JP4548703B2 - Polyether-modified polysiloxane composition, method for producing the same, and method for measuring total amount of carbonyl in polyether-modified polysiloxane composition - Google Patents

Description

  The present invention relates to a polyether-modified polysiloxane composition, a method for producing the same, and a method for measuring the total amount of carbonyl in the polyether-modified polysiloxane composition. More specifically, the present invention relates to an organopolysiloxane-polyoxyalkylene copolymer obtained by a hydrosilylation reaction. A highly purified polyether-modified polysiloxane composition containing a polymer; a method for producing a polyether-modified polysiloxane composition comprising a step of highly purifying a crude polyether-modified polysiloxane composition; detectable by the prior art The present invention relates to a method for measuring the total amount of carbonyl in a polyether-modified polysiloxane composition that can detect and quantify even a trace amount of carbonyls.

  The polyether-modified polysiloxane composition is obtained by hydrosilation reaction of a polysiloxane having a hydrosilyl group (organohydrogenpolysiloxane) and a polyoxyalkylene having a carbon-carbon double bond at the terminal. It is substantially constituted by an oxyalkylene copolymer.

  However, since the polyether-modified polysiloxane composition thus obtained is odorized over time, it has been difficult to apply it to cosmetic applications such as hair cosmetics and skin cosmetics.

  Propenyl etherified polyoxyalkylene has been pointed out as a cause of odor of the polyether-modified polysiloxane composition over time (for example, see Patent Document 1). That is, in the production of a polyether-modified polysiloxane composition, part of the allyl etherified polyoxyalkylene used as polyoxyalkylene has its double bond rearranged by the action of a platinum catalyst, Propenyl etherified polyoxyalkylene that has no reactivity with siloxane and remains in the polyether-modified polysiloxane composition, which is decomposed over time, resulting in ketones and aldehydes that cause odor. It is said that there is. Patent Document 1 discloses that, as a deodorization method, a method of hydrolyzing propenyl etherified polyoxyalkylene using an acidic aqueous solution to remove a generated odor causing substance is disclosed.

However, this deodorization method is considered effective if all the allyl groups of the polyoxyalkylene remaining in the composition are converted into propenyl groups, but in practice allyl etherification is difficult to hydrolyze. Since the polyoxyalkylene remains at a certain rate, the deodorization method of Patent Document 1 cannot sufficiently deodorize the composition.
Here, if a strong acid capable of hydrolyzing allyl etherified polyoxyalkylene is used, the carbon-oxygen bond at the polyoxyalkylene site and / or the silicon-oxygen bond at the polysiloxane site is broken. Absent.
Further, in order to quantitatively carry out the hydrolysis reaction, an excessive amount of water and acid are required, and these excessive amounts of water and acid complicate the post-treatment process, which is not preferable as a deodorization process.

  On the other hand, as a method for deodorizing the polyether-modified polysiloxane composition, hydrogenation treatment is performed, and alkenyl group-containing polyoxyalkylene remaining in the composition (either propenyl etherified polyoxyalkylene or allyl etherified polyoxyalkylene) A method for suppressing the generation of aldehyde (propionaldehyde) has been introduced by alkylating the alkenyl group (double bond) possessed by (including, for example, Patent Documents 2 to 5).

  However, in the deodorization method using a hydrogenation reaction, an aldehyde condensate having no unsaturated bond such as acetal cannot be removed. This aldehyde condensate is an odor-causing substance that generates aldehyde in an aqueous solution.

  In order to solve the above problems, a technique is disclosed in which a polyether-modified polysiloxane composition is used in combination with a hydrogenation treatment and a treatment using an acid substance-containing aqueous solution as a treatment agent. That is, in Patent Document 6, in a modified silicone compound synthesized by an addition reaction between an organohydrogenpolysiloxane and an alkenylated polyoxyalkylene compound, (A) a hydrogenation reaction is performed on the reaction solution after the addition reaction. After alkylating the remaining unsaturated bond, the aldehyde condensate is decomposed by treating the aqueous solution containing an acid substance as a treating agent (hydrogenation-acid treatment), or (B) in the reaction solution after the addition reaction By decomposing propenyl etherified polyoxyalkylene by treating with an aqueous solution containing an acid substance as a treating agent, the resulting aldehyde and alkenylated ether compound are alkylated by a hydrogenation reaction (acid treatment-hydrogenation). The degree of unsaturation of the purified and modified silicone compound as a whole (meq / g) Disclosed is a non-bromide-modified silicone compound having an aldehyde generation amount of not more than 0.002 and 70 ppm or less of the modified silicone compound when heated and aged at 50 ° C. for 0.5 hours in 0.23 normal hydrochloric acid. Yes.

However, as a result of the present inventors conducting a confirmation test, the technique disclosed in Patent Document 6 has the following problems.
(1) An acid substance-containing aqueous solution (dilute nitric acid, phosphoric acid aqueous solution, trifluoroacetic acid aqueous solution, acetic acid aqueous solution, carbonated water, formic acid aqueous solution, trichloroacetic acid aqueous solution, lactic acid aqueous solution, Even when a succinic acid aqueous solution or a citric acid aqueous solution) was used as a treating agent, the remaining aldehyde condensate could hardly be decomposed.
(2) A modified silicone compound (hydrogenation-acid treatment) that has been treated with an acid substance-containing aqueous solution after a hydrogenation reaction is more water / (multivalent) than a modified silicone compound that has undergone only a hydrogenation reaction. In a mixed system with alcohol, the degree of odor over time is extremely high. This suggests that decomposition of the remaining aldehyde condensate was hardly achieved, and that a new odor factor (for example, generation of aldehydes due to decomposition of the modified silicone compound) occurred due to acid treatment. is doing.
(3) In the case of purification using a hydrochloric acid aqueous solution as the acid substance-containing aqueous solution (hydrogenation-acid treatment or acid treatment-hydrogenation), compared to the case of purification using an aqueous solution of another acid substance. Although effective, in a mixed system of the modified silicone compound purified in this way and water / (polyhydric) alcohol, the odor over time cannot be sufficiently suppressed.
(4) The liquid acid substance-containing aqueous solution is dissolved in a modified silicone compound (polyether-modified polysiloxane that is hydrophilic) and remains in the system as an ionic impurity. Further, when the neutralization treatment is performed after the acid treatment, the neutralized salt also remains as an ionic impurity.
In a mixed system in which a modified silicone compound containing an ionic impurity such as an acid or a neutralized salt is mixed with water / (polyhydric) alcohol, (a) odor over time due to the acid or the neutralized salt , (B) Odor over time associated with decomposition of acid or neutralized salt, (c) Odor over time associated with decomposition of modified silicone compound by acid or neutralized salt (generation of aldehydes, etc. due to this) Tend.
(5) Ionic impurities (acid / neutralized salt) remaining in the system by acid treatment when a hydrogenation reaction is performed after treatment with an aqueous solution containing an acid substance such as aqueous hydrochloric acid (acid treatment-hydrogenation) ) Tends to inhibit the hydrogenation reaction.

  In order to suppress the odor over time in the mixed system of the modified silicone compound (polyether-modified polysiloxane composition) and water / (polyhydric) alcohol, carbonyls contained in the modified silicone compound ( It is essential to accurately grasp the total amount of aldehydes and ketones.

  Conventionally, as a method for indexing the carbonyl content in a sample, a method for measuring the carbonyl value from the absorbance of a reaction solution obtained by reacting carbonyls in the sample with 2,4-dinitrophenylhydrazine is known. (For example, refer nonpatent literature 1). In this test method, it is specified that benzene which is not easily oxidized and has good stability is used as a reaction solvent.

  However, benzene used as a reaction solvent is highly harmful to the human body. For this reason, in accordance with the provisions of the Industrial Safety and Health Act, etc., each operation of sample solution and reagent preparation, reaction of 2,4-dinitrophenylhydrazine with carbonyls in the sample (heating operation), and measurement of absorbance of the reaction solution A skilled measurer who wears protective equipment and protective glasses in an enclosed hood in a state where the local exhaust system is in operation needs to be performed with great care. Thus, the above test method is not a method that anyone can safely and easily measure.

  In addition, when benzene is used as a reaction solvent, the reaction between 2,4-dinitrophenylhydrazine and carbonyls is carried out in a non-aqueous system, so that aldehyde condensates (potential carbonyl compounds) such as acetals are quantitatively analyzed. Therefore, it is impossible to quantify the total amount of carbonyls including carbonyls derived from these which are odor-causing substances.

  On the other hand, in the above-mentioned Patent Document 6, alcohol (special grade) is used as a reaction solvent in measuring the total amount of aldehydes (the amount of aldehyde generated when heated and aged in 0.23 normal hydrochloric acid at 50 ° C. for 0.5 hour). Ethanol).

However, even a relatively high purity alcohol such as special grade ethanol contains a trace amount (about 5 to 15 ppm) of aldehyde / ketone as an impurity. If such an alcohol is used as a reaction solvent, the aldehyde / ketone in the alcohol reacts with 2,4-dinitrophenylhydrazine, and as a result, the carbonyl value (carbonyl content) of the sample cannot be measured properly. .
Moreover, about the sample with little carbonyl content, the light absorbency of a reaction solution becomes smaller than the light absorbency of a blank test, and a carbonyl value cannot be measured. For this reason, the permissible value (upper limit) of the total amount of carbonyl contained in the modified silicone compound that does not generate odor over time in a mixed system of water / (polyhydric) alcohol only by using alcohol as a reaction solvent. It cannot be specified.

As described above, in order to suppress the odor in the mixed system of the modified silicone compound (polyether-modified polysiloxane composition) with water / (polyhydric) alcohol, a numerical index corresponding to the odor is required. Nevertheless, there is no known method for accurately determining the total amount of carbonyl (total amount of aldehyde / ketone) in the polyether-modified polysiloxane composition by any conventional measurement method.
JP-A-2-302438 (Claims etc.) US Pat. No. 5,225,509 (claims, etc.) JP-A-7-330907 (Claims etc.) JP-A-9-165315 (Claims etc.) JP-A-9-165318 (Claims etc.) International Publication (WO) No. 02/055588 (claims) Standard fat analysis method (2.5.4-1996 carbonyl value)

The present invention has been made based on the above situation.
The first object of the present invention is to provide a highly purified polyether-modified polysiloxane composition that does not substantially generate odor over time in a water / (polyhydric) alcohol mixed system. There is.
A second object of the present invention is a method for producing a highly purified polyether-modified polysiloxane composition which does not substantially generate odor over time in a water / (polyhydric) alcohol mixed system. Is to provide.
The third object of the present invention is to accurately measure the total amount of carbonyl contained in the composition even in a polyether-modified polysiloxane composition having a very low content of carbonyls (aldehydes and ketones). It is to provide a method that can.

As a result of intensive studies by the inventors to achieve the above object,
1) A polyether whose total unsaturation is a certain value (0.00010 meq / g) or less and whose total amount of carbonyl in terms of propanal is very low (100 ppm) or less that cannot be accurately determined by a conventionally known method. Only when the modified polysiloxane composition can suppress odor over time in a mixed system of water / (polyhydric) alcohol;
2) Ionic impurities such as acids / neutralized salts contained in the polyether-modified polysiloxane composition affect the odor over time in the mixed system of the composition and water / (polyhydric) alcohol. In addition, the above two requirements concerning the total degree of unsaturation and the total amount of carbonyl are satisfied, and the index value (electrical conductivity) for the total amount of ionic impurities is set to a certain value (30 μS / m) or less. Can reliably suppress odor over time in a mixed system of water / (polyhydric) alcohol;
3) The reaction product (crude polyether-modified polysiloxane composition) obtained by the hydrosilylation reaction is subjected to a decomposition treatment using a solid acid and a hydrogenation treatment as purification treatments, respectively, so that the total unsaturation degree, All the above three requirements concerning the total amount of carbonyl and the total amount of ionic impurities can be satisfied;
4) The above-mentioned two requirements relating to the total degree of unsaturation and the total amount of carbonyl cannot be simultaneously provided by any conventionally known purification process including that disclosed in Patent Document 6;
5) By using an alcohol having a total amount of aldehyde / ketone of 3 ppm or less as a reaction solvent to be used in the method for measuring the carbonyl value for determining the total amount of carbonyl, a very small amount of alcohol that could not be detected by a conventionally known method was used. The present inventors have found that carbonyls (aldehydes, ketones, and potential carbonyl compounds) can be accurately quantified, and have completed the present invention based on such knowledge.

  The polyether-modified polysiloxane composition of the present invention is an organopolysiloxane-polyoxyalkylene copolymer obtained by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the end. (I) The total unsaturation measured according to JIS K 1557 is 0.00010 meq / g or less, and (ii) measured by the following method. The total amount of carbonyl in terms of propanal is 100 ppm or less.

<Measurement method of total amount of carbonyl>
The absorbance (A ₁ ) and absorbance (A ₂ ) measured by the following steps (1) to (9) are expressed by the formula: CV = (A ₁ -A ₂ ) / B [where B is the sample solution 5. It is the mass (g) of the sample contained in 000 g. The carbonyl value (CV) was determined by substituting for the standard sample having a known total carbonyl amount (propionaldehyde concentration) to obtain a calibration curve, which was employed to obtain this calibration curve. The carbonyl value of a sample (polyether-modified polysiloxane composition) whose total carbonyl amount is unknown is measured by the same method as the above method, and the total carbonyl amount in the sample is measured from the carbonyl value and the calibration curve. .
However, the following solvent used in the following step (1) and step (9) contains an alcohol having a total amount of aldehyde / ketone of 3 ppm or less (hereinafter also referred to as “ultra-high purity alcohol”) and water, The postscript solvent used by the following process (7) contains an ultra-high purity alcohol.

[Process]
(1) A step of preparing a sample solution by dissolving the sample in a solvent.
(2) A step of adding 3 mL of 20% (wt / wt) dilute sulfuric acid alcohol solution [sulfuric acid concentration 1.2% (wt / vol)] to 5.000 g of the sample solution.
(3) An alcohol solution [0.025% (wt / wt) of 2,4-dinitrophenylhydrazine (hereinafter abbreviated as “2,4-DNPH”) is added to the mixed solution obtained in the above step (2). vol)] adding 5 mL.
(4) A step of reacting the carbonyls in the sample with 2,4-DNPH by heating the mixed solution obtained in the above step (3) at 60 ° C. for 30 minutes.
(5) A step of leaving the reaction solution obtained in the above step (4) at room temperature for 30 to 70 minutes.
(6) A step of adding 10 mL of an alcohol solution of potassium hydroxide [4.0% (wt / vol)] to the reaction solution left in the step (5).
(7) A step of adding a solvent to the reaction solution after 5 to 10 minutes from the step (6), preparing a reaction solution having a total amount of 50 mL, and filtering the reaction solution.
(8) A step of measuring the absorbance (A ₁ ) at 430 nm or 460 nm of the reaction solution obtained in the step (7) after 10 to 20 minutes from the step (6).
(9) As a blank test, an absorbance at 430 nm or 460 nm is used for a solution obtained by performing the same operation as the above steps (2) to (7) using 5.000 g of the solvent instead of the sample solution. A step of measuring A ₂ ).

In the polyether-modified polysiloxane composition of the present invention, the following forms are preferable.
[A] A polyether-modified polysiloxane composition containing a water-soluble copolymer as the organopolysiloxane-polyoxyalkylene copolymer, wherein the composition is dissolved in purified water 2.00 % (Wt / wt) of the aqueous solution of (σ ₁ ) and (σ ₀ ) of the purified water, the total amount of ionic impurities obtained by (σ ₁ −σ ₀ ) The index value is 30 μS / m or less.

[B] A polyether-modified polysiloxane composition containing a copolymer that is insoluble or hardly soluble in water as the organopolysiloxane-polyoxyalkylene copolymer, and the composition is purified by 50 mass times of purified water. and by contacting, the electrical conductivity of the extract obtained by extracting the water soluble components in the composition as a (sigma _1), when the electrical conductivity of the purified water and (sigma _0), ( The index value of the total amount of ionic impurities determined by (σ ₁ −σ ₀ ) is 30 μS / m or less.

[C] Containing an organopolysiloxane-polyoxyalkylene copolymer represented by the following general formula (1) or the following general formula (2).

[Wherein, R ^{1 s} independently of each other represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and X represents a general formula: —C _x H _2x (OC ₂ H ₄ ) _y (OC ₃ H ₆ ) _z OA [wherein A is a hydrogen atom, monovalent hydrocarbon group, or general formula: R ³ — (CO) — (wherein R ³ represents a monovalent hydrocarbon group) X is an integer of 2 to 15, y is an integer of 0 to 100, z is an integer of 0 to 100, and y + z is a positive integer of 100 or less. ), M is 0 or a positive integer, and n is 0 or a positive integer. R ² is a group represented by R ¹ or X. When n is 0, at least one of R ² is X. ]

[Wherein, R ³ independently of each other represents a monovalent hydrocarbon group, a hydroxyl group or an alkoxy group free of aliphatic unsaturation, Y ¹ represents a divalent organic group, and R ⁴ represents Independently of each other, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group, or a formula: —Y ¹ —O— (C ₂ H ₄ O) _b1 (C ₃ H ₆ O) _b2 -Y ² (Y ² represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group), a is an integer of 1 or more, and b1 is an integer of 0 to 100. , B2 is an integer from 0 to 100 (where b1 + b2 is an integer from 1 to 100), and c is an integer from 1 to 100. ]

[D] An antioxidant is contained in the range of 10 ppm to 1000 ppm.

  The production method of the present invention (Claim 5) is a method for producing the polyether-modified polysiloxane composition of the present invention, comprising an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the terminal. Obtaining a crude polyether-modified polysiloxane composition containing an organopolysiloxane-polyoxyalkylene copolymer by a hydrosilylation reaction with; and using a solid acid in the crude polyether-modified polysiloxane composition By performing each of the decomposition treatment and the hydrogenation treatment, (i) a step of highly purifying so that the total unsaturation becomes 0.00010 meq / g or less and (ii) the total amount of carbonyl converted to propanal becomes 100 ppm or less It is characterized by including.

In the production method of the present invention, the following modes are preferred.
[A] Crude polyether containing a water-soluble organopolysiloxane-polyoxyalkylene copolymer by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the terminal A step of obtaining a modified polysiloxane composition; and (i) the total degree of unsaturation being 0.00010 meq by subjecting the crude polyether-modified polysiloxane composition to a decomposition treatment using a solid acid and a hydrogenation treatment, respectively. And (ii) highly purified so that the total amount of carbonyl converted to propanal is 100 ppm or less and (iii) the index value of the total amount of ionic impurities is 30 μS / m or less.

[B] Contains an organopolysiloxane-polyoxyalkylene copolymer that is insoluble or hardly soluble in water by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the terminal. A step of obtaining a crude polyether-modified polysiloxane composition; and (i) the total degree of unsaturation by subjecting the crude polyether-modified polysiloxane composition to a decomposition treatment using a solid acid and a hydrogenation treatment, respectively. And (ii) a highly purified step so that the total amount of carbonyl converted to propanal is 100 ppm or less, and (iii) the index value of the total amount of ionic impurities is 30 μS / m or less. Including.

[C] A hydrogenation treatment is performed after the crude polyether-modified polysiloxane composition is subjected to a decomposition treatment using a solid acid.
[D] A hydrogenation treatment is performed on the crude polyether-modified polysiloxane composition, followed by a decomposition treatment using a solid acid.
[E] Use at least one selected from solid acidic zirconium oxide, strongly acidic cation exchange resin, fluorinated sulfonic acid resin and zeolite as the solid acid.
[F] The solid acidic zirconium oxide is obtained by mixing a molded product obtained by kneading and molding aluminum hydroxide or hydrated oxide, zirconium hydroxide or hydrated oxide, and a compound containing sulfuric acid. It is obtained by firing at a temperature at which crystal structure zirconia is obtained.

  The measuring method of the present invention (Claim 12) is an organopolysiloxane-polyoxyalkylene copolymer obtained by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the terminal. A carbonyl value of the polyether-modified polysiloxane composition is obtained from the absorbance of the reaction solution obtained by reacting 2,4-DNPH with the carbonyls in the polyether-modified polysiloxane composition containing Is a method for measuring the total amount of carbonyl converted to propanal in the composition using a calibration curve measured in advance, and as a reaction solvent in the reaction of carbonyls with 2,4-DNPH, A high-purity alcohol and water are used in combination.

The measuring method of the present invention (Claim 13) is an organopolysiloxane-polyoxyalkylene copolymer obtained by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the terminal. In the method of measuring the total amount of carbonyl in terms of propanal in the polyether-modified polysiloxane composition containing, the absorbance (A ₁ ) and absorbance (A ₂ ) measured by the following steps (1) to (9) Formula: CV = (A ₁ −A ₂ ) / B [B is the mass (g) of the sample contained in 5.000 g of the sample solution. ) To obtain a calibration curve by measuring the carbonyl value of a standard sample having a known total amount of carbonyl (propionaldehyde concentration) by the method of obtaining the carbonyl number (CV) by substituting The carbonyl value of a sample (polyether-modified polysiloxane composition) whose total carbonyl amount is unknown is measured by the same method as the above method, and the total carbonyl amount in the sample is measured from this carbonyl value and the calibration curve. The following solvent used in the following step (1) and step (9) contains an ultra-high purity alcohol and water, and the latter solvent used in the following step (7) is an aldehyde / ketone. The total amount of the alcohol is 3 ppm or less.

[Process]
(1) A step of preparing a sample solution by dissolving the sample in a solvent.
(2) A step of adding 3 mL of 20% (wt / wt) dilute sulfuric acid alcohol solution [sulfuric acid concentration 1.2% (wt / vol)] to 5.000 g of the sample solution.
(3) A step of adding 5 mL of 2,4-DNPH alcohol solution [0.025% (wt / vol)] to the mixed solution obtained in the above step (2).
(4) A step of reacting the carbonyls in the sample with 2,4-DNPH by heating the mixed solution obtained in the above step (3) at 60 ° C. for 30 minutes.
(5) A step of leaving the reaction solution obtained in the above step (4) at room temperature for 30 to 70 minutes.
(6) A step of adding 10 mL of an alcohol solution of potassium hydroxide [4.0% (wt / vol)] to the reaction solution left in the step (5).
(7) A step of adding a solvent to the reaction solution after 5 to 10 minutes from the step (6), preparing a reaction solution having a total amount of 50 mL, and filtering the reaction solution.
(8) A step of measuring the absorbance (A ₁ ) at 430 nm or 460 nm of the reaction solution obtained in the step (7) after 10 to 20 minutes from the step (6).
(9) As a blank test, an absorbance at 430 nm or 460 nm is used for a solution obtained by performing the same operation as the above steps (2) to (7) using 5.000 g of the solvent instead of the sample solution. A step of measuring A ₂ ).

Further, an alcohol solution of dilute sulfuric acid added in the above step (2), an alcohol solution of 2,4-DNPH added in the above step (3), and an alcohol of potassium hydroxide added in the above step (6) It is preferable that alcohol which is each solvent of a solution is ultra high purity alcohol.
In the present invention, “% (wt / wt)” is a unit indicating the mass of the solute per unit mass of the solvent, and the numerical value indicated by the unit of “% (wt / wt)” is dissolved in 100 g of the solvent. It matches the number of grams of solute.
“% (Wt / vol)” is a unit indicating the mass of the solute per unit volume of the solvent, and the numerical value indicated by the unit “% (wt / vol)” is dissolved in 100 mL of the solvent. Consistent with grams of solute.

(1) The composition of the present invention is a highly purified product having a total unsaturation of 0.00010 meq / g or less and a total amount of carbonyl of 100 ppm or less. For example, the time-dependent odor in a mixed system of water / (polyhydric) alcohol can be suppressed (similar to the time-dependent odor in water / (polyhydric) alcohol in which the composition is not mixed). But less odor). In addition, according to the composition of the present invention in which the index value (σ ₁ −σ ₀ ) of the total amount of ionic impurities is 30 μS / m or less, odorization over time in a mixed system of water / (polyhydric) alcohol ( Odors over time due to ionic impurities) can be reliably suppressed.

(2) In the production method of the present invention, the crude polyether-modified polysiloxane composition obtained by the hydrosilylation reaction is subjected to a decomposition treatment using a solid acid and a hydrogenation treatment as a purification treatment. The composition obtained by the method can have the above-mentioned requirements relating to the total degree of unsaturation, the total amount of carbonyl and the total amount of ionic impurities, and the odor over time in a mixed system of water / (polyhydric) alcohol. It will be highly purified with virtually no generation.

(3) Since the measurement method of the present invention uses ultra-high purity alcohol and water as the reaction solvent used in the carbonyl value measurement method, not only aldehydes and ketones but also potential carbonyl compounds (acetal and (Such as propenyl ether, a compound that decomposes under certain conditions to generate a carbonyl group) can be quantified, and even a very small amount of carbonyls that could not be detected by a conventionally known method can be quantified accurately. .

Hereinafter, the present invention will be described in detail.
<Polyether-modified polysiloxane composition>
The polyether-modified polysiloxane composition of the present invention is a copolymer (organopolysiloxane-polyoxy) obtained by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the terminal. An alkylene copolymer).

  Although it does not specifically limit as a copolymer which comprises the composition of this invention, What is shown by said general formula (1) and said general formula (2) is preferable, These are independent, or Two or more kinds can be used in combination.

The composition of the present invention is most preferably composed only of an organopolysiloxane-polyoxyalkylene copolymer (contains no impurities), but the composition of the present invention usually contains other components (impurities). Has been.
Here, as a component other than the organopolysiloxane-polyoxyalkylene copolymer, a polyoxyalkylene derived from a polyoxyalkylene having a carbon-carbon double bond at the terminal used as a reaction raw material of the copolymer ( And polyoxyalkylene containing an unsaturated group / polyoxyalkylene containing no unsaturated group), carbonyls (including potential carbonyl compounds), and ionic impurities.
Of these components, (i) polyoxyalkylenes containing unsaturated groups, (ii) carbonyls (including potential carbonyl compounds) and (iii) ionic impurities are odor-causing substances, respectively. The content ratio is preferably as small as possible.
And the composition of this invention which comprises the requirements explained in full detail below has a very small ratio of these odor causing substances.

  The composition of the present invention is characterized in that (i) the total degree of unsaturation is 0.00010 meq / g or less, and (ii) the total amount of carbonyl in terms of propanal is 100 ppm or less. Further, (iii) the index value of the total amount of ionic impurities is preferably 30 μS / m or less. Hereinafter, these index values will be described.

[Total unsaturation]
In the composition of the present invention, the total degree of unsaturation measured according to JIS K 1557 is 0.00010 meq / g or less, preferably 0.00007 meq / g or less. When the total degree of unsaturation is 0.00010 meq / g or less, in a mixed system obtained by mixing the composition with water / (polyhydric) alcohol, it is possible to reliably smell over time due to unsaturated groups. Can be suppressed.

The “total degree of unsaturation” in the present invention is measured by a method according to JIS K 1557. The detection limit of total unsaturation by this method is usually 0.00007 meq / g, but the detection limit can be further reduced by increasing the amount of sample.
On the other hand, the detection limit by the method for measuring the degree of unsaturation described in Patent Document 6 is 0.001 meq / g (10 times the specified value of the total degree of unsaturation in the present invention). This is because even in the composition in which the unsaturated group was not detected by the method described in Patent Document 6, the unsaturated group not detected in the mixed system of this and water / (polyhydric) alcohol. It means that the odor caused by the time may occur.

[Total amount of carbonyl]
In the composition of the present invention, the total amount of carbonyl in terms of propanal is 100 ppm or less, preferably 50 ppm or less.
Here, the “total amount of carbonyl” is the total amount of carbonyls relative to the composition.
In addition, carbonyls quantified as “total amount of carbonyl” include compounds having a carbonyl group, such as aldehydes and ketones, as well as acetals and propenyl ethers. Also included are potential carbonyl compounds that yield carbonyl groups.
When the total amount of carbonyl (propanal conversion value) is 100 ppm or less, the time-dependent odor caused by carbonyls is reliably suppressed in a mixed system obtained by mixing the composition with water / (polyhydric) alcohol. can do.

  The “total amount of carbonyl” in the composition of the present invention is measured according to the measurement method of the present invention (method according to claim 13). The details of the measurement method of the present invention will be described later. According to this method, a very small amount of carbonyls that could not be detected by a conventionally known method can be accurately quantified.

[Index value of total amount of ionic impurities]
In the composition of the present invention, the index value (σ ₁ −σ ₀ ) of the total amount of ionic impurities is preferably 30 μS / m or less, more preferably 20 μS / m or less.
When the index value of the total amount of ionic impurities is 30 μS / m or less, it is caused by ionic impurities such as acids and neutralized salts in a mixed system obtained by mixing the composition with water / (polyhydric) alcohol. Certain odors over time (odd over time due to ionic impurities, over time odor accompanying decomposition of ionic impurities, over time due to degradation / decomposition of modified silicone compounds and polyoxyalkylenes due to ionic impurities) Can be suppressed.

The electrical conductivity (σ ₁ ) measured to determine the index value (σ ₁ −σ ₀ ) of the total amount of ionic impurities is the composition of the present invention containing a water-soluble copolymer. The electrical conductivity of a 2.00% (wt / wt) aqueous solution dissolved in purified water (Claim 2), and the composition of the present invention containing a copolymer insoluble or sparingly soluble in water The electrical conductivity of the extract obtained by extracting the water-soluble component in the composition by bringing the composition into contact with purified water 50 times in mass (Claim 3).
The electrical conductivity (σ ₀ ) measured for obtaining the index value (σ ₁ -σ ₀ ) of the total amount of ionic impurities is the electrical conductivity of the purified water used above.

The composition of the present invention preferably contains an antioxidant, whereby oxidation of the copolymer or the like constituting the composition can be prevented.
Examples of such antioxidants include phenols, hydroquinones, benzoquinones, aromatic amines, vitamins and the like. Specific examples of preferable antioxidants include BHT (2,6-di-t-butyl-p-cresol), vitamin E, and the like.
As addition amount of antioxidant, it is preferable that it is 10-1000 ppm with respect to the composition of this invention, More preferably, it is set as 50-500 ppm.

<Method for producing polyether-modified polysiloxane composition>
The production method of the present invention includes a step of obtaining a crude polyether-modified polysiloxane composition containing an organopolysiloxane-polyoxyalkylene copolymer by a hydrosilylation reaction (hereinafter also referred to as “synthesis step”); By subjecting the crude polyether-modified polysiloxane composition to a decomposition treatment using a solid acid and a hydrogenation treatment, (i) the total degree of unsaturation is 0.00010 meq / g or less, and (ii) conversion to the propanal A step (hereinafter also referred to as a “purification step”) that is highly purified so that the total amount of carbonyl is 100 ppm or less (preferably (iii) the index value of the total amount of ionic impurities is 30 μS / m or less). Including.

[Synthesis process]
Examples of the organohydrogenpolysiloxane used in the synthesis reaction (hydrosilylation reaction) of the organopolysiloxane-polyoxyalkylene copolymer include those represented by the following general formulas (3) to (4). These can be used alone or in combination of two or more.

General formula (3): R ¹¹ ₃ SiO (R ¹¹ ₂ SiO) _p SiR ¹¹ ₃

[Wherein, R ¹¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group (for example, an alkyl group having 1 to 19 carbon atoms such as a methyl group or an ethyl group, a phenyl group, an alkylphenyl group, or a naphthyl group). Group, alkylnaphthyl group, phenylalkyl group, 3,3,3-trifluoropropyl group, etc.), formula: —O— (R ¹² ₂ SiO) _q SiR ¹² _{3 wherein} R ¹² is the same or different substituent Or an unsubstituted monovalent hydrocarbon group (for example, an alkyl group having 1 to 19 carbon atoms such as a methyl group or an ethyl group, a phenyl group, an alkylphenyl group, a phenylalkyl group, 3,3,3-trifluoropropyl; Group) or a hydrogen atom, q is 0 or a positive integer. ] Or a hydrogen atom, and p is 0 or a positive integer. However, it has at least one Si-H group in one molecule. ]

[Wherein, R ¹¹ is the same group as described in formula (3), and r is an integer of 3 or more. However, it has at least one Si-H group in one molecule. ]

  Examples of the polyoxyalkylene to be used in the synthesis reaction (hydrosilylation reaction) of the organopolysiloxane-polyoxyalkylene copolymer include those represented by the following general formula (5), and these may be used alone. , Or a combination of two or more.

Formula (5): R ¹³ O (R ¹⁴ O) _s R ¹³

[Wherein, R ¹³ represents the same or different monovalent hydrocarbon group optionally substituted with an unsaturated group (for example, allyl group, methallyl group, 3-butenyl group, alkyl having 1 to 19 carbon atoms) Group, phenyl group, alkylphenyl group, naphthyl group, alkylnaphthyl group, etc.), acyl group or hydrogen atom, and R ¹⁴ is the same or different, substituted or unsubstituted divalent hydrocarbon group (for example, ethylene group) , Propylene group, butylene group, etc.). s is 0 or a positive integer. However, at least one of the groups represented by R ¹³ is a hydrocarbon group having an unsaturated substituent. ]

  The hydrosilylation reaction can be performed according to a known technique. That is, this reaction is carried out in an organic solvent such as ethanol, isopropyl alcohol or the like, aromatic hydrocarbon such as toluene or xylene, ether such as dioxane or THF, aliphatic hydrocarbon or chlorinated hydrocarbon. It is carried out without solvent.

The hydrosilylation reaction may be carried out in the absence of a catalyst, but it is preferable to carry out the reaction in the presence of a catalyst because the reaction proceeds at a low temperature in a short time. Examples of such a catalyst include compounds such as platinum, ruthenium, rhodium, palladium, osmium and iridium, and platinum compounds are particularly effective because of their high catalytic activity. Examples of platinum compounds include: chloroplatinic acid; metal platinum; a metal platinum supported on a carrier such as alumina, silica, carbon black; platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex And platinum complexes such as platinum alcoholate catalysts. The amount of the catalyst used is about 0.5 to 100 ppm as platinum metal when using a platinum catalyst.
The reaction temperature of the hydrosilylation reaction is usually 50 to 150 ° C., and the reaction time is usually 10 minutes to 24 hours, preferably 1 to 10 hours.
In the hydrosilylation reaction, the polyoxyalkylene is usually reacted in excess. Therefore, the polyether-modified polysiloxane composition unavoidably contains unreacted polyoxyalkylene together with the organopolysiloxane-polyoxyalkylene copolymer.

[Purification process]
By subjecting the reaction solution obtained by the hydrosilylation reaction in the synthesis step to neutralization, removal of low-boiling components (evaporation), separation of solid components (solid residue), etc., as necessary, An ether-modified polysiloxane composition is obtained.
In this composition (crude product), in addition to the organopolysiloxane-polyoxyalkylene copolymer (target product), unreacted polyoxyalkylene (for example, allyl etherified polyoxyalkylene) and its isomers ( For example, propenyl etherified polyoxyalkylene) is contained.
Propenyl etherified polyoxyalkylene, which is an isomer of unreacted polyoxyalkylene, is a vinyl ether type compound, and therefore easily hydrolyzes to produce a light component. That is, propenyl etherified polyoxyalkylene is gradually hydrolyzed by the presence of moisture and a small amount of acid in the air to produce propionaldehyde, which is an odor substance.

In addition, allyl etherified polyoxyalkylene, which is an unreacted polyoxyalkylene, gradually changes to propenyl etherified polyoxyalkylene, which is an isomerized product (by extension, propionaldehyde) by the action of the platinum catalyst remaining in the composition. Not only causes odor, but also allyl etherified polyoxyalkylene oxidizes with time, and this oxide also causes odor.
Therefore, in order to obtain a composition that does not generate odorous substances by hydrolysis and oxidation and is stable over time, not only removes propenyl etherified polyoxyalkylene, but also an unstable structure that causes odors. It is necessary to prevent the remaining compound from remaining in the polyether-modified polysiloxane composition, and for this purpose, a purification step is performed.

  In the purification step, a composition (the composition of the present invention) having the two requirements related to the total unsaturation and the total amount of carbonyl (preferably, the three requirements related to the total unsaturation, the total amount of carbonyl and the total amount of ionic impurities) ), The composition (crude product) is subjected to “decomposition treatment using a solid acid” and “hydrogenation treatment”.

  In the purification step, the crude polyether-modified polysiloxane composition may be subjected to a decomposition treatment using a solid acid and then subjected to a hydrogenation treatment; the crude polyether-modified polysiloxane composition may be subjected to a hydrogenation treatment. Thereafter, a decomposition treatment using a solid acid may be performed.

  The hydrogenation treatment is usually performed in the presence of a hydrogenation catalyst. Examples of such a hydrogenation catalyst include simple substances and compounds such as nickel, barium, platinum, rhodium, cobalt, chromium, copper and iron. Examples of the catalyst carrier used arbitrarily include activated carbon, silica, silica alumina, alumina, zeolite and the like. Also, the platinum catalyst used in the synthesis step (hydrosilylation reaction) can be used as it is. A hydrogenation catalyst can be used individually or in combination of 2 or more types.

  In the hydrogenation treatment, the solvent used arbitrarily can be selected from solvents inert to the hydrogenation reaction, specifically, alcohols such as ethanol and isopropyl alcohol, dioxane, THF and the like. An ether type, an aliphatic hydrocarbon type, a chlorinated hydrocarbon type, water, etc. can be mentioned, These can be used individually or in combination of 2 or more types. In addition, the solvent used in the synthesis step (hydrosilylation reaction) (the solvent constituting the reaction solution) can be used as it is.

The hydrogenation reaction can be performed at normal pressure or under pressure. Actually, it is performed under hydrogen pressure (hydrogen pressure = 1 to 200 kg / cm ² ). The reaction temperature is usually 0 to 200 ° C., and preferably 50 to 170 ° C. from the viewpoint of shortening the reaction time.

The hydrogenation reaction may be performed by either a batch system or a continuous system. The reaction time in the case of the batch system is approximately 3 to 12 hours, although it varies depending on the amount of catalyst and reaction temperature.
In the case of a batch system, the end point of the hydrogenation reaction can be set to a time point at which the reaction is further performed for 1 to 2 hours from the time point when almost no decrease in the hydrogen pressure is observed. When the hydrogen pressure is reduced during the reaction, it is preferable from the viewpoint of shortening the reaction time that hydrogen gas is reintroduced to keep the hydrogen pressure high.

  After completion of the hydrogenation reaction, the hydrogenation reaction catalyst (hydrosilylation reaction catalyst if present in the reaction system) is separated and removed using filter paper, diatomaceous earth, or activated carbon under nitrogen pressure.

Further, when a solvent is used and / or when light components are present in the reaction system after hydrogenation, these light components are distilled off while introducing nitrogen gas under reduced pressure as necessary.
The light component removal operation may be performed as a pretreatment for performing a hydrogenation reaction, or may be performed before and after the hydrogenation reaction.

The unsaturated group is alkylated by the hydrogenation treatment, so that the composition after the treatment can generally have the above-mentioned requirement relating to the total degree of unsaturation (total degree of unsaturation ≦ 0.00010 meq / g). , The amount of odorous substances caused by unsaturated groups (for example, propionaldehyde resulting from propenyl etherified polyoxyalkylene) can be reduced.
However, only the hydrogenation treatment cannot remove an aldehyde condensate having no unsaturated bond, such as acetal, and the composition after the treatment has the above-mentioned requirement relating to the total amount of carbonyl (total amount of carbonyl ≦ 100 ppm). In such a composition, it is impossible to suppress odor formation over time due to carbonyls in a water / (polyhydric) alcohol mixed system.

  Therefore, in the present invention, by performing a decomposition treatment using a solid acid, the aldehyde condensate present in the composition is decomposed, and the above-mentioned requirement relating to the total amount of carbonyl is provided in the composition after the treatment.

As described above, in the purification step, the decomposition treatment using the solid acid can be preceded by the hydrogenation treatment.
In such cases, the decomposition treatment using the solid acid decomposes the propenyl etherified polyoxyalkylene and aldehyde condensate in the crude polyether-modified polysiloxane composition, then the aldehyde formed and the remaining alkenyl Polyoxyalkylene (allyl etherified polyoxyalkylene) and the like are reduced by the hydrogenation treatment, and thus the composition purified by this method (acid treatment-hydrogenation) has a total unsaturation degree. And the above two requirements relating to the total amount of carbonyl.

In the present invention, “decomposition treatment using a solid acid” means, for example, in a composition to be treated (crude polyether-modified polysiloxane composition or polyether-modified polysiloxane composition subjected to hydrogenation treatment). Decomposition treatment that stirs the system by adding a solid acid, and a water that stirs the system by adding solid acid, water, and, if necessary, an organic solvent to the polyether-modified polysiloxane composition. It means a decomposition treatment and the like, and a hydrolysis treatment is particularly preferable.
As the reaction conditions (temperature / time) in the hydrolysis treatment, the temperature is 15 to 160 ° C., preferably 50 to 100 ° C., and 1 to 24 hours, preferably 1 to 12 hours.

  Further, the composition to be treated may be passed (circulated / circulated) through a reaction tower filled with a solid acid. The reaction conditions in this case are 15 to 160 ° C., preferably 50 to 100 ° C., and 1 to 24 hours, preferably 1 to 12 hours.

  If light components are present in the composition to be treated, if necessary, these light components are distilled off while introducing nitrogen gas under reduced pressure during the decomposition treatment using a solid acid. It is preferable to do. Moreover, you may perform removal operation of a light part as pre-processing and / or post-processing of the decomposition process which uses a solid acid.

  As described above, the decomposition treatment using a solid acid is preferably performed in the presence of water, and the organopolysiloxane-polyoxyalkylene copolymer constituting the composition to be treated is hardly soluble in water. In the case of water, water and a water-soluble organic solvent can be used in combination. Examples of such an organic solvent include saturated monohydric alcohols having 1 to 5 carbon atoms, THF, dioxane and the like.

  "Solid acid" used for the decomposition treatment is an acidic solid substance, such as solid acidic zirconium oxide (solid acidic zirconia), strong acidic cation exchange resin, fluorinated sulfonic acid resin, zeolite acidic clay, alumina, silica alumina, etc. These may be used alone or in combination of two or more. Of these, solid acidic zirconium oxide, strong acidic cation exchange resin, fluorinated sulfonic acid resin and zeolite are preferable, and solid acidic zirconium oxide is particularly preferable.

Suitable solid acidic zirconium oxides are those prepared by treating zirconium hydroxide with sulfuric acid and then at 300 ° C. or higher, more specifically, aluminum hydroxide or hydrated oxide, zirconium hydroxide or hydrated A product obtained by kneading and molding an oxide and a compound containing sulfuric acid at a temperature (300 ° C. or higher) at which tetragonal zirconia is obtained (zirconia sulfate) is obtained. Can be mentioned.
As a commercial item of solid acidic zirconium oxide, “SZA-60” [manufactured by Japan Energy Co., Ltd.] can be mentioned.

As the strong acid cation exchange resin which is a solid acid, a cation exchange resin having a sulfonic acid group (—SO ₃ H) as a functional group can be exemplified. Organo Corporation (Rohm and Haas, USA) Amber list 15 "," Amber list 16 "," Amber list 31 "," Amber list 35 "," Amber list A36 ", etc. are on sale.
Examples of the fluorinated sulfonic acid resin that is a solid acid include a perfluorinated polymer having a suspended sulfonic acid group bonded to a polymer chain (disclosed in Japanese Patent Publication No. 59-4446). .

By performing the decomposition treatment using a solid acid, the composition after the treatment can have the above-mentioned requirement relating to the total amount of carbonyl (total amount of carbonyl ≦ 100 ppm) and the requirement relating to the total amount of ionic impurities (the above-mentioned index) Value (σ ₁ −σ ₀ ) ≦ 30 μS / m).

The reason why the composition after the treatment has the above-mentioned requirement relating to the total amount of ionic impurities is presumed as follows.
(1) Unlike the acid substance-containing aqueous solution (Patent Document 6), the solid acid is not dissolved in the organopolysiloxane-polyoxyalkylene copolymer and therefore does not remain in the composition. Further, the constituent component of the solid acid does not elute into the copolymer.
(2) Since no acid (solid acid) remains, neutralization is not necessary, and no neutralized salt remains.
(3) Ionic impurities present in the composition to be treated are adsorbed on the surface of the solid acid and removed from the composition together with the solid acid.

In the composition having the above requirements relating to the total amount of ionic impurities (the composition of the present invention), deterioration over time of the organopolysiloxane-polyoxyalkylene copolymer due to residual ionic impurities (for example, co-polymerization by acid) Ionicity such as oxidation of coalescence, depolymerization of copolymer with acid or neutralized salt), deterioration of polyoxyalkylene contained in composition over time (eg oxidation of polyoxyalkylene group by acid) Problems caused by impurities do not occur.
Therefore, in a mixed system obtained by mixing the composition with water / (polyhydric) alcohol, odors over time due to ionic impurities [time odors due to ionic impurities / decomposition of ionic impurities over time. Odor and time-dependent odor caused by degradation / decomposition of the modified silicone compound and residual polyoxyalkylene due to ionic impurities] is reliably suppressed.
Further, when the hydrogenation treatment is performed after the decomposition treatment using the solid acid, the problem of inhibition of the hydrogenation reaction due to ionic impurities does not occur.

<Measurement method of total amount of carbonyl in polyether-modified polysiloxane composition>
The measuring method of the present invention (measuring method according to claim 12) is based on the absorbance of the reaction solution obtained by reacting carbonyls in the polyether-modified polysiloxane composition with 2,4-DNPH. In this method, the carbonyl value of the modified polysiloxane composition is obtained, and the total amount of carbonyl converted to propanal in the composition is measured from the carbonyl value using a calibration curve measured in advance.

Here, the “carbonyl value” is an index value of the carbonyl content, and the absorbance (absorbance at 430 nm or 460 nm) of the reaction solution obtained by reacting 2,4-DNPH with the sample is converted per 1 g of the sample. The value obtained by
By measuring the carbonyl value of a standard sample having a known carbonyl concentration (propionaldehyde concentration) to obtain a calibration curve, various samples (polyether-modified polysiloxane composition) were analyzed for carbonyl concentrations ( Total amount of carbonyl) can be measured.

  The carbonyl value is measured by utilizing the property that a hydrazone produced by reacting a carbonyl with 2,4-DNPH in the presence of an acid is basic and forms a quinoid ion. The carbonyl value is determined from the absorbance at 430 nm (maximum wavelength derived from saturated carbonyl in the vicinity) or 460 nm (maximum wavelength derived from unsaturated carbonyl in the vicinity) indicating the degree.

  The measuring method of the present invention is characterized in that ultrahigh purity alcohol and water are used in combination as a reaction solvent in the reaction of carbonyls with 2,4-DNPH.

  In the present invention, the “reaction solvent” refers to a solvent present in the reaction system of carbonyls in the sample and 2,4-DNPH, (a) In addition to the solvent used for preparing the sample solution, The reaction solvent is constituted by (b) the solvent used for preparing the acid solution to be added, (c) the solvent used for preparing the 2,4-DNPH solution, and the like.

  Note that (a) the alcohol that constitutes the sample solution, (b) the alcohol that constitutes the acid solution, and (c) the alcohol that constitutes the 2,4-DNPH solution may not be an ultra-high purity alcohol. The alcohol in the reaction solvent obtained by mixing these materials only needs to satisfy the requirements as an ultra-high purity alcohol (the total amount of aldehydes and ketones is 3 ppm or less).

In the measurement method of the present invention, when measuring the absorbance of the reaction solution, alcohol is used as a solvent (hereinafter also referred to as “diluting solvent”) to be added in order to keep the volume of the reaction solution constant. It is particularly preferable to use ultra-high purity alcohol.
Note that it is not necessary that all of the dilution solvent is alcohol, and water and / or an organic solvent (having no carbonyl group in its structure) as a part of the reaction solvent as long as the effect of the present invention is not impaired And less harmful) may be used.

Examples of the ultra high purity alcohol constituting the reaction solvent and the alcohol constituting the dilution solvent include monovalent saturated alcohols. Unsaturated alcohols are less stable and may contain carbonyls that are produced as a result of some oxidation, which causes measurement errors.
Specific examples of the monovalent saturated alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl hexanol, 2-ethyl hexanol, 2-propyl hexanol, 2-butyl hexanol, etc. can be mentioned, These can be used individually or in combination of 2 or more types. . Among these, ethanol and 2-propanol are preferable from the viewpoint of solubility and safety of the sample (polyether-modified polysiloxane composition).

  These alcohols are not harmful like benzene and can dissolve various substances having different polarities and molecular weights. Therefore, by using these alcohols as the reaction solvent and the diluting solvent, each operation for obtaining the carbonyl value can be performed safely and easily.

The total amount of aldehydes and ketones contained in the ultrahigh purity alcohol used as the reaction solvent is 3 ppm or less, preferably 2 ppm or less.
When the total amount of aldehydes and ketones exceeds 3 ppm in the alcohol used as the reaction solvent, the baseline rises when the absorbance of the resulting reaction solution is measured, and samples containing a low carbonyl content are included. An appropriate (highly accurate) index value cannot be obtained, for example, the absorbance measured for the reaction solution is smaller than the absorbance measured for the solution for the blank test (solution not containing the sample).
Only when using ultra-high-purity alcohol with a total amount of aldehyde / ketone of 3 ppm or less as a reaction solvent, properly determine the carbonyl value of samples with low carbonyl content (eg, carbonyl value less than 3). Can do.

As a preparation method (purification method) of ultra-high purity alcohol, an appropriate amount of 2,4-DNPH and an acid having no oxidizing action (for example, hydrochloric acid or trichloroacetic acid) are added to the alcohol to be purified, and this system is taken for several hours. And a method of distilling alcohol under normal pressure or reduced pressure after heating and stirring.
These purification treatments are preferably carried out within 24 hours before measuring the absorbance of the reaction solution.

Moreover, it is preferable to use the commercially available high purity reagent refine | purified as ultra high purity alcohol until the total amount of aldehyde ketone becomes 3 ppm or less.
Commercially available high purity reagents that can be used as ultra high purity alcohol include ethanol (99.8%) Infinity Pure, ethanol (99.8%) for precision analysis, ethanol (99.5%) high performance liquid chromatograph For ethanol, 99.5% spectroscopic analysis, 2-propanol (99.9%) Infinity Pure, 2-propanol (99.9%) for precision analysis, 2-propanol (99.5%) high performance liquid chromatography For graph, 2-propanol (99.5%) for spectroscopic analysis, 1-propanol (99.8%) Infinity Pure, 1-propanol (99.5%) for high performance liquid chromatograph, methanol (99.8%) Infinity pure, methanol (99.8%) for precision analysis, methanol (99.5%) high performance liquid chromatograph , Methanol (99.5%) for spectroscopy, n- butyl alcohol high speed liquid chromatography, n- butyl alcohol spectroscopic analysis (Wako Pure Chemical Industries, Ltd.) and the like can be exemplified.

Even in the case of the high-purity reagent as described above, the total amount of aldehyde / ketone may increase with time and the total amount of aldehyde / ketone may exceed 3 ppm. Further, after opening, the total amount exceeds 3 ppm in a relatively short time (for example, within 24 hours).
Therefore, from the viewpoint of satisfying the essential requirements as an ultra-high purity alcohol (total amount of aldehyde / ketone is 3 ppm or less), a commercially available high-purity reagent is:
(A) manufactured within 6 months before use, and
(B) It is preferably opened within 24 hours before use.

  Alcohols that do not satisfy the above conditions (a) or (b) are likely to oxidize and the total amount of aldehydes and ketones exceeds 3 ppm. , The exact total amount of carbonyl) may not be obtained.

  Here, a lot of ethanol (99.8) Infinity Pure was opened after the production in May and the total amount of aldehyde / ketone was measured to be 2.8 ppm. The same lot of ethanol (99.99) was measured. 8) When Infinity Pure was manufactured and opened in July, the total amount of aldehyde / ketone was measured and found to be 5.0 ppm (insufficient requirement for ultra-high purity alcohol).

Moreover, even if it is a sample (polyether-modified polysiloxane composition) containing an aldehyde condensate (potential carbonyl compound) such as acetal by using water together with ultra-high purity alcohol as a reaction solvent, The carbonyl value can be reliably obtained with high accuracy, and it is possible to quantify the total amount of carbonyl in consideration of carbonyls derived from these which are odor-causing substances. The reason for this is not clear, but it is presumed that the presence of water in the reaction system decomposes the aldehyde condensate and ensures the reaction with 2,4-DNPH.
As a mixing ratio of both in the reaction solvent composed of ultra high purity alcohol and water, ultra high purity alcohol: water (mass ratio) is 99.9: 0.1-50: 50, preferably 99: 1 75:25.

In the measurement method of the present invention, the solvent used as the reaction solvent does not need to be composed only of a mixed solvent of ultra-high purity alcohol and water, and as long as the effect of the present invention is not impaired, An organic solvent which does not have a carbonyl group in the structure and has little harmfulness may be used.
However, when an organic solvent other than ultra high purity alcohol is used as a part of the reaction solvent, the reaction solvent (water) obtained by mixing the organic solvent (part) and the ultra high purity alcohol (remainder) It is necessary that the total amount of aldehydes and ketones contained in all) except 3) be 3 ppm or less.

In the measurement method of the present invention, an acid and 2,4-DNPH are added to a sample solution obtained by dissolving a sample (polyether-modified polysiloxane composition) in a solvent, and the system is heated to treat the sample. After reacting the carbonyls with 2,4-DNPH and cooling, an alkali is added to the system, and then adjusted to a certain volume with a diluting solvent. Reaction solution) can be prepared.
Here, as a container for preparing a basic reaction solution, it is preferable to use a 10-100 mL volumetric flask.

(1) Sample solution:
Since the solvent used for preparing the sample solution constitutes the reaction solvent as it is, a mixed solvent of ultrahigh purity alcohol and water is usually used as the solvent.
The mass of the sample solution (sample and solvent) used for measuring the absorbance is usually about 2 to 6 g, preferably about 5 g.
The mass of the sample included in the sample solution varies depending on the amount of the reaction solution prepared for measuring the absorbance (volume of the volumetric flask used) and the carbonyl content (carbonyl value) in the sample. When preparing a reaction solution (reaction solution used for measuring absorbance) using a volumetric flask, the pure content is preferably 5 to 250 mg, more preferably 10 to 150 mg.

(2) Acid:
Examples of acids added to the sample solution include mineral acids such as dilute sulfuric acid, hydrochloric acid, dilute nitric acid, and phosphoric acid, organic acids such as trichloroacetic acid, trifluoroacetic acid, formic acid, acetic acid, sulfonic acid, and phenolic acid, AlCl ₃ , FeCl ₃ , Examples include Lewis acids such as TiCl ₄ , and these can be used alone or in combination of two or more. Of these, dilute sulfuric acid (especially with a concentration of 20% or less) and hydrochloric acid (especially with a concentration of 37% or less) from the viewpoint that the total amount of carbonyl in the highly purified polyether-modified polysiloxane composition can be accurately determined. Is preferred. Moreover, it is preferable that the acid used in the present invention has a purity as high as possible (reagent special grade or higher purity).

These acids may be added to the sample solution as they are, but it is preferable to add them in a solution state in which they are dissolved in an appropriate solvent from the viewpoint of accurate measurement.
In addition, since the solvent used for preparing the solution of the acid constitutes the reaction solvent as it is, an ultra-high purity alcohol or a mixed solvent of ultra-high purity alcohol and water is used as the solvent. It is preferable.
When preparing a reaction solution (reaction solution containing 5 to 250 mg of sample in a pure fraction) in a 50 mL volumetric flask, the amount of acid added is preferably 0.03 to 3.0 g in a pure fraction.

(3) 2,4-DNPH:
As 2,4-DNPH added to the sample solution, it is preferable to use a reagent grade containing equal amount of water or having a purity of higher. Further, the purity may be further increased by a purification operation such as recrystallization.
2,4-DNPH may be added to the sample solution as it is, but it is preferable to add it in a solution state dissolved in an appropriate solvent from the viewpoint of performing accurate measurement. In addition, since the solvent used for preparing the solution of 2,4-DNPH constitutes the reaction solvent as it is, as such a solvent, ultra high purity alcohol, or ultra high purity alcohol and water are used. It is preferable to use a mixed solvent.
When preparing a reaction solution (reaction solution containing 5 to 250 mg of pure sample) in a 50 mL volumetric flask, the amount of 2,4-DNPH added is preferably 0.5 to 10 mg in pure fraction. .

(4) Heat treatment:
The heat treatment conditions for the mixed solution containing the sample, acid and 2,4-DNPH are 20 to 180 minutes at 30 to 120 ° C. (however, a temperature lower than the boiling point of the reaction solvent).
When the treatment temperature is less than 30 ° C., the reaction between the carbonyls in the sample and 2,4-DNPH requires a long time and is not efficient. On the other hand, when heated at a temperature higher than 120 ° C., the produced hydrazone may be decomposed.
When the treatment time is less than 20 minutes, it is difficult to complete the reaction with 2,4-DNPH. On the other hand, if the treatment time exceeds 180 minutes, the produced hydrazone may be decomposed.

(5) Alkali:
As the alkali added to the reaction solution by the reaction between carbonyls in the sample and 2,4-DNPH, it is preferable to use an inorganic strong base such as potassium hydroxide or sodium hydroxide.
These alkalis may be added to the sample solution as they are, but it is preferable to add them in a solution state in which they are dissolved in an appropriate solvent from the viewpoint of accurate measurement. As such a solvent, one that can dissolve an alkali and has no carbonyl group in its structure, is compatible with the solvent used as a reaction solvent, and is less harmful. Alternatively, two or more kinds can be selected and used, specifically, monovalent saturated lower alcohols such as methanol, ethanol, 2-propanol, 1-propanol, or water and / or other organics. Examples include a mixed solvent obtained by mixing a suitable amount of a solvent (having no carbonyl group in its structure and less harmful), ultra-high purity alcohol, or ultra-high purity alcohol and water. It is preferable to use a mixed solvent.
When preparing a reaction solution (reaction solution containing 5 to 250 mg of pure sample) in a 50 mL volumetric flask, the amount of alkali added is preferably 0.05 to 5.0 g in pure content.

(6) Diluting solvent:
The reaction solution to which the alkali is added is adjusted to a certain volume (for example, 50 mL) with a diluent solvent mainly composed of alcohol. As the alcohol constituting the diluting solvent, it is preferable to use an ultra-high purity alcohol.

(7) Specific preparation method:
If an example of the preparation method of the reaction solution used for the measurement of absorbance is shown, a sample of 5 to 250 mg (polyether-modified polysiloxane composition) is mixed with ultra high purity alcohol and water in a 50 mL volumetric flask. Sample solution 5g dissolved in a solvent was charged, then 0.03-3.0g acid dissolved in ultra high purity alcohol and 0.5-10mg 2,4-DNPH ultra high purity After adding the solution dissolved in alcohol, the volumetric flask was stoppered and heated at 30 to 120 ° C. for 20 to 180 minutes, so that the carbonyls and 2,4-DNPH in the sample were removed. After the reaction and cooling to room temperature, a solution in which 0.05 to 5.0 g of alkali is dissolved in alcohol is added to the volumetric flask, and then a diluent solvent consisting of alcohol is added. The volume is adjusted to 50mL by.

In the measurement method of the present invention, the basic reaction solution obtained as described above is subjected to filtration treatment as necessary, and then the absorbance at 430 nm or 460 nm is measured.
Here, when it is estimated that the carbonyl contained in the sample is mainly saturated carbonyl, the absorbance at 430 nm is measured for the reaction solution, and the carbonyl contained in the sample is mainly unsaturated carbonyl. If it is estimated, the absorbance at 460 nm is measured for the reaction solution.
In measuring the absorbance, it is preferable to use a quartz cell as the absorption cell for containing the reaction solution. The length (thickness) of the liquid layer defined by the absorption cell is preferably 1 cm.

The measurement of absorbance is preferably carried out 10 minutes to 20 minutes after the addition of alkali to the reaction solution obtained by the reaction of carbonyls in the sample with 2,4-DNPH.
Absorbance measured before 10 minutes from the addition of alkali may lack stability, and after 20 minutes from addition of alkali, the reaction solution will fade and the absorbance will decrease. There is a tendency to decrease.
Based on experience with various samples, the most reproducible value can be obtained by measuring the absorbance after 15 minutes from the addition of alkali.

In the measurement method of the present invention, the carbonyl value of a sample (polyether-modified polysiloxane composition) is obtained from the absorbance measured as described above, and a calibration curve measured in advance is used from the carbonyl value. The total amount of carbonyl in the composition is measured.
Here, the calibration curve is obtained by measuring the carbonyl value of a plurality of standard samples whose total carbonyl amount (propionaldehyde concentration) is known according to the above-described method (measurement method of carbonyl value).

The measurement method of the present invention (measurement method according to claim 13) is a method for measuring the total amount of carbonyl in terms of propanal in the polyether-modified polysiloxane composition, and is measured by the above steps (1) to (9). The absorbance (A ₁ ) and absorbance (A ₂ ) are expressed by the formula: CV = (A ₁ -A ₂ ) / B [where B is the mass (g) of the sample contained in 5.000 g of the sample solution. . ] To obtain a calibration curve by measuring the carbonyl value of a standard sample having a known total carbonyl amount (propionaldehyde concentration) by the method of determining the carbonyl value (CV) by substituting By the same method, the carbonyl value of a sample (polyether-modified polysiloxane composition) whose total carbonyl amount is unknown is measured, and the total carbonyl amount in the sample is measured from the carbonyl value and the calibration curve. Yes, the postscript solvent used in the above step (1) and step (9) contains an ultra high purity alcohol and water, and the postscript solvent used in the following step (7) contains an ultra high purity alcohol. It has the characteristics.

  Note that either the measurement of the calibration curve (measurement of the carbonyl value of the standard sample) or the measurement of the carbonyl value of the unknown sample may be performed first.

Hereinafter, each step will be described.
In addition, process (2)-(7) which concerns on preparation of a reaction solution is normally performed using a 50 mL volumetric flask.

Step (1) is a step of preparing a sample solution by dissolving a sample in a solvent containing ultra high purity alcohol and water.
The proportion of the sample in the sample solution is changed according to the carbonyl value predicted for the sample. For example, a sample in which the carbonyl value is predicted to be less than 6 is 2 to 3% by mass (100 to 150 mg per 5.000 g of the sample solution), and a sample in which the carbonyl value is predicted to be in the range of 6 to 15 is 0.8. 8 to 2% by mass (40 to 100 mg per 5.000 g of sample solution), 0.4 to 0.8% by mass (20 per 5.000 g of sample solution) for samples predicted to have a carbonyl number in the range of 15 to 30. ˜40 mg), 0.2 to 0.4% by mass (10 to 20 mg per 5.000 g of sample solution) in the sample where the carbonyl value is predicted to be in the range of 30 to 60, and the carbonyl value is expected to exceed 60 It is preferable that the amount of the sample is less than 0.2% by mass (less than 10 mg per 5.000 g of the sample solution).

Moreover, when preparing a sample solution, it is preferable to dilute a sample in steps. For example, as a method of preparing 5.000 g of a 2% by mass sample solution, first, 2.00 g of a sample is dissolved in 2.00 g of ultra-high purity alcohol and 21.00 g of water to obtain an 8% by mass solution 25. 00 g is prepared.
Next, a method in which 1.250 g of an 8% by mass solution and 3.750 g of ultrahigh purity alcohol are accurately added to a 50 mL volumetric flask and diluted four times can be mentioned.

In the step (2), an alcohol solution of 20% (wt / wt) dilute sulfuric acid [sulfuric acid concentration 1] is added to 5.000 g (sample: 0.100 g) of the 2 mass% sample solution obtained in the above step (1). .2% (wt / vol)] 3 mL is added using a whole pipette or the like.
The solvent (alcohol) of the alcohol solution of dilute sulfuric acid is preferably an ultra-high purity alcohol.
The alcohol solution of dilute sulfuric acid was opened in a bottle containing 100 mL of ultra high purity alcohol, and 6.44 g of 20% (wt / wt) dilute sulfuric acid was directly added to the bottle, and the bottle was capped. It is preferable to prepare by homogenizing in the bottle by shaking.
The alcohol solution of dilute sulfuric acid is preferably prepared within 24 hours before measuring the absorbance of the reaction solution.

In step (3), 5 mL of 2,4-DNPH alcohol solution [0.025% (wt / vol)] is added to the mixed solution obtained in step (2) using a whole pipette or the like. It is a process.
The solvent (alcohol) of the 2,4-DNPH alcohol solution is preferably an ultra-high purity alcohol.
The alcohol solution of 2,4-DNPH opens a bottle containing 100 mL of ultra-high purity alcohol, and 50 mg of 2,4-DNPH (special grade reagent containing an equal amount of water) is directly added to the bottle, After the bottle is covered, it is preferably prepared by completely dissolving 2,4-DNPH in the bottle by placing it in an ultrasonic cleaner for about 5 minutes.
The 2,4-DNPH alcohol solution is preferably prepared within 24 hours before measuring the absorbance of the reaction solution.

  Step (4) is a step in which the mixed solution obtained in the above step (3) is heated at 60 ° C. for 30 minutes to cause the carbonyls in the sample to react with 2,4-DNPH. A reaction solution containing hydrazone is obtained.

  Step (5) is a step in which the reaction solution obtained in step (4) is allowed to cool at room temperature for 30 to 70 minutes.

Step (6) is a step of adding and mixing 10 mL of an alcohol solution of potassium hydroxide [4.0% (wt / vol)] using a whole pipette or the like to the reaction solution after being left standing. As a result, the reaction solution shows basicity, and the produced hydrazone becomes quinoid ions and develops color.
The solvent (alcohol) of this potassium hydroxide alcohol solution is preferably an ultra-high purity alcohol.
For the potassium hydroxide alcohol solution, open a bottle containing 100 mL of ultra-high purity alcohol, and add 4.0 g of potassium hydroxide (special grade reagent in pellet form) directly to the bottle, and cover the bottle. It is preferable to prepare the solution by completely dissolving potassium hydroxide in the bottle by shaking the mixture until the pellet disappears and then placing it in an ultrasonic cleaner for about 5 to 10 minutes.
The alcohol solution of potassium hydroxide is preferably prepared within 24 hours before measuring the absorbance of the reaction solution.

  In the step (7), after 5 to 10 minutes from the step (6), a diluted solvent composed of ultra-high purity alcohol is added to the reaction solution, and the total amount of the reaction solution is 50 mL (basic reaction solution). Is prepared, the reaction solution is filtered, and the precipitated neutralized salt (potassium sulfate) is removed.

In the step (8), the reaction solution obtained in the above step (7) is 430 nm (when it is estimated that the carbonyl contained in the sample is mainly saturated carbonyl) or (the carbonyl contained in the sample is This is a step of measuring the absorbance (A ₁ ) at 460 nm (when presumed to be mainly unsaturated carbonyl).
The absorbance measurement is required to be performed 10 minutes to 20 minutes after the addition of the potassium hydroxide alcohol solution in the above step (6), and from the time of addition of the potassium hydroxide alcohol solution. Most preferably, the absorbance is measured after 15 minutes.

In the step (9), as a blank test, instead of the sample solution, 3.850 g of ultrahigh purity alcohol and 1.150 g of water were used, and the same operation as the above steps (2) to (7) (rare) Addition of an alcohol solution of sulfuric acid; addition of an alcohol solution of 2,4-DNPH; heating and cooling of the resulting mixed solution; addition of an alcohol solution of potassium hydroxide; addition of a diluting solvent consisting of ultra high purity alcohol) This is a step of measuring the absorbance (A ₂ ) at 430 nm or 460 nm for the obtained solution.

Said steps (1) to the absorbance obtained by (8) (A ₁₎ and the absorbance obtained by the above step (9) to (A _2), respectively, the _{formula: CV = (A 1 -A 2} ) / By substituting for B, the carbonyl value (CV) can be determined.
In the above mathematical formula, B is the mass (g) of the sample contained in 5.000 g of the sample solution, and 0.1 (5.000 × 0.02) in the sample solution of 2% by mass.

  In the measuring method of the present invention (claims 12 and 13), since the reaction solvent used in the method for measuring the carbonyl value contains ultra high purity alcohol and water, according to the measuring method of the present invention. Even in polyether-modified polysiloxane compositions containing not only aldehydes and ketones, but also aldehyde condensates (potential carbonyl compounds) such as acetals, the carbonyl value can be reliably determined with high accuracy. Therefore, it is possible to quantify the total amount of carbonyl in consideration of carbonyls derived from these which are odor-causing substances.

<Use of polyether-modified polysiloxane composition>
The composition of the present invention can be used for various applications. In particular, mainly in the field of cosmetics (skin cosmetics and hair cosmetics) to be made unscented and cosmetics, conventionally polyether-modified polysiloxanes. It can also be used in fields where the use of the composition has been difficult due to its odor (especially odor over time in a mixed system of water / (polyhydric) alcohol).

  When using the composition of this invention for the use of cosmetics or cosmetics, it is preferable that the mixture ratio is about 0.1-40 mass%. The cosmetic or cosmetic obtained by blending the composition of the present invention may be blended with components constituting the skin cosmetic or the hair cosmetic within the range where the effects of the present invention are not impaired.

  In skin cosmetics and hair cosmetics, silicone compounds in the form of oil, resin, gum, rubber, powder, etc. (for example, dimethylpolysiloxane, dimethylmethylphenylpolysiloxane, amino-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane) , Polycaprolactone modified dimethyl polysiloxane, methyl hydrogen polysiloxane, diphenyl polysiloxane, carboxylic acid modified dimethyl polysiloxane, cyclic siloxanes such as decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, trimethylsiloxysilicic acid, stearoxy silicone, etc. Higher alkoxy modified silicone, higher fatty acid modified silicone, alkyl modified silicone, alkyl modified trisiloxane, fluorine modified silicone, silicone Water; alcohols (lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, isostearyl alcohol, hexadecyl alcohol and other higher alcohols, ethanol, isopropyl alcohol and other lower alcohols, sorbitol, Sugar alcohols such as maltose, cholesterol as a sterol, sitosterol, phytosterol, lanosterol, etc.); various oils (eg avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, kapok wax, kayak oil, carnauba wax, liver oil, Candelilla wax, beef tallow, beef leg fat, beef bone fat, hydrogenated beef tallow, kyounin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, Menuka oil, sugarcane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojoballow, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed Oil, Japanese Kiri Oil, Nukarou, Germ Oil, Horse Fat, Persic Oil, Palm Oil, Palm Core Oil, Castor Oil, Hardened Castor Oil, Castor Oil Fatty Acid Methyl Ester, Sunflower Oil, Grape Oil, Bayberry Wax, Jojoba Oil, Macadamia Nuts Oil , Beeswax, mink oil, cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil, fatty acid glyceride, sheep oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard Lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate "Natural animal and plant oils and semi-synthetic oils" such as polyoxyethylene (POE) lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, egg yolk oil, ozokerite, squalane, squalene, ceresin , Paraffin, paraffin wax, liquid paraffin, liquid isoparaffin, pristane, polyisobutylene, microcrystalline wax, petrolatum and other “hydrocarbon oils”, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, (12 -Hydroxystearic acid), oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostere "Higher fatty acids" such as phosphoric acid and erucic acid, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, n-alkyl glycol monoisostearate, isocetyl isostearate, trimethylol triisostearate Propane, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, olein Oleyl acid, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, stearic acid Socetyl, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, 12 -Cholesteryl hydroxy stearyl, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl- L-glutamic acid-2-octyldodecyl ester, diisostearyl malate, etc .; glyceride oil includes acetoglyceryl, triisooctanoic acid glyceride "Ester oil" such as ceryl, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, diglyceryl myristate mysterate]; surfactant ( Alkyl benzene sulfonate, polyoxyalkylene alkyl sulfate, alkyl sulfate, alkane sulfonate, alkyl ethoxy carboxylate, succinic acid derivative, alkyl amine oxide, imidazoline type compound, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene Alkylphenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof), polymer compounds [hydroxyethylcellulose, Roxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, cationized cellulose, cationized polymer, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, vinylpyrrolidone-vinyl acetate-alkylaminoacrylate copolymer, methyl vinyl ether-anhydrous maleic Lower alkyl half ester of acid copolymer, vinyl acetate-crotonic acid copolymer, acrylic acid-acrylic ester-N-alkylacrylamide copolymer, vinyl acetate-crotonic acid- (tert-butyl-vinyl benzoate) Polymer, sodium poly (2-acrylamido-2-methylpropanesulfonate), vinylpyrrolidone-methacrylic acid-acetic acid (tert-butyl) copolymer, vinylpyrrolidone- (meth) acrylic Amino acids (glycine, serine, proline), powder (sericite, silica alumina, silica gel, kaolin, talc, bengara, gunjo, mica, mica titanium, iron oxide, titanium oxide, magnesium oxide, chromium oxide) , Antimony oxide, zinc monoxide, zinc dioxide, magnesium carbonate, calcium carbonate, calcium phosphate, barium sulfate, aluminum hydroxide, chromium hydroxide, magnesium metasilicate aluminate, magnesium aluminate, polyethylene powder, etc.); UV absorption Agents, moisturizers (eg glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, Loridone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, etc.), perfumes, dyes, pigments, pigments, preservatives, vitamins, hormones, deodorants, fixing agents, anti-inflammatory agents, etc. May be.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in full detail, this invention is not limited by this.

[Preparation Example 1: Preparation of crude polyether-modified polysiloxane composition]
In a glass reaction vessel equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet, the formula: (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₁₀ [(CH ₃ ) HSiO] ₅ Si ( 240 parts by mass of an organohydrogenpolysiloxane represented by CH ₃ ) ₃ (hydrogen gas generation amount = 93.2 mL / g) and represented by the formula: CH ₂ ═CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ After charging 222 parts by mass of polyoxyalkylene (a part of the amount used), the temperature was increased with stirring to stabilize the liquid temperature at 74 ° C., and then 0.10 mass of a 10% ethanol solution of chloroplatinic acid (catalyst). When part (a part of the amount used) was added, heat generation due to an addition reaction (hydrosilylation reaction) was observed, and the liquid temperature rose to about 120 ° C.
When the liquid temperature dropped to 109 ° C., 445 parts by mass of polyoxyalkylene represented by CH ₂ ═CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ (the remainder of the amount used) was added, and the liquid temperature was 73 ° C. After adding 0.10 parts by mass of a 10% ethanol solution of chloroplatinic acid (catalyst) (the remainder of the amount used), heat generation due to the addition reaction was observed again, and the liquid temperature was about 110 ° C. The appearance of the reaction solution became transparent.
The reaction solution was sampled 3 hours after the remainder of the catalyst solution was added, and when this was mixed with a water / ethanol solution of potassium hydroxide, no hydrogen gas was generated. Therefore, the addition reaction was completed. It was judged.
Next, 7.6 parts by mass of sodium hydrogen carbonate was added to the reaction solution at 85 ° C., and the mixture was neutralized by mixing for 30 minutes, and then the pressure was reduced to 9.3 kPa at 90 ° C. Was removed. The obtained reaction mixture was cooled to room temperature, returned to normal pressure, mixed with 2 parts by mass of diatomaceous earth, and subjected to pressure filtration to perform solid-liquid separation. As a filtrate, 860 parts by mass of a polyether-modified polysiloxane composition (hereinafter referred to as “crude product (ZA)”) having a light brown transparent uniform liquid appearance was obtained.

<Example 1>
(1) Hydrogenation treatment:
700 g of the crude product (ZA) obtained in Preparation Example 1 was transferred to a 1000 mL autoclave, 35 g of Raney nickel catalyst, 4 g of water, and 35 g of IPA were added, and then hydrogen gas was introduced at 140 ° C./8.0 MPa. The hydrogenation treatment was performed for 6 hours under the conditions described above. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Next, the Raney nickel catalyst was removed by pressure filtration, and the obtained filtrate was charged into a 1000 mL two-necked flask equipped with a reflux condenser and a nitrogen inlet, and the pressure was reduced to 140 ° C. and the temperature was increased to 1.3 kPa. 645 g of a polyether-modified polysiloxane composition having a colorless and transparent uniform liquid appearance (hereinafter referred to as “hydrogenated composition (ZB1)”) as a concentrate of the filtrate after removing a low boiling point over 5 hours. Got.

(2) Decomposition treatment using solid acid:
600 g of the hydrogenated composition (ZB1) obtained as described above was charged into a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, and zirconia sulfate “SZA- 60 "(manufactured by Japan Energy Co., Ltd.) and 6.0 g of purified water were added, and the system was stirred at 95 ° C for 7 hours for hydrolysis treatment.
The system was then depressurized to 1.2 kPa and heated to 115 ° C. to remove low boiling points over 2 hours. The obtained reaction mixture was cooled to 50 ° C. and returned to normal pressure, 6 g of activated carbon was added, and stirring was continued for 6 hours while allowing to cool, followed by solid-liquid separation by pressure filtration. As a filtrate, 561 g of a polyether-modified polysiloxane composition (composition of the present invention) having a colorless transparent uniform liquid appearance was obtained.

<Example 2>
Hydrogenation of crude product (ZA) in the same manner as in Example 1 except that 1.0 g of strongly acidic cation exchange resin “Amberlyst A36” (sold by Organo Corporation) was added instead of zirconia sulfate. By performing the treatment and the decomposition treatment using a solid acid, 568 g of a polyether-modified polysiloxane composition (the composition of the present invention) having a slightly yellow transparent uniform liquid appearance was obtained.

<Example 3>
By replacing with zirconia sulfate, 1.0 g of zeolite β was added, and the crude product (ZA) was subjected to hydrogenation treatment and decomposition treatment using a solid acid in the same manner as in Example 1 to obtain a colorless and transparent material. 565 g of a polyether-modified polysiloxane composition (composition of the present invention) having a uniform liquid appearance was obtained.

<Example 4>
(1) Decomposition treatment using solid acid:
600 g of the crude product (ZA) obtained in Preparation Example 1 was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet, and zirconia sulfate “SZA-60” [(stock) ) Manufactured by Japan Energy] 6.0 g and 6.0 g of purified water were added, and this system was stirred at 95 ° C. for 12 hours for hydrolysis treatment.
The system was then depressurized to 400 Pa, the temperature was raised to 119 ° C., and low-boiling components were removed over 1 hour. The obtained reaction mixture was cooled to room temperature and returned to normal pressure, and 10 g of diatomaceous earth was added and mixed, followed by pressure filtration to perform solid-liquid separation. As a filtrate, 535 g of a polyether-modified polysiloxane composition (hereinafter referred to as “decomposition-treated composition (ZC1)”) having a light brown transparent uniform liquid appearance was obtained.

(2) Hydrogenation treatment:
500 g of the decomposition-treated composition (ZC1) obtained as described above was transferred to a 1000 mL autoclave, and after adding 25 g of Raney nickel catalyst, 3.5 g of water, and 25 g of IPA, hydrogen gas was introduced, Hydrogenation treatment was performed for 6 hours under the conditions of 140 ° C. and 8.0 MPa. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Next, the Raney nickel catalyst was removed by pressure filtration, and the obtained filtrate was charged into a 1000 mL two-necked flask equipped with a reflux condenser and a nitrogen insertion port, and the pressure was reduced to 140 ° C. and the temperature was increased to 1.3 kPa. Remove low-boiling components over 5 hours, cool the filtrate concentrate to 50 ° C., return to normal pressure, add 5 g of activated carbon and allow to cool for 6 hours, then perform pressure filtration. Was subjected to solid-liquid separation to obtain 461 g of a polyether-modified polysiloxane composition (composition of the present invention) having a colorless and transparent uniform liquid appearance.

<Example 5>
(1) Decomposition treatment using solid acid:
600 g of the crude product (ZA) obtained in Preparation Example 1 was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, and a strongly acidic cation exchange resin ““ Amberlist A36 "(sold by Organo Co., Ltd.) (6.0 g) and purified water (60 g) were added, and the system was stirred at 95 ° C. for 12 hours for hydrolysis treatment.
The system was then depressurized to 800 Pa, heated to 117 ° C., and low-boiling components were removed over 1 hour. The obtained reaction mixture was cooled to room temperature and returned to normal pressure, and 10 g of diatomaceous earth was added and mixed, followed by pressure filtration to perform solid-liquid separation. As a filtrate, 540 g of a polyether-modified polysiloxane composition having a brown transparent uniform liquid appearance (hereinafter referred to as “decomposition-treated composition (ZC2)”) was obtained.

(2) Hydrogenation treatment:
500 g of the decomposition-treated composition (ZC2) obtained as described above was transferred to a 1000 mL autoclave, and after adding 25 g of Raney nickel catalyst, 3.5 g of water, and 25 g of IPA, hydrogen gas was introduced, Hydrogenation treatment was performed for 6 hours under the conditions of 140 ° C. and 8.0 MPa. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Next, the Raney nickel catalyst was removed by pressure filtration, and the obtained filtrate was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen insertion port, and the pressure was reduced to 140 ° C. After removing the low boiling point at 1.3 kPa for 5 hours, the filtrate concentrate was cooled to 50 ° C. and returned to normal pressure, 5 g of activated carbon was added, and the mixture was allowed to cool and then stirred for 6 hours. Solid-liquid separation was performed by pressure filtration to obtain 455 g of a polyether-modified polysiloxane composition (the composition of the present invention) having a slightly yellow transparent uniform liquid appearance.

<Example 6>
(1) Decomposition treatment using solid acid:
600 g of the crude product (ZA) obtained in Preparation Example 1 was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet, and 12.0 g of zeolite β and purified water 60 g was added, and the system was stirred at 95 ° C. for 12 hours for hydrolysis treatment.
The system was then depressurized to 700 Pa and heated to 115 ° C. to remove low boiling points over 1 hour. The obtained reaction mixture was cooled to room temperature and returned to normal pressure, and 10 g of diatomaceous earth was added and mixed, followed by pressure filtration to perform solid-liquid separation. As a filtrate, 540 g of a polyether-modified polysiloxane composition (hereinafter referred to as “decomposition-treated composition (ZC3)”) having a light brown transparent uniform liquid appearance was obtained.

(2) Hydrogenation treatment:
500 g of the decomposition-treated composition (ZC3) obtained as described above was transferred to a 1000 mL autoclave, and after adding Raney nickel catalyst 25 g, water 3.5 g, and IPA 25 g, hydrogen gas was introduced, Hydrogenation treatment was performed for 6 hours under the conditions of 140 ° C. and 8.0 MPa. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Next, the Raney nickel catalyst was removed by pressure filtration, and the obtained filtrate was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen insertion port, and the pressure was reduced to 140 ° C. The low-boiling fraction was removed at 1.3 kPa for 5 hours, and the filtrate concentrate was cooled to 50 ° C. and returned to normal pressure. 451 g of a polyether-modified polysiloxane composition (the composition of the present invention) having a uniform liquid appearance was obtained.

<Example 7>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Example 1 and uniformly dissolving it, a polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Example 8>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Example 2 and dissolving it uniformly, a polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Example 9>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Example 3 and uniformly dissolving it, a polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Example 10>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Example 4 and uniformly dissolving it, a polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Example 11>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Example 5 and uniformly dissolving it, a polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Example 12>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Example 6 and uniformly dissolving it, a polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Comparative Example 1>
The crude product (ZA) obtained in Preparation Example 1 was prepared.

<Comparative example 2>
In a 1000 mL four neck flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet, the formula: (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₁₀ [(CH ₃ ) HSiO] ₅ Si 240 g of organohydrogenpolysiloxane represented by (CH ₃ ) ₃ (hydrogen gas generation amount = 93.2 mL / g) and poly represented by the formula: CH ₂ ═CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ Oxyalkylene 222g (a part of the amount used) was charged, the temperature was increased under stirring to stabilize the liquid temperature at 74 ° C, and then 0.10g of 10% ethanol solution of chloroplatinic acid (catalyst) (catalyst) When a part of the solution was added, heat generation due to an addition reaction (hydrosilylation reaction) was observed, and the liquid temperature rose to about 120 ° C.
When the liquid temperature dropped to 109 ° C., 445 g of polyoxyalkylene represented by CH ₂ ═CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ (remaining amount used) was added, and the liquid temperature was stabilized at 73 ° C. After confirming that, 0.10 g of 10% ethanol solution of chloroplatinic acid (catalyst) (the remainder of the amount used) was added, heat generation due to the addition reaction was observed again, and the liquid temperature rose to about 110 ° C., The appearance of the reaction solution became transparent.
The reaction solution was sampled 3 hours after the remainder of the catalyst solution was added, and when this was mixed with a water / ethanol solution of potassium hydroxide, no hydrogen gas was generated. Therefore, the addition reaction was completed. It was judged.
Next, 9.1 g of 0.1 mol / L hydrochloric acid was added to the reaction solution at 90 ° C. and subjected to hydrolysis treatment for 5 hours. Then, the pressure was reduced to 1.6 kPa, and the temperature was increased as it was to 115 ° C. and 130 Pa. After removing hydrochloric acid and low-boiling components for 1 hour, the reaction solution was returned to normal pressure and cooled, and 4.5 g of sodium bicarbonate was added to the reaction solution at 93 ° C. and mixed for 1 hour, and then the pressure was reduced to 130 Pa. The temperature was raised as it was, and the low boiling point content was removed again at 118 ° C. and 130 Pa for 1.5 hours. The obtained reaction mixture was cooled to room temperature, returned to normal pressure, 10 g of diatomaceous earth was mixed, and solid-liquid separation was performed by performing pressure filtration. As a filtrate, 805 g of a polyether-modified polysiloxane composition (comparative composition purified by a hydrolysis method using dilute hydrochloric acid) having a brown transparent uniform liquid appearance was obtained.

<Comparative Example 3>
4000 g of the crude product (ZA) obtained in Preparation Example 1 was transferred to a 10 L autoclave, 200 g of Raney nickel catalyst, 25 g of water, and 200 g of IPA were added, hydrogen gas was introduced, and 140 ° C./8.0 MPa The hydrogenation treatment was performed for 6 hours under the conditions described above. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Next, the Raney nickel catalyst was removed by pressure filtration, and the obtained filtrate was charged into a 5000 mL two-necked flask equipped with a thermometer, a reflux condenser and a nitrogen inlet, and the pressure was reduced to 140 ° C. Polyether-modified polysiloxane composition having a colorless and transparent uniform liquid appearance (comparative composition purified by hydrogenation) as a concentrate of the filtrate after removing low boiling point at 1.3 kPa for 6 hours 3760 g was obtained.

<Comparative example 4>
700 g of the crude product (ZA) obtained in Preparation Example 1 was transferred to a 1000 mL autoclave, and 35 g of Raney nickel catalyst and a phosphate buffer (pH consisting of phosphoric acid, citric acid and sodium hydroxide were adjusted to 3.3. Buffer solution) 3.5 g, water 4 g, and IPA 35 g were added, hydrogen gas was introduced, and hydrogenation treatment was performed for 6 hours at 140 ° C. and 8.0 MPa. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Subsequently, Raney nickel catalyst and the like are removed by pressure filtration, and the obtained filtrate is charged into a 1000 mL two-necked flask equipped with a reflux condenser and a nitrogen insertion port, and the pressure is reduced to 140 ° C. and the temperature is increased to 130 Pa at 5 Low boiling content was removed over time, and the resulting concentrate was cooled to room temperature, returned to normal pressure, mixed with 10 g of diatomaceous earth, and subjected to pressure filtration to perform solid-liquid separation. As a filtrate, 590 g of a polyether-modified polysiloxane composition (comparative composition purified by hydrogenation in the presence of a phosphate buffer) having a pale yellow transparent uniform liquid appearance was obtained.

<Comparative Example 5>
700 g of the crude product (ZA) obtained in Preparation Example 1 was transferred to a 1000 mL autoclave, 35 g of Raney nickel catalyst, 1.4 g of acid clay, 8 g of water, and 35 g of IPA were added, and hydrogen gas was introduced. The hydrogenation treatment was performed for 6 hours under the conditions of 140 ° C. and 8.0 MPa. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Next, the Raney nickel catalyst and the acid clay were removed by pressure filtration, and the obtained filtrate was charged into a 1000 mL two-necked flask equipped with a reflux condenser and a nitrogen inlet, and the pressure was reduced to 140 ° C. and the temperature was raised to 270 Pa. The low-boiling fraction was removed for 5 hours, and the resulting concentrate was cooled to room temperature, returned to normal pressure, 10 g of diatomaceous earth was mixed, and solid-liquid separation was performed by pressure filtration. As a filtrate, 595 g of a polyether-modified polysiloxane composition (comparative composition purified by hydrogenation in the presence of acid clay and water) having a light yellow transparent uniform liquid appearance was obtained.

<Comparative Example 6>
600 g of the composition obtained in Comparative Example 3 (comparative composition purified by hydrogenation) was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. Then, 6.0 g of 0.1 mol / L nitric acid aqueous solution was added, and this system was stirred at 93 ° C. for 1 hour for hydrolysis treatment. Here, the reaction solution was colored orange.
Next, 3.0 g of sodium bicarbonate was added to the reaction solution and mixed for 1 hour for neutralization, and then the pressure was reduced and the temperature was raised to 115 ° C., and the low boiling point was removed at 130 Pa for 2 hours. The obtained reaction mixture was cooled to 50 ° C., returned to normal pressure, mixed with 10 g of diatomaceous earth, and subjected to pressure filtration to perform solid-liquid separation. As a filtrate, 540 g of a polyether-modified polysiloxane composition (comparative composition purified by hydrolysis using hydrogenation and dilute hydrochloric acid) having a dark reddish brown uniform liquid appearance was obtained.
In addition, since it was clear that the obtained composition was changing severely judging from color tone, the various measurement mentioned later was not performed.

<Comparative Example 7>
600 g of the composition obtained in Comparative Example 3 (comparative composition purified by hydrogenation) was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. Then, 6.0 g of a 0.1 mol / L phosphoric acid aqueous solution was added, and the system was stirred at 94 ° C. for 3.5 hours for hydrolysis treatment.
Next, the pressure was reduced to 650 Pa and the temperature was raised. After removing the low boiling point at 111 ° C. for 1 hour, the temperature was lowered to 93 ° C., and 3.0 g of sodium bicarbonate was added and mixed for 30 minutes for neutralization treatment. went. The pressure was reduced again, the temperature was raised to 113 ° C., and low-boiling components were removed at 130 Pa for 1 hour. The reaction mixture was cooled to 50 ° C. and returned to normal pressure, and 10 g of diatomaceous earth was mixed and subjected to pressure filtration to perform solid-liquid separation. As a filtrate, 548 g of a polyether-modified polysiloxane composition (comparative composition purified by hydrolysis using hydrogenation and phosphoric acid aqueous solution) having a colorless transparent uniform liquid appearance was obtained.

<Comparative Example 8>
600 g of the composition obtained in Comparative Example 3 (comparative composition purified by hydrogenation) was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. Then, 6.0 g of 0.1 mol / L trifluoroacetic acid was added, and the system was stirred at 60 ° C. for 1 hour for hydrolysis treatment.
Next, the pressure was reduced to 130 Pa and the temperature was raised. After removing the low boiling point at 115 ° C. for 1 hour, the temperature was lowered to 83 ° C., and 3.0 g of sodium hydrogencarbonate was added and mixed for 30 minutes for neutralization treatment. went. The pressure was reduced again, the temperature was raised to 116 ° C., and low-boiling components were removed at 130 Pa for 1.5 hours. The reaction mixture was cooled to 50 ° C. and returned to normal pressure, and 10 g of diatomaceous earth was mixed and subjected to pressure filtration to perform solid-liquid separation. As a filtrate, 556 g of a polyether-modified polysiloxane composition (comparative composition purified by a hydrolysis method using hydrogenated and trifluoroacetic acid aqueous solution) having a colorless transparent uniform liquid appearance was obtained.

<Comparative Example 9>
600 g of the composition obtained in Comparative Example 3 (comparative composition purified by hydrogenation) was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. Then, 6.0 g of 0.1 mol / L acetic acid aqueous solution was added, and the system was stirred at 95 ° C. for 3 hours for hydrolysis treatment.
Next, the pressure is reduced to 130 Pa, the temperature is raised, low boiling components are removed at 117 ° C. for 2 hours, the temperature is lowered to 50 ° C., and the pressure is returned to normal pressure. 591 g of a composition (comparative composition purified by a hydrolysis method using hydrogenation and aqueous acetic acid) was obtained.

<Comparative Example 10>
600 g of the composition obtained in Comparative Example 3 (comparative composition purified by hydrogenation) was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. Then, 6.0 g of 0.1 mol / L acetic acid aqueous solution was added, and the system was stirred at 95 ° C. for 3 hours for hydrolysis treatment.
Next, the temperature was lowered to 90 ° C., 3.0 g of sodium hydrogen carbonate was added, and the mixture was mixed for 30 minutes for neutralization. The pressure is reduced, the temperature is raised to 118 ° C., the low boiling point is removed at 130 Pa for 1 hour, the temperature is lowered to 50 ° C., the pressure is returned to normal pressure, 10 g of diatomaceous earth is mixed, and solid-liquid separation is performed by pressure filtration. did. As a filtrate, 573 g of a polyether-modified polysiloxane composition (comparative composition purified by hydrolysis using hydrogenation and acetic acid aqueous solution) having a colorless transparent uniform liquid appearance was obtained.

<Comparative Example 11>
600 g of the composition obtained in Comparative Example 3 (comparative composition purified by hydrogenation) was charged into a 1000 mL four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet. Then, 6.0 g of 0.1 mol / L hydrochloric acid aqueous solution was added, and the system was stirred at 95 ° C. for 1 hour for hydrolysis treatment.
Next, 3.0 g of sodium bicarbonate was added and mixed for 1 hour for neutralization, and then the pressure was reduced to 130 Pa, the temperature was raised, and the low boiling point was removed at 119 ° C. for 1 hour. The reaction mixture was cooled to 50 ° C. and returned to normal pressure, and 10 g of diatomaceous earth was mixed and subjected to pressure filtration to perform solid-liquid separation. As a filtrate, 561 g of a polyether-modified polysiloxane composition (comparative composition purified by hydrolysis using hydrogenation and dilute hydrochloric acid) having a colorless and transparent uniform liquid appearance was obtained.

<Comparative Example 12>
In a 1000 mL four neck flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet, the formula: (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₁₀ [(CH ₃ ) HSiO] ₅ Si 240 g of organohydrogenpolysiloxane represented by (CH ₃ ) ₃ (hydrogen gas generation amount = 93.2 mL / g) and poly represented by the formula: CH ₂ ═CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ Oxyalkylene 222g (a part of the amount used) was charged, the temperature was increased under stirring to stabilize the liquid temperature at 74 ° C, and then 0.10g of 10% ethanol solution of chloroplatinic acid (catalyst) (catalyst) When a part of the solution was added, heat generation due to an addition reaction (hydrosilylation reaction) was observed, and the liquid temperature rose to about 120 ° C.
When the liquid temperature dropped to 109 ° C., 445 g of polyoxyalkylene represented by CH ₂ ═CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ (remaining amount used) was added, and the liquid temperature was stabilized at 73 ° C. After confirming that, 0.10 g of 10% ethanol solution of chloroplatinic acid (catalyst) (the remainder of the amount used) was added, heat generation due to the addition reaction was observed again, and the liquid temperature rose to about 110 ° C., The appearance of the reaction solution became transparent.
The reaction solution was sampled 3 hours after the remainder of the catalyst solution was added, and when this was mixed with a water / ethanol solution of potassium hydroxide, no hydrogen gas was generated. Therefore, the addition reaction was completed. It was judged.
Next, 9.1 g of a 0.1 mol / L hydrochloric acid aqueous solution was added to the reaction solution at 84 ° C. and the temperature was raised. After hydrolysis at 90 ° C. for 1.5 hours, 3.9 g of sodium bicarbonate was added. Was added and mixed for 1 hour for neutralization, and then the pressure was reduced to 130 Pa, and the low boiling point content was removed at 88 ° C. for 1 hour. The obtained reaction mixture was cooled to 50 ° C., returned to normal pressure, mixed with 10 g of diatomaceous earth and subjected to pressure filtration to separate into solid and liquid to obtain 824 g of a filtrate having a light brown transparent uniform liquid appearance. It was.

  500 g of the obtained filtrate was transferred to a 1000 mL autoclave, Raney nickel catalyst 25 g, water 1 g, and IPA 25 g were added, hydrogen gas was introduced, and the conditions were 140 ° C. and 8.0 MPa for 6 hours. Hydrogenation treatment was performed. Next, the treated reaction mixture was cooled to 60 ° C. and blown with hydrogen gas, and then replaced with nitrogen gas. Subsequently, the Raney nickel catalyst was removed by pressure filtration, and the obtained filtrate was charged into a 1000 mL two-necked flask equipped with a reflux condenser and a nitrogen insertion port, and the temperature was reduced to 140 ° C. and the temperature was increased to 130 Pa for 5 hours. The low boiling point was removed over time. As a concentrate of the filtrate, 466 g of a polyether-modified polysiloxane composition having a colorless and transparent uniform liquid appearance (comparative composition purified by hydrolysis using dilute hydrochloric acid and hydrogenation) was obtained.

<Comparative Example 13>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Comparative Example 11 and dissolving it uniformly, a comparative polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Comparative example 14>
By adding 0.10 g of vitamin E to 200 g of the composition obtained in Comparative Example 12 and uniformly dissolving it, a comparative polyether-modified polysiloxane composition containing an antioxidant at a ratio of 500 ppm was obtained.

<Measurement of total unsaturation of composition>
Each of the compositions of the present invention obtained in Examples 1 to 12 above and the comparative compositions obtained in Comparative Examples 1 to 5 and Comparative Examples 7 to 14 was determined according to JIS K 1557. Saturation was measured. The results are shown in Table 1 below.
Here, the total degree of unsaturation is calculated by the following formula described in JIS K1557.

Calculation formula: D = 0.1 × A × f / S ₁

Calculation formula: U = [0.1 × (CB) × f / S ₂ ] −D

here,
D: Acidity [meq (milli equivalent) / g],
A: Amount of methyl alcohol solution of 0.1 mol / L potassium hydroxide required for acidity measurement (mL),
f: factor of 0.1 mol / L potassium hydroxide in methyl alcohol,
S ₁ : Mass (g) of acidity measurement sample,
U: total degree of unsaturation [meq (milli equivalent) / g],
C: Amount (mL) of 0.1 mol / L potassium hydroxide methyl alcohol solution required for measurement of total unsaturation,
B: The amount (mL) of 0.1 mol / L potassium hydroxide methyl alcohol solution required for the blank test for measuring the total unsaturation,
S ₂ : Mass (g) of the total unsaturation measurement sample.

  The acidity measurement operation and the total unsaturation operation were performed as follows.

(Measurement of acidity)
Take 75 mL of methyl alcohol in an Erlenmeyer flask, add a few drops of a phenolphthalein methyl alcohol solution as an indicator, and titrate with a 0.1 mol / L potassium hydroxide methyl alcohol solution to give a slight red color for at least 15 seconds. Was properly weighed up to 0.01 g, dissolved well, titrated with the 0.1 mol / L potassium hydroxide methyl alcohol solution, and the end point was kept at a slight red color for at least 15 seconds. In the above, “methyl alcohol” used was a reagent-grade product.

(Measurement of total unsaturation)
75 mL of a mercuric acetate methyl alcohol solution was taken into a 200 mL Erlenmeyer flask using a whole pipette, and about 45 g of a sample was accurately weighed to 0.01 g, dissolved well, and allowed to stand at room temperature for 30 minutes. After standing, add 4.50 g of sodium bromide (special grade reagent) to the Erlenmeyer flask and shake well, add the phenolphthalein methyl alcohol solution as an indicator, The end point was determined by titration and maintaining a slight red color for at least 15 seconds.
This test was performed separately under the same conditions. In addition, the methyl alcohol solution of mercuric acetate was prepared by dissolving 40 g of mercuric acetate (reagent special grade) in methyl alcohol (reagent special grade) to 1000 mL. During the blank test, 1 to 2 drops of acetic acid was added so that 0.30 to 1.5 mL of the potassium hydroxide methyl alcohol solution was consumed. This solution was prepared immediately before the measurement and filtered before use.

In Table 1, the units of acidity (D) and total unsaturation (U) are “meq (milli equivalent) / g”, respectively. In Table 1,
S ₁ : Mass (g) of acidity measurement sample,
A: Amount of methyl alcohol solution of 0.1 mol / L potassium hydroxide required for acidity measurement (mL),
S ₂ : Mass (g) of the total unsaturation measurement sample,
C: Amount (mL) of 0.1 mol / L potassium hydroxide methyl alcohol solution required for measurement of total unsaturation,
B: The amount (mL) of 0.1 mol / L potassium hydroxide methyl alcohol solution required for the blank test for measuring the total unsaturation.

For reference, the compositions obtained in Comparative Example 2 and Comparative Example 12 were subjected to ¹ H NMR measurement at 500 MHz using CDCl ₃ as a solvent, and ¹ H signal of unsaturated double bond. The degree of unsaturation was calculated from Here, 5.1 ppm to 5.3 ppm of d, d (2H) was used for the allyl group, and 6.1 ppm to 6.3 ppm of d (1H) was used for the calculation.
As a result, the degree of unsaturation of the composition according to Comparative Example 2 (measured value according to JIS K 1557 = 0.1364 meq / g) was 0.105, and the degree of unsaturation of the composition according to Comparative Example 12 (JIS The measured value according to K 1557 = 0.00120 meq / g) was not detected because no signal was obtained.

<Measurement of total amount of carbonyl in composition (A)>
For each of the compositions of the present invention obtained in Examples 1 to 12 and the comparative compositions obtained in Comparative Examples 1 to 5 and Comparative Examples 7 to 14, the total amount of carbonyl was determined according to the measurement method of the present invention. (Measurement of carbonyl value, measurement of calibration curve, quantification of carbonyls).
Here, as the “ultra high purity alcohol (A)” constituting the reaction solvent and the diluting solvent, a commercially available product “ethanol (99.8) Infinity Pure” manufactured in 3 months before use (Wako Pure Chemical Industries, Ltd.) And unopened (total amount of aldehyde / ketone = 2.4 to 2.9 ppm) until just before use.

[Preparation Example 1A]
To 1.29 g of concentrated sulfuric acid (96%) for precise analysis, 5.15 g of purified water was added and dissolved to prepare dilute sulfuric acid having a concentration of about 20%. Next, the bottle containing 100 mL of ultra-high purity alcohol (A) is opened, and 6.44 g of the above diluted sulfuric acid is directly added to the bottle, and the bottle is capped and shaken and homogenized. Then, an alcohol solution of diluted sulfuric acid [1.2% (wt / vol) as sulfuric acid concentration] was prepared. Hereinafter, this solution is referred to as “dilute sulfuric acid solution (1A)”. This preparation operation was performed within 1 hour before measuring the absorbance.

[Preparation Example 2A]
After opening the bottle containing 100 mL of ultra high purity alcohol (A), 50 mg of 2,4-DNPH (special grade reagent containing an equal amount of water) was directly added to the bottle, and the bottle was capped. The 2,4-DNPH is completely dissolved by the ultra-high purity alcohol (A) by applying it to an ultrasonic cleaner for 5 minutes to obtain a 0.025% (wt / vol) 2,4-DNPH alcohol solution. Was prepared. Hereinafter, this solution is referred to as “2,4-DNPH solution (2A)”. This preparation operation was performed within 1 hour before measuring the absorbance.

[Preparation Example 3A]
Open the bottle containing 100 mL of ultrapure alcohol (A), add 4.0 g of potassium hydroxide (pellet-like reagent special grade) directly to this bottle, cover the bottle, and until the pellet disappears After shaking and mixing, it is applied to an ultrasonic cleaner for 10 minutes to completely dissolve potassium hydroxide with ultra high purity alcohol (A), and a 4.0% (wt / vol) potassium hydroxide alcohol solution Was prepared. Hereinafter, this solution is referred to as “potassium hydroxide solution (3A)”. This preparation operation was performed within 1 hour before measuring the absorbance.

[Measurement of carbonyl value]
2.00 g of a sample (composition of the present invention or a composition for comparison), 2.00 g of ultra-high purity alcohol (A), and 21.00 g of purified water are charged into a 50 mL screw tube with a lid and mixed. Then, 25.00 g of a sample solution (Sa) having a sample concentration of 8% by mass was prepared.
The composition obtained in Comparative Example 1 has a very large carbonyl value, and the absorbance (A ₁ ) is 0 when the subsequent step is performed using a sample solution (Sa) having a sample concentration of 8% by mass. Since it was expected that accurate absorbance measurement could not be performed exceeding .80, when the composition obtained in Comparative Example 1 was used as a sample, 0.200 g of the sample and 3.80 g of ultra high purity alcohol (A) were used. Then, 21.00 g of purified water was charged in a 50 mL screw tube with a lid, and a liquid prepared by mixing them (sample concentration = 0.8% by mass) was used as a sample solution (Sa).

  1.250 g of the obtained sample solution (Sa) and 3.750 g of ultra-high purity alcohol (A) were charged into a 50 mL volumetric flask and mixed together to obtain a sample solution (Sb) having a sample concentration of 2% by mass. 5.000 g was prepared.

In the volumetric flask containing 5.000 g of the sample solution (Sb), 3 mL of the diluted sulfuric acid solution (1A) obtained in Preparation Example 1A and the 2,4-DNPH solution (2A) obtained in Preparation Example 2A 5 mL was added with a whole pipette.
Next, after plugging the volumetric flask and winding a Teflon (registered trademark) seal around it to ensure airtightness, the volumetric flask is placed in a constant temperature bath at 60 ° C. and heated for 30 minutes. Was reacted with 2,4-DNPH.
Subsequently, the said volumetric flask was taken out from the thermostat and left to stand at room temperature for 30 minutes.
Next, the stopper of the volumetric flask was opened, 10 mL of the potassium hydroxide solution (3A) obtained in Preparation Example 3A was added with a whole pipette, and the volumetric flask was shaken and mixed.
After 8 minutes from the addition of 10 mL of potassium hydroxide solution (3A), ultra high purity alcohol (A) was added as a diluent solvent, and this system was shaken to mix a reaction solution with a total volume of 50 mL (basic reaction solution). ) Was prepared. Next, a part of the reaction solution (about 3 mL) was passed through a membrane filter having a pore size of 0.2 μm, and the precipitated neutralized salt (potassium sulfate) was separated by filtration to remove the turbidity of the reaction solution.
After 15 minutes from the addition of 10 mL of potassium hydroxide solution (3A), the above-mentioned reaction solution from which turbidity had been removed was placed in an absorption cell (the length of the liquid layer = 1 cm), and the absorbance at 430 nm (with a spectrophotometer) a ₁₎ was measured.

On the other hand, as a blank test, instead of the sample solution (Sb), a mixed solvent 5.000 g composed of 3.850 g of ultrahigh purity alcohol (A) and 1.150 g of purified water was used, and the same operation as above [ Addition of dilute sulfuric acid solution (1A), addition of 2,4-DNPH solution (2A), heating and cooling of the resulting mixed solution, addition of potassium hydroxide solution (3A), ultra high purity alcohol (A) the solution obtained by performing the filtration removal] of addition and neutralization salts of diluting solvent were placed in the absorption cell (length of the liquid layer = 1 cm), the absorbance of 430nm in the same manner as described above the (a ₂₎ was measured .

The carbonyl value (CV) was determined by substituting the absorbance (A ₁ ) and absorbance (A ₂ ) thus obtained into the formula: CV = (A ₁ -A ₂ ) /0.1.
When the composition obtained in Comparative Example 1 was used as a sample, the carbonyl value was determined by substituting into the formula: CV = (A ₁ −A ₂ ) /0.01.

[Measurement of calibration curve]
By dissolving propanal (propionaldehyde) in the ultra high purity alcohol (A), standard samples (i) to (viii) having a propanal concentration of 5 ppm, 20 ppm, 50 ppm, 100 ppm, 200 ppm, 800 ppm, 4000 ppm, 40000 ppm Was prepared.

For the standard samples (i) to (v), the absorbance was measured in the same manner as in the method for measuring the carbonyl value of the composition of the present invention or the comparative composition (excluding the composition obtained in Comparative Example 1). (A ₁ ) and absorbance (A ₂ ) were measured, and these were substituted into the formula: CV = (A ₁ -A ₂ ) /0.1 to determine the carbonyl value.

For the standard sample (vi), 1.00 g of the standard sample (vi), 3.00 g of ultra-high purity alcohol (A), and 21.00 g of purified water were charged into a 50 mL screw tube with a lid and mixed. In the same manner as in the method for measuring the carbonyl value of the composition of the present invention or the comparative composition, except that the liquid prepared (sample concentration = 4.0% by mass) was used as the sample solution (Sa). The absorbance (A ₁ ) and the absorbance (A ₂ ) were measured, and these were substituted into the formula: CV = (A ₁ -A ₂ ) /0.05 to determine the carbonyl value.

For the standard sample (vii), 0.200 g of the standard sample (vii), 3.80 g of ultra-high purity alcohol (A), and 21.00 g of purified water were charged into a 50 mL screw tube with a lid and mixed. In the same manner as the method for measuring the carbonyl value of the composition of the present invention or the comparative composition, except that the liquid prepared (sample concentration = 0.8% by mass) was used as the sample solution (Sa). The absorbance (A ₁ ) and absorbance (A ₂ ) were measured, and these were substituted into the formula: CV = (A ₁ -A ₂ ) /0.01 to determine the carbonyl value.

For the standard sample (viii), 0.020 g of the standard sample (viii), 3.98 g of ultra high purity alcohol (A), and 21.00 g of purified water were charged into a 50 mL screw tube with a lid, and these were mixed. In the same manner as in the method for measuring the carbonyl value of the composition of the present invention or the composition for comparison, except that the liquid prepared (sample concentration = 0.08 mass%) was used as the sample solution (Sa). The absorbance (A ₁ ) and absorbance (A ₂ ) were measured, and these were substituted into the formula: CV = (A ₁ -A ₂ ) /0.001 to determine the carbonyl value.

  The relationship between the carbonyl value of the standard samples (i) to (viii) and the propanal concentration determined as described above is shown in Table 2 below and FIGS.

As shown in FIGS. 1 to 3, the carbonyl values of the standard samples (i) to (viii) increased linearly depending on (proportional to) the propanal concentration, and an effective calibration curve was obtained. .
From the obtained calibration curve, for the sample (composition of the present invention and comparative composition) for which the total amount of carbonyl is unknown, the carbonyl total amount in terms of propanal is calculated from the measured carbonyl value (CV) according to the following formula. Can be sought.

  Formula: Propanal concentration [ppm] = CV / 0.0041

[Quantification of carbonyls (measurement of total amount of carbonyl)]
For each of the composition of the present invention and the comparative composition, the total amount of carbonyl (propanal conversion) in the composition from the measured carbonyl value and the calibration curve (propanal concentration [ppm] = CV / 0.0041) Value). The results are shown in Table 3 below.

<Measurement of carbonyl value of composition (B)>
For each of the composition of the present invention obtained in Example 1 and the comparative composition obtained in Comparative Example 3 and Comparative Example 11, a method different from the measurement method of the present invention, that is, non-patent literature The carbonyl value was measured according to a method in accordance with 1 [Standard oil analysis test method (2.5.4-1996 carbonyl value)].
Here, the “benzene (B)” constituting the reaction solvent and the dilution solvent is a commercially available benzene “benzene (for spectroscopic analysis)” (manufactured by Wako Pure Chemical Industries, Ltd.), which is unopened until just before use. I used one.

[Preparation Example 1B]
Open the bottle containing 100 mL of benzene (B), add 4.30 g of trichloroacetic acid (special grade reagent) directly to this bottle, cap the bottle, shake and mix with benzene (B) Trichloroacetic acid was completely dissolved to prepare a benzene solution of 4.30% (wt / vol) trichloroacetic acid. Hereinafter, this solution is referred to as “trichloroacetic acid solution (1B)”.
In addition, this preparation operation was performed wearing protective gear and protective glasses in an enclosure hood in a state where the local exhaust device was operated. This preparation operation was performed within 1 hour before measuring the absorbance.

[Preparation Example 2B]
A 0.025% (wt / vol) 2,4-DNPH benzene solution was prepared in the same manner as in Preparation Example 2A, except that 100 mL of benzene (B) was used in place of the ultra high purity alcohol (A). . Hereinafter, this solution is referred to as “2,4-DNPH solution (2B)”.
In addition, this preparation operation was performed wearing protective gear and protective glasses in an enclosure hood in a state where the local exhaust device was operated. This preparation operation was performed within 1 hour before measuring the absorbance.

[Measurement of carbonyl value]
2.00 g of a sample (the composition of the present invention or a composition for comparison) and 23.00 g of benzene (B) were charged into a 50 mL screw tube with a lid, and both were mixed to obtain a sample concentration of 8% by mass. 25.00 g of sample solution (Sa) was prepared.
1.250 g of the obtained sample solution (Sa) and 3.750 g of benzene (B) were charged into a 50 mL volumetric flask, and both were mixed to obtain 5.000 g of sample solution (Sb) having a sample concentration = 2 mass%. Was prepared.
The sample solution (Sa) and the sample solution (Sb) were prepared by wearing protective gear and protective glasses in an enclosure hood in a state where the local exhaust device was operated.

In the volumetric flask containing 5.000 g of the sample solution (Sb), 3 mL of the trichloroacetic acid solution (1B) obtained in Preparation Example 1B and the 2,4-DNPH solution (2B) obtained in Preparation Example 2B 5 mL was added with a whole pipette.
The addition operation of the trichloroacetic acid solution (1B) and the 2,4-DNPH solution (2B) was performed by wearing protective equipment and protective glasses in an enclosure hood in a state where the local exhaust device was operated.

Next, the volumetric flask is stoppered, and a Teflon (registered trademark) seal is wound around the volumetric flask to ensure airtightness. Then, the volumetric flask is placed in a closed thermostatic oven (60 ° C.) equipped with an exhaust device. The carbonyls contained in the sample were reacted with 2,4-DNPH by heating for 30 minutes while operating the exhaust device.
Subsequently, the said volumetric flask was taken out from the thermostat and left to stand at room temperature for 30 minutes.

Next, the stopper of the volumetric flask was opened, 10 mL of the potassium hydroxide solution (3A) obtained in Preparation Example 3A in the method of the present invention was added with a whole pipette, and the volumetric flask was shaken and mixed.
8 minutes after adding 10 mL of potassium hydroxide solution (3A), benzene (B) was added as a diluent solvent, and shaken to prepare a reaction solution (basic reaction solution) having a total amount of 50 mL. This operation was performed by wearing protective equipment and protective glasses in an enclosed hood with the local exhaust device operated.

15 minutes after adding 10 mL of potassium hydroxide solution (3A), the reaction solution is put into an absorption cell (length of liquid layer = 1 cm), and absorbance (A ₁ ) at 430 nm is measured with an absorptiometer. did. The absorbance was measured after the absorption cell containing the reaction solution was completely sealed and sealed.

On the other hand, as a blank test, 5.00 mg of benzene (B) was used instead of the sample solution (Sb), and the same operation as above [addition of trichloroacetic acid solution (1B), 2,4-DNPH solution (2B ), Heating and cooling of the resulting mixed solution, addition of potassium hydroxide solution (3A), addition of diluting solvent consisting of benzene (B)] are added to the absorption cell (the length of the liquid layer). The absorbance (A ₂ ) at 430 nm was measured in the same manner as described above.

The carbonyl value (CV) was determined by substituting the absorbance (A ₁ ) and absorbance (A ₂ ) thus obtained into the formula: CV = (A ₁ -A ₂ ) /0.1. The results are shown in Table 4 below together with those obtained according to the measurement method of the present invention.

The following is considered from the results shown in Table 4.
(1) This method has a higher detection limit than the method of the present invention.
(2) The magnitude relationship between the carbonyl value measured by this method and the carbonyl value measured by the method of the present invention is the same.
(3) The carbonyl value measured by this method is smaller than the carbonyl value measured by the method of the present invention. This is because, when benzene is used as a solvent as in this method, the reaction between 2,4-DNPH and carbonyls is carried out in a non-aqueous system, so aldehyde condensates such as acetals (potential carbonyl compounds) This is considered to be because it could not be hydrolyzed quantitatively.
Therefore, this method cannot measure the total amount of carbonyl including potential carbonyl compounds.

<Measurement of carbonyl value of composition (C)>
About each of the composition of this invention obtained in said Example 1, the comparative composition obtained in the comparative example 3 and the comparative example 11, as a reaction solvent and a diluting solvent, an ultrahigh purity alcohol (A) is used. Instead, the present invention was used except that commercially available ethanol “special grade ethanol” (manufactured by Wako Pure Chemical Industries, Ltd.), which was not opened until just before use (total amount of aldehyde / ketone = 13 ppm), was used. The absorbance (A ₁ ) and absorbance (A ₂ ) were measured in the same manner as in the above measurement method [Measurement (A) above] to determine the carbonyl value. The results are shown in Table 5 below together with those obtained according to the measurement method of the present invention.

  As shown in Table 5, when ethanol with a total amount of aldehydes and ketones (in the table, AK total amount) of 13 ppm was used instead of ultra-high purity alcohol (A), all three types of compositions measured The carbonyl value (CV) became a negative value. Therefore, it is impossible to measure the proper total amount of carbonyl by this method.

<Measurement of carbonyl value of composition (D)>
For each of the composition of the present invention obtained in Example 1 and the comparative composition obtained in Comparative Example 11, a reaction solvent and a dilution solvent were used instead of the ultrahigh purity alcohol (A). A commercially available product “Ethanol (99.8) Infinity Pure” (manufactured by Wako Pure Chemical Industries, Ltd.) manufactured in the previous 7 months and unopened until the time of use (total amount of aldehyde / ketone = 5 ppm) Except for the use, the absorbance (A ₁ ) and absorbance (A ₂ ) were measured in the same manner as in the measurement method of the present invention [Measurement (A) above] to determine the carbonyl value.
The results are shown in Table 6 below together with those obtained according to the measurement method of the present invention.

  As shown in Table 6, instead of the ultra-high purity alcohol (A), when ethanol having a total amount of aldehyde / ketone (in the table, AK total amount) of 5 ppm was used, the two types of compositions measured were The carbonyl value (CV) became a negative value. Therefore, it is impossible to measure the proper total amount of carbonyl by this method.

<Measurement of index value of total amount of ionic impurities>
About each of the composition of this invention obtained in said Examples 1-12 and the comparative composition obtained in Comparative Examples 1-5 and Comparative Examples 7-14, this was melt | dissolved in purified water. The electrical conductivity (σ ₁ ) of the 2.00% (wt / wt) aqueous solution and the electrical conductivity (σ ₀ ) of the purified water are measured, and the ionicity determined by (σ ₁ −σ ₀ ) The index value of the total amount of impurities was measured. The results are shown in Table 7 below.
In addition, the detail of the measuring method of electrical conductivity is as follows. The purified water used has an electric conductivity (σ ₀ ) of 200 μS / m or less. The narrow bottle used was made of polypropylene with a capacity of 125 mL, put 115 g of purified water, covered and shaken for 1 minute, allowed to stand still for 1 minute, and discarded the purified water, It has been washed.

〔Measuring method〕
(1) Electrical conductivity of purified water (σ ₀ ):
Place 100.0 g of purified water in a narrow-mouthed bottle, quickly dip the cell (detector) of the electric conductivity meter “EC METERCM-40G” (manufactured by Toa Denpa Kogyo Co., Ltd.), Conductivity (σ ₀ ) was measured.
After measuring the electrical conductivity (σ ₀ ) of purified water, the electric conductivity meter cell was washed with purified water, immersed in purified water, and kept waiting until the next measurement. At this time, it was confirmed that the electrical conductivity of the purified water used for immersing the cell was within a range of ± 2 μS / m with respect to the measured value of the electrical conductivity (σ ₀ ) of the purified water.

(2) electrical conductivity of the sample solution (sigma _1):
2.00 g of a sample (a composition of the present invention or a composition for comparison) is added to the narrow mouth bottle containing 100.0 g of purified water whose electrical conductivity (σ ₀ ) has been measured, The bottle was capped, shaken for 1 minute, and allowed to stand at room temperature for 3 minutes to prepare an aqueous sample solution. Next, the cap of the narrow mouth bottle was opened, the cell of the electric conductivity meter was quickly immersed in the sample aqueous solution, and the electric conductivity (σ _s ) was measured after 5 minutes.
On the other hand, as a blank test, 100.0 g of purified water was put into a narrow-necked bottle, the electric conductivity meter cell was quickly immersed, and the electric conductivity immediately after (σ _b0 ) and the electric conductivity after 5 minutes (σ _b ) And the change in electrical conductivity (σ _x = σ _b −σ _b0 ) due to absorption of carbon dioxide by air contact for 5 minutes was measured. It is confirmed that the electric conductivity (σ _b0 ) immediately after the cell is immersed is within a range of ± 2 μS / m with respect to the measured value of the electric conductivity (σ ₀ ) of purified water in (1) above. did.
From the measured values of above-obtained electric conductivity (sigma _s) and electrical conductivity change (sigma _x), wherein: the σ ₁ = σ _s -σ _x, the electric conductivity of the sample solution (sigma ₁ )

As shown in Table 7, the index value (σ ₁ −σ ₀ ) of the total amount of ionic impurities in the compositions of the present invention obtained in Examples 1 to 12 is as low as 20 μS / m or less.
On the other hand, the comparative compositions obtained in Comparative Example 1, Comparative Example 2, Comparative Example 4, Comparative Example 5 and Comparative Examples 7 to 10 are index values (σ ₁ −σ ₀ ) of the total amount of ionic impurities. It is understood that the acid / neutralized salt is contained in a high ratio.

<Evaluation of composition>
About each of the composition of this invention obtained in Examples 1-12 and the composition for a comparison obtained in Comparative Examples 2-5 and Comparative Examples 7-14, mixing with water / (polyhydric) alcohol The degree of odor formation over time in the system was traced, and the effect of suppressing odor formation over time was evaluated. The results are shown in Table 8 below together with index values for the total degree of unsaturation, the total amount of carbonyl (propanal conversion value) and the total amount of ionic impurities.

Here, the mixed system of water / (polyhydric) alcohol is 50 mL of 3.0 g of a sample (the composition of the present invention or a composition for comparison), 3.0 g of propylene glycol, and 24.0 g of purified water. It was prepared by charging into a screw tube, capping and shaking.
Evaluation of odors over time was carried out after being left in a 70 ° C. environment for 14 days and 30 days based on the following criteria.

〔Evaluation criteria〕
“◎”: Almost odorless (same level as control (no sample) or less odor).
“O”: Slight odor is felt.
“Δ”: A slight odor is observed.
“X”: A strong odor is recognized.
“XX”: Extremely strong odor is recognized.

  The composition of the present invention can be used for various applications, and in particular, mainly in the field of cosmetics and cosmetics to be made unscented, conventionally, the use of a polyether-modified polysiloxane composition has resulted in its odor. It can also be used in fields that have been difficult due to odors over time in a mixed system of water / (polyhydric) alcohol.

It is a diagram which shows the relationship between the carbonyl value about a standard sample (I)-(IV), and a propanal density | concentration. It is a diagram which shows the relationship between the carbonyl value about a standard sample (IV)-(VII), and a propanal concentration. It is a diagram which shows the relationship between the carbonyl value about a standard sample (VI)-(VIII), and a propanal density | concentration.

Claims (3)

In a polyether-modified polysiloxane composition containing an organopolysiloxane-polyoxyalkylene copolymer obtained by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the end. From the absorbance of the reaction solution obtained by reacting carbonyls with 2,4-dinitrophenylhydrazine, the carbonyl value of the polyether-modified polysiloxane composition is obtained, and a calibration curve measured in advance is obtained from the carbonyl value. A method of measuring the total amount of carbonyl in terms of propanal in the composition,
In a polyether-modified polysiloxane composition, characterized in that, as a reaction solvent in the reaction of carbonyls with 2,4-dinitrophenylhydrazine, an alcohol having a total amount of aldehyde / ketone of 3 ppm or less and water are used in combination. Method for measuring the total amount of carbonyl. In a polyether-modified polysiloxane composition containing an organopolysiloxane-polyoxyalkylene copolymer obtained by a hydrosilylation reaction between an organohydrogenpolysiloxane and a polyoxyalkylene having a carbon-carbon double bond at the end. In the method of measuring the total amount of carbonyl in terms of propanal,
The absorbance (A ₁ ) and absorbance (A ₂ ) measured by the following steps (1) to (9) are expressed by the formula: CV = (A ₁ -A ₂ ) / B [where B is the sample solution 5. It is the mass (g) of the sample contained in 000 g. ] To obtain a calibration curve by measuring the carbonyl value of a standard sample having a known total carbonyl amount by the method of determining the carbonyl value (CV) by substituting
Measure the carbonyl value of a sample for which the total amount of carbonyl is unknown by the same method used to obtain this calibration curve, and measure the total amount of carbonyl in the sample from this carbonyl value and the calibration curve. Is the way
The following solvent used in the following step (1) and step (9) contains alcohol and water having a total amount of aldehyde / ketone of 3 ppm or less, and the following solvent used in the following step (7) is an aldehyde. A method for measuring a total amount of carbonyl in a polyether-modified polysiloxane composition, wherein the total amount of ketone contains an alcohol having a concentration of 3 ppm or less.
[Process]
(1) A step of preparing a sample solution by dissolving the sample in a solvent.
(2) A step of adding 3 mL of 20% (wt / wt) dilute sulfuric acid alcohol solution [sulfuric acid concentration 1.2% (wt / vol)] to 5.000 g of the sample solution.
(3) A step of adding 5 mL of an alcohol solution [0.025% (wt / vol)] of 2,4-dinitrophenylhydrazine to the mixed solution obtained in the step (2).
(4) A step of reacting the carbonyls in the sample with 2,4-dinitrophenylhydrazine by heating the mixed solution obtained in the above step (3) at 60 ° C. for 30 minutes.
(5) A step of leaving the reaction solution obtained in the above step (4) at room temperature for 30 to 70 minutes.
(6) A step of adding 10 mL of an alcohol solution of potassium hydroxide [4.0% (wt / vol)] to the reaction solution left in the step (5).
(7) A step of adding a solvent to the reaction solution after 5 to 10 minutes from the step (6), preparing a reaction solution having a total amount of 50 mL, and filtering the reaction solution.
(8) A step of measuring the absorbance (A ₁ ) at 430 nm or 460 nm of the reaction solution obtained in the step (7) after 10 to 20 minutes from the step (6).
(9) As a blank test, an absorbance at 430 nm or 460 nm is used for a solution obtained by performing the same operation as the above steps (2) to (7) using 5.000 g of the solvent instead of the sample solution. A step of measuring A ₂ ). Alcohol solution of dilute sulfuric acid added in step (2) above, alcohol solution of 2,4-dinitrophenylhydrazine added in step (3) above, alcohol solution of potassium hydroxide added in step (6) above 3. The method for measuring the total amount of carbonyl in a polyether-modified polysiloxane composition according to claim 2 , wherein the alcohol as each solvent is an alcohol having a total amount of aldehyde / ketone of 3 ppm or less.

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