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WO2012038192A1 - A silicone composition containing fluorine - Google Patents

A silicone composition containing fluorine Download PDF

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Publication number
WO2012038192A1
WO2012038192A1 PCT/EP2011/064730 EP2011064730W WO2012038192A1 WO 2012038192 A1 WO2012038192 A1 WO 2012038192A1 EP 2011064730 W EP2011064730 W EP 2011064730W WO 2012038192 A1 WO2012038192 A1 WO 2012038192A1
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och
group
fluorine
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component
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French (fr)
Inventor
Kotaro Kuwata
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Wacker Chemie AG
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Wacker Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • the present invention relates to a fluorine-containing silicone composition, which can be utilized in various applications since a cured product obtained therefrom has a low surface energy, and exhibits excellent oil-repellent properties.
  • the present invention relates to a composition that is useful as, for example, a sealing material, a packing material, and a coating material in industrial fields such as automotive, electronic, electric, and construction.
  • curable silicone compositions having a polyorganosiloxane as a main component exhibit, after curing, oil-repellent properties, release properties, antifouling properties, peeling properties, and the like.
  • a curable silicone composition for example, a composition formed from a vinyl group-containing polyorganosiloxane, a
  • composition containing a third component include: a releasable silicone composition that includes a polydimethylsiloxane containing a perfluoroalkyl group and a hydrogen atom bonded to a silicon atom (refer to Patent
  • Patent Literature 1 an adhesive composition that includes a cyclic siloxane containing a hydrogen atom bonded to a silicon atom, a fluoroalkyl group bonded to a silicon atom, and an epoxy group (refer to Patent Literature 2) ; and a curable polymer
  • Patent Literature 1 Japanese Patent Publication No. Sho 63-48901 (JP63048901A)
  • Patent Literature 2 Japanese Patent Publication No. Hei 5-5872 (JP5005872B)
  • Patent Literature 3 Japanese Patent Application Laid-open No. 2008-144024 ⁇ JP2004144024A
  • a fluorine-containing silicone composition characterized by comprising: (A) 100 parte by weight of a polyorganoslloxane with a viscosity at 25°C of 0.5 to 100,000 Pa.s and having in one molecule at least two constituent units represented by the general formula (1) ,
  • R 1 represents an alkenyl group
  • R 2 represents a substituted or unsubstituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond
  • a denotes 1 or 2;
  • b denotes 0, 1, or 2;
  • R f represents an alkyl group, an alkenyl group, or an aromatic hydrocarbon group having 1 to 20 carbon atoms which have at least one or more fluorine atoms;
  • X represents a spacer group selected from -O- , -OC (O) - , -NHC (O) - , -NH-, -CH(-OH)-, and a divalent hydrocarbon group having 1 to 8 carbon atoms;
  • Y represents a spacer group represented by -(CH(Z)-) n - (in the formula, Z is a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and n denotes an integer of 2 to 8) ;
  • R 3 and R 4 may be the same or different hydrocarbon group (s) having 1 to 10 carbon atoms; m denotes an integer of 1 or 2;
  • c denotes an integer of 0 to 2) ;
  • R 5 represents a substituted or unsubstituted monovalent hydrocarbon group
  • d denotes 1, 2, or 3;
  • e denotes 0, 1, or 2;
  • d + e is 1, 2, or 3
  • the fluorine-containing silicone composition according to [1] to [3] characterized in that X in the component (B) is -0C ⁇ 0)-.
  • the fluorine-containing silicone composition of the present invention rapidly cures by heating and exhibits excellent oil-repellent properties after curing while maintaining mechanical strength. Consequently, the fluorine-containing silicone composition of the present invention can be utilized in various applications, and is useful as, for example, a sealing material, a packing material, and a coating material in industrial fields such as automotive, electronic, electric, and construction.
  • the polyorganosiloxane of the component (A) used in the present invention has at least two alkenyl groups directly bonded to a silicon atom in one molecule.
  • This polyorganosiloxane is composed of at least two siloxane units represented by the above general formula (1) and further, a siloxane unit represented by the general formula (4) ,
  • This polyorganosiloxane may be linear, branched, resinous, or a mixture thereof.
  • This polyorganosiloxane may be produced by a method that is known to a person skilled in the art.
  • a linear polyorganosiloxane is preferred, as synthesis is simple, fluidity is high, and a high-elasticity silicone rubber can be obtained.
  • a resinous polyorganosiloxane is used in combination.
  • Examples of the alkenyl group of R 1 in the above general formula (1) include vinyl, allyl, l-butenyl, 1-hexenyl and the like. Prom an economic and a production perspective, a vinyl group is preferred.
  • Examples of the R 2 in the general formulae (1) and (4) include: an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, and dodecyl; an aryl group such as phenyl; an aralkyl group such as 2-phenylethyl and 2-phenylpropyl; and a substituted hydrocarbon group such as chloromethyl and
  • a methyl group as the economic efficiency is excellent and production is simple, yet the resultant cured product has the degree of polymerization required for the product to maintain favorable physical properties, and the component has a low pre-curing viscosity.
  • a phenyl group can optionally be incorporated in the molecule.
  • the cured composition needs to have oil resistance, a
  • 3,3, 3 -trifluoropropyl group can be Incorporated in the molecule . These are optionally selected.
  • the component (A) serves as a base polymer for the curable polyorganosiloxane.
  • the unit containing the alkenyl group represented by the above general formula (1) may be positioned on the end of the polyorganosiloxane molecular chain, or somewhere along the chain. However, to give the cured composition excellent mechanical properties, it is preferred that this unit be positioned at least on the end of the chain.
  • the viscosity of the component (A) is not especially limited, the viscosity at 25°C is preferably 0.5 to 100, 000 Pa-s. For applications requiring high pre-curing fluidity and excellent post-curing mechanical properties, it is preferred that the viscosity be 1 to 50,000 Pa ⁇ s.
  • the fluorine compound of the component (B) used in the present invention is an essential component in order for the composition of the present invention to have excellent oil-repellent properties.
  • This fluorine compound is an alkoxysilane represented by the following general formula (2) , which has a hydrocarbon group to which at least one or more fluorine atoms is bonded.
  • R f in the general formula (2) represents an alkyl group, an alkenyl group, or an aromatic hydrocarbon group having l to 20 carbon atoms which have at least one or more fluorine atoms. More specifically, if R f is an aromatic hydrocarbon group, R c is a group like that illustrated below,
  • R f is an alkyl group
  • R f is a group like that is illustrated below, CF 3 -, C a P 5 - C 3 F 7 - C 4 F 9 - C s F 11 -, C 6 F 13 -, C 7 F 15 -, C 8 F 17 -, C 9 F 19 - , C 10 F 21 -, C 31 F 23 -, C 12 F35- C l3 F 27 -/ C14P29-, Ci 5 F 3 i-, Ci «P 33 -, Ci 7 F 3S -/ C2HF4- , C 3 HF 6 -, C 4 HF 8 -, C 5 HF 1 o-, C 6 HF 1 2-, C 7 HF 14 -, C 8 HF 16 -/ C 9 HF i8 -, CioHP2o- C HF 2a -, Ci 2 HF 24 -, CF3CH2-, C 2 F S -(CH 2 ) 8 - (herein,
  • R f may also include an ether bond, a sulfonyl group, a carboxyl group, or some other halogen atom, as illustrated below. Specifically, examples thereof include CF 3 CF(-OCF 3 )-, CF 3 CF(-OCF 3 ) -CF 2 -, CF 3 CF ( -OCF 3 ) -C 2 F- ,
  • CF 3 CF(-OCF 3 )-C 3 F «-, CF 3 CF(-OCF 3 ) -C 4 F 8 -, CF 3 CF (-OCF 3 ) ⁇ C $ F 10 - , CF 3 CF ⁇ -OCF 3 ) -C 6 F 12 -, CF 3 CF(-OCF 3 ) -C 7 F 14 -, CF 3 CF (-OCF 3 ) -C 8 F 1 «- , CF 3 CF(-OCF 3 ) -C 9 F 1 e-, CF 3 CF ( -OCF 3 ) -C10F20- , F-S0 2 -C 2 F 4 - ,
  • Rf having a fluorine atom is an alkyl group or an alkenyl group
  • Rf may be linear or branched.
  • X in the general formula (2) represents a spacer group selected from -0-, -OC(O)-, -NHC(O)-, -NH-, -CH(-OH) - , and a divalent hydrocarbon group having 1 to 8 carbon atoms .
  • This spacer group links a spacer group Y, which is bonded to the silicon atom in the general formula (2) , and the fluorine-containing group R f .
  • X is a hydrocarbon group, in conjunction with the Y hydrocarbon group, an -X-Y- hydrocarbon group having three or more carbon atoms acts as the linking space group between R f and the silicon atom.
  • Y in the general formula (2) represents a linking spacer group represented by -(CH(Z)-) horr-, wherein Z is a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and n denotes an integer of 2 to 8.
  • Y examples include - ⁇ CH 2 ⁇ 2 -, -(CH 2 ) 3 -, -(CH 3 ) 4 -, -(C ⁇ )s-, -(CH 2 )e ⁇ , -CH 2 -CH(CH 3 )- , -CH (CH 3 ) -CH 2 - , -(CHF) 2 -, - ⁇ CHCl) 2 -, -(CHBr) 2 -, -(CHI ⁇ 2 -, -CH2-CHF-, -CH 2 -CHCl-, -CH 2 -CHBr-, -CH a -CHI-, -CHF-CHCl- , -CHF-CHBr- , -CHF-CHI-, -CHCl-CHBr-, -CHCl-CHI-, -CHBr-CHI-, and the like.
  • R 3 and R* in the general formula (2) may be the same or different hydrocarbon grou (s) having 1 to 10 carbon atoms.
  • R 3 and R 4 may be the same hydrocarbon groups as exemplified for R 2 .
  • R 3 it is preferred to use a methyl group.
  • R 4 it is preferred to use a methyl group or an ethyl group, m denotes an integer of 1 or 2, and c denotes an integer of 0 to 2. However, it is pr erred that m be 1 and c be 0.
  • the silicone composition of the present invention in order to give the silicone composition of the present invention excellent oil-repellent properties, it is especially preferred to use a compound in which the X in the component (B) is -OC ⁇ 0)-.
  • a compound in which the X in the component (B) is -OC ⁇ 0)- include the following, C 6 F 5 -CH 2 -OC(0) - (CH 3 ) 3 -Si (0CH 3 ) 3 ,
  • These organosilicon compounds can be prepared by a known synthesis method.
  • a representative example is to add an alkoxysilane compound having a Si-H group onto an organic compound having an alkenyl group and a fluorine atom by a hydrosilylation reaction.
  • These fluorine compounds of the component (B) are necessary in order to give the silicone rubber composition of the present invention excellent oil-repellent properties.
  • These fluorine compounds may be used alone, using at least two types or more of them together achieves an even greater improvement .
  • the used amount of these fluorine compounds is, based on 100 parts by weight of the component (A) , 0.001 to 50 parts by weight, more preferably 0.01 to 30 parts by weight, and even more preferably 0.1 to 15 parts by weight. If the used amount of the component (B) is less than 0.001 parts by weight, sufficient oil-repellent properties are not obtained, if the used amount exceeds 50 parts by weight, not only are sufficient
  • the curing agent of the component (C) of the present invention is a curing agent that works based on a known addition reaction or an organic peroxide curing agent. If the curing agent of the component (C) is an addition reaction curing agent, such a curing agent is used as a combination of a polyorganohydrogensiloxane ⁇ C-1) represented by the general formula (3) and an addition reaction catalyst (C-2) . Further, the addition reaction curing agent and organic peroxide curing agent can be used individually or in combination.
  • the polyorganohydrogensiloxane (C-l) of the present invention is a component for curing the composition of the present invention into a rubber elastic body or a gel-like substance based on an addition reaction with the alkenyl group in the component (A) .
  • the molecular structure of this component (C-l) is not especially limited, as long as it has two or more Si-H groups in one molecule.
  • a conventionally known linear, cyclic, or branched polyorganohydrogensiloxane can be used, from the perspective of ease of production, a linear polyorganohydrogensiloxane or a branched
  • polyorganohydrogensiloxane formed from an R a 2 HSiOi/2 unit and a Si0 2 unit is preferred.
  • R s in the general formula (3) include the same examples as described for R 2 in the above general formula (1) .
  • R 5 may be the same as or di rent f om that in the general formula (1) or even the same as or different from the other one in the general formula (3) .
  • a methyl group and/or a phenyl group is preferred.
  • Preferred examples of the component (C-l) include
  • methylhydrogensiloxane/dimethylsiloxane cyclic copolymer a methylhydrogenpolysiloxane blocked at either end with a trimethylsiloxy group, a
  • dimethylsiloxane/methylhydrogensiloxane copolymer blocked at either end with a trimethylsiloxy group, a diraethylpolysiloxane blocked at either end with a dimethylhydrogensiloxy group, a methylhydrogenpolysiloxane blocked at either end with a dimethylhydrogensiloxy group, a
  • methylhydrogensiloxane/diphenylsiloxane/dimethylslloxane copolymer blocked at either end with a trimethylsiloxy group a copolymer formed from a (CH 3 ) jHSiOia unit and a Si0 4 / 2 unit, a copolymer formed from a ⁇ CH 3 ) 2 HSi0i/ 2 unit, a Si0 4 /a unit, and a (C 6 H 5 )Si0 3 2 unit, and compounds in which in the above exemplified compounds some or all of the methyl groups are substituted with an alkyl group such as an ethyl group, and a propyl group, an aryl group such as a phenyl group, and a halogen-substituted alkyl group such as a 3, 3, 3-trifluoropropyl group.
  • the molecular structure of the polyorganohydrogensiloxane may be linear, cyclic,
  • polyorganohydrogensiloxane is 2 to 1,000, preferably 3 to 500, more preferably 3 to 300, and especially preferably 4 to 15.
  • This polyorganohydrogensiloxane may be produced by a method known to the skilled person in the art.
  • the used amount of the component (C-l) is an amount such that, based on one alkenyl group in the R l of the component (A) , 0.5 to 7.0 hydrogen atoms are bonded to the silicon atom, preferably 0.7 to 5.0 hydrogen atoms, and more preferably 0.8 to 3.0 hydrogen atoms.
  • the number of hydrogen atoms is less than 0.5, the curing of the component does not proceed su ficiently, while if the number of hydrogen atoms is more than 7.0, foaming tends to occur during the curing, and the post-curing physical properties, especially heat resistance, tend to significantly deteriorate.
  • the addition reaction catalyst (C-2) is a catalyst for promoting the hydrosilylation addition reaction between the alkenyl group bonded to the silicon atom in the component (A) and the Si-H group of the polyorganohydrogensiloxane (C-l) .
  • this addition reaction catalyst include metals and compounds thereof, such as platinum, rhodium, palladium, ruthenium, and iridium.
  • platinum or a platinum compound are especially preferred.
  • platinum compound examples include platinum black, a platinum halide (for example, PtCl ⁇ , ⁇ PtCl4' 6H 2 0, H 2 PtCl 6 « 6H 2 O, NaiPtCl 4 -4H a O, or a reaction product formed from a cyclohexane and Na 2 PtCls ⁇ 4H 2 0) , a platinum-olefin complex, a platinum-alcohol complex, a platinum-alcoholate complex, a platinum-ether complex, a platinum-aldehyde complex, a platinum-ketone complex, a platinum-vinylsiloxane complex (for example, a
  • the hydrosilylation catalyst can be used in a microencapsulated from, such as a particulate solid.
  • the particulate solid that contains the catalyst and that is insoluble in the polyorganosiloxane is, for example, a thermoplastic resin (for example, a polyester resin or a silicone resin) .
  • the hydrosilylation catalyst can also be used in the form of a clathrate compound, for example, in cyclodextrin.
  • the used amount of the hydrosilylation catalyst of the component (C-2) is the effective amount, specif cally, the catalytic amount, which is normally in the range of 0.1 to 1,000 ppm based on the component (A) in terms of the metal.
  • the used amount is preferably in the range of 0.5 to 200 ppm.
  • organic peroxide curing agent (C-3) a conventionally-known organic peroxide curing agent may be used, as long as it is used for promoting the crosslinking reaction of the component (A) in the organic peroxide-curable
  • polyorganosiloxane composition examples include 1 , 1-bis (t-butylperoxy) -3 , 5 , 5-trimethylcyclohexane ,
  • the type and added amount of the organic peroxide curing agent (C-3) can be selected based on the amount of active group -0-0- and the decomposition temperature. Normally, the added amount is, based on 100 parts by weight of component (A), preferably in the range of 0.01 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.
  • various inorganic or organic fillers may also be used to improve the physical properties.
  • examples of such fillers include fumed silica, precipitated silica, ground silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, barium sulfate, magnesium silicate (talc) , aluminum silicate (clay) , diatomaceous earth, calcium metasillcate, zeolite, hydrotalclte , graphite, carbon black, quartz, alumina and the like.
  • the used amount of these fillers is arbitrary, as long as the purpose of the present invention is not harmed.
  • the composition of the present invention may include a known reaction control agent, for example, acetylene alcohol, a polyvinyl-containing polyorganosiloxane, triallyl cyanurate, triallyl isocyanurate, triacrylic formal, triallyl trimellitate, ⁇ , ⁇ ' -m-phenylene bismalelmide, di-propargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate and the like.
  • an acetylene group-containing silane or siloxane may also be added.
  • the composition of the present invention may be dispersed or dissolved in a suitable organic solvent such as toluene, xylene and the like.
  • the fluorine-containing silicone rubber composition of the present invention can be obtained just by uniformly mixing arbitrary amounts of the above-described components (A) to (C) at room temperature.
  • the composition can be preferably obtained by heat treating the component (A) and the optional components such as a filler with a planetary mixey, a kneader and the like in the range of 100 to 200°C for 1 to 4 hours, and then admixing components (B) and (C) at room temperature.
  • the molding method can be f eely selected based on the viscosity of the mixture .
  • molding may be carried out by casting, compression molding, injection molding, extrusion molding, transfer molding, dip molding by dissolving in a solvent, coating and the like .
  • the curing can be carried out by hot molding under conditions of, normally, €0 to 200°C, in the range of 10 seconds to 24 hours.
  • the fluorine-containing silicone composition of the present invention rapidly cures by heating and exhibits excellent oil-repellent properties after curing. Consequently, the fluorine-containing silicone composition of the present invention can be utilized in various applications, and is useful as, for example, a sealing material, a packing material, and a coating material in industrial fields such as automotive, electronic, electric, and construction.
  • the contact angle was measured using the Contact Angle meter CA-X150 manufactured by FACE Co., Ltd. A drop (about 0.002 cc) of n-hexadecane (Reagent Grade, manufactured by Kanto Chemical Co., Ltd.) was dropped using a micro-syringe onto the surface of a cleaned cured silicone rubber sheet, and the contact angle was measured after 1 minute had elapsed. The average value from
  • test sample was cut out from the -cured silicone rubber sheet into a No. 3 dumbbell shape based on!JlS 6251 (sample thickness 2 mm) using a dumbbell cutter. This test sample was used in a tension test. The tensile strength was measured at a tension rate of 500 mm/min using the Autograph AGS-J 5 kN manufactured by Shimadzu Corporation, and the maximum value when the sample fractured was taken. The average value from 3 samples was employed for the tensile strength.
  • a universal kneader was charged with 100 parts of a
  • polydimethylsiloxane (component (A) ) blocked at either end with a dimethylvinylsilyl group having a viscosity at 25°C of 20,000 mPa*s, 40 parts of fumed silica having a specific surface area of 200 mVg, 8 parts of hexamethyldisilazane, and 1 part by weight of deionized water, and the resultant mixture was stirred and mixed for 1 hour at room temperature. The temperature was then increased to 150°C, and the mixture was heated and mixed for 2 hours.
  • the silicone rubber composition was prepared in the same manner as in Example 1, except that 5 parts of the fluorine-containing alkoxysllane represented by the following formula (ii) were added as the component (B) . Then, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table 1. ⁇ OCH 3 ) 3 Si- (CH 2 ) 2 - ⁇ 0)C- (CP 3 ) 6 -OC(0) - (CH 2 )2-Si(OCH 3 ) 3 ... (ii)
  • the silicone rubber composition was prepared in the same manner as in Example 1, except that 5 parts of the fluorine-containing alkoxysilane represented by the following formula (iil) were added as the component (B) . Then, the cured sheet was produce prepared, and the contact angle and tensile strength were measured. The results are shown in Table 1. CF 3 (CF 2 )s- (CH 2 ) 2 -OC(0 ⁇ - (CH 2 ) 2 -SiCH 3 (0CH 3 ) 2 ... (iii)
  • the silicone rubber composition was prepared in the same manner as in Example 1, except that 5 parts of the fluorine-containing alkoxysilane represented by the following formula (iv) were added as the component (B) . Then, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown In Table l.
  • a universal kneader was charged with 100 parts of a
  • polydimethylslloxane (component (A) ) blocked at either end with a dimethylvinyls lyl group having a viscosity at 25°C of 20,000 mPa «s and 40 parts of precipitated silica having a specific surface area of 200 m 2 /g, and the resultant mixture was stirred and mixed for 1 hour at room temperature . The temperature was then increased to 150°C, and the mixture was heated and mixed for 2 hours. Then, the mixture was cooled to room temperature.
  • a cured sheet was produced, using the obtained silicone composition, in the same manner as in Example 1, and the contact angle and tensile strength were measured. The results are shown in Table 1.
  • a universal kneader was charged with 100 parts of a
  • a cured sheet was produced, using the obtained silicone composition, in the same manner as in Example 1, and the contact angle and tensile strength were measured. The results are shown in Table 1.
  • the silicone rubber composition was prepared in the same manner as in Example 1, except that the component (B) was not added, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table 1.
  • the silicone rubber composition was prepared in the same manner as in Example 5, except that the component (B) was not added, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table l.
  • the silicone rubber composition was prepared in the same manner as in Example 6, except that the component (B) was not added, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table l.

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Abstract

A curable silicone composition is provided which can be cured by heating and whose cured product has excellent post-curing oil-repellent properties. A fluorine-containing silicone composition includes (A) an alkenyl group-containing polyorganosiloxane, (B) an alkoxysilane represented by the general formula (2) Rf [-X-Y-SiR3 c(OR4) 3-c] m in the formula, Rf represents a group containing a fluorine atom; X is selected from -0-, -OC (O)-, -NHC (O)-, -NH-, -CH (-OH)-, and a hydrocarbon group having 1 to 8 carbon atoms; Y represents a linking spacer group represented by -(CH(Z)-)n- (in the formula, Z is a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and n denotes an integer of 2 to 8); R3 and R4 represent a hydrocarbon group having 1 to 10 carbon atoms; m denotes an integer of 1 or 2; and c denotes an integer of 0 to 2), and (C) a curing agent.

Description

A SILICONE COMPOSITION CONTAINING FLUORINE
The present invention relates to a fluorine-containing silicone composition, which can be utilized in various applications since a cured product obtained therefrom has a low surface energy, and exhibits excellent oil-repellent properties. The present invention relates to a composition that is useful as, for example, a sealing material, a packing material, and a coating material in industrial fields such as automotive, electronic, electric, and construction.
It is known that curable silicone compositions having a polyorganosiloxane as a main component exhibit, after curing, oil-repellent properties, release properties, antifouling properties, peeling properties, and the like. As such a curable silicone composition, for example, a composition formed from a vinyl group-containing polyorganosiloxane, a
polyorganohydrogensiloxane, and a platinum catalyst is known. Proposals for this composition containing a third component include: a releasable silicone composition that includes a polydimethylsiloxane containing a perfluoroalkyl group and a hydrogen atom bonded to a silicon atom (refer to Patent
Literature 1) an adhesive composition that includes a cyclic siloxane containing a hydrogen atom bonded to a silicon atom, a fluoroalkyl group bonded to a silicon atom, and an epoxy group (refer to Patent Literature 2) ; and a curable polymer
composition formed by adding a compound containing an aliphatic unsaturated bond and a fluoroolefin copolymer to a copolymer formed from a siloxane macromonomer having in the molecule a hydrogen atom bonded to a silicon atom and a
(meth) acryloyloxyalkyl group bonded to a silicon atom and an ethylenic unsaturated monomer (refer to Patent Literature 3) . Although all of these compositions exhibit water-repellent properties and oil-repellent properties after curing, these compositions are inadequate when used in applications that demand even greater water-repellent properties and
oil-repellent properties. Furthe , the fluorine
atom-containing polyorganosiloxanes serving as a third component added to these compositions to exhibit
water-repellent properties and oil-repellent properties are all complex and difficult to produce. Further, a large amount is required in order for an effect to be exhibited. Therefore, from an economic perspective, these polyorganosiloxanes are disadvantageous. In addition, there is also the problem that to produce this component a fluorine solvent has to be used.
PRIOR ART LIST PATENT LITERATURE
Patent Literature 1: Japanese Patent Publication No. Sho 63-48901 (JP63048901A)
Patent Literature 2: Japanese Patent Publication No. Hei 5-5872 (JP5005872B)
Patent Literature 3 s Japanese Patent Application Laid-open No. 2008-144024 {JP2004144024A)
In view of the abov -described circumstances, it is an object of the present invention to provide a curable silicone composition that cures by heating, and that after curing can produce a cured product which has excellent oil-repellent properties while maintaining properties such as mechanical strength as a cured silicone product.
As a result of continued diligent research to resolve the above-described problems, the present inventor made the surprising discovery that the problems could be resolved by blending a specific compound containing a fluorine atom with a silicone composition, there arriving at the present invention. More specifically, the present invention is as follows. [1] A fluorine-containing silicone composition characterized by comprising: (A) 100 parte by weight of a polyorganoslloxane with a viscosity at 25°C of 0.5 to 100,000 Pa.s and having in one molecule at least two constituent units represented by the general formula (1) ,
R1 aR2 bS O(4-a-b) 2 (1)
(in the formula (1) ,
R1 represents an alkenyl group;
R2 represents a substituted or unsubstituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond;
a denotes 1 or 2;
b denotes 0, 1, or 2;
and a + b is 1, 2, or 3);
(B) 0.001 to 50 parts by weight of an alkoxysilane, represented by the following general formula (2), having a hydrocarbon group to which at least one or more fluorine atoms are bonded,
Rf[-X-Y-SiR3 c(OR)3-c]m (2)
(in the formula (2),
Rf represents an alkyl group, an alkenyl group, or an aromatic hydrocarbon group having 1 to 20 carbon atoms which have at least one or more fluorine atoms;
X represents a spacer group selected from -O- , -OC (O) - , -NHC (O) - , -NH-, -CH(-OH)-, and a divalent hydrocarbon group having 1 to 8 carbon atoms;
Y represents a spacer group represented by -(CH(Z)-)n- (in the formula, Z is a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and n denotes an integer of 2 to 8) ;
R3 and R4 may be the same or different hydrocarbon group (s) having 1 to 10 carbon atoms; m denotes an integer of 1 or 2;
and c denotes an integer of 0 to 2) ; and
(C) a curing agent in an amount that can cure the above component (A) .
[2] The fluorine-containing silicone composition according to [lj , characterized in that the curing agent component (C) is a combination of a polyorganohydrogensiloxane and an addition curing catalyst, wherein the polyorganohydrogensiloxane has at least two hydrogen atoms bonded to a silicon atom in one molecule/ is formed from a constituent unit represented by the general formula, R5 dHeSiO(4-d-e)/2 (3)
(in the formula (3) ,
R5 represents a substituted or unsubstituted monovalent hydrocarbon group;
d denotes 1, 2, or 3;
e denotes 0, 1, or 2; and
d + e is 1, 2, or 3,
and is used in an amount thereof such that an amount of hydrogen atoms bonded to the silicon atom is 0.5 to 7.0 based on the alkenyl groups in the component (A) .
[3] The fluorine-containing silicone composition according to [11 , characterized in that the curing agent component (C) is an organic peroxide.
[4] The fluorine-containing silicone composition according to [1] to [3] , characterized in that X in the component (B) is -0C{0)-. The fluorine-containing silicone composition of the present invention rapidly cures by heating and exhibits excellent oil-repellent properties after curing while maintaining mechanical strength. Consequently, the fluorine-containing silicone composition of the present invention can be utilized in various applications, and is useful as, for example, a sealing material, a packing material, and a coating material in industrial fields such as automotive, electronic, electric, and construction.
The present invention will now be described in more detail. The polyorganosiloxane of the component (A) used in the present invention has at least two alkenyl groups directly bonded to a silicon atom in one molecule. This polyorganosiloxane is composed of at least two siloxane units represented by the above general formula (1) and further, a siloxane unit represented by the general formula (4) ,
Ra bSiO(4-b)/2 (4) .
In the formula (4) , R2 and b are the same as described in the formula (1). This polyorganosiloxane may be linear, branched, resinous, or a mixture thereof. This polyorganosiloxane may be produced by a method that is known to a person skilled in the art. A linear polyorganosiloxane is preferred, as synthesis is simple, fluidity is high, and a high-elasticity silicone rubber can be obtained. On the other hand, to obtain high strength, typically a resinous polyorganosiloxane is used in combination.
Examples of the alkenyl group of R1 in the above general formula (1) include vinyl, allyl, l-butenyl, 1-hexenyl and the like. Prom an economic and a production perspective, a vinyl group is preferred. Examples of the R2 in the general formulae (1) and (4) include: an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, and dodecyl; an aryl group such as phenyl; an aralkyl group such as 2-phenylethyl and 2-phenylpropyl; and a substituted hydrocarbon group such as chloromethyl and
3,3, 3-trifluoropropyl . Among these , most preferred is a methyl group as the economic efficiency is excellent and production is simple, yet the resultant cured product has the degree of polymerization required for the product to maintain favorable physical properties, and the component has a low pre-curing viscosity. When the cured composition needs to have cold resistance and special optical properties, a phenyl group can optionally be incorporated in the molecule. When the cured composition needs to have oil resistance, a
3,3, 3 -trifluoropropyl group can be Incorporated in the molecule . These are optionally selected.
The component (A) serves as a base polymer for the curable polyorganosiloxane. In the component (A) , the unit containing the alkenyl group represented by the above general formula (1) may be positioned on the end of the polyorganosiloxane molecular chain, or somewhere along the chain. However, to give the cured composition excellent mechanical properties, it is preferred that this unit be positioned at least on the end of the chain. Although the viscosity of the component (A) is not especially limited, the viscosity at 25°C is preferably 0.5 to 100, 000 Pa-s. For applications requiring high pre-curing fluidity and excellent post-curing mechanical properties, it is preferred that the viscosity be 1 to 50,000 Pa·s.
The fluorine compound of the component (B) used in the present invention is an essential component in order for the composition of the present invention to have excellent oil-repellent properties. This fluorine compound is an alkoxysilane represented by the following general formula (2) , which has a hydrocarbon group to which at least one or more fluorine atoms is bonded.
Rf[-X-y-SiR3 o(OR4)3-c]m (2)
Rf in the general formula (2) represents an alkyl group, an alkenyl group, or an aromatic hydrocarbon group having l to 20 carbon atoms which have at least one or more fluorine atoms. More specifically, if Rf is an aromatic hydrocarbon group, Rc is a group like that illustrated below,
C6F5-, C6H4P-, C6H3F2-, C6H2F3-, C6H3FCl-, C6H3BrF- , C6H3FI-, and C6H3(CF3)2-.
If Rf is an alkyl group, Rf is a group like that is illustrated below, CF3-, CaP5- C3F7- C4F9- CsF11-, C6F13-, C7F15-, C8F17-, C9F19- , C10F21-, C31F23-, C12F35- Cl3F27-/ C14P29-, Ci5F3i-, Ci«P33-, Ci7F3S-/ C2HF4- , C3HF6-, C4HF8-, C5HF1o-, C6HF12-, C7HF14-, C8HF16-/ C9HFi8-, CioHP2o- C HF2a-, Ci2HF24-, CF3CH2-, C2FS-(CH2)8- (herein, s is an integer of 1 to 8, the same is applied to the followings) , C3F7-(Cな)e-, C4F9~(CH2)8-, C5Fu- (CHa) fl- , C6Fi3- (CH2) s- ,
C7F1s-(CH2)e-, C«F17- (CH¾)8-, C9F19- (Cな) s- , C10P2i- (CH2) β- ,
CnF23- (CH2)s- , and C12F2S- (CH2) e- ·
If Rf is an alkenyl group, RE is a group like that is illustrated below, CF3CF=CF-, CF3CF=CF-CF2-, CF3CF»CF-C2F4~ , CP3CF»CF-C3F6- , CF3CF*CF-C4F8-, CF3CF»CF-C3F1o-, CF3CF»CF-C6F12- , CF3CF*CF-C7F14~ , CP3CFaCF-CeF16-/ CF3CFeCF-C9F1$-, and CF3CF«CF-C10Fao- .
If Rf is an alkyl group, Rf may also include an ether bond, a sulfonyl group, a carboxyl group, or some other halogen atom, as illustrated below. Specifically, examples thereof include CF3CF(-OCF3)-, CF3CF(-OCF3) -CF2-, CF3CF ( -OCF3) -C2F- ,
CF3CF(-OCF3)-C3F«-, CF3CF(-OCF3) -C4F8-, CF3CF (-OCF3) ~C$F10- , CF3CF{-OCF3) -C6F12-, CF3CF(-OCF3) -C7F14-, CF3CF (-OCF3) -C8F1«- , CF3CF(-OCF3) -C9F1e-, CF3CF ( -OCF3) -C10F20- , F-S02-C2F4- ,
F-S02-C3F6-, F-S02-C4F8-, F-S02-C5F1o- > F-S02-C6Fj.2- , F-SOa-C7F14- , F~S02-C8F16- , F-S02-C9F1e-, F-S02-Ci0F2o- * F"S02-CtF2t-0-CwF2u- (t and u each are an integer of 1 to 10) , HOOC-C2F4-, HOOC-C3F6-, HOOC-C4F8-, HOOC-CBF10-, HOOC-C6F12~ , HOOC-C7F1 - , HOOC-C8F1«-, HOOC-C9Fl8-, HOOC-C10F20- C,F5-0-C2F4-, C3F7-0-C2F4- , CF9-0-C2F4- , CsF1i-0-C2F4-, C6F13-0-C2F4-, C7F15-0-C2F4~ , C8FX7-0-C2F4- ,
C9F19-0-C2F-/ Ci0F2i-O-C2F4-, CnF23-0-C2F4- , C2BrF4-, C3BrF«- , CiBrPe-r C5BrF1o-/ C6BrF12-, C7BrF14-, C$BrFj.6-, C*BrF1$-, CioBrF20- C3CIF4- C3ClF6-, C4C1F„-, CsClFw-, C6C1F12- , C7ClF14~, C8ClFi$-, CsClF1e-, C10CIF20-/ C3IF4-, C3IF«-, C4IF8-, C5IF10-, C6IF12-, C7IF14-/ C8IFx6-, CjIF1e-, C10IF20-/ and the like. If the above-described hydrocarbon group Rf having a fluorine atom is an alkyl group or an alkenyl group, Rf may be linear or branched.
X in the general formula (2) represents a spacer group selected from -0-, -OC(O)-, -NHC(O)-, -NH-, -CH(-OH) - , and a divalent hydrocarbon group having 1 to 8 carbon atoms . This spacer group links a spacer group Y, which is bonded to the silicon atom in the general formula (2) , and the fluorine-containing group Rf. If X is a hydrocarbon group, in conjunction with the Y hydrocarbon group, an -X-Y- hydrocarbon group having three or more carbon atoms acts as the linking space group between Rf and the silicon atom.
Further, Y in the general formula (2) represents a linking spacer group represented by -(CH(Z)-)„-, wherein Z is a substituent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and n denotes an integer of 2 to 8. Specific examples of Y include -{CH2}2-, -(CH2)3-, -(CH3)4-, -(Cな)s-, -(CH2)e~, -CH2-CH(CH3)- , -CH (CH3) -CH2- , -(CHF)2-, -<CHCl)2-, -(CHBr)2-, -(CHI}2-, -CH2-CHF-, -CH2-CHCl-, -CH2-CHBr-, -CHa-CHI-, -CHF-CHCl- , -CHF-CHBr- , -CHF-CHI-, -CHCl-CHBr-, -CHCl-CHI-, -CHBr-CHI-, and the like.
R3 and R* in the general formula (2) may be the same or different hydrocarbon grou (s) having 1 to 10 carbon atoms. R3 and R4 may be the same hydrocarbon groups as exemplified for R2. For R3, it is preferred to use a methyl group. For R4, it is preferred to use a methyl group or an ethyl group, m denotes an integer of 1 or 2, and c denotes an integer of 0 to 2. However, it is pr erred that m be 1 and c be 0. Among the above-described alkoxysilanes containing fluorine, in order to give the silicone composition of the present invention excellent oil-repellent properties, it is especially preferred to use a compound in which the X in the component (B) is -OC{0)-. Specific examples of such a compound include the following, C6F5-CH2-OC(0) - (CH3) 3-Si (0CH3) 3,
C6Fs~CH3-OC(0) - (CH2)2-SiCH3 (OCH3)2,
C6F5-CH2-0C<O) -CH(CH3) -CH3-Si (OCH3) 3,
C6F6-CH3-OC(0) -CH{CH3) -CH2-SiCH3 (0CH3) 2,
F-S02- (CF2)4- (CH2)2-OC{0 -(CH2)2-Si<OCH3)3;
F-SO2- (CF2)4- (CH2)2-0C{0 - (CH2)2-SiCH3(OCH3)2,
F-S02- (CF2) 6- (CH2) 2-0C (O -{CH2)2-Si(OCH3)3,
F~S02- <CF2) 9- <CH2) a-OC (0 - (CH2)2-SiCH3(OCH3)2,
F-SO2- (CF2)8- (CH2)2-0C{0 -(GH2)2-Si(OCH3)3,
F-S02- (CF2)8- (CH2)2-OC{0 (CHs)2-SiCH3{OCH3)2i
F-SO2- (CF2)4- (CH2)2-OC(0 -CH(CH3) -CH2-Si(OCH)3/
F-SO2- (CF2) 4- (CH2) 2-0C (0 -CH{CH3) -CH2-SiCH3(OCH3)
F-S02- (CF2) 6- (CH2) 2-OC(0 -CH(CH3) -CH2-Si{OCH3)3,
F-S02- (CF2) 6- (CH2) 2-OC (0 -CH(CH3) -CH2-SiCH3 (0CH3)
F-S02- (CF2) 8- (CH2) 2-OC (0 -CH(CH3) -CH2-Si(0CH3)3,
F-S02- (CF2)8- (CH2)2-0C(0 -CH (CH3) -CH2-SiCH3 (OCHs)
H00C- (CF2) 4- (CH2) 2-OC (O -<CH2)2-Si(OCH3)3,
H0OC- (CF2) 4- (CH3) 2-OC (O - (CH2)2-SiCH3(OCH3)2,
H00C- (CF2)6- <CH2)2-OC{0 - (CH2)2-Si(OCH3)3,
HOOC- (CF2)6- (CH2)2-OC(0 - (CH2)2-SiCH3 (OCH3)2/
HOOC- <CF2)*- (CH2)2-0C(0 -{CH2)2-Si(OCH3)3,
HOOC- (CF2)4- (CH2)2-0C(0 -(CH2)2-SiCH3(OCH3)2,
HOOC- (CF2) - (CH2)2-OC(0 -CH(CH3) -CH2-Si(OCH3)3,
HOOC- (CF2) 4- (CH2) 2-OC (0 -CH{CH3) -CH2-SiCH3(OCH3)2
HOOC- (CF2)6-<CH2)2-OC(0 -CH(CH3) -CH2-Si(OCH)3,
HOOC- (CF2) 6- (CH2) 2-0C(0 -CH(CH3) -CH2-SiCH3(OCH3)j
HOOC- (CF2)8- (CH2)2-OC(0 -CH(CH3) -CH2-S1{0CH3)3/
HOOC- (CF2)e- (CH2)2-0C{0 -CH (CH3) -CH2-SiCH3 (0CH3) 2
CF3(CF2)3- (CH2)2-0C(0) CH2)2-Si(OCH3)3,
CF3{CF2)3- (CH2)2-0C(0) CH2)3-SiCH3(OCH3)2,
CF3(CF2)4-(CH2)2-0C(0) CH2)2-Si(OCH3)3, CF3<CF2) (CH2] 2-oc<o) - {CH2)2-SiCH3(OCH3)2/
CF3(CF2) B-(CH2] 2-OC( 0>-(CH2)2-Si<OCH3)3,
CF3(CF2) 6-(CH2] 2-0C<o)- (CH2)2-SiCH3(OCH3)2/
CP3 (CF2) 6- (CH2] 2-0C( 0)-(CH2)2-Si(OCH3)3,
CP3 <CF2) «- (CH2)l2-OC<o) - (CH2) 2-SiCH3 (OCK3) 2
CF3 (CP2) i~ (CH2,f2-OC( 0) - (CH2)2-Si(0CH3)3,
CF3(CF2) 7- (CH2] >2-0C< 0)- (CH2)j,-SiCH3(OCH3)a,
CF3 (CF2) 3- (CH2) 2-0C( 0) -CH (CH3) -CH2-Si (OCH3) 3,
CP3 (CF2) 3-{CH2] 2-0C< 0) -CH(CH3) -CH2-SiCな (OCH3)
CF3{CP2) (CH2] 2-0C< 0) -CH(CH3) -CH2-Si(OCH3)3,
CP3(CP2) (CH2 2-0C< 0) -CH (CH ) -CH2-SiCH3 (OCH3)
CF3(CP2) s- (CH2] 2-0C< 0) -CH(CH3) -CH2-Si (OCH3) 3/
CP3 (CP2) 5- (CH2] -0C( 0) -CH(CH3) -CH2-SiCH3(OCH3)
CF3<CF2) «- <CH2]lA-OC< 0) -CH(CH3)-CH2-Si(OCH3)3,
CP3(CP2) i- (CH2! 2-0C< 0) -CH(CH3) -CH2-SiCH3{OCH3)
CP3 (CP2) 7- (CH2I >2-0C( 0)-CH(CH3) -CH2-Si(OCH3)3/
CP3 (CF2) i- (CH2; 2-0C( 0) -CH(CH3) -CH2-SiCH3 (OCな)
H<CF2)4- (CH2)2- -0C(0' (CH2)2-Si(OCH3)3,
H<CF2)4- (Cな)2 -0C(0 iCH2)2-SiCH3{OCH3)2
H (CF2) si(CH2)2- -0C(0 1 - (CH2)2-Si(OCH3)3, ll (CF2),r (CH¾)2- •oc<o; - (CH2)2-SiCH3(OCH3)2,
H(CF2)6- (CH2)2. -00(0, > - (CH2)2-Si<OCH3)3,
H(CF2)«- (CH2)2- -0C(0" I - (CH2)2-SiCH3{OCH3)2,
H(CP2)7- (CH2)2. -0C(0 1 - (CH2)2-Si(OCH3)3
H(CF2)7- (CH2)2. -oc (o; 1 - (CH2)2-SiCH3(OCHj)2
H(CF2)«- (CH2)2- -ocio, (CH2)2-Si(0CH3)3,
H(CP2)8- (CHA)2- -OC(0' (CH2)2-SiCH3(OCH3)a,
H<CF2)4- (CH2)2- -OC(0 CH(CH3) -CH2- -Si(OCH3)3,
H(CF2)4- (CH2)2- -OC(0 CH(CH3) -CH2- -SiCH3 (OCH3)
H(CP2)s- (CH2)2- -oc(o ! - CH,(CH3) -CH2- -Si(OCH3)3,
H(CF2)s- (CH2)2 ■oc(o CH{CH3) -CH2- *SlCH3(OCH3)
H(CF2)6- (CH2>2- -0C(0 1 - CH(CH3) -CH2- -Si (OCH3)3/
H(CF2)6- (CH2) · •OC(0 CH<CH3) -CH2- -S1CH3(0CH3)
H(CF2)7- (CH2)2- ■OC{0 1 - CH(CH3) -CH2. -Si{OCH3)3,
H(CF2)7- (CH2) 2' -0C(0; CH(CH3) -CH2- -SiCH3(OCH3)
H(CF (CH2)2- -0C(0' CH(CH3) -CH2' -Si(OCH3)3, H (CP2) 8- (CH2) 2-OC (O) -CH (CH3) -CH2-SiCH3 (OCH3) a,
(CF3)2CF- (CH2)2- C(0) - (CH2)2-Si (OCH3)3,
(CF3) 2CF- (CH2) 2-OC (O) - (CH3) 2-SiCH3 (OCH3) 2,
<CF3)2CFCF2- (CH2)2-OC(0) - (CH2) 2-Si (OCH3) 3 ,
(CP3) 2CFCF2- (CH2) 2-OC {O) - (CH2) 2-SiCH3 (OCH3) 2/
(CF3)2CF-(CF2)2- <CH2)2-OC(0)-(CHa)a-S±(OCH3)3,
(CP3) 2CF- (CFa) a- (CH2) 2-OC (0) - (CH2) 2-SiCH3 (OCH3) 2,
(CP3)2CF- (CF2)3-(CH2)2-OC(0)- (CH2)2-Si(OCH3)3,
(CP3) 2CF- (CF2) 3- (CH2) 2-OC (0) - (CH2) 2-SiCな (OCH3) 2,
(CF3)2CP» (CF2) - (CH2)2-OC{0) - (CH2)2-Si (OCH3)3,
(CP3) 2CF- (CF2) 4- (CH2) a-OC (0) - <CH2) 2-SiCH3 (0CH3) 2,
(CF3)2CF- (CFa) 5- (CH2) 2-OC(0) - (CH2) 2-Si (OCH3) 3,
(CF3)2CF- (CP2)S- (CH2)a-0C(0)- (CH2) 2-SiCH3 (OCH3) 2,
(CF3)2CF- (CH2)2-OC(0) -CH(CH3) -CH2-S1 (OCH3) 3 ,
(CF3) 2CF- (CH2) 2-OC (0) -CH (CH3) -CH2-SiCH3 (OCH3) 2
(CF3) 2CPCF2- (CH2) 2-OC(0) -CH (CH3) -CH2-Si (OCH3) 3,
(CF3)2CFCF2- (CH2)2-OC(0)-CH(CH3) -CH2-SiCH3 (OCH3) 2 ,
(CF3) 2CF- (CP2) a- (CH2) 2-OC (0) -CH (CH3) -CHa-Si (OCH3) 3 ,
(CF3) 2CF- (CF2) a- (CHa) a-OC (0) -CH(CH3) -CH2-SiCH3 (OCH3) 2,
(CF3) aCF- (CF2) 3- (CH2) 2-0C (O) -CH (CH3) -CHa-Si (OCH3) 3
(CFs)2CF- (CF¾)3- (CH2)2-OC(0) -CH(CH3) -CH2-SlCH3 (OCH3) 2 ,
(CF3)2CF- (CF2)4-(CH2)2-OC(0) -CH(CH3) -CH2-S1 (OCH3) 3 ,
(CF3)2CF- (CF2)4- (CH3)2-OC(0) -CH(CH3) -CH2-SiCH3 (OCH3) 2/
(CF3)2CF- (CF2)5-(CH2)2-OC(0)-CH(CH3) -CH2-Si (OCH3) 3,
(CF3)2CF- (CFa) 5- (CH2) 2-0C (0) -CH(CH3) -CH2-SiCH3 (OCH3)3,
(OCH3)3Si- (CH2)a-(0)C-C6H4-C(CF3)2-C6H4-OC(0) - (CH2) a-Si (OCH3) 3, (OCH3) 2CH3Si- (CH2) 2- (O) C-C6H4-C (CF3) 2-C*H4-OC (O) - (CH2) 2-SiCH3 (OC H3)2 ,
(OCH3) 3Si-CH2-CH (CH3) - (0) C-C6H4-C (CF3) 2-C6H4-OC {O) -CH(CH3) -CH¾- Sl(OCH3)3,
(OCH3)aCH3Si-CH2-CH(CH3) - (O) C-C6H4-C (CF3) 2-C6H4-OC (O) -CH(CH3) -C H2-SiCH3(OCH3)2/
(OCH3)3Si- (CH2)2- (0)C- (CF3)2-0C(O) - (CH2) 2-Sl (OCH3) 3 ,
(OCH3)3Si-(CH2)2- (0)C- (CF3)3-OC(0) - (CH2) 2-Si (OCH3) 3 ,
(OCH3)3Si- (CH2)4- (0)C- (CF3)4-OC(0)- (CH2) 2-Si (OCH3) 3 ,
(OCH3)3Si- (CHa) a- (0) C- (CF3) 5-0C (O) - (CH2) 2-Si (OCH3) 3, (OCH3)3Si- (CH3)3- (0)C-<CF3)6~OC(0) - (CH2)2-Si (OCH3) 3,
<OCH3)3Si- (CH2)2- (O)C- (CF3)7-OC(0) - (CH2)2-Si <OCH3)3,
(OCH3)2CH3Si- (CH3)3- 0)C- (CF3)2-OC(0)- CH2)3-SiCH3(OCH3}3, (OCH3)2CH3Si-(CH2)2- 0)C- (CF3)3-OC{0) - CH2)2-SiCH3(OCH3)2, (OCH3)3CH3Si-(CH2)3- 0)C- (CF3)4-OC(0)- CH2)2-SiCH3<OCH3}3, (OCH3)2CH3Si-<CH3)2- 0)C- (CF3)5-OC(0) - CH2)a~SiCH3(OCH3)2, (OCH3)2CH3Si- (Cな)2- O) C- (CF3)6-OC(0) - CH2)2-SiCH3<OCH3)2, (OCH3)2CH3Si-(CH2)2- 0)C- (CF3)7-OC(0) - CH2)2-SiCH3(OCH3)2, (OCH3)2CH3Si-(CH3)2- 0)C- (CF3)$-OC(0)- CH2)2-SiCH3(OCH3)j, (OCH3)3Si-CH2-CH(CH3 -(0)C-(CF3)2-0C(O -CH(CH3) -CH2-Si(OCH3) (OCH3) 3Si-CHa-CH (CH3 - (O)C- (CF3)3-OC(0 ~CH(CH3) ~CH¾-Si (OCH3) (OCH3)3Si-CH2-CH(CH3 - (O)C- (CF) -OC(0 -CH(CH3> -CH2-Si (OCH3) (OCH3)3Si-CH2-CH(CH3 -(0)C-(CF3)5-0C(O -CH(CH3) ~CH2-Si(OCH3) <OCH3) 3Si-CH2-CH (CH3 -(O)C- (CF3)€-OC{0 -CH(CH3) -CH2-Si (OCH3) (OCH3) 3Si-CH2-CH (CH3 -(0)C-(CF3)7-OC (O) -CH (CH3) -CH2-Si {OCH3) (OCH3)2CH3Si-CH2-CH(CH3) - (O) C- (CF3)2-OC(0) -CH(CH3) -CH2-SiCH3(0 CH3)2,
(OCH3)2CH3Si-CH2-CH(CH3) - (O)C- (CF3)3-OC(0) -CH{CH3) -CH2-SiCH3 (0 CH3)2
(OCH3)2CH3Si~CH2~CH(CH3) - (O) C- (CF3)4-OC(0) -CH(CH3) -CH2-SiCH3(0 CH3)2
(OCH3)aCH3Si-CH2-CH(CH3) - (O)C- (CF3)s-OC{0) -CH{CH3> -CH¾-S±CH3 <0 CH3) 2/
(OCH3)2CH3Si-CH2-CH(CH3) - (O) C- (CF3) e-OC (O) -CH (CH3) -CH2-SiCH3 <0 CH3)3,
(OCH3) 2CH3Si-CH2-CH (CH3) - (0) C- (CF3) 7-OC (0) -CH <CH3> -CH2-SiCH3 (0 CH3)3/ and
(OCH3)3CH3Si-CH3-CH(CH3) - (O) C- (CF3) 9-OC{0) ~CH(CH3) -CH3-SiCH3<0 CH3)a.
These organosilicon compounds can be prepared by a known synthesis method. A representative example is to add an alkoxysilane compound having a Si-H group onto an organic compound having an alkenyl group and a fluorine atom by a hydrosilylation reaction. These fluorine compounds of the component (B) are necessary in order to give the silicone rubber composition of the present invention excellent oil-repellent properties. Although these fluorine compounds may be used alone, using at least two types or more of them together achieves an even greater improvement , The used amount of these fluorine compounds is, based on 100 parts by weight of the component (A) , 0.001 to 50 parts by weight, more preferably 0.01 to 30 parts by weight, and even more preferably 0.1 to 15 parts by weight. If the used amount of the component (B) is less than 0.001 parts by weight, sufficient oil-repellent properties are not obtained, if the used amount exceeds 50 parts by weight, not only are sufficient
oil-repellent properties not obtained, but the physical properties of the post-curing molded elastic body deteriorate.
The curing agent of the component (C) of the present invention is a curing agent that works based on a known addition reaction or an organic peroxide curing agent. If the curing agent of the component (C) is an addition reaction curing agent, such a curing agent is used as a combination of a polyorganohydrogensiloxane <C-1) represented by the general formula (3) and an addition reaction catalyst (C-2) . Further, the addition reaction curing agent and organic peroxide curing agent can be used individually or in combination.
The polyorganohydrogensiloxane (C-l) of the present invention is a component for curing the composition of the present invention into a rubber elastic body or a gel-like substance based on an addition reaction with the alkenyl group in the component (A) . The molecular structure of this component (C-l) is not especially limited, as long as it has two or more Si-H groups in one molecule. Although a conventionally known linear, cyclic, or branched polyorganohydrogensiloxane can be used, from the perspective of ease of production, a linear polyorganohydrogensiloxane or a branched
polyorganohydrogensiloxane formed from an Ra 2HSiOi/2 unit and a Si02 unit is preferred.
Examples of the Rs in the general formula (3) include the same examples as described for R2 in the above general formula (1) . R5 may be the same as or di rent f om that in the general formula (1) or even the same as or different from the other one in the general formula (3) . However, from the perspective of heat resistance, a methyl group and/or a phenyl group is preferred. Preferred examples of the component (C-l) include
t i (dimethylhydrogensiloxy)methylsi1ane,
tris (dimethyIhydrogensiloxy) henylsilan ,
1, 1, 3, 3-1et methyldisiloxane,
1,3,5 , 7-tetramethylcyclotetrasiloxane,
methylhydrogencyclopolysiloxane, a
methylhydrogensiloxane/dimethylsiloxane cyclic copolymer, a methylhydrogenpolysiloxane blocked at either end with a trimethylsiloxy group, a
dimethylsiloxane/methylhydrogensiloxane copolymer blocked at either end with a trimethylsiloxy group, a diraethylpolysiloxane blocked at either end with a dimethylhydrogensiloxy group, a methylhydrogenpolysiloxane blocked at either end with a dimethylhydrogensiloxy group, a
dimethylsiloxane/methylhydrogensiloxane copolymer blocked at either end with a dimethylhydrogensiloxy group, a
methylhydrogensiloxane/diphenylsiloxane copolymer blocked at either end with a trimethylsiloxy group, a
methylhydrogensiloxane/diphenylsiloxane/dimethylslloxane copolymer blocked at either end with a trimethylsiloxy group, a copolymer formed from a (CH3) jHSiOia unit and a Si04/2 unit, a copolymer formed from a {CH3)2HSi0i/2 unit, a Si04/a unit, and a (C6H5)Si032 unit, and compounds in which in the above exemplified compounds some or all of the methyl groups are substituted with an alkyl group such as an ethyl group, and a propyl group, an aryl group such as a phenyl group, and a halogen-substituted alkyl group such as a 3, 3, 3-trifluoropropyl group. The molecular structure of the polyorganohydrogensiloxane may be linear, cyclic, branched, or a three-dimensional network structure. The number of silicon atoms (or the degree of polymerization) in one molecule of the
polyorganohydrogensiloxane is 2 to 1,000, preferably 3 to 500, more preferably 3 to 300, and especially preferably 4 to 15. This polyorganohydrogensiloxane may be produced by a method known to the skilled person in the art. The used amount of the component (C-l) is an amount such that, based on one alkenyl group in the Rl of the component (A) , 0.5 to 7.0 hydrogen atoms are bonded to the silicon atom, preferably 0.7 to 5.0 hydrogen atoms, and more preferably 0.8 to 3.0 hydrogen atoms. If the number of hydrogen atoms is less than 0.5, the curing of the component does not proceed su ficiently, while if the number of hydrogen atoms is more than 7.0, foaming tends to occur during the curing, and the post-curing physical properties, especially heat resistance, tend to significantly deteriorate.
The addition reaction catalyst (C-2) is a catalyst for promoting the hydrosilylation addition reaction between the alkenyl group bonded to the silicon atom in the component (A) and the Si-H group of the polyorganohydrogensiloxane (C-l) . Examples of this addition reaction catalyst include metals and compounds thereof, such as platinum, rhodium, palladium, ruthenium, and iridium. Among these hydrosilylation catalysts, platinum or a platinum compound are especially preferred. Specific examples of the platinum compound include platinum black, a platinum halide (for example, PtCl^, なPtCl4' 6H20, H2PtCl6« 6H2O, NaiPtCl4-4HaO, or a reaction product formed from a cyclohexane and Na2PtCls · 4H20) , a platinum-olefin complex, a platinum-alcohol complex, a platinum-alcoholate complex, a platinum-ether complex, a platinum-aldehyde complex, a platinum-ketone complex, a platinum-vinylsiloxane complex (for example, a
platinum-1,3-divinyl-l,1,3, 3-tetramethyldisiloxane complex, bis- (γ-pieoline) -platinum dichloride, trimethylene
pyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, and
cyclopentadiene-platinum dichloride), a
bis (alkynyl)bis (triphenylphosphine)platinum complex, a bis(alkynyl) (cyclooctadiene)platinum complex and the like.
Further, the hydrosilylation catalyst can be used in a microencapsulated from, such as a particulate solid. In this case, the particulate solid that contains the catalyst and that is insoluble in the polyorganosiloxane is, for example, a thermoplastic resin (for example, a polyester resin or a silicone resin) . in addition, the hydrosilylation catalyst can also be used in the form of a clathrate compound, for example, in cyclodextrin. The used amount of the hydrosilylation catalyst of the component (C-2) is the effective amount, specif cally, the catalytic amount, which is normally in the range of 0.1 to 1,000 ppm based on the component (A) in terms of the metal. When considering the curing properties and the post-curing physical properties, the used amount is preferably in the range of 0.5 to 200 ppm.
On the other hand, as the organic peroxide curing agent (C-3) , a conventionally-known organic peroxide curing agent may be used, as long as it is used for promoting the crosslinking reaction of the component (A) in the organic peroxide-curable
polyorganosiloxane composition. Specific examples include 1 , 1-bis (t-butylperoxy) -3 , 5 , 5-trimethylcyclohexane ,
2,5-diraethylhexane-2, 5-dihydrope oxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide,
α,α' -di (t-butylperoxy) -p-diisopropylbenzene,
2, 5-dimethyl-di (t-butylperoxy) hexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, benzoyl peroxide, t-butylperoxy hexene, 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, t-butylperoxy maleic acid, t-butylperoxy isopropyl carbonate and the like. The type and added amount of the organic peroxide curing agent (C-3) can be selected based on the amount of active group -0-0- and the decomposition temperature. Normally, the added amount is, based on 100 parts by weight of component (A), preferably in the range of 0.01 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. Other than the above-described components (A) to (c) , various inorganic or organic fillers may also be used to improve the physical properties. Examples of such fillers include fumed silica, precipitated silica, ground silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, barium sulfate, magnesium silicate (talc) , aluminum silicate (clay) , diatomaceous earth, calcium metasillcate, zeolite, hydrotalclte , graphite, carbon black, quartz, alumina and the like. The used amount of these fillers is arbitrary, as long as the purpose of the present invention is not harmed. Further, the composition of the present invention may include a known reaction control agent, for example, acetylene alcohol, a polyvinyl-containing polyorganosiloxane, triallyl cyanurate, triallyl isocyanurate, triacrylic formal, triallyl trimellitate, Ν,Ν' -m-phenylene bismalelmide, di-propargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate and the like. Further, an acetylene group-containing silane or siloxane may also be added. When carrying out the present invention, depending on the application, the composition of the present invention may be dispersed or dissolved in a suitable organic solvent such as toluene, xylene and the like.
The fluorine-containing silicone rubber composition of the present invention can be obtained just by uniformly mixing arbitrary amounts of the above-described components (A) to (C) at room temperature. The composition can be preferably obtained by heat treating the component (A) and the optional components such as a filler with a planetary mixey, a kneader and the like in the range of 100 to 200°C for 1 to 4 hours, and then admixing components (B) and (C) at room temperature.
The molding method can be f eely selected based on the viscosity of the mixture . For example, molding may be carried out by casting, compression molding, injection molding, extrusion molding, transfer molding, dip molding by dissolving in a solvent, coating and the like . The curing can be carried out by hot molding under conditions of, normally, €0 to 200°C, in the range of 10 seconds to 24 hours. The fluorine-containing silicone composition of the present invention rapidly cures by heating and exhibits excellent oil-repellent properties after curing. Consequently, the fluorine-containing silicone composition of the present invention can be utilized in various applications, and is useful as, for example, a sealing material, a packing material, and a coating material in industrial fields such as automotive, electronic, electric, and construction.
Examples
The present invention will now be described in more detail by illustrating with the following examples and comparative examples. However, the present invention is not limited to the following examples. Further, in the examples, the term mparts" refers to "parts by weight" .
Method for Measuring Contact Angle
The contact angle was measured using the Contact Angle meter CA-X150 manufactured by FACE Co., Ltd. A drop (about 0.002 cc) of n-hexadecane (Reagent Grade, manufactured by Kanto Chemical Co., Ltd.) was dropped using a micro-syringe onto the surface of a cleaned cured silicone rubber sheet, and the contact angle was measured after 1 minute had elapsed. The average value from
5 measurements was employed as the contact angle.
Measurement of Tensile Strength
A test sample was cut out from the -cured silicone rubber sheet into a No. 3 dumbbell shape based on!JlS 6251 (sample thickness 2 mm) using a dumbbell cutter. This test sample was used in a tension test. The tensile strength was measured at a tension rate of 500 mm/min using the Autograph AGS-J 5 kN manufactured by Shimadzu Corporation, and the maximum value when the sample fractured was taken. The average value from 3 samples was employed for the tensile strength.
Example 1
A universal kneader was charged with 100 parts of a
polydimethylsiloxane (component (A) ) blocked at either end with a dimethylvinylsilyl group having a viscosity at 25°C of 20,000 mPa*s, 40 parts of fumed silica having a specific surface area of 200 mVg, 8 parts of hexamethyldisilazane, and 1 part by weight of deionized water, and the resultant mixture was stirred and mixed for 1 hour at room temperature. The temperature was then increased to 150°C, and the mixture was heated and mixed for 2 hours. Then, the mixture was cooled to room temperature, and 3.1 parts of a polymethylhydrogensiloxane (component (C-l) ) , which was formed from 67 mole% of a (CH3)HSi02/2 unit and 33 mole* of a (CH3)2SiOji/2 unit and which had a viscosity at 25°C of 20 mPa*s, was added to the mixture. 0.8 parts of acetylene alcohol to extend the time until curing at room temperature, and 0.3 parts of a platinum-vinylsiloxane complex solution (component (C-2)J in which the platinum atom content was 0.5% by weight were added, and the resultant mixture was mixed until uniform. Next, 5 parts of a fluorine atom-containing alkoxysilane represented by the following formula (i) as the component (B) of the present invention was added to this composition to prepare the silicone rubber composition according to the present invention. The silicone rubber composition was f lled into a mold having internal cavity dimensions of 150 mm x 150 mm x thickness 2 mm, and hot-pressed at 170°C for 10 minutes to produce a sheet sample. This sheet sample was then placed in an air-circulation type oven set at 200°C, and heated for 4 hours to perform secondary curing, whereby an oil-repellent test sample was obtained. The results of contact angle measurement and the tension test are shown in Table 1. C6F5-CH2-OC(0) -{CH2)2-SiCH3(OCH3)2 ... (1)
Example 2
The silicone rubber composition was prepared in the same manner as in Example 1, except that 5 parts of the fluorine-containing alkoxysllane represented by the following formula (ii) were added as the component (B) . Then, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table 1. {OCH3)3Si- (CH2)2- {0)C- (CP3)6-OC(0) - (CH2)2-Si(OCH3)3... (ii)
Example 3
The silicone rubber composition was prepared in the same manner as in Example 1, except that 5 parts of the fluorine-containing alkoxysilane represented by the following formula (iil) were added as the component (B) . Then, the cured sheet was produce prepared, and the contact angle and tensile strength were measured. The results are shown in Table 1. CF3(CF2)s- (CH2)2-OC(0}- (CH2) 2-SiCH3 (0CH3) 2 ... (iii)
Example 4
The silicone rubber composition was prepared in the same manner as in Example 1, except that 5 parts of the fluorine-containing alkoxysilane represented by the following formula (iv) were added as the component (B) . Then, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown In Table l.
(CF3)2CF- (CF2)3- (CH2)2-OC(0) - (CH2) 2-SiCな (OCH3) 2 ... <iv)
Example 5
A universal kneader was charged with 100 parts of a
polydimethylslloxane (component (A) ) blocked at either end with a dimethylvinyls lyl group having a viscosity at 25°C of 20,000 mPa«s and 40 parts of precipitated silica having a specific surface area of 200 m2/g, and the resultant mixture was stirred and mixed for 1 hour at room temperature . The temperature was then increased to 150°C, and the mixture was heated and mixed for 2 hours. Then, the mixture was cooled to room temperature. 3.1 parts of a polymethylhydrogensiloxane (component (C-D), which was formed from 67 mole% of a (CH3) HSiOa/2 unit and 33 mole% of a (CH3)2Si02/2 unit and which had a viscosity at 25°C of 20 mPa*s, was added to the mixture. 0.8 parts of acetylene alcohol to extend the time until curing at room temperature, and 0.3 parts of a platinum-vinylsiloxane complex solution (component (C-2)) in which the platinum atom content was 0.5% by weight, and the resultant mixture was mixed until uniform. Next, 5 parts of a fluorine atom-containing alkoxysilane represented by the formula (i) as the component (B) of the present invention was added to this composition to prepare the silicone rubber composition according to the present invention.
A cured sheet was produced, using the obtained silicone composition, in the same manner as in Example 1, and the contact angle and tensile strength were measured. The results are shown in Table 1.
Example 6
A universal kneader was charged with 100 parts of a
polydimethylslloxane (component (A)) blocked at either end with a dimethylvinylsilyl group having a viscosity at 25°C of 3,000,000 mPa«s, 40 parts of fumed silica having a specific surface area of 200 m2/g, 8 parts of hexamethyldisilazane, and 1 part by weight of deionized water, and the resultant mixture was stirred and mixed for 1 hour at room temperature. The temperature was then increased to 150*0/ and the mixture was heated and mixed for 2 hours. Then, the mixture was cooled to room temperature to obtain a base compound.5 parts of a luorine atom-containing alkoxysilane represented by the formula (i) as the component (B) of the present invention, and 0.8 parts of 2, 5-dimethyl-di (t-butylperoxy)hexane as the component (C) were added separately, and then kneaded using a twin-screw roll until uniform.
A cured sheet was produced, using the obtained silicone composition, in the same manner as in Example 1, and the contact angle and tensile strength were measured. The results are shown in Table 1.
Comparative Example 1
The silicone rubber composition was prepared in the same manner as in Example 1, except that the component (B) was not added, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table 1.
Comparative Example 2
The silicone rubber composition was prepared in the same manner as in Example 5, except that the component (B) was not added, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table l.
Comparative Example 3
The silicone rubber composition was prepared in the same manner as in Example 6, except that the component (B) was not added, the cured sheet was produced, and the contact angle and tensile strength were measured. The results are shown in Table l.
Figure imgf000024_0001

Claims

1. A fluorine-containing silicone composition characterized by comprising:
(A) 100 parts by weight of a polyorganoslloxane with a viscosity at 25°C of 0.5 to 100, 000 Pa.s and having in one molecule at least two constituent units represented by the general formula (1) , R^R^SiO -a-b)/* (1) in the formula (1) ,
R1 represents an alkenyl group;
R2 represents a substituted or unsubstituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond;
a denotes 1 or 2;
b denotes 0, 1, or 2; and
a + b is 1, 2, or 3;
(B) 0.001 to 50 parts by weight of an alkoxysilane, represented by the following general formula (2) , having a hydrocarbon group to which at least one or more fluorine atoms are bonded, Rf [-X-Y-SiR3 0(OR4)3-o-m (2) in the formula (2) ,
Rf represents an alkyl group, an alkenyl group, or an aromatic hydrocarbon group having 1 to 20 carbon atoms which have at least one or more fluorine atoms; X represents a linking spacer group selected from -0-, -OC(0)-, -NHC(O)-, -NH-, -CH(-OH)-, and a divalent hydrocarbon group having 1 to 8 carbon atoms;
Y represents a linking spacer group represented by - (CH(Z) -),_·* (in the formula, Z is a substltuent selected from a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and n denotes an integer of 2 to 8) ; R3 and R4 may be the same or different hydrocarbon group (s) having
1 to 10 carbon atoms;
m denotes an integer of 1 or 2; and
c denotes an integer of 0 to 2) ; and
(C) a curing agent in an amount that can cure the above component (A) .
2. The fluorine-containing silicone composition according to claim 1, characterized in that the curing agent component (C) is a combination of a polyorganohydrogensiloxane and an addition curing catalyst/ wherein the polyorganohydrogensiloxane has at least two hydrogen atoms bonded to a silicon atom in one molecule, is formed from a constituent unit represented by the general formula (3),
R5 aHeSiOU-4-e)/2 (3) in the formula (3),
R5 represents a substituted or unsubstituted monovalent hydrocarbon group;
d denotes 1, 2, or 3;
e denotes 0, 1, or 2; and
d + e is 1, 2, or 3,
and is used in an amount thereof such that an amount of hydrogen atoms bonded to the silicon atom is 0.5 to 7.0 based on the alkenyl groups in the component (A) .
3. The fluorine-cont ining silicone composition according to claim 1, characterized in that the curing agent component (C) is an organic peroxide.
4. The fluorine-containing silicone composition according to claims 1 to 3, characterized in that X in the component (B) is -OC(0)-.
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