POLYETHER-POLYSILOXANE BLOCK COPOLYMER COMPOSITION, SURFACTANT AND FOAM STABILIZER INCLUDING SAME, POLYURETHANE FOAM-FORMING COMPOSITION, COSMETIC, AND PREPARATION METHOD THEREOF

Abstract

A polyether-polysiloxane block copolymer composition is disclosed. The copolymer composition comprises (A) a polyether-polysiloxane block copolymer having in a molecule structural units as expressed by General Formula (1) below:

##STR00001## where a terminal group thereof is an alkenyl group or the like bonded to a polyether portion. The copolymer composition further comprises (B) a liquid monool organic compound, which is (B1) a glycol ether compound having a low degree of polymerization, a terminal hydrogen substituted with a hydrocarbon group, and a secondary alcoholic hydroxyl group provided on another terminal, or (B2) a higher alcohol compound having a branched alkyl group with 12 or more carbon atoms. The copolymer composition generally does not contain a dimethyl polysiloxane at more than the mass of component (A). A manufacturing method, foam stabilizer or the like containing the copolymer composition, and a polyurethane foam are also disclosed.

Claims

1. A polyether-polysiloxane block copolymer composition, comprising the following component (A) and component (B) at a mass ratio of (A)/(B)=10/90 to 90/10, and not containing a dimethyl polysiloxane at more than the mass of component (A): (A) a polyether-polysiloxane block copolymer having in a molecule structural units as expressed by General Formula (1): ##STR00020## where R individually represent a monovalent hydrocarbon group with 1 to 9 carbon atoms, which does not have an aliphatic unsaturated bond; x represents a number from 2 to 4; a represents a number from 1 to 200; y represents a number where the molecular weight of a polyether portion as expressed by (CxH2xO)y is within a range of 400 to 5000; and n represents a number of at least 2, wherein a terminal group (Z) thereof is at least one type of functional group selected from Z.sup.1: alkenyl groups, hydroxyl groups, alkoxy groups, or acetoxy groups bonded to a polyether portion; and Z.sup.2: monovalent hydrocarbon groups that do not have a hetero atom, hydroxyl groups, or alkoxy groups, bonded to a silicon atom; (B) one or two or more types of monool organic compounds selected from (B1) or (B2), which is a liquid at 5 C., has one alcoholic hydroxyl group in a molecule, and does not contain a hetero atom other than oxygen: (B1) glycol ether compounds where a terminal hydrogen is substituted by a hydrocarbon group with 1 to 8 carbon atoms, a secondary alcoholic hydroxyl group is provided on another terminal, and the repeating number of oxyalkylene units with 2 to 4 carbon atoms is a number within a range of 1 to 3, and (B2) higher alcohol compounds having a branched alkyl group with 12 or more carbon atoms.

2. The polyether-polysiloxane block copolymer composition according to claim 1, wherein in the aforementioned General Formula (1) of component (A), a represents a number within a range of 10 to 45, y represents a number where the molecular weight of a polyether portion as expressed by (CxH2xO)y is within a range of 2000 to 5000, and the mass ratio of an oxyethylene (C.sub.2H.sub.4O) unit configuring the entire polyether portion is within a range of 35 to 90% on average.

3. The polyether-polysiloxane block copolymer composition according to claim 1 or 2, wherein component (A) is a polyether-polysiloxane block copolymer obtained by hydrosilylation reacting an organopolysiloxane containing a SiH group on both terminals as expressed by General Formula (2): ##STR00021## where R represents the same groups as described above, and a represents the same numbers as described above, and a polyether containing a methallyl group on both terminals as expressed by General Formula (3): ##STR00022## where x and y represent the same numbers as described above, and having structural units as expressed by General Formula (1): ##STR00023## where R represents the same groups as described above, and x, a, y, and n represent the same numbers as described above.

4. A polyether-polysiloxane block copolymer composition according to any one of claims 1 to 3, wherein component (B) is a monool organic compound having a boiling point where distillation or purification by distilling is possible.

5. The polyether-polysiloxane block copolymer composition according to any one of claims 1 to 4, wherein component (B) is one or two or more types of monool organic compound selected from propylene glycol monobutyl ethers, dipropylene glycol monobutyl ethers, tripropylene glycol monobutyl ethers, propylene glycol monomethyl ethers, dipropylene glycol monomethyl ethers, tripropylene glycol monomethyl ethers, propylene glycol mono(iso)propyl ethers, dipropylene glycol mono(iso)propyl ethers, tripropylene glycol mono(iso)propyl ethers, propylene glycol monoethyl ethers, dipropylene glycol monoethyl ethers, tripropylene glycol monoethyl ethers, 2-butyl-1-octanols, 2-hexyl-1-decanols, 2-octyl-1-dodecanols, isostearyl alcohols, and 2-decyl-1-tetradecanols.

6. The polyether-polysiloxane block copolymer composition according to any one of claims 1 to 5, wherein the mass ratio of the aforementioned component (A) and component (B) is within a range of 20/80 to 70/30.

7. The polyether-polysiloxane block copolymer composition according to any one of claims 1 to 6, further comprising: (C) at least one type of polyalkylene glycol or derivative thereof, which is a liquid at 25 C., where one terminal hydroxyl group may be substituted by a hydrocarbon group with 1 to 8 carbon atoms selected from alkyl, aralkyl, and aryl groups, and the repeating number of oxyalkylene units with 2 to 4 carbon atoms is within a range of 4 to 50, within a range of 10 to 300 parts by mass with regard to a total of 100 parts by mass of component (A), and component (B), wherein the viscosity of the entire composition at 25 C. is within a range of 100 to 35000 mm.sup.2/s.

8. A surfactant, comprising the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7.

9. A foam stabilizer, comprising the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7.

10. A polyurethane foam-forming composition, comprising the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7.

11. A polyurethane foam-forming composition, comprising: (a) a polyol; (b) a polyisocyanate; (c) a catalyst; (d) a foam stabilizer containing the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7; and (e) optionally, at least one added component selected from a group consisting of foam stabilizers other than component (d), foaming agents, diluting agents, chain extenders, crosslinking agents, water, nonaqueous foaming agents, fillers, reinforcing agents, pigments, dyes, coloring agents, flame retardants, antioxidants, anti-ozone agents, UV stabilizers, antistatic agents, disinfectants, and antibacterial agents.

12. The polyurethane foam-forming composition according to claim 10 or 11, comprising 0.5 to 8.0 parts by mass of the polyether-polysiloxane block copolymer (A) in the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7, with regard to 100 parts by mass of (a) the polyol.

13. Polyurethane foam obtained from the polyurethane foam-forming composition according to any one of claims 10 to 12.

14. The polyurethane foam according to claim 13, which is hard foam, semi-hard foam, soft foam, or microcellular foam.

15. Cosmetic raw material, comprising the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7.

16. A cosmetic, comprising the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7.

17. A method of manufacturing the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7, at least comprising the steps of: essentially initiating a hydrosilylation reaction between an organopolysiloxane containing a SiH group on both terminals as expressed by the aforementioned General Formula (2) and a polyether containing a methallyl group on both terminals as expressed by the aforementioned General Formula (3), without a solvent; and diluting or promoting the reaction by adding the monool organic compound which is the aforementioned component (B).

18. A method of manufacturing the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7, at least comprising the step of initiating or advancing the hydrosilylation reaction between an organopolysiloxane containing a SiH group on both terminals as expressed by the aforementioned General Formula (2) and a polyether containing a methallyl group on both terminals as expressed by the aforementioned General Formula (3), in the presence of the monool organic compound which is the aforementioned component (B).

19. A method of manufacturing the polyether-polysiloxane block copolymer composition according to any one of claims 1 to 7, at least comprising the steps of: initiating or advancing a hydrosilylation reaction between an organopolysiloxane containing a SiH group on both terminals as expressed by the aforementioned General Formula (2) and a polyether containing a methallyl group on both terminals as expressed by the aforementioned General Formula (3), in the presence of a volatile organic solvent (B) which is different from the aforementioned component (B); and solvent exchanging the volatile organic solvent (B) which is different from the aforementioned component (B) with the monool organic compound which is the aforementioned component (B).

20. The method of manufacturing a polyether-polysiloxane block copolymer composition according to claim 17 or 18, wherein a stripping step is essentially not provided.

Description

EXAMPLES

[0190] Hereinafter, the present invention will be further described in detail based on examples and comparative examples, but the present invention is not limited thereto. Note that in the following composition formulas, a Me.sub.3SiO group (or Me.sub.3Si group) is expressed as M, a Me.sub.2SiO group is expressed as D, a MeHSiO group is expressed as M.sup.H, and units where a methyl group in M and D is modified by any substitution group is expressed as M.sup.R and D.sup.R. Furthermore, IPA is isopropanol.

Example 1-1

[0191] 75.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 174.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 250 g of dipropylene glycol monobutyl ether (BDPG), and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 80 to 90 C. while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 2.5 hours. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00009## [0192] (where a=20, x1=33, y1=25, and n=6) [0193] and BDPG were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 7:6, and therefore, both terminals of the copolymer have a form blocked by a polyether (=terminal functional group is a methallyl group bonded to a polyether). Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or BDPG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a BDPG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Example 1-2

[0194] An experiment was performed similarly to Example 1-1 except that the BDPG was substituted with a propylene glycol monobutyl ether (BPG). Behaviors such as reactivity and the like in the synthesis reaction of the straight chain organopolysiloxane-polyether block copolymer was similar to Example 1-1.

Example 2-1

[0195] 85.55 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 164.45 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 250 g of dipropylene glycol monobutyl ether (BDPG), and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 80 to 90 C. while stirring under a nitrogen flow. 0.056 g of an IPA solution (Pt concentration: 4.5 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 3 hours. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00010## [0196] (where a=20, x1=33, y1=25, and n >10) [0197] and BDPG were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 1:1 and polyether is slightly in excess, and therefore, both terminals of the copolymer have a form blocked by a polyether (=terminal functional group is a methallyl group bonded to a polyether). Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or BDPG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a BDPG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Example 2-2

[0198] An experiment was performed similarly to Example 2-1 except that the BDPG was substituted with a propylene glycol monobutyl ether (BPG). Behaviors such as reactivity and the like in the synthesis reaction of the straight chain organopolysiloxane-polyether block copolymer was similar to Example 2-1.

Example 2-3 Without Solvent

[0199] 84.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 165.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 85 to 95 while stirring under a nitrogen flow. When 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 2.5 hour, the solution changed into a very high viscosity liquid. Next, when 1 g of reaction liquid was collected and diluted with toluene to reduce the viscosity, and then the reaction rate was confirmed by an alkali decomposition gas generation method, the gas generation amount was a trace amount, and therefore, the reaction was determined to be essentially completed. Next, 250 g of dipropylene glycol monobutyl ether (BDPG) was added to the reaction liquid, mixed homogenization was performed for 1 hour, and then when sampling was performed as a precaution to examine the reaction rate, approximately 36 ppm of silicon-bonded hydrogen atoms were detected. Therefore, after aging was performed for 3.5 hours at 85 to 95 C., the reaction was completed. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00011## [0200] (where a=20, x1=33, y1=25, and n >10) [0201] and BDPG were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 1:1 and polyether is slightly in excess, and therefore, both terminals of the copolymer have a form blocked by a polyether (=terminal functional group is a methallyl group bonded to a polyether). Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or BDPG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a BDPG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Example 2-4 Solvent Substitution Method

[0202] 84.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 165.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 250 g of toluene, and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 80 to 90 while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 2 hours. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. The reaction system was further heated to 125 C. while gradually reducing pressure, and then the toluene was gradually distilled while paying attention to bumping caused by foaming. Pressure was restored at a stage where approximately of the toluene was removed, and after 250 g of dipropylene glycol monobutyl ether (BDPG) was added to the reaction system, the pressure was again reduced and the remaining toluene was carefully distilled. The weight ratio of the copolymer and BDPG was 50:50 at a point in time where distillation of the toluene was completed, but the contents at this stage had a very high viscosity, and thus stirring was difficult. Therefore, 250 g2 times of BDPG was further added and introduced to perform dilution. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00012## [0203] (where a=20, x1=33, y1=25, and n >10) [0204] and BDPG were included at a 33:67 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. After confirming the contents of the flask the next morning, the viscosity was found to still be very high at room temperature, and handling was difficult. Therefore, 60 g of the contents of the flask were dispensed into a 200 mL glass bottle, 20 g of BDPG was added thereto, and then mixing was performed at 1600 rpm5 minutes using a homodisper mixer. Thereby, a straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the aforementioned average composition formula and BDPG were included at a 25:75 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 1:1 and polyether is slightly in excess, and therefore, both terminals of the copolymer have a form blocked by a polyether (=terminal functional group is a methallyl group bonded to a polyether). Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr. Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Example 2-5

[0205] However, BDPG was changed to 2-hexyl-1-decanol (HDL) and then an experiment was performed in accordance with the aforementioned Example 2-1. Behaviors such as reactivity and the like in the synthesis reaction of the straight chain organopolysiloxane-polyether block copolymer was similar to Example 2-1.

Example 3-1

[0206] 102.15 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 231.2 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 166.7 g of BDPG, and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 100 to 110 while stirring under a nitrogen flow. 0.74 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 3 hours. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00013## [0207] (where a=20, x1=33, y1=25, and n=6) [0208] and BDPG were included at a 67:33 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 7:6, and therefore, both terminals of the copolymer have a form blocked by a polyether (=terminal functional group is a methallyl group bonded to a polyether). Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or BDPG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a BDPG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Example 3-2

[0209] 112.9 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 262.1 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 125 g of propylene glycol monobutyl ether (BPG), and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 90 C. while stirring under a nitrogen flow. 0.83 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 3 hours at 100 C. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00014## [0210] (where a=20, x1=33, y1=25, and n=6) [0211] and BPG were included at a 75:25 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 7:6, and therefore, both terminals of the copolymer have a form blocked by a polyether (=terminal functional group is a methallyl group bonded to a polyether). Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or BPG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a BPG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Example 4-1

[0212] 76.75 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 173.25 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.52(C.sub.3H.sub.6O).sub.10CH.sub.2C(CH.sub.3)CH.sub.2, 250 g of BDPG, and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 85 to 95 while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 2 hours. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00015## [0213] (where a=20, x1=52, y1=10, and n=6) [0214] and BDPG were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 7:6, and therefore, both terminals of the copolymer have a form blocked by a polyether (=terminal functional group is a methallyl group bonded to a polyether). Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or BDPG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a BDPG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Example 4-2

[0215] An experiment was performed similarly to Example 4-1 except that the BDPG was substituted with a propylene glycol monobutyl ether (BPG). Behaviors such as reactivity and the like in the synthesis reaction of the straight chain organopolysiloxane-polyether block copolymer was similar to Example 4-1.

Example 5-1

[0216] 60 g of the polyether-polysiloxane block copolymer composition obtained in the aforementioned Example 3-1 and 20 g of polypropylene glycol monobutyl ether {BPPG-13} as expressed by n-BuO(C.sub.3H.sub.6O).sub.13H were inserted in a 200 mL glass bottle, and then mixing was performed at 1600 rpm5 minutes using a homodisper mixer at room temperature. Thereby, a liquid polyether-polysiloxane block copolymer composition having an abundance ratio of copolymer: BDPG: {BPPG-13}=2:1:1.

Example 5-2

[0217] 60 g of the gum-like polyether-polysiloxane block copolymer composition obtained in the aforementioned Comparative Example 3-1 and 20 g of polypropylene glycol monobutyl ether {BPPG-13} as expressed by n-BuO(C.sub.3H.sub.6O).sub.13H were inserted in a 200 mL glass bottle, and the bottle was stopped, and heating and shaking operations were repeated to partially dissolve the gum. Thereafter, mixing was performed to homogenize at 1600 rpm5 minutes at room temperature using a homodisper mixer. Thereby, a liquid polyether-polysiloxane block copolymer composition having an abundance ratio of copolymer: BDPG: {BPPG-13}=2:1:5.

Example 5-3

[0218] 40 g of the polyether-polysiloxane block copolymer composition obtained in the aforementioned Example 2-4 and 40 g of polypropylene glycol (PPG-7) as expressed by HO(C.sub.3H.sub.6O).sub.7H were inserted in a 200 mL glass bottle, and then mixing was performed at 1600 rpm5 minutes using a homodispersion mixer at room temperature. Thereby, a liquid polyether-polysiloxane block copolymer composition having an abundance ratio of copolymer: BDPG: {PPG-7}=1:3:4.

Example 5-4

[0219] 40 g of the polyether-polysiloxane block copolymer composition obtained in the aforementioned Example 3-2 and 35 g of dodecylbenzene (DB) were inserted in a 200 mL glass bottle, and then mixing was performed at 16005 minutes using a homodisper at room temperature. Thereby, a liquid polyether-polysiloxane block copolymer composition having an abundance ratio of copolymer: BPG:DB=3:1:3.5.

Comparative Example 1-1

[0220] 75.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 174.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 250 g hexylene glycol (HG, separate name: 2-methylpentane-2,4-diol), and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 80 to 90 while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 1.5 to 2 hours. Next, 1 g of the reaction liquid was collected, and when the reaction rate was confirmed by an alkali decomposition gas generation method (the remaining SiH groups are decomposed using a KOH ethanol/water solution, and the reaction rate is calculated from the volume of the produced hydrogen gas), the reaction was found to be slow and not completed. Therefore, as a result of heating the reaction liquid to 115 to 120 C. and then continuing the reaction for 2 to 3 hours, the reaction was completed. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00016## [0221] (where a=20, x1=33, y1=25, and n=6) [0222] and HG were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 7:6, and therefore, both terminals of the copolymer have a form blocked by a polyether. Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or HG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a HG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Comparative Example 1-2 to Comparative Example 1-6

[0223] An experiment was performed similarly to Comparative Example 1-1 except that the HG was changed to another diol compound with a low molecular weight below.

Comparative Example 1-2: Propylene glycol (PG)

Comparative Example 1-3: Dipropylene glycol (DPG)

Comparative Example 1-4: Tripropylene glycol (TPG)

Comparative Example 1-5: 1,2-Butylene glycol (1,2-BG)

Comparative Example 1-6: 1,3-Butylene glycol (1,3-BG)

[0224] In the aforementioned experiments, behaviors such as reactivity and the like in the synthesis reaction of the straight chain organopolysiloxane-polyether block copolymer was similar to Comparative Example 1-1.

Comparative Example 1-7

[0225] 75.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 174.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 250 g of polypropylene glycol (PPG-7) as expressed by HO(C.sub.3H.sub.6O).sub.7H, and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 80 to 90 C. while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 1.5 to 2 hours. 1 g of the reaction liquid was collected, and when the reaction rate was confirmed using an alkali decomposition gas generation method, the reaction was found to not have advanced at all. Therefore, two times the amount of a catalyst was further added, the reaction liquid was heated to 115 to 120 C., the reaction was continued for 2 to 3 hours, and the reaction rate was similarly confirmed, but the reaction did not advance at all. When heating and stirring were stopped, the reaction liquid was left to stand overnight, and then the contents of the flask were confirmed, the contents were found to be separated into two layers of a siloxane layer and polyether ether layer, and synthesis of the copolymer was found to be impossible under this condition.

Comparative Example 1-8

[0226] An experiment was performed in accordance with the aforementioned Comparative Example 1-7 except that PPG-7 was changed to polypropylene glycol monobutyl ether as expressed by n-BuO(C.sub.3H.sub.6O).sub.13H. However, the hydrosilylation react similarly did not advance at all, two-layer separation of a siloxane layer and polyether layer was confirmed, and synthesis of the copolymer was found to be impossible.

Comparative Example 1-9

[0227] 75.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 174.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.250 C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 250 g of diethylene glycol monobutyl ether (BDEG), and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 80 to 90 C. while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 3 hours. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. Thereby, similar to Comparative Example 1, a straight chain organopolysiloxane-polyether block copolymer and BDEG were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition.

Comparative Example 2-1

[0228] 75.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 174.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 375 g of toluene, and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 70 to 80 while stirring under a nitrogen flow. 0.05 g of a 10% IPA solution of chloroplatinic acid (Pt concentration: 3.8 wt %) was added, and a reaction was performed for 2 hours. 1 g of the reaction liquid was collected, and the reaction was confirmed to be completed using an alkali decomposition gas generation method. The reaction system was further heated to 125 C. while gradually reducing pressure, and then the toluene was gradually distilled while paying attention to bumping caused by foaming. Pressure was restored at a stage where approximately 3/4 of the toluene was removed, and after 125 g of polypropylene glycol monobutyl ether 1 BPPG-131 as expressed by n-BuO(C.sub.3H.sub.6O).sub.13H was added to the reaction system, the pressure was again reduced and the remaining toluene was carefully distilled. Pressure was restored, 125 g of BPPG-13 was added and then homogeneously mixed. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00017## [0229] (where a=20, x1=33, y1=25, and n=6) [0230] and BPPG-13 were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 7:6, and therefore, both terminals of the copolymer have a form blocked by a polyether. Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr. Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Comparative Example 2-2

[0231] 84.25 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 165.75 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.33(C.sub.3H.sub.6O).sub.25CH.sub.2C(CH.sub.3)CH.sub.2, 250 g of benzyl alcohol (BZL), and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 80 to 90 while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 1.5 hours, but the appearance was strongly cloudy, and the reaction was observed to not have advanced. Therefore, the reaction temperature was set to 100 C. and aging was further performed for 2 hours, but the reaction rate and appearance did not change. Even though the same amount of a catalyst was added, the reaction temperature was increased to 120 to 125 C., and aging was further performed for 7 hours, the reaction was not completed, and therefore, the experiment was stopped.

Comparative Example 3-1

[0232] 76.75 g of methyl hydrogen polysiloxane as expressed by average composition formula M.sup.HD.sub.20M.sup.H, 173.25 g of a bis-methallyl polyether as expressed by average composition formula CH.sub.2C(CH.sub.3)CH.sub.2O(C.sub.2H.sub.4O).sub.52(C.sub.3H.sub.6O).sub.10CH.sub.2C(CH.sub.3)CH.sub.2, 250 g hexylene glycol (HG, separate name: 2-methylpentane-2,4-diol), and 0.25 g of natural vitamin E were inserted into a 1 L reactor and then heated to 85 to 110 while stirring under a nitrogen flow. 0.56 g of an IPA solution (Pt concentration: 0.45 wt %) of a platinum-2,4,6,8-tetraemethyl-2,4,6,8-tetravinyl tetrasiloxane complex was added and a reaction was performed for 2 hours. 1 g of the reaction liquid was collected, and when the reaction rate was confirmed using an alkali decomposition gas generation method, the reaction was found to be slow and not completed. Therefore, as a result of heating the reaction liquid to 120 C. and then continuing the reaction for 7 hours, the reaction was completed. A straight chain organopolysiloxane-polyether block copolymer at least containing a structural unit as expressed by the average composition formula:

##STR00018## [0233] (where a=20, x1=52, y1=10, and n=6) [0234] and HG were included at a 50:50 ratio to obtain a liquid polyether-polysiloxane block copolymer composition. Note that the average composition formula is simply expressed, but the molar ratio of CC groups and SiH groups of raw material is approximately 7:6, and therefore, both terminals of the copolymer have a form blocked by a polyether. Furthermore, a portion of the SiH groups in the reaction can cause a dehydrogenative condensation reaction with a hydroxyl group of the IPA or HG, and therefore, a portion of the copolymer terminal is considered to include a structure of SiO-iPr or SiOR.sup.1 (R.sup.1 represents a HG residual group). Note that herein, a polyether portion is a random adduct of ethylene oxide and propylene oxide.

Comparative Example 3-2

[0235] An experiment was performed similarly to Comparative Example 3-1 except that the HG was substituted with a diethylene glycol monobutyl ether (BDEG). However, the reactivity during the synthesis experiment was inferior, which was similar to Comparative Example 3-1.

Physical Properties of Composition According to Examples and Comparative Examples

[0236] The following Table 1 and Table 2 show the design structures, contents, appearances, kinematic viscosity (mm2/s) at 25 C., and the like of the obtained compositions for the aforementioned Examples 1-1 and 1-2, Examples 2-1 to 2-5, Examples 3-1 and 3-2, Examples 4-1 and 4-2, Examples 5-1 to 5-3, Comparative Examples 1-1 to 1-9, Comparative Examples 2-1 and 2-2, and Comparative Examples 3-1 and 3-2.

[0237] Note that all compositions other than Comparative Example 1-7 and 1-8 which did not synthesize at all contain a straight chain organopolysiloxane-polyether block copolymer as expressed below as component (A).

##STR00019##

TABLE-US-00001 TABLE 1 Design structures, contents, and the like of samples obtained in the examples Structure of Example Composition Properties Copolymer (A) No. Reactivity Appearance Viscosity a x1 y1 n (B) (C) A/B/C 1-1 Favorable Transparent 1700 20 33 25 6 BDPG None 50/50/0 1-2 Favorable Transparent 500 20 33 25 6 BPG None 50/50/0 2-1 Favorable Transparent 6600 20 33 25 >10 BDPG None 50/50/0 2-2 Favorable Transparent 1200 20 33 25 >10 BPG None 50/50/0 2-3 Pass Semi- 50400 20 33 25 >10 BPDG None 50/50/0 transparent 2-4 Favorable Transparent 17500 20 33 25 >10 BPDG None 25/75/0 2-5 Favorable Semi- 12300 20 33 25 >10 HDL None 50/50/0 transparent 3-1 Pass Semi- 15000 20 33 25 6 BDPG None 67/33/0 transparent 3-2 Pass Semi- 21600 20 33 25 6 BPG None 75/25/0 transparent 4-1 Favorable Semi- 4500 20 52 10 6 BDPG None 50/50/0 transparent 4-2 Favorable Transparent 1500 20 52 10 6 BPG None 50/50/0 5-1 Pass Semi- 2300 20 33 25 6 BDPG BPPG-13 50/25/25 transparent 5-2 Pass Transparent 9100 20 33 25 >10 BDPG BPPG-13 25/12/63 5-3 Favorable Transparent 2500 20 33 25 >10 BDPG PPG-7 12/38/50 5-4 Pass Semi- 1000 20 33 25 6 BPG DB* 40/13/47 transparent Optional Components Note *Dodecylbenzene

TABLE-US-00002 TABLE 2 Design structures, contents, and the like of samples obtained in the comparative examples Structure of Comparative Composition Properties Copolymer (A) Example No. Reactivity Appearance Viscosity a x1 y1 n (B) (C) A/B/C 1-1 Defective Opaque 20 33 25 6 HG None 50/50/0 1-2 Defective Separated 20 33 25 6 PG None 50/50/0 1-3 Defective Separated 20 33 25 6 DPG None 50/50/0 1-4 Defective Separated 20 33 25 6 TPG None 50/50/0 1-5 Defective Separated 20 33 25 6 1,2BG None 50/50/0 1-6 Defective Turbid 20 33 25 6 1,3BG None 50/50/0 1-7 Not Possible Separated None PPG-7 1-8 Not Possible Separated None BPPG-13 1-9 Favorable Opaque 20 33 25 6 BDEG None 50/0/50 2-1 Favorable Transparent 10000 20 33 25 6 None BPPG-13 50/0/50 2-2 Defective Opaque 20 33 25 BZL None 50/50/0 3-1 Defective Opaque 20 52 10 6 HG None 50/50/0 3-2 Defective Opaque 20 52 10 6 BDEG None 50/50/0

[0238] Based on the aforementioned results, diol compounds with a low molecular weight not corresponding to component (B) were found to be not suitable as a solvent for the (AB)n type polyether-polysiloxane block copolymer. This is because affinity with the copolymer is thought to be low, but in most cases, separation of the composition is caused. Although HG is considered to have relatively high affinity with the copolymer in this group, the compositions obtained using the HG as a reaction solvent has strong turbidity and slow advancement of hydrosilylation, and therefore, HG is difficult to use in an industrial production process.

[0239] Furthermore, polyglycols in the related art used as a diluting agent of the (AB)n type polyether-polysiloxane block copolymer could not be used as a synthesizing agent of the copolymer. This is because a hydrosilylation reaction did not advance at all. This is because the polyglycols have a high molecular weight, and therefore, the ability to compatibilize the organopolysiloxane containing a SiH group on both terminals and polyether containing a methallyl group on both terminals, and the effect of increasing chances of contacting or mixing both by reducing the viscosity of the system are inferior. Furthermore, alkali catalysts are often used in a manufacturing process of the polyglycols, and therefore, there is considered to be a high possibility that a trace amount of residual alkal components deactivate the platinum catalyst used in the hydrosilylation reaction. Furthermore, the polyglycols have a high number of ether bonds in a molecule, and therefore are easily oxidized by contact with air, and thus easily generates peroxide. Peroxide also deactivates the platinum catalyst and disrupts the catalyst cycle of hydrosilylation, and therefore, general polyglycols are accompanied by a significant disadvantage when used as a hydrosilylation reaction solvent.

[0240] Based on the aforementioned, glycol ethers that are distilled purified and having a low molecular weight and low amount of repeating units are generally sold, and therefore, there is no problem with inhibiting hydrosilylation due to impurities, the ability to compatibilize the organopolysiloxane containing a SiH group on a terminal and polyether containing a methallyl group on both terminals is high in a molecular structure, and thus the glycol ethers are considered to be useful as a reaction solvent and diluting agent of an (AB)n type polyether-polysiloxane block copolymer. Note that cases mentioning that glycol ethers having a low molecular weight and low amount of repeating units, which are component (B) of the present invention are useful as the reaction solvent and diluting agent of the (AB)n type polyether-polysiloxane block copolymer according to the present invention have not been reported within a scope investigated by the present inventors.

[0241] In addition thereto, the present inventors made further discoveries. In the related art, the glycol ethers with a low molecular weight and low amount of repeating units often have relatively similar structures and properties, and therefore are often collectively treated as a so-called glycol ether. However, as a result of detailed examination as reaction solvent and residual diluting agent of the (AB)n type polyether-polysiloxane block copolymer, a large difference in usefulness was found between glycol ethers of an E0 derivative and glycol ethers of a PO derivative. This is clear not only from the appearance of the obtained composition, but also from comparison of the GPC analysis results of Comparative Example 1-9 and Examples 1-1 and 1-2, and comparison of GPC analysis of Comparative Example 3-2 and Examples 4-1 and 4-2 as shown in the following Table 3.

TABLE-US-00003 TABLE 3 GPC data of several samples obtained in the examples and comparative examples (degree of polymerization n = 6 in design of the copolymer) Peak Area Ratio % of Unreacted Number Methallyl Hydroxyl Peak average Polyether group of Number, molecular With Diluting diluting Shape of weight of Regard to Sample agent agent Copolymer copolymer Copolymer Comparative BDEG Primary Two peaks 20000 85.8 Example 1-9 Example 1-1 BDPG Secondary One peak 39300 11.5 Example 1-2 BPG Secondary One peak 31800 19.8 Comparative BDEG Primary Two peaks 26200 23.2 Example 3-2 Example 4-1 BDPG Secondary One peak 46100 8.6 Example 4-2 BPG Secondary One peak 40200 11.3

[0242] The measurement conditions in the aforementioned GPC analysis are as follows. [0243] GPB Measurement Conditions [0244] Eluent: Chloroform (reagent special grade) [0245] Measurement temperature: 40 C. [0246] Detector: Refractometer (peak detection on plus side) [0247] Flow rate: 1.0 mL/min [0248] Calibration: Performed by standard polystyrene [0249] Injection amount of sample solution: 100 L (sample concentration: 1 wt %)

[0250] In other words, if BDEG having a primary hydroxyl group was used as the reaction solvent, a copolymer with a high molecular weight was not obtained, and the ratio of unreacted and remaining polyethers containing a methallyl group on both terminals was high. On the other hand, if BPDG and BPG having a secondary hydroxyl group were used as the reaction solvent, a copolymer with a molecular weight exceeding 30000, used as measure for exhibiting performance as a foam stabilizing agent for polyurethane microcellular foam was obtained, and the ratio of unreacted and remaining polyethers containing a methallyl group on both terminals was low. In the case of the former, reactivity of the primary hydroxyl group is high, and therefore, this was considered to be a copolymer with a low molecular weight far from design where the ratio of block terminals of the organopolysiloxane containing a SiH group on both terminals is unignorably high. In other words, glycol ethers with a low molecular weight and low amount of repeating units, where the terminal hydroxyl group is secondary was clearly specifically useful in an application according to the present invention.

[0251] Next, the present inventors predicted that even with a monool organic compound having a primary hydroxyl group, a reaction of the hydroxyl group (corresponding to the side reaction in the case of the present invention) was less likely to occur with a compound having high hydrophobicity or a compound having a bulky substitution group near a carbon atom where a hydroxyl group is bonded, and thought that a substance was available as a hydrosilylation reaction solvent and residual diluting agent according to the present invention. Considering low melting point properties (convenience where the polyether-polysiloxane block copolymer composition does not easily solidify even in the winter), compatibility performance, ease of availability at an industrial production scale, cost, and the like desired as a diluting agent, benzyl alcohol and a liquid higher alcohol compound having a branched alkyl group with 12 to 24 carbon atoms were taken and tested. As a result, only the former case (Example 2-5) was surprisingly discovered to have an effect that achieves the objective. The following table 4 shows the results of GPC measuring the polyether-polysiloxane block copolymer composition (Example 2-5) according to the present invention, obtained in this manner, under the same conditions as described above.

TABLE-US-00004 TABLE 4 GPC data of several samples obtained in the examples and comparative examples (degree of polymerization n > 10, n = 6 in design of the copolymer) Peak Area Ratio % of Number Unreacted average Methallyl molecular Polyether Methallyl/ weight of With Reaction Diluting SiH co- Regard to Sample Catalyst agent Molar Ratio polymer Copolymer Comparative Toluene BPPG- 1.18 46500 7.3 Example 2-1 13 (n = 6) Example 1-1 BDPG 1.18 39300 11.5 (n = 6) Example 2-1 BDPG Approximately 57900 6.3 1.0 Example 2-2 BPG Approximately 40300 12.5 1.0 Example 2-3 None BDPG Approximately 102000 1.5 1.0 Example 2-5 HDL Approximately 62900 5.0 1.0

[0252] Based on the aforementioned results, liquid higher alcohol compounds having a branched alkyl group with 12 to 24 carbon atoms were also confirmed to be useful as a reaction solvent and diluting agent of the polyether-polysiloxane block copolymer according to the present invention. Furthermore, by comparing Examples 1-1 and 2-1, it is confirmed that the molar ratio of the polyether containing a methallyl group on both terminals with regard to the organopolysiloxane containing a SiH group on both terminals can be adjusted to control the molecular weight of the copolymer within a practical range as a microcellular foam stabilizing agent.

[0253] Next, the present inventors tested a solution by the composition of the present invention for problems of limiting use in a urethane foam formulation (such as soft foam or the like) where open cell ratio adjustment or making an open cell is desired, based on a trend where an (AB)n copolymer indicated in Patent Literature 10 (JP 2010-539280 T) forms a hydrogel in the presence of water. Specifically, Examples 1-1 was taken as the polyether-polysiloxane block copolymer composition of the present invention, and Comparative Example 2-1 was taken as the (AB)n type polyether-polysiloxane block copolymer according to technology in the related art (Patent Literature 6: JP 08-156143 A), and a miscibility test of both with water was performed. The test method is shown below.

[0254] 50 g of the polyether-polysiloxane block copolymer composition and 50 g of water were inserted in a 200 mL glass bottle, and then mixing was performed at 1600 rpm5 minutes using a homodisper at room temperature. The properties immediately after preparing the obtained mixture and properties after allowing to stand for one day at room temperature were observed and recorded. The drastic results discovered herein are shown in the following Table 5.

TABLE-US-00005 TABLE 5 Results of water miscibility test Properties Co- Diluting Immediately Properties polymer agent Water After One Day Sample % % % Preparing Later Comparative 25% BPPG-13 50% Entire body Entire body Example 2-1 25% is a is a dark dark white white powdered powdered solid gel solid gel Example 1-1 25% BDPG 50% Semi- Small amount 25% transparent of creaming homogeneous at the top, liquid with but favorable favorable fluidity fluidity

[0255] Based on the aforementioned results, the polyether-polysiloxane block copolymer composition of the present invention was verified to completely resolve the hydrogel forming problem due to contact with water, which occurred with a (AB)n type polyether-polysiloxane block copolymer in the related art. Furthermore, forming the aforementioned composition by combining the polyether-polysiloxane block copolymer (A) and component (B) according to the present invention was clearly a key to resolving the problem. Therefore, the polyether-polysiloxane block copolymer composition of the present invention can be widely used for urethane foam formulations (such as soft foam or the like) where open cell ratio adjustment or making an open cell is desired.

[0256] Furthermore, the present inventors added several picked up samples to a hard urethane foam formulation to perform a foaming test, based on the knowledge with regard to the tendency of the type of polyurethane foam and molecular weight of the polyether-modified silicone suitable thereto. A composition with a relatively low molecular weight was selected as the polyether-polysiloxane block copolymer composition (sample) according to the present invention, and then compared with Comparative Example 2-1 which is an (AB)n type polyether-polysiloxane block copolymer composition based on technology in the related art (Patent Literature 6: JP 08-156143 A). The tested hard foam formulation is shown below.

TABLE-US-00006 TABLE 6 Hard polyurethane foam-forming composition Amount of Added wt. Component Content Parts % Components Polyol Sorbitol-based 100 32.62 for polyether polyol Premixing (Hydroxyl group value: 450) Tertiary Me.sub.2N(CH.sub.2).sub.6NMe.sub.2 1.8 0.59 amine catalyst Water (Foaming agent) * 6.0 1.96 Polyether- Surfactant 1.0 0.33 polysiloxane block copolymer composition Isocyanate Polymethylene 197.8 64.50 polyphenyl polyisocyanate (index: 110, NCO % = 31.5) Total 306.6 100.00 * Carbon dioxide gases generated due to a reaction with isocyanate

Formation of Hard Polyurethane Foam

[0257] The polyurethane foam-forming composition of the present invention was adjusted and the polyurethane foam was formed at a scale where the total amount was 16.7% in Table 6. Note that operations were performed in a thermostatic chamber at approximately 25 C., and all raw materials were used from a condition achieved at a constant temperature.

[0258] A polyol, water, catalyst, and surfactant were accurately weighed in a 200 mL polycup, and then stirred at 3500 rpm for 15 seconds using a disk blade type disper mixer.

[0259] Thereafter, isocyanate was added to the premixed solution mixed in advanced, and then mixed at 3500 rpm for 7 seconds using the same blade.

[0260] A uniformly mixed urethane foam-forming composition was poured into a 1 L paper cup over 8 seconds to allow free foaming.

[0261] The composition was allowed to stand for 40 to 60 minutes as is in a thermostatic chamber.

[0262] After two hours, the foam was cut in half from above, and then the foam height and cell structure of the cut surface were observed and recorded.

TABLE-US-00007 TABLE 7 Evaluation results of hard polyurethane foam Number average Diluting agent Foam Type of molecular weight (50% Included Height Cell Surfactant of copolymer in Surfactant) cm Structure Comparative 46500 BPPG-13 19 Rough Example 2-1 Example 1-1 39300 BDPG 19 Fine Example 1-2 31800 BPG 19 Fine

[0263] Based on the aforementioned results, the polyether-polysiloxane block copolymer composition according to the present invention was confirmed to have an excellent effect as a surfactant or foam stabilizing agent for hard polyurethane foam.

[0264] Finally, Table 8 shows foam formulation examples of a microcellular polyurethane foam-forming composition, and simply shows manufacturing processes thereof.

TABLE-US-00008 TABLE 8 Examples of microcellular polyurethane foam-forming compositions Formulation Formulation Formulation Formulation Component Type Content Example 1 Example 2 Example 3 Example 4 Premixing Polymer polyol Polymer particle 100 100 100 100 Components (hydroxyl group dispersion obtained value: 33) by polymerizing acrylonitrile styrene in polyol Catalyst Product diluted 10 2.0 2.0 2.0 2.0 times with nickel acetyl acetate Foam Stabilizing Example 1-1 10 agent Example 2-1 10 Example 5-2 15 Example 5-3 20 Isocyanate Modified MDI Carbodiimide- 15.8 15.8 15.8 15.8 modified MDI, NCO % = 29.0 Total 127.8 127.8 132.8 137.8

Examples of Manufacturing Processes

[0265] 1) The premixed solution and isocyanate (at an amount where the isocyanate index is 107) is stirred and mixed for 1 minute using a dynamic mixer while feeding nitrogen gas, and then injecting as is in a mold. [0266] 2) After primary curing for 30 minutes at 160 C., secondary curing is performed for 4 hours at 110 C. [0267] 3) Thereafter, A metal shaft is press-fitted and adhered thereto, and end portions are cut, surfaces are polished, and the like to obtain microcellular polyurethane foam.

Expected Effects

[0268] The polyurethane foam according to the present invention does not include residual substances such as nonreactive dodecyl benzene in the foam stabilizer (foam stabilizing agent), and therefore, problems such as migration (oozing) in the obtained microcellular foam is less likely to occur. Diluting agent included in the foam stabilizing agent of the present invention: Component (B) has appropriate reactivity and volatility in the urethane foam formulation, and therefore, an increase in cell opening function (forming flexible foam with high air permeability) due to a volatilization effect is expected in Formulation Examples 1 and 2, for example. Furthermore, formation of a foam with excellent strength and low air permeability due to contributing increasing foam crosslinking density is expected in Formulation Example 4 using a foam stabilizing agent where the amount of component (B) used is reduced and nonvolatile PPG-7 is added. Formation of physical foam with an intermediate balance in physical properties with the two previous examples is expected in Formulation Example 4.