JP2000034326A - Siloxane copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a siloxane copolymer capable of being made as a higher molecular weight than usual, expectable increases of water repellency, surface sliding property and solvent resistance, and therefore usable as a release agent for a tacky tape, a coating material for the surface sliding property and a mold releasing agent, especially usable as a coating material hardening by ultraviolet rays or electric rays, and a method for producing it. SOLUTION: This siloxane copolymer is produced by block polymerizing a siloxane polymer having a vinyl group at one chain end with a first vinyl compound having a functional group (e.g. isocyanate group) and reacting with a second compound having a functional group (e.g. hydroxyl group) reactive to the functional group of the first vinyl compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a siloxane copolymer used as a release agent for pressure-sensitive adhesive tapes, a paint for surface lubrication, and a release agent, and a method for producing the same. In particular, the present invention relates to a siloxane copolymer useful as a coating curable by ultraviolet rays or electron beams, and a method for producing the same.

[0002]

2. Description of the Related Art Polysiloxane resins are excellent in heat resistance, water repellency, weather resistance, surface lubrication, and releasability, and are widely used in paints and release agents. Since the elastic modulus and strength of the resin composed of polysiloxane alone are too low, the application of the coating composed of this resin alone is limited to a narrow range.
For that purpose, conventionally, a combination of a polysiloxane resin and an acrylic resin or a polyester resin has been devised to make use of the characteristics of each resin. Among them, block graft copolymers, which are particularly interesting, differ from random copolymers in that they exhibit independent behavior for each segment, so that polymers with very different properties (eg, glass transition point, compatibility, etc.) By binding, it is possible to find new materials that simultaneously fulfill conflicting functions that could not be expressed before.

One method for synthesizing a block / graft copolymer is to use a macromonomer. The macromonomer is a general term for a polymer having a molecular weight of 1000 or more and having a group capable of polymerizing with another monomer at a terminal. By using a macromonomer, it is possible to design a polymer of a graft copolymer having a clear structure of a trunk and a branch component. Therefore, in recent years, much research has been conducted on a graft copolymer using a macromonomer. Proceedings, Vol49, N
o5, PP433-439 (May, 1992)]. However, the polysiloxane resin according to the prior art has a limit in increasing the molecular weight and has a weight average molecular weight of about 20,000, so that improvement in water repellency, surface lubricity and solvent resistance cannot be expected.

Further, Kawakami et al. Have reported that a silicone-containing graft polymer obtained by a reaction between methyl methacrylate and a macromonomer is blended with polymethyl methacrylate by several percent to coat the silicone. Has been reported to be siliconized [Macromolecu
les, 18, 580 (1982)]. However, even with this method, poor compatibility occurs, and improvement in water repellency, surface lubrication, and solvent resistance cannot be expected.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the drawbacks of the prior art, and an object of the present invention is to provide a polymer having a higher molecular weight than the conventional one.
Accordingly, an object of the present invention is to provide a siloxane copolymer having improved solvent resistance and water resistance and a method for producing the same.

[0006]

In view of this situation, the present inventors have conducted intensive studies to achieve the above object, and as a result, the unsaturated siloxane copolymer was added to the siloxane copolymer in order to increase the molecular weight of the siloxane copolymer. The present invention has been completed as a result of intensive studies with a focus on the introduction of. That is, the present invention is a siloxane copolymer represented by the following (1) to (5) and a method for producing the same.

(1) A siloxane copolymer comprising a siloxane polymer and a polymer block having a vinyl group in a side chain.

(2) The above (1), wherein the vinyl group is bonded to the main chain through a urethane bond, an ester bond, an amide bond or a urea bond in the side chain of the polymer block having a vinyl group in the side chain. Siloxane copolymer.

(3) After copolymerizing a siloxane polymer having a vinyl group at one end with a first vinyl compound having a functional group, a siloxane polymer having a functional group capable of reacting with a functional group of the first vinyl compound is obtained. A method for producing a siloxane copolymer, comprising reacting a divinyl compound.

(4) The method for producing a siloxane copolymer according to the above (3), wherein the functional group is a hydroxyl group, an epoxyalkyl group, an isocyanate group, a carboxyl group or an amino group.

(5) a siloxane polymer represented by the following general formula:

[0012]

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(Wherein R represents a hydrogen atom or a methyl group,
R ^{1 to} R ⁵ each represent an alkyl group having 1 to 12 carbon atoms;
n is a 5 to 200, A ¹ represents an alkylene group having 1 to 12 carbon atoms. )

After reacting with one or more primary vinyl compounds selected from the vinyl compound group represented by the following general formula,

[0015]

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(Wherein, R is as defined above, R ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and 2 to 12 carbon atoms.)
Represents an epoxyalkyl group. )

[0017]

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(Wherein, R has the same meaning as described above, and A ² represents an alkylene group having 2 to 12 carbon atoms.)

[0019]

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(Wherein, R and A ² have the same meanings as described above, and A ³ represents an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, or a phenylene group.)

A method for producing a siloxane copolymer by reacting a second vinyl compound having a functional group which binds to R ⁶ or an isocyanate group in the first vinyl compound.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The siloxane copolymer of the present invention comprises:
It comprises a siloxane polymer and a polymer block having a vinyl group in a side chain, and contains the siloxane polymer in an amount of 10 mol% to 99 mol%, preferably 30 mol% to 50 mol% of the entire siloxane copolymer. Also, based on the amount of silicon atoms, the siloxane copolymer contains 5 mol% of unsaturated groups.
６０60 mol%, preferably 10 to 30 mol%.

The siloxane copolymer of the present invention is obtained by block-polymerizing (a) a siloxane polymer having a vinyl group at one end and (b) a first vinyl compound having a functional group, It is produced by reacting a second vinyl compound having a functional group capable of reacting with the functional group of the vinyl compound. Hereinafter, each compound of (a) to (c) will be described.

(A) Siloxane Polymer The siloxane polymer is a siloxane polymer such as polydimethylsiloxane having a vinyl group as an unsaturated group at one end.

Examples of the siloxane polymer include compounds represented by the following general formula.

[0026]

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(Wherein R represents a hydrogen atom or a methyl group,
R ^{1 to} R ⁵ each represent an alkyl group having 1 to 12 carbon atoms;
n is a 5 to 200, A ¹ represents an alkylene group having 1 to 12 carbon atoms. )

The alkyl group represented by R ^{1 to} R ⁵ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl, tert-butyl, pentyl, isopentyl,
Refers to a linear or branched alkyl group having 1 to 12 carbon atoms such as neopentyl, t-pentyl, hexyl, heptyl, octyl and the like. The alkyl groups of R ^{1 to} R ⁵ may be the same or different.

The alkylene group represented by A ¹ is a linear or branched alkylene group having 1 to 12 carbon atoms such as methylene, ethylene, trimethylene and propylene.

(B) Primary vinyl compound The primary vinyl compound has a functional group at one end,
The other terminal has a vinyl group as an unsaturated group. Examples of the functional group include a hydroxyl group, a carboxyl group, an isocyanate group, an epoxyalkyl group, and an amino group.

Examples of the first vinyl compound include the following.

[0032]

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Wherein R is as defined above, R ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and 2 to 12 carbon atoms.
Represents an epoxyalkyl group. )

The alkyl group for R ⁶ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl, tert-butyl, pentyl, isopentyl,
It refers to a linear or branched alkyl group having 1 to 18 carbon atoms such as neopentyl, t-pentyl, hexyl, heptyl, octyl and the like. Further, an epoxyalkyl group refers to a group having 2 to 12 carbon atoms such as epoxyethyl and 1,2-epoxypropyl.
Means an epoxyalkyl group.

[0035]

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(Wherein, R has the same meaning as described above, and A ² represents an alkylene group having 2 to 12 carbon atoms.)

The alkylene group represented by A ² means a linear or branched alkylene group having 2 to 12 carbon atoms such as ethylene, trimethylene and propylene.

[0038]

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(Wherein, R and A ² have the same meanings as described above, and A ³ represents an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, or a phenylene group.)

The alkylene group for A ^{3 has} the same meaning as the alkylene group for A ² , and the cyclohexylene group includes 1,2-
Cyclohexylene, 1,3-cyclohexylene, 1,4
-Cyclohexylene. The phenylene group includes o-phenylene, m-phenylene, and p-phenylene.

Specific examples of the vinyl compound include acrylic acid, methacrylic acid, and methyl (meth) acrylate [which means both methyl acrylate and methyl methacrylate.
The same applies hereinafter), ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, n-
Tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, isononyl (meth) acrylate, isophoronyl (meth) acrylate, (meth) acrylamide, N-methylolacrylamide, styrene, glycidyl (meth) acrylate, α-methylstyrene, -Hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, allyl glycidyl ether, and the like.

(C) Second Vinyl Compound The second vinyl compound has a functional group capable of reacting with the functional group of the first vinyl compound, and has a vinyl group as an unsaturated group at one end. The functional group capable of reacting with the functional group of the first vinyl compound is, for example, a glycidyl group or a carboxyl group when the functional group of the first vinyl compound is an epoxyalkyl group, and the functional group of the first vinyl compound is a hydroxyl group. Is an isocyanate group. Examples of the second vinyl compound include those similar to the specific examples of the first vinyl compound.

[Production Method of Siloxane Copolymer] The siloxane copolymer of the present invention is prepared by reacting the above (a) siloxane polymer and (b) a macromonomer obtained by copolymerizing a first vinyl compound. And (c) reacting the second vinyl compound. The above-mentioned (a) siloxane polymer and (b) the first vinyl compound can react at an arbitrary ratio.
0 mol%, (b) 90 to 10 mol% of the first vinyl compound is preferable, (a) 20 to 80 mol% of the siloxane polymer,
(B) More preferably 80 to 20 mol% of the first vinyl compound. The quantitative relationship between the macromonomer obtained by copolymerizing the (a) siloxane polymer and (b) the first vinyl compound with the (c) second vinyl compound is as follows: The macromonomer is preferably 70 to 90 mol% and (c) the second vinyl compound 10 to 30 mol%.

The process for producing the siloxane copolymer of the present invention will be described by dividing into (A) the production of a macromonomer and (B) the reaction of the macromonomer with a second vinyl compound.

(A) Production of Macromonomer The method of producing a macromonomer by polymerizing the above (a) siloxane polymer and (b) a first vinyl compound includes a bulk polymerization method, a solution polymerization method, and an emulsion polymerization method. And a suspension polymerization method, but a polymerization method using water or an organic solvent is preferable. Hereinafter, a solution polymerization method using an organic solvent and an aqueous emulsion or suspension polymerization method will be described.

(I) Polymerization method using organic solvent This is a method in which the above (a) siloxane polymer and (b) the first vinyl compound are dissolved in an organic solvent and copolymerized. As the organic solvent, any of aromatic, ester, ketone, and alcohol solvents may be used. Examples of the aromatic solvent include toluene, benzene, xylene, heptane and the like, and examples of the ester solvent include ethyl acetate and the like. Examples of ketone solvents include acetone and methyl ethyl ketone, and examples of alcohol solvents include:
Methanol, isopropyl alcohol, n-butyl alcohol and the like, all having a boiling point of 50 ° C to 150 ° C
Up to solvents are usually used. The amount of organic solvent used is from 10 to 90% by weight, based on all monomers.

Examples of the polymerization initiator include azo compounds such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, and azobisisobutylnitrile. The amount of polymerization initiator used is from 0.01 to 5% by weight, based on all monomers.

The polymerization temperature is suitably from 30 ° C. to 150 ° C., and more preferably from 50 ° C. to 120 ° C. If the reaction temperature is lower than 30 ° C., the polymerization rate is too low.
When the temperature exceeds 0 ° C., the organic solvent has a boiling point or higher, the reflux temperature is too high, and the reaction rate is too fast. Also, the molecular weight cannot be controlled.

(Ii) Aqueous polymerization method This is a method in which the above (a) siloxane polymer and (b) the first vinyl compound are dispersed or suspended in water and copolymerized. The amount of water used is between 10 and 90
% By weight.

As the polymerization initiator, peroxides such as potassium persulfate, ammonium persulfate, benzoyl peroxide and the like are used. The amount of polymerization initiator used is from 0.01 to 5% by weight, based on all monomers.

A dodecyl mercaptan compound as a polymerization regulator, and poly (oxyethylene) nonylphenyl ether, poly (oxyethylene) octyl phenyl ether, poly (oxyethylene) octyl phenyl ether, poly (oxyethylene) alkyl ether as an emulsifier Poly (oxyethylene) lauryl ether, poly (oxyethylene) oleyl ether, poly (oxyethylene) tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,
Polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan stearate, sorbitan fatty acid ester, anionic reactive emulsifier [POE nonylpropenyl phenyl ether sulfate ammonium (EO (ethylene oxide) 5 Mol to 30 mol addition)] and sodium-2-sulfoethyl methacrylate. Particularly, from the viewpoint of surface bleed and the like, a reactive emulsifier [POE nonylpropenyl phenyl ether sulfate ammonium (EO (ethylene oxide) 5
Mol to 30 mol addition)]. The amount of the polymerization modifier used is 0.0001 to 1% by weight based on all monomers, and the amount of the emulsifier is 0.01%
-10% by weight.

The polymerization temperature is suitably from 30 ° C. to 100 ° C., but more preferably from 50 ° C. to 80 ° C. Reaction temperature is 30
If the temperature is lower than ℃, the reaction is delayed and residual monomer is easily generated.
If the temperature exceeds 00 ° C., the reaction cannot be controlled.

(B) Reaction of Macromonomer with Second Vinyl Compound In this step, the functional group of the macromonomer obtained by polymerizing (a) the siloxane polymer and (b) the first vinyl compound is Then, a side group vinyl group is introduced into the macromonomer by reacting a functional group of the second vinyl compound.

For example, as shown below, in order to introduce a vinyl group which is an unsaturated group into a polydimethylsiloxane graft polymer containing a carboxyl group, a monomer which reacts with the carboxyl group, for example, glycidyl (meth) acrylate is added to the carboxyl group. It can be introduced by an addition reaction with a group.

[0055]

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Further, as shown below, a half acrylate of 2-isocyanatoethyl methacrylate or 2-hydroxyethyl acrylate and isophorone diisocyanate is added as an isocyanate group-containing monomer to a hydroxyl group-containing polydimethylsiloxane graft polymer. By reacting, an unsaturated group can be introduced.

[0057]

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Further, an unsaturated group can be introduced by a reaction between an epoxy group and a carboxyl group. As described below, an unsaturated group can be introduced by subjecting a polydimethylsiloxane graft polymer containing an epoxy group to an addition reaction with a carboxyl group monomer such as acrylic acid, methacrylic acid, or acrylic acid dimer.

[0059]

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As described above, the functional group-containing polydimethylsiloxane graft polymer is reacted with a monomer having a functional group capable of reacting with the functional group by an addition reaction (urethane-forming reaction, etc.), a condensation reaction or the like. , An unsaturated group can be introduced.

The reaction between the macromonomer and the second vinyl compound can be carried out in any system of water or an organic solvent. Depending on the molecular weight of the polymer and the type of the functional group, any reaction system of water or an organic solvent should be employed. The perception can be determined. For example, in the case of a urethanization reaction, an aqueous type macromonomer cannot be used, but an organic solvent type macromonomer can be used favorably. The esterification reaction (for example, the reaction between a carboxyl group and an epoxy group) is suitable for both aqueous and organic solvent systems. However, even with organic solvent-based macromonomers,
In the case of a urethanization reaction, an alcohol solvent cannot be used. This is because the alcohol solvent reacts with the isocyanate group.

In the esterification, quaternary ammonium salts and tertiary amines are suitable as catalysts. Examples of the quaternary ammonium salt include benzyltriethylammonium chloride and benzyltributyrylammonium salt, and examples of the tertiary amine include triethylamine and tributyrylamine. In general, benzyltriethylammonium chloride is suitable as a quaternary ammonium salt, and triethylamine is suitable as a tertiary amine from the viewpoints of reaction rate, reaction temperature, and reaction solvent. The used amount is 0.001 to 10% by weight, the preferred used amount is 0.01 to 10% by weight, and the particularly preferred used amount is 0.1 to 10% by weight.
~ 5% by weight. Known catalysts are used for reactions other than esterification.

The reaction between the macromonomer and the second vinyl compound is generally carried out in the presence of a polymerization inhibitor. This is because if an addition reaction or the like is performed without using a polymerization inhibitor, gelation or the like may occur during the reaction. As the polymerization inhibitor, known polymerization inhibitors such as hydroquinone, phenothiazine, and hydroquinone monomethyl ether can be used. The amount of the polymerization inhibitor is 10 to 5000 ppm, the preferred amount is 10 to 2000 ppm, and the particularly preferred amount is 100 ppm. ５００500 ppm.

The reaction between the macromonomer and the second vinyl compound may be carried out at a temperature of 30 ° C. to 250 ° C., particularly at a temperature as low as possible to prevent gelation. It is particularly preferable to carry out the reaction at a temperature lower than the boiling point of the solvent.

In order to prevent gelation, a suitable reaction temperature is 60 to 100 ° C. Besides adding a polymerization inhibitor to prevent gelation, there is also a method of introducing air. Often used in combination with air and polymerization inhibitors.

[0066]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples, and Experimental Examples, but the present invention is not limited thereto.

Example 1 400 g of toluene was charged into a 1-liter four-necked flask equipped with a condenser, a nitrogen gas inlet tube, a thermometer, a dropping funnel and a stirrer. 200 g of methyl methacrylate, methacryloyl polydimethylsiloxane at one end [Siraprene FM-0725: MW, manufactured by Chisso Corporation]
(Weight average molecular weight: 10,000) A mixed monomer obtained by mixing 50 g, 50 g of 2-hydroxyethyl acrylate and 3 g of azobisisobutylnitonyl was added dropwise,
The reaction was started at ℃. Dropping was performed for 2 hours and aging was performed for 6 hours to produce a hydroxyl group-containing polydimethylsiloxane graft polymer.

Thereafter, 65 g of 2-isocyanatoethyl methacrylate (Karen MOI, manufactured by Showa Denko KK), 0.1 g of dibutyltin dilaurate as a catalyst and 0.1 g of hydroquinone as a polymerization inhibitor were added, and the mixture was heated at 80 ° C. for 10 hours. The reaction was carried out. 225 by IR
The reaction was stopped when the absorption at 0 cm ^-1 disappeared. Concentration 47.5%, viscosity 26,000 (mpas / 25
C), and an unsaturated group-containing polydimethylsiloxane graft polymer having a MW of 36,500 was obtained.

100 g of an unsaturated group-containing polydimethylsiloxane graft polymer and 2 g of a photoinitiator (Irgacure 651 manufactured by Ciba-Geigy Co., Ltd.) were blended, and a PET film (1
00 μm) (coating amount 3 μm), and drying
The test was carried out at 30 ° C. for 30 seconds and irradiated with ultraviolet rays at 300 mJ / cm ² (Ushio Electric Co., Ltd., ultraviolet ray irradiator) to obtain test samples. Table 2 shows the evaluation results.

Example 2 An epoxy group-containing polydimethylsiloxane graft polymer was produced in the same manner as in Example 1, except that 50 g of glycidyl methacrylate and 3 g of azobisisobutylnitrile were used instead of 50 g of 2-hydroxyethyl acrylate.

Thereafter, 25 g of acrylic acid, 10 g of triethylbenzylammonium chloride as a catalyst and 0.1 g of hydroquinone as a polymerization inhibitor were added, and the mixture was added at 80 ° C. for 1 hour.
The addition reaction was performed for 0 hour, and the reaction was stopped when the acid value became 2 mgKOH / g or less. Concentration 44%, viscosity 16.0
An unsaturated group-containing polydimethylsiloxane graft having an MW of 46,000 was obtained at 00mpas / 25 ° C. The other operations were the same as in Example 1.

Example 3 A hydroxyl group-containing polydimethylsiloxane graft polymer was produced in the same manner as in Example 1.

2-hydroxyethyl acrylate and isophorone diisocyanate half acrylate (MW 33
8) 67.6 g, dibutyltin laurate as catalyst,
0.1 g of hydroquinone was added as a polymerization inhibitor.
The reaction was performed at 10 ° C. for 10 hours. The reaction was stopped when the absorption at 2250 cm ^-1 disappeared by IR. Concentration 47.7
%, Viscosity 62,500 (mgas / 25 ° C.), MW 62,
000 unsaturated group-containing polydimethylsiloxane graft polymer was obtained. The other operations were the same as in Example 1.

Reference Example (Synthesis example of half acrylate ester) A stirrer, a condenser, and a thermometer were attached to a 500 ml four-necked flask, and 116 g of 2-hydroxyethyl acrylate and 222 g of isophorone diisocyanate were attached.
And dibutyltin dilaurate 0.03 as a catalyst
g, 0.01 g of hydroquinone as a polymerization inhibitor was added, and the mixture was reacted at 60 ° C. for 8 hours to obtain a half acrylate.

Examples 4 to 10 According to the composition shown in Table 1, an unsaturated group-containing polydimethylsiloxane graft polymer was obtained in the same manner as in Example 1.

Example 11 A 1 liter four-necked flask was charged with a condenser, a thermometer,
500 ml of water, 3 g of sodium dodecylbenzenesensulfonate and 1 g of potassium persulfate as an emulsifier were placed in a device equipped with a stirrer, a dropping funnel and an N ₂ introduction tube. One-end methacryloyl polydimethylsiloxane (manufactured by Chisso Corporation,
Sairaprene FM-0725, MW 10,000) 50
g, 200 g of methyl methacrylate and 50 g of glycidyl methacrylate were added dropwise. The dropping was performed at a reaction temperature of 80 ° C. for 2 hours.
Aging was performed for 6 hours to obtain an epoxy group-containing polydimethylsiloxane graft polymer.

Thereafter, 25 g of acrylic acid, 10 g of benzyltriethyl chloride as a catalyst and 0.1 g of hydroquinone as a polymerization inhibitor were added, and an addition reaction was carried out at 80 ° C. for 10 hours. The acid value was 10 (mg KOH / g) solid. Viscosity 250mpas / 25 ° C, MW25
As a result, 5,000 unsaturated group-containing polydimethyl graft polymers were obtained. Others were performed similarly to Example 1. However, darcure 1173 (manufactured by Merck) was used as a photoinitiator in 3
g used.

Comparative Example 1 The same test as in Example 1 was performed using the hydroxyl group-containing polydimethylsiloxane graft polymer obtained during the production process of Example 1.

Comparative Example 2 Using the epoxy group-containing polydimethylsiloxane graft polymer obtained during the production process of Example 2, the procedure of Example 1 was repeated.
The same test was performed.

Comparative Example 3 The same test as in Example 1 was conducted using the epoxy group-containing polydimethylsiloxane graft polymer obtained during the production process of Example 11.

[0081]

[Table 1]

In the table, FM-0725, FM-0721,
FM-0711 is Silaprene FM manufactured by Chisso Corporation used as methacryloyl polydimethylsiloxane at one end.
−0725 (MW 10,000), FM−0721 (M
W5,000) and FM-0711 (MW 1,000). MMA is methyl methacrylate, GM
A means glycidyl methacrylate, 2HEA means 2-hydroxyethyl acrylate, AA means acrylic acid, and MAA means methacrylic acid.

[0083]

[Table 2]

Water Resistance Test The sample was left standing in water at 50 ° C. for 24 hours to determine the appearance. In the table, “○” indicates no whitening, “△” indicates whitening,
“X” means whitening.

Solvent Resistance Test The surface of the sample was rubbed 50 times with a rag impregnated with methyl ethyl ketone, and the condition of the film surface was determined. In the table, “○” means no dropout, “△” means partial dropout, and “×” means complete dropout.

Adhesive tape (OPP adhesive tape, manufactured by Nichiban Co., Ltd.) was adhered to the coating film, and pressed with a 2 kg roller.
% Peeling test was carried out under a temperature condition of 0.1% (unit: g / 2)
5 mm).

Surface lubricity test A 1 kg weight was placed on the surface of the test coating film, and a constant speed (30
(0 mm / min), and the film was slid on the surface to determine the tensile strength (unit: g / 50 mm width).

[0088]

The siloxane copolymer of the present invention can have a higher molecular weight than conventional siloxane copolymers and can be expected to have improved water repellency, surface lubricity and solvent resistance. Therefore, it can be used as a release agent for an adhesive tape, a paint for surface lubrication, and a release agent, and is particularly useful as a paint that is cured by ultraviolet rays or electron beams. Further, according to the method for producing a siloxane copolymer of the present invention, the siloxane copolymer of the present invention can be produced with high productivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/00 C09K 3/00 RF term (Reference) 4J027 AF05 BA01 BA04 BA05 BA06 BA07 BA08 BA09 BA13 BA14 CB10 CC05 CD08 4J038 CG011 CG131 CH031 CH171 CH191 DL151 FA241 GA01 GA03 GA11 NA10 PA17 4J100 AL08P BA81P CA31 HA61 HC01 HC29 HC34 HC39 HC50 HC51 JA01

Claims (5)

[Claims] 1. A siloxane copolymer comprising a siloxane polymer and a polymer block having a vinyl group in a side chain. 2. The siloxane according to claim 1, wherein the vinyl group is bonded to the main chain through a urethane bond, an ester bond, an amide bond or a urea bond in the side chain of the polymer block having a vinyl group in the side chain. Copolymer. 3. A copolymer comprising a siloxane polymer having a vinyl group at one end and a first vinyl compound having a functional group, and then a second polymer having a functional group capable of reacting with the functional group of the first vinyl compound. A method for producing a siloxane copolymer, comprising reacting a vinyl compound. 4. The process for producing a siloxane copolymer according to claim 3, wherein the functional group is a hydroxyl group, an epoxyalkyl group, an isocyanate group, a carboxyl group or an amino group. 5. A siloxane polymer represented by the following general formula: (Wherein, R represents a hydrogen atom or a methyl group, R ^{1 to} R ⁵ each represent an alkyl group having 1 to 12 carbon atoms, and n represents 5 to 20)
0 and A ¹ represent an alkylene group having 1 to 12 carbon atoms. After reacting with one or more primary vinyl compounds selected from the group of vinyl compounds represented by the following general formula: (Wherein, R has the same meaning as described above, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an epoxyalkyl group having 2 to 12 carbon atoms.) (Wherein, R has the same meaning as described above, and A ² has 2 to 12 carbon atoms)
Represents an alkylene group. ) (In the formula, R and A ² have the same meanings as described above, and A ³ represents an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, or a phenylene group.) Bonding to R ⁶ or an isocyanate group in the first vinyl compound A method for producing a siloxane copolymer having a vinyl group in a side chain by reacting a second vinyl compound having a functional group.