Antifoaming agent composition based on organically functionalized polysiloxane

Abstract

To provide a defoaming agent composition excellent in both of effectiveness and compatibility.SOLUTION: A defoaming agent composition bases organic functional modified polysiloxane containing one or a plurality of lateral polyether modified polysiloxane as a component A and at least one terminal polyether modified polysiloxane as a component B.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an antifoaming agent composition based on organically functionalized polysiloxane. [Background technology]

[0002] Foaming is an unwanted phenomenon that frequently occurs during the manufacturing and processing of paints, coatings, and printing inks. Therefore, when foaming occurs, it can result in the inability to optimally fill production containers. This, in turn, can interrupt production and create unnecessary waiting times. For example, in printing operations, foaming can cause ink containers to overflow, impairing the transfer of ink from rollers to the substrate. Dry foam leaves defects on the surface of coating films. Foaming is caused by the influx of gas into liquid materials. This occurs, for example, through the following: • Mechanical inflow of air during manufacturing due to stirring or mixing, • Air movement when wetting pigments and fillers, Mechanical inflow of air during coating by rolling, spraying, printing, etc. • Air movement during coating of porous substrates.

[0003] Almost every component in a coating recipe can have a positive or negative effect on foaming behavior. Therefore, defoaming agents need to be added to the formulation to avoid foaming and to remove any foam that has already formed.

[0004] Typical active ingredients for defoaming agents are polysiloxanes, mineral oils, and vegetable oils, or polymers. It is known that by combining these active ingredients, as well as by adding finely fragmented hydrophobic solids such as silica, it is possible to create particularly effective defoaming agents tailored to specific applications.

[0005] Silicones have been used in the paint industry since the early 1950s. For example, the most important silicone properties, such as compatibility, slip resistance, and scratch resistance, could be controlled, particularly through the chemical modification of the dimethylpolysiloxane chain.

[0006] Known modified dimethylpolysiloxane chains are polyoxyalkylene-polysiloxanes, and the balanced ratio of the polyoxyalkylene block to the polysiloxane block, as well as the structure of the two blocks, are of great importance. There are numerous uncertainties in both the polyoxyalkylene block and the polysiloxane block when creating the most effective defoamers for use in wood, plastics, industrial and automotive coatings, or printing inks.

[0007] Polyoxyalkylene blocks can be composed of various oxyalkylene units, particularly oxyethylene, oxypropylene, and oxybutylene units. The relative weight ratios, arrangement, and molar weight of these units, as well as the molar weight of the polyoxyalkylene block, can be varied. Also important are the terminal groups of the polyoxyalkylene block, which may be reactive or inert (e.g., OH groups for reactive, alkoxy groups for inert). Polyoxyalkylene blocks can be bonded to polysiloxane blocks by hydrolysis-stable C-Si bonds or hydrolysis-unstable CO-Si bonds. Different polyoxyalkylene blocks can also be bonded to polysiloxane blocks. Polysiloxane blocks may be modified in terms of the properties and ratios of Si units. Siloxane blocks may be linear or branched and have a variety of molecular weights. Polyoxyalkylene blocks can be bonded to the ends and / or sides of polysiloxane blocks. Predictions regarding the effectiveness of polysiloxane-polyoxyalkylene block copolymers as antifoaming agents are limited. Therefore, those skilled in the art are compelled to study possible variations, primarily by empirical means. Given that there are virtually countless possible variations, finding specific structural parameters and corresponding polyoxyalkylene-polysiloxanes that are particularly effective in the manufacture of antifoaming agents would be an achievement that advances the art and is therefore progressive.

[0008] Polyoxyalkylene-polysiloxanes, used in coating technologies, have been described numerous times in prior art. The following documents are cited as representative examples from a large number of relevant publications. Patent Document 1 describes, for example, a silicone-based defoaming agent preparation comprising polydiorganosiloxane, silica, and modified silicone oil.

[0009] Patent Document 2 also discloses aqueous, radiation-curable printing coatings and printing inks containing a specific polyoxyalkylene-polysiloxane copolymer that has improved scratch resistance, high surface slipperiness, and very low foaming properties, resulting in smoother production of the printing ink while simultaneously achieving optically favorable printed images.

[0010] Patent Document 3 discloses an organically functionalized polysiloxane-based antifoaming emulsion obtained by mixing one or more detailed organically functionalized siloxanes with finely fragmented silica, and then emulsifying the mixture with water containing a hydrophilic organically functionalized polysiloxane using a low-shear stirrer.

[0011] Therefore, the use of organically functionalized polysiloxanes to remove foam from liquids is known in the art. There are numerous documents and patent specifications that describe the mechanism of action of siloxanes and provide indicators for selecting appropriate siloxanes and their preparation forms. The potential advantages of using mixtures of different polysiloxanes were recognized early on. For this purpose, numerous organically functionalized polysiloxanes have also been developed in various ways.

[0012] The essential characteristic of all defoamers is their targeted and controlled incompatibility with the medium they are intended to defoam. A defoamer that is too compatible does not specifically penetrate and destabilize the foam lamellae, but rather is present throughout the entire coating film. In this case, the defoaming effect, if any, is minimal. Excessive incompatibility leads to defects in the coating film, such as cloudiness and craters, resulting in a destructive appearance. Therefore, selecting the appropriate defoamer is like "balancing" compatibility and incompatibility. This means either sacrificing some of the defoamer's activity to make it more compatible with the coating system, or accepting defects in the coating film to eliminate waiting times during manufacturing, etc. This compromise seems unavoidable. [Prior art documents] [Patent Documents]

[0013] [Patent Document 1] European Patent No. 0427263 [Patent Document 2] European Patent No. 0785240B1 [Patent Document 3] European Patent No. 0 658 361 [Overview of the Initiative] [Problems that the invention aims to solve]

[0014] Therefore, the problem that the present invention aims to solve is to provide an antifoaming agent composition that overturns this rule of effectiveness and compatibility. [Means for solving the problem]

[0015] To solve the problem, the present inventors propose an antifoaming agent composition based on organically functionally modified polysiloxane, which includes the following: - Component A consists of one or more lateral polyether-modified polysiloxanes, and - Component B is at least one terminally polyether-modified polysiloxane. [Brief explanation of the drawing]

[0016] [Figure 1] Figure 1 shows the volume of the form of the composition according to the present invention, indicated by a circle, component A, indicated by a triangle, and component B, indicated by a square. [Figure 1a] Figure 1a shows the compatibility between the composition according to the present invention, indicated by the circle symbol, and component B, indicated by the triangle symbol. [Figure 2]Figure 2 shows the volumes of foam mixed with TEGO Foamex 810 and TEGO Wet 285 in different ratios (indicated by the × symbol), Tego Wet 285 (indicated by the × symbol in the black square), and TEGO Foamex 810 (indicated by the cross symbol in the black square). [Figure 2a] Figure 2a shows the compatibility of TEGO Foamex 810 and TEGO Wet 285 mixed in different ratios (indicated by the × symbol), as well as the compatibility of TEGO Foamex 810 (indicated by the × symbol in the black square) and Tego Wet 285 (indicated by the cross symbol in the black square). [Figure 3] Figure 3 shows the volumes of foam mixed with TEGO Foamex 830 and TEGO Foamex 844 in different ratios (indicated by black diamond symbols), as well as the volumes of Tego Foamex 844 (indicated by white square symbols) and TEGO Foamex 830 (indicated by white circle symbols). [Figure 3a] Figure 3a shows the compatibility of TEGO Foamex 830 and TEGO Foamex 844 mixed in different ratios (indicated by black diamond symbols), as well as the compatibility of Tego Foamex 830 (indicated by white circle symbols) and TEGO Foamex 844 (indicated by white square symbols). [Modes for carrying out the invention]

[0017] In the context of this specification, the terms medium, coating system, coating or paint formulation, coating recipe, and coating composition should be understood to be synonymous. They are systems to be defoamed.

[0018] The terms polyether-modified polysiloxane and polyetherpolysiloxane should be understood as synonymous.

[0019] Surprisingly, it was found that specific topologically distinct combinations of polyether-modified polysiloxanes resulted in synergistically improved properties regarding defoaming and compatibility in the media to be defoamed. These synergistic effects were astonishing.

[0020] Those skilled in the art will know, for example, that by combining a first polyetherpolysiloxane with high compatibility and low defoaming activity with a second polyetherpolysiloxane with low compatibility and high defoaming activity, a composition will be obtained that is less compatible than the first polyetherpolysiloxane and has lower defoaming activity than the second polyetherpolysiloxane.

[0021] According to the study, this reduction is based on a rule. Comparative Example 2 and Figure 2a illustrate this rule. According to this rule, the compatibility and antifoaming activity values ​​of the mixture lie between the values ​​of each individual polyether polysiloxane. They are substantially on a straight line.

[0022] Comparative Example 3, Figure 3, and Figure 3a also show this linear relationship (dashed line). Polyether was used as the compatible component.

[0023] The antifoaming compositions according to the present invention, which contain specifically selected topologically polyether-modified polysiloxanes, exhibit synergistic effects that do not conform to this rule, as shown in Figures 1 and 1a. The values ​​are outside the dashed lines that those skilled in the art would have expected. Furthermore, the antifoaming compositions according to the present invention exhibit superior antifoaming activity compared to the individual components.

[0024] The term "defoaming" is often used to describe the removal of gas bubbles from a coating. However, in some cases, it is necessary to distinguish between "defoaming" and "degassing". Gas bubbles need to first reach the surface. Then, the removal of foam bubbles occurring at the surface is called defoaming. The defoaming agent is active only at the surface where it removes the existing air bubbles. In contrast, the degassing agent must be active throughout the coating film. The defoaming agent destabilizes the foam bubbles. The coating film contains air. The degassing agent promotes the movement of bubbles to the surface.

[0025] The defoaming agent composition according to the present invention is suitable for defoaming and degassing. Hereinafter, the term "defoaming agent" is used for both effects, but in some cases, the term "degassing agent" may be more accurate in reality.

[0026] Preferably, the organically modified polysiloxane is a linear organically modified polysiloxane.

[0027] Component A is preferably a compound of general formula (I). [Chemical formula] (I)

[0028] (In the formula, R is the same and / or different alkyl radicals having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably 1 or 2 carbon atoms, R 1 is -C p H 2p O[(C2H4O) x (C3H6O) y R 2 (In the formula, p is 2, 3 or 4, R 2 is hydrogen and / or an alkyl radical having 1 to 3 carbon atoms, x and y are the polyoxyalkylene block -C p H 2pO[(C2H4O) x (C3H6O) y The molar weight of [the substance] is selected to be in the range of 500 to 10,000 g / mol, preferably 1,000 to 8,000 g / mol, and particularly preferably 2,000 g / mol to 6,000 g / mol. And, m is 10 to 400, preferably 20 to 300, and particularly preferably 30 to 200. n is 1 to 15, preferably 2 to 8.

[0029] R 2 It is considered preferable that this is hydrogen or an acetate group.

[0030] R 1 This radical-C p H 2p O(C3H6O) y ]R 2 It is also preferable to include it.

[0031] Component B is preferably a compound of general formula (II). [ka] (II)

[0032] (In the formula, R 3 These are identical and / or different alkyl radicals having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms. R 4 R 3 and / or -C p H 2p O[(C2H4O) x (C3H6O) y ]R 2 and / or -C p H 2p O(C3H6O) y ]R2 (In the formula, p is 2, 3, or 4, R 2This is an alkyl radical having 1 to 3 carbon atoms and / or hydrogen, preferably an alkyl radical having 1 to 3 carbon atoms. x and y are the polyoxyalkylene block-C p H 2p O[(C2H4O) x (C3H6O) y ]- and / or -C p H 2p O(C3H6O) y The molar weight of [the substance] is selected to be in the range of 200 to 4,000 g / mol, preferably 500 to 3,000 g / mol, and particularly preferably 750 to 2,000 g / mol. and, provided that at least one of the R 4 ga-C p H 2p O[(C2H4O) x (C3H6O) y ]- or -C p H 2p O(C3H6O) y ]- is the terminal, f is 20 to 500, preferably 25 to 200, and particularly preferably 35 to 100. g is 1 to 15, preferably 2 to 8.

[0033] Preferably, the polyoxyalkylene block-C p H 2p O[(C2H4O) x (C3H6O) y In ], y is greater than x, and x and y are natural numbers.

[0034] It will be obvious to those skilled in the art that the compounds obtained according to formulas (I) and (II) are in the form of mixtures whose distribution is substantially derived by statistical rules. Therefore, the values ​​of x, y, f, g, p, and n and m correspond to the mean values.

[0035] The values ​​of the indices n, m / f, and g are crucial for the properties of polyoxyalkylene-polysiloxanes. n / f indicates the number of methylalkylsiloxy units and determines the chain length of the siloxane fraction. It is a well-known concept to those skilled in the art that a compound is in the form of a mixture with a distribution substantially controlled by statistical rules. Therefore, the value of n / f represents the average number of methylalkylsiloxy units.

[0036] As shown in the following formula, the polysiloxane used in accordance with the present invention is generally produced by an addition reaction catalyzed by a metal (preferably platinum) between a polysiloxane containing silane hydrogen and a linear polyoxyalkylene oxide polyether. The linear chain of the linear polyoxyalkylene oxide polyether is functionalized at one end with an alkylene oxy group (such as allyl oxy or vinyl oxy), and the other end is capped with, for example, an OH functional group, or an alkoxy group, an aralkyl oxy group, or an acyl oxy group. XSiH+H2C=CHCH2OR 3 → XSiCH2CH2CH2OR 3 (Hydrosilylation reaction)

[0037] The polysiloxane according to the present invention is known in principle. Further manufacturing methods are disclosed in Patent Document 2.

[0038] According to the present invention, the polyoxyalkylene block preferably comprises oxyethylene units and oxypropylene units, and preferably derived from ethylene oxide and propylene oxide.

[0039] The polyoxyalkylene block may, in some cases, contain oxyphenylethylene units or oxybutylene units.

[0040] Polyoxyalkylene block-C in component A p H 2p O[(C2H4O) x (C3H6O) y]- preferably has a block-like structure.

[0041] The polyoxyalkylene block in component A preferably comprises three blocks, the central block consisting of pure oxypropylene units, and the remaining blocks consisting of a mixture of oxyethylene and oxypropylene.

[0042] R 4 ga-C p H 2p O[(C2H4O) x (C3H6O) y ]R 2 and / or -C p H 2p O(C3H6O) y ]R² (where p is 2, 3, or 4), where at least one R 4 ga-C p H 2p O[(C2H4O) x (C3H6O) y ]- or -C p H 2p O(C3H6O) y It is preferable that ]- is at the end.

[0043] Component B preferably comprises a polyoxyalkylene-polysiloxane with lateral and terminal denaturation.

[0044] Units of component B, called x and y, may exist as a statistical mixture or in block form within the chain. The statistical distribution may have a blocky structure with any number of blocks and any arrangement, or it may be a randomized distribution. They may also have an alternating structure or form a gradient along the chain. In particular, they may also form any mixed form in which different groups of distributions may follow each other as they wish. Certain embodiments may result in a restricted statistical distribution as a result of that embodiment. In all regions unaffected by such restrictions, the statistical distribution remains unchanged.

[0045] The molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component A is preferably smaller than the molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component B.

[0046] In the context of this specification, the siloxane fraction is R 1 Formula (I) / R that does not include 4 It is defined by formula (II), which does not include .

[0047] It is particularly preferable that the molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component A is 0.15 to 0.35.

[0048] It is preferable that the viscosity of component A, measured in accordance with DIN 53015, is in the range of 2,500 to 60,000 mPa·s, preferably 3,000 to 55,000 mPa·s, and particularly preferably 4,000 to 50,000 mPa·s.

[0049] It is particularly preferable that the molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component B is 0.4 to 2.

[0050] It is preferable that the viscosity of component B, measured in accordance with DIN 53015, is in the range of 250 to 1,200 mPa·s, preferably 300 to 1,000 mPa·s, and particularly preferably 350 to 900 mPa·s.

[0051] It is preferable that the compatibility of component A, as measured by the method described below, is higher than that of component B.

[0052] It is preferable that the antifoaming activity of component B, as measured by the method described below, is higher than that of component A.

[0053] The composition according to the present invention is preferably obtained by stirring components A and B using a low-shear stirrer.

[0054] Further additives (e.g., polyethers, natural and synthetic oils, organic polymers, organically modified silicone polymers, and solids) can be added to the compositions according to the present invention. Examples of such suitable finely divided solids include highly dispersible, exothermic, or wet chemically derived silica, which is commercially available as Aerosil or Sipernat and can be hydrophobized by treatment with organosilicon compounds. Further suitable solids include metal soaps such as magnesium, aluminum, and calcium soaps, and polyethylene and amide waxes or urea.

[0055] The composition is preferably, (a) As component A, 20 to 80% by weight, preferably 30 to 70% by weight, particularly preferably 40 to 60% by weight, of an organically functionalized polysiloxane of formula (I). (b) Component B is formula (II) (wherein at least one polyoxyalkylene block-C) p H 2p O[(C2H4O) x (C3H6O) y ]- is the terminal. 20-80% by weight, preferably 30-70% by weight, particularly preferably 40-60% by weight, of the organically functionally modified polysiloxane of ), and (c) As component B', formula (II) (wherein at least one polyoxyalkylene block-C p H 2p O(C3H6O) y ]- is the terminal. 0 to 70% by weight, preferably 0 to 60% by weight, particularly preferably 0 to 50% by weight, of the organically functionally modified polysiloxane (which is terminal). Includes, The reported amounts of components A, B, and B' are 100% by weight in total and are relative to the composition.

[0056] The composition according to the present invention is preferably obtained by adding component A to a mixture of components B and B' while stirring, preferably using a low-shear stirrer.

[0057] Similarly, it is thought that the defoaming activity can be further enhanced by adding additional solids (e.g., silica, waxes, and solids). Such additives are known to those skilled in the art.

[0058] The composition is preferably, (a) As component A, 20 to 80% by weight, preferably 30 to 70% by weight, particularly preferably 40 to 60% by weight, of an organically functionalized polysiloxane of formula (I). (b) Component B is formula (II) (wherein at least one polyoxyalkylene block-C) p H 2p O[(C2H4O) x (C3H6O) y ]- is the terminal. 20-80% by weight, preferably 30-70% by weight, particularly preferably 40-60% by weight, of the organically functionally modified polysiloxane of ). (c) As component B', formula (II) (wherein at least one polyoxyalkylene block-C p H 2p O(C3H6O) y ]- is the terminal. 0 to 70% by weight, preferably 0 to 60% by weight, particularly preferably 0 to 50% by weight, of the organically functionally modified polysiloxane of ). (d) A solid selected from silica, urea, or wax, in an amount greater than 0% by weight but less than 5% by weight, preferably 0.1 to 4.5% by weight, and particularly preferably 0.5 to 3.5% by weight. Includes, The reported amounts of components A, B, B' and the solid are 100% by weight in total and are relative to the composition.

[0059] It is also possible to add an emulsifier to produce an antifoaming emulsion starting from the composition according to the present invention. A commercially available emulsifier, preferably a nonionic emulsifier selected from fatty alcohol ethoxylates, may be used.

[0060] It is preferable that the viscosity of the composition, as measured in accordance with DIN 53015, is 250 to 5,000 mPa·s, preferably 300 to 50,000 mPa·s, and particularly preferably 350 to 40,000 mPa·s.

[0061] The static surface tension of the composition, as measured with a Kruss K100 static surface tensile meter in accordance with DIN EN 14370:2004, is 20 to 65 mN / m, preferably 25 to 60 nN / m, and particularly preferably 30 to 50 mN / m, and It is preferable that the dynamic surface tension of the composition, as measured with a Kruss BP50 bubble pressure tension meter in accordance with DIN EN 14370:2004, is 20 to 65 mN / m, preferably 25 to 60 nN / m, and particularly preferably 30 to 50 mN / m.

[0062] The compositions according to the present invention preferably have at least a bimodal distribution of polyether in the GPC spectrum.

[0063] In the composition according to the present invention, the weight ratio of component A to component B is preferably 9:1 to 1:9, more preferably 4:1 to 1:4, and particularly preferably 2:1 to 1:2.

[0064] An additional aspect of the present invention is the use of the composition as an antifoaming agent additive, as a flow control additive, and / or as a substrate wetting additive.

[0065] A further aspect of the present invention is the use of compositions for producing dispersions, mill bases, paints, coatings or printing inks, inkjet printers, grind-type resins, pigment concentrates, colorant preparations, pigment preparations, filler preparations, or coating compositions.

[0066] The coating composition may be solvent-based, solvent-free, or water-based coating or printing ink.

[0067] The present invention further provides the use of compounds represented by formulas (I) and (II) for producing antifoaming compositions.

[0068] Refer to the above for specific selection criteria for polyether-modified polysiloxanes.

[0069] The following examples are provided solely to illustrate the present invention to those skilled in the art and do not in any way limit the subject matter of the claims or the methods described in the claims. [Examples]

[0070] Test method The parameters or measured values ​​are preferably measured using the methods described below. These methods are used in particular in the embodiments of this intellectual property right.

[0071] Viscosity (mPa s) Viscosity is measured using a Heppler-type falling-ball viscometer in accordance with DIN 53015.

[0072] compatibility Compatibility is measured visually using a coating of the test formulation applied to a film (Melinex 401 CW manufactured by Putz Folien) using a spiral film applicator (Erichsen K-Stab No. 2). The evaluation will be conducted according to the following scale (for an area of ​​10 x 10 cm). 1 = The entire surface is defective. 2 = The entire surface is defective. 3 = The surface has a very large number of defects. 4 = The surface has many defects. 5 = There are independent defects on the surface (up to 50) 6 = There are independent defects on the surface (up to 30) 7 = There are a few independent defects on the surface (maximum 20). 8 = There are a few independent defects on the surface (maximum 10). 9 = The surface has very few independent defects (1-5). 10 = No defects on the surface

[0073] Activity of antifoaming agents The activity of the defoaming agent is measured by a stirring test. For this purpose, 50 g of the formulation and a test amount of defoaming agent (e.g., 0.2 g) are weighed into a plastic beaker. Using a stirrer (VMA Getzmann GmbH Dispermat type 60 / 2-457) equipped with a toothed dissolver disc (3 cm in diameter, VMA Getzmann GmbH), the defoaming agent is incorporated at 1000 rpm for 1 minute. Subsequently, the formulation is foamed at 3000 rpm for 2 minutes. Next, 45 g of the formulation is weighed into a 100 mL graduated cylinder, and the volume is read. A higher volume indicates lower defoaming agent activity.

[0074] Application Each coating composition is applied to a film (Melinex 401 CW manufactured by Putz Folien) using a spiral film applicator (Erichsen K-Stab No. 2). It is then dried at room temperature.

[0075] Additional conditions In the context of this specification, when values ​​are reported in percentages, they are weight percentages unless otherwise specified. For compositions, when values ​​are reported in percentages, they are values ​​relative to the entire composition unless otherwise specified. When average values ​​are given below, they are number averages unless otherwise specified. When measured values ​​are given below, these measurements were taken at a pressure of 101-325 Pa, a temperature of 23°C, and an ambient relative humidity of approximately 40%, unless otherwise specified.

[0076] Materials and equipment Dispersive mat type 60 / 2-457 (manufactured by VMA Getzmann GmbH) Dissolver disc (3cm diameter) (Manufactured by VMA Getzmann GmbH) Spiral film applicator (K-Stab No.2) (manufactured by Erichsen) Film (Melinex 401 CW) (manufactured by Putz Folien) K100 Tensiometer for static surface tension (manufactured by Kruss) BP50 Tensiometer for dynamic surface tension (manufactured by Kruss) Speed mixer DAC 150 FVZ (manufactured by Hauschild GmbH & Co. KG)

[0077] Comparative Example Tego Foamex 810 manufactured by Evonik is a polyether polysiloxane, and the polyether units and polysiloxane units are composed of alternating blocks. Tego Foamex830 manufactured by Evonik is a polyether. Tego Foamex 844 manufactured by Evonik is a polyether polysiloxane having terminal and lateral polyether modifications, and the polyether units are derived from ethylene oxide or propylene oxide. Therefore, the polyether modification consists of at least two polyoxyalkylene blocks each having only oxyethylene units or oxypropylene units. Tego Wet 285 manufactured by Evonik is a polyether polysiloxane modified laterally, and the polyoxyalkylene block is -C p H p+2 O2[(C2H4O) x (C3H6O) y -(where p = 10).

[0078] Example 1. Production of the antifoaming agent composition according to the present invention 1.1 Production of Component A In a 4 L three-necked flask equipped with a reflux condenser and a KPG stirrer, a siloxane represented by the general formula Me3SiO(SiMeHO) 6.5 (SiMe2O) 90 SiMe3 (300 g) and a compound represented by the general formula CH2=CHCH2O[(C2H4O) 13 (C3H6O) 72First, an allyl polyether (1,745 g) represented by -H was charged. The mixture was stirred and heated to 90 °C. A turbid emulsion was obtained. Subsequently, a solution (0.7 g) of Karstedt catalyst in decamethylcyclopentasiloxane was added to the mixture (w(Pt) = 1.5%). An exothermic reaction started after about 40 minutes, and the reaction mixture became significantly cleaner. Next, the reaction mixture was stirred at 90 °C for 4 hours. A turbid liquid product was obtained.

[0079] 1.2 Production of Component B Into a 1 L three-necked flask equipped with a reflux condenser and a KPG stirrer, a siloxane (200 g) represented by the general formula HSiMe2O(SiMeHO) 2,7 (SiMe2O) 39.3 SiMe2H and an allyl polyether (468 g) represented by the general formula CH2=CHCH2O[(C2H4O)2(C3H6O) 18 -Me were first charged. The mixture was stirred and heated to 90 °C. A turbid emulsion was obtained. Subsequently, a solution (0.25 g) of Karstedt catalyst in decamethylcyclopentasiloxane was added to the mixture (w(Pt) = 1.5%). An exothermic reaction started after about 30 minutes, and the reaction mixture became significantly cleaner. Next, the reaction mixture was stirred at 90 °C for 4 hours. A transparent liquid product was obtained.

[0080] 1.3 Manufacturing Method Weigh 25 g each of Component A and Component B into a 100 mL plastic container. Seal the plastic beaker with a screw cap and mix at a speed of 2,000 - 4,000 rpm for 2 - 6 minutes using a speed mixer. The composition according to the present invention is used for further testing.

[0081] 2. Tests for Compatibility and Defoaming Agent Activity 2.1 Production of Coatings To test compatibility and defoaming agent activity, coatings were first produced according to Table 1. A batch of solid resin solution was initially prepared. For this purpose, for a 3 kg batch, the equivalent amount of water reported in Table 1 was first filled into a 5 L capacity stainless steel container and heated to 70°C on a hot plate while stirring. Then, the equivalent amounts of the remaining components reported in Table 1 were added little by little. Stirring continued until the solid resin was completely dissolved. The pH was adjusted to a value of 8-9 using an amine. To produce a coating in a 1 kg batch, first mix the solid resin solution (400 g), polymer dispersion (400 g), and water (130 g) in a 2 L stainless steel container while stirring. Next, continuously add the wax dispersion, film-forming aid, and inhibitor while stirring. Finally, add the rheological additive while stirring, and stir the mixture with moderate shear force for 20 minutes. Use the coating for further testing.

[0082] 2.2 Compatibility Test The coating (50g) and the corresponding defoaming agent (0.3g) (Example 1 and Comparative Example) were weighed into a plastic beaker and stirred at 1,000 rpm for 1 minute using a stirrer (VMA Getzmann GmbH Dispermat type 60 / 2-457) equipped with a toothed dissolver disc (3cm in diameter, VMA Getzmann GmbH). Subsequently, this batch was foamed at 3,000 rpm for 2 minutes. After standing for 24 hours, a 2 mL batch was applied to the film as described above and visually evaluated. The results are reported in Tables 2 and 3.

[0083] 2.3 Antifoaming agent activity As described above, use the coating (50g) and the corresponding defoaming agent (0.3g) (Example 1 and Comparative Example). The results are reported in Tables 2-4. [Table 1]

[0084] 2.1 Results of compositions according to the present invention [Table 2]

[0085] In all cases, the results were converted into graphics. Figure 1 shows the foam volumes of the composition according to the present invention, indicated by a circle, component A, indicated by a triangle, and component B, indicated by a square. The dashed lines represent the expected foam volume according to the rules. The smaller the expected foam volume, the better the defoaming activity of the composition. The composition according to the present invention has been found to exhibit far superior antifoaming activity than the two individual components. This is outside the rules. Figure 1a shows the compatibility between the composition according to the present invention, indicated by a circle, and component B, indicated by a triangle. Component A is indicated by a square. Here again, the values ​​for the composition according to the present invention deviate from the rule (dashed line).

[0086] 2.2 Comparative Example 2 [Table 3]

[0087] In all cases, the results were converted into graphics. Figure 2 shows the volumes of foam mixed with TEGO Foamex 810 and TEGO Wet 285 in different ratios (indicated by the × symbol), Tego Wet 285 (indicated by the × symbol in the black square), and TEGO Foamex 810 (indicated by the cross symbol in the black square). The dashed lines indicate the rules. It was found that conventional defoaming agent mixtures exhibited foam volumes that lay midway between two values ​​related to each individual component. These values ​​are essentially on a straight line. Figure 2a shows the compatibility of TEGO Foamex 810 and TEGO Wet 285 mixed in different ratios (indicated by the × symbol), and of TEGO Foamex 810 (indicated by the × symbol in the black square) and Tego Wet 285 (indicated by the cross symbol in the black square). The dashed lines indicate the rule. Here again, the mixtures followed the rule (dashed line).

[0088] 2.3 Comparative Example 3 [Table 4]

[0089] In all cases, the results were converted into graphics. Figure 3 shows the volumes of foams mixed with TEGO Foamex 830 and TEGO Foamex 844 in different ratios (indicated by black diamond symbols), as well as the volumes of Tego Foamex 844 (indicated by white square symbols) and TEGO Foamex 830 (indicated by white circles). The dashed lines indicate a pattern. It was found that conventional defoaming agent mixtures exhibited foam volumes that lay midway between two values ​​related to each individual component. These values ​​are essentially on a straight line. Figure 2a shows the compatibility of TEGO Foamex 830 and TEGO Foamex 844 mixed in different ratios (indicated by black diamond symbols), and the compatibility of Tego Foamex 830 (indicated by white circles) and TEGO Foamex 844 (indicated by white square symbols). The dashed lines indicate the rule. Here again, the mixtures followed the rule (dashed lines).

Claims

1. Component A is one or more side-chain polyether-modified polysiloxanes, as shown in the general formula (I) below. 【Chemistry 1】 (In the formula, R is the same or different alkyl radical having 1 to 8 carbon atoms, R １ は、-C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ ]R ２ (In the formula, p is 2, 3, or 4, R ２ is an alkyl radical having hydrogen or 1 to 3 carbon atoms, x and y are the polyoxyalkylene block-C ｐ H ２ｐ O[(C ２ H ４ O) ｘ [(C ３ H ６ O) ｙ The molar mass of [the substance] is selected to be in the range of 500 to 10,000 g / mol. And, m is between 10 and 400. n is between 1 and 15. The components represented by, Component B is at least one terminally polyether-modified polysiloxane, as shown in the general formula (II) below. 【Chemistry 2】 (In the formula, R ３ These are identical or different alkyl radicals having 1 to 8 carbon atoms. R ４ R ３ or -C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ ] R ２ or -C ｐ H ２ｐ O[(C ３ H ６ O) ｙ ] R ２ (wherein p is 2, 3 or 4, R ２ x is an alkyl radical or hydrogen having 1 to 3 carbon atoms, and x and y are the polyoxyalkylene block-C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ ] - or - C ｐ H ２ｐ O(C) ３ H ６ O) ｙ The molar mass of [the substance] is selected to be in the range of 200 to 4,000 g / mol. and, provided that at least one of the R ４ ga-C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ ] - or -C ｐ H ２ｐ O(C) ３ H ６ O) ｙ ] is the end, f is between 20 and 500. g is between 1 and 15. The components represented by, An antifoaming agent composition containing an organically functionalized polysiloxane.

2. The composition according to claim 1, characterized in that the side chain of the side-chain polyether-modified polysiloxane is a linear modifying group.

3. The aforementioned polyoxyalkylene block-C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ The composition according to claim 1, characterized in that y in the expression is greater than x, and x and y are natural numbers.

4. The polyoxyalkylene block-C in component A. ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ The composition according to claim 1, characterized in that the ] has a block-like structure.

5. The above R ４ is -C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ R ２ or -C ｐ H ２ｐ O[(C ３ H ６ O) ｙ R ２ (where p is 2, 3 or 4), provided that at least one of the above R ４ is -C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ or -C ｐ H ２ｐ O[(C ３ H ６ O) ｙ is at the end, the composition according to claim 1.

6. The composition according to claim 1, characterized in that the molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component A is smaller than the molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component B.

7. The composition according to claim 1, characterized in that the molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component A is 0.15 to 0.

35.

8. The composition according to claim 1, characterized in that component A has a viscosity of 2,500 to 60,000 mPa·s as measured in accordance with DIN 53015.

9. The composition according to claim 1, characterized in that the molar ratio of the siloxane fraction to the polyoxyalkylene fraction of component B is 0.4 to 2.

10. The composition according to claim 1, characterized in that component B has a viscosity of 250 to 1,200 mPa·s as measured in accordance with DIN 53015.

11. The composition according to claim 1, characterized in that component B has a higher antifoaming activity than component A, as measured by the following method. The activity of the defoaming agent is measured by a stirring test. For this purpose, 50 g of the formulation and a test amount of defoaming agent (e.g., 0.2 g) are weighed into a plastic beaker. Using a stirrer (VMA Getzmann GmbH Dispermat type 60 / 2-457) equipped with a toothed dissolver disc (3 cm in diameter, manufactured by VMA Getzmann GmbH), the defoaming agent is incorporated at 1000 rpm for 1 minute. Subsequently, the formulation is foamed at 3000 rpm for 2 minutes. Next, 45 g of the formulation is weighed into a 100 mL graduated cylinder, and the volume is read.

12. The composition according to claim 1, obtained by stirring components A and B.

13. (a) As component A, 20 to 80% by weight of the organically functionalized polysiloxane of formula (I), (b) The component B is the formula (II) (wherein at least one polyoxyalkylene block - C ｐ H ２ｐ O[(C ２ H ４ O) ｘ (C ３ H ６ O) ｙ ] is the terminal end. 20 to 80% by weight of organically functionalized polysiloxane, and (c) As component B', the formula (II) (wherein at least one polyoxyalkylene block - C ｐ H ２ｐ O[(C ３ H ６ O) ｙ ] is the terminal end. 0-70% by weight of organically functionalized polysiloxane. A composition containing, The composition according to claim 1, wherein the reported amounts of components A, B, and B' total 100% by weight and are in proportion to the composition.

14. The composition according to claim 8, obtained by stirring component A in a mixture of components B and B'.

15. The composition according to claim 1, characterized in that its viscosity, as measured in accordance with DIN 53015, is 250 to 5,000 mPa·s.

16. The static surface tension measured with a Kruss K100 static surface tensile meter in accordance with DIN EN 14370:2004 is 20 to 65 mN / m, and The composition according to claim 1, characterized in that the dynamic surface tension measured with a Kruss BP50 bubble pressure tension meter in accordance with DIN EN 14370:2004 is 20 to 65 mN / m.

17. Use of the composition according to claim 1 as an antifoaming agent additive.

18. The use of component A represented by general formula (I) and component B represented by general formula (II) as described in claim 1 for the production of an antifoaming agent composition.

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