Production method for high-purity organosilicon compound

Abstract

The present invention relates to a production method for a liquid high-purity organosilicon compound, the method comprising the steps of: adding, to a mixture containing an organosilicon compound selected from a group consisting of organomodified silcones and organomodified silanes and impurities, an organic wax having affinity with the impurities and having a higher melting point than the organosilicon compound, melting and mixing while heating, and introducing the impurities into the melted organic wax; obtaining a solidified product of the organic wax by cooling the organic wax; and performing solid/liquid phase separation on the organosilicon compound and the solidified product of the organic wax. With the present invention, it is possible to provide a useful method for producing a high-purity organosilicon compound stably and on a commercial scale.

Claims

1. A production method for a liquid high-purity organosilicon compound, the method comprising the steps of: adding, to a mixture containing an organosilicon compound modified by an organic modifier having a (poly)oxyethylene site selected from the group consisting of organomodified silicones having an organic modified group containing a (poly)oxyethylene site and organomodified silanes having an organic modified group containing a (poly)oxyethylene site and impurities originating from the organic modified group, an organic wax having a (poly)oxyethylene site having affinity with the impurities and having a higher melting point than the organosilicon compound, melting and mixing while heating, and introducing the impurities into the melted organic wax; obtaining a solidified product of the organic wax by cooling the organic wax; and performing solid/liquid phase separation on the organosilicon compound and the solidified product of the organic wax.

2. The production method according to claim 1, wherein the organosilicon compound is a liquid at least at 100 C.

3. The production method according to claim 1, wherein the organic wax has a melting point of from 45 C. to 150 C.

4. The production method according to claim 1, wherein the organic wax has an average molecular weight of at least 900.

5. The production method according to claim 1, wherein silicon atoms of the organosilicon compound bond with organic modified groups via SiC bonds or SiOC bonds.

6. The production method according to claim 1, wherein the organosilicon compound is a compound of Formula (1):
R.sup.1.sub.aR.sup.2.sub.bL.sup.1.sub.cQ.sub.dSiO.sub.(4abcd)/2(1) wherein R.sup.1 represents a monovalent organic group (however, excluding R.sup.2, L, and Q), a hydrogen atom or a hydroxyl group; and R.sup.2 is a substituted or unsubstituted, straight or branched monovalent hydrocarbon group having 9 to 60 carbon atoms, or the chain organosiloxane group of Formula (2-1): ##STR00043## wherein R.sup.11 are each independently a substituted or unsubstituted monovalent hydrocarbon group having from 1 to 30 carbon atoms, hydroxyl groups, or hydrogen atoms and at least one of the R.sup.11 moieties is the monovalent hydrocarbon group; t is a number in a range of 2 to 10; and r is a number in a range of 1 to 500); or the Formula (2-2): ##STR00044## wherein, R.sup.11 and r are synonymous with those described above; and L.sup.1 represents a silylalkyl group having a siloxane dendron structure expressed by Formula (3) when i=1; ##STR00045## wherein the R.sup.3 moieties are each independently a substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon group having from 1 to 30 carbon atoms; the R.sup.4 moieties are each independently an alkyl group or a phenyl group having from 1 to 6 carbon atoms; Z is a divalent organic group; i is a generation of a silylalkyl group represented by L.sup.i and is an integer from 1 to k when the number of generations serving as a number of repetitions of the silylalkyl group is k; L.sup.i+1 is the silylalkyl group when i is less than k, and R.sup.4 when i=k; and h.sup.i is a number in a range of 0 to 3); Q is a (poly)oxyethylene group-containing organic group; and a, b, c, and d are each numbers in the ranges of 1.0a2.5, 0b1.5, 0c1.5, and 0.0001d1.5).

7. The production method according to claim 1, wherein the organosilicon compound is obtained by reacting (A) an organohydrogenpolysiloxane; (B) a (poly)oxyethylene group-containing organic compound having one or more reactive unsaturated groups in each molecule; and (C) one or more types of organic compounds selected from a group consisting of (C1) an organic compound having a number of reactive unsaturated groups greater than 1 on average in each molecule and (C2) an organic compound having one or more reactive unsaturated groups and one or more epoxy groups in each molecule (however, the use of the component (B) is optional when the component (C) contains a (poly)oxyethylene group); and the organomodified silicone is further characterized by having a silicon-bonded (poly)oxyethylene group-containing organic group and having a crosslinked structure containing a SiC bond in a crosslinking part.

8. The production method according to claim 1, wherein the organosilicon compound is an organomodified silicone in the form of a straight-chain (poly)oxyalkylene group-containing alternating copolymer obtained by reacting at least: (D) an organopolysiloxane having reactive functional groups at both terminals of a molecular chain; and (E) an organic compound having two reactive functional groups capable of reacting with the reactive functional groups positioned at both of the molecular chain terminals of the organopolysiloxane (D) in the molecule.

9. The production method according to claim 1, wherein the organosilicon compound has a crosslinked structure containing a SiOC chain in the crosslinking part, and the (poly)oxyethylene group-containing organic block constituting the crosslinking part has at least two carbon atom bonds in the organic block and binds to a siloxane block with a chain, while the siloxane block consists of siloxane units in which 1 to 3 monovalent organic groups bind to silicon atoms, and the siloxane block has a least two silicon atom bonds.

10. The production method according to claim 1, wherein the organosilicon compound is an organomodified silane represented by Formula (8): ##STR00046## wherein R.sup.16 is a group selected from a hydrogen atom and substituted or unsubstituted, straight-chain or branched monovalent hydrocarbon groups having from 1 to 30 carbon atoms; X.sup.1 is a hydrolyzable group selected from alkoxy groups, aryloxy groups, acyloxy groups, secondary amino groups, and aminoxy groups; Z.sup.1 is a monovalent organic group differing from R.sup.16 which is linked to the silicon atoms of general formula (8) by SiC bonds; 1k3; 0j2; and k+j3.

11. The production method according to claim 1, wherein the mixture further contains a solvent of the organosilicon compound.

12. The production method according to claim 1, wherein a mixture containing the organosilicon compound and the impurities is treated by an acidic aqueous solution, and water and odorizing substances produced by treatment with the acidic aqueous solution are removed by heating or depressurization.

Description

EXAMPLES

(1) The present invention will be described in detail hereinafter using working examples and comparative examples, but the present invention is not limited to the working examples described below.

(2) Note that in the production examples and comparative examples below, the language production of polyether-modified silicone No. X is used for the sake of convenience, but the obtained products are in the form of mixtures containing a small amount of unreacted starting material and the like in addition to the main components.

(3) In the following compositional formulae, Me represents a methyl (CH.sub.3) group, M represents a Me.sub.3SiO group (or an Me.sub.3Si group), D represents an Me.sub.2SiO group, D.sup.H represents an MeHSiO group, and M.sup.R and D.sup.R respectively represent units in which a methyl group in M or D is modified by any substituent. Additionally, in the production examples, IPA represents isopropyl alcohol.

Production Example 1

(4) <Production of PolyetherModified Silicone No. 1>

(5) Step 1: First, 15.801 kg of a methylhydrogenpolysiloxane expressed by the average composition formula MD.sub.37D.sup.H.sub.13M, 16.9 g of a vinyl tris (trimethylsiloxy)silane expressed by the average composition formula CH.sub.2CHSi(OSiMe.sub.3).sub.3, and 33.1 g of an IPA solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxne complex (Pt concentration: 0.45 wt. %) were charged into a reaction vessel, and heating was started while stirring under a nitrogen stream. After a reaction was performed for 2.5 hours at 50 to 75 C., the reaction liquid was collected, and 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) was used to confirm that the reaction was proceeding as planned.

(6) Step 2: The reaction liquid was set to 48 C., and when 1.42 g (first time) of dodecene (-olefin purity=95.4%) was added, an increase in temperature to 65 C. was observed. When 1.46 kg (second time) of dodecene (-olefin purity=95.4%) was added at the point when the temperature of the reaction liquid dropped to 52 C., an increase in temperature to 67 C. was observed. When 1.84 kg (third time) of dodecene (-olefin purity=95.4%) was added at the point when the temperature of the reaction liquid dropped to 53 C., an increase in temperature to 71 C. was observed. When 1.83 kg (fourth time) of dodecene (-olefin purity=95.4%) was added at the point when the temperature of the reaction liquid dropped to 55 C., an increase in temperature to 75 C. was observed. The total reaction time in step 2 was 2.5 hours. The reaction liquid was collected and the reaction was confirmed to be proceeding as planned with the same method as in step 1.

(7) Step 3: First, 4.77 kg of a polyoxyethylene (9.5) monoallyl ether, 3.0 g of natural vitamin E, and 2.8 kg of IPA were added to the reaction liquid, and 33.3 g of the same platinum catalyst solution as described above was additionally added. A reaction was performed for 1.5 hours at 60 to 70 C., and when confirmed with the same method as in step 1, the reaction rate indicated that the reaction was roughly completed. Here, the charged amount of the polyoxyethylene (9.5) monoallyl ether was over 1.16 times the molar amount of the SiH groups (for D.sup.H.sub.2 units) of the methylhydrogenpolysiloxane. Therefore, the excess unreacted polyether remains in the reaction liquid.

(8) Step 4: First, 1.45 kg (fifth time) of dodecene (-olefin purity=95.4%) was added, and when a reaction was performed for three hours at 50 to 70 C. and then confirmed with the same method as in step 1, the reaction was compete.

(9) Step 5: The reaction liquid was heated under reduced pressure and held for five hours under conditions at 135 to 145 C. and 25 to 55 mmHg while bubbling due to nitrogen gas, and the low-boiling-point matter such as dodecene was distilled out. When the pressure was then restored after cooling to 75 C. or lower, the content of the reaction vessel was a light brown, uniform liquid with a slight feeling of transparency.

(10) Step 6: An aqueous solution prepared by dissolving 4.5 g of a sodium hydrogen sulfate monohydrate in 450 g of ion-exchanged water was charged into the content of the reaction vessel, and acid treatment was performed for one hour at 60 to 70 C. while stifling under a nitrogen stream. The pressure was then reduced at 60 C., and the pressure was restored when the distillation of water and other low-boiling-point matter stopped (first cycle of acid treatment). Next, 450 g of water was added, and after treatment was performed for ten minutes, the pressure was similarly reduced and then restored when the distillation of water and other low-boiling-point matter stopped (second cycle of acid treatment). After 450 g of water was once again added and acid treatment was performed for 1.3 hours, the pressure was similarly reduced. A heated, depressurized state was maintained for 12 hours at 60 to 75 C., and the pressure was restored after the water droplets in the system disappeared (third cycle of acid treatment). As a result, 28.2 kg of a composition containing a polyether-modified silicone represented by the average composition formula MD.sub.37D.sup.R*11.sub.10D.sup.R*31.sub.1D.sup.R*21.sub.2M was obtained as a grayish brown, opaque, cloudy liquid. (Yield=10028.2/30.0=94.0%)

(11) Here, R*.sup.11, R*.sup.21, and R*.sup.31 are as follows. R*.sup.11=C.sub.12H.sub.25 R*.sup.21=C.sub.3H.sub.6O(CH.sub.2CH.sub.2O).sub.9.5H R*.sup.31=C.sub.2H.sub.4Si(OSiMe.sub.3).sub.3

(12) The turbidity of the appearance of the content increased dramatically due to acid treatment, but this is considered to be due to the result of a greater increase in polarity and a decrease in the compatibility with the modified silicone serving as the main component as the unreacted unsaturated polyether (monool) was hydrolyzed and transformed into a corresponding polyethylene glycol (diol).

Comparative Example 1

(13) <Preparation of Comparative Composition RE-1 Containing Polyether-Modified Silicone No. 1>

(14) First, 20 kg of the grayish brown, opaque, uniform liquid obtained in Production Example 1 was filtered with a pressure filter at room temperature and an N2 pressure of 150 kPa using 100 g of Hiflo Super Cell (Celite Corporation, flux calcined diatomaceous earth) and 50 g of Filter Cell (Celite Corporation, natural diatomaceious earth) as filter aids and using ADVANTEC No. 424 (diameter: 28 mm, Toyo Roshi Co., Ltd.) as filter paper. Immediately after filtration was begun, a filtrate with transparency emerged, but once approximately 2 kg of the filtrate emerged, a cloudy liquid leaked out within one hour. As a result, 19.5 kg of a grayish brown, opaque, cloudy liquid was obtained over the course of ten hours. (Yield=19.5/20=97.5%) This composition exhibited no improvement in the transparency of the appearance whatsoever in comparison to the composition obtained in Production Example 1. That is, with the technique of Comparative Example 1, rarefaction equivalent to only approximately 10% of the total amount of the reaction mixture obtained in Production Example 1 could be obtained. Here, the total amount of treatment liquid/filtration area=20,000 g/615 cm.sup.2=32.5; total filtration time=10 hr; and transparent filtrate/filtration area=2,000 g/615 cm.sup.2=3.25.

Comparative Example 2

(15) <Preparation of Comparative Composition RE-2 Containing Polyether-Modified Silicone No. 1>

(16) Next, 2.1 g of the grayish brown, opaque, uniform liquid obtained in Comparative Example 1 was extracted and pressure-filtered at an N2 pressure of 150 kPa using a specialized filter with a Zeta Plus Filter 30C (diameter: 90 mm, 3M Corporation, zeta-potential adsorption filter). At this time, filtration was very slow at room temperature, so filtration was performed while maintaining a temperature of from 40 to 50 C. Approximately 700 g of the initial filtrate improved to a roughly transparent appearance, but it took five hours to achieve this improvement. Turbidity appeared thereafter, so the composition was mixed so that the entire amount of the filtrate that was ultimately obtained was uniform, and as a result, 2.0 kg of a grayish, light brown, opaque, uniform liquid was obtained. (Yield=2.0/2.1=95.2%) This composition exhibited a slight improvement in the transparency of the appearance in comparison to the composition obtained in Production Example 1 (Comparative Example 1). That is, with the technique of Comparative Example 2, rarefaction equivalent to only approximately 33% of the total amount of the reaction mixture obtained in Production Example 1 could be obtained. Here, the total amount of treatment liquid/filtration area=2,100 g/63.6 cm.sup.2=33.0; total filtration time=15 hr; and transparent filtrate/filtration area=700 g/63.6 cm.sup.2=11.0.

Working Example 1

(17) <Preparation of High-Purity Polyether-Modified Silicone No. 1>

(18) First, 2.9 g of the grayish brown, opaque, uniform liquid obtained in Comparative Example 1 and 22.7 g of a flaked product (organic wax) of PEG#20000 (polyethylene oxide with a molecular weight of 20,000, melting point: approximately 65 C.) were charged into a flask, and heating was started while stirring under a nitrogen stream. When mixing and stifling were performed aggressively for 40 minutes at 90 C., the appearance was a cloudy white, uniform dispersion. The composition was then left to cool (2.5 hours) while stirring until the temperature reached 40 C. or lower, and treatment was ended. The appearance of the flask content was the same as described above. Next, the flask content was filtered with a pressure filter at room temperature and an N.sub.2 pressure of 150 kPa using 10 g of Hiflo Super Cell (Celite Corporation, flux calcined diatomaceous earth) as a filter aid and using ADVANTEC No. 424 (diameter: 110 mm, Toyo Roshi Co., Ltd.) as filter paper. As a result, a completely transparent, uniform, light yellow filtrate was surprisingly obtained from start to finish, and the total amount was 2.83 kg. (Yield=2.83/2.9=97.6%) That is, with the technique of the present invention demonstrated in Working Example 1, it was possible to achieve the rarefaction of the entire amount of the reaction mixture obtained in Comparative Example 1. Here, the total amount of treatment liquid/filtration area=2,900 g/95.0 cm.sup.2=30.5; total filtration time=14 hr; and transparent filtrate/filtration area=2,830 g/95.0 cm.sup.2=30.8.

Working Example 2

(19) <Preparation of High-Purity Polyether-Modified Silicone No. 1 (2)>

(20) First, 829 g of the grayish brown, opaque, cloudy liquid obtained in Comparative Example 1, 24.9 g of a flaked product (organic wax) of PEG #20000 (polyethylene oxide with a molecular weight of 20,000, melting point: approximately 65 C.), and 80 g of isooctane serving as a diluent were charged into a 1 L flask, and heating was started while stirring under a nitrogen stream. When mixing and stirring were performed aggressively for 50 minutes at 70 to 95 C., the appearance was a cloudy white, uniform dispersion. The composition was then left to cool (two hours) while stifling until the temperature reached 40 C. or lower, and treatment was ended. The appearance of the flask content was similar to that described above, but there was an increase in whiteness, and a white sediment was also observed at the base of the flask. Next, the flask content was filtered with a pressure filter at room temperature and an N2 pressure of 150 kPa using 10 g of Hiflo Super Cell (Celite Corporation, flux calcined diatomaceous earth) as a filter aid and using ADVANTEC No. 424 (diameter: 110 mm, Toyo Roshi Co., Ltd.) as filter paper. As a result, a completely transparent, uniform filtrate was surprisingly obtained from start to finish, and the total amount was 796 g. (Filtration time=2.5 hr) Next, 744 g of this composition was collected and charged into a clean 1 L flask. This was heated under reduced pressure and held for 1 hour and 15 minutes under conditions at 105 to 115 C. and 10 mmHg or lower while bubbling due to nitrogen gas so as to distill out the low-boiling-point matter. When the pressure was then restored, it was observed that 683 g of a completely transparent, light yellow liquid was obtained. That is, with the technique of the present invention demonstrated in Working Example 2 as well, it was possible to achieve the rarefaction of the entire amount of the reaction mixture obtained in Comparative Example 1.

Comparative Example 3

(21) <Preparation of Comparative Composition RE-3 Containing Polyether-Modified Silicone No. 2>

(22) Step 1: First, 751.1 g of a methylhydrogenpolysiloxane expressed by the average composition formula MD.sub.45D.sup.H.sub.2M, 249 g of a polyoxyethylene (9.5) monoallyl ether, 300 g of toluene, and 2.0 g of a 5 wt. % methanol solution of sodium acetate were charged into a reaction vessel, and heating was started while stifling under a nitrogen stream. When the liquid temperature reached 70 C., 0.20 ml of an IPA solution of chloroplatinic acid (platinum concentration: 3.7 wt. %) was added. An increase in temperature to 85 C. occurred due to heat generation, and the appearance of the reaction liquid had changed to a roughly transparent appearance after 30 minutes. When the reaction liquid was collected and confirmed by an alkali decomposition gas generation method, the reaction was complete. Here, the charged amount of the polyoxyethylene (9.5) monoallyl ether was over 1.26 times the molar amount of the SiH groups (for D.sup.H.sub.2 units) to be reacted. Therefore, the excess unreacted polyether remains in the reaction liquid.

(23) Step 2: First, 3.0 g of baking soda was added, and after the composition was neutralized by mixing and stifling for one hour at 75 to 80 C., the reaction mixture was heated under reduced pressure and held for 1.5 hours under conditions at 120 to 125 and 10 mmHg or lower while bubbling due to nitrogen gas so as to distill out low-boiling-point matter such as toluene. The pressure was then restored after cooling to 70 C. or lower, and 920 g of a light yellow, transparent, uniform liquid was obtained as a result of performing filtration with a pressure filter at room temperature and an N2 pressure of 150 kP using 10 g of Hiflo Super Cell (Celite Corporation, flux calcined diatomaceous earth) as a filter aid and using ADVANTEC No. 424 (diameter: 110 mm, Toyo Roshi Co., Ltd.) as filter paper.

(24) Step 3: Next, 600 g of this filtrate was transferred to a 1 L autoclave, and after 30 g of a sponge nickel catalyst, 15 g of water, and 15 g of IPA were added, hydrogen gas was introduced. After a hydrogenation reaction was performed for six hours at a temperature of 140 C. and a pressure of 80 kg/cm.sup.2, the resulting reactive product was cooled to 60 C. and restored to normal pressure. Next, 6 g of activated carbon was mixed into the composition, and the sponge nickel catalyst was removed by precision filtration to obtain 530 g of a colorless, transparent filtrate.

(25) Step 4: This filtrate was charged into a 1 L flask, heated under reduced pressure, and held for three hours under conditions at 70 to 75 C. and 10 mmHg or lower while bubbling due to nitrogen gas so as to distill out low-boiling-point matter, and 500 g of a composition containing a polyether-modified silicone represented by the average composition formula MD.sub.45D.sup.R*21.sub.2M was obtained as a colorless, transparent, uniform liquid.

(26) Here, R*.sup.21 is as follows. R*.sup.21=C.sub.3H.sub.6O(CH.sub.2CH.sub.2O).sub.9.5H

(27) In addition, due to the fact that acid treatment was not performed in Comparative Example 3 and the fact that the wt. % of the polyether part of the polyether-modified silicone, which is a copolymer, was greater than in Production Example 1, and the polarity of the modified silicone was therefore greater than in Production Example 1, it is thought that the compatibility of the unreacted polyether (monool) and the modified silicone was good and that a composition with a transparent appearance was therefore obtained in Comparative Example 3.

(28) The contents of high-purity polyether-modified silicone No. 1 and high-purity polyether-modified silicone No. 1 (2), which are high-purity organosilicon compounds of the present invention, and comparative compositions RE-1 and RE-2 containing polyether-modified silicone No. 1 and comparative composition RE-3 containing polyether-modified silicone No. 2 of the comparative examples are shown in the following Table 1.

(29) TABLE-US-00002 TABLE 1 Transparent filtrate/filtration Chemical structure main Sample Appearance area [g/cm.sup.2] component*.sup.2) Working Light yellow, transparent, uniform >30.8 MD.sub.37D.sup.R*.sup.11.sub.10D.sup.R*.sup.31.sub.1D.sup.R*.sup.21.sub.2M Example 1 liquid Working Light yellow, transparent, uniform *.sup.1) Example 2 liquid Comparative Grayish brown, opaque, cloudy 3.25 Example 1 liquid Comparative Grayish, light brown, opaque, uniform 11.0 Example 2 liquid Comparative Colorless, transparent, uniform *.sup.1) MD.sub.45D.sup.R*.sup.21.sub.2M Example 3 liquid Note *.sup.1)The numerical value of the [total amount of the treatment solution/filtration area] different from other experiments and was therefore omitted. Note *.sup.2)The chemical structure of the polyether-modified silicone serving as the main component is expressed by the average composition formula.

(30) In the table, the structures and types of the functional groups are as follows.

(31) Group having a Siloxane Dendron Structure: R*.sup.3>

(32) R*.sup.31=C.sub.2H.sub.4Si(OSiMe.sub.3).sub.3
<Oxyethylene Group: R*.sup.2> R*.sup.21=C.sub.3H.sub.6O(CH.sub.2CH.sub.2O).sub.9.5H
<Other Organic Groups: R*.sup.1> R*.sup.11=C.sub.12H.sub.25

(33) [Measurement of total carbonyl amount] The total carbonyl amounts of the polyether-modified silicones (samples) obtained in Working Examples 1 and 2 and Comparative Examples 2 and 3 were measured as carbonyl values (COV) in accordance with the following procedure so as to qualitatively evaluate carbonyls, which cause the odor of the composition.

Preparation Example 1A

(34) Reagent special-grade n-butanol (A) was measured in a 100 mL brown glass vial, and 4.3 g of reagent special-grade trichloroacetic acid was further added. After a lid was placed on the vial, the mixture was shaken and homogenized so as to prepare an alcohol solution of trichloroacetic acid (acid concentration: 4.3% (wt/vol). This solution is defined as trichloroacetic acid solution (1A) hereafter. This preparation operation was performed within three hours prior to the measurement of light absorbance.

Preparation Example 2A

(35) Reagent special-grade n-butanol (A) was measured in a 100 mL brown glass vial, and 50 mg of 2,4-dinitrophenylhydrazine (reagent special-grade product containing an equal amount of water; abbreviated as 2,4-DNPH hereafter) was further added. After a lid was placed on the vial, the vial was placed in an ultrasonic washer for ten minutes so as to completely dissolve the 2,4-DNPH with the alcohol (A), and a 0.025% (wt/vol) alcohol solution of 2,4-DNPH was thus prepared. This solution is defined as 2,4-DNPH solution (2A) hereafter. This preparation operation was performed within three hours prior to the measurement of light absorbance.

Preparation Example 3B

(36) Reagent special-grade ethanol (B) was measured in a 100 mL brown glass vial, and 4.0 g of potassium hydroxide (pellet-shaped reagent special-grade product) was further added directly. After a lid was placed on the vial, the vial was placed in an ultrasonic washer for 20 minutes so as to completely dissolve the potassium hydroxide with the alcohol (B), and a 4.0% (wt/vol) alcohol solution of potassium hydroxide was thus prepared. This solution is defined as potassium hydroxide solution (3B) hereafter. This preparation operation was performed within three hours prior to the measurement of light absorbance.

(37) (Measurement of Carbonyl Value)

(38) First, 2.00 g of a sample and 23.00 g of the reagent special-grade butanol (A) were charged into a 50 mL screw tube with a lid, and these were mixed so as to prepare 25.00 g of a sample solution (Sa) with a sample concentration of 8 mass %.

(39) Next, 1.250 g of the obtained sample solution (Sa) and 3.750 g of the reagent special-grade n-butanol (A) were charged into a 50 mL volumetric flask, and both were mixed so as to prepare 5.000 g of a sample solution (Sb) with a sample concentration of 2 mass %.

(40) Next, 3 mL of the trichloroacetic acid solution obtained in Preparation Example 1A and 5 mL of the 2,4-DNPH solution (2A) obtained in Preparation Example 2A were added with a transfer pipet to the volumetric flask containing 5.000 g of the sample solution (Sb). Further, 1.050 g of purified water was added and mixed. This is to hydrolyze precursors of carbonyl compounds such as acetal which may be present in the sample and to detect the precursors as carbonyls.

(41) Next, a stopper was placed in the volumetric flask, and after air tightness was secured by wrapping a Teflon (registered trademark) seal around the stopper, the volumetric flask was placed in a constant-temperature bath at 60 C. and heated for 30 minutes so as to react the carbonyls contained in the sample and the 2,4-DNPH. Next, the volumetric flask was removed from the constant-temperature bath and left to stand for 30 minutes at room temperature.

(42) Next, the stopper of the volumetric flask was removed, and 10 mL of the potassium hydroxide solution (3B) obtained in Preparation Example 3B was added with a transfer pipet and mixed by shaking the volumetric flask. Eight minutes after 10 mL of the potassium hydroxide solution (3B) was added, the reagent special-grade n-butanol (A) was added as a dilution solvent, and this system was shaken to prepare a reaction solution with a total volume of 50 mL (basic reaction solution). Next, 15 minutes after 10 mL of the potassium hydroxide solution (3B) was added, the reaction solution was placed in an absorption cell (liquid layer length=1 cm), and the absorbance (A.sub.1) at 430 nm was measured with an absorptiometer.

(43) On the other hand, as a blank test, a solution obtained by performing the same operation as described above (addition of the trichloroacetic acid solution (1A), addition of the 2,4-DNPH solution (2A), heating and cooling of the obtained mixed solution, addition of the potassium hydroxide solution (3B), and addition of a dilution solvent containing the reagent special-grade n-butanol (A)) using 5.000 g of the reagent special-grade n-butanol (A) instead of the sample solution (Sb) was placed in an absorption cell (liquid layer length=1 cm), and the absorbance (A.sub.2) at 430 nm was measured in the same manner as described above.

(44) The absorbance (A.sub.1) and the absorbance (A.sub.2) obtained as described above were substituted into the numerical formula: CV=(A.sub.1-A.sub.2)/0.1 so as to find the carbonyl value (COV).

(45) The evaluation results of the total carbonyl amounts (COV) of the polyether-modified silicones obtained in Working Examples 1 and 2 and Comparative Examples 2 and 3 are shown in the following Table 2. The high-purity polyether-modified silicones of Working Examples 1 and 2 of the present invention achieved a level in which the COV was almost completely zero, which clearly surpassed the technical level of hydrogenation methods typically considered to be satisfactory. The COV is approximately 0.3 in Comparative Examples 2 and 3, but this is equivalent to approximately 80 ppm in terms of the amount of propanol. Therefore, when the polyether-modified silicone compositions of Comparative Examples 2 and 3 are blended into cosmetics or external preparations containing water, low-molecular-weight odor substances originating from an equivalent of 80 ppm of propanol may be ultimately generated over time. The level of 80 ppm is a sufficiently high concentration for detection by means of the human sense of smell. On the other hand, in Working Examples 1 and 2, the total amounts of odor-causing substances were suppressed by two orders of magnitude from this level, and a level of essentially zero (0.8 ppm) was reached. In this way, there is not only a difference in the purity of the main components between the Working Examples and the Comparative Examples, but there is also a 100-fold difference in the attained odor level, and these differences validate the excellence of the present invention.

(46) TABLE-US-00003 TABLE 2 Polyether-modified Odor reduction Purification-increasing COV Sample silicone structure Treatment treatment (Abs/g) Working MD.sub.37D.sup.R*.sup.11.sub.10D.sup.R*.sup.31.sub.1D.sup.R*.sup.21.sub.2M NaHSO.sub.4 water (yes) 0.02 Example 1 treatment Working NaHSO.sub.4 water (yes) N.D. Example 2 treatment Comparative Same as above NaHSO.sub.4 water X (no) 0.29 Example 2 treatment Comparative MD.sub.45D.sup.R*.sup.21.sub.2M Hydrogenation X (no) 0.34 Example 3

(47) In the table, the structures and types of the functional groups are as follows.

(48) <Group having a Siloxane Dendron Structure: R*.sup.31>

(49) R*.sup.31=C.sub.2H.sub.4Si(OSiMe.sub.3).sub.3
<Oxyethylene Group: R*.sup.2> R*.sup.21=C.sub.3H.sub.6O(CH.sub.2CH.sub.2O).sub.9.5H
<Other Organic Groups: R*.sup.1> R*.sup.11=C.sub.12H.sub.25

(50) [Odor accelerated test] Polyether-modified silicones are known to tend to develop a unique odor over time in a formulation containing water and a specific polyhydric alcohol. Therefore, samples having the compositions shown in Table 3 were produced and stored under accelerated conditions of one week at 70 C. The samples were then returned to room temperature and unsealed, and functional evaluations were performed on the potency and amount of the odor produced using the sense of smell.

(51) TABLE-US-00004 TABLE 3 No. Starting material name Mass [g] 1 Polyether-modified silicones of Working Examples 3.0 1 and 2 or Comparative Examples 2 and 3 2 1,3-Butylene glycol 3.0 3 Purified water 24.0 Total 30.0

(52) [Preparation of Samples for Accelerated Tests] 1. The starting materials (Nos. 1 to 3) shown in Table 3 were charged into a 50 ml screw tube, and the tube was stopped and shaken well. Samples were produced for each of the polyether-modified silicones obtained in the working examples and the comparative examples. (Total of 4 samples) 2. Only the starting materials of Nos. 2 and 3 were charged into a separate 50 ml screw tube, and the tube was stopped and shaken well so as to prepare a blank sample. (Total of 1 sample) 3. The samples described above were left to stand for one week in a constant-temperature bath at 70 C.

(53) [Odor Test]

(54) The samples left to stand for one week in a constant-temperature bath at 70 C. as described above were removed after 1 day and after 7 days and returned to room temperature, and the degree of the specific odor when unsealed was evaluated by the sense of smell in accordance with the following criteria.

(55) Odor test evaluation criteria: : No specific odor is perceived whatsoever. : A specific odor is perceived very slightly. : A specific odor is observed slightly. X: An unpleasant solvent odor is clearly observed. XX: A strong and very unpleasant solvent odor is observed.

(56) [Odor test results] The results of odor acceleration tests in the formulations are shown in the following Table 4 together with the COV of the polyether-modified silicones. The high-purity polyether-modified silicones of the present invention used in Working Examples 1 and 2 demonstrated odorlessness of the same level as the hydrogenated product (Comparative Example 3) and the blank without silicone under the accelerated test conditions of the formulation. On the other hand, although the sample using Comparative Example 2 prepared by performing only acid treatment with NaHSO.sub.4/water had a COV value approximately the same as the sample using Comparative Example 3 as a hydrogenated product, it was confirmed that a strong odor was generated at the initial stage of the acceleration tests. These phenomena are understood as follows. When only acid treatment is performed, the excess unsaturated polyether contained in the polyether-modified silicone composition or acetal compound originating from the unsaturated polyether is not completely decomposed. The proof of this is the numerical value of COV=0.29 (approximately 80 ppm in terms of propanol). In addition, it is thought that a minute amount of acid is transferred to and dissolved in the sample of Comparative Example 2. As a result, the formulation becomes acidic, so conditions advantageous for hydrolyzation were also achieved from the perspective that the composition was diluted and left at a high temperature. Therefore, hydrolyzation was completed in only one day, and low-molecular-weight odor components originating from propanol were generated at once. Once the screw tube was unsealed to confirm the odor, most of the odor components volatilized in the atmosphere and disappeared. Even if aging is continued further, there are no precursors with an odor that should be hydrolyzed, which may be why only the residual odor from day 1 was detected in the confirmation after 7 days. On the other hand, the sample of Comparative Example 3, which is a hydrogenated product, is treated with alkali water due to the activation of the surface of the sponge nickel catalyst for hydrogenation, so it contains a minute alkali content even if the metal catalyst itself is completely removed. Therefore, the formulation also becomes alkaline, resulting in conditions in which the hydrolysis of acetal compounds does not occur. In general, unsaturated groups completely disappear due to hydrogenation, but acetal compounds are not decomposed for the most part and remain in the polyether-modified silicone composition. The proof of this is the numerical value of COV=0.34 (approximately 80 ppm in terms of propanol). In particular, when the formulation is acidic, low-molecular-weight odor substances originating from propanol may be ultimately generated in an amount equivalent to 80 ppm over time. In contrast, it can be seen that the high-purity polyether-modified silicones of the present invention used in Working Examples 1 and 2 demonstrate excellent properties from the perspective of the COV value and the perspective of the odor acceleration tests.

(57) TABLE-US-00005 TABLE 4 Polyether-modified Odor test Odor test COV Sample silicone structure After 1 day After 7 days (Abs/g) Working MD.sub.37D.sup.R*.sup.11.sub.10D.sup.R*.sup.31.sub.1D.sup.R*.sup.21.sub.2M - - 0.02 Example 1 (High-purity product) Working N.D. Example 2 (High-purity product) Comparative Same as above X - 0.29 Example 2 Comparative MD.sub.45D.sup.R*.sup.21.sub.2M - - 0.34 Example 3 Blank (no silicone) (0)

(58) In the table, the structures and types of the functional groups are as follows.

(59) <Group having a Siloxane Dendron Structure: R*.sup.31>

(60) R*.sup.31=C.sub.2H.sub.4Si(OSiMe.sub.3).sub.3
<Oxyethylene Group: R*.sup.2> R*.sup.21=C.sub.3H.sub.6O(CH.sub.2CH.sub.2O).sub.9.5H
<Other Organic Groups: R*.sup.1> R*.sup.11=C.sub.12H.sub.25

(61) It can be seen from the above results that the samples of the working examples are far superior to the samples of the comparative examples from the perspectives of high purity and odorlessness.

(62) Hereinafter, formulation examples of the cosmetic composition and the external use preparation according to the present invention are described, but the cosmetic composition and the external use preparation according to the present invention are not limited to the types and compositions recited in these formulation examples.

(63) The high-purity organosilicon compound obtained by the present invention can be used in various external preparations and cosmetics, for example. A specific formulation example thereof is one in which components corresponding to silicone compound Nos. 1 to 16 in Formulation Examples 1 to 43 of various cosmetics and external preparations described in Patent Document 20 (WO/2011/049248) and/or various polyether-modified silicones are substituted with the high-purity organosilicon compounds of the present invention (high-purity organosilicon compound No. 1 and the like) or solutions thereof.

(64) In addition, a specific formulation example thereof is one in which components corresponding to silicone compound Nos. 1 to 14 in Formulation Examples 1 to 24 of various cosmetics and external preparations disclosed in Patent Document 21 (WO/2011/049247) and/or various polyether-modified silicones are substituted with the high-purity organosilicon compounds of the present invention (high-purity organosilicon compound No. 1 and the like) or solutions thereof.

(65) Yet another formulation example is one in which components corresponding to the AB-type organopolysiloxane copolymers P1 to P6 contained in Formulation Examples 1 to 10 of various cosmetics and external preparations disclosed in Patent Document 22 (WO/2011/049246) (Synthesis Examples 1 to 12) and/or various oxyethylene-modified silicones are substituted with the high-purity organosilicon compounds of the present invention (high-purity organosilicon compound No. 1 and the like) or solutions thereof.

(66) In addition, another formulation example is one in which components corresponding to silicone compound Nos. 1 to 8 contained in Formulation Examples 1 to 14 of various cosmetics and external preparations disclosed in Patent Document 23 (Japanese Unexamined Patent Application Publication No. 2012-046507) and/or various polyether-modified silicones are substituted with the high-purity organosilicon compounds of the present invention (high-purity organosilicon compound No. 1 and the like) or solutions thereof.

(67) The high-purity organosilicon compound of the present invention has the advantage that, since an organic modifier with a polarity substantially differing from that of the organosilicon compound is removed, problems related to poor compatibility at the time of the addition of various starting materials are unlikely to occur when designing a formulation for a cosmetic or external preparation, so the scope of formulation design widens. At the same time, it is also possible to reduce the risk or concerns related to the stability of the final product. Since the composition has high purity, it is advantageous from the perspectives of the tactile feel improving effect, moisturizing effect, minimal degradation phenomena such as odorization over time, surface active effect, emulsification performance, powder dispersion stability, powder surface treatment effect, or the duration of these effects in comparison to typical organosilicon compounds with large impurity content. In particular, in a formulation containing a powder or a formulation containing a small amount of water, the characteristics of the high-purity organosilicon compound obtained by the present invention make it possible to finely disperse medicinal components or powders into a cosmetic or external preparation more stably than with conventional methods. As a result, a substantial advantage arises in that the effects of the original formulation are amplified, such as an improvement in evenness in application, in cosmetic duration or coloring or an improvement in a skin care or UV filter effect. In addition, in a formulation not containing a powder, the characteristics of the high-purity organosilicon compound obtained by the production method of the present invention make it possible to easily obtain a stable product with excellent transparency, even if the composition has low viscosity.