POLYETHER-MODIFIED SILICONE COMPOSITION, SURFACTANT, FOAM STABILIZER, POLYURETHANE FOAM FORMING COMPOSITION, AND COSMETIC PREPARATION INCLUDING SAID COMPOSITION, AND METHOD FOR PRODUCING SAID COMPOSITION

Abstract

Provided is a polyether-modified silicone composition. The composition comprises (A) a polyether-modified silicone, and (B) a monool organic compound. The monool organic compound (B) is selected from (B1) a glycol ether compound having a hydrogen atom substituted by an alkyl group having from 2 to 8 carbon atoms at one end, a secondary alcoholic hydroxy group at the other end, from 2 to 3 repeating oxyalkylene units having from 2 to 4 carbon atoms, and (B2) a tripropylene glycol monomethyl ether. Isopropyl alcohol does not exceed 1 mass % of the entire composition. Applications and manufacturing methods for the composition are also provided.

Claims

1. A polyether-modified silicone composition comprising: (A) at least one polyether-modified silicone represented by the general Formula (1) below:
R.sub.aQ.sub.bSiO.sub.(4-a-b)/2(1) where each R independently represents a monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bond or a silicon atom-containing organic group, each Q independently represents a polyoxyalkylene-containing organic group represented by the general formula: C.sub.xH.sub.2xO(C.sub.2H.sub.4O).sub.t1(C.sub.3H.sub.6O).sub.t2(C.sub.4H.sub.8O).sub.t3Y where x, t1, t2 and t3 are numbers satisfying 2x8, 0t60, 0t250, 0t350, and 2(t1+t2+t3)110, and Y is selected from among a hydrogen atom, alkyl groups having from 1 to 4 carbon atoms, and a COCH.sub.3 group, and a and b are numbers in the ranges 1.0a2.5 and 0.0001b1.5; (B) at least one monool organic compound selected from (B1) and/or (B2) below and being a liquid at 5 C. and having one secondary alcoholic hydroxyl group but no heteroatom other than oxygen in the molecule: (B1) a glycol ether compound having a hydrogen atom substituted by an alkyl group having from 2 to 8 carbon atoms at one end, a secondary alcoholic hydroxy group at the other end, and from 2 to 3 repeating oxyalkylene units having from 2 to 4 carbon atoms, (B2) a tripropylene glycol monomethyl ether; wherein isopropyl alcohol (IPA) does not exceed 1 mass % of the composition.

2. The polyether-modified silicone composition according to claim 1, wherein component (A) is a linear polyether-modified silicone represented by the general Formula (1) below: ##STR00004## where R and Q are each as defined above, X is R or Q, n is a number from 0 to 1000, and m is a number in a range from 0 to 200, provided at least one X is Q when m is 0.

3. The polyether-modified silicone composition according to claim 2, wherein n and m in Formula (1) are numbers in the range 25(m+n)230.

4. The polyether-modified silicone composition according to claim 1, wherein Q is a polyoxyalkylene group-containing organic group excluding a polyoxyethylene group-containing organic group represented by the general formula: C.sub.xH.sub.2xO(C.sub.2H.sub.4P).sub.t1Y where 2x8, 10t160, and Y is selected from a hydrogen atom, alkyl groups having from 1 to 4 carbon atoms, and a COCH.sub.3 group.

5. The polyether-modified silicone composition according to claim 1, wherein component (B) is selected from a group consisting of dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, dipropylene glycol mono (iso) propyl ether, tripropylene glycol mono (iso) propyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether.

6. The polyether-modified silicone composition according to claim 1, wherein component (B) is a distilled and refined monool organic compound.

7. The polyether-modified silicone composition according to claim 1, wherein the mass ratio of component (A) and component (B) is in a range from 20/80 to 96/4.

8. The polyether-modified silicone composition according to claim 1, wherein Q is a polyoxyalkylene group-containing organic group represented by the general formula: C.sub.xH.sub.2xO(C.sub.2H.sub.4O).sub.t1(C.sub.3H.sub.6O).sub.t2(C.sub.4H.sub.8O).sub.t3Y where x, t1, t2 and t3 are numbers satisfying 2x8, 0t160, 1t250, 0t350, and 6(t1+t2+t3)50, and Y is selected from a hydrogen atom, alkyl groups having from 1 to 4 carbon atoms, and a COCH.sub.3 group.

9. A surfactant comprising the polyether-modified silicone composition according to claim 1.

10. A foam stabilizer comprising the polyether-modified silicone composition according to claim 1.

11. A polyurethane foam-forming composition comprising the polyether-modified silicone composition according to claim 1.

12. A polyurethane foam-forming composition comprising: (a) a polyol; (b) a polyisocyanate; (c) a catalyst; (d) a foam stabilizer comprising the polyether-modified silicone composition according to claim 1; and (e) optionally at least one additional component selected from a group consisting of a foam stabilizer other than component (d), a blowing agent, a diluent, a chain extender, a crosslinker, water, a non-aqueous blowing agent, a filler, a strengthening agent, a pigment, a dye, a colorant, a flame retardant, an antioxidant, an anti-ozone agent, an ultraviolet light stabilizer, an antistatic agent, a fungicide, and an antimicrobial agent.

13. The polyurethane foam-forming composition according to claim 12, comprising from 0.3 to 8.0 parts by mass of (A) the polyether-modified silicone in the polyether-modified silicone composition according to claim 1 per 100 parts by mass of (a) the polyol.

14. A polyurethane foam obtained from the polyurethane foam-forming composition according to claim 11, optionally wherein the polyurethane foam is a rigid foam, semi-rigid foam, high-resilience (HR) foam, flexible foam, or microcellular foam, and optionally wherein the polyurethane foam has low emission properties.

15. (canceled)

16. A cosmetic raw material comprising the polyether-modified silicone composition according to claim 1.

17. A cosmetic comprising the polyether-modified silicone composition according to claim 1.

18. A method for manufacturing the polyether-modified silicone composition according to claim 1, the method comprising the steps of: (I) initiating a substantially solvent-free hydrosilylation reaction between an organic hydrogen polysiloxane and a polyether compound having an alkenyl group at one end of the molecular chain; and (II) diluting and/or accelerating the reaction by adding the monool organic compound serving as component (B).

19. A method for manufacturing the polyether-modified silicone composition according to claim 1, the method comprising the step of: (I) initiating and/or promoting a hydrosilylation reaction between an organic hydrogen polysiloxane and a polyether compound having an alkenyl group at one end of the molecular chain in the presence of the monool organic compound serving as component (B).

20. A method for manufacturing the polyether-modified silicone composition according to claim 1, the method comprising the steps of: (I) initiating and/or promoting a hydrosilylation reaction between an organic hydrogen polysiloxane and a polyether compound having an alkenyl group at one end of the molecular chain in the presence of a volatile organic solvent (B) different from component (B); and (II) conducting solvent exchange of the volatile organic solvent (B) with the monool organic compound serving as component (B).

21. The method according to claim 18, wherein the hydrosilylation reaction between the organic hydrogen polysiloxane and the polyether compound having an alkenyl group at one end of the molecular chain is performed in a continuous hydrosilylation process.

Description

EXAMPLES

[0207] The following is a more detailed description of the present invention with reference to examples and comparative examples. Note that the present invention is not limited to these examples. In the compositional formulas, Me is a methyl group, M is a Me.sub.3SiO group (or Me.sub.3Si group), D is a Me.sub.2SiO group, M.sup.H is a Me.sub.2HSiO group, and D.sup.H is a MeHSiO group. Units in which the methyl group in M or D has been modified by a substituent are denoted by M* or D*. Also, IPA is isopropyl alcohol.

<Example 1-1> Surfactant Usable in Both Rigid and Flexible Foams

[0208] A 500-mL reaction vessel was charged with 43.78 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.43.3D.sup.H.sub.6.7M, 184.22 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3, and 10 g of dipropylene glycol monobutyl ether (BuDPG), and the temperature was raised to 93 to 98 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.567. Once 2.0 g of a BuDPG solution of platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex (Pt concentration: 0.01 wt %) had been added, the reaction solution was clear within 35 minutes. The reaction was conducted for a total of 2.5 hours. Next, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method.

[0209] In this way, a polyether-modified silicone composition was obtained in the form of a clear, homogeneous liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.43.3D*.sub.6.7M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3} to unreacted polyether to BuDPG was 67.2:27.8:5. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide. (Yield: 235 g)

<Example 1-2> Surfactant Usable in Both Rigid and Flexible Foams

[0210] A 500-mL reaction vessel was charged with 40.8 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.43.3D.sup.H.sub.6.7M, 171.7 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3, and 35 g of dipropylene glycol monobutyl ether (BuDPG), and the temperature was raised to 92 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.567. Once 2.5 g of a BuDPG solution of platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex (Pt concentration: 0.02 wt %) had been added, the reaction solution was clear within 30 minutes. The reaction was conducted for a total of 2.5 hours. Next, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method.

[0211] In this way, a polyether-modified silicone composition was obtained in the form of a clear, homogeneous liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.43.3D*.sub.6.7M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3} to unreacted polyether to BuDPG was 60:25:15. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide. (Yield: 242 g)

<Example 1-3> Surfactant Usable in Both Rigid and Flexible Foams

[0212] A polyether-modified silicone composition was obtained in the form of a clear, homogeneous liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.43.3D*.sub.6.7M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3} to unreacted polyether to BuDPG was 53:22:25 by weighing out 25.0 g of the polyether-modified silicone composition obtained in Example 1-2 in a 35-mL glass bottle, adding 3.3 g of dipropylene glycol monobutyl ether (BuDPG), stoppering the glass bottle, and shaking the contents thoroughly.

<Example 2-1> Surfactant for Flexible Foams

[0213] A 500-mL reaction vessel was charged with 50.6 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.78D.sup.H.sub.5.0M, 153.4 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.22(C.sub.3H.sub.6O).sub.22H, and 34 g of dipropylene glycol monobutyl ether (BuDPG), and the temperature was raised to 90 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.64. Once 2.0 g of a BuDPG solution of platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex (Pt concentration: 0.02 wt %) had been added, the reaction solution was clear within an hour. The reaction was conducted for a total of 3 hours. Next, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method.

[0214] In this way, a polyether-modified silicone composition was obtained in the form of a liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.78D*.sub.5.0M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.22(C.sub.3H.sub.6O).sub.22H} to unreacted polyether to BuDPG was 60:25:15. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide.

<Example 3-1> Surfactant for Flexible Foams

[0215] A 500-mL reaction vessel was charged with 50.6 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.78D.sup.H.sub.5.0M, 65.4 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.12(C.sub.3H.sub.6O).sub.16CH.sub.3, 65.3 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.25(C.sub.3H.sub.6O).sub.37CH.sub.3, and 58 g of dipropylene glycol monobutyl ether (BuDPG), and the temperature was raised to 90 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.58. Once 2.0 g of a BuDPG solution of platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex (Pt concentration: 0.01 wt %) had been added, the reaction solution was clear within an hour. The reaction was conducted for a total of 3 hours. Next, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method.

[0216] In this way, a polyether-modified silicone composition was obtained in the form of a liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.78D*.sub.3.4D**.sub.1.6M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.12(C.sub.3H.sub.6O).sub.16CH.sub.3} to unreacted polyether to BuDPG was 55:20:25. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide.

<Example 4-1> Surfactant for Flexible Foams

[0217] A 500-mL reaction vessel was charged with 48.0 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.171D.sup.H.sub.19M, 6.7 g of a one-ended allyl polyether (1) represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.12H, 78.9 g of a one-ended allyl polyether (2) represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.12(C.sub.3H.sub.6O).sub.16(CO)CH.sub.3, 78.9 g of a one-ended allyl polyether (3) represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.25(C.sub.3H.sub.6O).sub.37(CO)CH.sub.3, and 37.5 g of dipropylene glycol monobutyl ether (BuDPG), and the temperature was raised to 95 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.31. Once 9 L (corresponding to 0.01 g) of a platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex catalyst solution (Pt concentration: 24.7 wt %) had been added, the reaction solution was semi-clear within 10 minutes. After aging for 2.5 hours, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method. It was found that the conversion rate was 75% and that the reaction was not yet complete. After raising the temperature to 125 C. and aging the solution for another 2 hours, the solution had become a clear liquid, and the conversion rate had reached 90%. In order to complete the reaction, 25 g of BuDPG and 14.4 g each of allyl polyethers (2) and (3) were added to the reaction system, 9 L (equivalent to 0.01 g) of the catalyst solution was added, and the reaction was continued for 5 hours at 125 C. As a result, the reaction was completed. The final allyl/SiH mass ratio was 1.52. The liquid was a brown transparent liquid, and it was found that only a slight amount of brown platinum catalyst aggregate (gel-like) was attached to the stirring rod.

[0218] After filtration, a polyether-modified silicone composition was obtained in the form of a clear, homogeneous liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.171D*.sub.10.9D**.sub.5.1D***.sub.3M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.12(C.sub.3H.sub.6O).sub.16(CO)CH.sub.3, **C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.25(C.sub.3H.sub.6O).sub.37(CO)CH.sub.3, =C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.12H} to unreacted polyether to BuDPG was 49.3:25.7:25. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide.

<Comparative Example 1-1> Surfactant Usable in Both Rigid and Flexible Foams

[0219] A 500-mL reaction vessel was charged with 43.50 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.43.3D.sup.H.sub.6.7M, 183.09 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3, and 44.3 g of toluene, and the temperature was raised to 75 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.567. Then, 200 ppm of a 5% IPA solution of chloroplatinic acid (Pt concentration: 1.9 wt %) was added, and the reaction was conducted for 2 hours. Next, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method. After neutralization with 550 ppm of sodium bicarbonate, the reaction system was heated to 125 C. while gradually reducing the pressure in order to gradually distill off the toluene while watching out for bumping. After stopping distillation of toluene and maintaining the reaction system at 40 hPa or less for one hour, the reaction system was cooled to 70 C., and repressurized. Next, 28.9 g of the one-end allyl polyether was added (for dilution) and the mixture was homogenized. Solid-liquid separation was then performed by filtration using diatomaceous earth.

[0220] In this way, a polyether-modified silicone composition was obtained in the form of a liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.43.3D*.sub.6.7M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3} to unreacted polyether was 62.8:37.2. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide. (Yield: 230 g)

Comparative Example 1-2

[0221] A 500-mL reaction vessel was charged with 49.0 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.43.3D.sup.H.sub.6.7M, 206.0 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3, and 45 g of diethylene glycol monobutyl ether (BuDEG), and the temperature was raised to 80 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.567. Once 10 L (corresponding to 0.012 g) of a platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex catalyst solution (Pt concentration: 24.7 wt %) had been added and heated to 90 C. to 100 C., the reaction solution was almost clear within 40 minutes. The reaction was conducted for a total of 2.5 hours. Next, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method. However, it was found that a considerable amount (approx. 1-2 cm.sup.3 by volume) of brown platinum catalyst aggregate (gel-like) was attached to the stirring rod, and some gel particles were suspended in the liquid.

[0222] After filtration, a polyether-modified silicone composition was obtained in the form of a liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.43.3D*.sub.6.7M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3} to unreacted polyether to BuDEG was 60:25:15. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide.

Comparative Example 1-3

[0223] A 500-mL reaction vessel was charged with 49.0 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.43.3D.sup.H.sub.6.7M, 206.0 g of a one-ended allyl polyether represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3, and 45 g of polypropylene glycol monobutyl ether (BuPPG) represented by an average composition formula of C.sub.4H.sub.9O(C.sub.3H.sub.6O).sub.11H, and the temperature was raised to 100 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.567. Once 10 L (corresponding to 0.012 g) of a platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex catalyst solution (Pt concentration: 24.7 wt %) had been added, the reaction solution was almost clear within 1.5 hours. The reaction was conducted for a total of 3 hours. Next, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method. However, it was found that a considerable amount (approx. 1-2 cm.sup.3 by volume) of brown platinum catalyst aggregate (gel-like) was attached to the stirring rod, and some gel particles were suspended in the liquid.

[0224] In this way, a polyether-modified silicone composition was obtained in the form of a liquid in which the ratio of polyether-modified silicone represented by an average composition formula MD.sub.43.3D*.sub.6.7M {where, *C.sub.3H.sub.6O(C.sub.2H.sub.4O).sub.24(C.sub.3H.sub.6O).sub.6CH.sub.3} to unreacted polyether to BuPPG was 60:25:15. Here, the polyether moiety was a random adduct of ethylene oxide and propylene oxide.

<Comparative Example 4-1> Surfactant for Flexible Foams

[0225] A 500-mL reaction vessel was charged with 48.0 g of a SiH group-containing organopolysiloxane represented by an average composition formula of MD.sub.171D.sup.H.sub.19M, 6.7 g of a one-ended allyl polyether (1) represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.12H, 78.9 g of a one-ended allyl polyether (2) represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.12(C.sub.3H.sub.6O).sub.16(CO)CH.sub.3, 78.9 g of a one-ended allyl polyether (3) represented by an average composition formula of CH.sub.2CHCH.sub.2O(C.sub.2H.sub.4O).sub.25(C.sub.3H.sub.6O).sub.37(CO)CH.sub.3, and 37.5 g of polypropylene glycol monobutyl ether (BuPPG) represented by an average composition formula of C.sub.4H9-O(C.sub.3H.sub.6O).sub.11H, and the temperature was raised to 100 C. while stirring the contents under a nitrogen flow. The allyl/SiH mass ratio in the hydrosilylation reaction was 1.31. Once 9 L (corresponding to 0.01 g) of a platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinyl tetrasiloxane complex catalyst solution (Pt concentration: 24.7 wt %) had been added, the reaction solution was almost clear within 15 minutes. After aging for 3.5 hours, 1 g of reaction solution was collected and completion of the reaction was verified using the alkali decomposition gas generation method. It was found that the conversion rate was 75% and that the reaction was not yet complete. Also, a considerable amount of brown platinum catalyst aggregate (gel-like) was attached to the stirring rod. In order to complete the reaction, 25 g of BuPPG and 14.7 g each of allyl polyethers (2) and (3) were added to the reaction system, 9 L (equivalent to 0.01 g) of the catalyst solution was added, and aging was conducted for 3 hours at 125 C. However, there was no significant change in the conversion rate. Another 24.6 g each of allyl polyethers (2) and (3) had to be added again to the reaction system. When the situation was observed after one hour, the liquid had gelled and become caked on the stirring rod. At this point, the test was ended.

[Properties of Reaction Solvent or Diluent]

[0226] In order to select a suitable solvent for a polyether-modified silicone, the physical properties of many industrial produced candidate compounds are shown in Table 1. In order to take into account use as a foam stabilizer for polyurethane foam and reduce migration from the foam, non-reactive compounds have been excluded. Compounds that solidify at low winter temperatures and compounds with a low flash point have also been excluded. The terminal structure represented by (C.sub.3H.sub.6O)H in the chemical structures of Table 1 may include isomers. However, secondary alcoholic hydroxyl groups represented by CH.sub.2CH(CH.sub.3)OH are usually formed.

TABLE-US-00001 TABLE 1 Solvent for Polyether-Modified Silicone (Diluent) Freezing Pt. or Chemical Visc. [cs] Pour Pt. Boiling Pt. Flash Pt. No. Abbreviation Structure* (25 C.) [ C.] [ C.] [ C.] RE1 ISA Me.sub.2CH(CH.sub.2).sub.15OH 56 <30 292-302 194 RE2 TEXANOL Me.sub.2CH(CO)OCH.sub.2CHMe.sub.2CH(OH)CHMe.sub.2 13.6 <50 255-260 120 RE3 PPG HO (C.sub.3H.sub.6O).sub.8.6H 68 45 NA 180 (Polymer) RE4 BuPPG Butyl-O (C.sub.3H.sub.6O).sub.10.5H 70 <35 NA 210 (Polymer) RE5 PG HO(C.sub.3H.sub.6O)H 47 <57 187 99 RE6 DPG HO(C.sub.3H.sub.6O).sub.2H 73 39 232 132 RE7 TPG HO(C.sub.3H.sub.6O).sub.3H 56 41 265 141 RE8 PhEG Phenyl-O(C.sub.2H.sub.4O)H 20.5 14 245 127 RE9 PhDEG Phenyl-O(C.sub.2H.sub.4O).sub.2H >20.5 <30 283 160 RE10 PhPG Phenyl-O(C.sub.3H.sub.6O)H 21.4 11 241 115 RE11 BuEG Butyl-O(C.sub.2H.sub.4O)H 3 <70 171 62 RE12 BuDEG Butyl-O(C.sub.2H.sub.4O).sub.2H 6 <70 230 107 RE13 BuTEG Butyl-O(C.sub.2H.sub.4O).sub.3H 8 48 271 156 RE14 MeDPG MeO(C.sub.3H.sub.6O).sub.2H 3.8 80 190 79 RE15 BuPG Butyl-O(C.sub.3H.sub.6O)H 3.3 80 170 62 1 MeTPG MeO(C.sub.3H.sub.6O).sub.3H 5.5 80 242 122 2 BuDPG Butyl-O(C.sub.3H.sub.6O).sub.2H 4.9 <60 229 106 3 BuTPG Butyl-O(C.sub.3H.sub.6O).sub.3H 7.3 <75 274 138 4 PrDPG Propyl-O(C.sub.3H.sub.6O).sub.2H 4.3 <60 212 94 *Phenyl = C.sub.6H.sub.5, Butyl = C.sub.4H.sub.9, Propyl = C.sub.3H.sub.7, Me = CH.sub.3

[0227] Among the solvents listed in Table 1 Nos. RE1 to RE15 are components that do not fall under component (B) of the invention in the present application, but No. 1 to No. 4 are components that fall under component (B) of the invention in the present application. The following is a comparison of the suitability of these components as a solvent for polyether-modified silicone compositions.

[0228] Based on the data in Table 1, when branched higher alcohols such as isostearyl alcohol (ISA, RE1), PPG derivatives (RE3, RE4) that are polymer-type diluents, diols (RE5 to RE7), and phenyl glycol derivatives (RE8 to RE10) are used to dilute a highly viscous polyether-modified silicone, the viscosity-reducing effect is not very dramatic. In other words, it is clear that the amount of diluent used has to be increased in order to lower the viscosity of a surfactant composition, and there is a trade-off between efficient surface activity and the isocyanate index.

[0229] In addition, ISA has a compatibility problem with high polarity components such as polyols and surfactants, PPG derivatives have an affinity problem with water, and phenyl ether derivatives generally have a high melting point and are too expensive to be used in polyurethane foam production. Texanol (RE2) is good from the standpoint of a relatively low viscosity, but has few structural elements similar to an oxyalkylene group in the molecule. As a result, it has compatibility problems with strongly hydrophilic polyethylene glycol (PEG) homopolymers.

[0230] Therefore, in order to improve formulations of polyurethane foam-forming compositions and compatibility with each component, stabilize and improve foam properties, and contribute to the realization of a stable production process for foam, only solvents in the group of compounds known as glycol ethers are selected and combined with polyether-modified silicones. These are preferably used as surfactant solutions. From a safety standpoint, the solvent preferably has a flash point of 80 C. or higher, preferably 90 C. or higher.

[0231] Also, there is growing market demand for polyurethane foams with low emission properties. This is expressed as demand for low volatile organic compounds (low VOC) which have fewer volatile components, low emission compounds (which have fewer chemical substances released from the foam), and low fogging compounds (which reduce adhesion of components volatilized from foam used in car interiors from adhering to window glass). The meaning of these terms is essentially the same. Therefore, the solvent is preferably expected to become incorporated into the polyurethane backbone chain, and essentially be non-volatile (equal to having a boiling point of 200 C. or higher). Based on this study, among the compounds listed in Table 1, the solvents that can suitably be used in a polyether-modified silicone composition are No. 1 to No. 4, RE12, and RE13. In other words, the other solvent compounds are not preferred because they include an inappropriate physical property. As described below, RE12 and RE12, which do not include secondary alcoholic hydroxyl groups (but rather primary alcoholic hydroxyl groups) perform poorly compared to the invention of the present application when used as solvents for polyether-modified silicone compositions, especially synthesis solvents, in terms of reproducibility and side reaction risk due to variations in raw material lots (such as in acidic impurities), composition usefulness, and production efficiency.

[Properties of Compositions in the Examples and Comparative Examples]

[0232] The design structures, details, appearance, and viscosity at 25 C. (mm.sup.2/s) of the resulting compositions in Examples 1-1 to 1-2, Examples 2-1 to 4-1, and Comparative Examples 1-1 to 1-3 are shown in Table 1 and Table 2 below.

TABLE-US-00002 TABLE 2 Design Structure and Content of Each Material Obtained in the Examples Properties Structure of Polyether- Example of Composition Modified Silicone (A) Solvent (A)/(B) No. Reactivity Appearance Visc. m n t1/t2 Y (B) mass ratio 1-1 Good Clear 750 6.7 43.3 24/6 Me BuDPG 93/7 Uniform 1-2 Good Clear 369 6.7 43.3 24/6 Me BuDPG 80/20 Uniform 1-3 Clear 216 6.7 43.3 24/6 Me BuDPG 68/32 Uniform 2-1 Good Clear No data 5.0 78 22/22 H BUDPG 80/20 3-1 Good Clear No data 5.0 78 12/16 & Me & BuDPG 69/31 25/37 Me 4-1 Bit some- 23,770 19 171 12/0 & H & BuDPG 66/34 Low what 12/16 & COCH3 & Clear* 25/37 COCH3 Note *A slight amount of catalyst aggregate (gel) adhered to the stirrer before filtration (after the reaction).

TABLE-US-00003 TABLE 3 Design Structure and Content of Each Material Obtained in the Comparative Examples Comp. Properties Structure of Polyether- Example of Composition Modified Silicone (A) Solvent (A)/(b) No. Reactivity Appearance Visc. m n t1/t2 Y (b) mass ratio 1-1 Good Clear 764 6.7 43.3 24/6 Me None Uniform 1-2 Good Generally 405 6.7 43.3 24/6 Me BuDEG 80/20 Clear* 1-3 Good Generally 571 6.7 43.3 24/6 Me BuPPG 80/20 Clear* 4-1 Poor Gel Unmeasurable 19 171 12/0 & H & BuPPG 66/34 12/16 & COCH3 & 25/37 COCH3 Note *A considerable amount of catalyst aggregate (gel) adhered to the stirrer before filtration (after the reaction).

[0233] In Comparative Example 1-3 and Comparative Example 4-1, an attempt was made to use polyglycols (BuPPG) commonly used as diluents in polyether-modified silicones as the synthesis solvent for the copolymers. In the case of the former where the molecular weight of the modified silicone was not so high, the hydrosilylation in the main reaction proceeded well and the desired product was obtained. However, in the case of the latter where the molecular weight of the modified silicone was somewhat high, the main reaction proceeded very slowly and was never completed because the entire reaction system gelled up. The cause was the high molecular weight of polyglycols, their inability to compatibilize a SiH group-containing organopolysiloxane and terminal alkenyl group-containing polyether, and their ineffectiveness at lowering the viscosity of the reaction system to increase opportunities for contact and mixing. Therefore, the visible gel structure of the entire reaction solution is thought to be the result of a non-negligible side reaction that causes crosslinking as the main reaction becomes stagnant. Also, in the case of Comparative Example 1-3, where the molecular weight of the modified silicone is not that high, a significant amount of catalyst aggregate (gel) adhered to the stirring rod unlike Example 1-1 and Example 1-2. This is because the compatibility between polyglycols BuPPG and the catalyst is insufficient, and because it does not effectively dissolve and disperse the catalyst throughout the entire reaction system. Because polyglycols are generally not recognized or used as reaction solvents for modified silicones and alkali catalysts are often used in the manufacturing process, manufacturers of the raw materials have not recognized the need to remove all traces of residual alkalis from each production batch. Therefore, when such a raw material is used as a solvent in the hydrosilylation reaction, the reaction is greatly affected by fluctuations in the impurity levels in each production lot of the raw material (alkalis can stop reactions by deactivating platinum catalysts, etc.), which makes stable production of modified silicones impossible on an industrial scale. Also, because polyglycols have several ether bonds in the molecule, they readily oxidized in contact with air to form peroxides. Because peroxides also interrupt the hydrosilylation catalytic cycle by deactivating the platinum catalysts, there are significant industrial disadvantages when general polyglycols are used as a hydrosilylation reaction solvent.

[0234] In Comparative Example 1-1, the hydrosilylation reaction proceeded well and produced a polyether-modified silicone. However, toluene is toxic, flammable, hydrophobic and cannot produce a composition of the present invention unless solvent substitution occurs.

[0235] In Comparative Example 1-2, diethylene glycol monobutyl ether (BuDEG) which does not fall under component (B) of the present invention was used as a solvent. Although the hydrosilylation in main reaction proceeded well and the desired product was obtained, a considerable amount of catalyst aggregate (gel) adhered to the stirring rod. This is thought to be due to the lack of compatibility of BuDEG with the catalyst, which could not effectively dissolve and disperse the catalyst throughout the reaction system. Furthermore, BuDEG is a hazardous air pollutant that falls under the Hazardous Air Pollutants Act, and is regulated in the United States. As a result, industrial use is greatly restricted compared to the BuDPG used in the examples due to safety and environmental concerns.

[0236] Glycol ethers with low molecular weights and a small number of repeating units have been considered glycol ethers because of their relatively similar structures and properties. However, as a result of extensive research on these compounds as reaction solvents and residual diluents in polyether-modified silicones, a considerable difference in usefulness has been discovered in the case of glycol ether EO derivatives having no secondary alcoholic hydroxyl group and glycol ether PO derivatives having secondary alcoholic hydroxyl groups. In Example 1-2, no gel was observed in the solution after completion of the reaction. However, in Comparative Example 1-2, a considerable amount of catalyst aggregate (gel) was found to be adhering to the stirring rod by the end of the reaction. During industrial production, catalyst aggregates such as these clogging filters during filtration and building up in reaction vessels often cause significant decline in production efficiency. Even the small amounts observed in the laboratory have an undesirable effect on industrial production. Also, the reactivity of the hydroxyl group is high in BuDEG, which has a primary alcoholic hydroxyl group. Therefore, when trace amounts of acidic impurities from raw materials are present in the reaction system, the hydroxyl group is believed to have an increased likelihood of competitively reacting with and blocking the reaction point of the SiH group-containing organopolysiloxane. There is also a higher risk of obtaining polyether-modified silicones with a lower molecular weight (fewer polyether pendant chains attached to the polysiloxane backbone) than called for in the design of the hydrosilylation reaction. Because of these concerns, Table 4 shows a comparison of GPC analysis results from Comparative Examples 1-1 to 1-3, Examples 1-1, and Example 1-2. During this analysis, filtered samples from the synthesis testing performed on the comparative examples were subjected to GPC because of the production of gel.

[0237] The following were the measurement conditions in the GPC analysis.

<GPC Measurement Conditions>

[0238] Eluent: Chloroform (reagent grade)

Measurement Temperature: 40 C.

[0239] Detector: Refractometer (peak detection on positive side)
Flow rate: 1.0 mL/min
Calibration: Performed with standard polystyrene
Sample solution injection volume: 100 L (sample concentration 1 wt %)

TABLE-US-00004 TABLE 4 Relationship Between Alcoholic Hydroxyl Group Properties and Polyether-Modified Silicone GPC Data Peak Area Ratio % Alcoholic of Unreacted Diluent Properties No. Avg. Mol. Wt. Polyether to SiOC Signal Intensity Sample (After Added) of Diluent of Copolymer Copolymer (.sup.29Si-NMR) C. Ex. 1-1 Raw Polyester None 23,700 175 ND (Not Detected) Ex. 1-1 BuDPG Secondary 23,000 115 ND (Not Detected) Ex. 1-2 BuDPG Secondary 23,600 122 ND (Not Detected) C. Ex. 1-2 BuDEG Primary 23,500 130 ND (Not Detected) C. Ex. 1-3 BuPPG Secondary 23,700 149* ND (Not Detected) Note *BuPPG diluent peaks overlap with unreacted polyether peaks and are counted in the calculations.

[0240] In the case of the relatively high molecular weight polyether-modified silicone samples, the target polyether-modified silicones (copolymers) are believed to be obtained normally based on GPC and .sup.29Si NMR. However, when the GPC of Comparative Example 1-2, which uses BuDEG having a primary alcoholic hydroxyl group as the reaction solvent, is compared to the GPC of Example 1-1 and Example 1-2, which use BuDPG having a secondary alcoholic hydroxyl group as the reaction solvent, it is clear that a larger amount of unreacted polyether remains in the copolymer in the comparative example. Therefore, while it cannot be detected at current levels of .sup.29Si NMR sensitivity, it is believed that, in those portions of Comparative Example 1-2 without an allyl polyether to react with as intended (quantitatively, the probability for BuDEG is high), the SiH group in the raw material polysiloxane was consumed by a dehydrogenation reaction.

[0241] Specifically, it is believed that glycol ethers having a low molecular weight and a small number of repeating units and in which the terminal hydroxyl group is a secondary alcoholic hydroxyl group do not participate in the aforementioned competitive reaction, the hydrosilylation reaction of the organic hydrogen polysiloxane and the allyl group-containing polyether starting materials proceeds selectively as designed, and produce a polyether-modified silicone having a single molecular weight distribution and a molecular weight close to that of the designed structure.

[0242] It is clear from Table 2 and Table 4 that a polyether-modified silicone having a single molecular weight distribution and high utility close to that of the designed structure can be obtained by using a monool organic compound serving as component (B) of the present invention. Also, component (B) of the invention in the present application has a much better viscosity-reducing effect on polyether-modified silicone compositions (contributing to improved handling, production efficiency, and reactivity) than the diluents in the comparative examples. The reaction solvent and residual diluent for a polyether-modified silicone in the present invention is component (B) in the present invention, which is a specific type of glycol ether compound that is liquid at 5 C., that has one secondary alcoholic hydroxyl group in the molecule, and that does not contain any heteroatom other than oxygen. Other such cases have not been reported within the scope researched by the present inventors.

[0243] Because glycol ethers having a low molecular weight and a small number of repeating units serving as component (B) are available in the market in distilled and purified form, they do not impede hydrosilylation due to impurities, they can easily compatibilize a SiH group-containing organopolysiloxane and a polyether with an alkenyl group on one end from the standpoint of molecular structure, and they can be used as reaction solvents and diluents to obtain a polyether-modified silicone composition having a singular primary component molecular weight distribution while minimizing side reactions.

[Properties of Compositions in the Examples and Comparative Examples: Hydrogel-Forming Properties]

[0244] Next, the present inventors tested the ability of compositions of the present invention to solve the problem usage restrictions due to the tendency of polyether-modified silicones to thicken or form a hydrogel in the presence of water. This problem affects, for example, urethane foam formulations in which the open cell rate is to be adjusted or in which open cells are desired, cases in which the storage stability of a premix solution has to be good, and cases in which some components are blended together beforehand and sold as a formula system. Here, Examples 1-1 and 1-2 served as polyether-modified silicone compositions of the present invention, Comparative Examples 1-1 and 1-3 served as polyether-modified silicone compositions of the prior art, and a water miscibility test was conducted on the examples and on the comparative examples. The following was the testing method.

<Testing Method>

[0245] A 200-mL glass bottle was charged with 40 g of a polyether-modified silicone composition and 20 g of water, and the contents were mixed for 5 minutes at room temperature using a Homo Disper mixer set to 1,600 rpm. The properties of the resulting mixture were observed and recorded immediately after preparation and after standing at room temperature for a day. The results are shown in Table 5 below.

TABLE-US-00005 TABLE 5 Results of Water Miscibility Test Component Unreacted Diluent (B) Properties Right Properties Sample (A) % Polyether % or (b) % Water % After Preparation After 1 Day C. Ex. 42% 25% NA 33% Clear Viscous Liquid Same as Left 1-1 Ex. 45% 19% BuDPG 33% Clear Viscous Liquid Same as Left 1-1 3% Ex. 40% 17% BuDPG 33% Clear Low-Viscosity Liquid Same as Left 1-2 10% C. Ex. 40% 17% BuPPG 33% Cloudy Viscous Liquid Same as Left 1-3 10%

[0246] It was clear from these results that a polyether-modified silicone composition of the present invention is less likely to experience thickening or hydrogel formation due to contact with water than a polyether-modified silicone composition of the prior art even when the concentration of modified silicone is higher, and the problems described above are effectively eliminated by increasing the amount of the component (B). It is also clear that formation of a composition using both a polyether-modified silicone (A) and component (B) of the present invention is key to solving these problems. Meanwhile, it is clear from the results of the water miscibility test on Comparative Example 1-3 that a polyether-modified silicone composition using BuPPG as the diluent has poor compatibility with water, becomes cloudy, and has no effect on suppressing thickening due to hydrogel formation.

[0247] As mentioned above, a polyether-modified silicone composition of the present invention can be used in urethane foam formulations in which the open cell rate is to be adjusted or in which open cells are desired, cases in which the storage stability of a premix solution has to be good, and cases in which some components are blended together beforehand and sold as a formula system, whether they be rigid, flexible, or HR applications.

[Low-Temperature Stability of Examples and Comparative Examples]

[0248] About 28 g to 29 g of each composition in the examples and comparative examples were weighed out in a 35-mL glass bottle and stoppered, the glass bottles were stored for two hours in an explosion-proof refrigerator set to an internal temperature of 1 C., and the appearance of each composition was observed and recorded at a constant temperature. The results are shown in the following Table.

TABLE-US-00006 TABLE 6 Amt. of Diluent Type of Diluent in Composition Appearance Appearance Sample (After Added) (mass %) (25 C.) (1 C.) C. Ex. 1-1 Raw Polyether 11.3 Slightly/Semi-Clear Liquid Cloudy Liquid C. Ex. 1-2 BuDEG 15 Clear Homogeneous Liquid Cloudy Liquid C. Ex. 1-3 BuPPG 15 Clear Homogeneous Liquid Cloudy Liquid Ex. 1-1 BuDPG 5 Clear Homogeneous Liquid Cloudy Liquid Ex. 1-2 BuDPG 15 Clear Homogeneous Liquid Cloudy Liquid Ex. 1-3 BuDPG 25 Clear Homogeneous Liquid Clear Homogeneous Liquid Ex. 4-1 BuDPG 25 Clear Homogeneous Liquid Clear Homogeneous Liquid

[0249] It is clear from the comparative results of Comparative Examples 1-1 to 1-3 and Examples 1-1 to 1-2 for appearance at 25 C./1 C. that polyether-modified silicone compositions having a raw material EO/PO ratio (mass ratio) of 75/25 in the reaction and a long polyether chain became cloudy at low temperatures, but that increasing the amount of BuDPG serving as the diluent in the present invention to 25% dramatically improved low temperature stability and remained clear and homogeneous at 25 C. Example 4-1 used a monoallyl etherified PEG-12 homopolymer believed to cause cloudiness in modified silicone compositions as a raw material polyether for the reaction but contained 25% of the BuDPG diluent of the present invention, and so had excellent low-temperature stability and remained clear and homogeneous at 25 C.

[Polyurethane Foam Formulation and Testing Results for Compositions in the Examples and Comparative Examples]

[0250] The present inventors used samples taken from the examples and comparative examples in a rigid urethane foam formulation based on findings related to the different types of polyurethane foam and the molecular weights of compatible polyether-modified silicones, and conducted a foaming test. Examples 1-1 and 1-2, which are polyether-modified silicone compositions (samples) of the present invention that do not have very high molecular weights, were selected and compared to Comparative Example 1-1, which is a polyether-polysiloxane copolymer composition of the prior art prepared using a reaction in toluene.

<Testing Method>

[0251] The rigid foam formulations that were tested are shown in Table 7 below. The amount of surfactant added (parts by mass) was changed in three stages, the compositions were foamed, and the appearance of the resulting foam was observed.

TABLE-US-00007 TABLE 7 Rigid Polyurethane Foam-Forming Composition Component Name Details Parts Added Mass % Premix Polyol Sorbitol-Based 100 32.62 Components Polyether Polyol (Hydroxyl Value 450) Tert. Amine Catalyst Me.sub.2N(CH.sub.2).sub.6NMe.sub.2 1.8 0.59 Water (Foaming Agent) * 6.0 1.96 Polyether-Modified Surfactant Composition or 0.7 0.33 or 0.23 Silicone Composition or 0.4 or 0.13 Isocyanate Polymethylene Polyphenyl 197.8 64.50 Polyisocyanate (Index 110, NCO % = 31.5) Total 306.6 ** 100.00 ** * Carbon dioxide gas is produced by the reaction with the isocyanate. ** The total when the number of parts of surfactant is 1.0.

[Formation of Flexible Polyurethane Foam]

[0252] A polyurethane foam-forming composition of the present invention was prepared on a scale so that the total amount in Table 6 was 16.7%, and a polyurethane foam was formed. These operations were carried out in a temperature-controlled room at about 25 C., and all of the raw materials were used after this constant temperature state was reached.

<Testing Method>

[0253] The polyol, water, catalyst, and surfactant were accurately weighed out in a 200-mL polycup and stirred at 3,500 rpm for 15 seconds using a disc blade-type disperser mixer. The isocyanate was then added to this premix and the contents were mixed for 7 seconds at 3,500 rpm using the same type of blade. The uniformly mixed urethane foam-forming composition was poured into a 1-L paper cup over 8 seconds and then allowed to foam freely. Next, the foam was left standing for 40 to 60 minutes in the temperature-controlled room. After two hours, the foam was cut in half from the top, and the foam height and cross-sectional cell structure were observed and recorded.

TABLE-US-00008 TABLE 8 Evaluation Results for Rigid Polyurethane Foam Activator 1.0 parts Activator 0.7 parts Activator 0.4 parts Type of Cell Cell Cell Surfactant Foam Height Structure Foam Height Structure Foam Height Structure C. Ex. 1-1 Standard Fine Standard Fine Standard Coarse Ex. 1-1 Equal to Standard Fine Somewhat Fine Somewhat Bit Higher than Higher than Coarse Standard Standard Ex. 1-2 Equal to Standard Fine Somewhat Fine Somewhat Bit Higher than Higher than Coarse Standard Standard

[0254] It is clear from the results that a rigid polyurethane foam using a polyether-modified silicone composition containing solvent component (B) of the present invention had a rigid polyurethane foam cell structure and foam height equal to or better than the composition in Comparative Example 1-1 using toluene as the solvent, confirming the excellent effect and usefulness of a polyether-modified silicone composition of the present invention as a cell stabilizer or surfactant.

[0255] The following are formulation examples of polyurethane foam-forming compositions in which the flexible foam surfactants prepared in Examples 2-1, 3-1, and 4-1 can be used.

TABLE-US-00009 TABLE 9 Flexible Polyurethane Foam-Forming Composition Component Name Details Parts Added Mass % Premix Polyol Glycerin-Based 100 53.95 Components Polyether Polyol (Hydroxyl Value 56) Amine Catalyst NN-dimethylethanol 0.2 0.11 amine/bis (2-dimethyl aminoethyl) ether/ triethylene diamine/ dipropylene glycol = 28/11/11/50 mixture Water (Foaming Agent) * 5.5 2.97 Dichloromethane CH.sub.2Cl.sub.2 10.0 5.39 Tin Catalyst Tin Octoate 0.27 0.15 Polyether-Modified Surfactant Composition 0.8 0.43 Silicone Composition e.g.) Ex. 2-1 or Ex. 3-1 or Ex. 4-1 Isocyanate Tolylene diisocyanate 68.6 37.00 (Index 110) Total 185.37 100.00 * Carbon dioxide gas is produced by the reaction with the isocyanate.

TABLE-US-00010 TABLE 10 Flexible Polyurethane Foam-Forming Composition Component Name Details Parts Added Mass % Premix Polyol Glycerin-Based 100 59.70 Components Polyester Polyol (Hydroxyl Value 56) Amine Catalyst Triethylene diamine/ 0.2 0.12 dipropylene glycol = 33/67 mixture N-ethyl morpholine 0.1 0.06 Water (Foaming Agent) * 3.3 1.97 Dichloromethane CH.sub.2Cl.sub.2 20.0 11.94 Tin Catalyst Tin Ocloate 0.6 0.36 Polyether-Modified Surfactant Composition 0.6 0.36 Silicone Composition e.g.) Ex. 2-1 or Ex. 3-1 or Ex. 4-1 Isocyanate Tolylene diisocyanate 42.7 25.49 (Index 105) Total 167.50 100.00 * Carbon dioxide gas is produced by the reaction with the isocyanate.