JPH0739549B2 - Fluorocarbon siloxane composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluorocarbon siloxane composition, and more particularly to a curable fluorocarbon siloxane composition having excellent solvent resistance, chemical resistance, water and oil repellency, processability and adhesiveness. .

[0002]

2. Description of the Related Art For curable fluorocarbon siloxane compositions, (A)

[Chemical 5] Random or alternating siloxanes, (B)

[Chemical 6] Or

[Chemical 7] And (C) an effective amount of a platinum-containing catalyst in a uniform mixture, wherein each R and R'in (A) is a methyl group, a phenyl group, or 3.3.
Is a 3-trifluoropropyl group, each Rf is a perfluoroalkylene group having 2 to 10 carbon atoms, a perfluorocycloalkylene group, or 2 to 2 containing one or more —C—O—C— bonds. When it is a perfluoroalkylene group or a perfluorocycloalkylene group having 10 carbon atoms, p has a value of 0 to 2q, and when p has a value larger than q, the siloxane (A) has 2
More not more adjacent _{CH 3 (CF 3 CH 2 CH} 2) SiO
Are alternating copolymers with units only, q has an average value of at least 5, there is an average of more than 2.0 silicon-bonded hydrogen atoms per molecule of (B), and the amount of (B) is the composition A curable composition having an amount such that 0.5 to 3.0 silicon-bonded hydrogen atoms are present for each silicon-bonded vinyl group is known (see JP-B-58-56582).

[0003]

However, this composition has the disadvantage that it has insufficient adhesiveness to various adherends and has a problem in practical use when used as an adhesive.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a fluorocarbon siloxane composition which overcomes these disadvantages and which comprises A) the general formula

[Chemical 8] [Wherein R ¹ , R ² and R ³ are unsubstituted or substituted monovalent hydrocarbon groups containing no aliphatic unsaturated group, and Rf ¹ is represented by the following general formula:

[Chemical 9] (Where f and h are integers from 0 to 5, g is an integer from 0 to 8 and e and i are 0 or 1) and have 1 to 3 carbon atoms.
0 divalent perfluoroalkylene group or 1 to 3 carbon atoms
0 divalent perfluoropolyether group, a is 2 to 30
0 is an integer, b is an integer of 0 to 300, and c is 0 to 5,000.
Is an integer, d is an integer of 2 to 8, and X is a general formula.

[Chemical 10] (Here, R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group containing an aliphatic unsaturated group, and R ⁵ and R ⁶ are C 1-8.
Monovalent hydrocarbon group) of 100 parts by weight of fluorocarbon siloxane represented by [1], B) a hydrogen atom bonded to a silicon atom with respect to the total aliphatic unsaturated group in the component A). Group having (≡SiH group)
Is present in a ratio of 0.5 to 5.0, 2 in one molecule.
Organohydrogensiloxane containing at least one ≡SiH group, C) general formula

[Chemical 11] (Here, Rf ² has the same carbon number of 3 to ² as Rf ¹ described above.
0 to 50 parts by weight of an epoxy group-containing fluorocarbon hydrogen siloxane represented by 0, a divalent perfluoroalkylene group or a divalent perfluoropolyether group, j and k are integers of 1 to 3, and D) an effective amount. Periodic table V
It is characterized by comprising a uniform composition with a Group III element-containing catalyst.

That is, the present inventors have conducted various studies to develop a curable fluorocarbon siloxane composition having excellent solvent resistance, chemical resistance, water repellency, oil repellency, processability, and adhesiveness, When the Rf ¹ group in the main chain of fluorocarbon siloxane has 1 to 30 carbon atoms, this composition has excellent solvent resistance, water repellency and oil repellency. Copolymerizing with the Rf ¹ group-containing segment of ( ¹ ), the cured rubber has a crystalline portion, so that the obtained rubber has improved strength. Further, this composition has an epoxy group-containing fluorocarbon hydrogen siloxane. It has been found that the addition of the composition makes the composition excellent in adhesiveness to various substrates, and the composition has a high fluorine content for solvent resistance. It has excellent properties, chemical resistance, water repellency and oil repellency, and is useful as a rubber material with low moisture permeability. Also, if fluorocarbon siloxane as the main component has a viscosity of 100,000 cS or less, FIP
The present invention has been completed by confirming that it is useful as a liquid rubber material by a G machine. This will be described in more detail below.

[0006]

The present invention has solvent resistance, chemical resistance, water repellency, oil repellency,
The present invention relates to a curable fluorocarbon siloxane composition having excellent processability and adhesiveness, which comprises the above-mentioned A) the fluorocarbon siloxane represented by the general formula (1), and B) an organohydrogensiloxane as a crosslinking agent. C) General formula (4) that acts as an adhesion aid
The epoxy group-containing fluorocarbon hydrogen siloxane and the catalyst for addition reaction D) are added.

The fluorocarbon siloxane as component A) which constitutes the composition of the present invention is

[Chemical 12] And R ¹ , R ² and R ³ in the formula are alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group, Or a chloromethyl group in which a part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc.
The same or different unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group, selected from a 3-trifluoropropyl group, a cyanoethyl group and the like.

Further, this Rf ¹ is represented by the following general formula

[Chemical 13] And f and h are integers of 0 to 5, g
Is an integer of 0 to 8, e and i are 0 or 1 and are a divalent perfluoroalkylene group having 1 to 30 carbon atoms or a divalent perfluoropolyether group having 1 to 30 carbon atoms, -CF ₂ This _{CFO-CF 2 CF 2 O-} CF 2 CF 2 -,

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19] Are exemplified.

Note that this a is an integer of 2 to 300 and b is 0.
To an integer of 300, c is an integer of 0 to 5,000, and d is 2
Is an integer of 8 and X is a general formula

[Chemical 20] And R ⁴ is an aliphatic unsaturated group such as vinyl group, allyl group, isopropenoxy group, etc., R ⁵ and R ⁶ are alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cyclohexyl group Such as cycloalkyl group, vinyl group, allyl group, alkenyl group such as isopropenoxy group, aryl group such as phenyl group and tolyl group, or chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group , 6, 6, 6, 5, 5, 4, 4,
A triorganosiloxy group which is an unsubstituted or substituted monovalent hydrocarbon having 1 to 8 carbon atoms such as a 3,3-nonafluorohexyl group, and the fluorocarbon siloxane represented by the general formula (1) is as follows. Are exemplified.

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

Next, the organohydrogen siloxane as the component B) constituting the composition of the present invention acts as a cross-linking agent in the present invention, and it has a hydrogen atom bonded to a silicon atom in the molecule. Group (≡SiH
It is said that it has at least two groups)

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35] What is shown by is illustrated.

Further, this organohydrogensiloxane is, for example,

[Chemical 36] When

[Chemical 37] and

[Chemical 38] Can be prepared by an equilibration reaction using an acid catalyst such as sulfuric acid, or by subjecting the corresponding silane or siloxane to a cohydrolysis reaction, but those with special functional groups can be prepared by a partial addition reaction. . This organohydrogensiloxane is linear, branched, cyclic,
Either low molecular weight or high molecular weight may be used, but generally, those having a relatively low molecular weight of 30,000 or less are used because of easy production.

If the amount of component B) is too small, the degree of crosslinking will be insufficient, and if it is too large, the desired rubber-like material will be foamed and its properties such as heat resistance and compression set will be improved. In the range of 0.5 to 5 moles relative to 1 mole of the aliphatic unsaturated group contained in the entire composition,
The amount is preferably 1.2 to 3.0 mol, but
It should also be compatible with component A) in order to obtain a homogeneous cured product.

Next, the epoxy group-containing fluorocarbon hydrogen siloxane as the component C) which constitutes the composition of the present invention operates as an adhesion aid in the present invention, and it has the general formula

[Chemical Formula 39] And Rf ² has the same carbon number of 3 to Rf ¹ as described above.
20 divalent perfluoroalkylene groups or divalent perfluoropolyether groups, where j and k are integers from 1 to 3, including the following:

[Chemical 40]

[Chemical 41]

[Chemical 42] What is shown by is illustrated.

If the amount of component C) added is too small, the adhesive strength will be insufficient, and if it is too large, the desired rubber-like material will foam, its heat resistance, compression set and other characteristics. Therefore, this is because the total ≡S of the components B) and C) per 1 mol of the aliphatic unsaturated group contained in the entire composition.
iH group amount is 0.5 to 5 mol, preferably 1.2 to 3.0
Since it is necessary to set the molar range, the C) component is in the range of 0.1 to 3 mol, preferably 0.3 to
Since it may be in the range of 2.0 moles, in terms of weight, it may be 0.1 to 50 parts by weight with respect to 100 parts by weight of the component A).

Further, the catalyst for addition reaction as the component D) which constitutes the composition of the present invention is supposed to contain an element of Group VIII of the periodic table, but this is a precious metal and is expensive. A platinum compound that is easily available may be used. Therefore, this is chloroplatinic acid, chloroplatinic acid and olefins such as ethylene, alcohols, vinyl siloxane complexes,
It may be such that platinum is supported on a solid catalyst such as silica, alumina or carbon, but this is because chloroplatinic acid or the above complex is dissolved in an appropriate organic solvent in order to obtain a uniform composition. It is preferable to use it by making it compatible with the above-mentioned component A). The addition amount of the component D) is not particularly limited, but is generally 1 to 1 because it is expensive.
It may be used in the range of 1,000 ppm, preferably 10-500 ppm, according to which the composition of the present invention
It can be cured at 00 to 200 ° C. in a short time of several minutes to several hours.

The composition of the present invention comprises the above A), B),
It can be obtained by uniformly mixing the predetermined amounts of the components C) and D), but various additives may be added to this if necessary. That is, for the composition in order to reinforce the strength of the elastic body obtained by the curing, SiO _{2 units, CH 2 = CH (R 2} ) SiO 0.5 units, R ₃ SiO _{0. 5} units (R is an aliphatic Organopolysiloxane having a resin structure composed of a monovalent hydrocarbon group (which does not contain a group unsaturated group) may be added, and for the purpose of controlling the curing rate of the composition, a polysiloxane containing CH ₂ ═HRSiO units is added thereto. Siloxane, an acetylene compound, an ionic compound of a heavy metal may be added, and further, a non-functional organopolysiloxane may be added to improve the thermal shock resistance and flexibility of the obtained elastic body.

Furthermore, the composition of the present invention has a reduced thermal shrinkage during curing, a reduced thermal expansion coefficient of the elastic body obtained by curing, thermal stability, weather resistance, chemical resistance, flame retardancy or mechanical properties. For the purpose of improving the mechanical strength and lowering the gas permeability,
Fillers may be added, for example, fumed silica, quartz powder, glass fiber, carbon, iron oxide, titanium oxide, metal oxides such as cerium oxide, and metal carbonates such as calcium carbonate and magnesium carbonate. I can give you
It is also possible to add a suitable pigment, dye or antioxidant to this, if necessary. In practical use of the present composition, the composition may be dissolved in an appropriate organic solvent such as toluene or xylene at a desired concentration depending on the intended use and purpose.

[0018]

EXAMPLES Next, examples and comparative examples of the present invention will be described. Example 1, Comparative Example 1 Formula

[Chemical 43] (Rf ¹ in the formula is such that e, g and i in the general formula 2 are 0 and f = 2 and h = 3), and the viscosity is 5,
Fluorocarbon siloxane polymer [A) component having a vinyl group content of 0.008 mol / 100 g at 700 cS]
To 100 g, 15 g of fumed silica treated with a trimethylsiloxy group was added, and the mixture was mixed by a kneader at 150 ° C. for 2 hours and then mixed by a triple roll.

Then, the expression

Embedded image 1.8 g of the organohydrogensiloxane [B) component represented by:

[Chemical formula 45] Epoxy group-containing fluorocarbon hydrogen siloxane [C) component 1.8 g, carbon black 0.47 g, chloroplatinic acid [CH ₂ ═CHSi (CH _2
3 ) ₂ ] ₂ O modified catalyst in toluene solution (platinum concentration 1.0
0.1% by weight) and 0.002 g of 2-ethylisopropanol are added and mixed homogeneously to prepare a composition I. For comparison, the above-mentioned fluorocarbon hydrogen siloxane containing an epoxy group is not added, and the above organo Composition II was made by treating as above with the addition of 3.6 g of hydrogen siloxane.

Next, the compositions I and II were treated at 150 ° C. for 12 hours.
Pressing for 20 minutes under the condition of 0 kg / cm ² and thickness of 2 m
m sheet is made, and the rubber physical properties of this sheet are
When measured according to the method of ISK6301, the result as shown in Table 1 was obtained. For this, the sample used for the shear force measurement method shown in FIG. 1 was prepared, and glass, aluminum, iron, epoxy resin was prepared. When the shear adhesive strength was measured, the results shown in Table 2 were obtained.

[0021]

[Table 1]

[Table 2]

Example 2, Comparative Example 2 The fluorocarbon siloxane polymer used in Example 1 was formulated

[Chemical formula 46] (Rf ¹ in the formula is such that e, g, i in the general formula 2 are 0 and f = 2, h = 3), and the viscosity is 8,
Fluorocarbon siloxane polymer [A) component having a vinyl group content of 0.007 mol / 100 g at 200 cS]
Composition III was prepared in the same manner as in Example 1 except that the amount was 100 g, and composition IV was prepared in the same manner as in Comparative Example 1 for comparison. When the rubber physical properties and the shear adhesive strength were examined in the same manner as in Example 1, the results shown in Tables 3 and 4 were obtained.

[0023]

[Table 3]

[Table 4]

Example 3 The epoxy group-containing fluorocarbon hydrogen siloxane used in Example 1 was formulated

[Chemical 47] (Rf ² in the formula is f when e, g, and i in the general formula 2 are 0.
= 2, h = 2) was used to prepare a composition V by the same treatment as in Example 1. This V composition had the same rubber physical properties and shear adhesion in the same manner as in Example 1. When the force was investigated, the results shown in Tables 5 and 6 were obtained.

[0025]

[Table 5]

[Table 6]

Example 4, Comparative Example 3 The fluorocarbon siloxane polymer used in Example 1 was formulated

[Chemical 48] (Rf ¹ in the formula is e = f = h = i = 1 in the general formula 2.
G = 2), the viscosity is 10,200 cS
The amount of vinyl group is 0.005 mol / 100g, and 21g of fumed silica treated with trimethylsiloxy group is added to 120g of this and mixed with a kneader at 150 ° C for 2 hours, then mixed with 3 rolls. did.

Then, the expression

Embedded image 1.8 g of an organohydrogen siloxane [B) component represented by:

[Chemical 50] (Rf2 in the formula is such that f and h in formula ² are 0 and e and i are
1, g = 2), and a toluene solution of a [CH ₂ ═CHSi (CH ₂ ) ₂ ] ₂ —O-modified catalyst of chloroplatinic acid (1.8 g). 0.1%) and 0.002 g of 2-ethylisopropanol,
A composition VI was prepared by uniformly mixing and treated in the same manner as above, except that the epoxy group-containing fluorocarbon hydrogen siloxane in the above was not added for comparison and 2.0 g of the above organohydrogen siloxane was added. To make composition VII.

Then, the rubber properties and the shear adhesive strength of the compositions VI and VII were examined in the same manner as in Example 1, and the results shown in Tables 7 and 8 were obtained.

[0029]

[Table 7]

[Table 8]

Example 5 Compositions I, III, V, obtained in Examples 1 to 4 above
Using a rubber sheet having a thickness of 2 mm prepared by the method of Example 1 from VI, its chemical resistance test, solvent resistance test and surface property test were carried out. The results are shown in Table 9, Table 10 and Table 11. The exact result was obtained.

[0031]

[Table 9]

[Table 10]

[Table 11]

[0032]

INDUSTRIAL APPLICABILITY The present invention relates to a fluorocarbon siloxane composition, which comprises, as described above, A) a fluorocarbon siloxane represented by the general formula (1),
B) Organohydrogen siloxane as a cross-linking agent, C) an epoxy group-containing fluorocarbon hydrogen siloxane represented by the general formula (4) which acts as an adhesion aid, and D) a catalyst for addition reaction are added and uniformly mixed. However, this product is easily cured by addition reaction of the A) component with the B) and C) components to form a rubber elastic body,
This product has excellent solvent resistance, chemical resistance, water and oil repellency, workability, and adhesiveness, so engine oil, gear oil, automotive seal materials such as gasoline, dust from the outside, moisture It is advantageous for being used as a sealant for electric and electronic parts that is difficult to intrude.

[Brief description of drawings]

FIG. 1 shows a perspective view of a method for measuring the shear adhesive strength of a rubber sheet made from the composition of the present invention.

[Explanation of symbols]

 1 Adhered material 2 Seal material 3 Spacer 4 Weight

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Sato, 1-person, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Noriyuki Koike Usui-gun, Gunma Prefecture Matsuida-machi Ojimi Hitomi 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Takashi Matsuda 1-Ota Hitomi, Matsuida-cho, Usui District, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology In the laboratory (72) Toshio Takago, Toshio Takago, 1 Hitomi, Katsura, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicon Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. A) General formula: [Wherein R ¹ , R ² and R ³ are unsubstituted or substituted monovalent hydrocarbon groups containing no aliphatic unsaturated group, and Rf ¹ is represented by the following general formula: (Where f and h are integers from 0 to 5, g is an integer from 0 to 8 and e and i are 0 or 1) and have 1 to 3 carbon atoms.
0 divalent perfluoroalkylene group or 1 to 3 carbon atoms
0 divalent perfluoropolyether group, a is 2 to 30
0 is an integer, b is an integer of 0 to 300, and c is 0 to 5,000.
Is an integer, d is an integer of 2 to 8, and X is a general formula: (Here, R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group containing an aliphatic unsaturated group, and R ⁵ and R ⁶ are C 1-8.
Monovalent hydrocarbon Application Benefits organosiloxy fluorocarbon siloxane 100 parts by weight represented by the radical represented by hydrogen group), B) relative to the total aliphatic unsaturated groups in the A) component, hydrogen atoms bonded to silicon atoms An organohydrogensiloxane containing two or more ≡SiH groups in one molecule in an amount such that groups having ≡SiH groups are present in a ratio of 0.5 to 5.0, C) General formula ] (Here, Rf ² has the same carbon number of 3 to ² as Rf ¹ described above.
0.1 to 50 parts by weight of epoxy group-containing fluorocarbon hydrogen siloxane represented by 0, a divalent perfluoroalkylene group or a divalent perfluoropolyether group, j and k are integers of 1 to 3, and D) of an effective amount. A fluorocarbon siloxane composition comprising a homogeneous composition with a Group VIII element-containing catalyst of the periodic table.