Polysiloxane-polyoxyethylene-polyoxypropylene triblock-copolymers and antifoam compounds containing the same
Abstract
A polysiloxane-polyoxyethylene-polyoxypropylene tri-block copolymer of formula (I) where the ratio of x/y is 0.12-0.20 is claimed. R1 = 1-8 C alkyl; R2 = -(CH2)pO-; p = 2, 3 or 4; R3 = H or 1-4 C alkyl; n = 40-80; m = 3-10; x = 3-6; y = 20-30.

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5 claims: 5 independent, 0 dependent
- 1Polysiloxan-Polyoxyethylen-Polyoxypropylen-Triblockcopolymer der allgemeinen Formel wobei R1 = Alkylrest mit 1 bis 8 Kohlenstoffatomen,R2 = -(CH2)pO-, wobei p = 2, 3 oder 4 ist,R3 = Wasserstoffrest oder Alkylrest mit 1 bis 4 Kohlenstoffatomen,n = 40 bis 80,m = 3 bis 10,x = 3 bis 6 undy = 20 bis 30, mit der Maßgabe, daß das Verhältnis x/y 0,12 bis 0,20 beträgt. Polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymer of the general formula in whichR1 Alkyl radical with 1 to 8 carbon atoms,R2 = - (CH2)pO-, where p = 2, 3 or 4,R3 = Hydrogen radical or alkyl radical with 1 to 4 carbon atoms,n = 40 to 80,m = 3 to 10,x = 3 to 6 andy = 20 to 30, with the proviso that the ratio x / y is 0.12 to 0.20.
- 2Defoamer compound for defoaming aqueous emulsion paints, containing a polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymer according to claim 1 as an effective defoamer component. Entschäumercompound zur Entschäumung von wäßrigen Dispersionsfarben, enthaltend ein Polysiloxan-Polyoxyethylen-Polyoxypropylen-Triblockcopolymer gemäß Anspruch 1 als wirksame Entschäumerkomponente.
- 3Defoamer compound for defoaming aqueous emulsion paints, consisting ofa) 72 to 85 parts by weight of a polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymer according to claim 1,b) 15 to 28 parts by weight of a nonionic ethoxylation derivative with an HLB value of 8 to 12 andc) 0.1 to 10.0% by weight, based on components a) and b), of an inorganic or organic solid. Entschäumercompound zur Entschäumung von wäßrigen Dispersionsfarben, bestehend aus a) 72 bis 85 Gew.-Teilen eines Polysiloxan-Polyoxyethylen-Polyoxypropylen-Triblockcopolymers gemäß Anspruch 1,b) 15 bis 28 Gew.-Teilen eines nichtionischen Ethoxylierungsderivates mit einem HLB-Wert von 8 bis 12 sowiec) 0,1 bis 10,0 Gew.-%, bezogen auf die Komponenten a) und b), eines anorganischen oder organischen Feststoffes.
- 4Defoamer compound according to claim 3 in the form of an aqueous emulsion. Entschäumercompound gemäß Anspruch 3 in Form einer wäßrigen Emulsion.
- 5Defoamer compound according to claim 4, characterized in that the average droplet size of the emulsion is between 1 and 10 µm. Entschäumercompound gemäß Anspruch 4, dadurch gekennzeichnet, daß die mittlere Tröpfchengröße der Emulsion zwischen 1 und 10 µm liegt.
Independent claims5
35 paragraphs, as filed
The invention relates to polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymers and compounds for defoaming aqueous emulsion paints which contain the copolymers as an effective defoamer component.
The use of silicone oils, in particular dimethylpolysiloxanes of low to medium viscosity, for defoaming aqueous solutions or dispersions is known and is described, for example, in the book W. Noll "Chemistry and Technology of Silicones". To improve the defoaming effect of mineral oil-based and / or organosilicon defoamers, highly disperse inorganic or organic substances, in particular generally pyrogenic silicas, are often added (DE-PS 10 67 003, DE-OS 19 14 684).
It is also known to use polyoxyalkylene-polysiloxane copolymers as defoamers. US Pat. No. 3,763,021 describes a preparation for defoaming aqueous latices which consists of (1) 1 to 20% by weight of a siloxane glycol copolymer of the general formula<chemistry id="chem0001" num="0001"><img file="EP0777010A2_D0001.tif" /></chemistry> where x has an average value from 6 to 420 and y has an average value from 3 to 30 and G has a remainder of the structure -D (OR)<sub>e.g.</sub> A means in which D is an alkylene radical, R is composed of ethylene radicals and propylene or butylene radicals in a ratio of ethylene to the other alkylene radicals such that the ratio of carbon atoms to oxygen atoms in all blocks OR is in the range from 2.3: 1 up to 2.8: 1 z has an average value of 25 to 100 and A is a terminating group, (2) 65 to 98% by weight of polypropylene glycol with an average molecular weight in the range of 1000 to 2000 and (3) 1 to 15% by weight of one hydrophobic silica.
Typical manufacturing methods of these aforementioned polyoxyalkylene-polysiloxane copolymers are described in U.S. Patent 3,402,192, U.S. Patent 3,746,653, U.S. Patent 3,784,479 and U.S. Patent 3,865,544.
DE-PS 38 07 247 describes the use of polyoxyalkylene-polysiloxane block copolymers of the general formula R.<sub>1</sub> OA- (BA)<sub>m</sub>R<sub>1</sub>where A is a polyoxyalkylene block of the average formula (C<sub>n</sub>H<sub>2</sub><img file="EP0777010A2_D0002.tif" />O-)<sub>y</sub> where n is 2.8 to 4.0 and y is 15 to 100, B is a polysiloxane block of the average formula<chemistry id="chem0002" num="0002"><img file="EP0777010A2_D0003.tif" /></chemistry> where R<sub>2</sub> is identical or different and is an alkyl radical having 1 to 4 carbon atoms or a phenyl radical, but at least 90% of the radicals R<sub>2</sub> Are methyl radicals and x has a value from 10 to 100, R<sub>1</sub> is the same or different and is a hydrogen or alkyl radical having 1 to 4 carbon atoms and m has a value of 4 to 20, for defoaming aqueous dispersions of polymeric, organic substances, in particular dispersions of binders, coatings and adhesives.
These preparations, which are known from the prior art and contain silicone oils or polyoxyalkylene-polysiloxane copolymers, are more or less suitable for preventing the foaming of aqueous emulsion paints or for destroying foam that has already formed. It has been shown, however, that aqueous dispersion paints mixed with such preparations have disadvantages in use due to the addition of such defoaming agents, which are due to the addition of these defoaming agents.
It has been shown in particular that high-gloss emulsion paints, to which polysiloxanes or polyoxyalkylene-polysiloxane copolymers have been added for defoaming, have diverse wetting defects and reduced gloss when applied to surfaces. These wetting defects manifest themselves in uneven wetting of the substrate and lead to the formation of coatings of uneven thickness and, in extreme cases, to coatings which have imperfections of different dimensions.
These wetting errors are avoided by the polyoxyalkylene-polysiloxane block copolymers described in DE-PS 38 07 247, the skilled worker being aware that the defoaming effect of the additive emulsion paints wears off over time.
The object of the present invention is to find suitable polyoxyalkylene-polysiloxane copolymers which have good defoaming properties in aqueous emulsion paints, which retain this effect over a long period of time, but at the same time do not cause any wetting problems when these emulsion paints are applied to a surface.
This object on which the invention is based is surprisingly achieved by certain polyoxyalkylene-polysiloxane copolymers, namely by polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymers of the general formula I<chemistry id="chem0003" num="0003"><img file="EP0777010A2_D0004.tif" /></chemistry> in which<dl id="dl0001" compact="compact"><dt>R<sup>1</sup> =</dt><dd>Alkyl radical with 1 to 8 carbon atoms,</dd><dt>R<sup>2</sup> =</dt><dd>- (CH<sub>2</sub>)<sub>p</sub>O-, where p = 2, 3 or 4,</dd><dt>R<sup>3</sup> =</dt><dd>Hydrogen radical or alkyl radical with 1 to 4 carbon atoms,</dd><dt>n =</dt><dd>40 up to 80</dd><dt>m =</dt><dd>3rd until 10,</dd><dt>x =</dt><dd>3rd to 6 and</dd><dt>y =</dt><dd>20 up to 30</dd></dl> with the proviso that the ratio x / y is 0.12 to 0.20.
Another object of the invention is a defoamer compound for defoaming aqueous emulsion paints, which contains this polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymer as an effective defoamer component.
An advantageous compound consists of<dl id="dl0002" compact="compact"><dt>a) 72 to 85 parts by weight</dt><dd>a polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymer according to claim 1,</dd><dt>b) 15 to 28 parts by weight</dt><dd>a nonionic ethoxylation derivative with an HLB value of 8 to 12 and</dd><dt>c) 0.1 to 10.0% by weight,</dt><dd>based on components a) and b), an inorganic or organic solid.</dd></dl>
Of particular importance for the properties of the polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymers used in the compounds according to the invention is the polyoxyalkylene radical, where x and y are chosen such that x = 3 to 6, y = 20 to 30, but the molar ratio x / y is in each case 0.12 to 0.20, the polyoxalkylene blocks are arranged in blocks so that in each case the polypropylene oxide block is terminal.
It is known to the person skilled in the art that the compounds are in the form of a mixture with a distribution essentially regulated by statistical laws. In this respect, all indices represent mean values. As can be seen from the comparative examples, it has surprisingly been found that the values x and y, their ratio and in particular the block structure of the polyoxyethylene and polyoxypropylene fragments are decisive for the fact that the polyoxyalkylene-polysiloxane copolymers contained in the preparation according to the invention are excellent Are defoamers, whereby the effectiveness remains guaranteed over a longer period of time, without at the same time causing wetting errors when applying the emulsion paints containing defoamers.
As a nonionic surfactant, the preparations according to the invention contain nonionic ethoxylation derivatives whose HLB value (hydrophilic, lipophilic balance; definition according to WC Griffin; J. Soc. Cosmet. Chem. 1, 311 (1950), J. Soc. Cosmet. Chem. 5, 249 (1954)) is 8 to 12. Examples are the fatty acid esters of polyhydric alcohols, their polyethylene glycol derivatives, the polyglycol derivatives of fatty acids and fatty alcohols, alkylphenol ethoxylates and block copolymers of ethylene oxide and propylene oxide (Pluronics). Ethoxylation derivatives of oleochemical raw materials are preferably used. Nonionic oleyl and stearyl derivatives are particularly preferred.
Examples of inorganic solids are, if appropriate, hydrophobicized silica, aluminum oxide, alkaline earth metal carbonates or similar fine particulate solids known from the prior art. Known alkaline earth metal salts of long-chain fatty acids with 12 to 22 carbon atoms or the amides of these fatty acids can be used as organic fine-particle substances for this purpose.
The preparations according to the invention can be used as such or in the form of aqueous emulsions. The use of emulsions is preferred because of the better dosage options. Defoamer emulsions whose average particle size is between 1 and 10 μm are particularly preferred. In particular, aqueous emulsions containing 5 to 50% of the polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymer are used.
Examples of polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymers according to the invention and particularly suitable in the defoamer compounds are<chemistry id="chem0004" num="0004"><img file="EP0777010A2_D0005.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP0777010A2_D0006.tif" /></chemistry>
These polyoxyalkylene-polysiloxane copolymers are obtained by adding polyoxyalkylene ethers built up in blocks to olefinically unsaturated alcohols, such as. B. allyl polyoxyalkylene ethers, prepared on corresponding hydrogen siloxanes. This reaction is catalyzed by platinum compounds and is e.g. B. described in DE-PS 11 65 028.
Any contents of free polyoxyalkylene glycols or their monoethers or monoesters, which may be contained in the compounds to be used according to the invention for production reasons, can be tolerated and do not have to be separated from the product.
The compounds according to the invention are added to the emulsion paints in amounts of 0.01 to 0.50% by weight, based on the paint formulation, as defoamers.
The polyoxyalkylene-polysiloxane (co) polymers used in the preparations according to the invention and not according to the invention to be checked correspond to the general formula I. The radicals R<sup>1</sup> the meaning methyl, R<sup>2</sup> the meaning propoxy and R<sup>3</sup> and the indices n, m, x and y have the meanings or values shown in the table below. 5% silica is added as a solid.<tables id="tabl0001" num="0001"><img file="EP0777010A2_D0007.tif" /></tables>
As additional examples according to the invention, emulsions 9 and 10 are prepared from self-emulsifiable preparations 1 and 2. They are prepared in a manner known per se by stirring the preparation and the aqueous solution of a polyacrylate-based, neutralized thickener together with a disk stirrer for fifteen minutes.
Preparation 9 according to the invention is characterized in that it represents a 20% aqueous emulsion of preparation 1 with an average particle diameter of 2 μm. Preparation 10 according to the invention is also characterized in that it represents a 40% emulsion of preparation 2 with an average particle diameter of 5 μm.
The performance properties of the various preparations according to the invention and of the comparative examples are shown below.
To check the application properties, the following emulsion paint formulations are selected (quantities in% by weight):
Recipes 1 to 5:
<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="left">Dispersion paint 1</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Propylene glycol</entry><entry namest="col2" nameend="col2" align="char" char=",">4,8</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Collacral AS35</entry><entry namest="col2" nameend="col2" align="char" char=",">5,0</entry><entry namest="col3" nameend="col3" align="left">BASF, wetting and dispersing agent</entry></row><row><entry namest="col1" nameend="col1" align="left">Titanium dioxide</entry><entry namest="col2" nameend="col2" align="char" char=",">23,2</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Mergal K7</entry><entry namest="col2" nameend="col2" align="char" char=",">0,2</entry><entry namest="col3" nameend="col3" align="left">Riedel de Haen, preservative</entry></row><row><entry namest="col1" nameend="col1" align="left">Butyl glycol</entry><entry namest="col2" nameend="col2" align="char" char=",">2,6</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Dowanol DPM</entry><entry namest="col2" nameend="col2" align="char" char=",">1,4</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">6,9</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Acronal A603</entry><entry namest="col2" nameend="col2" align="char" char=",">54,3</entry><entry namest="col3" nameend="col3" align="left">BASF, pure acrylic dispersion</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Rheolate 278</entry><entry namest="col2" nameend="col2" align="char" char=",">4,0</entry><entry namest="col3" nameend="col3" align="left">Rheox, thickener</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="left">Emulsion paint 2</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">36,4</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Coatex P50</entry><entry namest="col2" nameend="col2" align="char" char=",">0,4</entry><entry namest="col3" nameend="col3" align="left">Coatex, dispersant</entry></row><row><entry namest="col1" nameend="col1" align="left">Calgon N</entry><entry namest="col2" nameend="col2" align="char" char=",">0,1</entry><entry namest="col3" nameend="col3" align="left">BK Ladenburg, dispersant</entry></row><row><entry namest="col1" nameend="col1" align="left">Mergal K7</entry><entry namest="col2" nameend="col2" align="char" char=",">0,2</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Coatex BR100</entry><entry namest="col2" nameend="col2" align="char" char=",">2,3</entry><entry namest="col3" nameend="col3" align="left">Coatex, PU thickener</entry></row><row><entry namest="col1" nameend="col1" align="left">Calcidar Extra</entry><entry namest="col2" nameend="col2" align="char" char=",">22,1</entry><entry namest="col3" nameend="col3" align="left">Omya, filler</entry></row><row><entry namest="col1" nameend="col1" align="left">Titanium dioxide</entry><entry namest="col2" nameend="col2" align="char" char=",">17,5</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Finntalk M15</entry><entry namest="col2" nameend="col2" align="char" char=",">4,7</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">NaOH, 10%</entry><entry namest="col2" nameend="col2" align="char" char=",">0,1</entry><entry namest="col3" nameend="col3" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Acronal 290D</entry><entry namest="col2" nameend="col2" align="char" char=",">16,2</entry><entry namest="col3" nameend="col3" align="left">BASF, styrene acrylate dispersion</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="left">Emulsion paint 3</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">2,3</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Propylene glycol</entry><entry namest="col2" nameend="col2" align="char" char=",">5,0</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Orotan 681</entry><entry namest="col2" nameend="col2" align="char" char=",">1,2</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, dispersant</entry></row><row><entry namest="col1" nameend="col1" align="left">Titanium dioxide</entry><entry namest="col2" nameend="col2" align="char" char=",">21,2</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Ethyl diglycol</entry><entry namest="col2" nameend="col2" align="char" char=",">2,0</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Dowanol DPnB</entry><entry namest="col2" nameend="col2" align="char" char=",">1,3</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Primal 2595</entry><entry namest="col2" nameend="col2" align="char" char=",">56,0</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, acrylic dispersion</entry></row><row><entry namest="col1" nameend="col1" align="left">Acrysol RM1020</entry><entry namest="col2" nameend="col2" align="char" char=",">4,4</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, thickener</entry></row><row><entry namest="col1" nameend="col1" align="left">Acrysol RM8</entry><entry namest="col2" nameend="col2" align="char" char=",">0,4</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, thickener</entry></row><row><entry namest="col1" nameend="col1" align="left">Tilcom AT23</entry><entry namest="col2" nameend="col2" align="char" char=",">0,3</entry><entry namest="col3" nameend="col3" align="left">Tioxide Chemicals, thixotropic agent</entry></row><row><entry namest="col1" nameend="col1" align="left">Triton GR5M</entry><entry namest="col2" nameend="col2" align="char" char=",">0,1</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, wetting agents</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">5,8</entry><entry namest="col3" nameend="col3" /></row></tbody></tgroup></table></tables><tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="left">Emulsion paint 4</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Mowolite DM123</entry><entry namest="col2" nameend="col2" align="char" char=",">51,6</entry><entry namest="col3" nameend="col3" align="left">Hoechst, PVAC copolymer</entry></row><row><entry namest="col1" nameend="col1" align="left">Ammonia, 25%</entry><entry namest="col2" nameend="col2" align="char" char=",">0,2</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Tylose H4000p, 2%</entry><entry namest="col2" nameend="col2" align="char" char=",">20,2</entry><entry namest="col3" nameend="col3" align="left">Hoechst, thickener</entry></row><row><entry namest="col1" nameend="col1" align="left">Calgon N, 10%</entry><entry namest="col2" nameend="col2" align="char" char=",">0,6</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Titanium dioxide</entry><entry namest="col2" nameend="col2" align="char" char=",">17,0</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Hydrocarb 90</entry><entry namest="col2" nameend="col2" align="char" char=",">8,0</entry><entry namest="col3" nameend="col3" align="left">Omya, filler</entry></row><row><entry namest="col1" nameend="col1" align="left">Parmetol A23</entry><entry namest="col2" nameend="col2" align="char" char=",">0,2</entry><entry namest="col3" nameend="col3" align="left">Schülke & Mayr, preservative</entry></row><row><entry namest="col1" nameend="col1" align="left">Butyl diglycol acetate</entry><entry namest="col2" nameend="col2" align="char" char=",">1,0</entry><entry namest="col3" nameend="col3" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Texanol</entry><entry namest="col2" nameend="col2" align="char" char=",">1,2</entry><entry namest="col3" nameend="col3" /></row></tbody></tgroup></table></tables><tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col3" align="left">Emulsion paint 5</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">8,0</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Acrysol RM-2020, 20%</entry><entry namest="col2" nameend="col2" align="char" char=",">1,6</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Orotan 731 K.</entry><entry namest="col2" nameend="col2" align="char" char=",">1,1</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, dispersant</entry></row><row><entry namest="col1" nameend="col1" align="left">Triton CA.</entry><entry namest="col2" nameend="col2" align="char" char=",">0,4</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, wetting agents</entry></row><row><entry namest="col1" nameend="col1" align="left">Calgon N</entry><entry namest="col2" nameend="col2" align="char" char=",">0,2</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Titanium dioxide</entry><entry namest="col2" nameend="col2" align="char" char=",">15,5</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Finntalk M15</entry><entry namest="col2" nameend="col2" align="char" char=",">3,7</entry><entry namest="col3" nameend="col3" align="left">filler</entry></row><row><entry namest="col1" nameend="col1" align="left">Millicarb</entry><entry namest="col2" nameend="col2" align="char" char=",">7,3</entry><entry namest="col3" nameend="col3" align="left">filler</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">2,0</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Primal SF-012</entry><entry namest="col2" nameend="col2" align="char" char=",">39,4</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, styrene acrylate dispersion</entry></row><row><entry namest="col1" nameend="col1" align="left">Ropaque OP-62 LO-E</entry><entry namest="col2" nameend="col2" align="char" char=",">6,4</entry><entry namest="col3" nameend="col3" /></row><row><entry namest="col1" nameend="col1" align="left">Acrysol RM2020, 20%</entry><entry namest="col2" nameend="col2" align="char" char=",">3,2</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, thickener</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="char" char=",">11,0</entry><entry namest="col3" nameend="col3" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Acrysol ASE-60, 30%</entry><entry namest="col2" nameend="col2" align="char" char=",">0,2</entry><entry namest="col3" nameend="col3" align="left">Rohm & Haas, thickener</entry></row></tbody></tgroup></table></tables>
The emulsion paints are formulated in the usual way according to the recipes above. All recipe components are used in the delivery form. The corresponding defoamer preparation is added as the last ingredient in the recipe. The incorporation takes place for one minute at 1000 rpm.
The effectiveness of the preparations according to the invention is checked using the role test described below. The results are shown in the tables below.
Role test
The so-called roller test comes relatively close to the practical conditions, so that a good differentiation between the different defoamer preparations is also possible with regard to the concentrations to be used.
In the roller test, 40 g of the emulsion paint to be tested are placed on a non-absorbent test card with a total area of 500 cm using an open-pore foam roller<sup>2</sup> distributed. The foam roller is wetted with water before the paint is applied. It is ensured that the same additional amount of water is always introduced into the paint and thus the drying time of the paint is always the same. The wet film overlay is approx. 300 g / m<sup>2</sup> Surface. After drying the film for 24 hours, the test panels are checked for the macro foam (number of bubbles per 100 cm<sup>2</sup>), with regard to the existing micro foam (number of pinholes by comparison with test panels with differently pronounced malfunctions, scale from 1 (very good) to 5 (poor, many pinpricks)) and with regard to any wetting defects.
These tests are repeated with additive emulsion paints that have been stored at 50 ° C for 6 weeks.<tables id="tabl0007" num="0007"><img file="EP0777010A2_D0008.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0777010A2_D0009.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0777010A2_D0010.tif" /></tables>
As can be seen from the preceding tables, the preparations according to the invention are distinguished by their universal applicability and can be used in a wide variety of color formulations.
12 sheets
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Every citation, both waysCites: the store holds 24 of 25
| Document | Relation | Office | Cited during |
|---|---|---|---|
| GB2350117A | Cited by | United Kingdom | Search report |
| DE10020670A1 | Cited by | Germany | Search report |
| US8222303B2 | Cited by | United States of America | Applicant |
| EP2289977A1 | Cited by | European Patent Office (EPO) | Search report |
| EP0297614A2 | Cites | European Patent Office (EPO) | Search report |
| EP0659837A2 | Cites | European Patent Office (EPO) | Search report |
| EP0663225A1 | Cites | European Patent Office (EPO) | Search report |
| EP0719539A2 | Cites | European Patent Office (EPO) | Search report |
| DE1067003B | Cites | Germany | Applicant |
| DE1067003B | Cites | Germany | Applicant |
| DE1165028B | Cites | Germany | Applicant |
| DE1165028B | Cites | Germany | Applicant |
| DE1914684A1 | Cites | Germany | Applicant |
| DE1914684A1 | Cites | Germany | Applicant |
| US2829112A | Cites | United States of America | Search report |
| US3402192A | Cites | United States of America | Applicant |
| US3402192A | Cites | United States of America | Applicant |
| US3746653A | Cites | United States of America | Applicant |
| US3746653A | Cites | United States of America | Applicant |
| US3763021A | Cites | United States of America | Applicant |
| US3763021A | Cites | United States of America | Applicant |
| US3784479A | Cites | United States of America | Applicant |
| US3784479A | Cites | United States of America | Applicant |
| DE3807247C1 | Cites | Germany | Applicant |
| DE3807247C1 | Cites | Germany | Applicant |
| US3865544A | Cites | United States of America | Applicant |
| US3865544A | Cites | United States of America | Applicant |
| US5032662A | Cites | United States of America | Search report |
16 members in 9 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 19544586 | Germany | A | |
| 19544586 | Germany | A | |
| 19544586 | Germany | – | |
| 19544586 | – | – | – |
| DE1995144586 | – | – | – |
Members16
| Document | Office | Kind | |
|---|---|---|---|
| NO963828D0 | Norway | D0 | |
| CA2191507A1 | Canada | A1 | |
| NO963828L | Norway | L | |
| EP0777010A2This record | European Patent Office (EPO) | A2 | |
| JPH09157399A | Japan | A | |
| EP0777010A3 | European Patent Office (EPO) | A3 | |
| US5804099A | United States of America | A | |
| NO310922B1 | Norway | B1 | |
| CA2191507C | Canada | C | |
| EP0777010B1 | European Patent Office (EPO) | B1 | |
| AT232250T | Austria | T | |
| ATE232250T1 | Austria | T1 | |
| DE59610113D1 | Germany | D1 | |
| DK0777010T3 | Denmark | T3 | |
| ES2189851T3 | Spain | T3 | |
| JP3636817B2 | Japan | B2 |
73 legal events, as 12 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Announcement of lapse in spainLapsedFD2A | FD2A | ES | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Patent expired after termination of 20 yearsExpiredPE20 | PE20 | GB | |
| Patent expired because of reaching the maximum lifetime of a patentExpiredMK | MK | NL | |
| Expiry of rightR071 | R071 | DE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Ep patent lapsedLapsedEBP | EBP | DK | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Fee paymentPLFP | PLFP | FR | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Transmission of propertyTP | TP | FR | |
| Assignments of patentsSD | SD | NL | |
| Transfer of patentPC2A | PC2A | ES | |
| Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977)732E | 732E | GB | |
| Change of applicant/patenteeR081 | R081 | DE | |
| Assignments of patentsSD | SD | NL | |
| Modifications of names of proprietors of patentsTD | TD | NL | |
| Change of name or company nameCD | CD | FR | |
| Change of name or company nameCD | CD | FR | |
| Change in legal formCJ | CJ | FR | |
| Patent lapsedLapsedMM4A | MM4A | IE | |
| Annulment/lapse due to non-payment of fees, searched and examined patentLapsedMM4A | MM4A | PT | |
| Patent ceasedCeasedPL | PL | CH | |
| Se: european patent has lapsedLapsedEUG | EUG | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionPLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTAA | STAA | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Fr: translation filedET | ET | EP | |
| Definitive protectionFG2A | FG2A | ES | |
| Ep patent validated in greeceEP | EP | GR | |
| Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT | GBT | EP | |
| Translation of granted ep patentGrantedTRGR | TRGR | SE | |
| Ep patent with danish claimsT3 | T3 | DK | |
| Corresponds to:REF | REF | EP | |
| European patents granted designating irelandGrantedFG4D | FG4D | IE | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| Designated contracting statesAK | AK | EP | |
| European patent grantedGrantedFG4D | FG4D | GB | |
| (expected) grantGRAA | GRAA | EP | |
| Despatch of communication of intention to grant a patentGRAH | GRAH | EP | |
| Despatch of communication of intention to grantGRAG | GRAG | EP | |
| Despatch of communication of intention to grant a patentGRAH | GRAH | EP | |
| Despatch of communication of intention to grantGRAG | GRAG | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Party data changed (applicant data changed or rights of an application transferred)RAP1 | RAP1 | EP | |
| Designated contracting statesAK | AK | EP | |
| Search report despatchedPUAL | PUAL | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phasePUAI | PUAI | EP |
Numbers
- Publication
- 0777010
- Publication, DOCDB
- 0777010
- Publication, EPODOC
- EP0777010
- Application
- 96118332
- Application, DOCDB
- 96118332
- Application, EPODOC
- EP19960118332
Titles3
- German
- Polysiloxan-Polyoxyethylen-Polyoxypropylen-Triblockcopolymere und diese enthaltende Entschäumercompounds
- English
- Polysiloxane-polyoxyethylene-polyoxypropylene triblock-copolymers and antifoam compounds containing the same
- French
- Copolymères tribloc polysiloxane-polyoxyéthylène-polyoxypropylène et composés antimousses les contenant
Classification
- CPC, 5
- B01D19/0409
- C08G77/46
- D06P1/16
- D06P1/5292
- D06P3/54
- IPC, 6
- C09B67 46
- B01D19 04
- C08G77 46
- D06P1 16
- D06P1 52
- D06P3 54
Designated states16
- Contracting states, 16
- Austria
- Belgium
- Switzerland
- Germany
- Denmark
- Spain
- Finland
- France
- United Kingdom
- Greece
- Ireland
- Italy
- Liechtenstein
- Netherlands (Kingdom of the)
- Portugal
- Sweden