JP2015093979A - Method for producing organopolysiloxane graft polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an organopolysiloxane graft polymer, in which the odor intensity of the organopolysiloxane graft polymer obtained by utilizing a mercapto compound can be lowered and odor quantity thereof can be changed.SOLUTION: The method for producing the organopolysiloxane graft polymer comprises the steps of: radically polymerizing mercaptan-modified organopolysiloxane and an unsaturated monomer in the presence of a solvent to obtain a polymer solution (I); and distilling the solvent while introducing steam into the polymer solution. The amount of the steam to be introduced is 80-600 pts. mass when that of the solvent in the polymer solution (I) is 100 pts. mass.

Description

  The present invention relates to a method for producing an organopolysiloxane graft polymer, and more particularly to a method for producing an organopolysiloxane graft polymer useful as a hair cosmetic.

Mercapto compounds have long been used for the purpose of controlling the molecular weight of polymers due to their high chain transfer ability. However, it has a peculiar sulfur odor or decaying odor, and the threshold value is very low. Therefore, depending on the application, it cannot be used unless it is debrominated or deodorized. Various studies have been made.
For example, as a chemical treatment method, Patent Document 1 treats with a lead compound and a copper compound, Patent Document 2 treats with an oxidizing agent, and Patent Document 3 treats with hydrogen peroxide and a preservative. A method is described.
A method of combining chemical treatment with physical treatment such as heat treatment and distillation operation has also been proposed. For example, Patent Document 4 describes a method of performing distillation under reduced pressure after alkali hydrolysis treatment, and Patent Document 5 describes a method of removing a solvent by heating and pressure-reducing operations after adding a basic compound.

Further, when a graft polymer of polyorganosiloxane using a mercapto compound is used in cosmetics, particularly hair cosmetics, there is a problem of odor, so an improvement method has been studied. For example, Patent Document 6 describes a method for improving odor by free radical polymerization of a monomer and a silicon derivative in the presence of an alkanethiol having a carbon chain length of 10 to 12 carbon atoms.
Therefore, as shown in Patent Document 7 and Patent Document 8, it is known that mercapto compounds used in this field are generally high-boiling compounds. Therefore, it has been considered difficult to reduce to a target odor level only by physical treatment using hot water or steam.

JP-A-3-38531 Japanese Patent Laid-Open No. 7-2116018 JP 2007-92062 A JP 63-125502 A JP 2008-101120 A Special table 2005-513232 gazette JP-A-10-182727 JP 2003-221407 A

  In the method of Patent Document 1, coloring problems caused by metal ions may occur. In the method using the oxidizing agent of Patent Document 2, pH adjustment is performed to promote the decomposition, or the pH is returned to the original state. It is necessary to carry out complicated work to return to. In addition, Patent Document 3 also requires the same pH operation since peroxide acts as an oxidizing agent. In the case of using the oxidizing agent, if the oxidizing agent is not completely decomposed, it may affect the storage stability, and therefore it is necessary to further perform a reduction treatment.

Patent Documents 4 and 5 are a combination of a chemical treatment method and a physical treatment method, and the hue is deteriorated by the addition of a basic component, and it is necessary to go through a multi-stage manufacturing process.
Moreover, in the method shown in patent documents 6-8, a weak unpleasant odor may remain and sufficient deodorization cannot be performed.

  The present invention provides a method for producing an organopolysiloxane graft polymer that can reduce the odor intensity and change the odor quality of an organopolysiloxane graft polymer obtained by using a mercapto compound.

  The present invention relates to an organopolycarbonate which is obtained by radically polymerizing a mercaptan-modified organopolysiloxane and an unsaturated monomer in the presence of a solvent while distilling off the solvent while introducing water vapor. A method for producing a polysiloxane graft polymer, wherein the amount of the water vapor relative to 100 parts by mass of the solvent in the polymer solution (I) is 80 parts by mass or more and 600 parts by mass or less. provide.

  According to the present invention, there is provided an organopolysiloxane graft polymer production method capable of reducing the odor intensity and changing the odor quality of an organopolysiloxane graft polymer obtained by using a mercapto compound. be able to.

The present invention relates to an organopolycarbonate which is obtained by radically polymerizing a mercaptan-modified organopolysiloxane and an unsaturated monomer in the presence of a solvent while distilling off the solvent while introducing water vapor. A method for producing a polysiloxane graft polymer, wherein the amount of the water vapor relative to 100 parts by mass of the solvent in the polymer solution (I) is 80 parts by mass or more and 600 parts by mass or less. is there.
As described above, according to the present invention, the odor intensity of the organopolysiloxane graft polymer obtained by using the mercapto compound can be lowered and the odor quality can be changed. The reason for this is not clear, but it is thought that the odor-causing substance dissolved in the polymer solution (I) is altered by water vapor.
In the present specification, the step of obtaining a polymer solution (I) by radical polymerization of a mercaptan-modified organopolysiloxane and an unsaturated monomer in the presence of a solvent is referred to as “step (1)”. The step of distilling off the solvent while introducing water vapor to (I) may be referred to as “step (2)”.

[Step (1)]
In the step (1), a polymer solution (I) is obtained by radical polymerization of a mercaptan-modified organopolysiloxane and an unsaturated monomer in the presence of a solvent.
<Mercaptan-modified organopolysiloxane>
The mercaptan-modified organopolysiloxane can be obtained by reacting an organopolysiloxane having a reactive functional group with a radical reactivity imparting agent.
(Organopolysiloxane having a reactive functional group)
As the organopolysiloxane having a reactive functional group, those represented by the general formulas (1) and (2) are preferable. The organopolysiloxanes having reactive functional groups represented by the general formulas (1) and (2) are commercially available in various molecular weights and are easily available.

In the general formulas (1) and (2), R ¹ independently represents an alkyl group having 1 to 22 carbon atoms, and R ² represents an alkyl group having a reactive functional group (hereinafter referred to as “reactive group”). Also referred to as “containing alkyl group”. p represents a number of 2 to 4000, and q represents a number of 2 to 250. In the formula, the bonding mode of p repeating units and q repeating units may be such that each repeating unit is connected in a block shape or in a random shape.

In the general formulas (1) and (2), examples of the alkyl group represented by R ¹ include a linear, branched, or cyclic alkyl group. The carbon number of the alkyl group represented by R ¹ is From the viewpoint of water dispersibility of the graft polymer, it is preferably 1 or more and 10 or less, more preferably 6 or less. Specific examples of the alkyl group represented by R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group, nonadecyl group, eicosyl group, docosyl group and the like.

Among these, as R ¹ , from the viewpoint of water dispersibility of the graft polymer, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a linear or branched chain having 1 to 3 carbon atoms is preferable. An alkyl group is more preferable, and a methyl group is still more preferable.

In the general formulas (1) and (2), p represents a number of 2 to 4000, and q represents a number of 2 to 250.
p is preferably a number of 50 or more, more preferably 80 or more, and even more preferably 100 or more, from the viewpoint of hair feel (reducing stickiness) after setting the hair with a hair cosmetic using an organopolysiloxane graft polymer. From the viewpoint of water dispersibility of the graft polymer, the number is preferably 2000 or less, more preferably 1300 or less, still more preferably 700 or less, still more preferably 200 or less, and even more preferably 150 or less.
From the viewpoint of the water dispersibility of the graft polymer, q is preferably a number of 3 or more, more preferably 4 or more, and the setting power of hair cosmetics using an organopolysiloxane graft polymer and the maintenance of the hair shape after setting. From the viewpoint of properties, the number is preferably 50 or less, more preferably 30 or less, still more preferably 10 or less, and still more preferably 6 or less.

In the present invention, the reactive functional group means a hydroxyl group, an amino group, a carboxy group, or an epoxy group.
The organopolysiloxane having a reactive functional group has one or more substituents selected from a hydroxyl group, an amino group, a carboxy group, and an epoxy group.

In the general formulas (1) and (2), the number of carbon atoms of the reactive group-containing alkyl group represented by R ² is preferably 1 or more from the viewpoint of easy availability of the organopolysiloxane having a reactive functional group. More preferably, it is 2 or more. Further, from the viewpoint of water dispersibility of the graft polymer, it is preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less.

  Specific examples of the reactive group-containing alkyl group in the present invention include the following formulas (i) to (viii). From the viewpoint of availability, one or more selected from (i) to (iv) (Iv) is more preferable from the viewpoint of reactivity.

  The weight average molecular weight (MWsim) of the organopolysiloxane having a reactive functional group is determined from the viewpoint of the setting power when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the holding power of the hair shape after setting. , Preferably it is 3000 or more, More preferably, it is 5000 or more, More preferably, it is 10,000 or more, More preferably, it is 15,000 or more. From the viewpoint of the water dispersibility of the graft polymer, it is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, and still more preferably 40,000 or less.

  The number of moles of the reactive functional group present per unit mass of the organopolysiloxane having a reactive functional group is the setting force when the hair is set with a hair cosmetic containing an organopolysiloxane graft polymer and the hair after setting. From the viewpoint of improving the holding power of the shape, it is preferably 1/500 mol / g or less, more preferably 1/700 mol / g or less, still more preferably 1/1000 mol / g or less, and the water dispersibility of the graft polymer can be reduced. From the viewpoint, it is preferably 1/1000 mol / g or more, more preferably 1/5000 mol / g or more, and still more preferably 1/3000 mol / g or more.

(Radical reactivity imparting agent)
In the present invention, the radical reactivity imparting agent is an agent that adds a radical reactive functional group to an organopolysiloxane having a reactive functional group by reacting with the reactive functional group of the organopolysiloxane having a reactive functional group. Say.
As the radical reactivity imparting agent, a compound having a radical reactive functional group in the molecule and one or more functional groups selected from a carboxy group, an ester group, an epoxy group, a hydroxyl group, and a lactone, And thioesters, among which thioesters are preferred. That is, the mercaptan-modified organopolysiloxane in the present invention is preferably obtained by reacting an organopolysiloxane having a reactive functional group with a thioester.
The thioester is preferably a thiolactone which may have a substituent, and the thiolactone which may have a substituent may be γ-thiobutyrolactone, N-acetyl-DL-, from the viewpoint of reactivity during polymerization. Examples include homocysteine thiolactone and DL-homocysteine thiolactone hydrochloride. Among these, as the radical reactivity imparting agent, N-acetyl-DL-homocysteine thiolactone is more preferable from the viewpoint of reactivity with the reactive organopolysiloxane and reactivity during polymerization.

  The amount of the radical reactivity imparting agent used is preferably 0.8 equivalents or more from the viewpoint of reactivity with the reactive organopolysiloxane with respect to the total amount of reactive functional groups of the organopolysiloxane having a reactive functional group, 0.9 equivalent or more is more preferable. From the viewpoint of reducing the unreacted radical reactivity imparting agent after the reaction, 1.2 equivalents or less is preferable, and 1.1 equivalents or less is more preferable.

(Production of mercaptan-modified organopolysiloxane)
In the reaction between the radical reactivity imparting agent and the organopolysiloxane having a reactive functional group, a solvent may be used.
Solvents include water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane and cyclohexane, ethers such as diethyl ether and tetrahydrofuran. , Aromatic compounds such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform. From the viewpoint of productivity and reactivity with the reactive organopolysiloxane, it is preferable not to use a solvent.

The reaction temperature is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of reactivity, preferably 200 ° C. or lower, more preferably 150 ° C., from the viewpoint of chemical stability of the resulting mercaptan-modified organopolysiloxane. Below, it is 110 degrees C or less more preferably.
The reaction time is preferably 1 hour or more, more preferably 2 hours or more from the viewpoint of sufficiently allowing the reaction to proceed, and preferably 10 hours or less, more preferably 5 hours or less from the viewpoint of productivity.
The reaction is preferably performed until the reaction between the functional group of the reactive organopolysiloxane and the radical reactivity-imparting agent proceeds at least 80%, and proceeds at least 90% from the viewpoint of the reactivity of the obtained mercaptan-modified organopolysiloxane. It is more preferable to carry out until.
The mercaptan-modified organopolysiloxane obtained by this reaction is preferably in a solution state from the viewpoint of the viscosity of the radical-reactive organosiloxane solution. The concentration of the mercaptan-modified organopolysiloxane solution can be appropriately adjusted with a solvent that uniformly dissolves the mercaptan-modified organopolysiloxane.
Solvents used to adjust the concentration of mercaptan-modified organopolysiloxane solution include water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hexane and cyclohexane, etc. And hydrocarbons such as diethyl ether and tetrahydrofuran, aromatic compounds such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform.
Among these, from the viewpoint of obtaining a graft polymer having a more uniform side chain molecular weight distribution, it is possible to use one or two or more solvents selected from alcohols having 1 to 8 carbon atoms such as water, ethanol and isopropanol. It is preferable to use one or more solvents selected from water, ethanol, and isopropanol.
The concentration of the mercaptan-modified organopolysiloxane solution after the concentration adjustment is preferably 10% by mass or more, more preferably 30% by mass or more from the viewpoint of productivity, and from the viewpoint of the viscosity of the radical reactive organosiloxane solution, Preferably it is 100 mass% or less, More preferably, it is 80 mass% or less.
Further, mercaptan-modified organopolysiloxane whose radical reactive group is a mercapto group can be obtained as a commercial product, and examples thereof include KF-2001 (manufactured by Shin-Etsu Chemical Co., Ltd.).

<Unsaturated monomer>
The organopolysiloxane graft polymer is a mercaptan-modified organopolysiloxane in the main chain, and has a polymer segment derived from an unsaturated monomer in the side chain.
There are no particular limitations on the unsaturated monomer that can be used in the polymer segment derived from the unsaturated monomer, such as a nonionic unsaturated monomer, a cationic unsaturated monomer, and an anion. Unsaturated monomers can be used.

(Nonionic unsaturated monomer)
Although there is no restriction | limiting in particular as a nonionic unsaturated monomer, Tg is 60 from a viewpoint of the set retention property in the high humidity at the time of setting hair with the hair cosmetics using an organopolysiloxane graft polymer. It is preferable to use a nonionic unsaturated monomer having a temperature of 0 ° C. or higher.
Content of repeating unit derived from a nonionic unsaturated monomer (excluding an unsaturated monomer having an amino group) having a Tg of 60 ° C. or higher in the polymer segment derived from the unsaturated monomer Is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% from the viewpoint of set retention at high humidity when hair is set with a hair cosmetic using an organopolysiloxane graft polymer. It is 70% by mass or more, more preferably 70% by mass or more.
The repeating unit derived from an unsaturated monomer having an amino group is protonated depending on the environment in the product and the environment at the time of use, and is not a repeating unit derived from a nonionic unsaturated monomer. In the present invention, it is not included in “a repeating unit derived from a nonionic unsaturated monomer”.

  The Tg of the nonionic unsaturated monomer is preferably 80 ° C. from the viewpoints of setting power when hair is set with a hair cosmetic using an organopolysiloxane graft polymer and set retention under high humidity. Above, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, and preferably 190 ° C. or lower from the viewpoint of hair feel after setting the hair with a hair cosmetic using an organopolysiloxane graft polymer. More preferably, it is 170 degrees C or less, More preferably, it is 150 degrees C or less.

  In the present invention, the Tg of an unsaturated monomer refers to a Tg of a homopolymer obtained by polymerizing the monomer. In the present invention, the nonionic unsaturated monomer having a Tg of 60 ° C. or higher An unsaturated monomer having a Tg of 60 ° C. or higher described in “polymer handbook”, 4th edition, Volume VI / 193-VI / 277, published by Wiley-Interscience. Moreover, in this invention, the repeating unit derived from an unsaturated monomer means the repeating unit structure in the homopolymer obtained when this unsaturated monomer is polymerized.

Specific examples of the nonionic unsaturated monomer having a Tg of 60 ° C. or higher include acrylamide compounds, methacrylamide compounds, styrene compounds, and the like.
Among these, acrylamide, N-sec-butylacrylamide, N-tert-butyl are used from the viewpoint of setting power when hair is set with a hair cosmetic using an organopolysiloxane graft polymer and set retention under high humidity. Selected from acrylamide, N, N-dibutylacrylamide, N, N-diisopropylacrylamide, N, N-dimethylacrylamide, isohexylacrylamide, isooctylacrylamide, N- (1-methylbutyl) acrylamide, and N-tert-butylmethacrylamide 1 type or 2 types or more are preferable, 1 type or 2 types or more selected from N, N-dibutylacrylamide, N, N-diisopropylacrylamide and N, N-dimethylacrylamide are more preferable, N-ter - butyl acrylamide and N, a combination of N- dimethylacrylamide more preferred. Furthermore, in this case, the content of N, N-dimethylacrylamide in the polymerization segment derived from the unsaturated monomer is preferably 50% by mass or more, more preferably 70%, from the viewpoint of water dispersibility of the graft polymer of the present invention. From the viewpoint of hair feel after setting hair with a hair cosmetic using an organopolysiloxane graft polymer, it is preferably 100% by mass or less, more preferably 95% by mass or more. It is not more than mass%, more preferably not more than 90 mass%.
The repeating unit derived from a nonionic unsaturated monomer having a Tg of 60 ° C. or higher may be a single type, or two or more types may be mixed.

(Cationic unsaturated monomer)
The polymer segment derived from the unsaturated monomer that is the side chain of the organopolysiloxane graft polymer is composed of the setting power when the hair is set with a hair cosmetic using the organopolysiloxane graft polymer and the organopolysiloxane graft at the time of washing the hair. From the viewpoint of easy removal of the polymer (hereinafter also referred to as “detergency”), in addition to the nonionic unsaturated monomer, a repeating unit derived from a cationic unsaturated monomer may be included.
The polymer segment derived from the unsaturated monomer is cationic from the viewpoint of the setting power when the hair is set with a hair cosmetic using an organopolysiloxane graft polymer and the detergency of the organopolysiloxane graft polymer during washing. The repeating unit derived from an unsaturated monomer is preferably contained in an amount of 10% by mass or more, more preferably 15% by mass or more, and further preferably 19% by mass or more. Further, from the viewpoint of setting power when hair is set with a hair cosmetic using an organopolysiloxane graft polymer, the content is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. .
Nonionic property having a Tg of 60 ° C. or higher in the polymer segment derived from an unsaturated monomer when the polymer segment derived from an unsaturated monomer contains a repeating unit derived from a cationic unsaturated monomer The content of the repeating unit derived from the unsaturated monomer is preferably 40% by mass or more from the viewpoint of set retention under high humidity when the hair is set with a hair cosmetic using an organopolysiloxane graft polymer. More preferably, it is 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. When the hair is set with a hair cosmetic using an organopolysiloxane graft polymer, From the viewpoint of feel, it is preferably 100% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and still more preferably. Ku is 80 mass% or less.

In the present invention, the cationic unsaturated monomer means an unsaturated monomer having a cationic functional group, and the cationic functional group means a quaternary ammonium group, a pyridinium group or the like. In addition to a functional group having a positive charge regardless of the environment, a functional group that is protonated by the environment and has a positive charge, such as a primary, secondary, or tertiary amino group and a pyridino group.
The cationic unsaturated monomer is a compound represented by the following general formula (3) from the viewpoint of setting power and detergency when hair is set with a hair cosmetic using an organopolysiloxane graft polymer. Is preferred.

In the formula, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Represent. R ³ , R ⁴ and R ⁵ are preferably hydrogen atoms from the viewpoint of availability of raw materials during production of the organopolysiloxane graft polymer. R ⁶ and R ⁷ are preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoint of availability of raw materials during production of the organopolysiloxane graft polymer. R ⁸ is preferably a hydrogen atom from the viewpoint of availability of raw materials during production of the organopolysiloxane graft polymer. Y ¹ is an alkylene group having 1 to 12 carbon ^{atoms, -COOR 9 -, - CONHR 9} -, - OCOR 9 -, - R 10 -OCO-R 9 - is a group selected from. Here, R ⁹ and R ¹⁰ are each independently an alkylene group having 1 to 5 carbon atoms, and R ⁹ has 2 to 3 carbon atoms from the viewpoint of availability of raw materials during production of the organopolysiloxane graft polymer. An alkylene group is preferred, and R ¹⁰ is more preferably a methylene group. From the viewpoint of availability of raw materials at the time of preparation of the organopolysiloxane graft polymer, Y ¹ is -COOR ⁹ -, - CONHR ⁹ - more preferably, -CONHR ⁹ - further preferably.

X ¹⁻ is a halide ion such as chloride ion or bromide ion; alkyl sulfate ion having 1 to 3 carbon atoms, acetate ion, lactate ion, benzoate ion, adipate ion, formate ion, malate ion, glycol An anion such as an organic acid ion such as an acid ion; Alkyl sulfate ion, lactate ion, formate ion, malate ion from the viewpoint of hair feel after setting with hair cosmetics using organopolysiloxane graft polymer and set retention under high humidity Glycolic acid ions are preferable, and lactic acid ions are more preferable.

The side chain of the organopolysiloxane graft polymer is a repeating unit derived from a cationic unsaturated monomer represented by the structural formula in which at least one of R ^{6 to} R ⁸ is a hydrogen atom in the general formula (3). The repeating unit may be deprotonated under certain conditions to be a repeating unit derived from a nonionic unsaturated monomer, and the monomer has a Tg of 60 ° C. or higher. However, in the present invention, the repeating unit derived from the monomer is not regarded as a repeating unit derived from a nonionic unsaturated monomer having a Tg of 60 ° C. or higher, but derived from a cationic unsaturated monomer. It is considered as a repeating unit.
The side chain of the organopolysiloxane graft polymer is a repeating unit derived from a cationic unsaturated monomer represented by the structural formula in which at least one of R ^{6 to} R ⁸ is a hydrogen atom in the general formula (3). A part of the repeating unit may be deprotonated.

Specific examples of the cationic unsaturated monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and dimethylaminoethyl (meth). Acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, 2-vinylpyridine, 4-vinylpyridine and these were neutralized with an acid represented by H ⁺ X ^1- Structure is mentioned. Here, X ¹⁻ has the same meaning as X ¹⁻ in the general formula (3). Further, (meth) acryloyloxyethyltrimethylammonium having X ¹⁻ as a counter ion, (meth) acryloyloxypropyltrimethylammonium, (meth) acryloylaminoethyltrimethylammonium, (meth) acryloylaminopropyltrimethylammonium, Diallyldimethylammonium, 1-ethyl-4-vinylpyridinium, 1,2-dimethyl-5-vinylpyridinium, and the like. Setting power and washing when hair is set with a hair cosmetic using an organopolysiloxane graft polymer From the viewpoint of properties, dimethylaminopropylacrylamide is preferable.

(Anionic unsaturated monomer)
The polymer segment derived from the unsaturated monomer which is the side chain of the organopolysiloxane graft polymer is an anion from the viewpoint of the hair washability of the hair to which the hair cosmetic is attached and the dispersibility of the graft polymer in the solvent. It may contain a repeating unit derived from an unsaturated monomer.
In the polymer segment derived from the unsaturated monomer, the content of the repeating unit derived from the anionic unsaturated monomer is determined in terms of the hair washability of the hair to which the hair cosmetic is attached, and in the ethanol of the graft polymer. From the viewpoint of dispersibility, it is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more, and from the viewpoint of the feel of the hair after setting the hair, preferably 85%. It is at most 80% by mass, more preferably at most 80% by mass, even more preferably at most 75% by mass, even more preferably at most 70% by mass.

In the present invention, the anionic unsaturated monomer is preferably an unsaturated monomer having a carboxylic acid or a salt thereof, such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, Examples thereof include unsaturated carboxylic acid monomers such as crotonic acid. Among these, (meth) acrylic acid and maleic acid are preferable from the viewpoint of availability, and (meth) acrylic acid is more preferable.
The repeating unit derived from the unsaturated monomer having a carboxylic acid may be an acid or may be partially or wholly neutralized. Specific examples of the base compound used for neutralization include, for example, alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; ammonia; mono-, di-, or triethanolamine, triethylamine, morpholine And amine compounds such as aminomethylpropanol and aminoethylpropanediol. Among these, from the viewpoint of water dispersibility of the graft polymer, it is preferable that a part or the whole is neutralized.

<Method for producing organopolysiloxane graft polymer>
Although there is no restriction | limiting in particular as a manufacturing method of a graft polymer, In this invention, the graft-from method of radical-polymerizing an unsaturated monomer in presence of mercaptan modified organopolysiloxane is preferable.
As a method for polymerizing an unsaturated monomer in the presence of a mercaptan-modified organopolysiloxane, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or the like can be adopted, and a solution from the viewpoint of easy temperature control. A polymerization method is preferred.

  The amount of the unsaturated monomer used as the raw material is preferably 30 with respect to the total amount of the mercaptan-modified organopolysiloxane used as the raw material and the unsaturated monomer used as the raw material from the viewpoint of water dispersibility of the graft polymer. From the viewpoint of hair feel after setting the hair with a hair cosmetic containing an organopolysiloxane graft polymer, it is preferably 90% by mass or less, more preferably 40% by mass or more, more preferably 40% by mass or more. Is 80% by mass or less, more preferably 70% by mass or less.

When the polymerization of the unsaturated monomer is performed by a solution polymerization method, the solvent used is not particularly limited as long as the raw material mercaptan-modified organopolysiloxane, the unsaturated monomer, and the resulting organopolysiloxane graft polymer are dissolved. Absent.
Specific examples of the solvent include water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane and cyclohexane, diethyl ether and tetrahydrofuran. And ethers such as benzene, toluene and the like, and halogenated hydrocarbons such as dichloromethane and chloroform. These may be used alone or in combination of two or more.
Among these, from the viewpoint of obtaining a graft polymer having a more uniform side chain molecular weight distribution, it is possible to use one or two or more solvents selected from alcohols having 1 to 8 carbon atoms such as water, ethanol and isopropanol. preferable.
In the present invention, from the viewpoint of distilling off the solvent in the step (2), an aqueous solvent such as water and ethanol is preferable, and one or two or more selected from alcohols having 1 to 3 carbon atoms such as water and ethanol. Is more preferable, and ethanol is still more preferable.

  The amount of the solvent used is not particularly limited as long as the raw material, mercaptan-modified organopolysiloxane, unsaturated monomer, and the resulting organopolysiloxane graft polymer are dissolved, but the mercaptan-modified organopolysiloxane added at the time of production is used. And from the viewpoint of operability during production, preferably 60% by mass or more, more preferably 80% by mass or more, and from the viewpoint of reactivity, preferably 900% by mass with respect to the total mass of the unsaturated monomer. Hereinafter, it is more preferably 400% by mass or less, further preferably 200% by mass or less, and still more preferably 160% by mass or less.

  Examples of the polymerization initiator include azo-based initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), and peroxides such as lauroyl peroxide and benzoyl peroxide. Examples thereof include oxide initiators and persulfuric acid initiators such as ammonium persulfate, and 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable from the viewpoint of polymerization reactivity. Further, polymerization may be initiated by generating radicals by light irradiation or the like. Although there is no restriction | limiting in particular in the usage-amount of a polymerization initiator, From a viewpoint of the weight average molecular weight of the graft polymer obtained, Preferably it is 10 mass% or less with respect to the total mass of the unsaturated monomer thrown in, More preferably, it is 2 It is below mass%. Further, from the viewpoint of reactivity, the content is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, based on the total mass of the unsaturated monomers to be added.

  The temperature at the time of the polymerization reaction can be appropriately selected depending on the polymerization initiator to be used, the type of solvent, etc., but from the viewpoint of the polymerization reaction rate, it is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher. . Moreover, it is preferable to make it react by a normal pressure for the equipment load used for a polymerization reaction, and from the viewpoint of controlling molecular weight, the temperature at the time of a polymerization reaction becomes like this. Preferably it is 100 degrees C or less, More preferably, it is 90 degrees C or less. In order to keep the polymerization temperature more constant, the polymerization reaction is preferably performed under reflux at the boiling point.

The polymerization reaction is carried out until the conversion rate of the unsaturated monomer is preferably 80% or more, more preferably 90% or more. The conversion can be measured by the method of the example.
The polymerization reaction time is preferably 0.5 hours or more, more preferably 1 hour or more from the viewpoint of conversion, and from the viewpoint of productivity, preferably 60 hours or less, more preferably 30 hours or less, still more preferably. Is 20 hours or less, more preferably 10 hours or less. When the polymerization reaction is performed by dropping raw materials, the polymerization reaction time includes the dropping time. The time for the polymerization reaction can be adjusted by changing the polymerization reaction temperature.

Mercaptan-modified organopolysiloxane and unsaturated monomer, solvent, polymerization initiator, etc. that are raw materials may be added together to conduct the polymerization reaction, but in order to control the composition, molecular weight, etc. The polymerization reaction may be carried out by adding in portions or continuously over a certain period of time. For example, (1) A method in which a mercaptan-modified organopolysiloxane, an unsaturated monomer, and a solvent are mixed and heated, and a solution in which a polymerization initiator is dissolved is added all at once or dropwise; (2) the solvent is heated Then, a method of dropping a solution in which a mercaptan-modified organopolysiloxane, an unsaturated monomer and a polymerization initiator are separately or mixed and dissolved in a solvent; (3) a mercaptan-modified organopolysiloxane, an unsaturated monomer There is a method in which a part of a monomer and a solvent are mixed and heated, and a solution in which the polymerization initiator and the remainder of the unsaturated monomer are dissolved is added all at once or dropwise. From the viewpoint of safety and workability, when the solvent according to the above (2) is heated, a solution in which the mercaptan-modified organopolysiloxane, the unsaturated monomer, and the polymerization initiator are separately or mixed and dissolved in the solvent. The method of dripping is preferred.
Further, after completion of the polymerization reaction, purification or reduction of unreacted unsaturated monomers may be performed by a known method as necessary. For example, an unreacted unsaturated monomer or other impurities may be reduced by further adding a polymerization initiator and heating, membrane purification, adsorbent treatment, or the like.
In addition, after obtaining polymer solution (I) by the said method, you may adjust a density | concentration suitably using the solvent in which the said organopolysiloxane graft polymer melt | dissolves.
The concentration of the polymer in the polymer solution after the concentration adjustment is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more, from the viewpoint of productivity, and the organosiloxane graft polymer solution. From the viewpoint of the viscosity, it is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 40% by mass or less.

[Step (2)]
Step (2) is a step of distilling off the solvent while introducing water vapor to the polymer solution (I), and 80 mass of water vapor with respect to 100 parts by mass of the solvent in the polymer solution (I). This is a step of obtaining a polymer solution (II) to be described later by introducing at least 600 parts by mass.
By providing the step (2), the odor quality of the polymer solution changes, so that the graft polymer has an odor that can be blended into the product. Specifically, the odor of the polymer solution changes from a rotten odor such as sulfur (S-like odor) to a vinyl-like odor (vinyl-like odor). The reason why the odor changes is not clear, but the odor causing substance dissolved in the solution is altered by water vapor, or it changes to a unique odor as a combination of odors of the composition including a trace amount of odor causing substance. This is probably because of this. Obtaining such new knowledge has greatly expanded the range of blending formulations that can be used for perfume and masking, and it has become possible to use organopolysiloxane graft polymers substantially as cosmetics and the like.
The method for introducing water vapor to the polymer solution (I) is not particularly limited, but as a preferred embodiment, for example, the inside of the reaction vessel is under reduced pressure so that the polymer concentration of the polymer solution (I) does not fluctuate greatly, and the solvent Is gradually introduced so that the polymer solution (I) is not concentrated and is adjusted so that the amount of water introduced and the amount of solvent distilled are balanced. Next, since the distillation rate gradually decreases when some of the solvent is replaced with water, an external heating operation is also added, and when most of the solvent is replaced with water, the degree of vacuum is further increased. Then, operations such as promoting the distillation of the solvent are performed. After the water vapor introduction amount and the solvent distillate amount are balanced, an operation of fixing the water vapor introduction amount and changing the temperature and pressure while adjusting the distillate amount is preferable. Further, from the viewpoint of improving the gas-liquid contact efficiency, water vapor is preferably introduced by immersing a water vapor blowing nozzle in the polymer solution (I) under stirring in the solution. Further, when water vapor can be blown from another nozzle attached to the reaction tank, a plurality of water vapors may be introduced from different locations.
As the steam to be blown, either reduced-pressure steam or pressurized steam can be used. From the viewpoint of versatility of equipment, it is preferable to use steam at 100 ° C. (atmospheric pressure) to 150 ° C. (about 5 kg / cm ² ).

The amount of the water vapor with respect to 100 parts by mass of the solvent in the polymer solution (I) is 80 parts by mass or more, preferably 150 parts by mass, from the viewpoint of changing to a odor preferable for blending into the product and reducing the intensity of the odor. Part or more, more preferably 170 parts by weight or more, still more preferably 230 parts by weight or more, still more preferably 250% by weight or more, still more preferably 300 parts by weight or more, and 600 parts by weight or less, preferably Is 500 parts by mass or less, more preferably 450 parts by mass or less, and still more preferably 400 parts by mass or less.
The “100 parts by mass of the solvent” serving as a reference for the amount of water vapor introduced is 100 parts by mass of the solvent in the polymer solution (I) before the introduction of water vapor.
In the present specification, a value obtained by dividing the mass of the water vapor by the mass of the solvent is referred to as a “solvent substitution ratio”. That is, the solvent substitution ratio in the present invention is 0.8 or more and 6 or less.

  The temperature of the polymer solution (I) when introducing water vapor is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, from the viewpoint of changing to a odor preferable for blending into the product and reducing the odor intensity. Preferably it is 30 degreeC or more, Preferably it is 100 degreeC or less, More preferably, it is 90 degreeC or less, More preferably, it is 80 degreeC or less.

The pressure in the reaction tank when introducing water vapor is preferably 101 kPa or less, more preferably 90 kPa or less, and still more preferably 80 kPa or less, from the viewpoint of changing to a odor preferable for blending into a product and reducing the odor intensity. In view of economy, it is preferably 1 kPa or more, more preferably 5 kPa or more, still more preferably 10 kPa or more, and further preferably 30 kPa or more.
For example, when ethanol, which is a solvent having a boiling point lower than that of water, is used as a preferred embodiment of the temperature and pressure operation, the solvent is replaced from ethanol to water, and the saturated vapor pressure of the solvent changes sequentially. The temperature and pressure may be changed simultaneously or individually, or may be changed stepwise.
As the heating medium for distilling off the solvent, heating from the outside may be performed in addition to the steam to be blown, and warm water or steam higher than the boiling point of the polymer solution (I) may be used.

  The amount of water vapor introduced per hour with respect to 100 parts by mass of the solvent in the polymer solution in carrying out the step (2) is from the viewpoint of changing to a odor preferable for blending into the product, and from the viewpoint of reducing the odor intensity. Preferably it is 0.01 mass part or more, More preferably, it is 0.05 mass part or more, More preferably, it is 0.1 mass part or more, Preferably it is 1 mass part or less, More preferably, it is 0.5 mass part or less, More preferably 0.2 parts by mass or less.

  The mass ratio of the amount of solvent distilled off and the amount of water vapor introduced to the polymer solution (I) (water vapor / distilled solvent) changes the odor preferable for blending into the product, and the odor From the viewpoint of reducing the strength of the resin, it is preferably 0.8 or more, more preferably 1.5 or more, still more preferably 1.7 or more, still more preferably 2.3 or more, still more preferably 2.5 or more, and still more preferably. 3 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4.5 or less, and still more preferably 4 or less.

[Step of bringing the aqueous polymer solution (II) into contact with the adsorbent (step (3))]
In the present invention, it is preferable to bring the aqueous polymer solution (II) obtained by introducing water vapor into the polymer solution (I) and distilling off the solvent into contact with the adsorbent. By bringing the polymer solution (II) and the adsorbent into contact with each other, the odor intensity can be efficiently reduced. That is, by performing the step of bringing the aqueous polymer solution (II) into contact with the adsorbent, the amount of water vapor necessary for reducing the odor intensity in the step (2) can be reduced. As a result, the amount of wall adhesion generated in the tank can be reduced, and the yield can be improved.
In the present specification, the step of bringing the aqueous polymer solution (II) into contact with the adsorbent may be referred to as “step (3)”.

The adsorbent is one or more selected from activated carbon, synthetic adsorbent, and ion exchange resin. From the viewpoint of reducing odor strength, preferably one or two selected from activated carbon and synthetic adsorbent. More than a seed.
Examples of the activated carbon used as the adsorbent include commonly used wood, coal, coconut shells activated with chemicals or water vapor, etc., and the shape is also powder, crushed, spherical, or fibrous However, it is not particularly limited. Further, activated carbon washed with an acid is also preferably used from the viewpoint of suppressing elution of metal components in the activated carbon into the treatment liquid. For example, Filtrasorb600 (manufactured by Calgon Carbon Japan), ZN-50 (manufactured by Hokuetsu Carbon Industry Co., Ltd.), Kuraray Coal GLC, Kuraray Coal PK-D, Kuraray Coal PW-D (manufactured by Kuraray Chemical Co., Ltd.), Commercial products such as white birch AW50, white birch A, white birch M, and white birch C (manufactured by Nippon Enviro Chemicals Co., Ltd.) can be used. An activated carbon filter in which activated carbon fine powder is supported on a filter can also be used.

From the viewpoint of reducing the odor intensity, the iodine adsorption amount of the activated carbon is preferably 600 mg / g or more, more preferably 700 mg / g or more, and preferably 1100 mg / g or less, more preferably 1000 mg / g or less. is there.
The density of the activated carbon apparent, from the viewpoint of reducing the intensity of the odor, preferably 0.45 g / cm ³ or more, more preferably 0.50 g / cm ³ or more, and preferably 0.80 g / cm ³ or less, more preferably 0.70 g / cm ³ or less. These physical property values are values based on the nitrogen adsorption method.

  Synthetic adsorbents that can be used in the present invention include aromatic synthetic adsorbents, and specific examples thereof include Sepabeads SP700, SP825L, SP850, Diaion HP20, HP21 (Mitsubishi Chemical Corporation). ) And the like.

Examples of ion exchange resins that can be used in the present invention include cation exchange resins and anion exchange resins. These may be used alone or in combination.
As the cation exchange resin, a strong acid cation exchange resin and a weak acid cation exchange resin can be used.

As the anion exchange resin, a strong basic anion exchange resin and a weak basic anion exchange resin can be used.
Examples of the strongly basic anion exchange resin include resins having a quaternary ammonium group as an exchange group, and specific examples thereof include Diaion SA10A, SA11A, SA12A, NSA100, and SA20A manufactured by Mitsubishi Chemical Corporation. SA21A, PA308, PA312, PA316, PA408, PA412, PA418, HPA25, HPA75, Organo Corporation Amberlite IRA-400, IRA-400T, IRA-401, IRA-402, IRA-402BL, IRA-410, IRA-411S, IRA-440B, IRA-458, IRA-900, IRA-904, IRA-910, IRA-958, etc. are mentioned.

The step of bringing the polymer solution (II) obtained in the step (2) into contact with the adsorbent is, for example, passing the polymer solution (II) obtained in the step (2) through a column filled with the adsorbent. Can be performed.
When the adsorption treatment is performed by passing the polymer solution (II) obtained in step (2) through a column packed with an adsorbent, the liquid space velocity (LHSV) is a viewpoint that reduces adsorption equilibrium and odor intensity. Therefore, it is preferably 30 / hr or less, more preferably 25 / hr or less, and still more preferably 20 / hr or less. From the viewpoint of productivity, it is preferably 0.1 / hr or more, more preferably 0.5 / hr. As described above, more preferably 1 / hr or more.

The adsorption treatment may be a method of passing through the column a plurality of times. As the liquid flow system, an external circulation system that circulates from a storage tank equipped with an external circulation line with a column to an external circulation line, a line with a column interposed between the two storage tanks, and the storage tank through the line. The catch ball method that reciprocates the solution with a line connects the two storage tanks with one column so that the liquid circulates, and the liquid return system that returns the liquid to the original storage tank after the liquid passes through the entire column. From the viewpoints of simplicity of operation and economy, an external circulation system using one tank and one column is preferable.
In the case where the adsorption treatment is performed by an external circulation method using one tank and one column, the number of times of liquid passing is preferably 1 or more from the viewpoint of reducing the odor intensity, and preferably 10 or less from the viewpoint of productivity. Yes, more preferably 5 times or less.
The concentration of the polymer solution (II) subjected to the adsorption treatment is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more from the viewpoint of productivity, and the pressure loss of the adsorption column. From the viewpoint of reduction, it is preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

  The adsorption treatment temperature is 5 ° C. or more, preferably 10 ° C. or more from the viewpoint of reducing the pressure loss of the adsorption column, and 95 ° C. or less, preferably 90 ° C., from the viewpoint of preventing evaporation of the viscosity of the polymer solution (II) and the solvent. It is below ℃.

The ratio of the mass of the polymer solution (II) obtained in the step (2) to the mass of the adsorbent (polymer solution (II) / adsorbent) is preferably 300 or less, more preferably 100 from the viewpoint of economy. Hereinafter, it is more preferably 30 or less, and from the viewpoint of reducing the odor intensity, it is preferably 5 or more, more preferably 10 or more, and still more preferably 15 or more.
In addition, when implementing a process (3), the quantity of the water vapor | steam blown with respect to 100 mass parts of solvent at a process (2) is 80 from a viewpoint of changing into the smell preferable for the mixing | blending to a product, and a viewpoint of reducing the intensity | strength of an odor. More than 150 parts by mass, preferably 150 parts by mass or more, and since the two-stage purification by the step (2) and the step (3) is performed, the purification load in the step (2) is reduced, and the productivity and economy are reduced. From the viewpoint of improving the quality, it is 600 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, still more preferably 350 parts by mass or less, still more preferably 300 parts by mass or less, still more preferably 200 parts by mass. Or less. That is, the solvent substitution ratio in this case is 0.8 or more and 6 or less.
Although there is no restriction | limiting in particular as an apparatus and equipment used through process (1) from process (1), From the viewpoint of versatility and economical efficiency, the reaction of the stirring tank type | mold equipped with the cooler which can perform general temperature control It is preferable to use a vessel or a container.

  The organopolysiloxane graft polymer obtained by the production method of the present invention can be suitably used for cosmetics and the like.

  In the examples and comparative examples, the odor intensity was evaluated by a five-step evaluation by one panelist involved in the fragrance evaluation. Table 1 shows the evaluation levels.

Example 1
(Method for synthesizing mercaptan-modified organopolysiloxane)
As an organopolysiloxane having a reactive functional group in a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer, a side chain primary aminopropyl-modified organopolysiloxane (weight average molecular weight 30000, per unit mass) Mole number of amino group: 1/2030 mol / g, (Toray Dow Corning Co., Ltd.)) 100 g and N-acetyl-DL-homocysteine thiolactone (Tokyo Chemical Industry Co., Ltd.) 8 g were charged. Under a nitrogen atmosphere, the temperature was raised to 100 ° C. and stirred for 3 hours to obtain a mercaptan-modified organopolysiloxane.

(Process 1)
32.4 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device. While stirring ethanol under reflux at 80 ° C. in a nitrogen atmosphere, the following solution (a) and solution (b) were respectively added to separate dropping funnels, and simultaneously dropped over 1 hour.

Solution (a): DEMAPAA (dimethylaminopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)) 6.75 g, tBuAAm (N-tert-butylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., Tg = 135 ° C.)) 20 A solution in which .75 g and 49.5 g of ethanol are mixed.
Solution (b): 33 g of mercaptan-modified organopolysiloxane, 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., azo polymerization initiator, trade name: V-65B) A solution obtained by mixing 0.3 g and 49.5 g of ethanol.
After completion of the dropwise addition, the reaction mixture was stirred at 80 ° C. for 3 hours and then cooled, neutralized with 3.8 g of lactic acid, and referred to as an organopolysiloxane graft polymer solution (hereinafter referred to as “polymer solution (I)”). )

(Process 2)
After the step (1), the pressure is reduced to 70 kPa (abs), and while adjusting the liquid temperature to 45 to 60 ° C., 100 ° C. saturated water vapor is blown at 0.16 parts by mass per 100 parts by mass of solvent to evaporate. The ethanol-water mixture was collected with a reflux condenser. When the mass ratio of the amount of water vapor introduced into 100 parts by mass of the solvent in the polymer solution (I) [the amount of water vapor / the amount of solvent] (hereinafter also referred to as “solvent substitution ratio”) reaches 5.0, the saturated water vapor is blown in. And 75% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5 and the odor quality was a vinyl-like odor.

Comparative Example 1
After Step (1) in Example 1, Step (2) was not performed as Comparative Example 1.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5 and the odor quality was S odor (sulfur odor).

Comparative Example 2
The polymer solution (I) obtained in step (1) in Example 1 was treated by the method shown below.
150 g of ethanol was added to the polymer solution (I), and purification was performed with a ceramic membrane separator (fraction molecular weight of about 30,000) manufactured by Noritake Company. In addition, processing is performed while adding ethanol to the permeate volume so that the polymer concentration in the purification process is constant, and the process is terminated when the permeate volume becomes 7 times the polymer solution. The polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5, and the odor quality was a grapefruit-like odor (S-like odor).

Comparative Example 3
The polymer solution (I) obtained in step (1) in Example 1 was treated by the method shown below.
40 parts by mass of activated carbon (Filtrasorb600 (Calgon Carbon Japan Co., Ltd.)) is charged into a glass column having an inner diameter of 2 cm with respect to the polymer solution (I), and the polymer solution (I) is passed once through this to obtain a purified polymer. The solution was collected.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5 and the odor quality was a rotting tropical fruit-like odor (S-like odor).

Comparative Example 4
The polymer solution (I) obtained in step (1) in Example 1 was treated by the method shown below.
0.8 parts by mass of 35% by mass hydrogen peroxide water was added to the polymer solution (I), and the temperature in the tank was heated to 75 ° C. After stirring for 4 hours, the mixture was cooled and the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5 and the odor quality was a bitter grape-like odor (S-like odor).

Example 2
(Process 1)
In a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device, 39.07 g of ethanol was charged. While stirring ethanol under reflux at 80 ° C. in a nitrogen atmosphere, the following solution (a) and solution (b) were respectively added to separate dropping funnels, and simultaneously dropped over 1 hour.
Solution (a): DMAAm (N, N-dimethylacrylamide (Wako Pure Chemical Industries, Ltd.) 28.8 g, tBuAAm (N-tert-butylacrylamide (Wako Pure Chemical Industries, Ltd.) 7.2 g), ethanol The solution which mixed 42.26g.
Solution (b): Mercaptan-modified organopolysiloxane 24 g, 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., azo polymerization initiator, trade name: V-65B) A solution in which 0.01 g and 10.29 g of ethanol are mixed.
After completion of the dropping, the reaction mixture was stirred at 80 ° C. for 6 hours and then cooled, and 50 g of ethanol was added to obtain an organopolysiloxane graft polymer solution.

(Process 2)
After the step (1), the pressure is reduced to 40 kPa (abs), and while adjusting the liquid temperature to 45-60 ° C., 0.16 parts by mass of saturated water vapor at 100 ° C. is blown into 100 parts by mass of the solvent and evaporated. The coming ethanol / water mixture was recovered with a reflux condenser. When the solvent substitution ratio reached 1.7, blowing of saturated steam was terminated, and 95% by mass of the purified polymer solution (II) was recovered. The mass ratio of the amount of solvent distilled off and the amount of water vapor introduced (water vapor / distilled solvent) was 1.7.
When the odor of this polymer solution was evaluated, the odor intensity was 4.0 and the odor quality was a vinyl-like odor.

Example 3
In Example 2, the same treatment was performed except that the solvent substitution ratio in step (2) was 2.3, and 89% by mass of the purified polymer solution was recovered. Water vapor / distilled solvent was 2.3.
When the odor of this polymer solution was evaluated, the odor intensity was 3.5 and the odor quality was a vinyl-like odor.

Example 4
In Example 2, the same treatment was carried out except that the solvent substitution ratio in step (2) was changed to 3.3, and 85% by mass of the purified polymer solution was recovered. Water vapor / distilled solvent was 3.3.
When the odor of this polymer solution was evaluated, the odor intensity was 3.0 and the odor quality was a vinyl-like odor.

Example 5
In Example 2, the same treatment was performed except that the solvent substitution ratio in step (2) was 4.0, and 79% by mass of the purified polymer solution was recovered. Water vapor / distilled solvent was 4.0.
When the odor of this polymer solution was evaluated, the odor intensity was 3.0 and the odor quality was a vinyl-like odor.

Example 6
In Example 2, the same treatment was performed except that the solvent substitution ratio in step (2) was 5.0, and 75% by mass of the purified polymer solution was recovered. Water vapor / distilled solvent was 5.0.
When the odor of this polymer solution was evaluated, the odor intensity was 3.5 and the odor quality was a vinyl-like odor.

Comparative Example 5
In Example 2, the same treatment was performed except that the step (II) was not performed, and the purified polymer was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 4.0 and the odor quality was S odor.
Comparative Example 6
In Example 2, the same treatment was performed except that the solvent substitution ratio in step (2) was 0.5, and the purified polymer solution was recovered. Water vapor / distilled solvent was 0.5.
When the odor of this polymer solution was evaluated, the odor intensity was 3.5 and the odor quality was an S-like odor.

Example 7
The polymer solution (II) obtained in Step (2) in Example 6 was treated by the method shown below.
(Process 3)
A glass column having an inner diameter of 2 cm and a height of 30 cm was charged with 5 g of a synthetic adsorbent (Separbeads SP850 (manufactured by Mitsubishi Chemical Corporation)), and the polymer solution (with a flow rate adjusted to 20 / hr while adjusting the flow rate) II) 100 g (liquid temperature: 40 ° C.) was passed once, and 75% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.0 and the odor quality was a vinyl-like odor. The concentration of the polymer solution (II) was 29.8% by mass.

Example 8
The polymer solution (II) obtained in Step (2) in Example 6 was treated by the method shown below.
(Process 3)
A glass column having an inner diameter of 2 cm and a height of 30 cm was charged with 5 g of activated carbon (Filtrasorb 600 (produced by Calgon Carbon Japan, iodine adsorption amount: 850 mg / g, apparent density: 0.63 g / cm ³ )), and liquid space While adjusting the flow rate so that the speed was 20 / hr, 100 g of the polymer solution (liquid temperature: 40 ° C.) was passed once, and 75% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.0 and the odor quality was a vinyl-like odor.

Example 9
In Example 7, the same treatment was performed except that the liquid space velocity was 1.0 / hr, and 75% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.0 and the odor quality was a vinyl-like odor.

Example 10
In Example 8, the same treatment was performed except that the liquid hourly space velocity was 1.0 / hr, and 75% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.0 and the odor quality was a vinyl-like odor.

Example 11
In Example 9, the same treatment was performed except that the synthetic adsorbent was an ion exchange resin (Amberlite IRA910CT (Mitsubishi Chemical Corporation)), and 75% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5 and the odor quality was a vinyl-like odor.

Example 12
The polymer solution (II) obtained in Step (2) in Example 6 was treated by the method shown below.
Activated carbon filter MCK (manufactured by Loki Techno Co., Ltd.) is set in the housing, and the polymer solution (liquid temperature: 40 ° C.) is passed once while adjusting the flow rate so that the flow rate becomes 20 g / sec. Of 75% by weight was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5 and the odor quality was a vinyl-like odor.

Example 13
The polymer solution (II) obtained in step (2) in Example 2 was treated by the method shown below.
A glass column having an inner diameter of 2 cm and a height of 30 cm is charged with 5 g of activated carbon (Filtrasorb 600 (Calgon Carbon Japan Co., Ltd.)), and the polymer solution 100 g (liquid temperature is adjusted while adjusting the flow rate so that the liquid space velocity is 20 / hr. : 40 ° C.) once, and 95% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.5 and the odor quality was a vinyl-like odor.

Example 14
The polymer solution (II) obtained in step (2) in Example 2 was treated by the method shown below.
A glass column with an inner diameter of 2 cm and a height of 30 cm charged with 5 g of activated carbon (Filtrasorb 600 (Calgon Carbon Japan Co., Ltd.)) was placed in the external circulation line of a 500 mL stirrer vessel, and 100 g of polymer solution (II) (liquid temperature 40 ° C.) was passed through the activated carbon column 5 times while adjusting the flow rate so that the liquid space velocity was 20 / hr, and 95% by mass of the purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 2.0 and the odor quality was a vinyl-like odor.

Comparative Example 7
The polymer solution (I) obtained in step (1) in Example 2 was treated by the method shown below.
A glass column having an inner diameter of 2 cm and a height of 30 cm is charged with 5 g (Separ beads SP850 (manufactured by Mitsubishi Chemical Corporation)), and 100 g of the polymer solution is passed once while adjusting the flow rate so that the liquid space velocity is 20 / hr. The purified polymer solution was recovered.
When the odor of this polymer solution was evaluated, the odor intensity was 4.0 and the odor quality was an S-like odor.

Comparative Example 8
The polymer solution (I) obtained in step (1) in Example 2 was treated by the method shown below.
A glass column having an inner diameter of 2 cm and a height of 30 cm is charged with 5 g of activated carbon (Filtrasorb 600 (manufactured by Calgon Carbon Japan Co., Ltd.)), and 100 g of a polymer solution is added while adjusting the flow rate so that the liquid space velocity is 20 / hr. The solution was allowed to pass through to collect a purified polymer solution.
When the odor of this polymer solution was evaluated, the odor intensity was 4.0 and the odor quality was an S-like odor.

  From the results of Examples and Comparative Examples, according to the production method of the present invention, the organopolysiloxane graft polymer obtained by using the mercapto compound can reduce the odor intensity and change the odor quality. it can. As a result, the resulting organopolysiloxane graft polymer can be used for cosmetic applications.

Claims (10)

  Organopolysiloxane graft polymer in which the solvent is distilled off while introducing water vapor into the polymer solution (I) obtained by radical polymerization of mercaptan-modified organopolysiloxane and unsaturated monomer in the presence of a solvent. The method for producing an organopolysiloxane graft polymer, wherein the amount of the water vapor is from 80 parts by mass to 600 parts by mass with respect to 100 parts by mass of the solvent in the polymer solution (I).   The method for producing an organopolysiloxane graft polymer according to claim 1, wherein water is introduced into the polymer solution (I) and the aqueous polymer solution (II) obtained by distilling off the solvent is brought into contact with the adsorbent. .   The method for producing an organopolysiloxane graft polymer according to claim 1 or 2, wherein the mercaptan-modified organopolysiloxane is obtained by reacting an organopolysiloxane having a reactive functional group with a thioester.   The method for producing an organopolysiloxane graft polymer according to claim 3, wherein the thioester is thiolactone. The organopolysiloxane graft according to claim 3 or 4, wherein the organopolysiloxane having a reactive functional group is one or more selected from compounds represented by the following general formulas (1) and (2). A method for producing a polymer.

(In the formula, each R ¹ independently represents an alkyl group having 1 to 22 carbon atoms, R ² represents an alkyl group having a reactive functional group. P represents a number from 2 to 4000, q Represents a number of 2 or more and 500 or less.)   The mass ratio (water vapor / distilled solvent) of the amount of solvent distilled off and the amount of water vapor introduced to the polymer solution (I) is 0.8 or more and 6 or less, The manufacturing method of the organopolysiloxane graft polymer in any one.   The organopolysiloxane graft polymer according to any one of claims 1 to 6, wherein the solvent is distilled off by introducing the water vapor into the polymer solution (I) having a liquid temperature of 10 ° C or higher and 100 ° C or lower. Manufacturing method.   The method for producing an organopolysiloxane graft polymer according to any one of claims 1 to 7, wherein the water vapor is introduced into the polymer solution (I) under a pressure condition of 1 kPa or more and 101 kPa or less.   The polymer solution (II) is passed through the column filled with the adsorbent so that the liquid space velocity is 0.1 / hr to 30 / hr. A process for producing an organopolysiloxane graft polymer.   The method for producing an organopolysiloxane graft polymer according to any one of claims 1 to 9, wherein the solvent is an aqueous solvent.