hardness of the Coating mass, adhesion to the substrate, viscosity, color (in the case of UV-curing Color pastes) and the reactivity be set. If the purely organic (meth) acrylated Monomers or oligomers UV-curable Products are cheaper than the (meth) acrylated polysiloxanes can also commercial advantages can be achieved.

in the Traps of UV crosslinking become the latter organosilicon compounds Photoinitiators added. Suitable photoinitiators are described i.a. in "J. P. Fouassier, Polymerization photoinitiators: Exited state process and kinetic Aspects, Progress in Organic Coating, 18 (1990): 229-252, in J.P. Fouassier, Photochemical reactivity of UV radical photoinitiators of polymerization: A general Discussion, Recent Res. Devel. Photochem.Photobiol. & Photobiol., 4 (2000): 51-74 ", in" D. Ruhlmann et al, Relations structure-proprietes dans les photoamorphurs de polymerisation-2. Derives de Phenyl Acetophenone, Eur. Polym. J. Vol. 28, no. 3, pp. 287-292, 1992 "and" K.K. Dietliker, Chemistry & Technology of UV & EB formulation for Coatings, Inks & Paints, Volume 3, Sita Technology Ltd, UK "and DE-10248111.3 and US-4,347,111 called.

polysiloxanes can on diverse Type with (meth) acrylic acid ester groups be provided. Organopolysiloxanes in which the acrylic acid ester-containing organic groups over Si-C bonds are associated with the polysiloxane backbone, stand U.S. Patent 4,978,726, U.S. 4,963,438, U.S. Patent 6,211,322). The education a SiOC link US Pat. Nos. 4,301,268, 4,306,050, 5,310,842, US Pat. No. 6,359,097, US Pat. US-B-6,239,303. Especially chlorosiloxanes are for this Reaction type widely used.

However, chlorosiloxanes are difficult to handle because they are extremely reactive. The use of chlorosiloxanes is further associated with the disadvantage that the hydrogen chloride formed in the course of the reaction leads to ecological problems and be handling on corrosion-resistant plants be limits. In addition, in the presence of chlorosiloxanes and alcohols, organic chlorine compounds can be formed which are not desirable for toxicological reasons.

Farther it is not easy in the reaction of a chlorosiloxane with a Alcohol to achieve a quantitative turnover. Frequently, bases, as the HCl scavenger serve, be used to achieve good sales. By use These bases lead to the formation of large quantities of salt cargo, the in turn on an industrial scale Problems with removal and disposal.

The stability the Si-O-C bond via long periods is crucial for the use as abhesive Coating materials or as additives for radiation-curing coatings. It should therefore no reaction or catalyst residues remain in the coating, which are suitable for catalyzing the hydrolysis of the SiOC bond. In the mentioned methods, however, acid residues or a salt load, the not completely removable from the reaction mixture. It remains catalytic active amounts in the radiation-curing Coating that breaks down the SiOC bond even after crosslinking can. moreover are according to the above methods only terminally modified organopolysiloxanes accessible and thus no possibility for the synthesis of medium-sized via SiOC (meth) acrylate-modified organosiloxanes.

Next the widespread presentation of terminal (α, ω) organopolysiloxanes with chlorosiloxanes and alcohols are disclosed in U.S. Patent Nos. 5,310,842 and 6 239 303 for the synthesis of middle-class modified organopolysiloxanes via SiOC chemistry the dehydrogenative Hydrosilylation of long and short chain alcohols on SiH siloxanes using Ru or Pt compounds.

These Method is only suitable to end and different alcohols pendant dehydrogenatively to couple to SiH siloxanes.

For the expert however, it is readily apparent that these approaches described above are not practical for (meth) acrylic-containing alcohols, since various Pt- or Ru-catalyzed side reactions, such as Connection of the double bond or carbonyl group of the (meth) acrylate groups to the SiH units occur (Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 29, 1073-1076).

Of Furthermore, the products obtained should be in contrast to the process in the prior art, e.g. starting from chlorosiloxanes, not with hydrochloric acid originating from the substitution reaction, or whose neutralization products contaminated corresponding chlorides and thus the illustrated (meth) acrylate-modified polysiloxanes a higher one hydrolytic stability have the SiOC bond.

consequently is after the published State of the art no way for the synthesis of medium-sized (meth) acrylate-modified organosiloxanes via SiOC chemistry with defined structures available. The known processes which lead to terminal (via SiOC (meth) acrylate-modified) organosiloxanes leave catalytic amounts of SiOC bonds degrading substances.

In the not previously published DE-A-103 59 764 discloses a technically simple method, which allows new, end-capped and / or pendent, (meth) acrylate-modified, via SiOC chemistry, radiation-curable polysiloxanes without degradation of the Siloxangrundgerüsts manufacture.

Under Use of a Lewis acid catalyst or a mixture of a carboxylic acid and the salt of a carboxylic acid can (meth) acrylate-containing alcohols selectively to terminal and / or pendant SiH siloxanes be coupled, without any degradation of the siloxane skeleton observed becomes. Furthermore, occur in the in DE-A-103 59 764 described Procedure for the use of Lewis Acid catalysts no hydrosilylation reactions of the (meth) acrylate groups on SiH groups under SK link as described in WO-A-02/12386 for olefinic compounds and SiH siloxanes using boron-containing catalysts is described.

It was now more surprising Way found that according to DE-A-103 59,764 described method to compounds with improved abhesive properties leads, if in addition fluorinated or perfluorinated alcohols are used.

she point it over In addition, a very good long-term stability and a very uniform Trennwertverhalten without increased Trennwertpeak when starting the separation process and a small Variation of the separation value during the separation process of the abhesive Coatings on.

worin
R¹ gleiche oder verschiedene Reste sind, ausgewählt aus linearen oder verzweigten, gesättigten, ein- oder mehrfach ungesättigten Alkyl-, Aryl-, Alkaryl- oder Aralkylresten mit 1 bis 20 Kohlenstoffatomen, vorzugsweise C_1-5-Alkylreste, insbesondere der Rest -CH₃,
R² gleiche oder verschiedene Reste R¹, R³ oder R⁴,
R³ gleiche oder verschiedene einfach oder mehrfach (meth)acrylierte Monoalkoxylate oder (meth)acrylierte Polyalkoxylate, oder eine Mischung derselbigen, oder eine Mischung der einfach oder mehrfach (meth)acrylierten Monoalkoxylate oder Polyalkoxylate mit beliebigen anderen Alkoxylaten, die ausgewählt sind aus der Gruppe der linearen oder verzweigten, gesättigten, ein- oder mehrfach ungesättigten, aromatischen, aliphatisch-aromatischen Mono- oder Polyalkohole, Polyethermonoalkohole, Polyetherpolyalkohole, Polyestermonoalkohole, Polyesterpolyalkohole, Aminoalkohole, insbesondere N-Alkyl-, Arylamino-Ethylenoxyd-, -Propylenoxyd-Alkohole, N-Alkyl- oder Arylaminoalkoxylate sowie deren Gemische, wobei das Verhältnis der einfach oder mehrfach (meth)acrylierten Monoalkoxylate oder Polyalkoxylate zu den beliebigen anderen Alkoxylaten so gewählt wird, dass mindestens ein einfach oder mehrfach (meth)acrylierter Monoalko xylat- oder Polyalkoxylat-Rest in dem Organopolysiloxan enthalten ist,
R⁴ gleiche oder verschiedene fluorierte oder perfluorierte Monoalkoxylate oder Polyalkoxylate, oder eine Mischung derselbigen,
a 0 bis 1.000, vorzugsweise 0 bis 500, insbesondere 0 bis 300,
b 0 bis 5,
c 1 bis 200, vorzugsweise 2 bis 100, insbesondere 3 bis 80,
d 0 bis 1.000, vorzugsweise 0 bis 500, insbesondere 0 bis 300,
e 1 bis 200, vorzugsweise 2 bis 100, insbesondere 3 bis 80.
wobei mindestens einer der Reste R² oder R³ ein (meth)acrylierter Monoalkoxylat- oder Polyalkoxylat-Rest und einer der Reste R² oder R⁴ ein fluorierter oder perfluorierter Monoalkoxylat- oder Polyalkoxylat-Rest ist.An object of the present invention are thus novel organopolysiloxanes having (meth) acrylic acid ester groups and fluorinated or perfluorinated radicals of the general average formula (I) bonded via SiOC groups by means of medium and terminal or only moderately bonded

wherein
R ^{1 are} identical or different radicals selected from linear or branched, saturated, mono- or polyunsaturated alkyl, aryl, alkaryl or aralkyl radicals having 1 to 20 carbon atoms, preferably C _1-5 -alkyl radicals, in particular the radical -CH ₃ ,
R ^{2 is the} same or different radicals R ¹ , R ³ or R ⁴ ,
R ^{3 are} identical or different mono- or poly (meth) acrylated monoalkoxylates or (meth) acrylated polyalkoxylates, or a mixture thereof, or a mixture of mono- or polysubstituted (meth) acrylated monoalkoxylates or polyalkoxylates with any other alkoxylates selected from the group the linear or branched, saturated, mono- or polyunsaturated, aromatic, aliphatic-aromatic mono- or polyalcohols, polyether monoalcohols, polyetherpolyalcohols, polyestermonoalcohols, polyesterpolyalcohols, aminoalcohols, in particular N-alkyl, arylamino-ethylene oxide, propylene oxide alcohols, N Alkyl or arylaminoalkoxylates and mixtures thereof, wherein the ratio of mono- or polysubstituted (meth) acrylated monoalkoxylates or polyalkoxylates to any other alkoxylates is chosen so that at least one mono- or polysubstituted (meth) acrylated Monoalko xylat- or polyalkoxylate radical in containing the organopolysiloxane,
R ^{4 are the} same or different fluorinated or perfluorinated monoalkoxylates or polyalkoxylates, or a mixture of the same,
a 0 to 1,000, preferably 0 to 500, in particular 0 to 300,
b 0 to 5,
c is 1 to 200, preferably 2 to 100, in particular 3 to 80,
d is 0 to 1,000, preferably 0 to 500, in particular 0 to 300,
e is from 1 to 200, preferably from 2 to 100, in particular from 3 to 80.
wherein at least one of R ² or R ^{3 is} a (meth) acrylated monoalkoxylate or polyalkoxylate radical and one of R ² or R ^{4 is} a fluorinated or perfluorinated monoalkoxylate or polyalkoxylate radical.

in denen
R⁵ gleiche oder verschiedene Reste sind, ausgewählt aus linearen oder verzweigten, gesättigten, ein- oder mehrfach ungesättigten Alkyl-, Aryl-, Alkaryl- oder Aralkylresten mit 1 bis 20 Kohlenstoffatomen,
R⁶ H oder R⁵,
R⁷ H,
f 0 bis 1.000, vorzugsweise 0 bis 500, insbesondere 0 bis 300,
g 0 bis 5,
h 0 bis 400,
i 0 bis 1.000, vorzugsweise 0 bis 500, insbesondere 0 bis 300,
wobei die Reste R⁶ und/oder R⁷ zusammen mindestens 2 mal H sein müssen,
in einem oder mehreren Verfahrensschritten unter Einsatz eines lewissauren Katalysators oder eines Katalysators bestehend aus einer Carbonsäure und deren Salze mit Alkoholen umsetzt, die ausgewählt sind aus der Gruppe der

• – einfach oder mehrfach (meth)acrylierten Monoalkohole oder Polyalkohole, oder aus einer Mischung derselbigen, oder aus Mischungen der einfach oder mehrfach (meth)acrylierten Monoalkohole oder Polyalkohole mit beliebigen anderen Alkoholen, die ausgewählt sind aus der Gruppe der linearen oder verzweigten, gesättigten, ein- oder mehrfach ungesättigten, aromatischen, aliphatisch-aromatischen Mono- oder Polyalkohole, Polyethermonoalkohole, Polyetherpolyalkohole, Polyestermonoalkohole, Polyesterpolyalkohole, Aminoalkohole, insbesondere N-Alkyl-, Arylamino-EO-, -PO-Alkoholen, N-Alkyl- oder Arylaminoalkohole sowie deren Gemischen und mit
• – gleichen oder verschiedenen fluorierten oder perfluorierten Monoalkoholen oder Polyalkoholen, oder mit einer Mischung derselbigen.

A further subject of the present invention is a process for the preparation of compounds having (meth) acrylic acid ester groups bonded via SiOC groups and fluorinated or perfluorinated radicals by reacting SiH groups-containing polysiloxanes of the general average formula (II)

in which
R ^{5 are the} same or different radicals selected from linear or branched, saturated, or polyunsaturated alkyl, aryl, alkaryl or aralkyl radicals having 1 to 20 carbon atoms,
R ⁶ H or R ⁵ ,
R ⁷ H,
f is 0 to 1,000, preferably 0 to 500, in particular 0 to 300,
g 0 to 5,
h 0 to 400,
i is 0 to 1,000, preferably 0 to 500, in particular 0 to 300,
where the radicals R ⁶ and / or R ⁷ together must be at least 2 times H,
in one or more process steps using a Lewis acid catalyst or a catalyst consisting of a carboxylic acid and its salts with alcohols, which are selected from the group of

• Mono- or poly (meth) acrylated monoalcohols or polyalcohols, or of a mixture thereof, or of mixtures of mono- or polysubstituted (meth) acrylated monoalcohols or polyalcohols with any other alcohols selected from the group of linear or branched, saturated, mono- or polyunsaturated, aromatic, aliphatic-aromatic mono- or polyalcohols, polyether monoalcohols, polyetherpolyalcohols, polyestermonoalcohols, polyesterpolyalcohols, aminoalcohols, in particular N-alkyl, arylamino-EO-, -PO-alcohols, N-alkyl- or arylaminoalcohols and theirs Mixtures and with
• - the same or different fluorinated or perfluorinated monoalcohols or polyalcohols, or with a mixture derselbigen.

The existing SiH groups of the polysiloxane are partially or completely replaced by alcohol radicals of the alcohols used.

A variant of the process comprises, before the reaction of the alcohols with the Si-H siloxanes using the Lewis-acid catalysts or the mixtures of at least one acid and at least one salt of an acid, any other reaction with proportions of the hydrogen of the Si-H siloxanes is carried out with the proviso that the remaining proportion of hydrogen in the radicals R ⁶ + R ⁷ ≥ 2H, in this case in particular a hydrosilylation.

One Another object of the present invention is the use the compounds of the general average formula (I) and the use of organopolysiloxanes prepared according to the previously described Processes were prepared as abhesive release coatings.

Further objects The invention is characterized by the content of the claims.

preferred effective Lewis acid catalysts in the context of the present invention are the Lewis Acid element compounds of III. Main group in particular boron-containing and / or aluminum-containing elemental compounds.

A preferred embodiment The invention provides that fluorinated and / or non-fluorinated Organoboric compounds are used.

The fluorinated alcohols used in accordance with the invention are preferably compounds of the general formula R _f (CH ₂ ) _n (OCH (R) CH ₂ ) _m -OH, where R _f = fluorinated or perfluorinated C _1-20 , preferably C _1-10 , in particular may be a C _3-10 -alkyl radical or an aryl radical, R is a short-chain alkyl radical having 1 to 3 C atoms or hydrogen and when m> = 2 both radicals may be present blockwise or in random distribution, n = 1 to 5, preferably 2 or 3, m = 0 to 20, preferably 0 such as in particular C ₈ F ₁₇ -C ₂ H ₄ -OH or C ₆ F ₁₃ -C ₂ H ₄ -OH or pentafluorophenol or mixtures thereof.

The reaction of the medium and terminal or only medium Si-H-functional siloxanes with the previously defined mono- or polysubstituted (meth) acrylated and the fluorinated or perfluorinated alcohols with boronic Lewis acids are carried out according to the general synthesis instructions:
The alcohols are initially charged with or without solvent and the borane catalyst under protective gas and heated to 70 ° C to 150 ° C. Subsequently, the Si-H-functional siloxane is added dropwise and the reaction mixture is stirred until complete reaction. The reaction procedure can be modified so that a one-pot reaction is carried out, characterized in that the Alko hol, the borane catalyst and that Si-H-functional siloxane are presented with or without solvent.

Furthermore, these reactions using inert gas, lean air or Inhibito be carried out.

Further effective catalysts in the context of the present invention are Mixtures of at least one acid and at least one salt an acid, preferably mixtures of at least one organic acid, such as z. A carboxylic acid, dithiocarboxylic, Aryl / alkyl sulfonic acid, Aryl / alkylphosphonic or aryl- / alkylsulfinic acid and at least one metal or ammonium salt of an organic Acid, being the metal cation may be monovalent or polyvalent used. The relationship of salt and acid can be varied within wide limits, preferably a molar ratio of Acid too Salt in the range of 1: 5 to 5: 1, in particular 2: 3 to 3: 2 molar equivalents. Furthermore you can polybasic acids or mixtures of mono- and polybasic acids and the corresponding Salts are used with mono- or polyvalent cations. Of the pKs value of the acid should not be negative, otherwise the equilibration of the siloxane backbone will occur.

A particularly preferred embodiment the invention consists in the use of catalytic systems, consisting of a 1: 1 mixture of a carboxylic acid and its metal or ammonium salt, wherein the metal is a main group element or transition metal, more preferred is a metal of the 1st and 2nd main group. The organic rest of the carboxylic acid is selected from cyclic, linear or branched, saturated, one or more times unsaturated Alkyl, aryl, alkylaryl or arylalkyl radicals having 1 to 40, in particular 1 to 20 carbon atoms.

The reaction of the medium or terminal Si-H-functional siloxanes with the previously defined alcohols with mixtures of at least one acid and at least one salt of an acid are carried out according to the general method of synthesis:
The alcohols are introduced with or without solvent and the catalyst (mixtures of at least one acid and at least one salt of an acid) and heated to 70 ° C to 150 ° C. Subsequently, the Si-H-functional siloxane is added dropwise and the reaction mixture is stirred until complete reaction. The reaction procedure can be modified so that a one-pot reaction is carried out, characterized in that the alcohols, the catalyst and the Si-H-functional siloxane are introduced with or without solvent.

Of Further can these reactions using inert gas, lean air or Inhibitors performed become.

consequently In an effort to overcome the disadvantages of the prior art Organopolysiloxanes with about SiOC groups bound acrylsäureestergruppen (meth) and fluorinated or perfluorinated radicals. These compounds are useful as an abhesive coating or as additives for abhesive Coatings do not have the disadvantages of the prior art: you cause a significant improvement of the release effect and the long-term stability and wise no strong variation of the separation value during the separation process (also Called Zipp).

The according to the invention via SiOC-modified polysiloxanes can be synthesized in a single step in different chain lengths and / or modification types are produced since the production done without the degradation of Siloxangrundgerüsts. Further occurred in the inventive via SiOC chemistry modified polysiloxanes no hydrosilylation reactions of the (meth) acrylate groups on SiH groups under SiC linkage.

mixtures various polysiloxanes according to the invention, which are mixed together only after separate preparation, are also suitable.

Further Is it possible Mixtures of Si-H-siloxanes of different chain lengths and different Si-H functionality with (meth) acrylated and fluorinated or perfluorinated alcohol directly.

Separate or mixtures of the invention via SiOC chemistry with (meth) acrylic acid ester groups and fluorinated or perfluorinated radicals modified polysiloxanes can in any mixture with any number of other (meth) acrylated Polysiloxanes are mixed according to the prior art. Also mixtures with epoxy-containing or vinyl-containing UV-curing silicones are possible.

Furthermore, the polysiloxanes or the mixtures according to the invention which have been modified via SiOC chemistry with (meth) acrylic ester groups and fluorinated or perfluorinated radicals can be mixed with other auxiliaries and additives according to the prior art. Here are especially Photoi nitiatoren, adhesion promoters, curing accelerators, photosensitizers, antioxidants, oxygen scavengers or organic (meth) acrylic groups containing or containing vinyl ether groups. Additives are also dyes, pigments and solid particulate fillers.

• • Wärme, nach Zugabe von beispielsweise geeigneten thermisch zersetzender Peroxide, oder
• • Strahlung wie Licht und UV-Licht, nach Zugabe geeigneter Photoinitiatoren, oder
• • Elektronenstrahlen

innerhalb kürzester Zeit zu mechanisch und chemisch widerstandsfähigen abhäsiven Schichten aus.The polysiloxanes or mixtures according to the invention which have been modified via SiOC chemistry with (meth) acrylic acid ester groups and fluorinated or perfluorinated radicals can be used for coating moldings and flat supports for the production of, for example, abhesive coatings or as additives for radiation-curing coatings in concentrations of from 0.01 to 10% can be used. They are cross-linked by free radicals and harden under the influence of

• • heat, after adding, for example, suitable thermally decomposing peroxides, or
• • Radiation such as light and UV light, after addition of suitable photoinitiators, or
• • electron beams

within a short time to mechanically and chemically resistant abhesive layers.

subsequent Examples are intended to illustrate the invention, they provide however no restriction represents.

Application check:

To check the performance properties of the curable examples and mixtures of examples, they are applied to two-dimensional support (oriented polypropylene film) after addition of 2% of the photoinitiator Darocur 1173 Ciba Specialty and by the action of UV light of the prior art medium pressure mercury vapor lamp with a UV power of 50 W / cm under nitrogen inerting with controlled residual oxygen content of <50 ppm at the web speed of 20 m / min cured. The order amount is in each case about 1 g / m ² .

Release value:

For the investigation The release value is a 25 mm wide adhesive tape that acts as a sellotape 1650 commercially available from Sellotape / UK.

To measure the release effect, these adhesive tapes are rolled onto the substrate and then stored at 40 ° C under a weight of 70 g / cm ² . After 24 hours, the force required to pull the respective adhesive tape from the substrate at a speed of 30 cm / min at a peel angle of 180 ° is measured. This force is referred to as release force or release value. The general test procedure essentially corresponds to the test method no. 10 of the "Fédération Internationale des Fabricants et Transformateururs d'Adhésifs et Thermocollants sur Papier et autres Supports" (FINAT).

Loop test:

The loop test is used to quickly determine the degree of hardening of a release coating. For this purpose, an approximately 20 cm long strip of the adhesive tape TESA ^® 4154 from Beiersdorf times rolled onto the base 3, and immediately peeled off by hand. Then, a loop is formed by folding the ends of the adhesive tape, so that the adhesive surfaces of both ends have contact at about an inch distance. Then the ends are pulled apart again by hand, with the contact surface should move evenly to the center of the tape. In the case of contamination with poorly cured release material, the adhesive force of the adhesive tape is no longer sufficient to hold the contact surface together when the ends are pulled apart. In this case, the test is failed.

subsequent adhesion:

The subsequent adhesion is determined largely according to the FINAT Test no. 11. For this purpose the tape TESA ^® 7475 from Beiersdorf is rolled onto the substrate and then stored at 40 ° C under a weight of 70 g / cm ^2. After 24 hours, the adhesive tape is separated from the release substrate and rolled on a defined substrate (steel plate, glass plate, foil). After one minute, the force needed to pull the tape off the ground at a speed of 30 cm / min at a peel angle of 180 ° is measured. The value measured in this way is divided by the value, which results in an untreated adhesive tape under otherwise identical test conditions. The result is referred to as residual adhesion and usually given in percent. Values over 80% are considered adequate by the skilled person and speak for a good curing.

Rub-Off:

Of the Rub-Off test is used to quickly determine adhesion of the coating to the underground. This is done in one place of the coating in 10 small circular movements rubbed with the finger at the same pressure. The rub-off test is only performed on well-cured coatings. He is considered passed if no silicone components are rubbed off can.

Radiation-curing organosilicon compounds:

Example 1:

Reaction of a medium-Si-H-functional siloxane (f = 156, h = 22, R ⁶ = Me) with 2-hydroxyethyl acrylate and Fluowet EA 600 (Clariant) using a boron-containing catalyst:
7.41 g of 2-hydroxyethyl acrylate, 19.36 g of Fluowet EA 600 and 20 g of toluene are in a four-necked flask equipped with stirrer, intensive condenser, thermometer and dropping funnel, together with 0.04 g of tris (pentafluorophenyl) borane as a catalyst, 400 ppm Methylhydroquinone heated in an inert atmosphere to 90 ° C. Upon reaching the temperature, 73.3 g of medium Si-H-functionalized polydimethylsiloxane (f = 156, h = 22, R ⁶ = Me) of the general formula Me ₃ SiO (SiMeHO) ₂₂ (SiMe ₂ O) ₁₅₆ SiMe ₃ (SiH Value 0.161%) was added dropwise within 15 minutes. After completion of the addition and cooling, the conversion was 100% according to the SiH value method.

To the distillation of the volatile Receives connections a clear, colorless liquid.

Example 2:

Reaction of a medium Si-H-functional siloxane (f = 9.3, h = 8.7, R ⁶ = Me) with 2-hydroxyethyl acrylate and heptadecylfluoro-1-decanol (Sigma-Aldrich) using a boron-containing catalyst:
13.8 g of 2-hydroxyethyl acrylate and 9.22 g of heptadecylfluoro-1-decanol are in a four-necked flask equipped with stirrer, intensive condenser, thermometer and dropping funnel, together with 0.14 g of tris (pentafluorophenyl) borane as a catalyst, 300 ppm Methylhydrochinon in heated inert atmosphere to 110 ° C. Upon reaching the temperature, 22.5 g of medium Si-H-functionalized polydimethylsiloxane (f = 9.3, h = 8.7, R ⁶ = Me) of the general formula Me ₃ SiO (SiMeHO) _8.7 (SiMe ₂ O) _9.3 SiMe ₃ (SiH value 0.624%) was added dropwise within 15 minutes. After completion of the addition and cooling the conversion was, according to the SiH value method at 100%.

To the distillation of the volatile Receives connections a clear, colorless liquid.

Comparative Example 3

Reaction of a medium Si-H-functional siloxane (f = 166, h = 12, R ⁶ = Me) with 2-hydroxyethyl acrylate using a boron-containing catalyst:
12.2 g of 2-hydroxyethyl acrylate is heated to 110 ° C. in a four-necked flask equipped with stirrer, intensive condenser, thermometer and dropping funnel, together with 0.01 g of tris (pentafluorophenyl) borane as catalyst, 400 ppm of methylhydroquinone in an inert atmosphere. When the temperature is reached 114.5 g of medium Si-H-functionalized polydimethylsiloxane (f = 166, h = 12, R ⁶ = Me) of the general formula Me ₃ SiO (SiMeHO) ₁₂ (SiMe ₂ O) ₁₆₆ SiMe ₃ (SiH Value: 0.088%) within 15 minutes. After completion of the addition and cooling, the conversion, according to the SiH value method was 100%.

To the distillation of the volatile Receives connections a clear, colorless liquid.

Comparative Example 4

As a further comparative example of an organopolysiloxane in which the acrylsäureesterhaltigen organic groups through Si-C bonds are linked to the polysiloxane, TEGO ^® RC 902 (according to US 6,211,322) has in the cured coating has a very good abhesive effect against sticky substances. The content of double bonds capable of polymerization is very low. TEGO RC 902 ^® is blended for improving the adhesion to the substrate with TEGO ^® RC 711 (according to DE-A-38 20 294). As Vergeichsbeispiel 3 therefore a mixture RC 902 / RC 711 70: 30 is used.

Example 5:

Reaction of a medium-Si-H-functional siloxane (f = 145, h = 32, R ⁶ = Me) with 2-hydroxyethyl acrylate and Fluowet EA 600 (Clariant) using a boron-containing catalyst:
6.5 g of 2-hydroxyethyl acrylate, 33.7 g of Fluowet EA 600 and 20 g of toluene are in a four-necked flask equipped with stirrer, intensive condenser, thermometer and dropping funnel, together with 0.07 g of tris (pentafluorophenyl) borane as catalyst, 400 ppm Methylhydroquinone heated in an inert atmosphere to 90 ° C. Upon reaching the temperature, 73.3 g of medium Si-H-functionalized polydimethylsiloxane (f = 145, h = 32, R ⁶ = Me) of the general formula Me ₃ SiO (SiMeHO) ₃₂ (SiMe ₂ O) ₁₄₅ SiMe ₃ (SiH Value: 0.249%) within 15 minutes. After completion of the addition and cooling the conversion was, according to the SiH value method at 100%.

To the distillation of the volatile Receives connections a clear, colorless liquid.

Example 6:

Reaction of a medium Si-H-functional siloxane (f = 156, h = 22, R ⁶ = Me) with 2-hydroxypropyl acrylate and Fluowet EA 600 (from Clariant) using a boron-containing catalyst:
8.3 g of 2-hydroxypropyl acrylate, 19.36 g of Fluowet EA 600 and 20 g of toluene are in a four-necked flask equipped with stirrer, intensive condenser, thermometer and dropping funnel, together with 0.05 g of tris (pentafluorophenyl) borane as catalyst, 400 ppm Methylhydroquinone heated in an inert atmosphere to 90 ° C. At Errei 73.3 g of medium Si-H-functionalized polydimethylsiloxane (f = 156, h = 22, R ⁶ = Me) of the general formula Me ₃ SiO (SiMeHO) ₂₂ (SiMe ₂ O) ₁₅₆ SiMe ₃ (SiH ₂ ) Value 0.161%) was added dropwise within 15 minutes. After completion of the addition and cooling the conversion was, according to the SiH value method at 100%.

To the distillation of the volatile Receives connections a clear, colorless liquid.

Example 7:

Reaction of a medium-Si-H-functional siloxane (f = 156, h = 22, R ⁶ = Me) with 2-hydroxybutyl acrylate and Fluowet EA 600 (Clariant) using a boron-containing catalyst:
9.2 g of 2-hydroxybutyl acrylate, 19.36 g of Fluowet EA 600 and 20 g of toluene are in a four-necked flask equipped with stirrer, intensive condenser, thermometer and dropping funnel, together with 0.05 g of tris (pentafluorophenyl) borane as catalyst, 400 ppm Methylhydroquinone heated in an inert atmosphere to 90 ° C. Upon reaching the temperature, 73.3 g of medium Si-H-functionalized polydimethylsiloxane (f = 156, h = 22, R ⁶ = Me) of the general formula Me ₃ SiO (SiMeHO) ₂₂ (SiMe ₂ O) ₁₅₆ SiMe ₃ (SiH Value 0.161%) was added dropwise within 15 minutes. After completion of the addition and cooling the conversion was, according to the SiH value method at 100%.

To the distillation of the volatile Receives connections a clear, colorless liquid.

Example 8:

Reaction of a medium-Si-H-functional siloxane (f = 156, h = 22, R ⁶ = Me) with 2-hydroxyethyl acrylate and Fluowet EA 800 (Clariant) using a boron-containing catalyst:
7.41 g of 2-hydroxyethyl acrylate, 24.7 g of Fluowet EA 800 and 20 g of toluene are in a four-necked flask equipped with stirrer, intensive condenser, thermometer and dropping funnel, together with 0.05 g of tris (pentafluorophenyl) borane as a catalyst, 400 ppm Methylhydroquinone heated in an inert atmosphere to 90 ° C. Upon reaching the temperature, 73.3 g of medium Si-H-functionalized polydimethylsiloxane (f = 156, h = 22, R ⁶ = Me) of the general formula Me ₃ SiO (SiMeHO) ₂₂ (SiMe ₂ O) ₁₅₆ SiMe ₃ (SiH Value: 0.161%) within 15 minutes. After completion of the addition and cooling the conversion was, according to the SiH value method at 100%.

To the distillation of the volatile Receives connections a clear, colorless liquid.

na: nicht anwendbarExamples 1, 2 and 5 to 8 according to the invention and also comparative examples 3 and 4 were tested as described under "Application Testing". In addition, mixtures of the examples were tested. The results (separation value with a silicone adhesive tape from Sellotape / UK, type 1650, loop test, rub-off and residual adhesion as described) are summarized in the following table:

na: not applicable

Out the application-technical examination shows that according to the invention organopolysiloxanes modified with fluorinated radicals over the very sticky silicone tape Sellotape 1650 one in comparison significantly improved to not so modified compounds Separation effect has been achieved. Also, the prior art in the comparative example 4 can not achieve such low separation values.

Furthermore may be the mixture of non-inventive compounds of the invention Benefits arise. Already the addition of 10% of the compound according to the invention of Example 1 or 8 to the compound of the prior art of Comparative Example 4 achieved significant improvement of the separation behavior. This results in particularly abhesive release coatings very good long-term stability and very uniform separation behavior without increased Cut-off peak when starting the separation process and little variation of the cut-off value during the separation process (also called Zipp).

Claims (18)

Organopolysiloxanes having (meth) acrylic acid ester groups and / or fluorinated or perfluorinated radicals of the general average formula (I) which are bonded via SiOC groups via medium and terminal or only intermediately bonded

wherein R ^{1 are} identical or different radicals selected from linear or branched, saturated, mono- or polyunsaturated alkyl, aryl, alkaryl or aralkyl radicals having 1 to 20 carbon atoms, R ² identical or different radicals R ¹ , R ³ or R ⁴ , R ^{3 are the} same or different singly or multiply (meth) acrylated monoalkoxylates or (meth) acrylated polyalkoxylates, or a mixture thereof, or a mixture of mono or poly (meth) acrylated monoalkoxylates or polyalkoxylates with any other alkoxylates selected from the group of linear or branched, saturated, mono- or polyunsaturated, aromatic, aliphatic-aromatic mono- or polyalcohols, polyether monoalcohols, polyetherpolyalcohols, polyester monoalcohols, polyesterpolyalcohols, amino alcohols, in particular N-alkyl-, arylamino-ethylene oxide-, propylene oxide Alcohols, N-alkyl or Arylaminoalkoxylate and mixtures thereof, wherein the ratio of the mono- or poly (meth) acrylated monoalkoxylates or polyalkoxylates to any other alkoxylates is chosen so that at least one single or multiple (meth) acrylated monoalkoxylate or polyalkoxylate radical is contained in the organopolysiloxane, R ⁴ identical or different fluorinated or perfluorinated monoalkoxylates or polyalkoxylates, or a mixture thereof, a 0 to 1,000, b 0 to 5, c 1 to 200, d 0 to 1,000, e 1 to 200. wherein at least one of R ² or R ^{3 is} a (meth) acrylated monoalkoxylate or polyalkoxylate radical and one of R ² or R ^{4 is} a fluorinated or perfluorinated monoalkoxylate or polyalkoxylate radical. Process for the preparation of compounds having (meth) acrylic acid ester groups bonded via SiOC groups and fluorinated or perfluorinated radicals by reacting SiH groups-containing polysiloxanes of the general average formula (II)

in which R ^{5 are} identical or different radicals selected from linear or branched, saturated, mono- or polyunsaturated alkyl, aryl, alkaryl or aralkyl radicals having 1 to 20 carbon atoms, R ⁶ H or R ⁵ , R ⁷ H, f 0 to 1,000, g 0 to 5, h 0 to 400, i 0 to 1000, wherein the radicals R ⁶ and / or R ⁷ together must be at least 2 times H, in one or more process steps using a Lewis acid catalyst or a catalyst consisting of a carboxylic acid and its salts with alcohols, which are selected from the group of mono- or polysubstituted (meth) acrylated monoalcohols or polyalcohols, or of a mixture thereof, or of mixtures of mono- or polysubstituted (meth) acrylated monoalcohols or polyalcohols with any other alcohols selected from the group of the linear or branched, saturated, mono- or polyunsaturated, aromatic, aliphatic-aromatic mono- or polyalcohols, polyether monoalcohols, polyetherpolyalcohols, polyestermonoalcohols, polyesterpolyalcohols, amino alcohols, in particular N-alkyl, arylamino-EO, -PO-alcohols, N-alkyl- or arylamino alcohols and mixtures thereof and with - identical or different fluorinated n or perfluorinated monoalcohols or polyalcohols, or with a mixture derselbigen. Process for the preparation of the compounds of the general Formula (I) by reacting SiH group-containing polysiloxanes the general average formula (II), characterized in that the catalyst used is tris (pentafluorophenyl) borane. Process for the reaction of SiH groups Polysiloxanes according to the claims 2 to 3, characterized in that both solvent-free and under Use of a solvent can be worked. Method according to at least one of claims 2 to 4, characterized in that the method is carried out in one stage. Method according to at least one of claims 2 to 5, characterized in that as (meth) acrylated alcohols 2-hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate or their Mixtures are used. A method according to any one of claims 2 to 6, characterized in that as fluorinated alcohols compounds of general formula (III) R _f (CH ₂ ) _n -OH, wherein R _f = fluorinated or perfluorinated C _1-20 alkyl radical and / or Alylrest may be preferably a C _1-10 alkyl, in particular a C _3-10 alkyl may be used. Method according to at least one of claims 2 to 7, characterized in that mixtures of different SiH polysiloxanes with the mono or poly (meth) acrylated monoalcohols or Polyalcohols or mixtures derselbigen and with the fluorinated Alcohols or mixtures of different fluorinated alcohols reacted become. Method according to at least one of claims 4 to 8, characterized in that as catalysts mixtures of at least one acid and at least one salt of an acid and at least one metal or ammonium salt an organic acid, where the metal cation may be monovalent or polyvalent used become. Method according to at least one of claims 2 to 9, characterized in that before the reaction of the alcohols, any other reaction with proportions of the hydrogen of the Si-H-siloxanes is carried out, with the proviso that the remaining portion of hydrogen in the radicals R ⁶ + R ⁷ ≥ 2H. curable abhesive Coating composition containing at least one compound according to claim 1. curable abhesive Coating composition containing at least one compound prepared according to procedure of one or more of claims 2 to 10. curable abhesive Coating composition according to a the claims 11 or 12, characterized in that mixed end and middle modified meth (acrylated) and fluorinated or perfluorinated alkoxide groups containing polysiloxanes are used. A curable, abhesive coating composition according to at least one of claims 11 to 13, characterized in that mixtures of different chain lengths and modification types of end and with tel- or only medially modified with acrylate and fluorinated alkyl groups polysiloxanes are used. curable abhesive Coating mass according to at least one of the claims 11 to 14, characterized in that auxiliaries and additives be admixed according to the prior art, in particular one or several selected from the group of photoinitiators, adhesion promoters, Curing accelerator, photosensitizers, Antioxidants, oxygen scavengers, organic (meth) acrylic groups or organic vinyl ether group-containing compounds and dyes, Pigments or solid particulate Fillers. Use of the hardenable Coating compositions according to at least one of the claims 11 to 15 for coating moldings and flat supports. abhesive Coating produced by curing the curable coating compositions according to at least one of the claims 11 to 16. abhesive Coating according to claim 17, characterized in that the hardening by application of heat or Radiation takes place.