JPH0925415A - Curable silicone composition containing fluorine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a specific organopolysiloxane having plural bulky trifluoro groups in a molecule, capable of giving a cured material excellent in mold release characteristics and having efficient releasability against a dimethylpolysiloxane adhesive. SOLUTION: This silicone composition is composed of (A) an alkenyl-type organopolysiloxane having at least two alkenyl groups bound to silicon atoms in a molecule and at least one fluorinated substituting group of formula I [R<1> is a trimethyl silyl intermediates with a 1-4C alkyl or a 2-5C straight chain alkylene; (k)=2-6; (m)=3-10] bound to a silicon atom in the molecule, (B) an organohydropolysiloxane having at least three hydrogen atoms bound to silicone atoms in a molecule and at least one substituent of formula I bound to a silicon atom in the molecule and (C) a catalyst for an addition reaction to the silicon atom having a hydrogen atom of an alkenyl group bound to the silicon atom. Further, the component A is preferably expressed by formula II (x=1,2; R is a 1-8C alkyl, etc.; R<2> is an alkenyl, etc.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable fluorine-containing silicone composition, and more specifically, it has a fluorobisether residue as a fluorocarbon group, and particularly has a small surface energy such as a release agent. And a curable fluorine-containing silicone composition that is useful for forming the composition.

[0002]

2. Description of the Related Art Curable silicones are used, for example, as release agents for pressure-sensitive adhesives and back treating agents. Generally, the adhesive tape is manufactured as a roll,
When sticking to the adherend, it is necessary to rewind from the roll, and this rewinding work is performed smoothly, and so that the adhesive on the tape does not so-called glue transfer to the back surface of the tape adjacent to the tape, The back surface of the tape is provided with a layer of back surface treatment agent made of curable silicone.

On the other hand, the silicone-based pressure-sensitive adhesive containing dimethylpolysiloxane as a main component is being used in an increasing amount due to its wide range of applications because of its excellent heat resistance and weather resistance. Since such a silicone-based pressure-sensitive adhesive has a very strong adhesive force, the conventional non-silicone-based pressure-sensitive adhesive, for example, the conventional silicone-based release agent that has been used as a back surface treatment agent for an acrylic-based pressure-sensitive adhesive is It does not have a sufficient mold release property with respect to the silicone-based pressure-sensitive adhesive, and it is difficult to rewind the tape.

Therefore, in order to solve such a problem, various mold releasing agents made of a curable fluorine-containing silicone having improved mold releasability have already been proposed. For example, JP-A-63-320 proposes a release agent containing a straight-chain type fluorine-containing alkyl substituent-containing organopolysiloxane as a main component, and JP-A-64-74268.
Japanese Patent Laid-Open Publication No. 2003-242242 proposes a release agent containing an organopolysiloxane having a branched type fluorine-containing alkyl substituent as a main component.

However, with respect to silicone-based pressure-sensitive adhesives, even a release agent composed of such a curable fluorine-containing silicone still has insufficient releasability, and such a release agent is applied to the back surface of the tape. However, even when the roll is provided, when the roll is rewound after being stored for a long period of time, the pressure-sensitive adhesive layer on the tape may cause interfacial peeling and lose its function as a pressure-sensitive adhesive tape. The same applies to an adhesive product such as an adhesive label provided with an adhesive layer and a release agent layer thereon.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the conventional curable fluorine-containing silicone type releasing agent, and it has fluorobisether residue as a fluorocarbon group. Has a group,
It is an object of the present invention to provide a curable fluorine-containing silicone composition which is useful for forming a coating having a small surface energy, and particularly has excellent releasability for silicone-based pressure-sensitive adhesives.

[0007]

The curable fluorine-containing silicone composition according to the present invention comprises (a) at least two silicon-bonded alkenyl groups in the molecule and a silicon-bonded general formula ( I)

[0008]

[Chemical 6]

(Wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group through a linear alkylene group having 2 to 5 carbon atoms, and k is an integer of 2 to 6) And m represents an integer of 3 to 10), and (b) has at least three silicon-bonded hydrogen atoms in the molecule, and (b) has at least one fluorine-containing substituent. An organohydropolysiloxane having at least one fluorine-containing substituent represented by the general formula (I) bonded to silicon in the molecule, and (c) a silicon atom having a hydrogen atom of an alkenyl group bonded to a silicon atom. It is characterized by containing a catalyst for the addition reaction of.

In the curable fluorine-containing silicone composition according to the present invention, the component (a) has at least two alkenyl groups bonded to silicon in the molecule and has the above general formula (I) bonded to silicon in the molecule. The alkenyl-type organopolysiloxane represented by the formula (1), which has at least one fluorine-containing substituent, wherein the alkenyl group is preferably a vinyl group or an allyl group for practical purposes. In the present invention, the component (a) needs to have at least two such alkenyl groups in the molecule, and is preferably linear.

Particularly in the present invention, such an alkenyl type organopolysiloxane is preferably represented by the general formula (II)

[0012]

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(Wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group through a linear alkylene group having 2 to 5 carbon atoms, and k is an integer of 2 to 6) , M is an integer of 3 to 10, and x is 1 or 2.
R is an alkyl group having 1 to 8 carbon atoms which may be the same or different from each other, or a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and R ² is Represents an alkenyl group, p, q and r are p ≧ 0 and q, respectively.
An integer that satisfies ≧ 0 and r ≧ 1 is shown. ).

In the curable fluorine-containing silicone composition according to the present invention, the component (b) has at least three silicon-bonded hydrogen atoms in the molecule and has the general formula (I) bonded to silicon in the molecule. An organohydropolysiloxane having at least one fluorine-containing substituent represented by formula (III)

[0015]

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(Wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group through a linear alkylene group having 2 to 5 carbon atoms, and k is an integer of 2 to 6) And m represents an integer of 3 to 10, and R may have an alkyl group having 1 to 8 carbon atoms, which may be the same or different from each other, or an alkyl group having 1 to 4 carbon atoms. Represents a good phenyl group, and s, t and u are s ≧ 1 and t, respectively.
Represents an integer satisfying ≧ 0 and u ≧ 1, T represents hydrogen or the above R, and when T is R, s represents an integer satisfying s ≧ 3. ).

The curable fluorine-containing silicone composition according to the present invention thus contains the components (a), (b) and (c), but as the organopolysiloxane represented by the above general formula (II), , Especially the general formula (IV)

[0018]

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(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group through a linear alkylene group having 2 to 5 carbon atoms, and k is an integer of 2 to 6 , M is an integer of 3 to 10, and x is 1 or 2.
R is an alkyl group having 1 to 8 carbon atoms, which may be the same or different from each other, or a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and p, q And r are integers satisfying p ≧ 0, q ≧ 0 and r ≧ 1 respectively. The terminal vinyl group-terminated organopolysiloxane represented by (4) is preferably used.

The organopolysiloxane terminated with a vinyl group represented by the above general formula (IV) is, for example, a compound represented by the general formula (V)

[0021]

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(Wherein R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group through a linear alkylene group having 2 to 5 carbon atoms, and k represents an integer of 2 to 6) And m represents an integer of 3 to 10, and R may have an alkyl group having 1 to 8 carbon atoms, which may be the same or different from each other, or an alkyl group having 1 to 4 carbon atoms. And a fluorine-containing cyclotrisiloxane represented by the general formula (VI)

[0023]

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(In the formula, w represents an integer of 1 or more, and R has an alkyl group having 1 to 8 carbon atoms, which may be the same or different, or an alkyl group having 1 to 4 carbon atoms. A vinyl group terminated with a vinyl group terminated with a phenyl group, which may be present in each group), at a suitable ratio according to the purpose, by an equilibration reaction in the presence of an acid or alkali catalyst. You can

Next, the fluorine-containing cyclotrisiloxane represented by the general formula (V) can be prepared, for example, by the general formula (VII)

[0026]

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(In the formula, R is an alkyl group having 1 to 8 carbon atoms which may be the same as or different from each other, or 1 to 1 carbon atoms.
4 represents a phenyl group which may have an alkyl group. ) And a general formula (VIII)

[0028]

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(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group through a linear alkylene group having 2 to 5 carbon atoms, and k is an integer of 2 to 6 And m represents an integer of 3 to 10, and R may have an alkyl group having 1 to 8 carbon atoms, which may be the same or different from each other, or an alkyl group having 1 to 4 carbon atoms. It can be obtained by reacting a dichlorosilane compound represented by a phenyl group) in the presence of a tertiary amine such as triethylamine.

Further, the dichlorosilane compound represented by the general formula (VIII) is a compound represented by the general formula (IX)

[0031]

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(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group through a linear alkylene group having 2 to 5 carbon atoms, and k is an integer of 2 to 6) And m is an integer of 3 to 10), and an alkenyl compound having a fluorobisether group represented by the general formula (X).

[0033]

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(In the formula, R's may be the same as or different from each other, or may be an alkyl group having 1 to 8 carbon atoms or 1 to 8 carbon atoms.
4 represents a phenyl group which may have an alkyl group. ) Can be easily obtained from the hydrosilane compound represented by the formula (1) using a platinum catalyst. Examples of the platinum-based catalyst include chloroplatinic acid and complex compounds of chloroplatinic acid and various olefins.

The alkenyl compound having a fluorobisether group represented by the general formula (IX) is, for example, the general formula (XI)

[0036]

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(In the formula, R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group via a linear alkylene group having 2 to 5 carbon atoms, and X represents chlorine, bromine or iodine. A halogen compound represented by the general formula (XII)

[0038]

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(In the formula, m represents an integer of 3 to 10), and a fluorine-containing diol represented by the general formula (XIII)

[0040]

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(In the formula, k represents an integer of 2 to 6, and X represents chlorine, bromine or iodine.) In the presence of a tertiary amine such as triethylamine or the like, a terminal halogenated alkenyl compound represented by It can be obtained by reacting with.

Specifically, for example, a halogen compound represented by the general formula (XI), a fluorine-containing diol represented by the general formula (XII) and an alkenyl compound represented by the general formula (XIII) are mixed with triethylamine. And the like in the presence of a tertiary amine such as.

As another method, first, the above general formula (XII)
The fluorine-containing diol represented by the formula (XIII) is reacted with the alkenyl compound represented by the formula (XIII) in the presence of a tertiary amine such as triethylamine.
V)

[0044]

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(In the formula, k represents an integer of 2 to 6, and m represents 3
And an integer of 10 to 10. ), A fluorine-containing alcohol compound represented by the formula (4) is isolated and purified, and then the halogen compound represented by the general formula (XI) is added to the presence of a tertiary amine such as triethylamine. It can be obtained by reacting under.

Further, as another method, the above-mentioned general formula (XIV)
By reacting a fluorine-containing alcohol compound represented by with sodium hydride or the like to give an alcoholate, and reacting this with an alkenyl compound represented by the general formula (XIII) and a halogen compound represented by the general formula (XI). Can also get

Next, in the curable fluorine-containing silicone composition according to the present invention, the organohydropolysiloxane which is the component (b) represented by the general formula (III) is represented by, for example, the general formula (V). Fluorine-containing cyclotrisiloxane and general formula (XV)

[0048]

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(In the formula, v represents an integer of 1 or more, and R has an alkyl group having 1 to 8 carbon atoms, which may be the same or different, or an alkyl group having 1 to 4 carbon atoms. 2 represents a phenyl group which may be present.
With siloxane, and general formula (XVI)

[0050]

[Chemical 21]

(In the formula, j represents an integer of 3 or more, and R represents an alkyl group having 1 to 8 carbon atoms or a phenyl group optionally having an alkyl group having 1 to 4 carbon atoms.) It can be obtained by polymerizing the hydrogroup-containing organosiloxane represented by the following by a known equilibration reaction using an acid or an alkali as a catalyst in a ratio according to the purpose.

In the curable fluorine-containing silicone composition according to the present invention, the above-mentioned components (a) and (b) are
Used in such a proportion that the silicon-bonded alkenyl group of component (a) is 0.1 to 10, preferably 1 to 3 silicon-bonded hydrogen atoms of component (b). To be

In the curable fluorine-containing silicone composition according to the present invention, the catalyst for the addition reaction of the alkenyl group bonded to the silicon atom, which is the component (c), to the silicon atom having a hydrogen atom, that is, the crosslinking reaction, is the component (a). ) And the component (b) for addition reaction, and examples thereof include platinum and rhodium, and complexes derived from them. Examples of such a complex include a platinum complex of divinyl type siloxane and a platinum complex of siloxane having an amino group.

In the present invention, such a catalyst is usually used in the range of 1 to 10,000 ppm in terms of platinum based on the total weight of the components (a) and (b). The curable fluorine-containing silicone composition according to the present invention,
The components (a), (b) and (c) as described above can be obtained by mixing each in a predetermined ratio, and further,
If necessary, a stabilizer for the catalyst may be added in order to stabilize the crosslinking activity. The curable fluorine-containing organic silicone composition according to the present invention may be diluted with an appropriate organic solvent such as a fluorine-containing solvent or a chlorine-based solvent, if necessary.

In this manner, the curable fluorine-containing silicone composition according to the present invention is prepared, coated on an appropriate substrate, heated and crosslinked to form a coating useful as a release agent. It can be formed on a substrate. Where the ingredients
The reaction temperature for the cross-linking reaction between (a) and component (b) is not particularly limited, but is usually 50 to 200 ° C.
And preferably in the range of 70 to 150 ° C.

[0056]

EXAMPLES The present invention will be described below with reference to Examples along with synthesis examples of each component, but the present invention is not limited to these Examples. In the following, in the structural formulas of H-OIL added to the table, R has the same or different alkyl group having 1 to 8 carbon atoms or alkyl group having 1 to 4 carbon atoms. Indicates a phenyl group which may be. Further, in the structural formula of H-OIL attached to Table 3, e represents an integer of 2 or more.

Synthesis Example 1 (Synthesis of allyl ether (C3)) 2,2,3,3,4,4-hexafluoro-1,5-pentanediol (63.6 g, 3
(00 mmol) in tetrahydrofuran (1.5 L) / dimethylsulfoxide (500 mL) solution, potassium t-butoxide (41.1 g, 330 mmol) in propanol (500 mL) / dimethylsulfoxide (500 mL)
The solution was gradually added dropwise and stirred overnight. Allyl bromide (29 mL, 330 mmol) was added to the obtained reaction mixture,
Stir on a 40 ° C. water bath.

The reaction solution thus obtained was added to an ether / water mixture. Dilute hydrochloric acid is added to this to adjust the pH of the aqueous layer to 1
After adding so that it became ~ 2, a liquid separation operation was performed. Then
The ether layer was thoroughly washed with brine, dried over anhydrous magnesium sulfate, the ether was removed by an evaporator, and the obtained residue was purified by silica gel chromatography to give an allyl ether (39.0 g). ,
Yield 51%) was obtained.

(Synthesis of ethyl type allyl ether (C3)) A solution of the allyl ether compound (21.0 g, 79 mmol) in tetrahydrofuran (300 mL) / dimethyl sulfoxide (120 mL) was added with potassium t-butoxide (14.
8 g, 119 mmol) propanol (120 mL)
/ Dimethyl sulfoxide (120 mL) solution was gradually added dropwise, and the mixture was stirred for 1.5 hours. Ethyl bromide (9.1 mL, 119 mmol) was added to the obtained reaction mixture, and the mixture was stirred overnight at room temperature.

The reaction solution thus obtained was added to an ether / water mixture. Dilute hydrochloric acid is added to this to adjust the pH of the aqueous layer to 1
After adding so that it became ~ 2, a liquid separation operation was performed. Then
The ether layer was washed well with brine, dried over anhydrous magnesium sulfate, the ether was removed by an evaporator, and the obtained residue was purified by silica gel chromatography to obtain an ethyl type allyl ether (1
7.8 g, yield 80%) was obtained.

(Perfluoroalkylsilane body (C3)
Synthesis of ethyl type allyl ether (17.4 g, 62.0)
(mmol) was placed in an eggplant-shaped flask having a capacity of 30 mL, and chloroplatinic acid (50 mg) was added thereto. 70 ℃
It is dissolved in water by heating, and hydrosilyl dichloride (10
(mL, 95 mmol) was gradually added, and the reaction was allowed to proceed at 70 ° C. for 3 hours. The obtained crude product was purified by a distillation method to obtain a dichlorosilane compound (13.7 g, yield 28.5).
%) Was obtained.

(Synthesis of Trisiloxane Body (C3)) A solution of triethylamine (4.9 mL, 35.4 mmol) in toluene (30 mL) was added to a dichlorosilane body (13.7 g, 1
A solution of 7.7 mmol of toluene (300 mL) and a solution of disiloxane diol (2.9 g, 17.7 mmol) of methyl ethyl ketone (30 mL) were gradually added dropwise at room temperature at the same dropping rate.

After stirring at room temperature for 1 hour, ether (500 mL) was added to the reaction solution, the ether layer was washed with water, dried over anhydrous magnesium sulfate, the ether was removed by an evaporator, and the residue was distilled. To give a trisiloxane body (2.5 g, yield 34%). The proton nuclear magnetic resonance spectrum of this trisiloxane body is shown in FIG. 1 together with its attribution. The infrared absorption spectrum is shown in FIG.

(Synthesis of Ethyl-Type Vi-OIL and H-OIL (Polymerization)) Vi-OIL (Component (a)) A predetermined amount of the trisiloxane body synthesized above and divinyldisiloxane are mixed, and trifluoromethane is added thereto. Sulfonic acid was added and stirred overnight. Then, a 10% triethylamine m-bistrifluoroxylene solution was added thereto, neutralized, and stripped at 100 ° C. for 1 hour under a reduced pressure of 1 mmHg to obtain a target Vi-OIL. The proton nuclear magnetic resonance spectrum of this Vi-OIL is shown in FIG. 3 together with its attribution. The infrared absorption spectrum is shown in FIG.

H-OIL (Component (b)) As a charge, a predetermined amount of trisiloxane and hexamethyldisiloxane / tetramethyltetrasiloxane were mixed, and the desired H-OIL was obtained in the same manner. This H
The proton nuclear magnetic resonance spectrum of -OIL is shown in Fig. 5 together with its assignment. The infrared absorption spectrum is shown in FIG. H-OIL and Vi-OI synthesized in this way
The molecular weight and the number of functional groups of L are shown in Tables 1 and 2.

[0066]

[Table 1]

[0067]

[Table 2]

Synthesis Example 2 (Synthesis of allyl ether (C3)) 2,2,3,3,4,4-hexafluoro-1,5-pentanediol (63.6 g, 3
00 mmol) in tetrahydrofuran (1.5 L) / dimethylsulfoxide (400 mL) solution and potassium t-butoxide (41.1 g, 330 mmol) in propanol (5 L).
(00 mL) / dimethyl sulfoxide (500 mL) solution was gradually added dropwise, and the mixture was stirred overnight. Then, allyl bromide (29 mL, 330 mmol) was added to the obtained reaction mixture, and the mixture was stirred on a water bath at 40 ° C.

The reaction solution thus obtained was added to ether / water. Dilute hydrochloric acid was added to this so that the pH of the aqueous layer was 1-2, and then liquid separation operation was performed. Then, the ether layer was washed well with saline, dried over anhydrous magnesium sulfate, and then the ether was removed by an evaporator.
Further, the residue was purified by silica gel chromatography to obtain an allyl ether compound (39.0 g, yield 51%).

(Synthesis of Bromopropyltrimethylsilane) Hydroxypropyltrimethylsilane (20.0 g,
151 mmol) in a 100 mL three-necked flask,
Stir on an ice bath to remove phosphorus tribromide (15.8 mL, 166 mm
ol) was added dropwise. After the dropping, the ice bath was removed, and the mixture was heated and reacted in a water bath at 60 ° C. for 2 hours. After the obtained reaction solution was added to ether / water, liquid separation operation was performed. Then, the ether layer was thoroughly washed with brine, dried over anhydrous magnesium sulfate, and the ether was removed by an evaporator to obtain bromopropyltrimethylsilane (21.4 g, yield 72%).

(Trimethylsilyl type allyl ether (C
Synthesis of 3)) Allyl ether (25.8 g, 103 mm
ol) in tetrahydrofuran (350 mL) / dimethylsulfoxide (150 mL) solution and potassium t-butoxide (15.3 g, 123 mmol) in propanol (150).
(mL) / dimethyl sulfoxide (150 mL) solution was gradually added dropwise, and the mixture was stirred for 1.5 hours. Then, bromotrimethylsilane (20 g, 103 mm was added to the obtained reaction mixture.
ol) and a catalytic amount of potassium iodide were added, and the mixture was stirred overnight at room temperature.

The reaction solution obtained was added to ether / water. Dilute hydrochloric acid was added to this so that the pH of the aqueous layer was 5 to 7, and then liquid separation operation was performed. Then, the ether layer was washed well with brine, dried over anhydrous magnesium sulfate, the ether was removed by an evaporator, and the residue was purified by silica gel chromatography to obtain the desired trimethylsilyl allyl ether. (17.9 g, yield 47.2%) was obtained.

(Perfluoroalkylsilane body (C3)
Synthesis of trimethylsilyl type allyl ether (17.8
g, 62.0 mmol) was put in a 30 mL capacity eggplant type flask, and chloroplatinic acid (50 mg) was added thereto. The reaction solution was dissolved by heating at 70 ° C., and hydrosilyl dichloride (7.7 mL, 73 mmol) was gradually added thereto, and the reaction was allowed to proceed at 70 ° C. for 3 hours. The crude product obtained (23.
The dichlorosilane compound (3 g, yield 28.5%) was used for the next reaction without purification.

(Synthesis of trisiloxane body (C3)) A solution of triethylamine (7.5 mL, 35.4 mmol) in m-bistrifluoroxylene (50 mL) was added with m-dichlorosilane body (23.3 g, 27.0 mmol). A solution of bistrifluoroxylene (50 mL) and a solution of disiloxane diol (4.5 g, 27.0 mmol) in methyl ethyl ketone (70 mL) were gradually added dropwise at the same dropping rate at room temperature.

After stirring at room temperature for 1 hour, ether (250 mL) was added to the obtained reaction solution, the ether layer was washed with water, dried over anhydrous magnesium sulfate, and then the ether was removed by an evaporator. Was purified by a distillation method to obtain a trisiloxane body (5.5 mg, yield 17%). The proton nuclear magnetic resonance spectrum of this trisiloxane body is shown in FIG. 7 together with its attribution. The infrared absorption spectrum is shown in FIG.

(Synthesis of Silyl-type Vi-OIL and H-OIL (Polymerization)) Vi-OIL (Component (a)) A predetermined amount of the trisiloxane body synthesized above and divinyldisiloxane are mixed, and trifluoromethane is added thereto. Sulfonic acid was added and stirred overnight.

Then, a 10% solution of triethylamine in m-bistrifluoroxylene was added to neutralize the solution to 1 mm.
Stripping at 100 ° C. for 1 hour under reduced pressure of Hg,
The target Vi-OIL was obtained. The proton nuclear magnetic resonance spectrum of this Vi-OIL is shown in FIG. 9 together with its attribution. The infrared absorption spectrum is shown in FIG.

H-OIL (Component (b)) As a charge, a predetermined amount of trisiloxane and hexamethyldisiloxane / tetramethyltetrasiloxane were mixed, and in the same manner, the desired H-OIL was obtained. This H
The proton nuclear magnetic resonance spectrum of -OIL is shown in Fig. 11 together with its assignment. In addition, the infrared absorption spectrum is shown in Fig. 1.
It is shown in FIG. Thus synthesized H-OIL and Vi-
The molecular weight and the number of functional groups of OIL are shown in Tables 3 and 4.

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

【Example】

Examples 1 to 35 (Crosslinking of Synthesized Vi-OIL and H-OIL) Synthesized Vi-OIL and H-OIL were converted into silicon at a predetermined ratio (H-OIL (component (b))) as shown in Table 5. Mixed at a ratio of bonded hydrogen atoms / Vi-OIL (component (a)) of silicon-bonded alkenyl groups (that is, abbreviated as functional group ratio, H / Vi ratio), and mixed with a fluorine-based solvent (1, The polymer was diluted with (3-bistrifluoromethylbenzene) so that the weight concentration of the polymer was 3%, and a toluene solution of a vinyl platinum catalyst prepared separately was added thereto to prepare a coating solution. Method (50 μm) and applied to a polyethylene terephthalate film, and heated at 150 ° C. for 10 minutes to be cured.

(Peeling Performance) Next, a silicone-based adhesive tape (336T, 50 mm width, manufactured by Nitto Denko Corporation) was attached to the treated surface of the polyethylene terephthalate film by using a hand roller to prepare a sample. It is sandwiched by a stainless steel plate with a width of 70 mm, a length of 1500 mm, and a weight of 500 g, and then both ends are held by clips.
It was stored in a dryer at 60 ° C.

After a certain period of time, the above sample was taken out from the dryer, and a tensile tester (Tensilon S manufactured by Toyo Baldwin Co., Ltd. was used.
TM-T-50BP) of the adhesive tape 18
The 0 ° peeling force (pulling speed 300 mm / min) was measured. Further, the 50 mm wide adhesive tape (336T) whose peeling force has been measured is cut into 2 cm width, and this is reciprocated by a 2 kg roller to form a stainless steel plate (SUS-304) having a width of 4 cm and a length of 10 cm. Pasted This was left at room temperature for 20 to 40 minutes, and the adhesive strength was measured using the same Tensilon (pulling speed: 300 mm / minute). This is the residual adhesive strength. Table 5 shows the above results.

[0084]

[Table 5]

[0085]

As described above, the curable fluorine-containing silicone composition according to the present invention comprises an alkenyl type organopolysiloxane, an organohydropolysiloxane having at least three hydrogen atoms bonded to silicon in the molecule, and a silicon atom. A catalyst for the addition reaction of an alkenyl group bound to and a hydrogen atom bound to a silicon atom,
Since the alkenyl-type organopolysiloxane has a plurality of bulky trifluoro groups in the molecule, its cured product is
It gives excellent releasability and has releasability effective for various pressure-sensitive adhesives, particularly dimethylpolysiloxane-based adhesives.

[Brief description of drawings]

FIG. 1 is a proton nuclear magnetic resonance spectrum of a trisiloxane body according to Synthesis Example 1.

FIG. 2 is an infrared absorption spectrum spectrum of a trisiloxane body according to Synthesis Example 1.

FIG. 3 is a proton nuclear magnetic resonance spectrum of Vi-OIL according to Synthesis Example 1.

FIG. 4 is an infrared absorption spectrum of Vi-OIL according to Synthesis Example 1.

FIG. 5 is a proton nuclear magnetic resonance spectrum of H-OIL according to Synthesis Example 1.

FIG. 6 is an infrared absorption spectrum of H-OIL according to Synthesis Example 1.

FIG. 7 is a proton nuclear magnetic resonance spectrum of a trisiloxane body according to Synthesis Example 2.

FIG. 8 is an infrared absorption spectrum spectrum of the trisiloxane body according to Synthesis Example 2.

FIG. 9 is a proton nuclear magnetic resonance spectrum of Vi-OIL according to Synthesis Example 2.

FIG. 10 is an infrared absorption spectrum of Vi-OIL according to Synthesis Example 2.

FIG. 11 is a proton nuclear magnetic resonance spectrum of H-OIL according to Synthesis Example 2.

FIG. 12 is an infrared absorption spectrum of H-OIL according to Synthesis Example 2.

Claims (5)

[Claims] 1. A compound represented by the general formula (I): (a) having at least two silicon-bonded alkenyl groups in a molecule and having silicon-bonded in the molecule. (In the formula, R ¹ represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group through a straight-chain alkylene group having 2 to 5 carbon atoms, and k represents an integer of 2 to 6,
m shows the integer of 3-10. ) An alkenyl-type organopolysiloxane having at least one fluorine-containing substituent, represented by (b) at least 3 hydrogen atoms bonded to silicon in the molecule.
And an organohydropolysiloxane having at least one fluorine-containing substituent represented by the general formula (I) bonded to silicon in the molecule, and (c) having a hydrogen atom of an alkenyl group bonded to a silicon atom. A curable fluorine-containing silicone composition comprising a catalyst for addition reaction to a silicon atom. 2. An alkenyl type organopolysiloxane is represented by the general formula (II): (In the formula, R ¹ represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group through a straight-chain alkylene group having 2 to 5 carbon atoms, and k represents an integer of 2 to 6,
m represents an integer of 3 to 10, x represents an integer of 1 or 2, and R's may have the same or different carbon numbers from 1 to 1.
8 is an alkyl group or a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, R ² is an alkenyl group, p, q and r are p ≧ 0, q ≧ 0 and r
An integer that satisfies ≧ 1 is shown. ) The curable fluorine-containing silicone composition according to claim 1, represented by 3. The organohydropolysiloxane has the general formula (III): (In the formula, R ¹ represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group through a straight-chain alkylene group having 2 to 5 carbon atoms, and k represents an integer of 2 to 6,
m represents an integer of 3 to 10, R is the same or different, and may be an alkyl group having 1 to 8 carbon atoms or a phenyl group optionally having an alkyl group having 1 to 4 carbon atoms. S, t and u are s ≧ 1, t ≧ 0 and u ≧, respectively.
1 represents an integer satisfying 1, T represents hydrogen or the above R, T
Is R, s represents an integer satisfying s ≧ 3. ) The curable fluorine-containing silicone composition according to claim 1, represented by (A) General formula (II): (In the formula, R ¹ represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group through a straight-chain alkylene group having 2 to 5 carbon atoms, and k represents an integer of 2 to 6,
m represents an integer of 3 to 10, x represents an integer of 1 or 2, and R's may have the same or different carbon numbers from 1 to 1.
8 is an alkyl group or a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, R ² is an alkenyl group, p, q and r are p ≧ 0, q ≧ 0 and r
An integer that satisfies ≧ 1 is shown. ) An alkenyl-type organopolysiloxane represented by the formula (b): (b) General formula (III) (In the formula, R ¹ represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group through a straight-chain alkylene group having 2 to 5 carbon atoms, and k represents an integer of 2 to 6,
m represents an integer of 3 to 10, R is the same or different, and may be an alkyl group having 1 to 8 carbon atoms or a phenyl group optionally having an alkyl group having 1 to 4 carbon atoms. S, t and u are s ≧ 1, t ≧ 0 and u ≧, respectively.
1 represents an integer satisfying 1, T represents hydrogen or the above R, T
Is R, s represents an integer satisfying s ≧ 3. And an organohydropolysiloxane represented by the formula (1), and (c) a catalyst for the addition reaction between a silicon atom-bonded alkenyl group and a silicon atom-bonded hydrogen atom. Fluorosilicone composition. 5. The curable fluorine-containing silicone composition according to claim 1, 2 or 4, wherein the alkenyl group is a vinyl group or an allyl group.