WO2006030774A1

WO2006030774A1 - Curable composition

Info

Publication number: WO2006030774A1
Application number: PCT/JP2005/016827
Authority: WO
Inventors: Toshiki Ichisaka; Daisuke Ota; Mitsuhiro Otani; Mitsuru Kishine
Original assignee: Daikin Industries, Ltd.
Priority date: 2004-09-15
Filing date: 2005-09-13
Publication date: 2006-03-23
Also published as: JP2006083274A; JP4617790B2

Abstract

Disclosed is a curable composition which is excellent in mold releasability and compatibility between a silicone crosslinked rubber and a fluoro rubber. Also disclosed is a molded article which is excellent in oil resistance, heat resistance, cold resistance, low hardness, amine resistance, chemical resistance and solvent resistance. Specifically disclosed is a curable composition composed of a silicone crosslinked rubber having a fluorine-containing substituent and a fluoro rubber.

Description

Specification

Curable composition

Technical field

The present invention relates to a curable composition comprising a silicone crosslinked rubber having a fluorine-containing substituent and a fluororubber. Also, a background art relating to a molded product obtained by crosslinking the curable composition

[0002] Silicone rubber and fluororubber are both rubbers having oil resistance and heat resistance, and are widely used in various fields. Silicone rubber has characteristics that are difficult to handle with fluororubbers, such as cold resistance, low hardness, and excellent amine resistance, and it can handle a wide range of processing methods such as LIM molding with liquid rubber on the surface. it can.

[0003] On the other hand, fluororubber exhibits outstanding chemical resistance, solvent resistance, and heat resistance, so it cannot be used with other materials because it exhibits high reliability that is not possible with silicone rubber! / Has been used for applications.

[0004] Since these two types of rubber have properties that complement each other, it is expected that new materials can be provided if they can be combined well with blends and alloys. Various studies have been made on composite polymers of various kinds of polymers.

[0005] For example, it has been disclosed that peroxide-crosslinking a blend of iodine-containing fluoroelastomer and a silicone rubber containing a bur group (see, for example, JP-A-55-50051). Also disclosed is a method of blending fluorine rubber and silicone rubber into which a double bond has been introduced to form a bridge (see, for example, JP-A-6-192524). However, even if two polymers with poor compatibility are simply blended and cross-linked, it is difficult to disperse both finely and uniformly! /, So good characteristics cannot be expected! ,.

[0006] As a technology related to block or grafting, silicone rubber is dissolved in Freon 113, and vinylidene fluoride (hereinafter abbreviated as VdF) Z-hexafluoropropylene (hereinafter abbreviated as HFP) is graft-polymerized. Further, an elastomer composition is disclosed (for example, see JP-A-1240552). However, in graft polymerization, fluorine-containing elastomer and silicon It is difficult to adjust the composition ratio of the elastomer, which is not practical.

[0007] In addition, a graft copolymer using tetrafluoroethylene (hereinafter abbreviated as TFE) Z propylene copolymer as fluororubber is disclosed (see, for example, JP-A-56-28219). . However, cure sites are epoxy groups, amino groups, organic acid groups, and vinyl groups, and good vulcanization characteristics cannot be expected.

[0008] In addition, there is a disclosure of a vulcanizable rubber composition in which the compatibility between fluororubber and organopolysiloxane is improved by using an organosiloxane having a specific functional group (see, for example, JP-A-4 180930). . However, the organosiloxane cannot be expected to have sufficient compatibility to improve the compatibility between the fluororubber polymer and the silicone, or to contain no fluororubber component.

[0009] Furthermore, a fluororubber vulcanized composition having specific fluororubber and epoxy group-containing silicone rubber powder having an average particle size of 100 μm or less is disclosed (for example, JP-A-4-252254, (See JP-A-4-293950). However, it has a fluorine-containing substituent

It ’s listed!

Disclosure of the invention

[0010] The present invention provides a curable composition excellent in the compatibility and release properties of a silicone crosslinked rubber and a fluororubber. We also provide molded products with excellent oil resistance, heat resistance, cold resistance, low hardness, amine resistance, chemical resistance, and solvent resistance.

That is, the present invention relates to a silicone cross-linked rubber having a fluorine-containing substituent and a curable composition having a fluoro rubber strength.

[0012] The silicone-crosslinked rubber having a fluorine-containing substituent is preferably capable of peroxide crosslinking, polyol crosslinking, or polyamine crosslinking.

[0013] The fluorine-containing substituent has the general formula (1):

[0014] [Chemical 1]!-R f ^1- ) — R _f ² "™ (1)

[In the formula, X ¹ is an iodine atom, a bromine atom, a hydrogen atom or a fluorine atom, and RR ^{2 is} Each is a fluorine-containing alkylene group having 1 to 2000 carbon atoms (however, R ¹ and R ² are different ff

M is an integer of 0 or 1, and n is 0 or 1. Where m + n≥l o)

It is preferably a fluorine-containing substituent represented by:

[0016] The present invention also relates to a molded product obtained by crosslinking the curable composition.

Brief Description of Drawings

FIG. 1 is a scanning electron microscope image of a rubber sheet after secondary vulcanization in Example 1.

2 is a scanning electron microscope image of the rubber sheet after secondary vulcanization in Comparative Example 4. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] The present invention relates to a curable composition comprising a silicone crosslinked rubber having a fluorine-containing substituent and a fluororubber.

Here, the silicone crosslinked rubber is a crosslinked silicone rubber.

[0020] Since the silicone crosslinked rubber used in the present invention has a fluorine-containing substituent, it has good compatibility with the fluorine rubber, and the fluorine-containing substituent has the same cure site as the cure site of the fluorine rubber. When it has, when cross-linking fluororubber, it is easy to co-crosslink with fluororubber.

[0021] The fluorine-containing substituent is not particularly limited, but the general formula (1):

[0022] [Chemical 2] j- R _f R _f ² -f- (i)

[0023] The fluorine-containing substituent represented by the formula (1) is preferred because of excellent compatibility with the silicone-crosslinked rubber and the possibility of peroxide crosslinking, polyol crosslinking or polyamine crosslinking.

In the formula, X ¹ is an iodine atom, a bromine atom, a hydrogen atom or a fluorine atom, and when a peroxide bridge is employed as the crosslinking system, X ¹ is preferably an iodine atom or a bromine atom. When employing polyol crosslinking, X ¹ may be a hydrogen atom or a fluorine atom. [0025] R ¹ is a fluorine-containing alkylene group having 1 to 2000 carbon atoms, and fluorine-containing f 1 to 1000 carbon atoms f

An alkylene group is preferred. In addition, it preferably has a structure capable of generating a double bond by dehydrofluoric acid from the viewpoint that polyol crosslinking or polyamine crosslinking is possible. In particular,

[0026] [Chemical 3]

CH ₂ CF, CF ₂ CF-, — CF— CH

CF CF! ¹ then Jr r, then Jr then 1_τ,

CFCF ₃

C H

CF CF

I

Among these, those having the structure [0027] are preferred,

[0028] [Chemical 4] One CF ₂ — CF— CH ₂ — CF ₂ —, -CF ₂ -CH- i 1

CF ₃ CF ₃

[0029] Those having a structure of [0029] are more preferred.

[0030] R ² is a fluorine-containing alkylene group having 1 to 2000 carbon atoms, and fluorine containing 1 to 1000 carbon atoms.

f

An alkylene group is preferred. Further, it may contain an etheric oxygen atom, nitrogen atom, hydroxyl group, carbonyl group or the like. However, it is different from the R ^1. [0031] Specifically, R ² is represented by the general formula (2):

f

(R ³ )-(Y)-(2)

f X y

[In the formula, R ³ is a group in which part or all of hydrogen atoms having 1 to 10 carbon atoms are substituted with fluorine atoms.

X is an integer of 0 or 1, and y is an integer of 0 or 1. However, x + y≥l. Y is the general formula (3) or (4):

[0032] [Chemical 5]

+ 0 R + _n (3) + R _f O _n (4)

[In the formula, n is an integer of 1 to 20, and R ⁴ is substituted with at least one hydrogen atom by a fluorine atom.

1 to 5 divalent fluorine-containing alkylene radicals, which are at least one selected, and each of n may be the same or different when n is 2 or more) ]

It is preferable to include a site represented by

[0034] Specifically, the general formula (3) or (4)

(OCF CF CF), I (CF CF CF O), I (OCFX ² CF), I (OCF CFX ²

2 2 2 2 2 2 2 2

) One, (OCFX ³ ) One,-(CFX ³ 0) One,-(OCH CF CF)-, — (OCF CF CH)

2 2 2 2 2 2 1, (OCH CH CF) —, 1 (OCF CH CH), 1 (OCF CF CF CF) —, 1 (

2 2 2 2 2 2 2 2 2 2

CF CF CF CF O) (OCFX ³ CH, (CFX ² CF O) (CH CF CF

2 2 2 2 2 2 2 2 2

O) (CH CFX ³ 0) (OCH (CH) CF CF) (OCF CF CH (CH)

2 3 2 2 2 2 3

) One, — (OCX ⁴ ) — and — (cx ⁴ o)-

twenty two

(Wherein X ² and X ³ are the same or different and are a hydrogen atom, a fluorine atom or —CF, and X ⁴

3 is CF)

Three

Y is preferably one or more of these repeating units. Above all, Y is

(OCFX ² CF (OCF CF CF) (OCH CF CF) (OCFX ³ )

2 2 2 2 2 2 2

(OCX ⁴ ) (CFX ² CF O) (CF CF CF O) (CH CF CF O) (CFX ³ 0) —and— (CX ⁴ O)

2

It is particularly preferred that the repeating unit is one or more repeating units selected from

(OCFX ² CF) (OCF CF CF) (OCH CF CF) (CFX'CF O

) (CF CF CF O) —and one (CH CF CF O)

One or more repeating units selected, and

(OCFX ² CF) (OCF CF CF)-(CFX CF O) and (CF CF CF O) —

2

It is preferable that it is one or two or more types of repeating units for which force is also selected. However, the unit γ of the fluorine-containing ether may contain a nitrogen atom, a hydroxyl group, a carbo group, etc., but O—O— (specifically, R—O—O—RO—O—). R—and fff and —R—O—O)).

f

[0035] A more specific example of R ² is as follows.

f

[0036] [Chemical 6]

CH ₂ CF ₂ CF

-

[0037] (wherein p is 0 to: an integer of LOO),

Etc.

[0038] m is an integer of 0 or 1. N is 0 or 1. Where m + n≥ 1. Ru

[0039] The silicone crosslinked rubber is not particularly limited, but the general formula (5):

[0040] [Chemical 7]

R ¹ R ³ R ^s R ⁷

I I I I

-S i-0-s i i o-^ S i-(5)

I I I I

R ² R ⁴ R ⁶ R ⁸

[In the formula, Ri to R ⁸ are each hydrogen, an alkyl group having 1 to 5 carbon atoms, a alkenyl group, a saturated or unsaturated fluorohydrocarbon group, a phenol group, or a substituent thereof. Ri to R 8 may be the same or different, a is 0 to 3000, b is 0 to 300, and 10≤a + b≤3000)

A silicone cross-linked rubber having a skeleton represented by

[0042] In addition, each of the repeating units represented by (R ³ R ⁴ SiO) and (R ⁵ R iO) in the general formula (5) force dimethylsiloxane unit, or methyl-1, 1, 1-trifluoropro The virsiloxane unit favors the heat resistance and chemical resistance of the resulting crosslinked product.

[0043] Further, (R ³ R ⁴ SiO) and (R ⁵ R ⁶ SiO) may be a silicone rubber segment in which each block segment is bonded, or a silicone in which both are randomly bonded. It may be a rubber segment or a silicone segment composed of one repeating unit.

[0044] Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, and a butyl group, and examples of the alkenyl group include a saturated or unsaturated fluorohydrocarbon group such as a vinyl group and an aryl group. ί, 1 CH CH CF, 1 CH CH CF CF, 1 CH CH CF CF CF, 1 CH CH

2 2 3 2 2 2 3 2 2 2 2 3 2

CF CF CH = CH etc. are mentioned, but among these, since synthesis is easy,

2 2 2 2

— CH CH CF is preferred.

2 2 3

[0045] In the formula, a is preferably 0 to 3000, more preferably 10 to 2000.

[0046] b is preferably 0 to 3000, and more preferably 0 to 2000.

[0047] Furthermore, a and b should satisfy 10≤ & + 1) ≤3000, and 10≤a + b≤2000. More preferably. If a + b is less than 10, the properties of the silicone crosslinked rubber tend to hardly appear, and if it exceeds 3000, the molecular weight is too high and handling tends to be difficult.

[0048] The primary particle diameter of the silicone-crosslinked rubber particles is 0.01 to L00 μm in average particle diameter, and preferably has a force S, and more preferably 0.01 to 10 / ζ πι. If the primary particle size is less than 0.01 / zm, the dispersibility of the silicone-crosslinked rubber particles in the fluororubber tends to decrease. If the primary particle size exceeds 100 m, the mechanical strength of the vulcanizate will greatly increase. There is a tendency to decrease.

[0049] In addition, the fluorine-containing substituent is preferably unevenly distributed on the silicone-crosslinked rubber from the viewpoint of compatibility with the fluororubber. Here, uneven distribution means that the fluorine-containing substituents of the silicone crosslinked rubber are present more in the vicinity of the surface of the silicone crosslinked rubber, and the surface force of the silicone crosslinked rubber particles is about 7 nm by an X-ray photoelectron analyzer. This can be confirmed by measuring the fluorine content. The fluorine content near the surface of the silicone crosslinked rubber particles should be 1.01-30.00 times the fluorine content of the entire silicone crosslinked rubber particles. Better than power! / ヽ.

[0050] The fluorine content of the entire silicone crosslinked rubber particles is more preferably be 0.1 to 35 weight ^_0/0 is signaling from 0.5 to 35 wt% preferred. If the fluorine content is less than 0.1% by weight, the compatibility between the silicone crosslinked rubber particles and the fluorine rubber is insufficient, and the silicone crosslinked rubber particles cannot be uniformly dispersed in the fluorine rubber! /, .

[0051] The method for introducing a fluorine-containing substituent into the silicone crosslinked rubber is not particularly limited. For example, fluorine having a substituent capable of reacting with the reactive substituent on the silicone crosslinked rubber having a reactive substituent. Examples thereof include a method of reacting a compound. The reactive substituents possessed by the silicone-crosslinked rubber include epoxy groups, vinyl groups, amino groups, amide groups, isocyanate groups, carboxyl groups, alkoxycarbon groups, hydroxy groups, sulfonic acid groups, phosphoric acid groups, Examples thereof include an acid halide group, a cyano group, an aryl group, an alkenyl group, a hydrosilyl group, and a halogen group. Examples of the substituent capable of reacting with the reactive substituent include an amino group, an amide group, an isocyanate group, and a hydroxy group. Carboxyl group, epoxy group, alkoxycarbonyl group, sulfonic acid group, phosphoric acid group, acid halide group, cyano group, aryl group, alkenyl group, hydrosilyl group, halogen group, etc. . In addition, this In order to react these reactive substituents, it is necessary to add various kinds of reaction reagents and catalysts. Among these, silicone crosslinked rubbers each having an epoxy group

Combination of fluorine rubber with Z amine group, silicone cross-linked rubber with bull group

A combination of a fluorine rubber having a Z iodine group, a bromine group or a hydrosilyl group, a silicone crosslinked rubber having a hydrosilyl group, an iodine group or a bromine group is particularly preferred.

[0052] The mixing ratio of the silicone crosslinked rubber and the fluororubber is not particularly limited, but is preferably 0.1 / 99.9 to 80Z20 in terms of weight ratio of the silicone crosslinked rubber Z fluororubber force. More preferably, it is 10/90 to 70/30. Silicone cross-linked rubber strength If the amount is less than the above range, the low temperature property of the fluororubber is not sufficiently improved, and if the range is exceeded, the mechanical strength of the vulcanizate tends to be extremely lowered.

[0053] The fluororubber used in the present invention is not particularly limited, and examples thereof include non-perfluorofluorocarbon rubber (a) and perfluorofluororubber (b).

[0054] Non-perfluoro fluorine rubber ( _a ) includes VdF fluorine rubber, TFEZ propylene fluorine rubber, TFEZ propylene ZVdF fluorine rubber, ethylene ZHFP fluorine rubber, ethylene ZHFPZVdF fluorine rubber, ethylene ZHFPZTFE Fluororubber, TFEZV dFZ perfluoromethyl ether ether fluororubber, fluorosilicone fluororubber, or fluorophosphazene fluororubber, etc., each of which can be used alone or as an effect of the present invention. Any combination can be used within a range without impairing the above.

[0055] The VdF type fluorine-containing rubbers, VdF45～85 mole ^_0/0, VdF copolymerizable with at least one other monomer 55-15 mol% and comprising a fluorinated elastomer one copolymer Say. Preferably, it refers to a fluorine-containing elastomeric copolymer having a strength of 50 to 80 mol% of VdF and 50 to 20 mol% of at least one other monomer copolymerizable with VdF.

[0056] Examples of at least one other monomer that can be copolymerized with VdF include TFE, black trifluoroethylene (hereinafter abbreviated as CTFE), trifluoroethylene, HFP, trifluoropropylene, and tetrafluoropropylene. , Pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro (alkyl butyl ether) (hereinafter abbreviated as PAVE) And non-fluorine monomers such as ethylene, propylene and alkyl butyl ether. These can be used alone or in any combination. Of these, TFE, HFP, and PAVE are preferable.

Specific rubbers include VdFZHFP rubber, VdFZHFPZTFE rubber, VdFZC TFE rubber, VdFZCTFEZTFE rubber, and the like.

[0058] The TFEZ propylene fluorine rubber, TFE45～70 mole ^_0/0, propylene consist 55-30 mol%, still based on the total amount of TFE and propylene, the monomer 0-5 moles giving a crosslinking site % Fluorine-containing copolymer.

[0059] Examples of monomers that give a crosslinking site include, for example, JP-A-4-505345 and JP-A-5.

As described in Japanese Patent No. 500070, examples thereof include a cyano group-containing monomer, a carboxyl group-containing monomer, and an alkoxycarbonyl group-containing monomer.

[0060] Examples of the perfluorofluororubber (b) include those made of a monomer that provides a TFEZPAVEZ crosslinking site. The composition of TFEZPAVE is more preferably it is preferred instrument is 50~90ZlO~50 mole ^_0/0, a 50~80Ζ20~50 mol%, more preferably 55~70Ζ30~45 mol%. Also, monomer to give a crosslinking site, the total amount of TFE and Roarufa VE, it is it is preferable Ri yo is preferred instrument 0-2 mole ^_0/0 0 to 5 mol ^_0/0 .

[0061] Examples of the PAVE in this case include perfluoro (methyl vinyl ether), perfluoro (propyl butyl ether), and the like, and these can be used alone or in any combination.

[0062] Examples of the monomer that gives a crosslinking site include the general formula (6):

CF = CFO (CF CF (CF) 0) (CF) — X ⁵ (6)

2 2 3 m 2 n

(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁵ is a cyano group, a carboxyl group, or an alkoxycarbonyl group). These can be used alone or in any combination.

[0063] The cyano group, carboxyl group, and alkoxy carbo group are cross-linked sites, and the cross-linking reaction proceeds with the silicone cross-linked rubber.

[0064] Further, an elastomeric 'fluorinated polymer chain segment and a non-elastomeric' fluorinated polymer A thermoplastic fluororubber composed of a single-chain segment can also be used, and the rubber composition comprising the thermoplastic fluororubber and the non-perfluoroolefin rubber (a) and Z or perfluoroolefin rubber (b) Can also be used.

[0065] The fluororubber used in the present invention can be produced by an ordinary emulsion polymerization method.

Polymerization conditions such as temperature and time during polymerization may be appropriately determined depending on the type of monomer and the target elastomer.

[0066] In the emulsion polymerization, an oil-soluble radical polymerization initiator or a water-soluble radical initiator can be used as the polymerization initiator.

[0067] As the oil-soluble radical polymerization initiator, generally known oil-soluble peracids are used, and for example, dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec butyl peroxydicarbonate. Peroxyesters such as t-butylperoxyisobutylate, t-butylperoxybivalate, dialkylperoxides such as di-tert-butylperoxide, and di (ω-hydride dodecafluoro Loheptanol) Dioxide, Di (ω Hydro-tetradecafluorootatanyl) Peroxide, Di (0) -Hydrohexadecafluorononanoyl) Peroxide, Di (perfluorobutyryl) peroxide Di (perfluorovaleryl) peroxide, di (perfluoro oral hex) ) Peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorootatanyl) peroxide, di (perfluorononanoyl) peroxide, di (0) -chlorohexafluor Robutyryl) peroxide, di (ω chlorodecafluor hexanoyl) peroxide, di (ω chloro tetradecafluoro otatanyl) peroxide, _ω hydrodedecafluor heptanoyl ω Hyde port to hexa deca full O Lono nano I looper oxide, .omega.-chloro to hexa full O Rob Chile Lou _omega - hexa Noi looper O Kisaido to chloro over deca full O port, omega hydro dodeca full O b hept Noi looper full O Rob Chile Louver oxide, di (dichroic pentafluorobutanol) peroxide, di (trick Mouth Ottafuro mouth hexanoyl) peroxide, di (tetrachloroundecafluorootatanol) peroxide, di (pentachlorotetradecafluorodecanoyl) peroxide, di (undecachlorodo) Triacontafluorodocosanoyl) peroxides and other di [perfluoro ( Or fluorochrome) acyl] peroxides are typical examples.

[0068] However, typical oil-soluble initiators such as di-isopropyl peroxycarbonate (IPP) and n-propyl peroxycarbonate (NPP) are not suitable for explosion. It is preferable to use a water-soluble radical polymerization initiator because it has a problem that it is expensive and has a problem that the adhesion tends to occur on the wall of the polymerization tank during the polymerization reaction.

[0069] As the water-soluble radically polymerizable initiator, generally known water-soluble peracids are used. For example, ammonia such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, etc. Salt, potassium salt, sodium salt, t-butyl permaleate, t-butyl hydride peroxide.

[0070] The amount of the water-soluble radical initiator to be added is not particularly limited, but it may be added at the initial stage of the polymerization or more than an amount that does not significantly reduce the polymerization rate (for example, several ppm to water concentration). It may be added next or continuously. The upper limit is the range in which the heat of polymerization reaction can be removed from the equipment surface.

[0071] As the emulsifier, nonionic surfactants, anionic surfactants, cationic surfactants, and the like can be used. In particular, fluorine-based ionic properties such as ammonium perfluorooctanoate are used. Surfactant, 1, 1, 2-trihydred perfluorinated hexanesulfonic acid (CH = CH (CF) SO H), 1, 1, 2-trihydred perfluorooctane sulphur

2 2 4 3

Nonionic surfactant such as on acid (CH = CH (CF) SO H) or its salt

2 2 6 3

Things are preferable. The addition amount (with respect to polymerization water) is preferably 50 to 5000 ppm.

[0072] Further, a molecular weight adjusting agent, a pH adjusting agent and the like may be added. The molecular weight regulator may be added all at once in the initial stage, or may be added continuously or dividedly.

[0073] Examples of the molecular weight regulator include esters of dimethyl malonate, jetyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, isopropanol, acetone, various mercaptans, carbon tetrachloride. , Cyclohexane, mono-iodomethane, 1-iodoethane, 1-iodo n-propane, isopropyl iodide, jodomethane, 1,2 jodoethane, 1,3 joodo n-propane, and the like. [0074] In addition, a buffering agent or the like may be added as appropriate, but the amount is within a range not impairing the effects of the present invention.

[0075] Mu-one viscosity (ML at 100 ° C) of fluororubber obtained by the above production method

1 + 10 is preferably 150 or less, more preferably 140 or less, and even more preferably 130 or less. In addition, the lower limit value of the Mu-1 viscosity is not particularly limited, and is preferably 2 or more, more preferably 5 or more. If the mu-viscosity is less than 2, the vulcanization characteristics are not sufficient, and if the viscosity exceeds 150, sufficient moldability tends to be not obtained.

[0076] The number average molecular weight (Mn) of fluororubber is preferably 3000 to 100000, more preferably <is 10,000 to 700,000, and further preferably <20000 to 500,000. If the number average molecular weight (Mn) is less than 3000, the vulcanization characteristics are not sufficient. If the number average molecular weight (Mn) exceeds 1000000, sufficient moldability tends to be obtained.

[0077] Further, the molded article of the present invention can be obtained by crosslinking such a fluorinated rubber and a curable composition having silicone crosslinked rubber strength.

[0078] The crosslinking agent that can be used in the present invention may be appropriately selected depending on the crosslinking system to be employed. As the crosslinking system, any of a polyamine crosslinking system, a polyol crosslinking system, and a peroxide crosslinking system can be adopted. From the viewpoint that the effects of the present invention can be exhibited remarkably, peroxide crosslinking and polyol crosslinking are particularly preferred. Oxide crosslinking.

[0079] As the crosslinking agent, for example, in a polyol crosslinking system, a polyhydroxy compound such as bisphenol AF, hydroquinone, bisphenol A, and diaminobisphenol AF. For a peroxide crosslinking system, for example, a, a 'bis (t butyl peroxide ) Diperoxybenzene, 2,5 Dimethyl-2,5 Di (t-butylperoxy) hexane, Dicumylperoxide and other organic peroxides S, and polyamine cross-linked systems such as hexamethylenediamine carbamate, N, N'-dicinnamylidene 1 , 6 Polyamine compounds such as hexamethylenediamine. However, it is not limited to these.

[0080] Among these, 2, 5 dimethyl-2,5 di (t-butylba) is preferred from the viewpoint of crosslinkability and handleability.

[0081] The amount of the crosslinking agent is 100 parts by weight in total of the fluororubber and the silicone crosslinked rubber. 0.1 to 15 parts by weight, preferably 0.3 to 5 parts by weight. If the cross-linking agent is less than 0.1 parts by weight, the degree of cross-linking is insufficient, and the performance of the molded product tends to be impaired. If the cross-linking agent exceeds 15 parts by weight, the cross-linking density becomes too high and the cross-linking time is long. In addition, there is a favorable economic trend.

[0082] As crosslinking aids for polyol crosslinking systems, various quaternary ammonium salts, quaternary phosphonium salts, cyclic amines, monofunctional amine compounds, etc. are usually used for vulcanization of elastomers. The organic base used can be used. Specific examples include quaternary ammonia such as tetraptylammonium bromide, tetraptylammonium chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, tetraptylammonium hydrogensulfate, and tetrabutylammonium hydroxide. Quaternary phosphoric acid salts such as benzyl triphenyl phospho-muc chloride, tributylaryl phosphoric chloride, tributyl-2-methoxypropylphosphonic chloride, benzylphenol (dimethylamino) phosphomethylene chloride; Monofunctional amines such as benzylmethylamine and benzylethanolamine; 1,8 diazabicyclo [5. 4. 0] cyclic amines such as undecou7.

[0083] Peroxide crosslinking type crosslinking aids include triallyl cyanurate, triallyl isocyanurate (TAIC), tris (diallylamine s triazine), triallyl phosphite, N, N diallylacrylamide, hexaryl. Phosphoramide, N, N, N ′, N ′ —tetraaryltetraphthalamide, N, N, N ′, N ′ —tetraarylmalonamide, tribule isocyanurate, 2,4,6 tribule Examples include methyltrisiloxane and tri (5-norbornene 2-methylene) cyanurate. Of these, triallyl isocyanurate (TAIC) is preferred because of its crosslinkability and physical properties of the molded product!

[0084] The blending amount of the crosslinking aid is preferably 0.1 to 15 parts by weight, more preferably 0.3 to 7 parts by weight with respect to 100 parts by weight of the total of the fluororubber and the silicone crosslinked rubber. is there. If the amount of the crosslinking aid is less than 0.1 parts by weight, the crosslinking time tends to be unpractical, and if it exceeds 15 parts by weight, the crosslinking time becomes too fast, and the compression time of the molded product is increased. There is a tendency for the strain to decrease.

[0085] Further, fillers, processing aids, carbon black, inorganic fillers that are ordinary additives, Metal oxides such as magnesium oxide and metal hydroxides such as calcium hydroxide may be used as long as the object of the present invention is not impaired.

[0086] Regarding the preparation of the composition of the present invention, it is desirable to mix the silicone cross-linked rubber, the fluororubber, and other additives as required sufficiently uniformly. Such mixing is performed by a rubber kneading roll, an ader, a Banbury mixer, or the like that has been conventionally used. The working conditions at the time of mixing are not particularly limited, but usually the silicone cross-linked rubber can be sufficiently uniformly mixed in the fluororubber by kneading at a temperature of about 20 to 200 ° C. for 1 to 180 minutes. Further, a strong silicone crosslinked rubber or additive compound can be appropriately dissolved and dispersed in a solvent to form a suspension solution. Furthermore, so-called wet mixing is also possible in which mixing is carried out in the medium from the beginning. In such a case, a mixture in a solution state can be obtained by using a mixer such as a roll, a ball mill, or a homogenizer. Moreover, both can be more effectively dispersed by making the silicone crosslinked rubber into an aqueous dispersion and mixing the pre-aqueous solution with the aqueous dispersion after the fluororubber production. In addition, it is desirable to select the optimum working conditions and operations for mixing according to the type and purpose of the raw materials and compounds used!

[0087] Regarding the curing of the composition of the present invention, the means for crosslinking is not particularly limited, and conventionally known methods such as compression molding, extrusion molding, transfer molding, injection molding and the like can be employed.

[0088] The molded article of the present invention can be suitably used in the following fields.

[0089] In semiconductor-related fields such as semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma addressed liquid crystal panels, field emission display panels, solar cell substrates, etc., o (square) rings, packings, sealing materials, tubes Rolls, coatings, linings, gaskets, diaphragms, hoses, etc., which are CVD equipment, dry etching equipment, wet etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, cleaning equipment, ion implantation equipment, exhaust equipment It can be used for chemical piping and gas piping. Specifically, as a gate valve O-ring and seal material, as a quartz window O-ring and seal material, as a chamber O-ring and seal material, as a gate O-ring and as a seal material, a bell jar O-ring and seal As a material, coupling O-ring, As a seal material, as a pump o-ring, as a seal material, as a diaphragm, as a o-ring as a semiconductor gas control device, as a seal material, as a resist developer, as an o-ring for stripping solution, as a seal material, as a hose for wafer cleaning liquid It can be used as a tube, as a roll for transporting a wafer, as a lining and coating of a resist developer bath and a stripping bath, as a lining and coating of a wafer cleaning bath, or as a lining and coating of a wet etching bath. In addition, sealing materials' sealing agent, optical fiber quartz coating material, electronic parts for insulation, vibration proofing, waterproofing, moisture proofing, circuit board potting, coating, adhesive seals, gaskets for magnetic storage devices, It is used as a modifier for sealing materials such as epoxy, sealant for clean rooms and clean rooms.

[0090] In the automotive field, gaskets, shaft seals, valve stem seals, sealing materials and hoses can be used for engines and peripheral devices, and hoses and sealing materials can be used for AT devices. Rings, tubes, packings, valve cores, hoses, seals and diaphragms can be used in fuel systems and peripheral devices. Specifically, engine head gasket, metal gasket, oil pan gasket, crankshaft seal, camshaft seal, valve stem seal, hold packing, oil hose, oxygen sensor seal, ATF hose, injector O-ring, Ettater packing, fuel pump O-ring, diaphragm, fuel hose, crankshaft seal, gear box seal, power piston packing, cylinder liner seal, knob stem seal, automatic transmission front pump seal, rear axle On-seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission O-ring, oil seal, exhaust gas re-burning unit scenery, bearing Shinore, EGR tubes, twin key bush tube for sensors Daiafuramu carburetor, rubber vibration isolator (engine mount, exhaust part, etc.), afterburners hoses, can be used as an oxygen sensor bush.

[0091] In the aircraft field, the rocket field, and the ship field, there are diaphragms, O (square) rings, valves, tubes, knockers, hoses, sealing materials, etc., which can be used for fuel systems. Specifically, in the aircraft field, jet engine valve steal seals, fuel supply hoses, gaskets and O-rings, rotating shaft seals, oil Used in gaskets for fire pressure equipment, firewall seals, etc. In the marine field, it is used for screw propeller shaft stern seals, intake / exhaust valve stem seals for diesel engines, valve seals for butterfly valves, shaft seals for butterfly valves, etc. It is done.

[0092] In the field of chemicals such as plants, linings, valves, knocks, rolls, hoses, diaphragms, o (square) rings, tubes, sealing materials, chemical-resistant coatings, etc., are available. It can be used in the production process of chemicals such as agricultural chemicals, paints, and fats. Specifically, chemical pumps, rheometers, pipe seals, heat exchanger seals, glass cooler packings for sulfuric acid production equipment, pesticide sprayers, seals for pesticide transfer pumps, gas pipe seals, plating solutions Seals, high-temperature vacuum dryer packing, paper belt roller seals, fuel cell seals, wind tunnel joint seals, trichlene-resistant rolls (for textile dyeing), acid-resistant hoses (for concentrated sulfuric acid), gas chromatography, pH It can be used as a packing for a tube connection part of a meter, a chlorine gas transfer hose, a benzene, a rainwater drain hose for a toluene storage tank, an analytical instrument, a seal for a scientific instrument, a tube, a diaphragm, a valve part, and the like.

[0093] In the pharmaceutical field such as pharmaceuticals, it can be used as a medicine stopper or the like.

[0094] In the photographic field such as a developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, rolls and the like can be mentioned, which are respectively used for a film developing machine, a tangential film developing machine, a printing roll, and a coating roll. be able to. Specifically, as a developing roll of a film developing machine / coiled film image forming machine, a gravure roll of a printing roll, a guide roll, a gravure roll of a magnetic tape manufacturing coating line of a coating tool, and a magnetic tape manufacturing coating It can be used as a line guide roll, various coating rolls, and the like. Furthermore, dry copying machine seals, printing equipment printing rolls, scrapers, tubes, valve parts, coating, coating equipment coating rolls, scrapers, tubes, valve parts, printer ink tubes, rolls, belts, dry copying machine belts It can be used as a roll, a roll for a printing press, a belt, or the like.

[0095] Tubes can also be used in the field of analysis and science machines.

[0096] In the field of food plant equipment, linings, valves, knockers, rolls, hoses, diaphragms, o (square) rings, tubes, sealing materials, belts, and the like can be mentioned and used for food production processes. Specifically, plate heat exchangers ^^ seals, vending machine solenoid valves It can be used as a seal or the like.

[0097] In the field of nuclear plant equipment, packing, O-rings, hoses, sealing materials, diaphragms

, Nozzles, rolls, tubes, etc.

[0098] In the steel field such as iron plate processing equipment, there are rolls and the like, which can be used for iron plate processing rolls and the like.

[0099] In general industrial fields, packing, O-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, rolls for PPC copiers, Examples include roll blades and belts. Specifically, oil pressure, lubrication machine seals, bearing seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seal (vacuum) valves, automatic packaging machine seals It is used for diaphragms (pollution measuring devices) for analysis of sulfur dioxide and chlorine gas in the air, printing press rolls, belts, pickling squeeze rolls, and so on.

[0100] In the electric field, specifically, it is used as an insulating oil cap for Shinkansen, a ventilator seal for liquid-sealed transformers, a jacket for oil well cables, and the like.

[0101] In the fuel cell field, specifically, a sealing material between electrodes and separators is used as a seal for hydrogen 'oxygen' product water piping.

[0102] Specifically in the electronic parts field, it is used as a heat-dissipating material raw material, an electromagnetic shielding material raw material, a modified material for printed wiring board pre-preda resin such as epoxy, an anti-scattering material for light bulbs, a gasket for computer hard disk drives, etc. Used.

[0103] There are no particular limitations on what can be used for on-site molding, including, for example, automotive engine metal gasket coatings, engine oil pan gaskets, copier printer rolls, Architectural sealant, gasket for magnetic recording device, sealant for clean room filter unit, coating agent for printed circuit board, electrical 'electronic component fixing agent, insulation moisture-proof treatment of electrical equipment lead wire terminal, electric furnace, etc. Examples include oven seals, end treatment of sheathed heaters, microwave oven window frame seals, adhesion of CRT wedges and necks, adhesion of automotive electrical components, joint seals for kitchens, bathrooms, and washrooms. Example

[0104] Next, the present invention will be described with reference to examples, but the present invention is not limited to only the examples of the invention.

[0105] Evaluation method

The O-ring (P-24) is produced by primary press vulcanization and secondary oven vulcanization of the curable composition shown in Table 1 under the following standard vulcanization conditions. Measure compression set after press vulcanization and compression set (CS) after secondary oven vulcanization (hold 70 hours at 150 ° C under pressure compression at 25% or 70 hours at 200 ° C) After that, we measured the sample left in a constant temperature room at 25 ° C for 30 minutes).

[0106] (Standard vulcanization conditions)

Kneading method: Roll kneading

Press vulcanization: 10 minutes at 160 ° C

Oven vulcanization: 4 hours at 180 ° C

[0107] <100% modulus (M100)>

The curable composition shown in Table 1 is subjected to primary press vulcanization and secondary oven calcining under standard vulcanization conditions to form a sheet with a thickness of 2 mm and measured according to JIS-K6251.

[0108] Tensile strength at break (Tb) and tensile elongation at break (Eb)>

[0109] <Vulcanization characteristics>

At the time of primary press vulcanization, a vulcanization curve at 160 ° C was obtained using JSR type chilastometer type II, minimum viscosity (ML), degree of vulcanization (MH), induction time (T10) and optimum vulcanization time ( T90).

[0110] Ku A Hardness>

Measure according to ASTM D2240. Specifically, measurement is performed using an A type analog hardness tester manufactured by Kobunshi Keiki Co., Ltd.

[0111] <Low Temperature Elasticity Recovery Test (TR Test)> Using a measuring device (TR test machine manufactured by Ueshima Seisakusho Co., Ltd.), measurement was performed in accordance with JIS-K6261, and 10% shrinkage temperature (TR10), 30% shrinkage temperature (TR30), 50% shrinkage temperature ( TR5 0), 70% shrinkage temperature (TR70) was determined.

[0112] <Rollability>

When the silicone cross-linked rubber and fluororubber were kneaded using an 8-inch open roll, the adhesion to the roll, the bloom of the silicone powder, and the surface skin of the kneaded product were visually observed and evaluated according to the following criteria.

(Bloom)

◯: Can be kneaded easily in 10 minutes or less without blooming silicone crosslinked rubber. Δ: Bloom of silicone crosslinked rubber is slightly seen, and the time required for kneading is 10 to 30 minutes.

X: The silicone cross-linked rubber blooms greatly, and it takes more than 30 minutes to knead. (Non-sticky)

◯: Rubber does not adhere to the roll surface.

X: Rubber adheres to the roll surface.

(Surface property)

◯: The surface of the rubber sheet after kneading is smooth.

X: The surface of the rubber sheet after kneading is smooth and rough.

[0113] Production Example 1 (Production of fluorinated compound)

Ethylenediamine 55g was dissolved in THF50g, and at room temperature,

[0114] [Chemical 8]

I—

— COOCH

(Where p = l)

lOOg was slowly added dropwise and stirred for 2 hours. Wash with water until the resulting THF solution is neutral, and remove the solvent. [0116] [Chemical 9]

[0117] (where P is 0 or any integer)

99.2 g was obtained.

[0118] Production Example 2 (Production of silicone crosslinked rubber powder 1)

100 g of silicone-crosslinked rubber powder having an epoxy group (Trefil E-601 Toray 'Dowco-One Silicone Co., Ltd.) was swollen in 800 g of tetrahydrofuran (THF). On the other hand, obtained in Production Example 1

[0119] [Chemical 10] T-J

I then 1 2 and 1 2

— C 1 N— CHCH _S NH

[0120] (where P is 0 or any integer)

7. After 5 g was dissolved in 80 g of THF, it was added dropwise to the previous solution and stirred at 70 ° C. After 18 hours, THF was removed by volatilization and dried under reduced pressure at 70 ° C. to obtain 110 g of silicone crosslinked rubber powder 1. From the elemental fluorine analysis, it was found that this silicone-crosslinked rubber powder 1 contained 2.4 wt% fluorine atoms. Also, according to the X-ray photoelectron analyzer (ESCA-7 50, manufactured by Shimadzu Corporation), the fluorine content in the region where the surface force of the particles is about 7 nm is 18.7% by weight and is unevenly distributed on the particle surface. I was strong.

[0121] Production Example 3 (Production of silicone crosslinked rubber powder 3)

100 g of silicone-crosslinked rubber powder having an epoxy group (Trefyl E-601 Toray 'Dauco Ijung' Silicone Co., Ltd.) was swollen in 800 g of tetrahydrofuran (THF). To the previous solution, 0.8 g of 2-aminoethanol was added dropwise and stirred at 70 ° C. After 2 hours, the solution was washed with water until neutrality, and THF was removed by volatilization, followed by drying under reduced pressure at 70 ° C. to obtain 98 g of silicone crosslinked rubber powder 2. Obtained silicone cross-linked rubber powder 2 50g Was swollen in THF500g

[0122] Meanwhile,

[0123] [Chemical 11] C F,

I-CH ₂ CF ₂ CF ₂ -t: OCFCF ₂

[0124] After dissolving 7 g in 30 g of THF, it was added dropwise to the previous solution and stirred at 70 ° C. After 18 hours, THF was volatilized and dried under reduced pressure at 70 ° C. to obtain 51 g of silicone crosslinked rubber powder 3. Elemental analysis, this silicone crosslinked rubber powder 3 2. comprise 1 wt ^_0/0 fluorine atom, Rukoto component force ivy. In addition, from the X-ray photoelectron analyzer (ESCA-750 manufactured by Shimadzu Corporation), the fluorine content in the region where the surface force of the particles is about 7 nm is 18.1% by weight and is unevenly distributed on the particle surface. I understood it.

[0125] Example 1

Silicone crosslinked rubber powder 1 29. 2 parts by weight and fluoro rubber (G902 made by Daikin Industries, Ltd.) 70. 8 parts by weight were kneaded using an 8-inch open roll. In addition, the silicone cross-linked rubber powder bloomed during roll kneading. To 100 parts by weight of the fluororubber / silicone crosslinked rubber composite thus obtained, 20 parts by weight of MT carbon black (manufactured by Cancarb Ltd), 4 parts by weight of triaryl isocyanate (manufactured by TAIC Nippon Kaisei Co., Ltd.), and 2, 5 Dimethyl-2,5 Di (t-butylperoxy) hexane (Perhexa 25B manufactured by Nippon Oil & Fats Co., Ltd.) 1. Add 5 parts by weight and knead using an 8-inch open roll. Press vulcanized at 160 ° C for 10 minutes to form a vulcanized rubber sheet. This vulcanized rubber sheet was subjected to secondary vulcanization for 4 hours in an oven at 180 ° C, and various physical properties were measured. The results are shown in Table 1.

[0126] Example 2

Using the same method as in Example 1, 39.2 parts by weight of silicone crosslinked rubber powder 3 and 70.8 parts by weight of fluoro rubber (G902, Daikin Industries, Ltd.) were kneaded. In the same manner as in Example 1, roll blending can be easily performed, and the silicone cross-linked rubber powder bloomed during roll kneading. Furthermore, using the same method as in Example 1, A vulcanized rubber sheet was molded and various physical properties were measured. The results are shown in Table 1.

[0127] Example 3

Using the same method as in Example 1, 29.2 parts by weight of silicone crosslinked rubber powder 12 and 70.8 parts by weight of fluoro rubber (LT303, Daikin Industries, Ltd.) were kneaded. In the same manner as in Example 1, roll blending can be easily performed, and the silicone cross-linked rubber powder bloomed during roll kneading. Furthermore, using the same method as in Example 1, a vulcanized rubber sheet was molded and various physical properties were measured. The results are shown in Table 1.

[0128] Comparative Example 1

Fluororubber (G902 manufactured by Daikin Industries, Ltd.) 100 parts by weight, MT carbon black (manufactured by Cancarb Ltd) 20 parts by weight, triallyl isocyanate (TAIC Nippon Iseisei Co., Ltd.) 4 parts by weight, and 2,5 Dimethyl-2,5 Di (t-butylperoxy) hexane (Perhexa 25B, Nippon Oil & Fats Co., Ltd.) 1. Add 5 parts by weight and knead using an 8-inch open roll. Press vulcanized at 160 ° C for 10 minutes to form a vulcanized rubber sheet. This vulcanized rubber sheet was subjected to secondary vulcanization for 4 hours in an oven at 180 ° C, and various physical properties were measured. The results are shown in Table 1.

[0129] Comparative Example 2

Using a method similar to that in Comparative Example 1, a fluororubber (LT303, Daikin Industries, Ltd.) vulcanized rubber sheet was molded and various physical properties were measured. The results are shown in Table 1.

[0130] Comparative Example 3

Silicone rubber (KE-551—U Shin-Etsu Silicone) 100 parts by weight, C-3 (Shin-Etsu Silicone Dicumyl Peroxide 20% by weight) 3 weights are added and kneaded using an 8-inch open roll. Then, this kneaded product was press vulcanized at 160 ° C. for 10 minutes to form a vulcanized rubber sheet. This vulcanized rubber sheet was subjected to secondary vulcanization for 4 hours in an oven at 180 ° C, and various physical properties were measured. The results are shown in Table 1.

[0131] Comparative Example 4

Silicone cross-linked rubber powder without fluorine-containing substituents (Trefil E-604 Toray 'Dow Co., Ltd. made by Silicone Co., Ltd.) 29.2 parts and fluoro rubber (G902 made by Daikin Industries, Ltd.) 70. 8 parts by weight Was kneaded using an 8-inch open roll. Winding was very difficult, and many silicone crosslinked rubber powder blooms were observed during roll kneading. 100 parts by weight of the fluororubber / silicone crosslinked rubber composite thus obtained, 20 parts by weight of MT carbon black (manufactured by Cancarb Ltd), 4 parts by weight of triallyl isocyanate (manufactured by TAIC Nippon Kasei Co., Ltd.), and 2, 5 Dimethyl-2,5 di (t-butylperoxy) hexane (Perhexa 25B manufactured by Nippon Oil & Fats Co., Ltd.) 1. Add 5 parts by weight and knead using an 8-inch open roll. Press vulcanized with C for 10 minutes to form a vulcanized rubber sheet. This vulcanized rubber sheet was subjected to secondary vulcanization in an oven at 180 ° C for 4 hours, and various physical properties were measured. The results are shown in Table 1.

[0132] Comparative Example 5

Silicone crosslinked rubber powder without fluorine-containing substituents (Narpow VP—601 SI NOPEC) 29. 2 parts by weight and fluororubber (LT303 made by Daikin Industries) 70. 8 parts by weight with 8 inch open roll When used and kneaded, roll blending was easy, and the silicone crosslinked rubber powder did not bloom during roll kneading, but the surface skin of the kneaded product was rough. 100 parts by weight of the fluororubber Z silicone crosslinked rubber composite thus obtained, 20 parts by weight of MT carbon black (manufactured by Cancarb Ltd), 4 parts by weight of triallyl isocyanate (manufactured by TAIC Nippon Kaisei Co., Ltd.) Parts, and 2,5 dimethyl-2,5 di (t-butylperoxy) hexane (TAIC manufactured by NOF Corporation) 1. After adding 5 parts by weight and kneading using an 8-inch open roll, this kneaded product Was vulcanized for 10 minutes at 160 ° C to form a vulcanized rubber sheet. This vulcanized rubber sheet was subjected to secondary vulcanization in an oven at 180 ° C. for 4 hours, and each physical property was measured. The results are shown in Table 1.

[0133] [Table 1] table 1

FIGS. 1 and 2 show scanning electrons obtained by freezing the rubber sheet after secondary vulcanization of Example 1 and Comparative Example 4 in liquid nitrogen and breaking in liquid nitrogen, respectively. It was observed with a microscope. Fig. 2 shows the strength of spherical materials with a diameter of several micrometers, that is, silicone-crosslinked rubber. This is because silicone-crosslinked rubber and fluororubber are not co-crosslinked. This is probably due to the appearance of the rubber Z fluoro rubber interface. On the other hand, in FIG. I can't see it anymore. This is presumably because the silicone-crosslinked rubber and fluororubber are co-crosslinked, and therefore the interface between the silicone-crosslinked rubber and fluororubber hardly appears when fractured in a frozen state.

Industrial applicability

In the present invention, a curable composition having excellent compatibility between a silicone crosslinked rubber and a fluororubber can be obtained by using a curable composition comprising a silicone crosslinked rubber having a fluorine-containing substituent and a fluororubber. Further, by cross-linking the curable composition, a molded product having excellent oil resistance, heat resistance, cold resistance, low hardness, amine resistance, chemical resistance and solvent resistance can be obtained.

Claims

The scope of the claims

[1] A curable composition comprising a silicone crosslinked rubber having a fluorine-containing substituent and a fluororubber.

[2] The curable composition according to claim 1, wherein the silicone-crosslinked rubber having a fluorine-containing substituent is capable of peroxide crosslinking, polyol crosslinking, or polyamine crosslinking.

[3] The fluorine-containing substituent has the general formula (1):

[Chemical 1] j- R _f ^f m R _f ^{f 2} -— n (i)

(Wherein x ¹ is an iodine atom, bromine atom, hydrogen atom or fluorine atom,

Each is a fluorine-containing alkylene group having 1 to 2000 carbon atoms (however, R ¹ and R ² are different)

f f

M is an integer of 0 or 1, and n is 0 or 1. Where m + n≥l o)

The curable composition according to claim 1 or 2, which is a fluorine-containing substituent represented by formula (1).

[4] A molded article obtained by crosslinking the curable composition according to any one of claims 1 to 3.