Polyalkylene oxide-containing organopolysiloxane composition and method for producing polyalkylene oxide-containing organopolysiloxane

Abstract

The present invention provides a high-grade polyalkylene oxide-containing organopolysiloxane composition and a method for producing a high-grade polyalkylene oxide-containing organopolysiloxane. [Solution] A method for producing a polyalkylene oxide-containing organopolysiloxane, comprising the step of carrying out an addition reaction in the presence of an antioxidant and a platinum catalyst, between (A) an organohydrogenpolysiloxane containing one or more hydrosilyl groups in its molecule and (B) a polyalkylene oxide compound containing one or more terminal unsaturated bonds in its molecule, characterized in that the amount of water in the reaction solution is 2,000 ppm or less.

Description

Technical Field

[0001] The present invention relates to a polyalkylene oxide-containing organopolysiloxane composition and a method for producing a polyalkylene oxide-containing organopolysiloxane.

Background Art

[0002] Conventionally, polyether-modified silicones have been used as cosmetics, paint additives, foam stabilizers for foamed urethane, and resin additives (Patent Documents 1 to 3). In particular, since polyether-modified silicones used in cosmetics come into direct contact with the skin, there is a concern that skin irritation may occur due to trace impurities, and high-quality polyether-modified silicones are in demand.

[0003] Generally, polyether-modified silicones are obtained by a hydrosilylation reaction of a hydrogen siloxane and an allylated polyether. Mainly, a platinum-based homogeneous catalyst is used. In some cases, the hydrosilylation reaction is carried out in an organic solvent, and the product is obtained as a composition of a polyether-modified silicone and unreacted polyether by performing a vacuum strip at a high temperature for solvent removal.

[0004] On the other hand, the allylated polyether has a double bond site that is easily oxidized, and the presence of the oxidized allyl group may deteriorate the reactivity. Also, it has been found that the polyether oxidatively deteriorates during the hydrosilylation reaction or during the strip at a high temperature, and ethylene oxide and ethylene glycol formed by its ring-opening are generated. In particular, the generated ethylene glycol is difficult to remove because of its high boiling point, and there is a concern that it may cause skin irritation when formulated in cosmetics.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] In view of the above circumstances, the present invention aims to provide a high-quality polyalkylene oxide-containing organopolysiloxane composition and a method for producing a high-quality polyalkylene oxide-containing organopolysiloxane.

Means for Solving the Problems

[0007] In order to solve the above problems, the present invention provides a method for producing a polyalkylene oxide-containing organopolysiloxane, which includes a step of subjecting (A) an organohydrogenpolysiloxane containing one or more hydrosilyl groups in the molecule, and (B) a polyalkylene oxide compound containing one or more terminal unsaturated bonds in the molecule, to an addition reaction in the presence of an antioxidant and a platinum catalyst, and the method for producing a polyalkylene oxide-containing organopolysiloxane is provided, wherein the amount of water in the reaction solution is 2,000 ppm or less.

[0008] According to such a method for producing a polyalkylene oxide-containing organopolysiloxane, a high-quality polyalkylene oxide-containing organopolysiloxane can be produced.

[0009] Furthermore, in the present invention, it is preferable to use one or more selected from carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopherol acetate, pt-butylphenol, butylhydroxyanisole, 4-hydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, gallic acid, gallic acid esters, sulfites, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, and quercetin as the antioxidant.

[0010] In the present invention, it is preferable to use such an antioxidant.

[0011] Furthermore, in the present invention, it is preferable to use an organohydrogenpolysiloxane represented by the following general formula (1) as component (A). [ka] (In the formula, R 1 The groups are independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, if b2 is 0, R 1 At least one of these atoms is a hydrogen atom. The bonding order of each siloxane unit may be in a block or random.

[0012] In the present invention, it is preferable to use such a component (A).

[0013] Furthermore, in the present invention, it is preferable to use a polyalkylene oxide compound represented by the following general formula (2) or (3) as component (B). [ka] (In the formula, R2 R is a hydrogen atom or a methyl group, A (where e is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50. The bonding of each oxyalkylene group may be blocked or random.)

[0014] In the present invention, it is preferable to use such a component (B).

[0015] Furthermore, in the present invention, it is preferable to include a step of adding an inorganic acid after the addition reaction step, and a step of performing a stripping under reduced pressure at 90°C or higher.

[0016] By including such a process, the odor can be reduced.

[0017] Furthermore, in the present invention, in the step of the addition reaction, in addition to component (A) and component (B), (C) Siloxane compounds selected from the following general formulas (4) and (5) having an unsaturated bond at the C terminus It is preferable to subject it to an addition reaction. [ka] (In the formula, h is a number from 0 to 6, i is from 1 to 100, and R' is a group selected from alkyl groups and phenyl groups having 1 to 10 carbon atoms.)

[0018] In the manufacturing method of the present invention, such component (C) can be subjected to an addition reaction.

[0019] At this time, in the step of carrying out the addition reaction, component (A), component (B), and component (C) can be subjected to the addition reaction all at once.

[0020] In this case, in the addition reaction step, component (C) can be subjected to the addition reaction after the addition reaction of component (A) and component (B).

[0021] In this case, in the step of the addition reaction, component (B) can be subjected to the addition reaction after the addition reaction of component (A) and component (C).

[0022] The manufacturing method of the present invention allows for such addition reactions.

[0023] Furthermore, the present invention relates to a polyalkylene oxide-containing organopolysiloxane composition, (X) Polyalkylene oxide-containing organopolysiloxane: 100 parts by mass, (Y) Polyalkylene oxide represented by the following general formula (2') or (3'): 1 to 40 parts by mass, and (Z) Ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol: 50 ppm or less each The composition contains (P) the amount of platinum contained in the composition and the total amount of (Z) component (Z A ) Mass ratio (P) / (Z A The present invention provides a polyalkylene oxide-containing organopolysiloxane composition having a ratio of 0.1 to 15. [ka] (In the formula, R A (where is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random. X is one or more groups independently selected from hydroxyl groups, -CH2CH=CH2, and -CH=CH2-CH3.)

[0024] Such polyalkylene oxide-containing organopolysiloxane compositions are of high quality because they have a low content of (Z).

[0025] In the composition of the present invention, it is preferable that the component (X) is an addition reaction product of an organohydrogenpolysiloxane represented by the following general formula (1) and a polyalkylene oxide compound represented by the following general formula (2) or (3).

Chemical formula

Chemical formula

[0026] The component (X) contained in the polyalkylene oxide-containing organopolysiloxane composition of the present invention is preferably such a component.

[0027] At this time, it is preferable that the component (X) is an addition reaction product with a siloxane compound selected from the following general formulas (4) and (5).

Chemical formula

[0028] It is more preferable that the (X) component be as described above. [Effects of the Invention]

[0029] As described above, the polyalkylene oxide-containing organopolysiloxane composition of the present invention can be made into a high-grade polyalkylene oxide-containing organopolysiloxane composition because it contains fewer impurities. Furthermore, the method for producing polyalkylene oxide-containing organopolysiloxane of the present invention can produce a polyalkylene oxide-containing organopolysiloxane composition in which the content of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol is 50 ppm or less for each component. [Modes for carrying out the invention]

[0030] As described above, there has been a need for the development of high-quality polyalkylene oxide-containing organopolysiloxane compositions and methods for producing high-quality polyalkylene oxide-containing organopolysiloxanes.

[0031] As a result of diligent research to achieve the above objective, the present inventors have found that by carrying out the hydrosilylation reaction in the presence of an antioxidant and a platinum catalyst, and with the water content in the reaction solution being 2,000 ppm or less, the content of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol in the resulting polyalkylene oxide-containing organopolysiloxane composition can be suppressed to 50 ppm or less for each component.

[0032] In other words, the present invention is a method for producing a polyalkylene oxide-containing organopolysiloxane in the presence of an antioxidant and a platinum catalyst, (A) An organohydrogenpolysiloxane containing one or more hydrosilyl groups in the molecule, (B) Polyalkylene oxide compounds containing one or more terminal unsaturated bonds within the molecule, This method provides a way to produce a polyalkylene oxide-containing organopolysiloxane, which includes a step of adding a substance to the reaction solution, and wherein the water content in the reaction solution is 2,000 ppm or less.

[0033] Furthermore, the present invention relates to a polyalkylene oxide-containing organopolysiloxane composition, (X) Polyalkylene oxide-containing organopolysiloxane: 100 parts by mass, (Y) Polyalkylene oxide represented by the following general formula (2') or (3'): 1 to 40 parts by mass, and (Z) Ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol: 50 ppm or less each The composition contains (P) the amount of platinum contained in the composition and the total amount of (Z) component (Z A ) Mass ratio (P) / (Z A This is a polyalkylene oxide-containing organopolysiloxane composition in which the ratio is 0.1 to 15. [ka] (In the formula, R A (where is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random. X is one or more groups independently selected from hydroxyl groups, -CH2CH=CH2, and -CH=CH2-CH3.)

[0034] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0035] [Organopolysiloxane composition containing polyalkylene oxide] The polyalkylene oxide-containing organopolysiloxane composition of the present invention is (X) Polyalkylene oxide-containing organopolysiloxane: 100 parts by mass, (Y) Polyalkylene oxide represented by the following general formula (2') or (3'): 1 to 40 parts by mass, and (Z) Ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol: 50 ppm or less each The composition contains (P) the amount of platinum contained in the composition and the total amount of (Z) component (Z A ) Mass ratio (P) / (Z A ) is between 0.1 and 15. [ka] (In the formula, R A (where is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random. X is one or more groups independently selected from hydroxyl groups, -CH2CH=CH2, and -CH=CH2-CH3.)

[0036] The (X) polyalkylene oxide-containing organopolysiloxane included in the polyalkylene oxide-containing organopolysiloxane composition of the present invention is not particularly limited.

[0037] Here, it is preferable that component (X) is an addition product of an organohydrogenpolysiloxane represented by the following general formula (1) and a polyalkylene oxide compound represented by the following general formula (2) or (3). [ka] (In the formula, R 1 The groups are independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, if b2 is 0, R 1At least one of these atoms is a hydrogen atom. The bonding order of each siloxane unit may be in a block or random. [ka] (In the formula, R 2 R is a hydrogen atom or a methyl group, A (where e is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50. The bonding of each oxyalkylene group may be blocked or random.)

[0038] In the above general formula (1), R 1 The group is independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a phenyl group.

[0039] In the above general formula (1), a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, when b2 is 0, R 1 One or more of these atoms are hydrogen atoms. The bonding order of each siloxane unit may be in a block or random. a is preferably 2≦a≦5, b1 is preferably 5≦b1≦800, b2 is preferably 2≦b2≦30, c is preferably 0≦c≦3, and d is preferably 0≦d≦3.

[0040] In the above general formulas (2) and (3), R 2 This is a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0041] In the above general formula (2), R A The group is a hydrogen atom, or a group selected from an alkyl group having 1 to 6 carbon atoms and an acyl group having 2 to 7 carbon atoms, preferably a hydrogen atom, a methyl group, or an acetyl group.

[0042] In the above general formulas (2) and (3), e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random. Preferably e is 1 ≤ e ≤ 6, f is 3 ≤ f ≤ 20, and g is 0 ≤ g ≤ 20.

[0043] Furthermore, it is preferable that component (X) is an addition product of a siloxane compound selected from the following general formulas (4) and (5). [ka] (In the formula, h is a number from 0 to 6, i is from 1 to 100, and R' is a group selected from alkyl groups and phenyl groups having 1 to 10 carbon atoms.)

[0044] In the above general formulas (4) and (5), h is a number from 0 to 6, preferably a number from 0 to 4.

[0045] In the above general formula (4), i is between 1 and 100, preferably between 2 and 30.

[0046] In the above general formula (4), R' is a group selected from alkyl groups having 1 to 10 carbon atoms and phenyl groups, preferably a methyl group, an ethyl group, a propyl group, or an n-butyl group.

[0047] The (Y) polyalkylene oxide contained in the polyalkylene oxide-containing organopolysiloxane composition of the present invention is represented by the following general formula (2') or (3'). [ka] (In the formula, R A(where is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random. X is one or more groups independently selected from hydroxyl groups, -CH2CH=CH2, and -CH=CH2-CH3.)

[0048] In the above general formula (2'), R A The group is a hydrogen atom or a group selected from an alkyl group having 1 to 6 carbon atoms and an acyl group having 2 to 7 carbon atoms, with a hydrogen atom, a methyl group, or an acetyl group being preferred.

[0049] In the above general formulas (2') and (3'), e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, with 1 ≤ e ≤ 6, 3 ≤ f ≤ 20, and 0 ≤ g ≤ 20 being preferred.

[0050] In the above general formulas (2') and (3'), X is independently one or more groups selected from a hydroxyl group, -CH2CH=CH2, and -CH=CH2-CH3, with a hydroxyl group being preferred.

[0051] The content of component (Y) is 1 to 40 parts by mass, preferably 3 to 30 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of component (X). If the content of component (Y) is less than 1 part by mass, a large amount of platinum catalyst will be required, resulting in a large amount of residual platinum catalyst in the composition. In addition, the hydrosilyl groups of the organohydrogenpolysiloxane may remain unreacted, and these hydrosilyl groups may reduce the platinum catalyst, potentially generating platinum black. This may result in a brownish appearance due to the platinum black, which is undesirable. Furthermore, if the content exceeds 40 parts by mass, it is undesirable because it will affect the functionality and appearance of the polyalkylene oxide-containing organopolysiloxane.

[0052] The content of (Z) ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol in the polyalkylene oxide-containing organopolysiloxane composition of the present invention is 50 ppm or less for each component, preferably 30 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less. If the content of any of the (Z) components exceeds 50 ppm, it may cause skin irritation from the polyalkylene oxide-containing organopolysiloxane composition, or, depending on the application, it may reduce the surfactant function of the polyalkylene oxide-containing organopolysiloxane, which is undesirable.

[0053] Furthermore, the polyalkylene oxide-containing organopolysiloxane composition of the present invention may also contain derivatives of component (Z). When derivatives of component (Z) are included, the content of each derivative is preferably 50 ppm or less. In this invention, the content of component (Z) and its derivatives is a value measured using gas chromatography (AGilent Technologies).

[0054] Furthermore, the platinum content (P) in the composition can be measured using an ICP emission spectrometer (manufactured by AGilent Technologies). The platinum content (P) in the composition and the total content (Z) of the (Z) component are measured. A ) Mass ratio (P) / (Z A The ratio is 0.1 to 15, preferably 0.2 to 13. A ratio below 0.1 is undesirable because it may reduce the surfactant function of the composition or cause skin irritation. A ratio above 15 is also undesirable because it may worsen the appearance of the composition or reduce the stability of the emulsion using the composition.

[0055] [Method for producing polyalkylene oxide-containing organopolysiloxanes] The present invention is a method for producing a polyalkylene oxide-containing organopolysiloxane in the presence of an antioxidant and a platinum catalyst. (A) An organohydrogenpolysiloxane containing one or more hydrosilyl groups in the molecule, (B) Polyalkylene oxide compounds containing one or more terminal unsaturated bonds within the molecule, This method for producing a polyalkylene oxide-containing organopolysiloxane includes a step of adding a substance to a reaction, wherein the water content in the reaction solution is 2,000 ppm or less.

[0056] The antioxidants mentioned above are preferably one or more selected from carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopherol acetate, pt-butylphenol, butylhydroxyanisole, 4-hydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, gallic acid, gallic acid esters, sulfites, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, and quercetin. More preferably, tocopherol, tocopherol acetate, 4-hydroxyanisole, and dibutylhydroxytoluene are used, and even more preferably, tocopherol and tocopherol acetate are used.

[0057] The amount of antioxidant added is preferably 1 to 2,000 ppm, more preferably 50 to 1,000 ppm, relative to the total of (A) organohydrogenpolysiloxane containing one or more hydrosilyl groups in the molecule and (B) polyalkylene oxide compound containing one or more terminal unsaturated bonds in the molecule. If the amount added is 1 ppm or more, the generation of alkylene oxides and their derivatives, such as ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol, which are generated during manufacturing or storage, can be suppressed. If the amount added is 2,000 ppm or less, no discoloration problem occurs. In the present invention, the hydrosilylation reaction is carried out in the presence of an antioxidant and a platinum catalyst, and by suppressing the oxidation of the terminal unsaturated bonds of component (B), it is possible to improve the efficiency of the hydrosilylation reaction and at the same time suppress the generation of alkylene oxides and their derivatives.

[0058] The platinum catalyst is preferably chloroplatinic acid or a divinyldisiloxane platinum complex (Karlstedt catalyst), and the amount added is preferably 0.1 to 50 ppm, more preferably 0.5 to 10 ppm, relative to the polyalkylene oxide-containing organopolysiloxane. By carrying out the reaction in the presence of an antioxidant, it is possible to reduce the amount of platinum catalyst and suppress discoloration of the composition.

[0059] Furthermore, in this invention, the water content in the reaction solution is 2,000 ppm or less, preferably 10 to 1,500 ppm, and more preferably 20 to 1,000 ppm. In this invention, the water content in the reaction solution is a value measured using a Karl Fischer method water content analyzer (manufactured by HIRANUMA).

[0060] If the water content in the reaction solution exceeds 2,000 ppm, the by-product alkylene oxide undergoes ring-opening, generating ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol, which are difficult to remove, and this is undesirable.

[0061] The aforementioned component (A) is preferably an organohydrogenpolysiloxane represented by the following general formula (1). [ka] (In the formula, R 1 The groups are independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, if b2 is 0, R 1 At least one of these atoms is a hydrogen atom. The bonding order of each siloxane unit may be in a block or random.

[0062] The aforementioned component (B) is preferably a polyalkylene oxide compound represented by the following general formula (2) or (3). [ka] (In the formula, R 2 R is a hydrogen atom or a methyl group, A (where e is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50. The bonding of each oxyalkylene group may be blocked or random.)

[0063] The addition reaction step may be carried out in the presence of an organic solvent as needed. Examples of organic solvents include: linear organopolysiloxanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; and aliphatic carbons such as hexane, heptane, octane, cyclohexane, and isododecane. Examples include hydrogen; monohydric aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol; dihydric aliphatic alcohols such as ethylene glycol and 1,2-propylene glycol; and ester oils such as tri(2-ethylhexanoic acid) glyceryl and jojoba oil. Ethanol, 1-propanol, 2-propanol, and toluene are particularly preferred from the viewpoint of reactivity.

[0064] The amount of organic solvent used is preferably 1 to 80% by mass of the total reaction solution (system), and more preferably 5 to 50% by mass. Within this range, the reaction system is kept uniform, and the reaction proceeds efficiently.

[0065] The reaction conditions for hydrosilylation are not particularly limited, but it is preferable to heat at a temperature of 50 to 150°C, more preferably 80 to 120°C, for about 1 to 10 hours.

[0066] In the present invention, in the step of the addition reaction, in addition to component (A) and component (B), (C) Siloxane compounds selected from the following general formulas (4) and (5) having an unsaturated bond at the C terminus It is preferable to subject to the addition reaction. The reaction conditions are the same as those for the hydrosilylation reaction described above. [ka] (In the formula, h is a number from 0 to 6, i is from 1 to 100, and R' is a group selected from alkyl groups and phenyl groups having 1 to 10 carbon atoms.)

[0067] As for the method of the addition reaction of component (A) and component (B), and optionally component (C), these raw materials may be reacted all at once, or one or more raw materials may be placed in the reaction system first, and the rest may be added sequentially.

[0068] For example, when the three components (A) to (C) above are subjected to an addition reaction, (1) A method of subjecting the component (A), the component (B), and the component (C) to the addition reaction in the step of the addition reaction, (2) In the step of carrying out the addition reaction, a method in which component (A) and component (B) are added together and then component (C) is subjected to the addition reaction, (3) In the step of the addition reaction, a method in which component (A) and component (C) are added together and then component (B) is subjected to the addition reaction, These are some examples.

[0069] Unreacted hydrosilyl groups may be present in the polyalkylene oxide-containing organopolysiloxane after the addition reaction. Furthermore, if the organic solvent used during the addition reaction is an aliphatic alcohol, a dehydrogenation reaction will proceed, and alkoxy groups may remain.

[0070] After the addition reaction, the process may include a step of substituting any remaining hydrosilyl groups with hydroxysilyl groups, if necessary. In particular, when used in cosmetics and the like, the hydrosilyl groups may become inactive over time due to dehydrogenation, potentially generating hydrogen gas, which poses a safety risk. Therefore, it is preferable to include a step of substituting hydrosilyl groups with hydroxysilyl groups.

[0071] One method for substituting hydrosilyl groups with hydroxysilyl groups involves adding a basic catalyst such as an alkali metal carbonate, alkali metal bicarbonate, or alkali metal hydroxide to hydrolyze the unreacted hydrosilyl groups, followed by neutralization with an acidic catalyst equal to the molar equivalent of the basic catalyst. Specific examples of basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide as examples of strong basic catalysts, and sodium carbonate, calcium carbonate, and sodium bicarbonate as examples of weak basic catalysts. A strong basic catalyst is particularly preferable in promoting the dehydrogenation reaction, and sodium hydroxide is specifically preferred. Specific examples of acidic catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, and phosphoric acid; sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; and carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, citric acid, and oxalic acid. In general, it is preferable to use acids or bases in combination with water and heat them at a temperature below the boiling point of water, rather than using them alone. Through this process, hydrosilyl groups (SiH groups) are replaced with hydroxysilyl groups (SiOH groups).

[0072] After the hydrosilylation reaction, a deodorization step may be included as needed to reduce the odor. In particular, when used in cosmetics and the like, it is preferable to include a deodorization step because odor develops over time. The odor development mechanism of typical polyether-modified silicones is explained as follows: When an addition reaction is carried out between an allyl ether-modified polyether and a hydrogen polyorganosiloxane in the presence of a platinum catalyst, the allyl group undergoes internal transition as a side reaction, producing a propenyl ether-modified polyether. Since this propenyl ether-modified polyether does not have addition reactivity with the hydrogen polyorganosiloxane, it remains in the system as an impurity. When water reacts with this propenyl ether-modified polyether, it is thought that the propenyl ether is hydrolyzed, generating propionaldehyde, which is the cause of the malodor. Furthermore, it is known that the above hydrolysis reaction is further accelerated in the presence of an acid catalyst, and when polyether-modified silicone is used in water-based cosmetics, the oxidative degradation of the polyether causes the solution to become acidic over time, which accelerates the hydrolysis reaction mentioned above and causes odor development.

[0073] Two typical formulations can be cited as examples of deodorization processes. The first formulation involves adding an acidic catalyst to the solution after the addition reaction to hydrolyze all of the remaining propenyl ether in the system, and then removing the resulting propionaldehyde by strip purification (Japanese Patent Publication No. 07-091389).

[0074] Specific examples of acidic catalysts used in the first formulation include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, and phosphoric acid; sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; and carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, oxalic acid, and citric acid. These acids are used in combination with water, but when it is necessary to remove the used acid, it is preferable to use one with a low boiling point, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Furthermore, from the viewpoint of processing efficiency, it is preferable to use strong acids such as hydrochloric acid or trifluoroacetic acid, but when using cyclic organopolysiloxane as a solvent, there is a risk of ring opening under strong acid conditions, so it is preferable to use a weak acid such as citric acid or acetic acid.

[0075] The processing temperature is preferably 80°C or lower. The amount of acidic aqueous solution added is preferably 0.1 to 100% by mass relative to the polyalkylene oxide-containing organopolysiloxane, and more preferably 5 to 30% by mass.

[0076] From a productivity standpoint, a preferred method involves adding an aqueous solution to the reaction solution to bring the pH down to 7 or below, followed by heating, stirring, and then strip purification. The above strip purification can be carried out under atmospheric pressure or reduced pressure, but the temperature is preferably 120°C or below. To efficiently perform strip purification under these temperature conditions, it is preferable to carry it out under reduced pressure, or, in the case of atmospheric pressure, under the flow of an inert gas such as nitrogen or argon.

[0077] The second formulation involves adding hydrogen to the post-reaction solution to alkylate the unsaturated double bond (a so-called hydrogenation reaction), thereby stably controlling the generation of propionaldehyde over time (U.S. Patent No. 5,225,509, Japanese Patent Publication No. 07-330907).

[0078] Hydrogenation reactions can be carried out using hydrogen or metal hydrides, and further categorized into homogeneous and heterogeneous reactions. These can be carried out individually or in combination. However, considering the advantage that no catalyst remains in the product, heterogeneous catalytic hydrogenation using a solid catalyst is the most preferred method.

[0079] Examples of solid catalysts include elements or compounds of nickel, palladium, platinum, rhodium, cobalt, chromium, copper, and iron. In this case, a catalyst support is not necessary, but if used, activated carbon, silica, silica-alumina, alumina, zeolite, etc., can be used. These catalysts can be used individually or in combination. The most preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is usually used by developing it in an alkali, it is especially important to carefully measure the pH of the reaction solution. Also, since the reaction system becomes weakly alkaline, hydrolysis reactions with acidic aqueous solutions are particularly effective for deodorization.

[0080] Hydrogenation reactions are generally preferably carried out at 1-100 MPa and 50-200°C. The hydrogenation reaction can be either palindromic or continuous. In the palindromic case, the reaction time depends on the amount of catalyst and temperature, but is generally 3-12 hours. The hydrogen pressure can be adjusted to a constant pressure as needed, but the endpoint of the hydrogenation reaction is the point where the hydrogen pressure stops changing, which can be determined by carefully observing the pressure gauge.

[0081] The amount of aldehyde contained in the polyalkylene oxide-containing organopolysiloxane composition purified by such acid treatment or hydrogenation reaction can preferably be 70 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less.

[0082] Furthermore, it is possible to combine the two deodorization treatment processes mentioned above. While acid treatment can decompose and remove aldehyde compounds, there are limitations to completely removing unsaturated double bonds, and therefore it is not possible to completely suppress the generation of aldehydes, which are the cause of the odor. Hydrogenation treatment can reduce the amount of aldehyde compounds generated by eliminating unsaturated double bonds, but aldehyde condensates formed by the condensation of some aldehydes remain in the system even after the above treatment and are difficult to remove by strip purification. Therefore, complete deodorization is possible by applying a hydrogenation reaction to the solution after the addition reaction to alkylate the remaining unsaturated double bonds, and then adding an acid catalyst to decompose the aldehyde condensates in the system (International Publication No. 2002 / 055588).

[0083] It is preferable to include a step of performing a vacuum strip at 90°C or higher after the above post-treatment steps. The vacuum strip is preferably performed at 90 to 130°C for 1 to 5 hours. This allows for the removal of any remaining solvent.

[0084] In other words, the present invention preferably includes, after the addition reaction step, a step of adding an inorganic acid, and a step of performing a stripping under reduced pressure at 90°C or higher.

[0085] In the present invention's method for producing polyalkylene oxide-containing organopolysiloxanes, the content of each alkylene oxide, such as ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol, and their derivatives is preferably 50 ppm or less, more preferably 10 ppm or less, and even more preferably less than 1 ppm. The polyalkylene oxide-containing organopolysiloxanes produced by this method exhibit suppressed changes in the content of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, dipropylene glycol, and their derivatives over time, from during production to immediately after production and during storage.

[0086] The polyalkylene oxide-containing organopolysiloxane composition is not particularly limited in terms of its use, but for example, when added to cosmetics, it can be applied to a variety of products such as lotions, serums, emulsions, creams, hair care products, foundations, makeup bases, sunscreens, concealers, blushes, lipsticks, glosses, balms, mascaras, eyeshadows, eyeliners, body makeup, deodorants, and nail cosmetics. Among these, makeup cosmetics such as foundations, makeup bases, sunscreens, concealers, blushes, lipsticks, and glosses, as well as formulations that provide sunscreen effects, are particularly preferred. As for the properties of the cosmetic, various forms such as liquid, cream, solid, paste, gel, mousse, soufflé, clay, powder, and stick can be selected.

[0087] The above cosmetic composition may take the form of an emulsion, an aqueous composition, or an oil-based composition, or it may be a powder composition. When an oily feel is desired, an oil-based composition or an emulsion can be selected. The emulsion can take the form of an aqueous emulsion such as an O / W emulsion or a W / O / W emulsion, or an oil-based emulsion such as a W / O emulsion or an O / W / O emulsion. When a fresh, dewy feel is desired, an aqueous composition or a powder composition can be selected. In any case, a good cosmetic composition can be obtained. The polyalkylene oxide-containing organopolysiloxane composition of the present invention can be used not only for purposes such as dispersing the oil phase component of an aqueous emulsion composition, but also when incorporated into the aqueous phase as an emulsifier or thickener. In this invention, "aqueous composition" refers to a composition that does not intentionally contain oils. "Oil-based composition" refers to a composition that does not intentionally contain aqueous components. A "powder composition" refers to a composition that, in addition to compositions such as powder foundation and loose powder, involves coating fine particles with an aqueous phase, or coating an aqueous phase with powder, so that although it has the appearance of a powder, it releases the aqueous phase immediately after application to the skin, resulting in a refreshing feel.

[0088] If the above cosmetic composition is an emulsion, the viscosity at 25°C is preferably 50 to 200,000 mPa·s. In particular, for shaking-type products, 50 to 5,000 mPa·s is preferred, and 100 to 1,500 mPa·s is more preferred from the viewpoint of balancing usability and redispersibility. For non-separating types that do not require shaking before use, 5,000 to 200,000 mPa·s is preferred, and 8,000 to 100,000 mPa·s is more preferred from the viewpoint of balancing usability and stability. The viscosity is measured at 25°C using a Type B viscometer according to the method described in JIS K 7117-1:1999. An example of a Type B viscometer is the TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.). [Examples]

[0089] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, the "%" in the compositions described below refers to "mass%". In addition, in the following examples and comparative examples, the content of polyalkylene oxide, which is component (Y) in the polyalkylene oxide-containing organopolysiloxane composition, is the value obtained by GPC (gel permuration chromatography) analysis using polystyrene as a standard substance under the following conditions. In addition, the platinum content (P) in the composition was measured by an ICP emission spectrometer (AGilent Technologies). [Measurement conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Differential refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N(6.0mmI.D.×15cm×1) TSKgel SuperH2500(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (THF solution with a concentration of 0.3% by mass)

[0090] [Example 1] 250 g of a hydrogen organopolysiloxane represented by the following formula, 160 g of a polyoxyalkylene compound represented by the following formula, 0.2 g of tocopherol, 150 g of 2-propanol, and 0.04 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex were charged into a reactor, and the mixture was aged at 80°C for 8 hours with stirring. The water content of the reaction solution was 400 ppm. 1 After confirming the disappearance of the hydrosilyl group by 1H-NMR, the solvent was removed by stripping under reduced pressure at 90°C and 2.5 kPa for 3 hours, and then filtered to obtain polyalkylene oxide-containing organopolysiloxane composition 1. The content of polyalkylene oxide (component Y) in this composition was 15 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The content of platinum (P) contained in the composition and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) were determined. A ) Mass ratio (P) / (Z A The value was 2.0. [ka]

[0091] [Example 2] 570 g of hydrogen organopolysiloxane represented by the following formula, 240 g of polyoxyalkylene compound represented by the following formula, 0.2 g of tocopherol acetate, 200 g of 2-propanol, and 0.1 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex were charged into the reactor, and the mixture was aged at 80°C for 5 hours with stirring. The water content of the reaction solution was 600 ppm. [ka]

[0092] Subsequently, 150 g of organopolysiloxane having terminally unsaturated groups represented by the following formula was added, and the mixture was aged at 80°C for 5 hours while stirring. The water content of the reaction solution was 600 ppm. 1 After confirming the disappearance of the hydrosilyl group by 1H-NMR, 50 g of 0.01 N hydrochloric acid was added and the mixture was aged at 60°C for 3 hours. 0.03 g of sodium bicarbonate was added to the resulting reaction product, and the solvent was removed by tape stripping under reduced pressure at 110°C and 2.5 kPa for 3 hours. The mixture was then filtered to obtain polyalkylene oxide-containing organopolysiloxane composition 2. The content of polyalkylene oxide (component Y) in this composition was 16 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The platinum content (P) and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) in the composition were also determined. A ) Mass ratio (P) / (Z A The value was 0.5. [ka]

[0093] [Example 3] 110 g of a hydrogen organopolysiloxane represented by the following formula, 560 g of a polyoxyalkylene compound represented by the following formula, 0.4 g of dibutylhydroxytoluene, and 0.08 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex were charged into a reactor, and the mixture was aged at 110°C for 12 hours with stirring. The water content of the reaction solution was 1,800 ppm. 1After confirming the disappearance of the hydrosilyl group by 1H-NMR, 80 g of 0.01 N hydrochloric acid was added and the mixture was aged at 60°C for 3 hours. 0.03 g of sodium bicarbonate was added to the resulting reaction product for neutralization. The solvent was then removed by stripping under reduced pressure at 110°C and 2.5 kPa for 3 hours, and the mixture was filtered to obtain polyalkylene oxide-containing organopolysiloxane composition 3. The content of polyalkylene oxide (component Y) in this composition was 25 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The platinum content (P) and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) in the composition were also determined. A ) Mass ratio (P) / (Z A The value was 3.0. [ka]

[0094] [Example 4] 600 g of a hydrogen organopolysiloxane represented by the following formula, 580 g of a polyoxyalkylene compound represented by the following formula, 0.4 g of ferulic acid, 0.15 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex, and 1,000 g of 2-propanol were charged into a reactor, and the mixture was aged at 80°C for 8 hours with stirring. The water content of the reaction solution was 1,200 ppm. 1After confirming the disappearance of the hydrosilyl group by 1H-NMR, 100 g of 0.01 N hydrochloric acid was added and the mixture was aged at 60°C for 5 hours. 0.06 g of sodium bicarbonate was added to the resulting reaction product, and the solvent was removed by stripping under reduced pressure at 100°C and 2.5 kPa for 3 hours. The mixture was then filtered to obtain polyalkylene oxide-containing organopolysiloxane composition 4. The content of polyalkylene oxide (component Y) in this composition was 20 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The platinum content (P) and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) in the composition were also determined. A ) Mass ratio (P) / (Z A The score was 4.0. [ka]

[0095] [Example 5] 400 g of a hydrogen organopolysiloxane represented by the following formula, 230 g of a polyoxyalkylene compound represented by the following formula, 1.0 g of propyl gallate, 0.2 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex, and 400 g of 2-propanol were charged into a reactor, and the mixture was aged at 110°C for 12 hours with stirring. The water content of the reaction solution was 200 ppm. 1After confirming the disappearance of the hydrosilyl group by 1H-NMR, 0.1 g of citric acid and 50 g of purified water were added and the mixture was aged at 60°C for 3 hours. After adding 0.04 g of sodium bicarbonate to the resulting reaction product, 1,000 g of undecamethylpentasiloxane was added, and the solvent was removed by tape stripping under reduced pressure at 110°C and 2.5 kPa for 3 hours. The mixture was then filtered to obtain polyalkylene oxide-containing organopolysiloxane composition 5. The content of polyalkylene oxide (component Y) in this composition was 15 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The content of platinum (P) in the composition and the total content of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) were determined. A ) Mass ratio (P) / (Z A The value was 3.5. [ka]

[0096] [Example 6] 570 g of a hydrogen organopolysiloxane represented by the following formula, 100 g of an organopolysiloxane having terminally unsaturated groups represented by the following formula, 0.4 g of tocopherol acetate, and 0.3 g of an ethanol solution (3.0%) of a divinyldisiloxane chlorplatinate complex were charged into the reactor, and the mixture was then aged at 90°C for 5 hours while stirring. The water content of the reaction solution was 80 ppm. [ka]

[0097] Subsequently, 360 g of a polyoxyalkylene compound represented by the following formula, 300 g of 2-propanol, and 0.1 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex were added, and the mixture was aged at 85°C for 5 hours with stirring. The water content of the reaction solution was 600 ppm. 1After confirming the disappearance of the hydrosilyl group by 1H-NMR, 50 g of 0.01 N hydrochloric acid was added and the mixture was aged at 60°C for 3 hours. 0.03 g of sodium bicarbonate was added to the resulting reaction product, and the mixture was stripped under reduced pressure at 110°C and 2.5 kPa for 3 hours, followed by filtration to obtain polyalkylene oxide-containing organopolysiloxane composition 6. The content of polyalkylene oxide (component Y) in this composition was 7 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The platinum content (P) and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) in the composition were also determined. A ) Mass ratio (P) / (Z A The value was 10.0. [ka]

[0098] [Comparative Example 1] 570 g of a hydrogen organopolysiloxane represented by the following formula, 240 g of a polyoxyalkylene compound represented by the following formula, 400 g of ethanol, and 0.1 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex were charged into a reactor, and the mixture was aged at 80°C for 5 hours while stirring. The water content of the reaction solution was 2,400 ppm. [ka]

[0099] Subsequently, 150 g of organopolysiloxane having terminal unsaturated groups represented by the following formula was added, and the mixture was further aged at 80°C for 5 hours while stirring. 1After confirming the disappearance of the hydrosilyl group by 1H-NMR, 50 g of 0.01 N hydrochloric acid was added and the mixture was aged at 60°C for 3 hours. 0.03 g of sodium bicarbonate was added to the resulting reaction product, and the solvent was removed by vacuum stripping at 110°C and 2.5 kPa for 3 hours to obtain comparative polyalkylene oxide-containing organopolysiloxane composition 1. The content of polyalkylene oxide (component Y) in this composition was 8 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The platinum content (P) and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) in the composition were also determined. A ) Mass ratio (P) / (Z A The value was 0.01. [ka]

[0100] [Comparative Example 2] 400 g of a hydrogen organopolysiloxane represented by the following formula, 230 g of a polyoxyalkylene compound represented by the following formula, 0.2 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex, and 500 g of ethanol were charged into a reactor, and the mixture was aged at 110°C for 12 hours while stirring. The water content of the reaction solution was 1,200 ppm. 1After confirming the disappearance of the hydrosilyl group by 1H-NMR, 0.1 g of citric acid and 50 g of purified water were added and the mixture was aged at 60°C for 3 hours. After adding 0.04 g of sodium bicarbonate to the resulting reaction product, 1,000 g of undecamethylpentasiloxane was added, and the solvent was removed by vacuum stripping at 110°C and 2.5 kPa for 3 hours to obtain comparative polyalkylene oxide-containing organopolysiloxane composition 2. The content of polyalkylene oxide (component Y) in this composition was 15 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The content of platinum (P) contained in the composition and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) were determined. A ) Mass ratio (P) / (Z A The value was 0.02. [ka]

[0101] [Comparative Example 3] 110 g of a hydrogen organopolysiloxane represented by the following formula, 590 g of a polyoxyalkylene compound represented by the following formula, 0.25 g of an ethanol solution (3.0%) of divinyldisiloxane chlorplatinate complex, and 200 g of toluene were charged into a reactor, and the mixture was aged at 110°C for 18 hours with stirring. The water content of the reaction solution was 3,500 ppm. 1After confirming the disappearance of the hydrosilyl group by 1H-NMR, 80 g of 0.01 N hydrochloric acid was added and the mixture was aged at 60°C for 3 hours. 0.03 g of sodium bicarbonate was added to the resulting reaction product for neutralization, then 0.2 g of ferulic acid was added. The solvent was removed by vacuum stripping at 100°C and 2.5 kPa for 3 hours to obtain comparative polyalkylene oxide-containing organopolysiloxane composition 3. The content of polyalkylene oxide (component Y) in this composition was 43 parts by mass per 100 parts by mass of polyalkylene oxide-containing organopolysiloxane (component X). The platinum content (P) and the total content (Z) of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (component Z) in the composition were also determined. A ) Mass ratio (P) / (Z A The value was 0.04. [ka]

[0102] The ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol content of each polyalkylene oxide-containing organopolysiloxane composition prepared in Examples 1-6 and Comparative Examples 1-3 was measured by gas chromatography (Agilent Technologies 8890 GC system, using a capillary column, FID detector, measured after 10-fold dilution with acetone). The results of measurements taken immediately after preparation and after 1 year of standing at room temperature are shown in Tables 1 and 2.

[0103] [Table 1]

[0104] [Table 2]

[0105] As shown in Tables 1 and 2, the polyalkylene oxide-containing organopolysiloxane compositions 1 to 6 of Examples 1 to 6, which contain polyalkylene oxide-containing organopolysiloxanes produced by the manufacturing method of the present invention, were stable with low content of ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol (50 ppm or less) both immediately after production and after one year.

[0106] On the other hand, in comparative polyalkylene oxide-containing organopolysiloxane compositions 1 to 3, which include polyalkylene oxide-containing organopolysiloxanes produced from Comparative Example 1 (where the water content of the reaction solution exceeded 2,000 ppm), Comparative Example 2 (where no antioxidant was used), and Comparative Example 3 (where an antioxidant was added after the reaction), the content of any one of the following components exceeded 50 ppm immediately after production: ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol. Furthermore, the content of these components tended to increase after one year, indicating that these compositions were unstable.

[0107] This specification includes the following embodiments: [1]: A method for producing a polyalkylene oxide-containing organopolysiloxane, wherein in the presence of an antioxidant and a platinum catalyst, (A) An organohydrogenpolysiloxane containing one or more hydrosilyl groups in the molecule, (B) Polyalkylene oxide compounds containing one or more terminal unsaturated bonds within the molecule, A method for producing a polyalkylene oxide-containing organopolysiloxane, comprising a step of adding to a compound, characterized in that the water content in the reaction solution is 2,000 ppm or less. [2]: A method for producing the polyalkylene oxide-containing organopolysiloxane described in [1] above, characterized in that one or more are selected from carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopherol acetate, pt-butylphenol, butylhydroxyanisole, 4-hydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, gallic acid, gallic acid esters, sulfites, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, and quercetin as the antioxidant. [3]: A method for producing the polyalkylene oxide-containing organopolysiloxane according to [1] or [2] above, characterized in that the component (A) is an organohydrogenpolysiloxane represented by the following general formula (1). [ka] (In the formula, R 1 The groups are independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, if b2 is 0, R 1 At least one of these atoms is a hydrogen atom. The bonding order of each siloxane unit may be in a block or random. [4]: A method for producing any one of the polyalkylene oxide-containing organopolysiloxanes described in [1] to [3] above, characterized in that the component (B) is a polyalkylene oxide compound represented by the following general formula (2) or (3). [ka] (In the formula, R 2 R is a hydrogen atom or a methyl group, A(where e is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50. The bonding of each oxyalkylene group may be blocked or random.) [5]: A method for producing any one of the polyalkylene oxide-containing organopolysiloxanes described in [1] to [4] above, characterized by further adding an inorganic acid after the addition reaction step, and performing a vacuum strip at 90°C or higher. [6]: In the step of the addition reaction, in addition to component (A) and component (B), (C) Siloxane compounds selected from the following general formulas (4) and (5) having an unsaturated bond at the C terminus A method for producing any one of the polyalkylene oxide-containing organopolysiloxanes described in [1] to [5] above, characterized by subjecting it to an addition reaction. [ka] (In the formula, h is a number from 0 to 6, i is from 1 to 100, and R' is a group selected from alkyl groups and phenyl groups having 1 to 10 carbon atoms.) [7]: A method for producing the polyalkylene oxide-containing organopolysiloxane according to [6], characterized in that, in the step of the addition reaction, the components (A), (B), and (C) are subjected to the addition reaction together. [8]: A method for producing the polyalkylene oxide-containing organopolysiloxane according to [6], characterized in that, in the step of the addition reaction, component (A) and component (B) are subjected to an addition reaction, and then component (C) is subjected to an addition reaction. [9]: A method for producing the polyalkylene oxide-containing organopolysiloxane according to [6], characterized in that, in the step of the addition reaction, component (A) and component (C) are subjected to an addition reaction, and then component (B) is subjected to an addition reaction.

[10] : A polyalkylene oxide-containing organopolysiloxane composition, (X) Polyalkylene oxide-containing organopolysiloxane: 100 parts by mass, (Y) Polyalkylene oxide represented by the following general formula (2') or (3'): 1 to 40 parts by mass, and (Z) Ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol: 50 ppm or less each The composition contains (P) the amount of platinum contained in the composition and the total amount of (Z) component (Z A A polyalkylene oxide-containing organopolysiloxane composition characterized in that the mass ratio (P) / with respect to ) is 0.1 to 15. [ka] (In the formula, R A (where is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random. X is one or more groups independently selected from hydroxyl groups, -CH2CH=CH2, and -CH=CH2-CH3.)

[11] : The polyalkylene oxide-containing organopolysiloxane composition according to

[10] , characterized in that the (X) component is an addition product of an organohydrogenpolysiloxane represented by the following general formula (1) and a polyalkylene oxide compound represented by the following general formula (2) or (3). [ka] (In the formula, R 1 The groups are independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, if b2 is 0, R 1At least one of these atoms is a hydrogen atom. The bonding order of each siloxane unit may be in a block or random. [ka] (In the formula, R 2 R is a hydrogen atom or a methyl group, A (where e is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50. The bonding of each oxyalkylene group may be blocked or random.)

[12] : The polyalkylene oxide-containing organopolysiloxane composition of

[11] , characterized in that the (X) component is further an addition product with a siloxane compound selected from the following general formulas (4) and (5). [ka] (In the formula, h is a number from 0 to 6, i is from 1 to 100, and R' is a group selected from alkyl groups and phenyl groups having 1 to 10 carbon atoms.)

[0108] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A method for producing a polyalkylene oxide-containing organopolysiloxane, wherein in the presence of an antioxidant and a platinum catalyst, (A) An organohydrogenpolysiloxane containing one or more hydrosilyl groups in the molecule, (B) Polyalkylene oxide compounds containing one or more terminal unsaturated bonds within the molecule, A method for producing a polyalkylene oxide-containing organopolysiloxane, comprising a step of adding to a compound, characterized in that the water content in the reaction solution is 2,000 ppm or less.

2. A method for producing a polyalkylene oxide-containing organopolysiloxane according to claim 1, characterized in that one or more selected from carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopherol acetate, p-t-butylphenol, butylhydroxyanisole, 4-hydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, gallic acid, gallic acid esters, sulfites, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, and quercetin is used as the antioxidant.

3. A method for producing a polyalkylene oxide-containing organopolysiloxane according to claim 1, characterized in that the (A) component is an organohydrogenpolysiloxane represented by the following general formula (1). 【Chemistry 1】 (In the formula, R １ The group is independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, if b2 is 0, R １ At least one of these atoms is a hydrogen atom. The bonding order of each siloxane unit may be in a block or random.

4. A method for producing a polyalkylene oxide-containing organopolysiloxane according to claim 1, characterized in that the component (B) is a polyalkylene oxide compound represented by the following general formula (2) or (3). 【Chemistry 2】 (In the formula, R ２ R is a hydrogen atom or a methyl group, Ａ (where is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random.)

5. A method for producing a polyalkylene oxide-containing organopolysiloxane according to claim 1, characterized in that it further includes the step of adding an inorganic acid after the addition reaction step, and the step of performing a stripping under reduced pressure at 90°C or higher.

6. In the step of the addition reaction, in addition to component (A) and component (B), (C) Siloxane compounds selected from the following general formulas (4) and (5) having an unsaturated bond at the terminus. A method for producing a polyalkylene oxide-containing organopolysiloxane according to any one of claims 1 to 5, characterized by subjecting to an addition reaction. 【Transformation 3】 (In the formula, h is a number from 0 to 6, i is from 1 to 100, and R' is a group selected from alkyl groups and phenyl groups having 1 to 10 carbon atoms.)

7. The method for producing a polyalkylene oxide-containing organopolysiloxane according to claim 6, characterized in that, in the step of carrying out the addition reaction, component (A), component (B), and component (C) are subjected to the addition reaction collectively.

8. The method for producing a polyalkylene oxide-containing organopolysiloxane according to claim 6, characterized in that, in the step of the addition reaction, component (A) and component (B) are subjected to an addition reaction, and then component (C) is subjected to an addition reaction.

9. A method for producing a polyalkylene oxide-containing organopolysiloxane according to claim 6, characterized in that, in the step of the addition reaction, component (A) and component (C) are subjected to an addition reaction, and then component (B) is subjected to an addition reaction.

10. A polyalkylene oxide-containing organopolysiloxane composition, (X) Polyalkylene oxide-containing organopolysiloxane: 100 parts by mass, (Y) Polyalkylene oxide represented by the following general formula (2') or (3'): 1 to 40 parts by mass, and (Z) Ethylene oxide, ethylene glycol, diethylene glycol, propylene oxide, propylene glycol, and dipropylene glycol: 50 ppm or less each The composition contains (P) the amount of platinum contained in the composition and the total amount of (Z) component (Z Ａ A polyalkylene oxide-containing organopolysiloxane composition characterized in that the mass ratio (P) / with respect to ) is 0.1 to 15. 【Chemistry 4】 (wherein, R Ａ is a hydrogen atom, or a group selected from an alkyl group having 1 to 6 carbon atoms and an acyl group having 2 to 7 carbon atoms, e is 1 ≦ e ≦ 10, f is 1 ≦ f ≦ 100, g is 0 ≦ g ≦ 50, and the bonds of each oxyalkylene group may be block or random. X is independently a hydroxyl group, -CH ２ CH=CH ２ and -CH=CH ２ -CH ３ and is one or more groups selected therefrom.)

11. The polyalkylene oxide-containing organopolysiloxane composition according to claim 10, characterized in that the (X) component is an addition product of an organohydrogenpolysiloxane represented by the following general formula (1) and a polyalkylene oxide compound represented by the following general formula (2) or (3). 【Transformation 5】 (In the formula, R １ The group is independently selected from a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a is 1 ≤ a ≤ 10, b1 is 0 ≤ b1 ≤ 1,000, b2 is 0 ≤ b2 ≤ 80, c is 0 ≤ c ≤ 10, d is 0 ≤ d ≤ 10, and 3 ≤ a + b1 + b2 + c + d ≤ 1,100. However, if b2 is 0, R １ At least one of these atoms is a hydrogen atom. The bonding order of each siloxane unit may be in a block or random. 【Transformation 6】 (In the formula, R ２ R is a hydrogen atom or a methyl group, Ａ (where is a hydrogen atom, or a group selected from C1-C6 alkyl groups and C2-C7 acyl groups, e is 1 ≤ e ≤ 10, f is 1 ≤ f ≤ 100, and g is 0 ≤ g ≤ 50, and the bonding of each oxyalkylene group may be block or random.)

12. The polyalkylene oxide-containing organopolysiloxane composition according to claim 11, characterized in that the (X) component is further an addition reaction product with a siloxane compound selected from the following general formulas (4) and (5). 【Transformation 7】 (In the formula, h is a number from 0 to 6, i is from 1 to 100, and R' is a group selected from alkyl groups and phenyl groups having 1 to 10 carbon atoms.)

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