JP2000344829A - Silicone graft copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone graft copolymer that is almost free from the irritating odor due to the presence of an unsaturated group because no radically polymerizable unsaturated groups remain and that has good storage stability, is safe, and imparts the stability of quality to an article manufactured therefrom because the copolymer is not oxidized. SOLUTION: A process for producing a silicone graft copolymer comprises dissolving (a) a radically polymerizable unsaturated monomer, (b1) an organopolysiloxane having a radically polymerizable group at its end as (b) a radically polymerizable monomer for introducing a crosslinking unit, and (c) a racial polymerization initiator in an organic solvent, heating the resultant solution until the copolymerization reaction is completed, and then hydrogenating the resulting copolymer solution under pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a polymer, wherein the main chain is a long carbon-carbon bond chain, the cross-linking part of the main chain carbon-carbon bond is made of an organopolysiloxane, and The present invention relates to a silicone graft copolymer which does not coexist with a polymerizable aliphatic unsaturated group, has high storage stability and safety, and has no pungent odor, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a polyether-modified organopolysiloxane having a main chain composed of an organopolysiloxane and a cross-linking part comprising a polyether group or a polyether alkylene group having a main chain comprising an organopolysiloxane and a cross-linking part comprising a polyoxyalkylene group. Polyoxyalkylene-modified organopolysiloxanes are obtained by a hydrosilylation reaction and are known, but are derived from unreacted alkenyl groups and odors derived from internal transfer by-products or aldehydes generated by oxidation and degradation of polyethers. The problem of emitting a bad odor has arisen. As a method of deodorizing the organopolysiloxane odorized in this way, a deodorizing technique for reducing unreacted alkenyl groups and preventing oxidation of polyether by performing hydrogenation treatment (hydrogenation) is disclosed ( US Patent 5
225509, JP-A-7-330907).

[0003] With the recent diversification of product development and high added value, silicone graft copolymers using a silicone macromer having a radical polymerizable group have been receiving attention. This silicone graft copolymer has weather resistance, water repellency,
It is often used as a coating material because it is often excellent in antifouling properties, release properties, lubricity, etc. (Japanese Patent Application Laid-Open No. 58-15476).
No. 6, JP-A-59-20360, JP-A-59-20360
JP-A-126478, JP-A-61-151272, and JP-A-62-156172), and in recent years, there has been a particular interest in application to cosmetics (Japanese Patent Laid-Open No. 5-3).
39125, JP-A-6-9332, JP-A-6-279232, JP-A-7-187951, JP-A-7-187954, JP-A-7-196
449, JP-A-8-143427 and JP-A-9-296134).

[0004]

However, the silicone graft copolymer is mainly obtained by a radical copolymerization reaction, and the (meth) acrylic group-containing monomer and the terminal (meth) acryloxy group-containing silicone are used as raw materials. In many cases, macromers are used, and the silicone graft copolymer obtained by copolymerizing them emits a unique irritating odor of a (meth) acrylic group, and the degree of this irritating odor depends on the hydrosilylation reaction. In addition, the (meth) acrylic group is rich in radical reactivity as compared with the aldehyde odor in the modified organopolysiloxane obtained by the method described above, and if this unreacted material remains, the storage stability and safety of the product may be lacking. For this reason, in spite of the great demand for the silicone graft copolymer, the use has to be limited and supplied.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a silicone graft copolymer which has almost no pungent odor and can be supplied as a stable and safe product for a wide range of applications. And

[0006]

That is, the present invention provides (A)
The main chain is composed of a long-chain carbon-carbon bond chain, and (B) the cross-linking part bonded to the carbon of the main chain carbon-carbon bond is composed of an organopolysiloxane and does not contain a polymerizable aliphatic unsaturated group. And a silicone graft copolymer.

[0007] The silicone graft copolymer of the present invention has almost no pungent odor and can be supplied as a stable and safe product for a wide range of applications.

[0008] The silicone graft copolymer of the present invention comprises
A silicone graft copolymer in which a long-chain alkyl group and / or a polyoxyalkylene group is further grafted as a crosslinking portion.

Further, a copolymer in which a long-chain alkyl group is grafted as a crosslinking portion has almost no pungent odor, and can be used stably and safely in a wide range of applications.
Properties such as weather resistance and water repellency can be imparted to the copolymer.

Further, a copolymer grafted with a polyoxyalkylene group as a cross-linking portion has almost no irritating odor, and can be used stably and safely in a wide range of applications. Properties such as lubricity can be imparted.

The method for producing the silicone graft copolymer of the present invention comprises: (1) (a) a radically polymerizable unsaturated monomer, and (b) a radically polymerizable monomer for introducing a crosslinking unit. (B1) An organopolysiloxane having a radical polymerizable group at the terminal, (c) a radical polymerization initiator dissolved in an organic solvent, (2) heating to complete the copolymerization reaction, and (3) obtained (B) as a radical polymerizable monomer for introducing a cross-linking unit, in addition to (b1) an organopolysiloxane having a radical polymerizable group at a terminal. , (B
2) A radically polymerizable group-containing long-chain alkyl compound and / or (b3) a radically polymerizable group-containing polyoxyalkylene compound can be used.

[0012]

Embodiments of the present invention will be described below. The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, (a) a radical polymerizable unsaturated monomer, and (b) a radical polymerizable monomer for introducing a crosslinking unit, b1) An organopolysiloxane having a radically polymerizable group at the terminal, and (c) a radical polymerization initiator dissolved in an organic solvent, and heated to complete the copolymerization reaction. The present inventors have found that a silicone graft copolymer obtained by hydrogenation under pressure in a reactor has almost no pungent odor and can be used stably and safely in a wide range of applications, and thus completed the present invention.

Hereinafter, the structure of the silicone graft copolymer of the present invention will be described in detail. The basic structure of the silicone graft copolymer of the present invention is a structure in which (a) a radical polymerizable unsaturated monomer is grafted to (b) a radical polymerizable monomer for introducing a crosslinking unit. If necessary, a long-chain alkyl group and / or a polyoxyalkylene group can be grafted to impart desired properties to the silicone graft copolymer.

The radically polymerizable unsaturated monomer (a) constituting the main chain of the silicone graft copolymer of the present invention is a hydrophilic and hydrophobic radically polymerizable monomer. For example, acrylic acid or methacrylic acid
[Hereinafter referred to as (meth) acrylic acid. And their alkyl esters, which are specifically exemplified by methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxy (meth) acrylate Ethyl, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like can be mentioned.

Further, the radically polymerizable unsaturated monomer of the unit (a) includes acid amides such as acrylamide; amine derivatives of acrylic acid such as dimethylaminoethyl (meth) acrylate; Japanese;
Aminoacetic acid betaine derivatives which are reactants of amine derivatives and sodium monochloroacetate; sulfobetaine-type derivatives which are sulfonates of amine derivatives; perfluorodecylethyl (meth) acrylate, perfluorooctyl (meth) acrylate Perfluoroesters such as ethyl, perfluorohexylethyl (meth) acrylate, and perfluorobutylethyl (meth) acrylate; other (meth)
Various derivatives of acrylic acid, for example, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate can be exemplified.

Further, as the compound other than the above (meth) acrylates, styrene or a styrene derivative; fumaric acid, itaconic acid, maleic acid, crotonic acid or a neutralized salt thereof such as sodium hydroxide, potassium hydroxide or ammonia may be used. Radical polymerizable silicon compounds such as vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane; acrylonitrile, vinylpyrrolidone, vinyl acetate, vinylalkyl ether and the like; at least one radical polymerizable in the molecule Radical polymerizable macromonomers such as polystyrene and polycaprolactone having a group are exemplified.
These radical polymerizable monomers can be used alone or in combination of two or more.

The organopolysiloxane having a radically polymerizable group at the terminal, which is a crosslinked portion of the silicone graft copolymer of the present invention, has the following general formula when the radically polymerizable group is a (meth) acryloxyalkyl group. Formula 1
Can be represented by

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent hydrocarbon group having 1 to 11 carbon atoms which may be interrupted by an oxygen atom, and R ³ is a same or different kind having 1 to 18 carbon atoms.) A monovalent hydrocarbon group or a halogen-substituted hydrocarbon group containing no aliphatic unsaturated group, m is 0, 1 or 2, n
Represents an average degree of polymerization and is a number from 0 to 200. )

Furthermore, diorganosiloxane units in the chemical formula 1 - (OSiR ³ ₂₎ - if specific examples of dimethylsiloxane, dialkyl siloxanes having 2 to 18 carbon atoms, methylphenylsiloxane, diphenylsiloxane, methyltri Examples include units composed of fluoropropylsiloxane, and among them, a dimethylsiloxane unit is preferable. Examples of the radically polymerizable group of the radically polymerizable group-containing organopolysiloxane include an acryloxy group, a methacryloxy group, a vinyl group, an allyl group, and a styryl group. The organopolysiloxane containing a radical polymerizable group is, for example, a (meth) acryloxy-modified organopolysiloxane represented by the above general formula (1).

The method for producing the compound represented by the general formula 1 is, for example, a method for preparing an acryloxy or methacryloxy group-substituted chlorosilane compound represented by the following general formula 2:

Embedded image (In the formula, R ¹ , R ² , R ³ and m are the same as described above.) A one-terminal-reactive diorganopolysiloxane represented by the following general formula ³ is subjected to a dehydrochlorination reaction or a dehydrochlorination according to a conventional method. It can be obtained by performing a salt reaction.

Embedded image (Wherein, R ³ and n are the same as above. X is a hydrogen atom or lithium metal.)

The silicone graft copolymer of the present invention may further comprise a long-chain alkyl group having a radical polymerizable group at a terminal as a crosslinking unit as a structural unit.
For example, when the radical polymerizable group is a (meth) acryloxy group, this structural unit can be represented by the following general formula 4.

Embedded image (In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is a linear or branched monovalent hydrocarbon group having 6 to 50, preferably 8 to 30 carbon atoms.) Examples of R ⁵ include a lauryl group, a cetyl group, a palmityl group, an oleyl group, a stearyl group, a behenyl group, and the like. As the radical polymerizable group in the radical polymerizable group-containing long chain alkyl group, a radical polymerizable group similar to the above-mentioned organopolysiloxane compound may be selected. Preferred radical polymerizable groups are (meth) acryloxy groups. As the radical polymerizable group-containing long-chain alkyl group, for example, a (meth) acryloxy cystearyl group and a (meth) acryloxybehenyl group are preferable.

The silicone graft copolymer of the present invention comprises
Further, a polyoxyalkylene group having a radical polymerizable group at the terminal as a cross-linking unit can be used as a structural unit. For example, when the radical polymerizable group is a (meth) acryloxy group, 5 can be represented.

Embedded image (Wherein, R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms or an acetyl group, i is a number of 2 or 3, and j is an average polymerization degree. Representation 2
The number is fifty. As the radical polymerizable group in the radical polymerizable group-containing polyoxyalkylene group, the same radical polymerizable group as in the above-mentioned organopolysiloxane can be selected. Preferred radically polymerizable groups include (meth) acryloxy groups. Preferred examples of the radical polymerizable group-containing polyoxyalkylene group include groups such as (meth) acryloxypolyoxyethylene, (meth) acryloxypolyoxypropylene, and (meth) acryloxypolyoxyethylene-polyoxypropylene. In addition,
The terminal hydrogen atom of the polyoxyalkylene group may be appropriately substituted with a methyl group, a butyl group, an acetyl group, or the like.

The proportion of each component constituting the crosslinked portion of the silicone graft copolymer of the present invention depends on the properties required for the silicone graft copolymer. (B1), (b2) and (b)
In the case of (3), generally, (b1) is 5 to 60% by weight, (b2) and (b3) are each 2 to 50% by weight, preferably (b1) is 10 to 50% by weight. , (B2) and (b3) each range from 5 to 30% by weight.

If (b1) is too small in the above composition ratio, the weather resistance, water repellency, antifouling property, releasability or lubricity may be insufficient, while if too large, the film-forming property may be insufficient. May be insufficient. If the content of (b2) is too small, the water repellency and the releasability may be insufficient. However, if a wax-like form is required, the amount can be increased depending on the desired melting point. On the other hand, if (b3) is too small, the hydrophilicity and antistatic properties may be insufficient, and if too large, the water repellency, release properties or lubricity may be insufficient.

Next, a method for producing the silicone graft copolymer of the present invention will be described. A mixture of (b1) to (b3) of the structural unit (a) radically polymerizable unsaturated monomer of the silicone graft copolymer of the present invention and (b) the radically polymerizable monomer for introducing a crosslinking unit into (c) ) Copolymerization in the presence of a radical polymerization initiator. When (b) is a silicone graft copolymer comprising an organopolysiloxane and a long-chain alkyl group and / or an oxyalkylene group, first,
A copolymerization reaction of the radically polymerizable group-containing organopolysiloxane with the radically polymerizable group-containing long-chain alkyl compound and / or the radically polymerizable group-containing polyoxyalkylene compound is performed. In this case, in order to efficiently carry out the copolymerization reaction and to improve the properties of the silicone graft copolymer, a predetermined amount of (a) a radical polymerizable unsaturated monomer copolymerizable therewith is used. Can be.

In the copolymerization reaction of the present invention, peroxides such as benzoyl peroxide, dicumyl peroxide, tert-butyl peroxy 2-ethylhexyl hexanoate, azobisisobutyronitrile, etc. are used as radical polymerization initiators. The reaction is carried out in the presence of a usual radical polymerization initiator such as azo compounds of the formula (1). The used amount of the radical polymerization initiator may be a usual used amount, 0.01 to 5% by weight of the total amount of the monomers involved in the copolymerization, a predetermined reaction rate, a desired degree of polymerization of the copolymer, It is appropriately selected according to the type of the radical polymerization initiator. The copolymerization method in the present invention,
Any of a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be applied. Of these,
The solution polymerization method is a particularly preferable method because it is easy to adjust the molecular weight of the obtained copolymer to an optimum range.

Solvents used in the copolymerization reaction include alcohols such as isopropyl alcohol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and acetic acid. Esters such as isobutyl may be mentioned, and these may be used alone or as a mixed solvent of two or more kinds. The reaction temperature is 50 to 180.
C, particularly preferably in the range of 60 to 120C,
Under this temperature condition, the reaction can be almost completed in about 5 to 10 hours.

After the copolymerization reaction is performed in this way, as described above, the product becomes unstable due to generation of pungent odor due to the presence of unreacted radically polymerizable unsaturated groups and generation of foreign matter due to oxidation. The silicone graft copolymer of the present invention can be obtained by hydrogenating an unreacted radically polymerizable unsaturated group to convert it into a saturated group in order to prevent the occurrence of problems with respect to safety. Hydrogenation can be performed by a conventionally known method.

As the hydrogenation reaction, there are a method in which hydrogen gas is pressurized in the presence of a hydrogenation catalyst, a method using a hydrogenating agent such as a metal hydride, and a combination of both. More specifically, this reaction includes a homogeneous reaction and a heterogeneous reaction, and these reactions can be performed alone or in combination. However, considering that the used catalyst does not remain in the product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is most preferable. As the solid catalyst, for example, there is a simple substance such as nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron or a compound thereof, and a catalyst carrier may be omitted, but when used, activated carbon, silica, silica alumina, alumina , Zeolite and the like are preferred. These catalysts can be used alone or in combination.

The hydrogenation reaction is generally 1 to 100 kg
/ Cm ² (absolute pressure) at 50 to 200 ° C. The hydrogenation reaction uses a pressure-resistant reactor, and may be a batch type or a continuous type. In the case of the batch system, the reaction time depends on the amount of the catalyst and the temperature, but is generally 3 to 12 hours. The hydrogen pressure can be adjusted as needed at a constant level, but the end point of the hydrogenation reaction is determined by observing the pressure gauge, and the point at which the hydrogen pressure no longer changes is determined as the reaction end point. After the hydrogenation, the reaction solvent is filtered off and the solvent is distilled off under reduced pressure, so that the reaction solvent does not contain an unreacted radically polymerizable unsaturated group,
A silicone graft copolymer can be obtained.

The silicone graft copolymer of the present invention comprises
The graft copolymer solution obtained as described above may be used as it is for each application, or the graft copolymer may be separated and dissolved in another solvent. If necessary, other solvents, crosslinking agents, resins other than the above graft copolymer, fillers, other stabilizers, and the like can be added in any combination.

The above-mentioned other solvent is used for the purpose of adjusting the viscosity of the composition of the silicone graft copolymer and each of the above-mentioned additives and adjusting the film thickness of the coating according to each application. There is no particular limitation as long as it is compatible with the polymer. For example, alcohols such as isopropyl alcohol and butanol; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane, n-octane and n-decane; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone And esters such as ethyl acetate and butyl acetate; and dioxane and dimethylformamide. Further, silicone oils such as hexamethyldisiloxane, octamethylcyclotetrasiloxane, dodecamethyl, and pentasiloxane are exemplified. These can be used alone or in combination of two or more. In addition, one or more of these copolymers can be used as needed.

[0032]

The present invention will be described below with reference to examples and comparative examples. Note that the present invention is not limited to the following embodiments. (Example 1) In a glass reaction vessel, 551 parts by weight of 3-methacryloxypropyldimethylpolysiloxane represented by Formula 6 below, 395 parts by weight of stearyl methacrylate (manufactured by Shin-Nakamura Chemical Co., NK Ester S), methacrylic acid 54 parts by weight of methyl, 1,000 parts by weight of toluene and 20 parts by weight of t-butylperoxy-2-ethylhexylhexanoate (manufactured by NOF CORPORATION, perbutyl O) were charged and stirred at 90 to 100 ° C. for 10 hours under a nitrogen gas atmosphere. As a result, a viscous solution having a solid content of 50% by weight was obtained.

Embedded image

A toluene solution of the obtained copolymer in 2,000
0 parts by weight were charged into a stainless steel autoclave, and 2 parts by weight of a hydrogenation catalyst in which 10% by weight of Pd was supported on activated carbon was added. The reaction temperature was 50 ° C., and the hydrogen pressure was 5 kg / cm ^2.
The hydrogenation reaction was performed at (absolute pressure). After 6 hours, the catalyst was filtered off, and the solvent was distilled off under reduced pressure of 120 ° C and 5 mmHg to obtain a pale yellow copolymer having a melting point of 28 to 30 ° C. About the obtained copolymer, infrared absorption spectrum and ¹
As a result of H-NMR spectrum analysis, it was confirmed that the copolymer was a copolymer in which a dimethylpolysiloxane residue and a stearyl group were grafted to carbon atoms of carbon-carbon bonds in the main chain. The weight average molecular weight in terms of polystyrene measured by GPC was about 57,000.

[0034] The residual amount of methacryl groups coexisting with so-obtained silicone graft copolymers described above, ¹ H
-NMR spectrum of the vinyl terminated acrylic group
^The amount of unsaturated groups was calculated from the ¹ H signal (6.1 ppm), but was not detected. The presence of a pungent odor is 100
After putting 50 g of the sample in a glass bottle of g and storing it in a thermostat at 60 ° C. for 24 hours, the smell was determined. As a result, all panelists did not sense the pungent odor. Table 1 shows the obtained results.

Example 2 1017 parts by weight of 3-methacryloxypropyldimerpolysiloxane represented by the following formula 7 was placed in a glass reactor.

Embedded image Terminal methacryloxy polyoxypropylene represented by Formula 8 below (manufactured by NOF Corporation, Blemmer P1000) 210
Parts by weight,

Embedded image 210 parts by weight of stearyl methacrylate (manufactured by Shin-Nakamura Chemical, NK ester S), 63 parts by weight of methyl methacrylate, 1500 parts by weight of toluene and t-butyl peroxy-2
-10 parts by weight of ethylhexyl hexanoate (manufactured by NOF CORPORATION, perbutyl O) was charged, and 90 parts of
The reaction was carried out while stirring at １００100 ° C. for 10 hours to obtain a viscous solution having a solid content of 50% by weight.

The toluene solution of the copolymer obtained above was 3,0
A hydrogenation catalyst 2 in which 00 parts by weight was charged into a stainless steel autoclave and activated carbon supported 10% by weight of Pd.
The reaction temperature was 50 ° C. and the hydrogen pressure was 5 kg / c.
The hydrogenation reaction was performed at m ² (absolute pressure). After 6 hours, the catalyst was filtered off, and the solvent was distilled off under reduced pressure of 5 mmHg at 120 ° C. to obtain a colorless transparent gel copolymer. About the obtained copolymer, infrared absorption spectrum and ¹ H-NM
As a result of R spectrum analysis, it was confirmed that the copolymer was a dimethylpolysiloxane residue, a long-chain alkyl group and a polyoxyalkylene residue grafted to the carbon atom of the main chain carbon-carbon bond. . The weight average molecular weight in terms of polystyrene by GPC is about 24,000.
Met. As a result of an evaluation test performed in the same manner as in Example 1, no residual unsaturated group was detected, and no pungent odor was detected. The results are shown in Table 1.

Example 3 334 parts by weight of a 3-methacryloxypropyldimethylpolysiloxane compound represented by the following formula 9 was placed in a glass reactor.

Embedded image Behenyl methacrylate (manufactured by NOF CORPORATION, Blemmer VM
A) 283 parts by weight, methyl methacrylate 33 parts by weight, toluene 975 parts by weight and t-butylperoxy-2-
16 parts by weight of ethylhexyl hexanoate (manufactured by NOF CORPORATION, Perbutyl O) was charged, and 90 to 90 parts of
The polymerization reaction was carried out at 100 ° C. for 10 hours.
A viscous solution of 0% by weight was obtained.

A toluene solution of the copolymer obtained above was charged into a stainless steel autoclave, and 1
1 part by weight of a hydrogenation catalyst supporting 0% by weight of Pd was added,
A hydrogenation reaction was performed at a reaction temperature of 50 ° C. and a hydrogen pressure of 5 kg / cm ² (absolute pressure). After 6 hours, the catalyst was filtered off and 120
The solvent was distilled off under a reduced pressure of 5 mmHg at
A colorless solid copolymer at 51 ° C. was obtained. The obtained copolymer was subjected to infrared absorption spectrum and ¹ H-NMR spectroscopy. As a result, it was found that a dimethylpolysiloxane residue and a long-chain alkyl group were grafted onto carbon atoms of carbon-carbon bonds in the main chain. It was confirmed that they were united. The weight average molecular weight in terms of polystyrene measured by GPC was about 44,000. When evaluated by the same method as in Example 1, no residual unsaturated group was detected and no pungent odor was detected. The results are shown in Table 1.

(Comparative Examples 1 to 3) Each of the copolymer solutions obtained by the copolymerization reaction in each of the above Examples was prepared by removing the solvent under reduced pressure at 120 ° C. and 5 mmHg without hydrogenation. And the amount of residual unsaturated groups and the presence or absence of pungent odor were evaluated in the same manner as in Example 1. The amounts of the residual aliphatic unsaturated groups detected for Comparative Examples 1 to 3 were 0.12 meq / g, 0.29 meq / g, and 0.09 meq / g, respectively.
g. In addition, all panelists perceived the irritating odor. The results are shown in Table 1.

[0040]

[Table 1]

[0041]

The silicone graft copolymer of the present invention is inactivated by converting the unreacted radically polymerizable unsaturated group contained therein into a saturated group, and thus is caused by the presence of the unsaturated group. There is almost no pungent odor and it is not oxidized. Therefore, product quality is stable and storage stability is good. Furthermore, since no radically polymerizable unsaturated groups remain, side reactions due to this are prevented, and a safe product can be supplied. Therefore, the product according to the present invention can be provided in large quantities as a raw material for cosmetics and the like for which provision of unscented products is expected, and the present invention is extremely useful.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J027 AF05 BA07 BA08 CD08 4J100 AB02P AE02P AG04P AJ01P AJ08P AJ09P AK19P AK20P AL08P AM02P AM15P AP16P AQ08P BA29P BA77P BB18P BC04P BC54P CA04 HC31 FA03 HA03 HA03 HA03

Claims (4)

[Claims] (1) a main chain comprising a long-chain carbon-carbon bond chain; and (B) a cross-linking portion bonding to the carbon-carbon bond of the main chain comprises an organopolysiloxane. A silicone graft copolymer containing no polymerizable aliphatic unsaturated group. 2. The silicone graft copolymer according to claim 1, wherein a long-chain alkyl group and / or a polyoxyalkylene group is grafted as a crosslinking portion. 3. An organopolysiloxane having (1) a radically polymerizable unsaturated monomer, and (b) a radically polymerizable monomer for introducing a crosslinking unit, and (b1) a radically polymerizable group at a terminal. (C) dissolving a radical polymerization initiator in an organic solvent, (2) heating the radical polymerization initiator to complete the copolymerization reaction, and (3) hydrogenating the obtained copolymer solution under pressure. The method for producing a silicone graft copolymer according to claim 1, wherein: (1) (a) a radical polymerizable unsaturated monomer, and (b) a radical polymerizable monomer for introducing a crosslinking unit, (b1) an organopolysiloxane having a radical polymerizable group at a terminal. In addition, (b2) a radical polymerizable group-containing long chain alkyl compound and / or (b3) a radical polymerizable group-containing polyoxyalkylene compound, and (c) a radical polymerization initiator are dissolved in an organic solvent, The method for producing a silicone graft copolymer according to claim 2, wherein 2) the mixture is heated to complete the copolymerization reaction, and (3) the obtained copolymer solution is hydrogenated under pressure. .