JP2015083292A - Defoaming agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a defoaming agent where the influence of defoaming performance to the variation of the service temperature of the defoaming agent is little as a non-aqueous coating composition.SOLUTION: A defoaming agent: which includes fluorine-modified organopolysiloxane A containing an organosiloxane unit a and aryl-modified organopolysiloxane B containing an organosiloxane unit b; where the content of the organosiloxane unit a is 10-80 mol% based on the moler number of all organosiloxane units constituting the fluorine-modified organopolysiloxane A; and where the content of the organosiloxane unit b is 50-99 mol% based on the moler number of all organosiloxane units constituting the aryl-modified organopolysiloxane B, and a non-aqueous coating composition including the defoaming agent are provided.

Description

  The present invention relates to an antifoaming agent. More specifically, the present invention relates to an antifoaming agent that exhibits excellent antifoaming properties for non-aqueous coating compositions.

［式中、Ｒｆはフルオロアルキル基、Ｒ１は炭素数１〜６のアルキル基またはフェニル基であり、これらは同一でも異なっていてもよく、Ｒ２は炭素数１〜６の炭化水素基、ＯＨ基またはアルコキシ基である。ｍは１〜２００００の整数を、ｎは１〜１０００の整数を示す。］で表される化合物なる非水系樹脂分散型塗料用消泡剤が知られている（特許文献１の請求項２等）。 Non-aqueous coating compositions (strong solvent paints, weak solvent paints, solvent-free paints, inks, floor coating agents, roofing waterproofing agents, etc.) for the suppression of foaming and the promotion of foam removal during production and use Antifoam is used.
As such an antifoaming agent, the following general formula (1)

[Wherein, Rf is a fluoroalkyl group, R1 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and these may be the same or different, and R2 is a hydrocarbon group having 1 to 6 carbon atoms, an OH group. Or an alkoxy group. m represents an integer of 1 to 20000, and n represents an integer of 1 to 1000. A defoaming agent for non-aqueous resin-dispersed paints, which is a compound represented by the formula (2) of Patent Document 1 is known.

JP 2002-301306 A

The conventional antifoaming agent has a problem that the defoaming performance may fluctuate greatly depending on the change in use temperature, and the defoaming performance may decrease depending on the season.
An object of the present invention is to provide an antifoaming agent that has less influence on the defoaming performance with respect to fluctuations in the use temperature of the antifoaming agent.

The antifoaming agent of the present invention is characterized by a fluorine-modified organopolysiloxane (A) containing an organosiloxane unit (a) represented by the formula (1) and an organosiloxane unit (b) represented by the formula (2). An aryl-modified organopolysiloxane (B) containing
The content of the organosiloxane unit (a) represented by the formula (1) is 10 to 80 mol% based on the number of moles of all the organosiloxane units constituting the fluorine-modified organopolysiloxane (A),
The gist is that the content of the organosiloxane unit (b) represented by the formula (2) is 50 to 99 mol% based on the number of moles of all organosiloxane units constituting the aryl-modified organopolysiloxane (B). And

  However, Rf is a fluoroalkyl group and R1 is a C1-C12 alkyl group.

  However, Ar is an aryl group and R2 is a C1-C12 alkyl group.

  The feature of the non-aqueous coating composition of the present invention is that it contains the antifoaming agent, filler and binder described above.

  The antifoaming agent of the present invention has a remarkably small variation in antifoaming performance due to changes in use temperature. Therefore, the defoaming performance does not deteriorate depending on the season.

  Since the non-aqueous coating composition of the present invention contains the above-mentioned antifoaming agent, the variation in the defoaming performance is remarkably small due to a change in use temperature. Therefore, the defoaming performance does not deteriorate depending on the season.

  As the fluoroalkyl group (Rf), a fluoroalkyl group having 3 to 8 carbon atoms can be used, and 3,3,3-trifluoropropyl, 4,4,4,3,3-pentafluoro-1-butyl, 6,6,6,5,5,4,4,3,3-nonafluoro-1-hexyl and 8,8,8,7,7,6,6,5,5,4,4,3,3- And tridecafluoro-1-octyl. Among these, 6,6,6,5,5,4,4,3,3-nonafluoro-1-hexyl is preferable from the viewpoint of defoaming performance.

  Examples of the alkyl group having 1 to 12 carbon atoms (R1) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, n-decyl and n- And dodecyl. Of these, methyl is preferred from the viewpoint of antifoaming properties.

  The content (mol%) of the organosiloxane unit (a) is 10 to 80, preferably 30 to 75, based on the number of moles of all organosiloxane units constituting the fluorine-modified organopolysiloxane (A). More preferably, it is 50-70.

The fluorine-modified organopolysiloxane (A) contains an organosiloxane unit other than the organosiloxane unit (a).
Other organosiloxane units include dimethylsiloxane units, methylhydrogensiloxane units, methylphenylsiloxane units, and diphenylsiloxane units. Of these, dimethylsiloxane units are preferred from the viewpoint of antifoaming performance.

  The content (mol%) of other organosiloxane units is preferably 20 to 90, more preferably 25 to 70, based on the number of moles of all organosiloxane units constituting the fluorine-modified organopolysiloxane (A). Especially preferably, it is 30-50.

  The fluorine-modified organopolysiloxane (A) can be produced by a known method (for example, Japanese Patent Application Laid-Open No. 59-130894) and can be easily obtained from the market. As products available from the market, FL100, FA-600, FA-630, X-22-821, X-22-822 (Shin-Etsu Chemical Co., Ltd.); FS-1265 (Toray Dow Corning Co., Ltd.), etc. Can be mentioned.

  The aryl group (Ar) includes an aromatic hydrocarbon group having 6 to 7 carbon atoms, and examples thereof include phenyl, benzyl and tolyl.

  As a C1-C12 alkyl group (R2), it is the same as that of a C1-C12 alkyl group (R1) in Formula (1).

  The content (mol%) of the organosiloxane unit (b) is 50 to 99, preferably 55 to 95, based on the number of moles of all organosiloxane units constituting the aryl-modified organopolysiloxane (B). More preferably, it is 60-90.

The aryl-modified organopolysiloxane (B) contains an organosiloxane unit other than the organosiloxane unit (b).
Other organosiloxane units include dimethylsiloxane units, methylhydrogensiloxane units, methylphenylsiloxane units, and diphenylsiloxane units. Of these, dimethylsiloxane units are preferred from the viewpoint of antifoaming performance.

  The content (mol%) of other organosiloxane units is preferably 1 to 50, more preferably 5 to 45, based on the number of moles of all organosiloxane units constituting the aryl-modified organopolysiloxane (B). Especially preferably, it is 10-40.

  The aryl-modified organopolysiloxane (B) can be produced by a known method (for example, Japanese translations of PCT publication No. 2009-506003) and can be easily obtained from the market. Commercially available products include TSF4300, TSF431, TSF433, TSF437, FQF501 (Momentive); KF-50, KF-53, KF-54, X-21-3265 (Shin-Etsu Chemical Co., Ltd.); SH-510 , SH-550, SH-710 (Toray Dow Corning Co., Ltd.) and the like.

  The content (% by weight) of the aryl-modified organopolysiloxane (B) is preferably 5 to 30, more preferably 5 to 15 based on the weight of the fluorine-modified organopolysiloxane (A) from the viewpoint of defoaming performance. It is.

  The antifoaming agent of the present invention preferably further contains a ketone (C) having 3 to 6 carbon atoms and a hydrocarbon (D) having 5 to 12 carbon atoms. When the ketone (C) and the hydrocarbon (D) are contained, the defoaming performance is further improved.

  Examples of the ketone (C) having 3 to 6 carbon atoms include dimethyl ketone (acetone), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone. Of these, methyl isobutyl ketone is preferred from the viewpoint of antifoaming performance.

  Examples of the hydrocarbon having 5 to 12 carbon atoms (D) include linear saturated hydrocarbons (n-pentane, n-hexane, n-heptane, n-dodecane, etc.), branched saturated hydrocarbons (sec-pentane, tert-pentane). And isododecane), linear unsaturated hydrocarbons (such as 1-pentene, 1-hexene and 1-dodecene) and branched unsaturated hydrocarbons (isopentene, 3-methyl-1-butene, 2,2-dimethyl-1-propene and Isododecene, etc.). Among these, from the viewpoint of defoaming performance, linear saturated hydrocarbons are preferable, linear saturated hydrocarbons having 5 to 8 carbon atoms are more preferable, and n-hexane and n-heptane are particularly preferable.

  1000-20000 are preferable based on the weight of fluorine-modified organopolysiloxane (A), and, as for the total content (weight%) of ketone (C) and hydrocarbon (D), More preferably, it is 8000-10000.

  The content (% by weight) of the hydrocarbon (D) is preferably 5 to 40, more preferably 10 to 30, based on the weight of the ketone (C).

  The antifoaming agent of the present invention may further contain hydrophobic silica. When the hydrophobic silica is contained, the defoaming performance is further improved.

The hydrophobic silica is not limited in size, type and the like as long as it can be finely dispersed in the antifoaming agent of the present invention, but the specific surface area of the hydrophobic silica by the BET method is preferably at least 50 m ² / g.

  The specific surface area by the BET method is based on JIS Z8830: 2013 “Method for measuring the specific surface area of a powder (solid) by gas adsorption”, and the hydrophobic silica in a dry state is a one-point method of gas adsorption method (carrier gas method). taking measurement. A nitrogen-helium mixed gas is used as the carrier gas. The specific surface area can be calculated from the value of the desorption peak.

  Hydrophobic silica can be easily obtained from the market. For example, as trade names, Nipsil SS-10, SS-40, SS-50 and SS-100 (Tosoh Silica Co., Ltd., “Nipsil” is Tosoh Silica Corporation AEROSIL R972, RX200 and RY200 (Nippon Aerosil Co., Ltd., “AEROSIL” is a registered trademark of Evonik Degussa BM Behrer.), TS-530, TS-610, TS-720 (Cabot Carbon) AEROSIL R202, R805 and R812 (Degussa Japan Co., Ltd.), REOLOSIL MT-10, DM-10 and DM-20S (Tokuyama Corporation, “REOLOSIL” is a registered trademark of the same company), and SYLOPHOBIC10 , 702,505 and 603 (Fuji Silysia Chemical Co., Ltd., "SYLOPHOBIC" is a registered trademark of the company.), And the like.

  When the hydrophobic silica is contained, the content (% by weight) of the hydrophobic silica is preferably 0.5 to 50, more preferably 1 to 30, based on the weight of the fluorine-modified organopolysiloxane (A). .

The antifoaming agent of the present invention is a homogeneous mixture of fluorine-modified organopolysiloxane (A) and aryl-modified organopolysiloxane (B), and, if necessary, ketone (C) and hydrocarbon (D) and / or finely divided silica. Can be prepared.
When the ketone (C) and the hydrocarbon (D) are contained, it is preferable to uniformly mix at a temperature as low as possible (preferably 10 to 50 ° C, more preferably 20 to 40 ° C) in consideration of their volatility. .

  The antifoaming agent of the present invention is effective for both the aqueous foaming liquid and the nonaqueous foaming liquid, but is more effective for the nonaqueous foaming liquid, and particularly effective for the nonaqueous coating composition. Among non-aqueous coating compositions, it is also effective for non-aqueous paints used for coating industrial products and buildings, floor coating materials, and roofing waterproof paints. The aqueous foaming liquid means a foaming liquid containing water, and the nonaqueous foaming liquid (nonaqueous coating composition or the like) means a foaming liquid (coating composition or the like) that does not contain water.

  The non-aqueous coating composition of the present invention contains the antifoaming agent, filler, and binder described above, and known components (filler and binder) other than the antifoaming agent can be used.

  As fillers, inorganic fine particles (mica, talc, kaolin, calcium carbonate, titanium oxide, barium sulfate, iron oxide, alumina, silica, carbon black, etc.) and organic fine particles (acrylic beads, silicon beads, polyethylene wax, etc.) can be used. .

  As the binder, polyester, polyurethane, polyamide, acrylic resin, phenol resin, alkyd resin, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, and a mixture thereof can be used.

  The content (% by weight) of the antifoaming agent is preferably 0.1 to 1, more preferably 0.3 to 0.5, based on the weight of the antifoaming agent, filler and binder.

  The content (% by weight) of the filler is preferably 4 to 80, more preferably 9.5 to 70, based on the weight of the antifoaming agent, filler and binder.

  The content (% by weight) of the binder is preferably 19 to 95, more preferably 29.5 to 90, based on the weight of the antifoaming agent, filler and binder.

  The non-aqueous coating composition of the present invention can contain an additive that can be blended with a general non-aqueous coating composition within a range that does not affect the effects of the present invention. Examples of such additives include curing agents, thickeners, plasticizers, antiseptics, antifungal agents, algaeproofing agents, leveling agents, pigment dispersants, anti-skinning agents, dryers, matting agents, and UV absorbers. , Light stabilizers, antioxidants, low pollution agents and catalysts.

  The non-aqueous coating composition of the present invention can be produced by a conventionally known method. That is, it can be obtained by uniformly mixing the antifoaming agent, filler, binder and, if necessary, additives.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

(Synthesis Example 1-1) Synthesis of Fluorine-modified Organopolysiloxane (A1) Octamethylcyclotetrasiloxane (Momentive Performance) was added to a four-necked flask equipped with a stirrer, thermometer, dry nitrogen inlet and calcium chloride tube. Materials Japan Godo Kaisha TSF404) 642 parts (2.2 mol parts), tetramethyltetrahydrogencyclotetrasiloxane (manufactured by Wako Pure Chemical Industries, Ltd.) 58 parts (0.24 mol parts), hexamethyldisiloxane 15 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) 15 parts (0.09 mol part) and 5 parts (0.03 mol parts) of trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are added at room temperature (25-30 ° C: The same shall apply hereinafter) for 24 hours (ring-opening polymerization), and then a 28% aqueous ammonia solution (Tokyo Chemical Industry Co., Ltd.). Neutralization was performed using a chemical company, and the precipitated salt was separated by filtration to obtain methylhydrogenpolysiloxane (650 parts, yield 90%, average degree of polymerization 104, dimethylsiloxane: methylhydrogensiloxane = 9: 1 (molar ratio)).

In a flask equipped with a thermometer, a stirrer, and a dropping funnel, 70 parts of the above-mentioned methyl hydrogen polysiloxane and 0.1 part of chloroplatinic acid (manufactured by Wako Pure Chemical Industries, Ltd.) are placed and heated to 110 ° C. 6,6,6,5,5,4,4,3,3-nonafluoro-1-hexene {CF ₃ (CF ₂ ) ₃ CH═CH ₂ } (manufactured by Alpha Acer) 23.8 parts (0 0.1 mol part) was added dropwise over 2 hours, and the mixture was further heated and stirred at 110 ° C. for 2 hours to obtain a reaction mixture.

  The reaction mixture was cooled to 60 ° C, 10 parts of a 0.1% aqueous sodium hydroxide solution was added, and the mixture was stirred at 60 ° C for 1 hour, and then under reduced pressure, water and unreacted 6,6,6,5,5,4 , 4,3,3-Nonafluoro-1-hexene was distilled off to obtain a concentrate. After adding 1 part of activated carbon to the concentrate and stirring with heating at 60 ° C. for 1 hour, the activated carbon was filtered off to obtain a fluorine-modified organopolysiloxane (A1) represented by the following formula (79.6 parts, yield). 85%). The resulting fluorine-modified organopolysiloxane (A1) was a colorless and transparent liquid.

(Synthesis Example 1-2) Synthesis of fluorine-modified organopolysiloxane (A2) The amount of octamethylcyclotetrasiloxane used was changed from 642 parts (2.2 mol parts) to 163 parts (0.55 mol parts). The amount of hydrogencyclotetrasiloxane used was changed from 58 parts (0.24 mole part) to 530 parts (2.2 mole parts) to 6,6,6,5,5,4,3,3-nonafluoro- It is represented by the following formula in the same manner as in Synthesis Example 1-1 except that the amount of 1-hexene used is changed from 23.8 parts (0.1 mole part) to 217 parts (0.88 mole part). Fluorine-modified organopolysiloxane (A2) was obtained (650 parts, yield 70%, average degree of polymerization 119, dimethylsiloxane: fluorine-modified siloxane = 2: 8 (molar ratio)). The resulting fluorine-modified organopolysiloxane (A2) was a colorless and transparent liquid.

(Synthesis Example 2-1) Synthesis of aryl-modified organopolysiloxane (B1) Methylphenylpolysiloxane (KF- manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a four-necked flask equipped with a vacuum distillation cooler, thermometer, and stirrer. 54) 65 parts (0.47 mol part as methylphenylsiloxane unit) and 35 parts (0.47 mol part as dimethylsiloxane unit) of dimethylpolysiloxane (KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred. While raising the temperature to 100 ° C., 0.09 part of a 15% aqueous solution of tetramethylammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and mixing and stirring were continued. After stirring for 4 hours, it became transparent, so it was stirred at 140 ° C. for 2 hours to decompose tetramethylammonium hydroxide into trimethylamine and methanol, distilled off under reduced pressure, cooled to room temperature, and 1 part of powdered activated carbon After addition and stirring for 6 hours, filtration was performed to obtain an aryl-modified organopolysiloxane (B1) of the following formula (90 parts, yield 90%, average polymerization degree 200, dimethylsiloxane: methylphenylsiloxane = 5: 5 (molar ratio)). The obtained aryl-modified organopolysiloxane (B1) was a colorless and transparent liquid.

(Synthesis Example 2-2) Synthesis of aryl-modified organopolysiloxane (B2) The amount of methylphenylpolysiloxane used was changed from 44 parts to 100 parts (0.74 mol parts as methylphenylsiloxane units), and the amount of dimethylpolysiloxane used. Was changed from 56 parts to 0.54 parts (0.007 mol parts as dimethylsiloxane units) in the same manner as in Synthesis Example 2-1, to obtain an aryl-modified organopolysiloxane (B2) of the following formula ( 90 parts, yield 90%, average degree of polymerization 200, dimethylsiloxane: methylphenylsiloxane = 1: 99 (molar ratio)). The aryl-modified organopolysiloxane (B2) obtained was a colorless and transparent liquid.

Example 1
10 parts of fluorine-modified organopolysiloxane (A1), 0.5 parts of aryl-modified organopolysiloxane (B1), 95 parts of methyl isobutyl ketone and 5 parts of n-heptane are uniformly mixed to obtain the antifoaming agent (1) of the present invention. Got.

(Example 2)
10 parts of fluorine-modified organopolysiloxane (A2), 0.5 parts of aryl-modified organopolysiloxane (B1), 1900 parts of methyl isobutyl ketone and 100 parts of n-heptane are uniformly mixed, and the antifoaming agent (2) of the present invention Got.

(Example 3)
10 parts of fluorine-modified organopolysiloxane (A2), 3 parts of aryl-modified organopolysiloxane (B2), 71.5 parts of methyl isobutyl ketone and 28.5 parts of n-heptane are uniformly mixed to produce antifoam 3 of the present invention Got.

Example 4
10 parts of fluorine-modified organopolysiloxane (A1), 3 parts of aryl-modified organopolysiloxane (B2), 1400 parts of methyl isobutyl ketone and 560 parts of n-heptane were uniformly mixed to obtain antifoaming agent 4 of the present invention.

(Comparative Example 1)
10 parts of the fluorine-modified organopolysiloxane (A1), 95 parts of methyl isobutyl ketone and 5 parts of n-heptane were uniformly mixed to obtain a defoaming agent (H1) for comparison.

(Comparative Example 2)
An antifoaming agent (H2) for comparison was obtained based on Production Example 1 of Patent Document 1 (Japanese Patent Laid-Open No. 2002-301306).

  The antifoaming agents (1) to (4) and comparative antifoaming agents (H1) to (H2) of the present invention were evaluated by the following antifoaming performance tests (1) to (3), and the evaluation results are shown in Table It was shown in 1.

1. Defoaming performance test (1)
The following compositions were uniformly mixed to prepare evaluation non-aqueous coating compositions (1) to (4) and (H1) to (H2) {each number is an antifoaming agent obtained in Examples and Comparative Examples Corresponds to the number. }.
After stirring the non-aqueous coating compositions (1) to (4) and (H1) to (H2) for evaluation under the conditions of 3,000 rpm × 5 minutes using a desktop disper mill, the specific gravity cup ( The specific gravity of the non-aqueous coating composition was measured at 50 mL). A non-aqueous coating composition (blank) was prepared in the same manner as above except that the evaluation sample (antifoaming agent) was not mixed, and the specific gravity was measured. It means that defoaming performance is excellent, so that specific gravity is large.

[Non-aqueous coating composition for evaluation]
ACRIDIC A-837 (* 1) 147 parts TYPAKE R-930 (* 2) 228 parts Mineral Spirit 80 parts EFKA RM 1920 (* 3) 2 parts ACRIDIC A-848 (* 1) 508 parts Mineral Spirit 30 parts Evaluation sample (Defoamer) 5 parts

* 1 “Aclidick”, a polyol resin manufactured by DIC Corporation, is a registered trademark of DIC Corporation.
* 2 Titanium dioxide manufactured by Ishihara Sangyo Co., Ltd., “Taipeke” is a registered trademark of Ishihara Sangyo Co., Ltd.
* 3 “EFKA”, a thickener made by BASF SE, is a registered trademark of Ciba Incorporated.

2. Defoaming performance test (2)
1000 parts of each of the non-aqueous coating compositions (1) to (4), (H1) to (H2) and (blank) were diluted with mineral spirits and adjusted to 77 KU (25 ° C.) with a Stormer viscometer. Thereafter, the temperature is adjusted to each coating temperature, and the curing agent {Bernock DN-990, DIC Corporation, polyisocyanate, "Bernock" are registered trademarks of DIC Corporation. ) 81.7 parts was uniformly mixed and coated under the following coating conditions, and the defoaming performance was evaluated based on the number of residual foam marks after drying.

(Coating test 1)
Paint temperature: 25 ° C
Object to be coated: Tin plate roller adjusted to 80 ° C .: Medium wool wool roller (Otsuka Brush Manufacturing Co., Ltd.)
Application amount: 50 g (per 30 cm × 30 cm)
Drying conditions: 80 ° C

(Coating test 2)
Paint temperature: 25 ° C
Object to be coated: Tin plate roller adjusted to 25 ° C .: Medium wool roller (manufactured by Otsuka Brush Manufacturing Co., Ltd.)
Application amount: 50 g (per 30 cm × 30 cm)
Drying conditions: 25 ° C

(Painting test 3)
Paint temperature: 2 ℃
Object to be coated: Tin plate roller adjusted to 2 ° C .: Medium wool wool roller (Otsuka Brush Manufacturing Co., Ltd.)
Application amount: 50 g (per 30 cm × 30 cm)
Drying conditions: 2 ° C

3. Defoaming performance test (3)
With the following composition, each was stirred under conditions of 3,000 rpm × 10 minutes using a desktop disper mill to prepare curing agents (1) to (4) and (H1) to (H2) {each number is This corresponds to the numbers of the antifoaming agents obtained in the examples and comparative examples. }. A curing agent (blank) was prepared in the same manner as described above except that the evaluation sample (antifoaming agent) was not mixed.

Cuamine ML-530 (* 4) 165 parts Dioctyl phthalate 77 parts Whiten SO (* 5) 233 parts Talc ND (* 6) 10 parts Chromium oxide G5 (* 7) 10 parts Evaluation sample (antifoaming agent) 5 parts

* 4 The 2-chloroaniline condensate solution “Cuamine” manufactured by Ihara Chemical Industry Co., Ltd. is a registered trademark of Ihara Chemical Industry Co., Ltd.
* 5 Calcium carbonate manufactured by Shiraishi Kogyo Co., Ltd., “Whiteon” is a registered trademark of Shiroishi Kogyo Co., Ltd.
* 6 Talc manufactured by Nippon Talc * 7 Chromium oxide (III) manufactured by Nippon Chemical Industry Co., Ltd.

  Subsequently, polyflex FL-83 (Daiichi Kogyo Seiyaku Co., Ltd., urethane prepolymer, “Polyflex” is a registered trademark of Daiichi Kogyo Seiyaku Co., Ltd.) and a uniform mixing with each curing agent, evaluation Non-aqueous coating composition {floor coating material} (1) to (4), (H1) to (H2), (blank) were prepared {each number is an antifoaming agent obtained in Examples and Comparative Examples Corresponds to the number. }.

Non-aqueous coating composition for evaluation {floor coating material} (1) to (4), (H1) to (H2), and (blank) were respectively converted into a polyethylene terephthalate film (Toray Co., Ltd., Lumirror S10, “ "Lumirror" is a registered trademark of the same company.) Poured into a tray (length 30cm, width 30cm, depth 1cm) to make the surface uniform and then dried at 25 ° C for 24 hours to prepare a flooring (Application amount: about 2 kg / m ² ). Then, the flooring material was cut in half with a cutter knife, and the surface (upper surface) and the cut surface were visually observed to evaluate the presence or absence of residual bubble marks.

Claims (6)

Fluorine-modified organopolysiloxane (A) containing an organosiloxane unit (a) represented by formula (1) and aryl-modified organopolysiloxane (B) containing an organosiloxane unit (b) represented by formula (2) And containing
The content of the organosiloxane unit (a) represented by the formula (1) is 10 to 80 mol% based on the number of moles of all the organosiloxane units constituting the fluorine-modified organopolysiloxane (A),
The content of the organosiloxane unit (b) represented by the formula (2) is 50 to 99 mol% based on the number of moles of all organosiloxane units constituting the aryl-modified organopolysiloxane (B). Defoaming agent.

However, Rf is a fluoroalkyl group and R1 is a C1-C12 alkyl group.

However, Ar is an aryl group and R2 is a C1-C12 alkyl group. The fluorine-modified organopolysiloxane (A) contains dimethylsiloxane units, and the content of dimethylsiloxane units is 20 to 90 mol% based on the number of moles of all organosiloxane units constituting the fluorine-modified organopolysiloxane (A). And
The aryl-modified organopolysiloxane (B) contains dimethylsiloxane units, and the content of dimethylsiloxane units is 1 to 50 mol% based on the number of moles of all organosiloxane units constituting the aryl-modified organopolysiloxane (B). The antifoaming agent according to claim 1, wherein   The antifoaming agent according to claim 1 or 2, wherein the content of the aryl-modified organopolysiloxane (B) is 5 to 30% by weight based on the weight of the fluorine-modified organopolysiloxane (A).   Furthermore, it contains a C3-C6 ketone (C) and a C5-C12 hydrocarbon (D), a C3-C6 ketone (C) and a C5-C12 hydrocarbon (D). The antifoaming agent according to any one of claims 1 to 3, wherein the total content of is 1000 to 20000% by weight based on the weight of the fluorine-modified organopolysiloxane (A).   The antifoaming agent according to claim 4, wherein the content of the hydrocarbon (D) having 5 to 12 carbon atoms is 5 to 40% by weight based on the weight of the ketone (C) having 3 to 6 carbon atoms.   A non-aqueous coating composition comprising the antifoaming agent, filler and binder according to any one of claims 1 to 5.