JP6584542B2 - Tire manufacturing method - Google Patents

Description

  The present invention relates to a tire manufacturing method.

2. Description of the Related Art Conventionally, a method of using a vulcanizing apparatus including a vulcanizing bladder that expands and contracts by supplying or discharging a heating medium such as steam supplied from the outside is known for vulcanizing a tire.
The vulcanization bladder is disposed on the inner peripheral side of an unvulcanized tire (green tire) set in the mold of the vulcanizer, and is heated and supplied with a heating medium at the start of vulcanization, before being vulcanized. The outer peripheral surface of the tire is pressed in the direction of the molding surface of the mold on which a predetermined pattern is formed. An unvulcanized tire that is pressed in the mold direction by the vulcanizing bladder is maintained in a state of being pressurized and heated through the vulcanizing bladder for a predetermined time until the predetermined degree of vulcanization is reached. The vulcanization proceeds gradually.

  Here, with respect to the vulcanization bladder, particularly from the viewpoint of improving durability, heat aging resistance and the like are required, and a technique for optimizing the composition of the material constituting the vulcanization bladder (see, for example, Patent Document 1) .)It has been known.

Japanese Patent Laid-Open No. 10-287779

Furthermore, in recent years, the vulcanization treatment using the vulcanization bladder is not limited to the above-mentioned problem of heat aging resistance, but is caused by the transfer of sulfur from the inner surface of the unvulcanized tire to the vulcanization bladder. The problem of deterioration due to curing of sulfur bladder has been known.
In particular, for an unvulcanized tire provided with a rubber member containing a high concentration of sulfur (hereinafter sometimes referred to as a “high concentration sulfur rubber member”) on the inner surface of the tire, Since the tendency of sulfur to shift to the vulcanization bladder appears remarkably, the curing of the vulcanization bladder is likely to proceed, the durability is lowered, and the life of the vulcanization bladder is shortened.

  In addition, when sulfur moves from the tire inner surface member to the vulcanizing bladder, the distribution of sulfur concentration in the tire thickness direction in the rubber member in contact with the vulcanizing bladder becomes non-uniform. There was a risk that the physical properties would change.

  Therefore, the object of the present invention is to effectively suppress the transfer of sulfur to the vulcanization bladder when vulcanizing an unvulcanized tire having a member containing a high concentration of sulfur on the tire inner surface. It is an object of the present invention to provide a tire manufacturing method capable of manufacturing a tire having physical properties as intended without reducing the amount of sulfur during sulfurization.

The method for producing a tire according to the present invention includes a run-flat reinforcing rubber that is a high-concentration sulfur rubber member made of a rubber composition containing 1.0 part by mass or more of sulfur with respect to 100 parts by mass of a rubber component, and at least a part of the innermost surface of the tire. Including a vulcanization step of vulcanizing an unvulcanized tire prepared for use in the vulcanization step, wherein a vulcanization bladder made of a rubber composition for a bladder containing 50 to 100% by mass of fluororubber is used. .
By providing the said structure, the transfer | transfer of the sulfur from the high concentration sulfur rubber member at the time of vulcanization | cure to the bladder for vulcanization | cure can be suppressed effectively.

  In the tire manufacturing method of the present invention, it is preferable that the rubber composition for bladders contains substantially 100% by mass of fluororubber. This is because sulfur migration from the high-concentration sulfur rubber member during vulcanization to the vulcanization bladder can be more effectively suppressed.

  Further, in the tire manufacturing method of the present invention, the fluororubber contains a structural unit (VdF unit) derived from vinylidene fluoride, hexafluoropropylene (HFP), 2,3,3,3-tetrafluoropropylene and perfluorocarbon. A vinylidene fluoride fluororubber having a structural unit derived from at least one selected from the group consisting of fluoro (alkyl vinyl ethers) (PAVE), and a VdF unit, HFP, 2, 3 in the fluororubber , 3,3-tetrafluoropropylene, and a molar ratio with a structural unit derived from at least one selected from the group consisting of PAVE is preferably 50/50 to 78/22, and the fluororubber is a rubber. In a dynamic viscoelasticity test using a process analyzer (RPA) (measurement frequency: 1 Hz, measurement temperature: 100 ° C.) Difference δG ′ (G ′ (1%) − G ′ (100%) between the shear elastic modulus G ′ (1%) at a dynamic strain of 1% and the shear elastic modulus G ′ (100%) at a dynamic strain of 100% )) Is more preferably 120 kPa or more and 3000 kPa or less. This is because sulfur migration from the high-concentration sulfur rubber member during vulcanization to the vulcanization bladder can be more effectively suppressed.

  Furthermore, in the tire manufacturing method of the present invention, it is preferable that the bladder rubber composition further includes at least one selected from the group consisting of fatty oils and aliphatic hydrocarbons. This is because the tensile break elongation and strength of the vulcanizing bladder at high temperatures can be improved.

  Furthermore, in the tire manufacturing method of the present invention, the fatty oil is preferably at least one selected from the group consisting of non-drying oils and semi-drying oils. This is because it is possible to obtain a rubber cross-linked product for bladder that exhibits a large tensile breaking elongation and low hardness.

In the tire manufacturing method of the present invention, the bladder rubber composition further contains carbon black, and the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 25 to 180 m ² / g, and dibutyl phthalate (DBP) The oil absorption is preferably 40 to 180 ml / 100 g. This is because the tensile break elongation and strength of the vulcanizing bladder at high temperatures can be improved.

The tire of the present invention is a tire obtained by the above-described tire manufacturing method of the present invention, and is characterized in that run-flat reinforcing rubber is exposed on at least a part of the innermost surface of the tire.
By providing the above configuration, the obtained tire can have the desired physical properties without reducing the amount of sulfur during vulcanization.

  According to the present invention, when vulcanizing an unvulcanized tire provided with a member containing sulfur at a high concentration on the inner surface of the tire, it is possible to effectively suppress the transfer of sulfur to the vulcanizing bladder. It is possible to provide a tire manufacturing method capable of manufacturing a tire having physical properties as intended without reducing the amount of sulfur.

It is sectional drawing of the tire width direction which showed typically the state at the time of vulcanizing an unvulcanized tire with a vulcanizing device provided with a vulcanizing bladder. It is the graph which showed the result of having measured the sulfur amount (%) in the depth direction from the tire innermost surface using the scanning electron microscope and the electronic probe microanalyzer about the sample of the vulcanized tire in an Example.

The tire manufacturing method and the tire according to one embodiment of the present invention will be specifically described below.
Here, FIG. 1 schematically shows a state in which an unvulcanized tire is vulcanized by a vulcanizing apparatus including a vulcanizing bladder.
The vulcanizing device 40 used in the tire manufacturing method of the present invention is not particularly limited except that it includes a vulcanizing bladder 10 and a mold 30 for molding an unvulcanized tire. Can be used.

And the manufacturing method of the tire of this invention is a high concentration sulfur rubber member (not shown) which consists of a rubber composition which contains 1.0 mass part or more of sulfur with respect to 100 mass parts of rubber components, as shown in FIG. ) Is vulcanized to the unvulcanized tire 20 provided on at least a part of the innermost tire inner surface 20a. In this vulcanization process, the rubber composition for bladders containing 50 to 100% by mass of fluoro rubber is used. The vulcanizing bladder 10 is used.
By forming the vulcanizing bladder 10 from a rubber composition for bladders containing 50 to 100% by mass of fluororubber, the tire innermost surface 20a of the unvulcanized tire 20 (the surface in contact with the vulcanizing bladder). It is possible to effectively suppress the migration of sulfur from the high concentration sulfur rubber member containing the provided sulfur at a high concentration (1.0 part by mass or more with respect to 100 parts by mass of the rubber component). As a result, it is possible to manufacture a tire having the desired physical properties without reducing the amount of sulfur in the unvulcanized tire during vulcanization. Furthermore, since sulfur in the unvulcanized tire 20 does not migrate to the vulcanizing bladder 10 during the vulcanization, it is possible to prevent curing of the vulcanizing bladder and extend the service life.

(Unvulcanized tire)
In the method for producing a tire according to the present invention, as a non-vulcanized tire, a high-concentration sulfur rubber member made of a rubber composition containing 1.0 part by mass or more of sulfur with respect to 100 parts by mass of a rubber component is at least part of the innermost surface of the tire. Use unvulcanized tires.

Here, the high-concentration sulfur rubber member is made of a rubber composition containing 1.0 part by mass or more of sulfur with respect to 100 parts by mass of the rubber component, and is located on at least a part of the tire innermost surface of the unvulcanized tire. If it is a thing, it will not specifically limit, A various member is mentioned. For example, chafer rubber, inner liner rubber, run flat reinforcing rubber (side reinforcing rubber), toe rubber and the like. Among them, the high-concentration sulfur rubber member is chafer rubber and / or run flat reinforcing rubber. Normally, these members have a high sulfur concentration among the members provided on the innermost surface of the unvulcanized tire, and the sulfur transfer from the high concentration sulfur rubber member during vulcanization, which is an effect of the present invention, to the vulcanizing bladder. This is because the suppression effect can be exhibited more remarkably.
As for the tire in which the run-flat reinforcing rubber is located on the innermost surface of the tire, for example, as shown in FIG. 2 of Japanese Patent Application Laid-Open No. 2014-31147, one inner liner rubber in a portion corresponding to the tire side portion. It is possible to take a configuration excluding parts. By adopting such a configuration, it is possible to prevent the curing of the vulcanization bladder and achieve the tire performance in accordance with the blending concept while obtaining the effect of reducing the tire weight and improving the ride comfort in the run-flat tire. .

Further, the sulfur concentration in the rubber composition constituting the high-concentration sulfur rubber member requires 1.0 part by mass or more with respect to 100 parts by mass of the rubber component, and preferably 1.5 parts by mass or more, The amount is more preferably 3.0 parts by mass or more, and particularly preferably 5.0 parts by mass or more. This is because when the sulfur concentration in the rubber composition is less than 1.0 part by mass with respect to 100 parts by mass of the rubber component, curing of the vulcanization bladder and non-uniform sulfur concentration in the rubber cannot be effectively suppressed. .
On the other hand, the upper limit of the sulfur concentration in the rubber composition is not particularly limited, but is preferably 10 parts by mass or less and more preferably 8 parts by mass or less with respect to 100 parts by mass of the rubber component. When the sulfur concentration in the rubber composition is 10 parts by mass or less with respect to 100 parts by mass of the rubber component, curing of the vulcanization bladder and non-uniformity of the sulfur concentration in the rubber can be more reliably suppressed. .

In addition, about the rubber composition which comprises the said high concentration sulfur rubber member, there is no limitation in particular except content of sulfur.
Moreover, about the rubber component contained in the said rubber composition, it can change suitably according to the objective and use of a high concentration sulfur rubber member. For example, the rubber component includes natural rubber (NR), polybutadiene rubber (BR), isoprene rubber (IR), styrene butadiene copolymer rubber (SBR), butyl rubber (IIR) and the like from the viewpoint of reinforcing properties. It is preferable to contain a diene rubber.

  Furthermore, about the rubber composition which comprises the said high concentration sulfur rubber member, the additive (other components) normally mix | blended with a rubber composition other than the rubber component and sulfur mentioned above can be included. For example, reinforcing fillers, anti-aging agents, vulcanization accelerators, crosslinking agents, vulcanization accelerators, silane coupling agents, glycerin fatty acid esters, softeners, stearic acid, ozone, which are commonly used in the rubber industry Additives such as deterioration inhibitors and surfactants can be appropriately blended.

  In addition, about the structure of the unvulcanized tire used for the manufacturing method of the tire of this invention, except the high concentration sulfur rubber member mentioned above, it does not specifically limit. Any unvulcanized tire can be used depending on the type of tire and the required performance.

(Bladder for vulcanization)
In the tire manufacturing method of the present invention, a vulcanizing bladder made of a rubber composition for bladders containing 50 to 100% by mass of fluororubber is used.
As described above, by constituting the vulcanization bladder from a rubber composition for bladders containing 50 to 100% by mass of fluoro rubber, it is possible to suppress the migration of sulfur from the high-concentration sulfur rubber member. .

-Fluorine rubber Here, the rubber composition for the bladder constituting the vulcanization bladder requires that the fluorine rubber is contained in an amount of 50 to 100% by mass, and the content of the fluorine rubber is 90 to 100% by mass. It is preferable that it is 95-100 mass%, and it is most preferable that it is substantially 100 mass%.
By containing 50 mass% or more of the fluoro rubber in the rubber composition for bladder, it is possible to improve the mold releasability and heat resistance of the bladder in addition to realizing a desired sulfur migration inhibiting effect.

Examples of the fluororubber include a structural unit derived from vinylidene fluoride (VdF unit), hexafluoropropylene (HFP), 2,3,3,3-tetrafluoropropylene, and perfluoro (alkyl vinyl ether) (PAVE). A structural unit derived from at least one selected from the group consisting of (hereinafter sometimes referred to as “second monomer unit”), and a vinylidene fluoride fluororubber having
In the fluororubber, the molar ratio of the VdF unit to the structural unit derived from at least one selected from the group consisting of HFP, 2,3,3,3-tetrafluoropropylene and PAVE is 50/50 to 78. / 22 is preferable.

When the ratio of the VdF unit and the second monomer unit of the fluororubber is in the above range, the vulcanization bladder obtained from the bladder rubber composition can realize a higher sulfur migration suppression effect. .
Here, the VdF unit / second monomer unit (molar ratio) is preferably 52/48 to 77/23, and more preferably 55/45 to 75/25.

  Further, the content of the VdF unit is preferably 50 mol% or more, more preferably 52 mol% or more, and further preferably 55 mol% or more with respect to all the structural units. The content of VdF units is preferably 78 mol% or less, more preferably 77 mol% or less, still more preferably 75 mol% or less, particularly preferably 74 mol% or less, and most preferably 70 mol% or less, based on the total structural units. preferable.

  Further, the content of the second monomer unit is preferably 22 mol% or more, more preferably 23 mol% or more, still more preferably 25 mol% or more, particularly preferably 26 mol% or more, based on the total structural unit, 30 mol% or more is most preferable. The content of the second monomer unit is also preferably 50 mol% or less, more preferably 48 mol% or less, still more preferably 45 mol% or less with respect to the total structural units.

  As the PAVE, perfluoro (methyl vinyl ether) (PMVE) and perfluoro (propyl vinyl ether) (PPVE) are preferable, and PMVE is particularly preferable.

  The second monomer is preferably at least one selected from the group consisting of hexafluoropropylene and 2,3,3,3-tetrafluoropropylene.

The rubber composition for bladders may contain a structural unit derived from another monomer in addition to the VdF and the second monomer. The other monomer other than VdF and the second monomer is not particularly limited as long as it is copolymerizable with VdF and the second monomer, and examples thereof include tetrafluoroethylene (TFE) and chlorotrifluoroethylene. (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, iodine-containing fluorinated vinyl ether, the following general formula (1):
CH ₂ = CFR _f (1)
(In the formula, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms) (1) (excluding 2,3,3,3-tetrafluoropropylene) Fluorine-containing monomers such as ethylene (Et), propylene (Pr), alkyl vinyl ether and other non-fluorine-containing monomers, monomers that give crosslinkable groups (cure sites), and reactive emulsifiers Among these monomers and compounds, one or a combination of two or more can be used.

Moreover, as said other monomer, general formula (2):
CF ₂ = CFOCF ₂ OR _f ¹ (2)
(In the formula, R _f ¹ is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or 2 to 3 carbon atoms containing 1 to 3 oxygen atoms. 6 per linear or branched perfluorooxyalkyl groups), CF ₂ = CFOCF ₂ OCF ₃ , CF ₂ = CFOCF ₂ OCF ₂ CF ₃ , or CF ₂ = CFOCF ₂ OCF ₂ CF ₂ OCF ₃ is preferably used.

The fluorine-containing monomer (1) represented by the general formula (1) is preferably a monomer in which R _f is a linear fluoroalkyl group, and R _f is a linear perfluoroalkyl group. Monomers are more preferred. R _f preferably has 1 to 6 carbon atoms. Examples of the fluorine-containing monomer (1) represented by the formula (1) include CH ₂ = CFCF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₂ CF _{3 and the} like. Is mentioned.

  Moreover, as the rubber composition for bladder, a copolymer obtained by copolymerizing a monomer that gives a crosslinkable group to the VdF and the second monomer can be suitably used. The monomer that gives the crosslinkable group may be any monomer that can introduce an appropriate crosslinkable group depending on the production method and the crosslinking system, such as an iodine atom, a bromine atom, a carbon-carbon double bond, a cyano group. , A known polymerizable compound containing a carboxyl group, a hydroxyl group, an amino group, an ester group and the like, a chain transfer agent and the like.

であり、ｎは0〜5の整数）
ＣＦ₂＝ＣＦＣＦ₂（ＯＣＦ（ＣＦ₃）ＣＦ₂）_m
（ＯＣＨ₂ＣＦ₂ＣＦ₂）_nＯＣＨ₂ＣＦ₂−Ｘ¹ （７）
（式中、ｍは0〜5の整数、ｎは0〜5の整数）
ＣＦ₂＝ＣＦＣＦ₂（ＯＣＨ₂ＣＦ₂ＣＦ₂）_m
（ＯＣＦ（ＣＦ₃）ＣＦ₂）_nＯＣＦ（ＣＦ₃）−Ｘ¹ （８）
（式中、ｍは0〜5の整数、ｎは0〜5の整数）
ＣＦ₂＝ＣＦ（ＯＣＦ₂ＣＦ（ＣＦ₃））_mＯ（ＣＦ₂）_n−Ｘ¹ （９）
（式中、ｍは0〜5の整数、ｎは1〜8の整数）
ＣＦＸ¹＝ＣＦ（ＯＣＦＸ¹ＣＦ（ＣＦＸ¹））Ｘ¹−Ｘ¹ （１０）
（式中、ｍは1〜5の整数）
ＣＦＸ¹＝ＣＦＯＣＦＸ¹（ＣＦ（ＣＦＸ¹）ＯＣＦ₂）Ｘ¹ＣＦ（−Ｘ¹）ＣＦＸ¹ （１１）
（式中、ｎは1〜4の整数）
ＣＦ₂＝ＣＦＯ（ＣＦ₂）_nＯＣＦ（ＣＦ₃）−Ｘ¹ （１２）
（式中、ｎは2〜5の整数）
ＣＦ₂₌ＣＦＯ（ＣＦ₂）_n−（Ｃ₆Ｈ₄）−Ｘ¹ （１３）
（式中、ｎは1〜6の整数）
ＣＦ₂＝ＣＦ（ＯＣＦ₂ＣＦ（ＣＦ₃））_nＯＣＦ₂ＣＦ（ＣＦ₃）−Ｘ¹ （１４）
（式中、ｎは1〜2の整数）
ＣＨ₂＝ＣＦＣＦ₂Ｏ（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）_nＣＦ（ＣＦ₃）−Ｘ¹ （１５）
（式中、ｎは0〜5の整数）、
ＣＦ₂＝ＣＦＯ（ＣＦ₂ＣＦ（ＣＦ₃）Ｏ）_m（ＣＦ₂）_n−Ｘ¹ （１６）
（式中、ｍは0〜5の整数、ｎは1〜3の整数）
ＣＨ₂＝ＣＦＣＦ₂ＯＣＦ（ＣＦ₃）ＯＣＦ（ＣＦ₃）−Ｘ¹ （１７）
ＣＨ₂＝ＣＦＣＦ₂ＯＣＨ₂ＣＦ₂−Ｘ¹ （１８）
ＣＦ₂＝ＣＦＯ（ＣＦ₂ＣＦ（ＣＦ₃）Ｏ）_mＣＦ₂ＣＦ（ＣＦ３）−Ｘ¹ （１９）
（式中、ｍは0以上の整数）
ＣＦ₂＝ＣＦＯＣＦ（ＣＦ₃）ＣＦ₂Ｏ（ＣＦ₂）_n−Ｘ¹ （２０）
（式中、ｎは1以上の整数）
ＣＦ₂＝ＣＦＯＣＦ₂ＯＣＦ₂ＣＦ（ＣＦ₃）ＯＣＦ₂−Ｘ¹ （２１）
ＣＨ₂＝ＣＨ−（ＣＦ₂）_nＸ¹ （２２）
（式中、ｎは2〜8の整数）
（前記一般式（５）〜（２２）中、Ｘ¹は前記と同様）
で表されるヨウ素含有モノマー、臭素含有モノマーなどが挙げられ、これらをそれぞれ単独で、又は任意に組合わせて用いることができる。 As a preferable monomer that gives the crosslinkable group,
The following general formula (3):
CY ¹ ₂ = CY ² R _f ² X ¹ (3)
Wherein Y ¹ and Y ² are the same or different and are a fluorine atom, a hydrogen atom or CH ₃ ; R _f ² may have one or more ether bonds and has an aromatic ring. Or a linear or branched fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms; X ¹ is an iodine atom or a bromine atom)
The compound shown by these is mentioned. Specifically, for example, the following general formula (4):
CY ¹ ₂ = CY ² Rf ³ CHR ¹ -X ¹ (4)
(In the formula, Y ¹ , Y ² and X ¹ are the same as above, and Rf ³ may have one or more ether bonds, and a part or all of the hydrogen atoms are substituted with fluorine atoms. Linear or branched fluorine-containing alkylene group, that is, a linear or branched fluorine-containing alkylene group in which part or all of the hydrogen atoms are substituted with fluorine atoms, or part or all of the hydrogen atoms are substituted with fluorine atoms A linear or branched fluorine-containing oxyalkylene group, or a linear or branched fluorine-containing polyoxyalkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms; R ¹ is a hydrogen atom or methyl Base)
Iodine-containing monomer, bromine-containing monomer represented by the following general formulas (5) to (22):
CY ⁴ ₂ = CY ⁴ (CF ₂ ) _n −X ¹ (5)
Wherein Y ⁴ is the same or different and is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8.
^{_{CF 2 = CFCF 2 R f 4}} -X 1 (6)
(Where

And n is an integer from 0 to 5)
CF ₂ = CFCF ₂ (OCF (CF ₃ ) CF ₂ ) _{m
(OCH 2 CF 2 CF 2)} n OCH 2 CF 2 -X 1 (7)
(Where m is an integer from 0 to 5 and n is an integer from 0 to 5)
CF ₂ = CFCF ₂ (OCH ₂ CF ₂ CF ₂ ) _m
(OCF (CF ₃ ) CF ₂ ) _n OCF (CF ₃ ) -X ¹ (8)
(Where m is an integer from 0 to 5 and n is an integer from 0 to 5)
_{CF 2 = CF (OCF 2 CF} (CF 3)) m O (CF 2) n -X 1 (9)
(Where m is an integer from 0 to 5, n is an integer from 1 to 8)
CFX ¹ = CF (OCFX ¹ CF (CFX ¹ )) X ¹ −X ¹ (10)
(Where m is an integer from 1 to 5)
CFX ¹ = CFOCFX ¹ (CF (CFX ¹ ) OCF ₂ ) X ¹ CF (−X ¹ ) CFX ¹ (11)
(Where n is an integer from 1 to 4)
_{CF 2 = CFO (CF 2)} n OCF (CF 3) -X 1 (12)
(Where n is an integer from 2 to 5)
_{CF 2 = CFO (CF 2)} n - (C 6 H 4) -X 1 (13)
(Where n is an integer from 1 to 6)
_{CF 2 = CF (OCF 2 CF} (CF 3)) n OCF 2 CF (CF 3) -X 1 (14)
(Where n is an integer from 1 to 2)
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) n CF (CF 3) -X 1 (15)
(Where n is an integer from 0 to 5),
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 1 (16)
(Where m is an integer from 0 to 5, n is an integer from 1 to 3)
_{CH 2 = CFCF 2 OCF (CF} 3) OCF (CF 3) -X 1 (17)
_{CH 2 = CFCF 2 OCH 2 CF} 2 -X 1 (18)
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m CF 2 CF (CF3) -X 1 (19)
(Where m is an integer greater than or equal to 0)
_{CF 2 = CFOCF (CF 3)} CF 2 O (CF 2) n -X 1 (20)
(Where n is an integer of 1 or more)
_{CF 2 = CFOCF 2 OCF 2 CF} (CF 3) OCF 2 -X 1 (21)
_{CH 2 = CH- (CF 2)} n X 1 (22)
(Where n is an integer from 2 to 8)
(In the general formulas (5) to (22), X ¹ is the same as above)
The iodine-containing monomer represented by these, the bromine-containing monomer, etc. are mentioned, These can be used individually or in arbitrary combinations, respectively.

（式中、ｍは１〜５の整数であり、ｎは0〜3の整数）
で表されるヨウ素含有フッ素化ビニルエーテルが好ましく挙げられ、より具体的には、

等が挙げられるが、これらの中でも、ＩＣＨ₂ＣＦ₂ＣＦ₂ＯＣＦ＝ＣＦ₂が好ましい。
前記一般式（５）で示されるヨウ素含有モノマー又は臭素含有モノマーとしてより具体的には、ＩＣＦ₂ＣＦ₂ＣＦ＝ＣＨ₂、Ｉ（ＣＦ₂ＣＦ₂）₂ＣＦ＝ＣＨ₂が好ましく挙げられる。
前記一般式（９）で示されるヨウ素含有モノマー又は臭素含有モノマーとしてより具体的には、Ｉ（ＣＦ₂ＣＦ₂）₂ＯＣＦ＝ＣＦ₂が好ましく挙げられる。
前記一般式（２２）で示されるヨウ素含有モノマー又は臭素含有モノマーとしてより具体的には、ＣＨ₂＝ＣＨＣＦ₂ＣＦ₂Ｉ、Ｉ（ＣＦ₂ＣＦ₂）₂ＣＨ＝ＣＨ₂が好ましく挙げられる。 Examples of the iodine-containing monomer or bromine-containing monomer represented by the general formula (4) include the following general formula (23):

(In the formula, m is an integer of 1 to 5, and n is an integer of 0 to 3)
Preferred examples include iodine-containing fluorinated vinyl ethers represented by:

Among them, ICH ₂ CF ₂ CF ₂ OCF═CF ₂ is preferable among these.
More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the general formula (5) include ICF ₂ CF ₂ CF═CH ₂ and I (CF ₂ CF ₂ ) ₂ CF═CH ₂ .
More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the general formula (9) include I (CF ₂ CF ₂ ) ₂ OCF═CF ₂ .
More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the general formula (22) include CH ₂ ═CHCF ₂ CF ₂ I and I (CF ₂ CF ₂ ) ₂ CH═CH ₂ .

Further, the ^{formula: R 2 R 3 C = CR} 4 -Z-CR 5 = CR 6 R 7
(In the formula, R ² , R ³ , R 4, R ⁵ , R ⁶ and R ⁷ are the same or different, and all are H or an alkyl group having 1 to 5 carbon atoms; Bis-olefin compounds which may contain oxygen atoms, preferably at least partially fluorinated alkylene or cycloalkylene groups having 1 to 18 carbon atoms, or (per) fluoropolyoxyalkylene groups) are also crosslinkable. Preferred as a monomer for providing a group. In the present specification, “(per) fluoropolyoxyalkylene group” means “fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group”.

Z is preferably a (per) fluoroalkylene group having 4 to 12 carbon atoms, and R ² , R ³ , R 4, R ⁵ , R ⁶ and R ⁷ are preferably hydrogen atoms.
Here, when Z is a (per) fluoropolyoxyalkylene group, the formula:
_{- (Q) p -CF 2 O-} (CF 2 CF 2 O) m - (CF 2 O) n -CF 2 - (Q) p -
(In the formula, Q is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 2 to 10 carbon atoms, p is 0 or 1, m and n have an m / n ratio of 0.2 to 5 and (Per) fluoropolyoxyalkylene group is preferably an (per) fluoropolyoxyalkylene group represented by the following formula: (per) fluoropolyoxyalkylene group having a molecular weight of 500 to 10,000, preferably 1000 to 4000. In this formula, Q is preferably selected from —CH ₂ OCH ₂ — and —CH ₂ O (CH ₂ CH ₂ O) _s CH ₂ — (s = 1 to 3).

Preferred bisolefins include
_{CH 2 = CH- (CF 2)} 4 -CH = CH 2,
_{CH 2 = CH- (CF2) 6} -CH = CH 2,
^{_{Formula: CH 2 = CH-Z 1}} -CH = CH 2
(In the formula, Z ¹ is —CH ₂ OCH ₂ —CF ₂ O— (CF ₂ CF ₂ O) _m — (CF ₂ O) _n —CF ₂ —CH ₂ OCH ₂ — (m / n is 0.5). )
Etc.
Among _{them, CH 2 = CH- (CF 2} ) 6 represented by -CH = CH ₂ 3,3,4,4,5,5,6,6,7,7,8,8- dodecafluoro -1 , 9-decadiene is preferred.

  When the rubber composition for bladder contains structural units derived from VdF and other monomers other than the second monomer, the content is 0 to 40 mol% with respect to 100 mol% of all structural units. It is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, particularly preferably 0 to 10 mol%.

Thus, although the said rubber composition for bladders may contain the structural unit derived from other monomers other than VdF and a 2nd monomer, the rubber | gum for bladders obtained from the fluororubber composition of this invention From the viewpoint of more effectively increasing the tensile properties of the crosslinked product at a high temperature, it is preferable that the rubber composition for bladders does not contain a structural unit derived from another monomer. That is, it is one of the preferred embodiments of the present invention that the rubber composition for bladders is a binary copolymer composed only of VdF units and second monomer units.
The bladder rubber composition is at least one selected from the group consisting of a VdF / HFP copolymer, a VdF / 2,3,3,3-tetrafluoropropylene copolymer, and a VdF / PAVE copolymer. More preferably, the binary copolymer is at least one binary copolymer selected from the group consisting of VdF / HFP copolymer and VdF / 2,3,3,3-tetrafluoropropylene copolymer. Particularly preferred is a polymer.

The rubber composition for bladders preferably has a number average molecular weight Mn of 5000 to 500000, more preferably 10 000 to 500000, and particularly preferably 20000 to 500000.

  The bladder rubber composition can be produced by a conventional method such as emulsion polymerization, suspension polymerization, or solution polymerization. In particular, according to a polymerization method using an iodine (bromine) compound known as iodine (bromine) transfer polymerization, a fluororubber having a narrow molecular weight distribution can be produced.

  For example, when it is desired to lower the viscosity of the fluororubber composition, other fluororubbers may be blended with the fluororubber (A). Examples of other fluororubber include low molecular weight liquid fluororubber (number average molecular weight of 1000 or more), low molecular weight fluororubber having a number average molecular weight of about 10,000, and fluororubber having a number average molecular weight of about 100,000 to 200,000.

  Furthermore, from the viewpoint of workability, the fluororubber (A) preferably has a Mooney viscosity at 100 ° C. of 20 to 200, more preferably 30 to 180. Mooney viscosity is measured according to JIS K6300.

Carbon black Further, the rubber composition for bladder further includes carbon black in addition to the above-described fluororubber, and the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 25 to 180 m ² / g. Preferably there is. By including carbon black having a nitrogen adsorption specific surface area (N ₂ SA) of 25 to 180 m ² / g, it is possible to improve the tensile elongation at break and strength of the vulcanizing bladder at high temperatures.

Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite due to differences in manufacturing methods, and carbon black for rubber, carbon black for color, and conductive carbon black due to differences in use. Examples include all commercially available carbon blacks. Specifically, for example, as carbon black for rubber, SAF-HS (N ₂ SA: 142 m ² / g, DBP: 130 ml / 100 g), SAF (N ₂ SA: 142 m ² / g, DBP: 115 ml / 100 g) N234 (N ₂ SA: 126 m ² / g, DBP: 125 ml / 100 g), ISAF (N ₂ SA: 119 m ² / g, DBP: 114 ml / 100 g), ISAF-LS (N ₂ SA: 106 m ² / g, DBP: 75 ml / 100 g), ISAF-HS (N ₂ SA: 99 m ² / g, DBP: 129 ml / 100 g), N339 (N ₂ SA: 93 m ² / g, DBP: 119 ml / 100 g), HAF-LS (N ₂ SA: 84 m ² / g, DBP 75 ml / 100 g), HAF-HS (N ₂ SA: 82 m ² / g, DBP: 126 ml / 100 g), HAF (N ₂ SA: 79 m ² / g, DBP: 101 ml / 100 g) _{, N351 (N 2 SA: 74m} 2 / g, DBP: 127ml / 100g), LI-HAF (N 2 SA: 74m 2 / g, DBP: 101ml / 100g), MAF-HS (N 2 SA: 56m 2 / g, DBP: 158 ml / 100 g), MAF (N ₂ SA: 49 m ² / g, DBP: 133 ml / 100 g), FEF-HS (N ₂ SA: 42 m ² / g, DBP: 160 ml / 100 g), FEF (N ₂ SA: 42 m ² / g, DBP: 115 ml / 100 g), SRF-HS (N ₂ SA: 32 m ² / g, DBP: 140 ml / 100 g), SRF-HS (N ₂ SA: 29 m ² / g, DBP: 152 ml / 100 g), GPF (N ₂ SA: 27 m ² / g, DBP: 87 ml / 100 g), SRF (N ₂ SA: 27 m ² / g, DBP : 68ml / 100g), etc., as the carbon black for color, HCC, MCC, RCC, LCC, HCF, MCF, RCF, LCF, LFF, and various acetylenes according to the classification of the Carbon Black Handbook 3rd edition (issued in 1995) Black etc. are mentioned. Among these, SAF-HS, SAF, N234, ISAF, ISAF-LS, ISAF-HS, N339, HAF-LS, HAF-HS, HAF, N351, LI-HAF, and MAF-HS are preferable. These carbon blacks may be used alone or in combination of two or more.

Among these, carbon black having a nitrogen adsorption specific surface area (N ₂ SA) of 25 to 180 m ² / g and a dibutyl phthalate (DBP) oil absorption of 40 to 180 ml / 100 g is preferable. It is done.
When the nitrogen adsorption specific surface area (N ₂ SA) is too small, the tensile elongation at break of the rubber crosslinked product for bladder (crosslinked product obtained by crosslinking the rubber composition for bladder) tends to decrease. From this viewpoint, The nitrogen adsorption specific surface area (N ₂ SA) is preferably 50 m ² / g or more, more preferably 70 m ² / g or more, further preferably 90 m ² / g or more, and particularly preferably 110 m ² / g or more. The upper limit is preferably 180 m ² / g from the viewpoint of easy availability.
If the dibutyl phthalate (DBP) oil absorption is too small, the tensile elongation at break of the rubber crosslinked product for bladder tends to decrease. From this viewpoint, 50 ml / 100 g or more is preferable, 60 ml / 100 g or more is more preferable, and 80 ml / 100 g. The above is more preferable, and 100 ml / 100 g or more is particularly preferable. The upper limit is preferably 175 ml / 100 g, more preferably 170 ml / 100 g from the viewpoint of easy availability.

  In the bladder rubber composition, the blending amount of carbon black is preferably 5 to 65 parts by mass with respect to 100 parts by mass of the fluororubber. If the amount of carbon black is too large, the hardness of the crosslinked rubber product for bladder tends to increase. If the amount is too small, the tensile elongation at break of the crosslinked rubber material for bladder tends to decrease. Furthermore, from the viewpoint of good physical property balance, 6 parts by mass or more is more preferable with respect to 100 parts by mass of fluororubber, more preferably 10 parts by mass or more, and from the point of good physical property balance, 55 parts by mass or less is more preferable, Less than or equal to 50 parts by weight is more preferred, 49 parts by weight or less is even more preferred, and 45 or less parts by weight is particularly preferred.

-At least one selected from the group consisting of fatty oils and aliphatic hydrocarbons. In addition to the fluororubber and carbon black described above, the rubber composition for bladders is selected from the group consisting of fatty oils and aliphatic hydrocarbons. It is preferable to further include at least one selected (hereinafter also referred to as “compound A”). By including the compound A in the rubber composition for bladder, the tensile break elongation and strength at high temperature of the vulcanizing bladder can be improved.

The compound (A) preferably has a boiling point of 250 ° C. or higher under atmospheric pressure and a melting point or freezing point of 15 ° C. or lower. Since the boiling point of the compound (A) under atmospheric pressure is within the above range, the compound (A) does not volatilize from the rubber cross-linked product for the bladder even in a high temperature environment, so that excellent thermal elongation is maintained. be able to.
In addition, the boiling point of the compound (A) under atmospheric pressure is preferably 280 ° C. or higher, and more preferably 300 ° C. or higher. The upper limit is not particularly limited, and may be 700 ° C. However, when there is no boiling point under atmospheric pressure, the temperature at which weight loss reaches 10% when heated from room temperature in an air atmosphere with a thermogravimetric measuring device is read as boiling point. When the melting point or freezing point of the compound (A) is within the above range, a vulcanization bladder having a high tensile elongation at break and low hardness can be obtained. Furthermore, the melting point or freezing point of the compound (A) is preferably 10 ° C. or lower, and more preferably 0 ° C. or lower. When the compound (A) having a melting point or a freezing point that is too high is used, it becomes a factor for increasing the hardness of the rubber crosslinked product for bladder. The lower limit is not particularly limited, and may be −100 ° C.

  Moreover, it is preferable that the compounding quantity of the said compound (A) is 1-30 mass parts with respect to 100 mass parts of said fluororubbers. When the compounding amount of the compound (A) is within the above range, it is possible to obtain a rubber crosslinked product for bladder that exhibits a large tensile elongation at break and low hardness. The compounding amount of the compound (A) is more preferably 3 parts by mass or more, and more preferably 5 parts by mass or more because a rubber cross-linked product for bladders having a higher tensile breaking elongation and lower hardness can be obtained. More preferably, more preferably 8 parts by mass or more, and more preferably 25 parts by mass or less from the viewpoint of obtaining a rubber crosslinked product for bladder having a practically sufficient tensile strength at break. The amount is more preferably at most 15 parts by mass, particularly preferably at most 15 parts by mass.

The aliphatic hydrocarbon has the general formula (X):
C _m H _n (X)
(In the formula, m is an integer, n is an even number of (2m + 2) or less)
Any one compound selected from the compound group represented by these, or a mixture consisting of two or more compounds. Examples of the aliphatic hydrocarbon include saturated aliphatic hydrocarbons and unsaturated aliphatic hydrocarbons. Specifically, examples of the saturated aliphatic hydrocarbon include liquid paraffin and naphthene, and examples of the unsaturated aliphatic hydrocarbon include terpenes. These aliphatic hydrocarbons may be used alone or in combination of two or more. Since it is chemically stable, it is preferable to use one or more aliphatic hydrocarbons classified as saturated aliphatic hydrocarbons, and it is more preferable to use liquid paraffin.

The compound (A) may contain a fatty oil having a boiling point of 250 ° C. or higher under atmospheric pressure and a melting point or freezing point of 15 ° C. or lower.
When the boiling point of the fatty oil under atmospheric pressure is within the above range, the fatty oil does not volatilize from the rubber cross-linked product for bladder even in a high temperature environment, and thus excellent hot elongation can be maintained. The boiling point of the fatty oil under atmospheric pressure is preferably 280 ° C. or higher, and more preferably 300 ° C. or higher. The upper limit is not particularly limited, and may be 700 ° C. However, when there is no boiling point under atmospheric pressure, the temperature at which weight loss reaches 10% when heated from room temperature in an air atmosphere with a thermogravimetric measuring device is read as boiling point.
When the melting point or freezing point of the fatty oil is within the above range, a rubber crosslinked product for bladder that exhibits large tensile elongation at break and low hardness can be obtained. The melting point or freezing point of the fatty oil is preferably 10 ° C. or lower, and more preferably 0 ° C. or lower. If a fatty oil having a melting point or a freezing point that is too high is used, it becomes a factor of increasing the hardness of the rubber crosslinked product for bladder. The lower limit is not particularly limited, and may be −100 ° C.

  The fatty oil is preferably at least one selected from the group consisting of non-drying oils and semi-drying oils, from the viewpoint of obtaining a rubber crosslinked product for bladders that exhibits a large tensile elongation at break and low hardness. . Non-drying oils include castor oil, rapeseed oil, peanut oil, olive oil and the like. Semi-drying oils include soybean oil, cottonseed oil, corn oil, sunflower oil and the like. Among these, the fatty oil is more preferably at least one selected from the group consisting of castor oil, rapeseed oil, peanut oil, soybean oil, and cottonseed oil, and more preferably castor oil.

  Furthermore, the blending amount of the fatty oil is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the fluororubber. When the blending amount of the fatty oil is within the above range, a rubber cross-linked product for bladder that exhibits a large tensile elongation at break and low hardness can be obtained. The blending amount of the fatty oil is more preferably 3 parts by mass or more, more preferably 5 parts by mass or more because a rubber cross-linked product for bladders having a higher tensile breaking elongation and lower hardness can be obtained. More preferably, it is more preferably 8 parts by mass or more, and from the viewpoint of obtaining a rubber crosslinked product for bladder having a practically sufficient tensile breaking strength, it is more preferably 25 parts by mass or less, and 20 parts by mass. More preferably, it is more preferably 15 parts by mass or less.

-Crosslinking agent, crosslinking accelerator In addition to the fluororubber, carbon black, and compound A, the rubber composition for bladders preferably further includes a crosslinking agent and a crosslinking accelerator. By including a crosslinking agent and a crosslinking accelerator in the rubber composition for bladder, the releasability of the vulcanizing bladder can be improved.

Here, the cross-linking agent and the cross-linking accelerator are a cross-linking system, the type of fluoro rubber to be cross-linked (for example, copolymer composition, presence / absence or type of cross-linkable group, etc.), specific use and usage form of the resulting cross-linked product, In addition, it can select suitably according to kneading | mixing conditions.
As the crosslinking system, for example, a peroxide crosslinking system, a polyol crosslinking system, a polyamine crosslinking system, an oxazole crosslinking system, a thiazole crosslinking system, an imidazole crosslinking system, a triazine crosslinking system, and the like can be employed.

  When cross-linking with a peroxide cross-linking system, since it has a carbon-carbon bond at the cross-linking point, a polyol cross-linking system having a carbon-oxygen bond at the cross-linking point and a polyamine cross-linking system having a carbon-nitrogen double bond. Compared with it, it is characterized by excellent chemical resistance and steam resistance.

  The peroxide crosslinking agent may be a peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. Specifically, for example, 1,1-bis (t -Butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t-butylperoxy) -p-diisopropylbenzene, α, α-bis (t-butylperoxy) -m-diisopropylbenzene, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, benzoyl peroxide, t-butylperoxybenzene t-butyl peroxybenzoate, t- butyl peroxy maleic acid, and organic peroxides such as t-butyl peroxy isopropyl carbonate. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane or 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 is preferable.

  In addition, in the peroxide crosslinking system, it is usually preferable to include a crosslinking accelerator. Examples of crosslinking accelerators for peroxide crosslinking agents, particularly organic peroxide crosslinking agents include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N '-M-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro -2-propenyl) -1,3,5-triazine-2,4,6-trione), tris (diallylamine) -S-triazine, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallyl Phosphoramide, N, N, N ′, N′-tetra Rylphthalamide, N, N, N ′, N′-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl Examples include phosphite. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  As a crosslinking accelerator used in the peroxide crosslinking system, a low self-polymerizable crosslinking accelerator can also be used. The low self-polymerizable cross-linking accelerator refers to a compound having low self-polymerizability unlike triallyl isocyanurate (TAIC), which is well known as a cross-linking accelerator.

で示されるトリメタリルイソシアヌレート（ＴＭＡＩＣ）、

で示されるｐ−キノンジオキシム（ｐ−ｑｕｉｎｏｎｅｄｉｏｘｉｍｅ）、

で示されるｐ，ｐ’−ジベンゾイルキノンジオキシム（ｐ，ｐ’−ｄｉｂｅｎｚｏｙｌｑｕｉｎｏｎｅｄｉｏｘｉｍｅ）、

で示されるマレイミド、

で示されるＮ−フェニレンマレイミド、

で示されるＮ，Ｎ’−フェニレンビスマレイミドなどがあげられる。
その中でも、好ましい低自己重合性架橋促進剤は、トリメタリルイソシアヌレート（ＴＭＡＩＣ）である。 As a low self-polymerization crosslinking accelerator, for example,

Trimethallyl isocyanurate (TMAIC) represented by

P-quinonedioxime represented by the formula:

P, p′-dibenzoylquinone dioxime represented by the formula (p, p′-dibenzoylquinonedioxime),

Maleimide represented by

N-phenylenemaleimide represented by

N, N′-phenylene bismaleimide represented by
Among them, a preferred low self-polymerizable crosslinking accelerator is trimethallyl isocyanurate (TMAIC).

Bis-olefins can also be used as the crosslinking accelerator used in the peroxide crosslinking system.
Examples of the bisolefin that can be used as a crosslinking accelerator include a formula:
^{R 2 R 3 C = CR 4} -Z-CR 5 = CR 6 R 7
(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and all are H or an alkyl group having 1 to 5 carbon atoms; Z is linear (linear Or a branched bisolefin which may contain an oxygen atom and which is an at least partially fluorinated alkylene or cycloalkylene group having 1 to 18 carbon atoms, or (per) fluoropolyoxyalkylene group) Is mentioned.

Z is preferably a C 4-12 perfluoroalkylene group, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably hydrogen atoms.

When Z is a (per) fluoropolyoxyalkylene group,
_{- (Q) p -CF 2 O-} (CF 2 CF 2 O) m - (CF 2 O) n -CF 2 - (Q) p -
(In the formula, Q is an alkylene or oxyalkylene group having 1 to 10 carbon atoms, p is 0 or 1, m and n have an m / n ratio of 0.2 to 5, and the (per) fluoropolyoxyalkylene. It is preferably a (per) fluoropolyoxyalkylene group represented by a group whose molecular weight is 500 to 10,000, preferably 1000 to 4000. In this formula, Q is preferably selected from —CH ₂ OCH ₂ — and —CH ₂ O (CH ₂ CH ₂ O) _s CH ₂ — (s = 1 to 3).

Preferred bisolefins include
_{CH 2 = CH- (CF 2)} 4 -CH = CH 2,
_{CH 2 = CH- (CF 2)} 6 -CH = CH 2,
^{_{Formula: CH 2 = CH-Z 1}} -CH = CH 2
(In the formula, Z ¹ represents —CH ₂ OCH ₂ —CF ₂ O— (CF ₂ CF ₂ O) _m — (CF ₂ O) _n —
CF ₂ —CH ₂ OCH ₂ — (m / n is 0.5))
Etc.
Among _{them, CH 2 = CH- (CF 2} ) 6 represented by -CH = CH ₂ 3,3,4,4,5,5,6,6,7,7,8,8- dodecafluoro -1 , 9-decadiene is preferred.

  Further, from the viewpoint of crosslinkability, the fluororubber suitable for the peroxide crosslinking system is preferably a fluororubber containing iodine atoms and / or bromine atoms as crosslinking points. The iodine atom and / or bromine atom content is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 3% by mass from the viewpoint of a good balance of physical properties.

  The amount of the peroxide crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 9 parts by weight, and particularly preferably 0.2 to 8 parts by weight with respect to 100 parts by weight of the fluororubber. . When the peroxide crosslinking agent is less than 0.01 part by mass, the crosslinking of the fluororubber tends not to proceed sufficiently, and when it exceeds 10 parts by mass, the balance of physical properties tends to decrease.

  The amount of the crosslinking accelerator is usually 0.01 to 10 parts by mass, preferably 0.1 to 9 parts by mass with respect to 100 parts by mass of the fluororubber. When the amount of the crosslinking accelerator is less than 0.01 parts by mass, the composition tends to be undercured, and when it exceeds 10 parts by mass, the physical property balance tends to be lowered.

  Further, the crosslinking by the polyol crosslinking system is preferable in that it has a carbon-oxygen bond at the crosslinking point, has a small compression set, and is excellent in moldability.

  As the polyol crosslinking agent, a compound conventionally known as a crosslinking agent for fluororubber can be used. For example, a polyhydroxy compound, particularly a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance.

  The polyhydroxy aromatic compound is not particularly limited, and examples thereof include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane. (Hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4 ′ -Dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2 , 2-Bis (4-hydroxyphenyl) Trafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.

  Among these, a polyhydroxy compound is preferable from the viewpoint that the compression set such as a rubber crosslinked product for bladder to be obtained is small and the moldability is excellent, and a polyhydroxy aromatic compound is more preferable because of excellent heat resistance, Bisphenol AF is more preferred.

  In addition, the polyol crosslinking system usually preferably contains a crosslinking accelerator. When a crosslinking accelerator is used, the crosslinking reaction can be promoted by promoting the formation of intramolecular double bonds in the dehydrofluorination reaction of the fluororubber main chain and the addition of polyhydroxy compounds to the generated double bonds. it can.

  As the polyol crosslinking accelerator, an onium compound is generally used. The onium compound is not particularly limited, and examples thereof include ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and monofunctional amine compounds. Of these, quaternary ammonium salts and quaternary phosphonium salts are preferred.

  The quaternary ammonium salt is not particularly limited, and examples thereof include 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5. 4.0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [. 5.4.0] -7-Undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [ 5.4.0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [ 4.0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5]. 4.0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl- 1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8- (3 -Phenylpropyl) -1,8-diazabicyclo [5.4.0] -7-undecenium chloride and the like. Among these, DBU-B is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

  The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, Examples thereof include tributyl-2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferred from the viewpoint of crosslinkability and physical properties of the crosslinked product.

  Further, as the crosslinking accelerator, a solid solution of quaternary ammonium salt or quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can be used.

  The blending amount of the polyol crosslinking agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the fluororubber. When the polyol crosslinking agent is less than 0.01 part by mass, the crosslinking of the fluororubber (A) tends not to proceed sufficiently, and when it exceeds 10 parts by mass, the balance of physical properties tends to decrease.

  The amount of the crosslinking accelerator is preferably 0.01 to 8 parts by mass, more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the fluororubber. When the crosslinking accelerator is less than 0.01 parts by mass, the crosslinking of the fluororubber (A) tends not to proceed sufficiently, and when it exceeds 8 parts by mass, the balance of physical properties tends to decrease.

  Furthermore, when it crosslinks by the said polyamine bridge | crosslinking, it has a carbon-nitrogen double bond in the bridge | crosslinking point, and it has the characteristics that it is excellent in the dynamic mechanical characteristic. However, the compression set tends to increase as compared with the case of cross-linking using a polyol cross-linking system or a peroxide cross-linking system.

  Examples of the polyamine-based crosslinking agent include polyamine compounds such as hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

  The compounding amount of the polyamine-based crosslinking agent is preferably 0.01 to 10 parts by mass, more preferably 0.2 to 7 parts by mass with respect to 100 parts by mass of the fluororubber. When the polyamine crosslinking agent is less than 0.01 parts by mass, the crosslinking of the fluororubber tends not to proceed sufficiently, and when it exceeds 10 parts by mass, the balance of physical properties tends to decrease.

  In the present invention, a peroxide crosslinking system or a polyol crosslinking system is preferable as the crosslinking system, and it is preferable to use a crosslinking agent suitable for each crosslinking system. Among these, it is more preferable to use a peroxide crosslinking type crosslinking agent.

Other components In addition to the above-described fluororubber, carbon black and compound A, cross-linking agent, and cross-linking accelerator, other components such as fillers, processing aids are included in the rubber composition for bladder. Agent, plasticizer, colorant, tackifier, adhesion assistant, acid acceptor, pigment, flame retardant, lubricant, light stabilizer, weathering stabilizer, antistatic agent, ultraviolet absorber, antioxidant, release agent In addition to foaming agents, fragrances, oils, and softening agents, other polymers such as polyethylene, polypropylene, polyamide, polyester, and polyurethane may be blended within a range that does not impair the effects of the present invention.

  Examples of the filler include metal oxides such as calcium oxide, titanium oxide, aluminum oxide, and magnesium oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; magnesium carbonate, aluminum carbonate, calcium carbonate, Carbonates such as barium carbonate; silicates such as magnesium silicate, calcium silicate, sodium silicate and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; synthetic hydrotalcite; molybdenum disulfide; Metal sulfides such as iron sulfide and copper sulfide; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon fluoride, calcium fluoride, coke, quartz fine powder, talc, mica powder, wollastonite , Carbon fiber, aramid fiber, each Whiskers, glass fibers, organic reinforcing agents, organic fillers, polytetrafluoroethylene, mica, silica, celite, clays, and others. Examples of the acid acceptor include calcium oxide, magnesium oxide, lead oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, hydrotalcite, and the like. These may be used alone or in combination of two or more. May be. These are kneading methods to be described later and may be added in any step, but are preferably added when the fluororubber and carbon black are kneaded in a closed kneader or a roll kneader.

Examples of the processing aid include higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; olein Higher fatty acid esters such as ethyl acid; Petroleum waxes such as carnauba wax and ceresin wax; Polyglycols such as ethylene glycol, glycerin and diethylene glycol; Aliphatic hydrocarbons such as petrolatum and paraffin; Silicone oils, silicone polymers, low molecular weight Examples thereof include polyethylene, phthalic acid esters, phosphoric acid esters, rosin, (halogenated) dialkylamines, surfactants, sulfone compounds, fluorine-based auxiliaries, and organic amine compounds.
Among them, the organic amine compound and the acid acceptor are preferable compounding agents from the viewpoint that the reinforcing property is improved by coexisting the fluororubber and the carbon black in a closed kneader or a roll kneader.

Preferred examples of the organic amine compound include a primary amine represented by R ¹ NH ₂ , a secondary amine represented by R ¹ R ² NH, and a tertiary amine represented by R ¹ R ² R ³ N. R ¹ , R ² and R ³ are the same or different, and all are preferably an alkyl group having 1 to 50 carbon atoms, and the alkyl group may contain a benzene ring as a functional group, a double bond, a conjugated double Bonds may be included. The alkyl group may be linear or branched.

  Examples of the primary amine include coconut amine, octylamine, laurylamine, stearylamine, oleylamine, beef tallow amine, 17-phenyl-heptadecylamine, octadec-7,11-dienylamine, octadec-7,9-dienylamine, octadec. -9-enylamine, 7-methyl-octadec-7-enylamine, and the like. Examples of the secondary amine include distearylamine. Examples of the tertiary amine include dimethyloctylamine, dimethyldecylamine, and dimethyllaurylamine. Dimethyl myristyl amine, dimethyl palmityl amine, dimethyl stearyl amine, dimethyl behenyl amine and the like. Of these, amines having about 20 carbon atoms, particularly primary amines, are preferred from the standpoint of easy availability and reinforcement.

  The amount of the organic amine compound is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the fluororubber. When the amount of the organic amine compound is too large, kneading tends to be difficult, and when the amount is too small, the reinforcing property tends to be lowered. A more preferable blending amount is 0.1 part by mass or more with respect to 100 parts by mass of the fluororubber from the viewpoint of reinforcement, and 4 parts by mass or less from the viewpoint of reinforcement and ease of kneading.

  As the acid acceptor, among those described above, for example, metal hydroxides such as calcium hydroxide; metal oxides such as magnesium oxide and zinc oxide, and hydrotalcite are preferable from the viewpoint of reinforcing properties, and in particular, oxidation. Zinc is preferred.

  As for the compounding quantity of the said acid acceptor, 0.01-10 mass parts is preferable with respect to 100 mass parts of fluororubber. If the acid acceptor is too much, the physical properties tend to be lowered, and if it is too little, the reinforcing property tends to be lowered. Further preferred blending amount is 0.1 parts by mass or more with respect to 100 parts by mass of fluororubber from the viewpoint of reinforcing properties, preferably 8 parts by mass or less, from the viewpoint of physical properties and ease of kneading, preferably 5 parts by mass or less. More preferred.

  In addition, the rubber composition for the bladder is sheared at a dynamic strain of 1% in a dynamic viscoelasticity test (measurement temperature: 100 ° C., measurement frequency: 1 Hz) with an unvulcanized rubber by a rubber process analyzer (RPA). Difference δG ′ (G ′ (1%) − G ′ (100%)) between the elastic modulus G ′ (1%) and the shear elastic modulus G ′ (100%) at a dynamic strain of 100% is 120 kPa to 3000 kPa It is preferable that When δG ′ is in the above range, the effect of suppressing sulfur migration from the high-concentration sulfur rubber member can be further enhanced, and advantageous effects can be obtained in terms of normal physical properties and tensile properties at high temperatures.

  The δG ′ is used as an index for evaluating the reinforcing property of the rubber composition, and is measured and calculated by a dynamic viscoelasticity test using a rubber process analyzer.

  The δG ′ is preferably 150 kPa or more, more preferably 160 kPa or more, further preferably 300 kPa or more, particularly preferably 300 kPa or more, and most preferably 500 kPa or more, from the viewpoint of good normal physical properties and tensile properties at high temperatures. . On the other hand, δG ′ is preferably set to 2800 kPa or less, more preferably 2500 kPa or less, from the viewpoints of normal properties, hardness, viscosity during extrusion molding, tensile properties at high temperature, and the like.

(Bridge rubber cross-linked product)
By crosslinking the rubber composition for bladder of the present invention, a crosslinked rubber product for bladder can be obtained.
The crosslinking method of the rubber composition for bladder may be appropriately selected. For example, a normal crosslinking method such as a molding method such as extrusion molding or roll-coating or a crosslinking method using a crosslinking can is employed. Further, when secondary crosslinking is required depending on the purpose of use of the crosslinked product, oven crosslinking may be further performed.

Moreover, the rubber cross-linked product for the bladder has a dynamic viscoelasticity test (measurement mode: tension, distance between chucks: 20 m, tensile strain: 1%, measurement frequency: 10 Hz, static load condition at strain dispersion is constant force) When the loss elastic modulus E ″ is 400 kPa or more and 6000 kPa or less at a static tension value of 157 cN and a measurement temperature of 160 ° C., the physical properties and tensile properties at high temperatures are particularly excellent.
The lower limit of the loss elastic modulus E ″ is preferably 420 kPa or more, more preferably 430 kPa or more, and the upper limit is preferably 5900 kPa or less, more preferably 5800 kPa or less.

  In addition, the rubber cross-linked product for the bladder has a dynamic viscoelasticity test (measurement mode: tension, distance between chucks: 20 mm, measurement temperature: 160 ° C., tensile strain: 1%, and static load conditions during strain dispersion with a constant force. The storage elastic modulus E ′ is more preferably 1500 kPa or more and 20000 kPa or less at a static tension value of 157 cN and a frequency of 10 Hz from the viewpoint of improving tensile properties at high temperatures. The lower limit of the storage elastic modulus E ′ is preferably 1600 kPa or more, more preferably 1800 kPa or more, and the upper limit is preferably 19000 kPa or less, more preferably 18000 kPa or less.

  The bladder rubber cross-linked product preferably has a tensile elongation at break of 100 to 700% at 160 ° C. because it is suitable for use in a high temperature environment. From the same viewpoint, the lower limit of the tensile elongation at break is more preferably 110% or more, further preferably 120% or more, and the upper limit is more preferably 680% or less, and 650% or less. More preferably it is.

  In addition, the rubber cross-linked product for bladder has a tensile breaking strength at 160 ° C. of 1 MPa or more, further 1.5 MPa or more, particularly 2 MPa or more, and 30 MPa or less, particularly 28 MPa or less in a high temperature environment. It is preferable because it is suitable for use in the above. The tensile strength at break and tensile elongation at break are measured using a No. 6 dumbbell according to JIS-K6251.

  Furthermore, the rubber cross-linked product for bladder has a tear strength of 3 to 30 kN / m, further 4 kN / m or more, particularly 5 kN / m or more, 29 kN / m or less, particularly 28 kN / m or less at 160 ° C. It is preferable that it is suitable for use in a high temperature environment.

  Furthermore, the rubber cross-linked product for bladder has a tensile elongation at break of 100 to 700%, further 110% or more, particularly 120% or more, or 680% or less, particularly 650% or less at 200 ° C. It is preferable because it is suitable for use in a high temperature environment.

  In addition, the rubber cross-linked product for bladders has a tensile breaking strength at 200 ° C. of 1 to 30 MPa, further 1.5 MPa or more, particularly 2 MPa or more, and 29 MPa or less, particularly 28 MPa or less in a high temperature environment. It is preferable because it is suitable for use in the above.

  Furthermore, the rubber cross-linked product for bladders has a tear strength of 3 to 30 kN / m, further 4 kN / m or more, particularly 5 kN / m or more at 200 ° C. It is preferable because it is suitable for use below.

(tire)
The tire of the present invention is obtained by the tire manufacturing method of the present invention described above.
The tire of the present invention obtained by the tire manufacturing method of the present invention can have the desired physical properties without reducing the amount of sulfur during vulcanization.

  In the tire of the present invention, a small amount of the fluororubber in the vulcanizing bladder is transferred to the innermost surface. Therefore, it can be used as one of indices when determining whether or not the tire is obtained by the manufacturing method according to the present invention.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

＊１１：ＩＳＡＦカーボンブラック、東海カーボン（株）製「シースト６」、Ｎ₂ＳＡ＝119m²／g、ＤＢＰ吸油量＝114ml／100g
＊１２：花王（株）製「ファーミン８６Ｔ」
＊１３：２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、日油（株）製「パーヘキサ２５Ｂ」
＊１４：トリアリルイソシアヌレート（ＴＡＩＣ）、日本化成（株）製「タイク」
＊１５：堺化学工業（株）製「酸化亜鉛（一種）」 (Production of vulcanization bladder)
(1) Fluororubber-containing bladder A vulcanization bladder containing a fluorine rubber was prepared from the bladder composition having the composition shown in Table 1 below.
In addition, about the fluororubber contained in the rubber composition for bladders, it produced on the following conditions. 3L stainless steel autoclave pure water 1.7 L, 50 of _{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) 50% aqueous solution of 0.17g of _{COONH 4, F (CF 2)} 5 COONH 4 A 6.8 g% aqueous solution was charged, and the inside of the system was sufficiently replaced with nitrogen gas. The temperature was raised to 80 ° C. while stirring at 600 rpm, and then the monomer was injected so that the initial monomer composition was VdF / HFP = 34/66 (molar ratio) and 1.52 MPa. Subsequently, a polymerization initiator solution in which 60 mg of ammonium persulfate (APS) was dissolved in 5 ml of pure water was injected with nitrogen gas to initiate the reaction. When the internal pressure dropped to 1.42 MPa as the polymerization progressed, an additional mixed monomer of VdF / HFP = 68/32 (molar ratio) as an additional mixed monomer was injected until the internal pressure became 1.52 MPa. At this time, 1.96 g of diiodine compound (CF ₂ ) ₄ I was injected. While repeatedly increasing and decreasing the pressure, an aqueous solution of 60 mg of APS / 5 ml of pure water was injected with nitrogen gas every 3 hours to continue the polymerization reaction. When 600 g of the mixed monomer was added, unreacted monomers were released, and the autoclave was cooled to obtain 2346 g of a fluororubber dispersion having a solid content concentration of 26.3% by mass. The polymerization time was 7.9 hours. When the copolymer composition of this fluororubber was examined by NMR analysis, it was VdF / HFP = 68/32 (molar ratio) and the Mooney viscosity (ML1 + 10 (100 ° C.)) was 69.
The rubber composition for bladders prepared had a shear modulus G ′ (1%) of 757 kPa, and a difference δG ′ (G ′) between the shear modulus G ′ (1%) and the shear modulus G ′ (100%). (1%)-G ′ (100%)) was 568 kPa.

* 11: ISAF carbon black, “Seast 6” manufactured by Tokai Carbon Co., Ltd., N ₂ SA = 119 m ² / g, DBP oil absorption = 114 ml / 100 g
* 12: “Farmin 86T” manufactured by Kao Corporation
* 13: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, NOF Corporation "Perhexa 25B"
* 14: Triallyl isocyanurate (TAIC), “Taike” manufactured by Nippon Kasei Co., Ltd.
* 15: “Zinc oxide (a type)” manufactured by Sakai Chemical Industry Co., Ltd.

＊２１：ＪＳＲ（株）製「Ｂｕｔｙｌ２６８ 」
＊２２：東海カーボン製「シースト９」
＊２３：新日本石油（株）製「Ｓｕｐｅｒ ＯｉｌＹ２２」
＊２４：ハクスイテック（株）製「３号亜鉛華」
＊２５：フェノールホルムアルデヒド樹脂 (2) Butyl rubber-containing vulcanization bladder A vulcanization bladder containing butyl rubber was prepared from a bladder composition having the formulation shown in Table 2 below. In addition, content of each component is the quantity (mass part) with respect to 100 mass parts of rubber components.

* 21: “Butyl 268” manufactured by JSR Corporation
* 22: “Seast 9” made by Tokai Carbon
* 23: “Super Oil Y22” manufactured by Nippon Oil Corporation
* 24: “No. 3 Zinc Hana” manufactured by Hakusui Tech Co., Ltd.
* 25: Phenol formaldehyde resin

<Example 1, Comparative Examples 1-3>
Using the vulcanization bladder described above, the sample unvulcanized tire was vulcanized.
In addition, about an unvulcanized tire of a sample, a tire (size: with two types of tire innermost surface member rubbers (low concentration sulfur rubber member A: inner liner, high concentration sulfur rubber member B: chafer) having different sulfur amounts) 195 / 60R15). Tables 3 and 4 show the composition of the rubber composition used for the tire innermost surface member rubber.

＊３１：ＲＳＳ＃３
＊３２：ＪＳＲ（株）製「ＢＲＯＭＯＢＵＴＹＬ ２２５５」
＊３３：ＧＰＦカーボンブラック、Ｎ６６０、旭カーボン（株）製「旭＃５５」、Ｎ₂ＳＡ＝２６m²／g、D B P吸油量＝87m L／100 g
＊３４：新日本石油（株）製「Ｓｕｐｅｒ ＯｉｌＹ２２」
＊３５：ハクスイテック（株）製「３号亜鉛華」
＊３６：２，２’−ジベンゾチアジルジスルフィド、大内新興化学工業社（株）製「ノクセラーＤＭ−Ｐ」
＊３７：細井化学工業（株）製「粉末硫黄」

＊４１：ＲＳＳ＃３
＊４２：ＪＳＲ（株）製「ＢＲ０１」
＊４３：ＨＡＦカーボンブラック、東海カーボン（株）製「シースト３」、Ｎ₂ＳＡ＝２６m²／g、D B P吸油量＝101m L／100 g
＊４４：新日本石油（株）製「Ｓｕｐｅｒ ＯｉｌＹ２２」
＊４５：ハクスイテック（株）製、３号亜鉛華
＊４６：２，２’−ジベンゾチアジルジスルフィド、大内新興化学工業社（株）製「ノクセラーＤＭ−Ｐ」
＊４７：細井化学工業（株）製「粉末硫黄」

* 31: RSS # 3
* 32: “BROMOBUTYL 2255” manufactured by JSR Corporation
* 33: GPF carbon black, N660, “Asahi # 55” manufactured by Asahi Carbon Co., Ltd., N ₂ SA = 26 m ² / g, DBP oil absorption = 87 ml / 100 g
* 34: “Super Oil Y22” manufactured by Nippon Oil Corporation
* 35: “No. 3 Zinc Hana” manufactured by Hakusui Tech Co., Ltd.
* 36: 2,2′-dibenzothiazyl disulfide, “Noxeller DM-P” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 37: “Powder sulfur” manufactured by Hosoi Chemical Co., Ltd.

* 41: RSS # 3
* 42: “BR01” manufactured by JSR Corporation
* 43: HAF carbon black, “Seast 3” manufactured by Tokai Carbon Co., Ltd., N ₂ SA = 26 m ² / g, DBP oil absorption = 101 mL / 100 g
* 44: “Super OilY22” manufactured by Nippon Oil Corporation
* 45: Hakusui Tech Co., Ltd., No. 3, zinc white * 46: 2,2'-dibenzothiazyl disulfide, Ouchi Shinsei Chemical Co., Ltd. "Noxeller DM-P"
* 47: “Powder sulfur” manufactured by Hosoi Chemical Co., Ltd.

<Evaluation>
For each vulcanized tire sample after vulcanizing the unvulcanized tire of each sample, the tire was measured using a scanning electron microscope (SEM) and an electron probe microanalyzer (EPMA). The results of measuring the sulfur amount (%) in the depth direction from the inner surface are shown in Table 5 and FIG.

From the results of Table 5 and FIG. 2, the sample of Example 1 shows that the reduction of sulfur is suppressed compared to the sample of Comparative Example 3, that is, the shift of sulfur to the vulcanization bladder is suppressed. all right.
Moreover, about Comparative Examples 1 and 2, since there is no difference in the amount of sulfur, it is understood that there is almost no change in the amount of sulfur transferred when the amount of sulfur on the innermost surface of the unvulcanized tire is small. It was.

  According to the present invention, when vulcanizing an unvulcanized tire provided with a member containing sulfur at a high concentration on the inner surface of the tire, it is possible to effectively suppress the transfer of sulfur to the vulcanizing bladder. It is possible to provide a tire manufacturing method capable of manufacturing a tire having physical properties as intended without reducing the amount of sulfur.

10 Vulcanizing bladder 20 Unvulcanized tire 20a Tire innermost surface 30 Mold 40 Vulcanizing device

Claims (5)

A vulcanized tire comprising at least a part of the innermost surface of the tire is vulcanized with a run-flat reinforcing rubber, which is a high-concentration sulfur rubber member made of a rubber composition containing 1.0 part by mass or more of sulfur with respect to 100 parts by mass of the rubber component. Including the vulcanization process
In the vulcanization step, using a bladder for vulcanization made of a rubber composition for bladder containing 50 to 100% by mass of fluoro rubber ,
The fluororubber is a group consisting of a structural unit derived from vinylidene fluoride (VdF unit), hexafluoropropylene (HFP), 2,3,3,3-tetrafluoropropylene and perfluoro (alkyl vinyl ether) (PAVE). A structural unit derived from at least one selected from vinylidene fluoride-based fluororubber,
In the fluororubber, the molar ratio of the VdF unit to the structural unit derived from at least one selected from the group consisting of HFP, 2,3,3,3-tetrafluoropropylene and PAVE is 50/50 to 78. / 22, and in a dynamic viscoelasticity test with a rubber process analyzer (RPA) (measurement frequency: 1 Hz, measurement temperature: 100 ° C.), the shear modulus G ′ (1) when the uncured dynamic strain is 1%. %) And the difference δG ′ (G ′ (1%) − G ′ (100%)) between the shear elastic modulus G ′ (100%) at a dynamic strain of 100% is 120 kPa or more and 3000 kPa or less. A method for manufacturing a tire.   The tire manufacturing method according to claim 1, wherein the rubber composition for bladder contains substantially 100% by mass of fluoro rubber. The bladder rubber composition, at least one further comprising a method for producing a tire according to claim 1 or 2 is selected from the group consisting of fatty oils and aliphatic hydrocarbons. The tire manufacturing method according to claim 3 , wherein the fatty oil is at least one selected from the group consisting of non-drying oil and semi-drying oil. The rubber composition for bladder further contains carbon black, the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 25 to 180 m ² / g, and the dibutyl phthalate (DBP) oil absorption is 40 to 180 ml / It is 100g, The manufacturing method of the tire of any one of Claims 1-4 characterized by the above-mentioned.

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