Patent ID: 12258533

EXAMPLES

The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples.

[Viscosity measurement]

Using a rotational viscometer (manufactured by SHIBAURA SEMTEK CO., LTD., product name: Vismetron VDA-2), measurement was performed on rotor No. 4 at a rotational speed of 12 rpm.

[Measurement of average particle diameter]

A self-emulsifying compound was dispersed in water and measured using a laser diffraction particle diameter distribution analyzer (LS-230 of Beckman Coulter) and the median diameter (particle diameter corresponding to 50% of the cumulative distribution, 50% particle diameter) was used as the average particle diameter.

[Evaluation of anti-foaming performance]

NS Cut S-20 (soluble-type water-soluble cutting liquid, 20% active component, manufactured by NS Chemical Co., Ltd.) diluted 4 times with tap water and temperature-controlled to 23° C. was used as a foaming liquid used for antifoaming performance evaluation. The viscosity of the foaming liquid at this time was 3.5 mPa·s. The anti-foaming agent to be evaluated was added at 25 ppm based on solid content.

400 g of the foaming liquid described above was added to a 1000 mL tall beaker, and stirred at 8000 rpm for 10 minutes using a homomixer (manufactured by Primix Co., Ltd., model HV-M) to cause foaming. Herein, the height of a baffle was 10 cm from the bottom of the homomixer and 11 cm from the bottom of the flask. After stopping the stirring, a foam layer was formed on an upper layer of a liquid portion, and a change in the thickness of the foam layer over time was measured. The time required for the thickness of the foam layer to decrease to 4 mm was defined as t (minutes), and evaluations were made as shown in the table below.

TABLE 1Evaluation of anti-foaming performanceAnti-foaming performanceTime◯t < 3⊚3 ≤ t < 5Δ5 ≤ t < 6Xt ≥ 6

In order to confirm the retention of the anti-foaming performance, this operation was repeated four times and the anti-foaming performance was evaluated each time.

[Production Example 1]

12.59 g of component (a) of a straight-chain organopolysiloxane expressed by the following chemical formula 1, where j=110 and k=10, and 4.57 g of component (b) of a straight-chain organopolysiloxane expressed by the following chemical formula 2, where m=290, were heated and mixed at 60° C. After mixing uniformly, 0.002 g of chloroplatinic acid and 0.15 g of isopropyl alcohol were mixed therein and allowed to react at 60° C. for 3 hours, and a transparent viscous liquid was obtained. 0.01 g of sodium acetate and 82.84 g of ethylene oxide, 22 mol of propylene oxide, and 22 mol of hydrogen-terminated allyl polyether were added to the obtained viscous liquid and reacted for 3 hours while maintaining the temperature at 80 to 90° C. After the reaction, the isopropyl alcohol in the viscous liquid was removed by heating at 80° C. for 1 hour under reduced pressure. A brown viscous liquid was obtained.

[Production Example 2]

12.20 g of component (a) of a straight-chain organopolysiloxane expressed by chemical formula 1 described above, where j=110 and k=10, 7.51 g of component (b) of a straight-chain organopolysiloxane expressed by chemical formula 2 described above, where m=493, and 20.00 g of toluene were heated and mixed at 60° C. After mixing uniformly, 0.002 g of chloroplatinic acid and 0.15 g of isopropyl alcohol were mixed therein and allowed to react at 60° C. for 3 hours, and a transparent viscous liquid was obtained. 0.01 g of sodium acetate and 80.29 g of ethylene oxide: 22 mol of propylene oxide: and 22 mol of hydrogen-terminated allyl polyether were added to the obtained viscous liquid and reacted for 3 hours while maintaining the temperature at 80 to 90° C. After the reaction, the isopropyl alcohol and toluene in the viscous liquid were removed by heating at 100° C. for 3 hours under reduced pressure. A brown viscous liquid was obtained.

[Production Example 3]

11.71 g of component (a) of a straight-chain organopolysiloxane expressed by chemical formula 1 described above, where j=110 and k=10, 11.19 g of component (b) of a straight-chain organopolysiloxane expressed by chemical formula 2 described above, where m=766, and 12.82 g of toluene were heated and mixed at 60° C. After mixing uniformly, 0.002 g of chloroplatinic acid and 0.15 g of isopropyl alcohol were mixed therein and allowed to react at 60° C. for 3 hours, and a transparent viscous liquid was obtained. 0.01 g of sodium acetate and 77.10 g of ethylene oxide: 22 mol of propylene oxide: and 22 mol of hydrogen-terminated allyl polyether were added to the obtained viscous liquid and reacted for 3 hours while maintaining the temperature at 80 to 90° C. After the reaction, the isopropyl alcohol and toluene in the viscous liquid were removed by heating at 100° C. for 3 hours under reduced pressure. A brown viscous liquid was obtained.

Comparative Production Example 1

21.46 g of component (a) of a straight-chain organopolysiloxane expressed by chemical formula 1 above, where j=110 and k=10, and 4.58 g of component (b) of a straight-chain organopolysiloxane expressed by chemical formula 2 above, where m=179, were heated and mixed at 60° C. After mixing uniformly, 0.002 g of chloroplatinic acid and 0.15 g of isopropyl alcohol were mixed therein and allowed to react at 60° C. for 3 hours, and a transparent viscous liquid was obtained. 0.01 g of sodium acetate and 73.80 g of ethylene oxide: 18 mol of propylene oxide: and 18 mol of hydrogen-terminated allyl polyether were added to the obtained viscous liquid and reacted for 3 hours while maintaining the temperature at 80 to 90° C. After the reaction, the isopropyl alcohol in the viscous liquid was removed by heating at 80° C. for 1 hour under reduced pressure. A brown viscous liquid was obtained.

Comparative Production Example 2

12.81 g of component (a) of a straight-chain organopolysiloxane expressed by chemical formula 1 above, where j=110 and k=10, and 2.88 g of component (b) of a straight-chain organopolysiloxane expressed by chemical formula 2 above, where m=179, were heated and mixed at 60° C. After mixing uniformly, 0.002 g of chloroplatinic acid and 0.15 g of isopropyl alcohol were mixed therein and allowed to react at 60° C. for 3 hours, and a transparent viscous liquid was obtained. 0.01 g of sodium acetate and 84.31 g of ethylene oxide: 22 mol of propylene oxide: and 22 mol of hydrogen-terminated allyl polyether were added to the obtained viscous liquid and reacted for 3 hours while maintaining the temperature at 80 to 90° C. After the reaction, the isopropyl alcohol in the viscous liquid was removed by heating at 80° C. for 1 hour under reduced pressure. A brown viscous liquid was obtained.

TABLE 2Amounts of each component used in Production Examples 1 to3 and Comparative Production Examples 1 and 2 (unit: g)Table 2-1ProductionProductionProductionExample 1Example 2Example 3Straight-chain12.5912.2011.71organopolysiloxaneexpressed by chemicalformula 1 (j = 110,k = 10)Straight-chain4.57——organopolysiloxaneexpressed by chemicalformula 2 (m = 290)Straight-chain—7.51—organopolysiloxaneexpressed by chemicalformula 2 (m = 493)Straight-chain——11.19organopolysiloxaneexpressed by chemicalformula 2 (m = 766)Straight-chain———organopolysiloxaneexpressed by chemicalformula 2 (m = 179)Toluene—20.0023.00Isopropyl alcohol0.150.150.15Chloroplatinic acid0.0020.0020.002AllylE0/P0 = 22/2282.8480.2977.10polyetherE0/P0 = 18/18———EO-POSodium acetate0.010.010.01Table 2-2Com-parativeComparativeProductionProductionExample 1Example 2Straight-chain21.4612.81organopolysiloxaneexpressed by chemicalformula 1 (j = 110,k = 10)Straight-chain——organopolysiloxaneexpressed by chemicalformula 2 (m = 290)Straight-chain——organopolysiloxaneexpressed by chemicalformula 2 (m = 493)Straight-chain——organopolysiloxaneexpressed by chemicalformula 2 (m = 766)Straight-chain4.582.88organopolysiloxaneexpressed by chemicalformula 2 (m = 179)Toluene——Isopropyl alcohol0.150.15Chloroplatinic acid0.0020.002AllylE0/P0 = 22/22—84.31polyetherE0/P0 = 18/1873.80—EO-POSodium acetate0.010.01
[Silicone-based anti-foaming agent oil compound #1]

Silicone-based anti-foaming agent oil compound #1 was manufactured by the following method. In other words, 59.10 parts by mass of polydimethylsiloxane blocked with a trimethylsilyl group (viscosity of 1,000 mPa·s at 25° C.), 30.60 parts by mass of polydimethylsiloxane blocked with a silanol group (viscosity of 12,500 mPa·s at 25° C.), and 3.06 parts by mass of polyethyl silicate (“Cilbond 50” manufactured by Evonik) were placed in a three neck flask with a capacity of 1 L provided with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas supply, while stirring, and the temperature was raised to 110° C. A mixture of 1.54 parts by mass of premixed potassium dimethylsilanolate, 5.15 parts by mass of polydimethylsiloxane blocked with a trimethylsilyl group (viscosity of 1,000 mPa·s at 25° C.), and 0.08 parts by mass of ethanol was added at 110° C. and stirring was continued for 30 minutes at 110° C. Next, silica (“Aerosil 200”, specific surface area: 200 m2/g, manufactured by Evonik) was added, and then homogeneously dispersed using a homomixer for 30 minutes while heating at 110° C. A mixture of 0.02 parts by mass of polyether-modified silicone 501W and 0.13 parts by mass of ion exchanged water was added. After stirring, 5.15 parts by mass of polydimethylsiloxane blocked with a silanol group (viscosity of 40 mPa·s at 25° C.) was added, and the temperature raised to 190° C. 1.05 parts by mass of potassium dimethylsilanolate catalyst was added and allowed to react at 190° C. for 1 hour. The obtained reaction product was neutralized, then 0.02 parts by mass of polyether-modified silicone 501W and 1.83 parts by mass of ion exchanged water were added, to obtain a silicone-based anti-foaming agent oil compound. All steps were performed under a nitrogen gas purge. The obtained silicone-based anti-foaming agent oil compound had a viscosity of 15,000 mPa·s.

Example 1

After mixing 45 parts by mass of a polyorganosiloxane polymer crosslinked product having a polyoxyalkylene group manufactured in Production Examples 1 to 3 and Comparative Production Examples 1 and 2 and 25 parts by mass of an EOPOEO copolymer (ADEKA Pluronic (registered trademark) L-31), 30 parts by mass of the silicone-based anti-foaming agent oil compound #1 above was added and a homomixer was used to obtain a self-emulsifying anti-foaming agent composition. The diluted appearance of the resulting anti-foaming agent composition was a slightly bluish emulsion.

Examples 2 and 3 and Comparative Examples 1 and 2

Anti-foaming agent compositions were prepared by the same procedure as in Example 1, except that the polyorganosiloxane polymer crosslinked product having a polyoxyalkylene group was changed as shown in Table 3. The diluted appearance of the resulting anti-foaming agent composition was a slightly bluish emulsion.

TABLE 3Anti-foaming agents of Examples 1 to 3 and Comparative Examples1 and 2, and anti-foaming retention (unit of each component: g)Table 3-1ExampleExampleExample 123Polyorganosiloxane polymer45——crosslinked product of ProductionExample 1Polyorganosiloxane polymer—45—crosslinked product of ProductionExample 2Polyorganosiloxane polymer——45crosslinked product of ProductionExample 3Polyorganosiloxane polymer———crosslinked product of ComparativeProduction Example 1Polyorganosiloxane polymer———crosslinked product of ComparativeProduction Example 2Silicone-based anti-foaming agent303030oil compound #1EOPOEO copolymer (Adeka252525Pluronic L-31)Anti-foaming retention 1 time⊚⊚⊚Anti-foaming retention 2 times◯◯⊚Anti-foaming retention 3 times◯◯◯Anti-foaming retention 4 timesΔ◯◯Table 3-2ComparativeComparativeExample 1Example 2Polyorganosiloxane polymer——crosslinked product of ProductionExample 1Polyorganosiloxane polymer——crosslinked product of ProductionExample 2Polyorganosiloxane polymer——crosslinked product of ProductionExample 3Polyorganosiloxane polymer45—crosslinked product of ComparativeProduction Example 1Polyorganosiloxane polymer—45crosslinked product of ComparativeProduction Example 2Silicone-based anti-foaming agent3030oil compound #1EOPOEO copolymer (Adeka2525Pluronic L-31)Anti-foaming retention 1 time◯◯Anti-foaming retention 2 times◯ΔAnti-foaming retention 3 timesΔΔAnti-foaming retention 4 timesXX

As can be seen from Table 3 summarizing the results of each example and comparative example, when using the silicone anti-foaming agent composition containing the polyorganosiloxane polymer crosslinked product having a polyoxyalkylene group containing moiety structures (I) and (II) of the present invention, the anti-foaming speed is fast from the first time, and anti-foaming properties are superior. In addition, it was found practical anti-foaming properties could be obtained even after repeating the test four times. On the other hand, in the comparative examples having a low number of repetitions of siloxane units in moiety structure (I), it was found that a sufficient anti-foaming speed was not obtained, and that the anti-foaming properties were lowered for repeated tests. These results suggest that the polyorganosiloxane polymer crosslinked product having a polyoxyalkylene group shown in the examples improves the performance of the anti-foaming agent against dilution and shear forces, and is expected to improve anti-foaming retention.

[Silicone-based anti-foaming agent oil compound #2]

59.1 parts by mass of polydimethylsiloxane blocked with a trimethylsilyl group (viscosity of 5,000 mPa·s at 25° C.), 30.60 parts by mass of polydimethylsiloxane blocked with a silanol group (viscosity of 12,500 mPa·s at 25° C.), and 3.06 parts by mass of polyethyl silicate (“Cilbond 50” manufactured by Evonik) were placed in a three neck flask with a capacity of 1 L provided with a stirrer, a thermometer, a reflux condenser, and nitrogen gas supply, while stirring, and the temperature was raised to 110° C. A mixture of 1.54 parts by mass of premixed potassium dimethylsilanolate, 5.15 parts by mass of polydimethylsiloxane blocked with a trimethylsilyl group (viscosity of 5,000 mPa·s at 25° C.), and 0.08 parts by mass of ethanol was added at 110° C. and stirring was continued for 30 minutes at 110° C. Next, silica (“Aerosil 200”, specific surface area: 200 m2/g, manufactured by Evonik) was added, and then homogeneously dispersed using a homomixer for 30 minutes while heating at 110° C. A mixture of 0.1 parts by mass of polyether-modified silicone 501W and 0.13 parts by mass of ion exchanged water was added. After stirring, 5.15 parts by mass of polydimethylsiloxane blocked with a silanol group (viscosity of 40 mPa·s at 25° C.) was added, and the temperature raised to 190° C. 1.25 parts by mass of potassium dimethylsilanolate catalyst and allowed to react at 190° C. for 1 hour. The obtained reaction product was neutralized, then 0.02 parts by mass of polyether-modified silicone 501W and 2.19 parts by mass of ion exchanged water were added, to obtain a silicone-based anti-foaming agent oil compound. All steps were performed under a nitrogen gas purge. The obtained silicone-based anti-foaming agent oil compound had a viscosity of 33,500 mPa·s.

Examples 4 to 6

As shown in Table 4, anti-foaming agent compositions for Examples 4 to 6 were prepared by the same procedure as in Example 1, except that the silicone-based anti-foaming agent oil compound #2 above was used instead of the silicone-based anti-foaming agent oil compound #1. The evaluation results are shown in Table 4.

TABLE 4Anti-foaming agents of Examples 4 to 6, particle diameter and anti-foaming retention (unit of each component: g)ExampleExampleExample456Silicone-based anti-foaming agent oil303030compound #2Polyorganosiloxane polymer crosslinked45——product of Production Example 1Polyorganosiloxane polymer crosslinked—45—product of Production Example 2Polyorganosiloxane polymer crosslinked——45product of Production Example 3EOPOEO copolymer (Adeka Pluronic252525L-31)Emulsion particle diameter after1.51.21.0emulsification (um)Anti-foaming retention 1 time⊚⊚⊚Anti-foaming retention 2 times⊚⊚⊚Anti-foaming retention 3 times◯◯◯Anti-foaming retention 4 times◯◯◯

When the polyorganosiloxane polymer crosslinked product of the present invention is used together with the silicone-based anti-foaming agent oil compound #2, which is a trimethylsilyl group-terminated polydimethylsiloxane with a slightly longer chain length (viscosity of 5,000 mPa·s at 25° C.), the anti-foaming retention is even more favorable, as shown in Table 4 (Examples 4 to 6), in addition to improved dilution stability against shear stress. Moreover, in the present invention, it is expected that more favorable anti-foaming properties can be achieved by using the anti-foaming agent oil compound according to the present invention in combination with a polyorganosiloxane polymer crosslinked product having a polyoxyalkylene group having an optimized structure.