JP3077536B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition which is easily cured when left or heated at room temperature to give a cured product having excellent solvent resistance, chemical resistance and heat resistance.

[0002]

2. Description of the Related Art Curable compositions comprising a fluorine-containing amide compound and a fluorine-containing organohydrogensiloxane have been used in various fields.

However, a cured product obtained from a conventional curable composition comprising a fluorinated amide compound and a fluorinated organohydrogensiloxane may not have sufficient solvent resistance and chemical resistance in some cases. A cured product having excellent chemical resistance is desired.

Further, the cured product used as a molded part, a copying machine roll, or the like is more desirably excellent in releasability and water repellency.

[0005] The present invention has been made in view of the above circumstances,
To provide a curable composition containing a fluorinated amide compound and a fluorinated organohydrogensiloxane as main components, which gives a cured product having excellent solvent resistance and chemical resistance, and excellent releasability and water repellency. With the goal.

[0006]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that a fluorine-containing amide compound represented by the following general formula (1) or (4): The following fluorinated organosiloxane is blended as a cross-linking agent and a chain extender, and by adding a platinum group compound as a catalyst, it is easily cured at room temperature and is excellent in solvent resistance, chemical resistance and heat resistance. The present inventors have found that a curable composition that gives a product can be obtained, and have accomplished the present invention.

Accordingly, the present invention relates to (A) a fluorine-containing amide compound represented by the following general formula (1), (B) one or more monovalent perfluoroalkyl ether groups or monovalent perfluoro A composition comprising a fluorine-containing organohydrogensiloxane having an alkyl group and two or more hydrosilyl groups, (C) a catalytic amount of a platinum group compound, wherein the amount of the component (B) is Provided is a curable composition characterized in that the amount of the hydrosilyl group is 0.5 to 5 mol per 1 mol of the aliphatic unsaturated group in the curable composition.

[0008]

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Further, the present invention provides (D) a compound represented by the following general formula (4):
(E) a fluorine-containing organohydrogensiloxane having one or more groups represented by the following general formula (6) in one molecule and having two or more hydrosilyl groups, (C) A composition containing a catalytic amount of a platinum group compound, wherein the amount of the component (E) is 0.5 to 5 hydrosilyl groups per mole of the aliphatic unsaturated group in the composition.
The present invention provides a curable composition characterized by a molar amount.

[0010]

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Hereinafter, the present invention will be described in further detail. The curable composition of the present invention comprises a fluorine-containing amide compound represented by the above formula (1) or (4), and a fluorine-containing amide compound as a crosslinking agent or a chain extender thereof. It contains an organohydrogensiloxane and a platinum group compound as a catalyst.

The first essential component [component (A)] of the first curable composition of the present invention is a fluorine-containing amide compound, and the fluorine-containing amide compound of the component (A) is represented by the following general formula (1). As shown, it has at least two aliphatic unsaturated groups in the molecule.

[0013]

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Here, R ¹ in the above formula (1) is:
A monovalent hydrocarbon group having 2 to 10 carbon atoms, particularly 2 to 8 carbon atoms having an aliphatic unsaturated group is preferable, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, and a hexenyl group. And the like, an alkenyl group such as a cyclohexyl group, and an aryl group substituted with an alkenyl group such as a styryl group.

As R ² , a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. , Vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, alkenyl group such as cyclohexenyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, benzyl group, Aralkyl groups such as phenylethyl group and phenylpropyl group or part of hydrogen atoms of these groups or Fluorine Department, chlorine, chloromethyl group substituted with a halogen atom such as a bromine, bromoethyl group, chloropropyl group, such as trifluoropropyl group.

In the above formula (1), Q ¹ is a group represented by the following formula (2) or (3).

[0017]

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R ² in the above formula (2) is the same as described above, and R ³ is not particularly limited as long as it is a substituted or unsubstituted divalent hydrocarbon group. ~
Preferred are hydrocarbon groups of 10, specifically methylene group, ethylene group, propylene group, methylethylene group, butylene group, alkylene group such as hexamethylene group, cycloalkylene group such as cyclohexylene group, phenylene group,
Arylene groups such as tolylene group, xylylene group, naphthylene group, biphenylene group, or groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms, or substituted or unsubstituted alkylene groups or arylene groups Are exemplified.

R ³ may contain one or more of an oxygen atom, a nitrogen atom and a silicon atom in the middle of the bond.

In this case, the oxygen atom is -O-, the nitrogen atom is -NR'- (R 'is a hydrogen atom or a group having 1 to 8 carbon atoms, especially 1
6 to an alkyl group or an aryl group), and the silicon atom is interposed as a group containing a linear or cyclic organosiloxane or an organosilylene group, for example, as shown below. Can be.

[0021]

Embedded image (However, R ″ is the same alkyl group or aryl group having 1 to 8 carbon atoms as exemplified as R ² above, and R ^{′ ″} is the same alkylene having 1 to 6 carbon atoms as exemplified as R ³ above. Or an arylene group, wherein n = 0 to 10, especially 0
Is an integer of up to 5. The following groups can be exemplified as such groups.

[0022]

Embedded image (Me represents a methyl group.)

Further, as R ⁴ and R ⁵ in the above formula (3), a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 2 to 6 carbon atoms, is preferred. Methylene group, ethylene group, propylene group, methylethylene group, butylene group, alkylene group such as hexamethylene group, cycloalkylene group such as cyclohexylene group, or part or all of hydrogen atoms of these groups is halogen atom or the like. Examples include a substituted group.

Specific examples of Q ¹ in the formula (1) represented by the above formula (2) or (3) include the following groups. In the following chemical formula, Me is a methyl group, P
h represents a phenyl group.

[0025]

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In the formula (1), Rf ¹ is a divalent perfluoroalkylene group or a divalent perfluoropolyether group. Particularly, as the divalent perfluoroalkylene group, -C _m F _2m- (where m = 1 to 10, and preferably 1 to 6.), and the divalent perfluoropolyether group is preferably a compound represented by the following formula.

[0027]

Embedded image Specific examples of Rf ¹ include the following.

[0028]

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In the above formula (1), a is an integer of 0 or more. Therefore, the fluorine-containing amide compound of the formula (1) contains a divalent perfluoroalkylene group or a divalent perfluoropolyether group in one molecule. Wherein a is preferably an integer of 0 to 10, especially 0,
1, 2, 3, 4, 5, and 6 are exemplified.

In the present invention, as the fluorine-containing amide compound as the component (A), a low-viscosity polymer having a viscosity (25 ° C., the same applies hereinafter) of several tens cs to a solid raw rubber-like polymer can be used. From the viewpoint of ease of handling, for example, a raw rubber-like polymer is used for hot vulcanized rubber, and a viscosity of 100 to 100000 is used for liquid rubber.
Polymers of the order of cs are preferably used. If the viscosity is too low, the resulting cured product will have a low elongation as an elastomer, and may not have balanced physical properties.

The fluorine-containing amide compound of the above formula (1) is
It can be obtained by the following method. That is, the fluorine-containing amide compound in which a is 0 in the formula (1) is
For example, it is synthesized by reacting a compound having an acid fluoride group at both terminals represented by the following general formula (7) with a secondary amine compound represented by the following general formula (8) in the presence of an acid acceptor such as trimethylamine. can do.

[0032]

Embedded image (R ¹ , R ² and Rf ¹ have the same meaning as described above.)

Further, the fluorine-containing amide compound in which a is an integer of 1 or more in the above formula (1) is, for example, a compound having an acid fluoride group at both terminals represented by the above formula (7) and the following general formula (9) H-Q ¹ -H (9) (wherein Q ¹ has the same meaning as described above) is reacted with a compound having an amino group at both terminals in the presence of an acid acceptor, and further reacted with the above formula ( It can be synthesized by reacting the secondary amine compound shown in 8).

In this case, the ratio of the charged amounts of the compound having an acid fluoride group at both terminals of the formula (7) and the secondary amine compound of the formula (8) is not particularly limited, but is calculated in terms of mol. The ratio (a) / (b) between the charged amount (a) of the compound of formula (7) and the charged amount (b) of the compound of formula (8) is 0.5 to
It is preferable to set it to 2 mol / mol.

The charged amount (a) of the compound of the formula (7) and the charged amount (c) of the compound of the formula (9) are not particularly limited as long as (a) is not smaller than (c) in terms of mole. It is not limited. The repeating unit a in the formula (1) is
By adjusting (a) / (c), an appropriate value according to the purpose can be obtained. By increasing (a) / (c), a polymer having a relatively small molecular weight can be synthesized,
When the value of (a) / (c) approaches 1, a polymer having a large molecular weight can be synthesized.

The conditions for the above reaction are not particularly limited.
20 to 100 ° C for 1 to 8 hours, preferably 20 to 50 ° C
For 2 to 4 hours.

In the fluorine-containing amide compound of the formula (1), the fluorine-containing amide compound in which Q ¹ has a silicon atom interposed therebetween is a secondary amine compound of the formula (8), for example, when R ¹ is an allyl group HR ² N—CH ₂ C
Using a secondary amine compound having an aliphatic unsaturated group represented by H = CH ₂ or the like, a compound having an allyl group at both terminals represented by the following general formula (10) is synthesized by the above reaction, and For example, it can be synthesized by reacting a compound represented by the following general formula (11) in the presence of an addition reaction catalyst.

[0038]

Embedded image (However, in the formula, R ² and Rf ¹ have the same meanings as described above.)

[0039]

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In this reaction, the ratio of the charged amount of the compound of the formula (11) to the compound of the formula (11) having allyl groups at both ends and the charged amount of the compound of the formula (10) is expressed in terms of mol. (D) must be greater than the charge (e) of the compound of formula (11), but the ratio (d) / (e) is at most 2. That is, 1 <(d) / (e) ≦ 2.

By increasing (d) / (e), a polymer having a relatively small molecular weight can be synthesized.
When the value of (d) / (e) approaches 1, a polymer having a large molecular weight can be synthesized.

[0042] In this case, the catalyst may be selected from the periodic table VI.
Group II elements or compounds thereof, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972), complexes of chloroplatinic acid with olefins (U.S. Pat.
No. 159601, No. 3159662, No. 3775
No. 452), platinum black or palladium is alumina,
Silica, carbon-supported carrier, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson's catalyst), etc.
The addition amount can be a catalyst amount. The above complex is preferably used after being dissolved in an alcohol, ketone, ether or hydrocarbon solvent.

The conditions for the above reaction are 50 to 150.
C., preferably at 80 to 120.degree. C. for 2 to 4 hours.

Next, the second essential component [component (B)] of the first curable composition of the present invention is a fluorinated organohydrogensiloxane, which is used as a crosslinking agent and a chain extender for the fluorinated amide compound. It works. The fluorine-containing organohydrogensiloxane of the component (B) has one or more monovalent perfluoroalkyl ether groups or monovalent perfluoroalkyl groups in one molecule, and has two or more, usually 2 to 50,
, Preferably 3-20 hydrosilyl groups, i.e. Si
Any compound having an H group may be used. Examples of the monovalent perfluoroalkyl ether group and the monovalent perfluoroalkyl group include those represented by the following general formula.

[0045]

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The fluorinated organohydrogensiloxane may be cyclic or chain-like, or may be three-dimensional network. Particularly, as a monovalent substituent bonded to a silicon atom, a perfluoroalkyl group or a perfluoroalkyl group represented by the following general formula: Examples include those having at least one monovalent organic group containing a fluoroalkyl ether group in the molecule.

[0047]

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Here, R ⁸ is a methylene group, an ethylene group,
Propylene group, methylethylene group, tetramethylene group,
A divalent hydrocarbon group having preferably 1 to 6 carbon atoms such as an alkylene group such as a hexamethylene group, and R ⁹ is preferably a hydrogen atom or 1 to 8 carbon atoms, preferably 1 to 8 carbon atoms, particularly the same as R ² described above.
6, a monovalent hydrocarbon group, Rf ^3, is a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl ether group described in the above general formula.

In the component (B), the monovalent substituent bonded to a silicon atom other than the monovalent organic group containing a perfluoroalkyl group or a perfluoroalkyl ether group in the fluorine-containing organohydrogensiloxane includes:
Similar to the above-mentioned R ² , preferred are monovalent hydrocarbon groups having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms which do not contain an aliphatic unsaturated bond.

The number of silicon atoms in the molecule of the fluorinated organohydrogensiloxane is not limited to a specific one, but is usually about 2 to 50, preferably about 4 to 30.

Examples of such a fluorine-containing organohydrogensiloxane include the following compounds. In addition,
These compounds may be used alone or in combination.

[0052]

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[0053]

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The curable composition of the present invention can be used to obtain a uniform cured product by using a fluorine-containing organohydrogensiloxane as the second essential component that is compatible with the fluorinated amide compound as the first essential component. Obtainable.

The amount of the component (B) is based on the total amount of the composition, especially 1 mole of the aliphatic unsaturated group such as a vinyl group, an allyl group or a cycloalkenyl group contained in the component (A). The amount of the hydrosilyl group, i.e., Si-H group, is preferably 0.5 to 5 mol, more preferably 1 to 2 mol. If the amount is less than 0.5 mol, the degree of crosslinking is insufficient, and if the amount is 5 mol or more, the chain length is prioritized and curing is insufficient, foaming, heat resistance, compression set properties and the like may be deteriorated. . The amount of the component (B) relative to the component (A) is usually in the range of 0.1 to 50 parts by weight based on 100 parts by weight of the component (A).

Further, the platinum group compound, which is the third essential component [component (C)] of the first curable composition of the present invention, undergoes an addition reaction between the above-mentioned fluorine-containing amide compound and the above-mentioned fluorine-containing organohydrogensiloxane ( Hydrosilylation) and acts as a curing accelerator. This platinum group compound is generally a compound of a noble metal and is expensive, so a platinum compound which is relatively easily available is often used.

Examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinylsiloxane, platinum / silica, alumina or carbon. However, the present invention is not limited to this. Examples of platinum group compounds other than platinum compounds include rhodium, ruthenium, iridium,
Palladium compounds are also known, for example, RhCl
(PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , RhC
l (C ₂ H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO)
(PPh ₃ ) ₂ , Pd (PPh ₃ ) _{4 and the} like.

In the use of these catalysts, when they are solid catalysts, they can be used in a solid state, but in order to obtain a more uniform cured product, chloroplatinic acid or a complex is dissolved in an appropriate solvent. It is preferable to use the compound obtained by compatibilizing the fluorinated amide compound as the first component.

The amount of the catalyst used is not particularly limited, and the desired curing rate can be obtained with the amount of the catalyst. However, in order to obtain an economical viewpoint or a good cured product, the curable composition must be used. The amount is preferably in the range of about 1 to 1000 ppm (in terms of platinum group), more preferably about 10 to 500 ppm (as described above), based on the total amount of the substance.

The present invention relates to the above (A), (B) and (C)
In addition to the first curable composition containing the components, a fluorine-containing amide compound of the following general formula (4) as a first essential component [(D) component] and a second essential component [(E) component] will be described later. The present invention also provides a second curable composition containing the same fluorine-containing organohydrogensiloxane as the third essential component [component (C)].

That is, in the second curable composition of the present invention, a fluorine-containing amide compound of the component (D) represented by the following general formula (4) is used instead of the fluorine-containing amide compound of the component (A). use.

[0062]

Embedded image Here, R ¹ , Rf ¹ and a in the above formula (4) are the same as in the case of the component (A).

Further, Q ² in the above formula (4) is a group represented by the following general formula (5).

[0064]

Embedded image R ^{3 in} the above formula (5) is the same as in the case of the above-mentioned component (A), and specific examples of Q ² include the following groups.

[0065]

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The viscosity of the fluorine-containing amide compound of the component (D) used in the present invention is as described in the above (A).
It is the same as the case of the fluorine-containing amide compound of the component.

Fluorine-containing amide compound of component (D) of the present invention
The compound is, for example, a compound represented by the following general formula (12): CH_ThreeOCO-Rf¹-COOCH_Three ... (12) (Rf¹Is Indicates the same meaning. )
A compound having an ester group at an end thereof, and a compound represented by the following general formula (13): HQ^Two−H (13) (Q^TwoHas the same meaning as described above. )
Can be obtained by reacting

In the above reaction, the molar equivalent charged amount (f) of the compound represented by the formula (12) and the molar equivalent charged amount (g) of the compound of (13) are obtained by dividing (f) by (g). There is no particular limitation unless it is reduced. The repeating unit a in the formula (4) can be set to an appropriate value according to the purpose by adjusting (f) / (g) which is a ratio of (f) to (g), By increasing) / (g), a polymer having a relatively small molecular weight can be synthesized,
When the value of (f) / (g) approaches 1, a polymer having a large molecular weight can be synthesized.

The conditions for the above reaction are not particularly limited.
20 to 100 ° C for 1 to 8 hours, preferably 20 to 50 ° C
For 2 to 4 hours.

On the other hand, the fluorine-containing organohydrogensiloxane of the component (E) has one or more compounds represented by the following general formula (6) per molecule.
Having a monovalent perfluoroalkyl group or a monovalent organic group containing a monovalent perfluoroalkyl ether group, and having 2 or more, usually 2 to 50, preferably 3 to 20 hydrosilyl groups. It has a group.

[0071]

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Here, Rf ² in the above formula (6) represents a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl ether group, and the above-mentioned perfluoroalkyl group or perfluoroalkyl ether as Rf ³ Examples are the same as the groups. R ⁶ is a divalent hydrocarbon group preferably having 1 to 8 carbon atoms, similar to R ⁸ described above.
⁷ is a hydrogen atom or a monovalent hydrocarbon group preferably having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, similar to R ⁹ described above.

The monovalent substituent bonded to a silicon atom other than a monovalent organic group having a perfluoroalkyl group or a perfluoroalkyl ether group in the fluorine-containing organohydrogensiloxane of the component (E) includes similar preferably with the R ² 1 to 10 carbon atoms free of aliphatic unsaturation, and in particular 1-8 monovalent hydrocarbon radical.

The number of silicon atoms in the molecule of the fluorinated organohydrogensiloxane is not limited to a specific number, but is usually about 2 to 50, preferably about 4 to 30.

Examples of the fluorine-containing organohydrogensiloxane as the component (E) include the following compounds. These fluorinated organohydrogensiloxanes may be used alone or as a mixture of two or more.

[0076]

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The compounding amount of the component (E) is based on 1 mole of the aliphatic unsaturated group such as vinyl group, allyl group, cycloalkenyl group, etc. contained in the component (D). The amount of the hydrosilyl group, i.e., Si-H group, is preferably 0.5 to 5 mol, more preferably 1 to 2 mol. If the amount is less than 0.5 mol, the degree of crosslinking is insufficient, and if the amount is 5 mol or more, the chain length is prioritized and curing is insufficient, foaming, heat resistance, compression set properties and the like may be deteriorated. . The amount of the component (E) relative to the component (D) is usually in the range of 0.1 to 50 parts by weight based on 100 parts by weight of the component (D).

The component (C) of the second curable composition of the present invention is the same as the component (C) of the first curable composition, and the amount thereof is also the same.

Incidentally, various additives can be added to the first and second curable compositions of the present invention as needed in order to enhance their practicality. Specifically, CH ₂ ＣＨCH added for the purpose of controlling the curing rate of the curable composition
(R) Polysiloxane containing SiO units (where R is a substituted or unsubstituted monovalent hydrocarbon group)
8-10947) and acetylene compounds (see U.S. Pat. No. 3,445,420 and Japanese Patent Publication No. 54-3774), and ionic compounds of heavy metals (see U.S. Pat. No. 3,532,649).

When these additives are added,
The blending amount of the fluorine-containing organohydrogensiloxane is determined in consideration of the blending amounts of these additives in addition to the component (A) or (D), and as described above, the vinyl group in the entire composition,
It is necessary that 0.5 to 5 mol of Si-H groups be present per 1 mol of an aliphatic unsaturated group such as an allyl group or a cycloalkenyl group.

Further, the curable composition of the present invention has a reduced heat shrinkage at the time of curing, a reduced coefficient of thermal expansion of an elastic material obtained by curing, a thermal stability, a weather resistance, a chemical resistance and a flame retardant. A filler may be added for the purpose of improving the properties or mechanical strength or lowering the gas permeability, such as fumed silica, quartz powder, glass fiber, carbon, iron oxide, titanium oxide, and cerium oxide. Oxides, metal carbonates such as calcium carbonate, magnesium carbonate and the like can be mentioned, and if necessary, suitable pigments, dyes or antioxidants can be added.

The method for producing the curable composition of the present invention is not particularly limited, and the curable composition can be produced by kneading the above components. The produced curable composition can be cured at room temperature depending on the functional group of the fluorine-containing amide compound as the first essential component and the type of the catalyst as the third essential component.
It is preferable to cure at 0 ° C. for several minutes to several hours.

When using the curable composition of the present invention, the composition is dissolved in a suitable fluorine-based solvent, for example, meta-xylene hexafluoride, florinate or the like at a desired concentration depending on the use and purpose. May be used.

[0084]

The curable composition of the present invention can be used for various uses. That is, the cured product obtained from the curable composition of the present invention has a high fluorine content, and thus has excellent solvent resistance and chemical resistance, and also has a low surface energy, and thus has excellent mold release properties and excellent water repellency. It can be effectively used as a rubber material for automobiles, a tent film material, a sealant, a molded part, an extruded part, a coating material, a release agent, etc., which require oil resistance.

[0085]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the following, Me indicates a methyl group and Ph indicates a phenyl group.

Example 1 100 parts by weight of a polymer represented by the following formula (14) (viscosity: 1190 cs, average molecular weight: 7000, allyl group content: 0.029 mol / 100 g) was treated with a trimethylsiloxy group in a specific surface area of 200 m ^2. / G
Was added, mixed and heat-treated, and then mixed on a three-roll mill.
10.8 parts by weight of the fluorinated cyclic hydrogen siloxane represented by 5) and chloroplatinic acid are converted to CH ₂ ＣＨCHSiMe ₂ OSiMe ₂
0.2 parts by weight of a toluene solution of a catalyst modified with CH = CH ₂ (platinum concentration: 1.0% by weight) was added and mixed.

[0087]

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This was defoamed under reduced pressure, placed in a rectangular frame having a thickness of 2 mm, evacuated again, and dried at 120 kg / cm ² ,
Press hardening was performed at 150 ° C. for 20 minutes. The test piece was cut out from the cured sample, and the physical properties were measured in accordance with JIS K6301, and the following results were obtained.

Hardness (JIS-A) 43 Elongation (%) 180 Tensile strength (kgf / cm ² ) 25 (JIS-A: Measured using an A-type spring hardness tester specified in JIS K6301)

Next, the heat resistance, solvent swelling property, chemical resistance and low-temperature characteristics were measured using the test pieces. The results are shown in Tables 1, 2, 3 and 4.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

Example 2 The composition was the same as in Example 1 except that 10.6 parts by weight of the fluorinated cyclic hydrogen siloxane represented by the following formula (16) was used instead of the fluorinated cyclic hydrogen siloxane of Example 1. An article was prepared and a cured sheet was prepared.

[0096]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 40 Elongation (%) 200 Tensile strength (kgf / cm ² ) 22

Example 3 Instead of the polymer of Example 1, a polymer represented by the following formula (17) (viscosity 28600
cs, average molecular weight 28,000, allyl group content 0.007 mol / 100 g) 100 parts by weight, and the same composition as in Example 1 except that 2.7 parts by weight of the fluorinated cyclic hydrogen siloxane of Example 1 was used. An article was prepared and a cured sheet was prepared.

[0100]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 33 Elongation (%) 340 Tensile strength (kgf / cm ² ) 45

Example 4 Instead of the polymer of Example 1, a polymer represented by the following formula (18) (having a viscosity of 13100)
cs, average molecular weight 19200, allyl group content 0.010 mol / 100 g) 100 parts by weight, and the same composition as in Example 1 except that 3.5 parts by weight of the fluorinated cyclic hydrogen siloxane of Example 1 was used. An article was prepared and a cured sheet was prepared.

[0104]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 45 Elongation (%) 280 Tensile strength (kgf / cm ² ) 53

Example 5 Instead of the polymer of Example 1, a polymer represented by the following formula (19) (having a viscosity of 2900 c
s, average molecular weight 6000, allyl group content 0.033 mol /
100 g) In the same manner as in Example 1 except that 100 parts by weight was used and 10.8 parts by weight of the fluorinated cyclic hydrogen siloxane represented by the following formula (20) was used instead of the fluorinated cyclic hydrogen siloxane of Example 1. To prepare a cured sheet.

[0108]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 47 Elongation (%) 310 Tensile strength (kgf / cm ² ) 46

Next, heat resistance, solvent swelling property, chemical resistance and low-temperature characteristics were measured using the test pieces. The results are shown in Tables 5, 6, 7, and 8.

[0112]

[Table 5]

[0113]

[Table 6]

[0114]

[Table 7]

[0115]

[Table 8]

Example 6 The composition was the same as in Example 5, except that 12.5 parts by weight of a fluorinated cyclic hydrogen siloxane represented by the following formula (21) was used instead of the fluorinated cyclic hydrogen siloxane of Example 5. An article was prepared and a cured sheet was prepared.

[0117]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 43 Elongation (%) 290 Tensile strength (kgf / cm ² ) 44

Example 7 Instead of the polymer of Example 5, a polymer represented by the following formula (22) (having a viscosity of 42,000)
cs, average molecular weight 9200, allyl group content 0.022 mol / 100 g) 100 parts by weight and the same composition as in Example 5 except that 6.1 parts by weight of the fluorinated cyclic hydrogen siloxane of Example 5 was used. An article was prepared and a cured sheet was prepared.

[0121]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 35 Elongation (%) 340 Tensile strength (kgf / cm ² ) 45

Example 8 Instead of the polymer of Example 5, a polymer represented by the following formula (23) (viscosity 17800)
0cs, average molecular weight 19200, allyl group content 0.010
A composition was prepared in the same manner as in Example 5 except that 100 parts by weight of the compound (mol / 100 g) was used and 3.5 parts by weight of the fluorinated cyclic hydrogen siloxane of Example 5 was used to prepare a cured sheet.

[0125]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 42 Elongation (%) 280 Tensile strength (kgf / cm ² ) 44

Example 9 Instead of the polymer of Example 1, a polymer represented by the following formula (24) (having a viscosity of 3300 c
s, average molecular weight of 18100, allyl group content of 0.011 mol / 100 g), and 100 parts by weight of fluorinated hydrogen siloxane 3.1 represented by the following formula (25) in place of the fluorinated cyclic hydrogen siloxane of Example 1. Except for using parts by weight, a composition was prepared in the same manner as in Example 1 to prepare a cured sheet.

[0129]

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A test piece of the obtained cured sheet was cut out,
When the physical properties were measured in the same manner as above, the following results were obtained.

Hardness (JIS-A) 46 Elongation (%) 200 Tensile strength (kgf / cm ² ) 23

Reference Example 1 189.2 g (viscosity: 430 cs; 25 ° C.) of a compound having an acid fluoride group at both terminals represented by the following formula (26) was equipped with a stirring bar, a thermometer, a Dim funnel, and a dropping funnel. A 300 ml four-necked flask was charged, and a mixture of 9.6 g of allylaniline and 6.1 g of triethylamine was added to the mixture from a dropping funnel while stirring.
It was added dropwise at ° C.

[0133]

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After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours, and the reaction mixture was filtered under pressure to obtain a filtrate obtained at 120 ° C./3 m
Stripping under reduced pressure at mHg gave 190.1 g of a pale yellow transparent liquid compound.

The obtained compound had a viscosity of 1192 cs (2
5 ° C.), specific gravity 1.841 (25 ° C.), refractive index 1.320
8 (25 ° C.). As a result of IR measurement of this compound, the following absorptions were recognized.

[0136]

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The amount of allyl groups in this compound was determined to be 0.031 mol / 100 g. It was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (27). Was done.

[0138]

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Reference Example 2 76.9 g (viscosity: 430 cs; 25 ° C.) of a compound having an acid fluoride group at both terminals represented by the above formula (26) was equipped with a stirring bar, a thermometer, a Dim funnel, and a dropping funnel. The mixture was charged in a 200 ml four-necked flask, and a mixture of 1.14 g of 2,5-dimethylpiperazine and 2.9 g of triethylamine was added dropwise at 20 ° C. from the dropping funnel with stirring. After the dropwise addition, the reaction was carried out at 60 ° C. for 2 hours.
g was added. Further, the reaction and post-treatment were carried out in the same manner as in Reference Example 1 to obtain 72.9 g of a pale yellow transparent liquid compound.

The obtained compound had a viscosity of 25200 cs
(25 ° C.). As a result of IR measurement of this compound,
The following absorptions were observed.

[0141]

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The amount of allyl groups in this compound was determined to be 0.005 mol / 100 g. It was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (28). Was done.

[0143]

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Reference Example 3 In the same apparatus as in Reference Example 2, 100.0 g of a compound having an allyl group at both ends represented by the following formula (29) (viscosity: 1192 cs; 25 ° C.) and m-xylene hexafluoride 50 Then, the mixture was heated to 90 ° C. while stirring, and 0.1 g of a 2% solution of chloroplatinic acid in isopropyl alcohol was added. Thereafter, 3.66 g of cyclotetrasiloxane represented by the following formula (30) was added dropwise from a dropping funnel, and a reaction was performed.

[0145]

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After the dropwise addition, the disappearance of cyclotetrasiloxane was confirmed by gas chromatography while aging. After cooling to room temperature, 1.5 g of activated carbon was added and the mixture was stirred for 2 hours. This was subjected to the same post-treatment as in Reference Example 1, whereby 99.2 g of a transparent liquid compound was obtained.

The obtained compound had a viscosity of 30700 cs.
(25 ° C.). As a result of IR measurement of this compound,
The following absorptions were observed.

[0148]

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The amount of allyl groups in this compound was determined to be 0.007 mol / 100 g. It was confirmed that the obtained compound was a polymer of an organic fluorine compound represented by the following structural formula (31). Was done.

[0150]

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──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koji Matsuda 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Hirofumi Kinoshita, Usui-gun, Gunma Prefecture Shinoda Chemical Co., Ltd. Silicone Electronic Materials Technology Research Laboratory (72) Inventor Masatoshi Arai 1-10 Hitomi, Matsuidamachi, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Material Technology Research (56) References JP-A-6-1920 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 83/05 C08L 83/08 C08L 77/06

Claims (2)

(57) [Claims] (A) a fluorine-containing amide compound represented by the following general formula (1): Wherein R ¹ is a monovalent hydrocarbon group having an aliphatic unsaturated group, R ² is a substituted or unsubstituted monovalent hydrocarbon group, and Q ¹ is the following general formula (2) or the following general formula (3 A group represented by) (However, in the formula, R ³ represents a substituted or unsubstituted divalent hydrocarbon group in which one or more of an oxygen atom, a nitrogen atom and a silicon atom may be interposed in the bond.) (Wherein, R ⁴ and R ⁵ each represent a substituted or unsubstituted divalent hydrocarbon group), Rf ¹ is a divalent perfluoroalkylene group or a divalent perfluoropolyether group, and a Is an integer of 0 or more. (B) a fluorine-containing organohydrogensiloxane having one or more monovalent perfluoroalkyl ether groups or monovalent perfluoroalkyl groups in one molecule and having two or more hydrosilyl groups, (C) a catalyst A platinum group compound, wherein the amount of the component (B) is such that the hydrosilyl group is 0.5 to 5 mol per 1 mol of the aliphatic unsaturated group in the composition. A curable composition comprising: (D) a fluorine-containing amide compound represented by the following general formula (4): Wherein R ¹ , Rf ¹ and a are the same as above,
² is a group represented by the following general formula (5). Embedded image (Wherein R ³ is the same as described above.) (E) Fluorine-containing compound having one or more groups represented by the following general formula (6) in one molecule and having two or more hydrosilyl groups Organo hydrogen siloxane, (Wherein, Rf ² represents a monovalent perfluoroalkyl group or a monovalent perfluoroalkyl ether group, R ⁶ represents a divalent hydrocarbon group, and R ⁷ represents a hydrogen atom or a monovalent hydrocarbon group.) C) A composition containing a catalytic amount of a platinum group compound, wherein the amount of the component (E) is such that the hydrosilyl group is 0.5 to 5 mol per 1 mol of the aliphatic unsaturated group in the composition. A curable composition, characterized in that: