JP6160714B2 - Compact - Google Patents

Description

The present invention relates to a molded body.

Fluoro rubber is widely used in various fields such as the automobile industry, semiconductor industry, chemical industry, etc., for example, in the automobile industry, hoses used for engines and peripheral devices, AT devices, fuel systems and peripheral devices, It is used as a sealing material.

However, fluororubber is inherently elastomeric and has a high coefficient of friction and adhesiveness on the surface of the molded body, and improvements have been demanded in applications that require low friction such as sliding members.

Under such circumstances, Patent Document 1 discloses a fluororubber molded product obtained by crosslinking a crosslinkable composition containing fluororubber (A) and fluororesin (B), and the surface of the fluororubber molded product. The area ratio of the region having the protrusion to the surface of the fluororubber molded product is 0.06 or more, and the volume ratio of the fluororesin (B) to the fluororubber molded product is 0.05 to 0.45, the area ratio of the region having the convex portion is 1.2 times or more the volume ratio of the fluororesin (B), and the fluororesin (B) is a tetrafluoroethylene / hexafluoropropylene copolymer. A fluororubber molded product characterized by being a polymer has been proposed.

JP 2012-153880 A

The objective of this invention is providing the molded object which has the outstanding non-adhesiveness and low friction property, although it has a softness | flexibility.

The present invention is a molded article made of a composition containing rubber (A), has a Shore A hardness of 95 or less, and has an indentation hardness of 400 N / mm ² or more measured with an indentation load of 10 μN. This is a featured molded article.

The rubber (A) is preferably fluororubber.

The composition preferably further contains a silicon dioxide-containing compound (B).

In the molded body, the following X and Y ratio [X / Y] is preferably 2.0 or more.
X: Ratio of the intensity (bX) at the absorption position 1097 cm ^{−1 and} the intensity (aX) at the absorption position 1395 cm ⁻¹ , which was measured by infrared spectroscopic analysis of the surface of the molded body [intensity (bX) / intensity (aX )]
Y: Ratio of the intensity (bY) at the absorption position 1097 cm ⁻¹ and the intensity (aY) at the absorption position 1395 cm ⁻¹ , which was measured by infrared spectroscopic analysis of the inside of the molded body [intensity (bY) / intensity (aY )]

It is preferable that content of a silicon dioxide containing compound (B) is 0.1-100 mass parts with respect to 100 mass parts of rubber | gum (A).

The composition preferably further contains a fluororesin (C).

It is preferable that the volume ratio of the rubber (A) and the fluororesin (C) is 60/40 to 99/1.

It is preferable that the said molded object has a linear convex part on the surface of the said molded object.

The said molded object is suitable as a sealing material, a sliding member, or a non-adhesive member.

The molded article of the present invention has excellent non-adhesiveness and low frictional properties despite having flexibility due to having the above-described configuration.

Several examples of surface shape images of Examples and Comparative Examples are shown.
It is the 3D image which observed the surface of the molded object obtained in Example 1 with the laser microscope. It is a schematic sectional view obtained by cutting the molded body in a plane containing a straight line perpendicular B ₁ and the line B ₂ on the surface of the molded body in Fig. It is a schematic sectional view obtained by cutting the molded body in a plane containing a straight line perpendicular C ₁ and the line C ₂ on the surface of the molded body in Fig. It is a schematic diagram which shows the surface which cut | disconnected the bottom part of the convex part in the plane parallel to the molded object surface in FIG. It is the 3D image which observed the surface of the molded object obtained in Example 1 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained in Example 2 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained in Example 3 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained in Example 4 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained in Example 5 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained in Example 6 with the laser microscope. It is a 3D image which observed the surface of the molded object obtained by the comparative example 1 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained by the comparative example 2 with the laser microscope. It is a 3D image which observed the surface of the molded object obtained by the comparative example 3 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained by the comparative example 4 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained by the comparative example 5 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained by the comparative example 6 with the laser microscope. It is a 3D image which observed the surface of the molded object obtained by the comparative example 7 with the laser microscope. It is a 3D image which observed the surface of the molded object obtained by the comparative example 8 with the laser microscope. It is the 3D image which observed the surface of the molded object of Unexamined-Japanese-Patent No. 2012-153880 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained in Example 10 with the laser microscope. It is the 3D image which observed the surface of the molded object obtained in Example 11 with the laser microscope.

The present invention is described in detail below.

The molded product of the present invention is characterized in that the Shore A hardness is 95 or less, and the indentation hardness measured with an indentation load of 10 μN is 400 N / mm ² or more. The molded product of the present invention has an unprecedented characteristic that the hardness of the surface is high at the same time as the Shore A hardness is small, and thus it has excellent non-adhesiveness despite having flexibility. Has low friction.

The Shore A hardness is preferably 90 or less, more preferably 85 or less, more preferably 60 or more, and even more preferably 65 or more, since the flexibility of the molded product is further improved. .

The Shore A hardness can be measured according to JISK6253.

The indentation hardness, since the non-adhesive and low friction properties of the molded article is excellent more, is preferably 450 N / mm ² or more, more preferably 500 N / mm ² or more, does not define the upper limit However, it is preferably 2000 N / mm ² or less and more preferably 1500 N / mm ² or less because followability to deformation is required.

The indentation hardness can be measured in accordance with the standard of ISO14577-1.

Since the molded article of the present invention also has the above-described configuration, when compared with a conventional molded article obtained by coating a rubber surface with a fluororesin, particularly low friction and wear resistance under a high load. Are better.

The molded product of the present invention is composed of a composition containing rubber (A). The rubber (A) is made of an amorphous polymer having rubber elasticity.

The rubber (A) preferably has a Mooney viscosity (ML _{1 + 10} (100 ° C.)) of 5 to 140, more preferably ₁₀ to 120, and preferably 20 to 100 from the viewpoint of good processability. Is more preferable.
The Mooney viscosity (ML _{1 + 10} (100 ° C.)) is a value measured according to ASTM D1646.

Examples of the rubber (A) include fluorine rubber, acrylonitrile-butadiene rubber (NBR) or a hydride thereof (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber ( NR), isoprene rubber (IR) and other diene rubbers, ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber (ACM) and the like.

The rubber (A) is preferably at least one selected from the group consisting of fluororubber, NBR, HNBR and ACM because of its excellent heat resistance, and since it has excellent non-adhesiveness and low friction properties, the rubber (A) is preferably fluororubber.

The fluororubber usually comprises an amorphous polymer having a fluorine atom bonded to a carbon atom constituting the main chain and having rubber elasticity. The fluororubber may be composed of one kind of polymer or may be composed of two or more kinds of polymers.

The fluororubber preferably has a Mooney viscosity (ML _{1 + 10} (100 ° C.)) of 5 to 140, more preferably ₁₀ to 120, and preferably 20 to 100 from the viewpoint of good processability. Further preferred.
The Mooney viscosity (ML _{1 + 10} (100 ° C.)) is a value measured according to ASTM D1646.

The fluororubber is preferably a fluororubber having a fluorine content of 64% by mass or more, and more preferably a fluororubber having a fluorine content of 66% by mass or more. When the fluorine content is less than 64% by mass, chemical resistance, fuel oil resistance and fuel permeability tend to be inferior. The upper limit of the fluorine content is not particularly limited, but the fluorine content is preferably 74% by mass or less. The fluorine content can be determined by calculation from the polymer composition.

Examples of the fluororubber include tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and formula (1):
CF ₂ = CF-Rf ^a (1)
Wherein Rf ^a is —CF ₃ or ORf ^b (Rf ^b is a C 1-5 perfluoroalkyl group)) (for example, hexafluoropropylene (HFP), It is preferable to include a polymer unit derived from at least one monomer selected from the group consisting of fluoro (alkyl vinyl ether) (PAVE) and the like.
In the present specification, the “polymerization unit” means a part of the molecular structure of fluororubber or fluororesin, which is based on the corresponding monomer.

Examples of the fluoro rubber include vinylidene fluoride (VdF) fluoro rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluoro rubber, tetrafluoroethylene (TFE) / propylene (Pr) / vinylidene fluoride (VdF). Fluoro rubber, ethylene (Et) / hexafluoropropylene (HFP) fluoro rubber, ethylene (Et) / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluoro rubber, ethylene (Et) / hexafluoropropylene (HFP) ) / Tetrafluoroethylene (TFE) -based fluororubber, fluorosilicone-based fluororubber, fluorophosphazene-based fluororubber, TFE / PAVE-based fluororubber, etc., each of which is independent or does not impair the effects of the present invention. Any In combination it can be used.

The TFE / PAVE fluororubber preferably has a TFE / PAVE composition of (50 to 90) / (50 to 10) (mol%), more preferably (50 to 80) / (50 to 20) (mol%), more preferably (55 to 75) / (45 to 25) (mol%). Examples of PAVE in this case include PMVE, PPVE, and the like, and these can be used alone or in any combination.

The TFE / propylene (Pr) -based fluororubber is a fluorine-containing copolymer having a TFE / propylene composition of (45 to 70) / (55 to 30) (mol%). The TFE / propylene (Pr) -based fluororubber may be composed of only these two components, and further, a specific third component (for example, PAVE) may be added in an amount of 0 to 40 mol with respect to the total of TFE units and propylene units. % May be included.

The ethylene (Et) / HFP fluororubber preferably has an Et / HFP composition of (35-80) / (65-20) (mol%), (40-75) / (60-25). (Mol%) is more preferable.

In the Et / HFP / TFE fluororubber, the composition of Et / HFP / TFE is preferably (35 to 75) / (25 to 50) / (0 to 15) (mol%), (45 to 75). ) / (25-45) / (0-10) (mol%) is more preferred.

The VdF fluororubber is a fluororubber containing at least polymerized units derived from VdF (VdF units).

In the VdF-based fluororubber, the content of VdF units is preferably 20 mol% or more, more preferably 40 mol% or more, based on the total number of moles of VdF units and polymerization units derived from other comonomers. More preferably 45 mol% or more, still more preferably 50 mol% or more, particularly preferably 55 mol% or more, and most preferably 60 mol% or more. The content of the VdF unit is preferably 90 mol% or less, more preferably 85 mol% or less, and further preferably 80 mol% or less, based on the total number of moles of the VdF unit and the polymerization unit derived from the other comonomer. Preferably, 78 mol% or less is even more preferable.

Further, the content of the polymerized unit derived from the other comonomer is preferably 10 mol% or more with respect to the total number of moles of the VdF unit and the polymerized unit derived from the other comonomer, and is 15 mol%. The above is more preferable, 20 mol% or more is further preferable, 22 mol% or more is further more preferable, 25 mol% or more is particularly preferable, and 30 mol% or more is most preferable. The content of polymerized units derived from other comonomers is preferably 80 mol% or less, preferably 60 mol% or less, based on the total number of moles of VdF units and polymerized units derived from other comonomers. More preferably, 55 mol% or less is still more preferable, 50 mol% or less is still more preferable, 45 mol% or less is especially preferable, and 40 mol% or less is the most preferable.

The comonomer in the VdF-based fluororubber is not particularly limited as long as it is copolymerizable with VdF. For example, TFE, HFP, PAVE, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, tetra Fluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, iodine-containing fluorinated vinyl ether, the following general formula (2):
CH ₂ = CFRf (2)
(Wherein Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms) a fluorine-containing monomer such as a fluorine-containing monomer (2); ethylene (Et), propylene (Pr) , Fluorine-free monomers such as alkyl vinyl ethers, monomers that give crosslinkable groups (cure sites), and reactive emulsifiers. One or two of these monomers and compounds A combination of the above can be used.

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

Further, as the above PAVE, the following general formula:
CF ₂ = CFOCF ₂ ORf ^c
(In the formula, Rf ^c 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 carbon atoms containing 1 to 3 oxygen atoms. A monomer represented by ˜6 linear or branched perfluorooxyalkyl groups), for example, 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.

As the fluorine-containing monomer (2) represented by the general formula (2), a monomer in which Rf is a linear fluoroalkyl group is preferable, and a monomer in which Rf is a linear perfluoroalkyl group. The body is more preferred. Rf preferably has 1 to 6 carbon atoms. Examples of the fluorine-containing monomer represented by the general formula (2) include CH ₂ = CFCF ₃ , 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, and 2,3,3,3-tetrafluoropropylene represented by CH ₂ ═CFCF ₃ is particularly preferable.

The VdF-based fluororubber is preferably a copolymer containing VdF units and copolymerized units derived from fluorine-containing monomers (however, VdF units are excluded). The copolymer containing VdF units preferably further contains a copolymer unit derived from a monomer copolymerizable with VdF and a fluorine-containing monomer.

Examples of the VdF-based fluororubber include VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / CTFE copolymer, VdF / CTFE / TFE copolymer, VdF / PAVE copolymer, VdF / TFE. / PAVE copolymer, VdF / HFP / PAVE copolymer, VdF / HFP / TFE / PAVE copolymer, VdF / TFE / propylene (Pr) copolymer, VdF / ethylene (Et) / HFP copolymer and VdF / at least one copolymer selected from the group consisting of copolymers of fluorine-containing monomer (2) represented by formula (2) is preferred.
Among these, in terms of heat resistance, compression set, workability, and cost, VdF / HFP copolymer, VdF / HFP / TFE copolymer, VdF / PAVE copolymer, VdF / TFE / PAVE copolymer are used. More preferably, at least one selected from the group consisting of VdF / HFP / PAVE copolymer and VdF / HFP / TFE / PAVE copolymer, VdF / HFP copolymer, and VdF / HFP / TFE More preferred is at least one selected from the group consisting of copolymers.

The VdF / HFP copolymer preferably has a VdF / HFP composition of (45 to 85) / (55 to 15) (mol%), more preferably (50 to 80) / (50 to 20). (Mol%), more preferably (60-80) / (40-20) (mol%).

The VdF / TFE / HFP copolymer preferably has a VdF / TFE / HFP composition of (30-80) / (4-35) / (10-35) (mol%).

As the VdF / PAVE copolymer, a VdF / PAVE composition having a composition of (65 to 90) / (35 to 10) (mol%) is preferable.

As the VdF / TFE / PAVE copolymer, a VdF / TFE / PAVE composition having a composition of (40-80) / (3-40) / (15-35) (mol%) is preferable.

As the VdF / HFP / PAVE copolymer, a VdF / HFP / PAVE composition having a composition of (65 to 90) / (3 to 25) / (3 to 25) (mol%) is preferable.

As a VdF / HFP / TFE / PAVE copolymer, the composition of VdF / HFP / TFE / PAVE is (40-90) / (0-25) / (0-40) / (3-35) (mol%). The thing of (40-80) / (3-25) / (3-40) / (3-25) (mol%) is more preferable.

The copolymer of VdF / fluorinated monomer (2) represented by the formula (2) has a molar ratio of VdF / fluorinated monomer (2) units of 85/15 to 20/80. , VdF and other monomer units other than the fluorine-containing monomer (2) are preferably 0 to 50 mol% of all monomer units, and VdF / mol% of the fluorine-containing monomer (2) unit. The ratio is more preferably 80/20 to 20/80. The molar ratio of VdF / fluorinated monomer (2) unit is 85/15 to 50/50, and other monomer units other than VdF and fluorine-containing monomer (2) are all monomer units. Those having a content of 1 to 50 mol% are also preferred. As monomers other than VdF and fluorine-containing monomer (2), TFE, HFP, PMVE, perfluoroethyl vinyl ether (PEVE), PPVE, CTFE, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, Monomers exemplified as the above-mentioned VdF comonomer, such as ethylene (Et), propylene (Pr), alkyl vinyl ether, a monomer providing a crosslinkable group, and a reactive emulsifier, are preferable, and among them, PMVE, CTFE, More preferably, they are HFP and TFE.

Among the above-mentioned fluororubbers, VdF-based fluororubber, TFE / Pr-based fluororubber, and TFE / Pr / VdF-based fluororubber are more preferable from the viewpoint of good heat aging resistance and oil resistance. VdF-based fluororubber is more preferable, and at least one selected from the group consisting of VdF / HFP copolymer and VdF / HFP / TFE copolymer is particularly preferable.

The fluororubber is preferably made of a copolymer containing copolymer units derived from a monomer that gives a crosslinkable group. Examples of the monomer giving a crosslinkable group include perfluoro (6,6-dihydro-6-iodo-3-oxa-1 as described in JP-B-5-63482 and JP-A-7-316234. -Hexene) and iodine-containing monomers such as perfluoro (5-iodo-3-oxa-1-pentene), bromine-containing monomers described in JP-A-4-505341, JP-A-4-505345 And cyano group-containing monomers, carboxyl group-containing monomers, alkoxycarbonyl group-containing monomers, and the like described in JP-T-5-500070.

The fluororubber is preferably a fluororubber having an iodine atom or a bromine atom at the end of the main chain. Fluororubber having iodine atom or bromine atom at the main chain end is produced by adding a radical initiator in the presence of a halogen compound in an aqueous medium in the absence of oxygen and performing emulsion polymerization of the monomer. it can. Representative examples of the halogen compound used include, for example, the general formula:
R ² I _x Br _y
(In the formula, x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms, carbon A saturated or unsaturated chlorofluorohydrocarbon group having 1 to 16 carbon atoms, a hydrocarbon group having 1 to 3 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms that may be substituted with an iodine atom or a bromine atom And these may contain an oxygen atom).

Examples of the halogen compound include 1,3-diiodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloro. Perfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2- diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 CF 2 Br, BrCF 2 CFBrOCF 3 1-bromo-2-iodo -Fluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2- Examples include bromo-4-iodoperfluorobutene-1, monoiodomonobromo substituent of benzene, diiodomonobromo substituent of benzene, and (2-iodoethyl) and (2-bromoethyl) substituents of benzene. These compounds may be used alone or in combination with each other.
Among these, it is preferable to use 1,4-diiodoperfluorobutane or diiodomethane from the viewpoints of polymerization reactivity, crosslinking reactivity, availability, and the like.

The fluororubber 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. In the above polymerization, the conditions such as temperature and pressure, the polymerization initiator, the emulsifier and other additives can be appropriately set according to the composition and amount of the fluororubber. A fluororubber can be produced by a production method disclosed in Japanese Patent Application Laid-Open No. 2009-52034 and International Publication No. 2008/001895.

Examples of the polymerization initiator include oil-soluble radical polymerization initiators typified by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP). Water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt and sodium salt can be used.

As the above-mentioned emulsifier, for example, salts of carboxylic acids having a fluorocarbon chain or a fluoropolyether chain are preferable from the viewpoint of suppressing a chain transfer reaction to an emulsifier molecule during polymerization.

Specifically, for example, ammonium perfluorooctanoate, CF ₃ (CF ₂ ) _n COONH ₄ (n = 2 to 8), CHF ₂ (CF ₂ ) _n COONH ₄ (n = 6 to 8), C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COONH ₄ , CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COONH _{4 and the} like.

The composition preferably further contains a silicon dioxide-containing compound (B).

Examples of the silicon dioxide compound (B) include silicon dioxide, generally called silica, and oxalates composed of various silicon dioxides and metal oxides such as talc, diatomaceous earth, and wollastonite, which are generally blended as fillers in rubber. Other compounds that contain silicon dioxide in the composition may be used.
Among them, from the viewpoint of dispersibility with respect to rubber, a powdery compound having a particle diameter of 10 μm or less, a liquid compound, or a compound that is liquefied and kneaded with rubber is preferable. As the silicon dioxide-containing compound (B), at least one selected from the group consisting of silicon dioxide and a metal oxide and a group consisting of silica is preferable, and a silicate consisting of silicon dioxide and a metal oxide Compounds are more preferred.
The silicate compound is more preferably a salt of silicon dioxide and an alkali metal such as water glass, sodium silicate compound such as sodium metasilicate or hydrate thereof, potassium silicate compound, lithium silicate compound. Of these, sodium silicate compounds are more preferable.
Examples of the silica include Carplex 1120 (manufactured by DSL. Japan), Vulkasil A1 (manufactured by Bayer Material Science AG), and the like.
Examples of the sodium silicate compound include sodium metasilicate nonahydrate such as sodium metasilicate 9 hydrate (manufactured by Osaka Shoso Co., Ltd. or Nippon Chemical Industry Co., Ltd.); No. 1 sodium silicate (Fuji Chemical Co., Ltd. or AGC S-Itech Co., Ltd.) and the like.
Examples of the potassium silicate compound include No. 1 potassium silicate (manufactured by Fuji Chemical Co., Ltd.), potassium silicate solution (manufactured by Pure Chemical Co., Ltd.), and the like.

Since it is excellent in non-adhesiveness and low friction, the silicon dioxide-containing compound (B) is preferably contained in an amount of 0.01 parts by mass or more with respect to 100 parts by mass of the rubber (A). More preferably, it is contained in an amount of at least parts. Moreover, since there exists a possibility that rubber elasticity may be impaired when a compounding quantity increases, it is preferable that the compounding quantity of a silicon dioxide containing compound (B) is 100 mass parts or less with respect to 100 mass parts of rubber | gum (A). .
The blending amount of the silicon dioxide compound (B) is 0.3 parts by mass or more because both the flexibility resulting from the rubber (A) and the low friction property resulting from the silicon dioxide compound (B) are good. It is more preferable that it is 0.5 mass part or more. Moreover, it is more preferable that it is 70 mass parts or less, It is still more preferable that it is 40 mass parts or less, It is especially preferable that it is 20 mass parts or less.

The composition containing the rubber (A) is a conventional compounding agent incorporated in the rubber as necessary, for example, a filler (for example, N990 (manufactured by Cancarb), Asahi Thermal (manufactured by Asahi Carbon Co., Ltd.), HTCII20. (Carbon black such as made by Nippon Kayaku Co., Ltd.), processing aids, plasticizers, colorants, stabilizers, adhesion aids, mold release agents, conductivity imparting agents, thermal conductivity imparting agents, non-surface It may contain various additives such as an adhesive, a flexibility imparting agent, a heat resistance improver, and a flame retardant. What is necessary is just to use these additives and a compounding agent in the range which does not impair the effect of this invention. For example, when carbon black is used as the filler, the content of carbon black is preferably 1 to 80 parts by mass, and 1 to 65 parts by mass with respect to 100 parts by mass of the rubber (A). More preferably, the amount is 1 to 50 parts by mass.

The molded article of the present invention is a molded article comprising a composition containing a fluororubber as the rubber (A) and further containing a silicon dioxide-containing compound (B), wherein the ratio of X and Y below [X / Y] It is preferable that it is 2.0 or more.
X: Ratio of the intensity (bX) at the absorption position 1097 cm ^{−1 and} the intensity (aX) at the absorption position 1395 cm ⁻¹ , which was measured by infrared spectroscopic analysis of the surface of the molded body [intensity (bX) / intensity (aX )]
Y: Ratio of the intensity (bY) at the absorption position 1097 cm ⁻¹ and the intensity (aY) at the absorption position 1395 cm ⁻¹ , which was measured by infrared spectroscopic analysis of the inside of the molded body [intensity (bY) / intensity (aY )]
Incidentally, the content of free silicon dioxide compound (B), there is a correlation with the intensity of the absorption position 1097cm ^-1 ((bX) and (bY)), and the content of fluorine rubber, the absorption position 1395Cm ^-1 Since there is a correlation with the strength ((aX) and (aY)), it can be confirmed from the ratio [X / Y] whether the silicon dioxide-containing compound (B) is segregated on the surface of the molded body.
The molded article of the present invention has excellent non-adhesiveness and low friction properties when the ratio [X / Y] is 2.0 or more as described above. When this ratio [X / Y] is 2.0 or more, it is estimated that the silicon dioxide-containing compound (B) is sufficiently segregated on the surface of the molded body.
The ratio [X / Y] is more preferably 2.5 or more, and further preferably 3.0 or more.
On the other hand, when the ratio [X / Y] is too large, normal physical properties are impaired. Therefore, the ratio is preferably 200 or less, more preferably 100 or less, and still more preferably 50 or less.
The IR analysis is performed, for example, by using a Fourier transform infrared spectrometer (FT-IR NICOLET6700) manufactured by Thermo Fisher Scientific Co., Ltd. This is one of the analytical methods for qualitatively measuring infrared absorption spectra.

The molded body of the present invention preferably has a linear protrusion on the surface. The said linear convex part consists of a composition containing rubber | gum (A). The molded body of the present invention has the above-mentioned specific convex portion, and thus has more excellent non-adhesiveness and low friction. It is preferable that the silicon dioxide-containing compound (B) is segregated on the surface of the linear protrusion.

The said convex part is linearly formed in the surface of a molded object, and has the top part which forms the ridgeline of a linear convex part, and the inclined surface which inclines toward a recessed part from a top part.
The convex portion may continuously extend while meandering, and forms a region extending continuously in a substantially linear or wavy shape, and forms an L shape, a U shape, a V shape, or a C shape. However, it may have a continuously extending region, and it tends to be excellent in low friction property when continuously extending while taking a complicated shape.

The shape of the convex portion will be described in more detail with reference to the drawings.
In FIG. 1, the 3D image which observed the surface of the molded object obtained in Example 1 mentioned later with the laser microscope is shown. In FIG. 1, a plurality of linear convex portions 11 are formed on the surface of the molded body, and a concave portion 12 is formed between two adjacent convex portions 11. Further, as can be seen from FIG. 1, the ridge line of the convex portion is a portion that is substantially linear or wavy when viewed from the plane, and a portion that is L-shaped, U-shaped, V-shaped or C-shaped. have. Moreover, the convex part 11 has the branch part 15, and the convex part (ridgeline) is extended from the branch part 15 in multiple directions.
2, in FIG. 1 is a schematic sectional view showing a cross-section of a molded body in a plane containing a straight line perpendicular B ₁ and the line B ₂ on the surface of the molded article. The convex portion 11 includes a top portion 13 and an inclined surface 14 that is inclined from the top portion 13 toward the concave portion 12. On the surface of the convex portion (for example, the top portion 13 or the inclined surface 14), the silicon dioxide-containing compound (B) that is a constituent material of the molded body is segregated, and the non-adhesiveness and low friction property of the molded body are realized. Moreover, as FIG. 2 shows, the cross-sectional shape of a convex part is a substantially elliptical shape or a substantially parabolic shape, and does not have a sharp-pointed top part. This characteristic cross-sectional shape is also one of the reasons why the molded article of the present invention is excellent in non-adhesiveness and low friction.
3, in FIG. 1 is a schematic sectional view obtained by cutting the molded body in a plane containing a straight line perpendicular C ₁ and the line C ₂ on the surface of the molded body. The top portion 13 forms a ridge line of the linear convex portion 11 at a constant height or while changing the height so as to wave.
FIG. 4 is a schematic diagram showing a surface (bottom section) obtained by cutting the bottom of the convex portion in a plane parallel to the surface of the molded body in FIG. The bottom cross-sectional area to be described later refers to the value of the area in the cross section of the convex portion 11 observed on a plane obtained by cutting the bottom portion of the convex portion in a plane parallel to the surface of the molded body.
In the embodiment shown in FIGS. 1-4, since the linear convex part which draws a complicated pattern on the surface of a molded object is provided, it is excellent in non-adhesiveness and low friction property.
FIG. 19 shows a 3D image obtained by observing the surface of the molded body described in JP 2012-153880 A with a laser microscope. Although this molded body also has a convex portion on the surface, the shape of all the convex portions is substantially circular or substantially elliptical when viewed from the plane, and since it does not have any convex portion extending linearly, The coefficient of friction is large and non-adhesiveness is reduced as compared with the molded article having the linear protrusions.

The linear convex portion preferably has a length in the linear direction of 50 μm or more. When the length in the linear direction is in the above range, the molded article of the present invention is excellent in non-adhesiveness and low friction. More preferably, it is 100 micrometers or more, More preferably, it is 150 micrometers or more.
The length in the linear direction is a value obtained by profile measurement analysis using the application software VK Analyzer attached to the color 3D laser microscope (VK-9700).

The linear convex part preferably has a bottom minimum width of 1 to 40 μm. When the width is in the above range, non-adhesiveness and low friction are excellent. More preferably, it is 1-25 micrometers, 4-20 micrometers, More preferably, it is 6-15 micrometers.
The width is a value obtained by profile measurement analysis using the application software VK Analyzer attached to the color 3D laser microscope (VK-9700), as in the case of measuring the length in the line direction.

Since the non-adhesiveness and the low friction property are excellent, it is preferable that the maximum height of the convex portion on the line is 1 to 100 μm. More preferably, it is 3-80 micrometers, More preferably, it is 5-50 micrometers.
Here, the height of a convex part means the height of the part which protruded from the molded object surface (refer H in FIG. 2).
The height of the convex portion is a value obtained by profile measurement analysis using the application software VK Analyzer attached to the color 3D laser microscope (VK-9700), as in the case of measuring the length in the linear direction.

Since the molded article of the present invention is excellent in non-adhesiveness and low friction, it is preferable that the area ratio (occupation ratio of convex parts) of a region having convex parts to the surface of the molded article is 40% or more. More preferably, it is 45% or more, More preferably, it is 50% or more.
The area ratio of the area | region which has a convex part with respect to the said molded object surface says the ratio of the area which a convex part occupies in the cut surface which evaluates the bottom part cross-sectional area of the said convex part.
The occupancy ratio of the area having the convexity (occupancy ratio of the convexity) is measured by measuring an arbitrary area (200 μm × 280 μm) on the surface of the molded product using a color 3D laser microscope (VK-9700) manufactured by Keyence Corporation. The bottom cross-sectional area of the convex portion is obtained, and the total value of the cross-sectional areas is the ratio of the total area of the measurement. As an analysis software for the laser microscope, WinRooF Ver. Use 6.4.0.

Since the non-adhesiveness and the low friction property are excellent, a plurality of (two or more) linear convex portions are formed on the surface of the molded body of the present invention. It is preferable that the distance (refer L in FIG. 2) with the ridgeline of an adjacent convex part is 3-50 micrometers. It is preferable that the plurality of convex portions extend in irregular directions. As for the distance with the ridgeline of the said adjacent convex part, it is more preferable that it is 5-40 micrometers, and it is still more preferable that it is 10-30 micrometers.
The distance from the ridge line of the adjacent convex portion is a value obtained by profile measurement analysis using the application software VK Analyzer attached to the color 3D laser microscope (VK-9700).

The line-shaped convex part does not necessarily extend so as to form a single line, has a branch part, and extends so as to form a plurality of lines extending in multiple directions from the branch part. Also good.
In the molded product of the present invention, linear convex portions may be connected or crossed.
When you look at a certain two linear projections, the two linear projections do not intersect, but the extension of one linear projection intersects the other linear projection. The shape is also preferred.

The linear convex part is composed of a composition containing fluororubber as the rubber (A) and further containing the silicon dioxide compound (B), and the silicon dioxide compound (B) is segregated on the surface. It is preferable that
Since the silicon dioxide-containing compound (B) has a remarkably low friction coefficient as compared with the fluoro rubber, the low friction property is remarkably improved as compared with the fluoro rubber. Such a convex part can be formed, for example, by depositing the silicon dioxide-containing compound (B) contained in the composition on the surface by a method as described later.
The segregation of the silicon dioxide-containing compound (B) on the surface of the convex part is that the surface and the inside of the molded body are subjected to IR analysis, and the strength of the fluororubber absorption position 1395 cm ⁻¹ and the silicon dioxide-containing compound ( This can be confirmed by detecting the intensity of the absorption position 1097 cm ⁻¹ of B). If the ratio [X / Y] is 2.0 or more as described above, it is estimated that the silicon dioxide-containing compound (B) is sufficiently segregated on the surface of the convex portion.

The molded body of the present invention preferably has the above-mentioned linear convex portion on the surface, but convex portions other than the linear shape (for example, dotted convex portions) may coexist.

The composition preferably further contains a fluororesin (C).

The fluororesin (C) is preferably a melt processable fluororesin. By using a melt-processable fluororesin, it is possible to obtain a molded article having more excellent low friction, non-adhesiveness and wear resistance.

The fluororesin (C) is tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride [VF], hexafluoropropylene [HFP], hexafluoroisobutene [HFIB]. ], CH ₂ = CX ¹ (CF ₂ ) _n X ² (wherein X ¹ is H or F, X ² is H, F or Cl, and n is an integer of 1 to 10). Body, CF ₂ = CF-ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms) and perfluoro (alkyl vinyl ether) [PAVE], and CF ₂ = (wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) _CF-OCH ² -Rf 2 alkyl perfluorovinyl ether derivative represented by, trifluoroethene Chile Having polymerized units based on at least one fluorine-containing monomer selected from the group consisting of trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and iodine-containing fluorinated vinyl ethers preferable. The fluororesin (C) has a polymer unit based on at least one monomer selected from the group consisting of ethylene [Et], propylene [Pr], and alkyl vinyl ether as a fluorine-free monomer. It may be.
The fluororesin (C) is more preferably a copolymer containing polymerized units based on at least one monomer selected from the group consisting of TFE, HFP, PAVE, CTFE, VdF and VF. The fluororesin (C) is also preferably a copolymer having a polymer unit based on Et as a fluorine-free monomer.
In the present specification, the “polymerized unit” means a part of the molecular structure of the fluorine-containing polymer (a) and a part based on the corresponding monomer.

The fluororesin (C) is composed of TFE / HFP copolymer [FEP], TFE / PAVE copolymer [PFA], Et / TFE copolymer, Et / TFE / HFP copolymer, polychlorotrifluoroethylene [PCTFE]. ], CTFE / TFE copolymer, Et / CTFE copolymer, polyvinylidene fluoride [PVdF], TFE / VdF copolymer, VdF / HFP / TFE copolymer, VdF / HFP copolymer, and polyfluoride It is preferably at least one selected from the group consisting of vinyl [PVF]. Moreover, if it is melt processability, it is also possible to use low molecular weight polytetrafluoroethylene [PTFE].
In the present specification, as described above, when “TFE / HFP copolymer” is described, a polymerization unit based on TFE (TFE unit) and a polymerization unit based on HFP (HFP unit) are included. It means that it is a copolymer containing. The same applies to other copolymers.

As PAVE in said PFA, what has a C1-C6 alkyl group is preferable, and PMVE, PEVE, or PPVE is more preferable. The PFA has a PAVE unit of more than 2% by mass and preferably 5% by mass or less, and more preferably 2.5 to 4.0% by mass.
The PFA may further be obtained by polymerizing other monomers as long as it has the above-described composition. As said other monomer, HFP is mentioned, for example. The said other monomer can use 1 type (s) or 2 or more types.
The other monomer to be polymerized with the PFA differs depending on the type, but it is usually preferably 1% by mass or less of the mass of the PFA. A more preferred upper limit is 0.5% by mass, and a still more preferred upper limit is 0.3% by mass.

The Et / TFE copolymer preferably has an Et unit: TFE unit molar ratio of 20:80 to 80:20. When the Et unit content is less than 20:80, productivity may be poor, and when the Et unit content exceeds 80:20, corrosion resistance may be deteriorated. More preferably, the molar ratio of Et units: TFE units is 35:65 to 55:45. The Et / TFE copolymer is a copolymer including a polymerized unit based on TFE and a polymerized unit based on Et, and may have a polymerized unit based on another fluorine-containing monomer.

The Et / TFE copolymer is at least one selected from the group consisting of other fluorine-containing monomers and monomers containing no fluorine in addition to Et units and TFE units as a monomer component. It is also one of the preferable forms that it has a monomer unit based on a seed monomer. The other fluorine-containing monomer is not particularly limited as long as it can be added to both ethylene and TFE, but a fluorine-containing vinyl monomer having 3 to 10 carbon atoms is easy to use. For example, hexafluoroisobutylene, _{CH 2 = CFC 3 F 6 H} , HFP and the like. Among them, the following general formula:
CH ₂ = CH-Rf ⁵
(Wherein Rf ⁵ represents a perfluoroalkyl group having 4 to 8 carbon atoms) and is preferably a fluorine-containing vinyl monomer. Moreover, as a monomer which does not contain fluorine at all, the following general formula:
CH ₂ = ^{CH-R 4}
(In the formula, R ⁴ is not particularly limited in carbon number, and may contain an aromatic ring, and may contain a carbonyl group, an ester group, an ether group, an amide group, a cyano group, a hydroxyl group, or an epoxy group. R ⁴ may not be fluorine.
In addition, the Et / TFE copolymer is an Et / TFE / HFP copolymer (EFEP), which is one of the preferred embodiments. Furthermore, other fluorine-containing monomers (excluding HFP), or You may have a monomer unit based on the monomer which does not contain a fluorine at all. The monomer other than ethylene and TFE is preferably 10 mol% or less, and more preferably 5 mol% or less of the total monomer component of the copolymer composed of ethylene and TFE. Et unit: TFE unit: The molar ratio of monomer units based on other fluorine-containing monomers or monomers not containing fluorine at all is 31.5 to 54.7: 40.5 to 64. 7: It is preferable that it is 0.5-10.

The above-mentioned PCTFE is a polymer whose polymer units are substantially composed only of CTFE units.

In the CTFE / TFE copolymer, the molar ratio of CTFE units to TFE units is preferably CTFE: TFE = 2: 98 to 98: 2, more preferably 5:95 to 90:10, More preferably, it is 20: 80-90: 10.
The CTFE / TFE copolymer is preferably a copolymer comprising CTFE, TFE, and a monomer copolymerizable with CTFE and TFE. Monomers copolymerizable with CTFE and TFE include ethylene, VdF, HFP, CH ₂ = CX ¹ (CF ₂ ) _n X ² (wherein X ¹ is H or F, X ² is H, F or Cl, n is an integer of from 1 to 10.) the monomer represented by, PAVE, _{and, CF 2 = CF-OCH 2} -Rf 3 ( wherein, Rf ³ is a perfluoroalkyl of 1 to 5 carbon atoms An alkyl perfluorovinyl ether derivative represented by the following formula :), among which at least one selected from the group consisting of ethylene, VdF, HFP and PAVE is preferable, and it is PAVE. More preferred. Examples of PAVE include those described above. The molar ratio of CTFE units, TFE units, and monomer units copolymerizable with CTFE and TFE is the total monomer units of CTFE units and TFE units: monomer units copolymerizable with CTFE and TFE = It is preferable that it is 90-99.9: 10-0.1.

In the Et / CTFE copolymer, the molar ratio of Et units to CTFE units is preferably CTFE: Et = 30: 70 to 70:30, and more preferably 40:60 to 60:40.

The PVdF is a polymer whose polymerization units are substantially composed only of VdF units.

The VdF / HFP copolymer preferably has a VdF / HFP molar ratio of 45 to 85/55 to 15, more preferably 50 to 80/50 to 20, and still more preferably 60 to 80/40. ~ 20. The VdF / HFP copolymer is a copolymer including a polymer unit based on VdF and a polymer unit based on HFP, and may have a polymer unit based on another fluorine-containing monomer. For example, VdF / HFP / TFE copolymer is also a preferred form.

As the VdF / HFP / TFE copolymer, a VdF / HFP / TFE molar ratio of 40 to 80/10 to 35/10 to 25 is preferable. The VdF / HFP / TFE copolymer may be a resin or an elastomer, but is usually a resin when having the above composition range.

The PVF is a polymer whose polymer units are substantially composed of only VF units.

The low molecular weight PTFE preferably has a number average molecular weight of 600,000 or less. S. The number average molecular weight can be determined by semi-treatment by the method of Wu (Polymer Engineering & Science, 1988, Vol. 28, 538, 1989, Vol. 29, 273).
The low molecular weight PTFE may be a TFE homopolymer or a modified PTFE. In the present specification, the above-mentioned “modified PTFE” means a product obtained by copolymerizing a small amount of a comonomer (modifier) with TFE so as not to impart melt processability to the obtained copolymer.
The modifier in the modified PTFE is not particularly limited as long as it can be copolymerized with TFE. For example, HFP and other perfluoroolefins; CTFE and other chlorofluoroolefins; trifluoroethylene and VdF and other hydrogen-containing materials Perfluorovinyl ether; perfluoroalkylethylene such as perfluorobutylethylene; ethylene and the like. Moreover, 1 type may be sufficient as the modifier used, and multiple types may be sufficient as it.
It does not specifically limit as perfluoro vinyl ether used as a modifier, For example, following general formula (I):
_{CF 2 = CF-ORf (I} )
(Wherein Rf represents a perfluoro organic group), and the like. In the present specification, the “perfluoro organic group” means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoro organic group may have ether oxygen.
As the perfluorovinyl ether used as the modifier, for example, perfluoro (alkyl vinyl ether) [PAVE] in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (I) is preferable. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.
In the modified PTFE, the proportion (mass%) of the modifier in the total amount of the modifier and TFE is usually preferably 1% by mass or less, and more preferably 0.001 to 1% by mass. It is also preferable that it is 0.001 mass% or more and less than 1 mass%.

The melting point of the fluororesin (C) is preferably 140 to 340 ° C, more preferably 160 to 320 ° C, and still more preferably 180 to 300 ° C. If the melting point of the fluororesin (C) is less than 140 ° C., it tends to bleed out at the time of cross-linking molding, and if it exceeds 340 ° C., it tends to be difficult to form convex portions on the surface of the molded product. is there.
The melting point is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].

The fluororesin (C) preferably has a melt flow rate [MFR] at 372 ° C. of 0.3 to 300 g / 10 min. If the MFR is too small, the low friction and non-stick properties may be inferior, and if the MFR is too large, the wear resistance may be inferior.
The MFR is a value obtained by measuring at a temperature of 372 ° C. and a load of 5 kg in accordance with ASTM D 1238.

Since the non-adhesiveness, low friction and wear resistance are excellent, the fluororesin (C) is a TFE / HFP copolymer, that is, a polymer unit based on tetrafluoroethylene, a polymer unit based on hexafluoropropylene, A copolymer (FEP) made of FEP is preferable from the viewpoint that the effect of reducing the friction coefficient of the molded article is good. FEP is particularly preferable in that the molded article has excellent heat resistance and exhibits excellent fuel barrier properties.

The FEP is preferably a copolymer comprising 70 to 99 mol% of TFE units and 1 to 30 mol% of HFP units, and a copolymer comprising 80 to 97 mol% of TFE units and 3 to 20 mol% of HFP units. It is more preferable that If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

FEP may be a copolymer comprising TFE, HFP, and a monomer copolymerizable with TFE and HFP. As the monomer, CF ₂ = CF-ORf ⁶ (wherein Rf ⁶ represents a perfluoroalkyl group having 1 to 5 carbon atoms.) Perfluoro (alkyl vinyl ether) [PAVE], CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and each represents a hydrogen atom or a fluorine atom, X ⁸ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10. And vinyl perfluorovinyl ether derivatives represented by CF ₂ ═CF—OCH ₂ —Rf ⁷ (wherein Rf ⁷ represents a perfluoroalkyl group having 1 to 5 carbon atoms). ,in , It is preferable that the PAVE.

The PAVE is preferably at least one selected from the group consisting of PMVE, perfluoro (ethyl vinyl ether) [PEVE], PPVE, and perfluoro (butyl vinyl ether). Among them, PMVE, PEVE and More preferably, it is at least one selected from the group consisting of PPVE.

Examples of the alkyl perfluorovinyl ether derivative is preferably a Rf ⁷ is a perfluoroalkyl group having 1 to 3 carbon _{atoms, CF 2 = CF-OCH 2 -CF} 2 CF 3 more preferred.

When FEP has a monomer unit derived from a monomer copolymerizable with TFE and HFP, the monomer unit derived from a monomer copolymerizable with TFE and HFP is 0.1 to 10 mol. It is preferable that the total of TFE units and HFP units is 90 to 99.9 mol%. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be poor, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

In the composition, the volume ratio of the rubber (A) to the fluororesin (C) (rubber (A)) / (fluororesin (C)) is preferably 60/40 to 99/1. If the amount of the fluororesin (C) is too small, the effect of reducing the friction coefficient may not be sufficiently obtained. On the other hand, if the amount of the fluororesin (C) is too large, the rubber elasticity may be remarkably impaired. From the viewpoint of good flexibility and low friction, (rubber (A)) / (fluororesin (C)) is more preferably 65/35 to 97/3, and 70/30 to 95 / More preferably, it is 5.

The molded body of the present invention preferably has a flexural modulus of 40 MPa or less. When the flexural modulus is 40 MPa or less, the molded article has excellent flexibility. The flexural modulus is more preferably 30 MPa or less, and still more preferably 20 MPa or less. The lower limit of the flexural modulus is not particularly limited.
The bending elastic modulus is a value measured by a method based on ASTM D790.

Next, the manufacturing method of the molded object of this invention is demonstrated.

The molded article of the present invention can be obtained by crosslinking a crosslinkable composition containing an uncrosslinked rubber (a) and a silicon dioxide-containing compound (B). In particular, the molded article of the present invention is preferably obtained by a production method described later.

The molded body of the present invention is
(I) a mixing step of mixing the uncrosslinked rubber (a) and the silicon dioxide-containing compound (B) to obtain a crosslinkable composition;
(II) a molding crosslinking step of molding and crosslinking the obtained crosslinkable composition; and
(III) The obtained crosslinked molded article can be produced by a method including a heat treatment step of heating to a temperature of 150 to 270 ° C.

The uncrosslinked rubber (a) is a rubber (A) before crosslinking.

(I) Mixing Step The method for obtaining the crosslinkable composition is not particularly limited as long as a method capable of uniformly mixing the uncrosslinked rubber (a) and the silicon dioxide-containing compound (B) is used. For example, there is a method of kneading the powder obtained by coagulating the uncrosslinked rubber (a) alone, the silicon dioxide-containing compound (B), and other additives and compounding agents as necessary with a kneader such as an open roll. It is done.
When the crosslinkable composition contains the silicon dioxide-containing compound (B), the Shore A hardness and the indentation hardness can be within the above-described ranges, and the ratio [X / Y] is 2.0 or more. Moreover, the molded object which has the said linear convex part can be obtained.

When the uncrosslinked rubber (a) is an uncrosslinked fluororubber, examples of the crosslinking system include a peroxide crosslinking system, a polyol crosslinking system, a polyamine crosslinking system, and the like, and a peroxide crosslinking system and a polyol crosslinking system. It is preferably at least one selected from the group consisting of systems. From the viewpoint of chemical resistance, a peroxide crosslinking system is preferred, and from the viewpoint of heat resistance, a polyol crosslinking system is preferred.
Therefore, as said crosslinking agent, at least 1 sort (s) of crosslinking agent selected from the group which consists of a polyol crosslinking agent and a peroxide crosslinking agent is preferable, and a polyol crosslinking agent is more preferable.
The blending amount of the cross-linking agent may be appropriately selected depending on the type of the cross-linking agent, but is preferably 0.2 to 5.0 parts by mass, more preferably 100 parts by mass of the uncrosslinked rubber (a). 0.3 to 3.0 parts by mass.

Peroxide crosslinking can be performed by using peroxide-crosslinkable uncrosslinked rubber and an organic peroxide as a crosslinking agent.

The non-crosslinked rubber capable of peroxide crosslinking is not particularly limited as long as it is an uncrosslinked rubber having a site capable of peroxide crosslinking. The site capable of peroxide crosslinking is not particularly limited, and examples thereof include a site having an iodine atom and a site having a bromine atom.

The organic peroxide may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. 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, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne -3, benzoyl peroxide, t-butyl peroxybenzene, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, t- Examples thereof include butyl peroxybenzoate. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.
0.1-15 mass parts is preferable with respect to 100 mass parts of uncrosslinked rubber (a), and, as for the compounding quantity of an organic peroxide, More preferably, it is 0.3-5 mass parts.

When the cross-linking agent is an organic peroxide, the cross-linkable composition preferably further contains a cross-linking aid. Examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N′-m-phenylenebismaleimide, 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, hexaallylphosphoramide, N, N, N ′, N′-tetra Allylphthalamide, N, N, N ′, N′-tetraa Rumaron'amido, trivinyl isocyanurate, 2,4,6-vinyl methyl trisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of excellent crosslinkability, mechanical properties, and flexibility.

The amount of the crosslinking aid is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 7.0 parts by weight, more preferably 100 parts by weight of the uncrosslinked rubber (a). Preferably it is 0.1-5.0 mass parts. When the amount of the crosslinking aid is less than 0.01 parts by mass, the mechanical properties are lowered or the flexibility is lowered. When it exceeds 10 parts by mass, the heat resistance is inferior and the durability of the molded product tends to be lowered.

Polyol crosslinking can be performed by using an uncrosslinked rubber capable of polyol crosslinking and a polyhydroxy compound as a crosslinking agent. As a compounding quantity of the polyhydroxy compound in a polyol bridge | crosslinking type | system | group, it is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of uncrosslinked rubber | gum (a) in which polyol crosslinking is possible. When the blending amount of the polyhydroxy compound is within such a range, the polyol crosslinking can be sufficiently advanced. More preferably, it is 0.02-8 mass parts. More preferably, it is 0.03-4 mass parts.

The uncrosslinked rubber that can be cross-linked with polyol is not particularly limited as long as it is a non-crosslinked rubber having a polyol cross-linkable site. The polyol-crosslinkable site is not particularly limited, and examples thereof include a site having a vinylidene fluoride (VdF) unit. Examples of the method for introducing the cross-linked site include a method of copolymerizing a monomer that gives a cross-linked site during polymerization of the uncrosslinked rubber (a).

As the polyhydroxy compound, a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance.

The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane. (Hereinafter referred to as bisphenol AF. Bisphenol AF can be obtained from Wako Pure Chemical Industries, Ltd., Central Glass Co., Ltd., etc.), 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) tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 ′, 5,5′-tetrabromobisphenol A and the like can be mentioned. 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. The compounding quantity of a polyhydroxy aromatic compound is 0.1-15 mass parts with respect to 100 mass parts of uncrosslinked rubber (a), Preferably it is 0.5-5 mass parts.

When the cross-linking agent is a polyhydroxy compound, the cross-linkable composition preferably further contains a cross-linking accelerator. A crosslinking accelerator accelerates | stimulates the production | generation of the intramolecular double bond in the dehydrofluorination reaction of a polymer principal chain, and the addition of the polyhydroxy compound to the produced | generated double bond.
The crosslinking accelerator may be used in combination with an acid acceptor such as magnesium oxide or a crosslinking aid.

Examples of the crosslinking accelerator include onium compounds. Among onium compounds, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and 1 It is preferably at least one selected from the group consisting of functional amine compounds, and more preferably at least one selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts.

The quaternary ammonium salt is not particularly limited. For example, 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. DBU-B For example, it can be obtained from Wako Pure Chemical Industries, Ltd.), 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-phenethyl-1,8- And diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3-phenylpropyl) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride, and the like. It is. Among these, DBU-B is preferable from the viewpoints of crosslinkability, mechanical properties, and flexibility.

The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltributylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. -2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and the like. Among these, benzyltriphenylphosphonium chloride (BTPPC) is preferable in terms of crosslinkability, mechanical properties, and flexibility. preferable.

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

The amount of the crosslinking accelerator is preferably 0.01 to 8.00 parts by mass, more preferably 0.02 to 5.00 parts by mass with respect to 100 parts by mass of the uncrosslinked rubber (a). . More preferably, it is 0.03-3.00 mass part. When the crosslinking accelerator is less than 0.01 parts by mass, the crosslinking of the uncrosslinked rubber (a) does not proceed sufficiently, and the heat resistance and the like of the resulting molded article may be lowered. When the amount exceeds 8.00 parts by mass, the moldability of the crosslinkable composition may decrease, the elongation in mechanical properties may decrease, and the flexibility may also decrease.

The acid acceptor is used to neutralize acidic substances generated during polyol crosslinking, and specific examples thereof include magnesium oxide and calcium hydroxide (for example, NICC5000 (manufactured by Inoue Lime Industry Co., Ltd.)). CALDIC # 2000, CALDIC # 1000 (Omi Chemical Industry Co., Ltd.)), calcium oxide, risurge (lead oxide), zinc white, dibasic lead phosphite, hydrotalcite, etc. It is preferably at least one selected from the group consisting of magnesium oxide and low activity magnesium.
In the polyol vulcanized fluororubber, the amount of the acid acceptor frequently used is a combination of 3 parts by mass of magnesium oxide (high activity) and 6 parts by mass of calcium hydroxide with respect to 100 parts by mass of the fluororubber. In the invention, the amount of the acid acceptor to be blended with the fluororubber is the viewpoint of obtaining an excellent low friction molded article, the viewpoint of realizing the indentation hardness in the above-mentioned range, and the linear convex portion on the molded article. From the viewpoint of formation, the amount of the acid acceptor is preferably reduced from the level.
For example, highly active magnesium oxide (for example, MA150 (manufactured by Kyowa Chemical Industry Co., Ltd.); U, U-2, CX-150 (manufactured by Kamishima Chemical Industry Co., Ltd.)) is not used in combination with other acid acceptors. If used, the blending amount is preferably 3.5 parts by mass or less and more preferably 2.5 parts by mass or less with respect to 100 parts by mass of the uncrosslinked rubber (A). Although a minimum is not specifically limited, 0.1 mass part may be sufficient.
When the crosslinkable composition contains a fluororesin, the highly active magnesium oxide is preferably 4.0 parts by mass or less, and 3.0 parts by mass or less with respect to 100 parts by mass of the uncrosslinked rubber (A). More preferably. Although a minimum is not specifically limited, 0.1 mass part may be sufficient.
For example, low-activity magnesium oxide (for example, MA30 (manufactured by Kyowa Chemical Industry Co., Ltd.); M, M-2, L (manufactured by Kamishima Chemical Industry Co., Ltd.)) is used without being used in combination with other acid acceptors. In the case, the blending amount is preferably 4.5 parts by mass or less, and more preferably 3.5 parts by mass or less with respect to 100 parts by mass of the uncrosslinked rubber (A). Although a minimum is not specifically limited, 0.1 mass part may be sufficient.
“Highly active magnesium oxide” is, for example, magnesium oxide having a BET specific surface area (m ² / g) of 130 to 170, and “low active magnesium oxide” is, for example, BET specific surface area (m ² / G) Magnesium oxide with 30-50.
The BET specific surface area can be measured using, for example, Autosorb-1 MP manufactured by Quantachrome.
Specifically, it can be measured by the following method.
Apparatus: Quantachrome Autosorb-1 MP
Measurement method: About 20 mg of a sample is introduced into a measurement cell, vacuum heat-treated at 482 K, measured at 77 K using a pure nitrogen gas having a purity of 99.99995% or more as a probe gas, and measured data is obtained by the BET method. Analyze with.
Measurement conditions: Measurement of nitrogen adsorption isotherm at 77K after vacuum heat treatment at 482K.

Polyamine crosslinking can be performed by using a polyamine-crosslinkable fluororubber and a polyamine compound as a crosslinking agent.

The fluoroamine crosslinkable fluororubber is not particularly limited as long as it is a fluororubber having a polyamine crosslinkable site. The polyamine-crosslinkable site is not particularly limited, and examples thereof include a site having a vinylidene fluoride (VdF) unit. Examples of the method for introducing the crosslinking site include a method of copolymerizing a monomer that gives a crosslinking site during the polymerization of the fluororubber.

Examples of the polyamine compound include hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-bis (aminocyclohexyl) methanecarbamate, and the like. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

In order to improve the compatibility of the silicon dioxide-containing compound (B) and the uncrosslinked rubber (a), the crosslinkable composition may contain at least one polyfunctional compound. The polyfunctional compound is a compound having two or more functional groups having the same or different structures in one molecule.
The functional groups possessed by the polyfunctional compound include carbonyl groups, carboxyl groups, haloformyl groups, amide groups, olefin groups, amino groups, isocyanate groups, hydroxy groups, epoxy groups, etc., which are generally known to have reactivity. Any group can be used. Compounds having these functional groups are expected not only to have high affinity with the rubber (A) but also to improve compatibility with the silicon dioxide-containing compound (B).

The above-mentioned crosslinkable composition is a usual additive blended in the rubber as necessary, for example, a filler, a processing aid, a plasticizer, a colorant, a stabilizer, an adhesion aid, a release agent, and imparting conductivity. Various additives such as an agent, a thermal conductivity imparting agent, a surface non-adhesive agent, a flexibility imparting agent, a heat resistance improving agent, and a flame retardant can be blended, and these additives do not impair the effects of the present invention. Use within a range.

The crosslinkable composition containing the uncrosslinked rubber (a) and the silicon dioxide-containing compound (B) has a silicon dioxide compound (B) content of 0.1 with respect to 100 parts by mass of the uncrosslinked rubber (a). It is preferably ~ 100 parts by mass.
When the silicon dioxide-containing compound (B) is too small, in the molded article of the present invention, the indentation hardness cannot be within the above-described range, and the ratio [X / Y] is 2.0 or more. In addition, the silicon dioxide-containing compound (B) does not segregate on the surface, and sufficient low friction may not be obtained. On the other hand, if the silicon dioxide-containing compound (B) is too much, rubber elasticity may be impaired. Crosslinking including the uncrosslinked rubber (a) and the silicon dioxide-containing compound (B) from the viewpoint that both the flexibility resulting from the rubber (A) and the low friction property resulting from the silicon dioxide-containing compound (B) are favorable. The content of the silicon dioxide-containing compound (B) is more preferably 0.3 parts by mass or more with respect to 100 parts by mass of the uncrosslinked rubber (a). Moreover, it is more preferable that it is 70 mass parts or less, and it is still more preferable that it is 40 mass parts or less.
As an example of the crosslinkable composition, 0.3 to 40 parts by mass of silicon dioxide-containing compound (B) with respect to 100 parts by mass of uncrosslinked fluororubber and uncrosslinked rubber (a) as uncrosslinked rubber (a). ), 0.03 to 4 parts by mass of a polyhydroxy compound, 0.03 to 3 parts by mass of a crosslinking accelerator, and 0.1 to 2.5 parts by mass of highly active magnesium oxide or 0.1 to 3 And a composition containing 5 parts by mass of low-activity magnesium oxide.

The crosslinkable composition preferably contains a fluororesin (C). The crosslinkable composition containing the fluororesin (C) is, for example,
A method of powder-mixing a powder obtained by coagulating each of the uncrosslinked rubber (a) and the fluororesin (C), a silicon dioxide-containing compound (B), and other additives and compounding agents as required,
The uncrosslinked rubber (a), the fluororesin (C) and the silicon dioxide-containing compound (B) are melt-kneaded, or the uncrosslinked rubber (a) and the fluororesin (C) are melt-kneaded and pre-compound (preliminary) A mixture), and then a silicon dioxide-containing compound (B), and if necessary, other additives and compounding agents are added and kneaded below the crosslinking temperature to obtain a full compound (crosslinkable composition),
After co-coagulating the uncrosslinked rubber (a) and the fluororesin (C) to obtain a co-coagulated composition, the co-coagulated composition, the silicon dioxide-containing compound (B), and others as necessary A method of obtaining a crosslinkable composition by kneading the additive and compounding agent,
Etc. can be obtained. Among them, pre-compound is obtained by melt-kneading uncrosslinked rubber (a), fluororesin (C) and silicon dioxide-containing compound (B), or by melt-kneading uncrosslinked rubber (a) and fluororesin (C). (Preliminary mixture) is prepared, then the silicon dioxide-containing compound (B), if necessary, other additives and compounding agents are added and kneaded below the crosslinking temperature to obtain a full compound (crosslinkable composition). Method, or after co-coagulating uncrosslinked rubber (a) and fluororesin (C) to obtain a co-coagulated composition, co-coagulated composition, silicon dioxide-containing compound (B), and necessary Accordingly, a method of obtaining a crosslinkable composition by kneading other additives and compounding agents is preferable.

Below, melt-kneading and co-coagulation will be described.

(Melt kneading)
The melt-kneading is performed at least with the uncrosslinked rubber (a) and the fluororesin (C) at a temperature not lower than the melting point of the fluororesin (C) by 5 ° C., preferably not lower than the melting point of the fluororesin (C). . The upper limit of the heating temperature is less than the lower thermal decomposition temperature of the uncrosslinked rubber (a) or the fluororesin (C).

Melt-kneading is not performed under conditions that cause crosslinking at that temperature (such as in the presence of a crosslinking agent, crosslinking accelerator, and acid acceptor), but at a melt-kneading temperature that is at least 5 ° C lower than the melting point of the fluororesin (C). Components that do not cause crosslinking (for example, a silicon dioxide-containing compound (B), only a specific crosslinking agent, only a combination of a crosslinking agent and a crosslinking accelerator, etc.) may be added and mixed during melt-kneading. Examples of conditions that cause crosslinking include a combination of a polyol crosslinking agent, a crosslinking accelerator, and an acid acceptor.

Therefore, in the melt kneading, the uncrosslinked rubber (a) and the fluororesin (C) are melt kneaded to prepare a precompound (preliminary mixture), and then the silicon dioxide-containing compound (B ), A two-stage kneading method in which a crosslinking agent and, if necessary, other additives and compounding agents are kneaded to form a full compound (crosslinkable composition) is preferred. Of course, a method of kneading all the components at a temperature lower than the crosslinking temperature of the crosslinking agent may be used.

Melt-kneading is carried out using a Banbury mixer, a pressure kneader, an extruder, etc. at a temperature of 5 ° C. lower than the melting point of the fluororesin (C), for example, 180 ° C. or higher, usually 220 to 300 ° C. It can be performed by kneading. Among these, it is preferable to use an extruder such as a pressure kneader or a twin screw extruder because a high shear force can be applied.

Further, full compounding in the two-stage kneading method can be performed using an open roll, a Banbury mixer, a pressure kneader, or the like at a temperature lower than the crosslinking temperature, for example, 100 ° C. or lower.

As a process similar to the melt kneading, there is a process (dynamic crosslinking) in which an uncrosslinked rubber is crosslinked in a fluororesin under the melt condition of the fluororesin. Dynamic crosslinking is a method in which uncrosslinked rubber is blended in a matrix of thermoplastic resin, the uncrosslinked rubber is crosslinked while kneading, and the crosslinked rubber is dispersed microscopically in the matrix. Is melt-kneaded under conditions that do not cause crosslinking (the absence of components necessary for crosslinking, or a compound that does not cause a crosslinking reaction at that temperature, etc.), and the matrix becomes uncrosslinked rubber (a). This is essentially different in that a crosslinkable composition in which the fluororesin (C) is uniformly dispersed in the rubber (a) is obtained.

(Coaggregation)
In the mixing step, the uncrosslinked rubber (a) and the fluororesin (C) are co-coagulated to obtain a co-coagulated composition, and then the co-coagulated composition and the silicon dioxide-containing compound (B) are mixed. It is preferable to obtain a crosslinkable composition by kneading.
By co-coagulating the uncrosslinked rubber (a) and the fluororesin (C), the linear convex portions formed on the surface can be formed more uniformly and finely, and the region having the convex portions The area ratio (occupancy) can be made sufficiently high. As a result, a molded body having a more excellent low friction property can be obtained.
When the crosslinkable composition contains a co-coagulated composition obtained by co-coagulating the uncrosslinked rubber (a) and the fluororesin (C), the uncrosslinked rubber (a) and the fluororesin ( C) is expected to be uniformly dispersed in the crosslinkable composition. It is considered that the molded article of the present invention having excellent low friction properties can be obtained by crosslinking and heat-treating such a crosslinkable composition.

Examples of the co-coagulation method include: (i) a method in which an aqueous dispersion of uncrosslinked rubber (a) and an aqueous dispersion of fluororesin (C) are mixed and then coagulated; (ii) uncrosslinked Method of coagulating after adding powder of rubber (a) to aqueous dispersion of fluororesin (C), (iii) Adding powder of fluororesin (C) to aqueous dispersion of uncrosslinked rubber (a) And then coagulating. As the co-coagulation method, the method (i) is preferable in that the uncrosslinked rubber (a) and the fluororesin (C) are particularly easily dispersed uniformly.

The coagulation in the coagulation methods (i) to (iii) can be performed using a flocculant, for example. Such a flocculant is not particularly limited, but examples thereof include aluminum salts such as aluminum sulfate and alum, calcium salts such as calcium sulfate, magnesium salts such as magnesium sulfate and magnesium chloride, sodium chloride and potassium chloride. And known aggregating agents such as monovalent cation salts. When coagulating with a flocculant, the pH may be adjusted by adding an acid or an alkali in order to promote aggregation.

The co-coagulated composition obtained by co-coagulating the uncrosslinked rubber (a) and the fluororesin (C) is, for example, an aqueous dispersion of the uncrosslinked rubber (a) and a fluororesin (C). It can be obtained by mixing with the aqueous dispersion and then coagulating, then collecting the coagulum and drying if desired.
Depending on the crosslinking system of the uncrosslinked rubber (a), a crosslinking agent may be required. Therefore, after coaggregating the uncrosslinked rubber (a) and the fluororesin (C) to obtain a coaggregated composition, A crosslinkable composition may be obtained by adding a silicon dioxide-containing compound (B) and a crosslinking agent to the depositing composition. That is, the crosslinkable composition may contain a crosslinking agent used in each crosslinking system. Moreover, the above-mentioned various additives may be included.
Usually, after adding a silicon dioxide compound (B) and a crosslinking agent to the co-coagulation composition, the co-coagulation composition, the silicon dioxide compound (B) and the crosslinking agent are mixed. The said mixing can be mixed at the temperature below melting | fusing point of a fluororesin (C) by the normal mixing method using a kneader etc., for example.

(II) Molding / Crosslinking Step This step is a step of molding and crosslinking the crosslinkable composition obtained in the mixing step (I) to produce a crosslinked molded product having substantially the same shape as the molded product to be produced.
The order of molding and crosslinking is not limited, and may be crosslinked after molding, may be molded after crosslinking, or may be molded and crosslinked simultaneously.

Examples of the molding method include, but are not limited to, a pressure molding method using a mold and the like, and an injection molding method.

As the cross-linking method, a steam cross-linking method, a normal method in which a cross-linking reaction is started by heating, a radiation cross-linking method, or the like can be adopted.
In the present invention, a crosslinking reaction by heating is preferable because the silicon dioxide-containing compound (B) smoothly moves to the surface layer of the crosslinkable composition.

The temperature at which crosslinking is performed is equal to or higher than the crosslinking temperature of the uncrosslinked rubber (a), and is preferably less than 200 ° C. When the crosslinking is performed at 200 ° C. or higher, the indentation hardness cannot be set to the above range, the ratio [X / Y] cannot be set to 2.0 or higher, or the convex portion on the line is There exists a possibility that the molded object which has can not be obtained.
Moreover, the temperature which performs bridge | crosslinking can make the said ratio [X / Y] 2.0 or more in the heat processing process (III) mentioned later, from the point which can form a linear convex part on the molded object surface, More preferably, it is 190 degrees C or less, More preferably, it is 180 degrees C or less. Moreover, the minimum of the temperature in bridge | crosslinking conditions is the bridge | crosslinking temperature of uncrosslinked rubber (a).
The crosslinking time may be appropriately determined depending on the type of the crosslinking agent used, but is usually 1 minute to 24 hours.

The molding and crosslinking methods and conditions may be within the range of known methods and conditions for the molding and crosslinking employed. Further, the molding and the crosslinking may be performed in any order, or may be performed in parallel at the same time. Furthermore, after the step (II), a step of cooling to less than the crosslinking temperature of the uncrosslinked rubber (a), for example, less than 150 ° C., may be performed.

In addition, in the crosslinking of uncrosslinked rubber, a post-treatment step called secondary crosslinking may be performed after the first crosslinking treatment (referred to as primary crosslinking), which will be described in the next heat treatment step (III). As described above, the conventional secondary crosslinking step is different from the molding crosslinking step (II) and the heat treatment step (III) of the present invention.

In addition, in the case where the molded article of the present invention encloses parts other than the composition containing the rubber (A) and the silicon dioxide-containing compound (B), in this step (II), for example, the above-mentioned in a mold in advance. It is only necessary to arrange parts and perform integral molding.

(III) Heat treatment step In the heat treatment step (III), the crosslinked molded product obtained in the step (II) is heated at a temperature of 150 to 270 ° C. By passing through the heat treatment step (III), the indentation hardness of the molded product can be in the above range, and the silicon dioxide compound (B) is segregated on the surface of the molded product to be produced, and linear protrusions are formed. Can be formed. When the cross-linked molded article contains a fluororesin (C), it is preferably heated to a temperature that is within the above-described temperature range and is equal to or higher than the melting point of the fluororesin (C). It is more preferable to heat to a temperature higher by at least ° C.

The heat treatment step (III) in the present invention is a treatment step performed for increasing the ratio of the silicon dioxide-containing compound (B) on the surface of the crosslinked molded product. ) And a temperature lower than the thermal decomposition temperature of the silicon dioxide-containing compound (B). The heating temperature is more preferably 155 ° C. or more, more preferably 160 ° C. or more, particularly preferably 170 ° C. or more, and 180 ° C. or more, from the viewpoint of easy friction reduction in a short time. It is especially more preferable that it is 200 degreeC or more. When the cross-linked molded article contains a fluororesin (C), it is preferably heated to a temperature that is within the above-described temperature range and is equal to or higher than the melting point of the fluororesin (C). It is more preferable to heat to a temperature higher by at least ° C.

When the heating temperature is lower than 150 ° C., the indentation hardness cannot be set in the above range, the ratio [X / Y] cannot be set to 2.0 or more, or cross-linking molding is performed. A sufficient convex portion cannot be formed on the product surface. In order to avoid the thermal decomposition of the rubber (A) and the silicon dioxide-containing compound (B), the heating temperature is the lower of the thermal decomposition temperature of the rubber (A) or the thermal decomposition temperature of the silicon dioxide-containing compound (B). Must be less than the temperature. When the cross-linked molded article contains a fluororesin (C), it must be lower than the lowest thermal decomposition temperature among the thermal decomposition temperatures of rubber (A), silicon dioxide-containing compound (B) or fluororesin (C). .

In the heat treatment step (III), the heating temperature is closely related to the heating time. When the heating temperature is relatively close to the lower limit, the heating is performed for a relatively long time, and when the heating temperature is relatively close to the upper limit, the heating is relatively short. It is preferable to employ time.
As described above, the heating time may be appropriately set in relation to the heating temperature. However, if the heat treatment is performed for a long time, the rubber (A) may be thermally deteriorated. Therefore, the heat treatment time is excellent in heat resistance. Practically up to 96 hours, except when using fluororubber.
Usually, the heat treatment time is preferably 1 minute to 72 hours, more preferably 1 minute to 48 hours, and further preferably 1 minute to 24 hours from the viewpoint of good productivity, but more excellent non-adhesiveness and low friction From the viewpoint of obtaining a molded body having a thickness of 8 hours or longer.

Further, the molded body produced through the steps (I) to (III) has the indentation hardness within the above-described range, the ratio [X / Y] is 2.0 or more, and the surface thereof. A convex part will be formed in the whole.
When the molded body of the present invention has a linear convex portion on its surface, if the convex portion is formed on the surface of the portion where non-adhesiveness and low friction properties are required, There may not be a convex part. And when manufacturing the compact | molding | casting of such an aspect, after performing the process of said (III), what is necessary is just to remove the convex part of an unnecessary part by grinding | polishing processing etc., for example.

By the way, in the conventional secondary crosslinking, the crosslinking agent remaining at the end of the primary crosslinking is completely decomposed to complete the rubber crosslinking, thereby improving the mechanical characteristics and compression set characteristics of the crosslinked molded product. This is a process performed for this purpose.
Therefore, the conventional secondary cross-linking conditions that do not assume the coexistence of the silicon dioxide-containing compound (B) are the same even if the cross-linking conditions accidentally overlap with the heating conditions of the heat treatment step. The heating conditions within the range of the objective of completion of crosslinking of the uncrosslinked rubber (a) (complete decomposition of the crosslinking agent) without considering the presence of B) as a factor for setting the crosslinking conditions are merely employed, When the silicon dioxide compound (B) is blended, the conditions for heat softening or melting the silicon dioxide compound (B) in the rubber crosslinked product (not the rubber uncrosslinked product) cannot be derived.

In the molding and crosslinking step (II), secondary crosslinking may be performed to complete the crosslinking of the uncrosslinked rubber (a) (to completely decompose the crosslinking agent).

Further, in the heat treatment step (III), the remaining crosslinking agent may be decomposed and the crosslinking of the uncrosslinked rubber (a) may be completed. However, the crosslinking of the uncrosslinked rubber (a) in the heat treatment step (III) is not limited. It is only a secondary effect.

The molded body obtained by the production method including the mixing step (I), the molding cross-linking step (II), and the heat treatment step (III) is convex on the surface of the molded body due to the surface migration phenomenon of the silicon dioxide-containing compound (B). It is presumed that the silicon dioxide-containing compound (B) ratio is increased in the surface region (including the inside of the convex portion) while the portion is formed.

The heat treatment step (III) is particularly excellent in heat treatment at 150 ° C. or higher, preferably 200 ° C. or higher, because the silicon dioxide-containing compound (B) is smoothly transferred to the surface layer.

Since the molded article of the present invention has excellent non-adhesiveness and low friction, it can be used as various parts in various fields such as automobile industry, aircraft industry, and semiconductor industry.
Fields used include, for example, semiconductor-related fields, automotive fields, aircraft fields, space / rocket fields, ship fields, chemical fields such as chemical plants, pharmaceutical fields such as pharmaceuticals, photographic fields such as developing machines, printing machines, etc. Printing field, painting field such as coating equipment, analysis equipment, analysis / physical machinery field such as instruments, food equipment field including food plant equipment and household goods, beverage food production equipment field, pharmaceutical production equipment field, medical parts field, chemical Chemical transportation equipment field, nuclear plant equipment field, steel field such as iron plate processing equipment, general industrial field, electrical field, fuel cell field, electronic parts field, optical equipment parts field, space equipment parts field, petrochemical plant equipment field Oil, gas and other energy resource exploration equipment parts field, oil refining field, oil transportation equipment parts field.

Examples of usage forms of the molded body of the present invention include, for example, a ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal, plunger seal, door seal, lip and face seal, gas delivery plate seal, wafer support seal, Various sealing materials such as barrel seals and packing can be used. As a sealing material, it can be used for the use by which the outstanding non-adhesiveness and low friction property are requested | required.
Also used as tubes, hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve discs, chemical-resistant coating materials, laminating materials, lining materials, etc. it can.
The cross-sectional shapes of the ring, packing, and seal may be various shapes. Specifically, for example, the ring, the packing, and the seal may have a square shape, an O shape, a ferrule shape, a D shape, Different shapes such as L, T, V, X, Y may be used.

In the semiconductor related field, for example, semiconductor manufacturing apparatus, liquid crystal panel manufacturing apparatus, plasma panel manufacturing apparatus, plasma display panel manufacturing apparatus, plasma address liquid crystal panel manufacturing apparatus, organic EL panel manufacturing apparatus, field emission display panel manufacturing apparatus, solar It can be used for a battery substrate manufacturing apparatus, a semiconductor transfer apparatus, and the like. Examples of such an apparatus include a gas control apparatus such as a CVD apparatus and a semiconductor gas control apparatus, a dry etching apparatus, a wet etching apparatus, a plasma etching apparatus, a reactive ion etching apparatus, a reactive ion beam etching apparatus, and a sputter etching. Apparatus, ion beam etching apparatus, oxidation diffusion apparatus, sputtering apparatus, ashing apparatus, plasma ashing apparatus, cleaning apparatus, ion implantation apparatus, plasma CVD apparatus, exhaust apparatus, exposure apparatus, polishing apparatus, film forming apparatus, dry etching cleaning apparatus, UV / O ₃ cleaning device, ion beam cleaning device, laser beam cleaning device, plasma cleaning device, gas etching cleaning device, extraction cleaning device, Soxhlet extraction cleaning device, high temperature high pressure extraction cleaning device, microwave extraction cleaning device, supercritical extraction Cleaning equipment Equipment, cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, stepper, coater / developer, CMP equipment, excimer laser exposure machine, chemical piping, gas piping, NF ₃ plasma treatment, O ₂ plasma treatment, fluorine plasma treatment Such as plasma processing equipment, heat treatment film forming equipment, wafer transfer equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD processes, equipment used in lamp annealing processes, reflow Examples include an apparatus used in the process.

Specific usage forms in the semiconductor-related field include, for example, gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, pump O-rings, gaskets, and other various sealing materials; resist developers and strips Various sealing materials such as O-rings for liquids, hoses and tubes; linings and coatings for resist developer tanks, stripping liquid tanks, wafer cleaning liquid tanks, wet etching tanks; pump diaphragms; rolls for wafer transfer; for wafer cleaning liquids Hose tube; Clean equipment sealant for clean equipment such as clean rooms; Sealing material for storage equipment for storing semiconductor manufacturing equipment and wafers; Diaphragm for transferring chemicals used in semiconductor manufacturing processes Can be mentioned.

In the automotive field, the engine body, main motion system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, basic electrical components, control It can be used for electrical components such as system electrical components and equipment electrical components. Note that the automobile field includes a motorcycle.
In the engine body and its peripheral devices as described above, the molded body of the present invention can be used for various sealing materials that are required to have heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance. Examples of such seal materials include seals such as gaskets, shaft seals, valve stem seals, and non-contact type or contact type packings such as self-seal packing, piston rings, split ring type packings, mechanical seals, and oil seals. In addition to types, bellows, diaphragms, hoses, tubes, electric wires, cushioning materials, anti-vibration materials, and various sealing materials used for belt AT devices.

Specific usage forms in the above fuel system include fuel injectors, cold start injectors, fuel line quick connectors, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, fuel O-rings used for tube bodies, fuel tube connectors, injectors, etc .; expiratory manifolds, fuel filters, pressure regulators, canisters, fuel tank caps, fuel pumps, fuel tanks, fuel tank sender units, fuel Used in injection devices, high-pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid subassemblies, fuel cut valves, etc. Seal, canister, purge, solenoid, valve seal, onboard, refueling, vapor, recovery (ORVR) valve seal, oil seal for fuel pump, fuel sender seal, fuel tank rollover valve seal, filler seal, Injector seal, filler cap seal, filler cap valve seal; fuel hose, fuel supply hose, fuel return hose, vapor (evaporation) hose, vent (breather) hose, filler hose, filler neck hose, hose in fuel tank (in Tank hoses), carburetor control hoses, fuel inlet hoses, fuel breather hoses and other hoses; gas filters used in fuel filters, fuel line connector systems, etc. Flange gaskets used for fuel tanks, carburetors, etc .; Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines; canisters, ORVR, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control Diaphragms used in equipment (CAC), pulsation dampers, canisters, auto cocks, etc., pressure regulator diaphragms for fuel injection devices; valves for fuel pumps, carburetor needle valves, rollover check valves, check valves; Breather), tubes used in fuel tanks; tank packings for fuel tanks, packings for accelerating pump pistons for carburetors; fuel sender anti-vibration parts for fuel tanks O-ring and diaphragm to control fuel pressure; accelerator pump cup; in-tank fuel pump mount; fuel injector injector cushion ring; injector seal ring; carburetor needle valve core valve; carburetor acceleration pump Examples include a piston; a valve seat of a composite air control device (CAC); a fuel tank main body; a seal part for a solenoid valve.

Specific usage forms in the brake system include: a diaphragm used for a master back, a hydraulic brake hose air brake, a brake chamber of an air brake; a hose used for a brake hose, a brake oil hose, a vacuum brake hose, etc .; an oil seal Various sealing materials such as O-ring, packing, brake piston seal, etc .; Master valve atmospheric valve, vacuum valve, brake valve check valve; Master cylinder piston cup (rubber cup), brake cup; Hydraulic brake Master cylinders and vacuum boosters, hydraulic brake wheel cylinder boots, anti-lock brake system (ABS) O-rings and grommets.

Specific usage forms of the basic electrical component include an insulator and sheath of an electric wire (harness), a tube of a harness exterior component, a grommet for a connector, and the like.
Specific usage forms in control system electrical components include coating materials for various sensor wires.
Specific use forms in the above-mentioned electrical equipment parts include car air conditioner O-rings, packing, cooler hoses, high pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug plugs for direct ignition, diaphragms for distributors, etc. Is mentioned. It can also be used for bonding electrical components.

Specific usage forms in the intake / exhaust system include packing used for intake manifolds, exhaust manifolds, etc., throttle body packing of throttles; EGR (exhaust gas recirculation), pressure control (BPT), wastegate, turbo waist Diaphragms used for gates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc .; EGR (exhaust recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbo Oil hose (return), turbo air hose, intercooler hose, turbocharger hose, hose connected to compressor of turbo engine equipped with intercooler, exhaust Hose such as air hose, air intake hose, turbo hose, DPF (diesel particulate filter) sensor hose; air duct or turbo air duct; intake manifold gasket; EGR seal material, AB valve afterburn prevention valve seat, (turbocharger etc. And a seal member used for groove parts such as a rocker cover and an air suction manifold used in an automobile engine.

In addition, in exhaust gas control parts, seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., and solenoids and armature seals for steam recovery and steam canisters; used as intake manifold gaskets, etc. Can do.
Further, in parts related to a diesel engine, it can be used as an O-ring seal for a direct injection injector, a rotary pump seal, a control diaphragm, a fuel hose, an EGR, a priming pump, a boost compensator diaphragm, and the like. It can also be used for O-rings, sealing materials, hoses, tubes, diaphragms used in urea SCR systems, urea water tank bodies of urea SCR systems, and urea water tank sealing materials.

Specific usage forms in the transmission system include transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, and the like.
Examples include a mission oil seal, an AT mission oil hose, an ATF hose, an O-ring, and packings.
Transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), and the like.
In addition to oil seals, gaskets, O-rings and packings for manual or automatic transmissions, oil seals, gaskets, O-rings and packings for continuously variable transmissions (belt type or toroidal type), ATF linear solenoids Packing, oil hose for manual transmission, ATF hose for automatic transmission, CVTF hose for continuous transmission (belt type or toroidal type), and the like.
Specific usage forms in the steering system include a power steering oil hose and a high pressure power steering hose.

Examples of forms used in the engine body of automobile engines include cylinder head gaskets, cylinder head cover gaskets, oil pan packings, gaskets such as general gaskets, seals such as O-rings, packings, timing belt cover gaskets, and control hoses. These include hoses, anti-vibration rubber for engine mounts, control valve diaphragms, and camshaft oil seals.
In a main motion system of an automobile engine, it can be used for a shaft seal such as a crankshaft seal and a camshaft seal.
In a valve system of an automobile engine, it can be used for a valve stem oil seal of an engine valve, a valve seat of a butterfly valve, and the like.
In automotive engine lubrication and cooling systems, engine oil cooler hoses, oil return hoses, seal gaskets, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, vacuum pumps In addition to a vacuum pump oil hose, etc., it can be used for a radiator hose, a radiator tank, an oil pressure diaphragm, a fan coupling seal, and the like.

Thus, specific examples of use in the automotive field include engine head gaskets, oil pan gaskets, manifold packings, oxygen sensor seals, oxygen sensor bushings, nitrogen oxide (NOx) sensor seals, and nitrogen oxide (NOx). Sensor bushing, sulfur oxide sensor seal, temperature sensor seal, temperature sensor bush, diesel particle filter sensor seal, diesel particle filter sensor bush, injector O-ring, injector packing, fuel pump O-ring and diaphragm, gearbox Seal, power piston seal, cylinder liner seal, valve stem seal, static valve stem seal, dynamic valve stem seal, automatic Speed pump front pump seal, rear axle pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission device O-ring and oil seal, exhaust gas recombustion device seal and bearing seal, Recombustion device hose, carburetor sensor diaphragm, anti-vibration rubber (engine mount, exhaust, muffler hanger, suspension bush, center bearing, strut bumper rubber, etc.), suspension anti-vibration rubber (strut mount, bush, etc.), Drive system anti-vibration rubber (damper, etc.), fuel hose, EGR tube and hose, twin cab tube, carburetor needle valve core valve, carburetor flange gasket, oil hose Oil cooler hose, ATF hose, cylinder head gasket, water pump seal, gear box seal, needle valve tip, motorcycle reed valve lead, automotive engine oil seal, gasoline hose gun seal, car air conditioner seal, engine intercooler Rubber hoses, seals for fuel line connector systems, CAC valves, needle tips, engine wires, filler hoses, car air conditioner O-rings, intake gaskets, fuel tank materials, distributor diaphragms, water hoses , Clutch hose, PS hose, AT hose, master back hose, heater hose, air conditioner hose, ventilation hose, oy Filler cap, PS rack seal, rack & pinion boot, CVJ boot, ball joint dust cover, strut dust cover, weather strip, glass run, center unit packing, body sight welt, bumper rubber, door latch, dash insulator, high tension cord, Flat belts, poly V belts, timing belts, toothed belts, V-ribbed belts, tires, wiper blades, diaphragms and plungers for LPG car regulators, diaphragms and valves for CNG car regulators, DME compatible rubber parts, diaphragms and boots for auto tensioners , Idle speed control diaphragms and valves, Auto speed control actuators, Negative pressure pump diaphragms and valves Kkubarubu and plunger, O. P. S. Diaphragms and O-rings, gasoline pressure relief valves, engine cylinder sleeve O-rings and gaskets, wet cylinder sleeve O-rings and gaskets, differential gear seals and gaskets (gear oil seals and gaskets), power steering devices Seals and gaskets (PSF seals and gaskets), shock absorber seals and gaskets (SAF seals and gaskets), constant velocity joint seals and gaskets, wheel bearing seals and gaskets, metal gasket coating agents, caliper seals, Examples include boots, wheel bearing seals, and bladders used for vulcanization molding of tires.

In the aircraft field, space / rocket field, and ship field, the fuel system and the lubricating oil system can be used.
In the aircraft field, for example, various aircraft seal parts, various aircraft parts for aircraft engine oil applications, jet engine valve stem seals, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc. They can be used as fuel supply hoses, gaskets, O-rings, aircraft cables, oil seals, shaft seals, and the like.

In the space and rocket field, for example, as lip seals, diaphragms, O-rings for spacecraft, jet engines, missiles, etc., O-rings for oil for gas turbine engines, anti-vibration stand pads for missile ground control, etc. Can be used.
In the marine field, for example, screw propeller shaft stern seals, diesel engine intake and exhaust valve stem seals, butterfly valve valve seals, butterfly valve valve seats and shaft seals, butterfly valve shaft seals, stern tube seals , Fuel hoses, gaskets, engine O-rings, marine cables, marine oil seals, marine shaft seals, and the like.

In the chemical field such as the above chemical plant and in the pharmaceutical field such as pharmaceuticals, it should be used in processes that require a high degree of chemical resistance, for example, processes for manufacturing chemicals such as pharmaceuticals, agricultural chemicals, paints, and resins. Can do.
Specific usage forms in the chemical field and chemical field include chemical equipment, chemical pumps and flow meters, chemical pipes, heat exchangers, agricultural chemical sprayers, agricultural chemical transfer pumps, gas piping, fuel cells, Analytical instruments and physics and chemistry instruments (for example, analytical instruments and instrument column fittings), exhaust gas desulfurization fittings, seals used in nitric acid plants, power plant turbines, etc., seals used in medical sterilization processes, Seals for plating solutions, roller seals for papermaking belts, joint seals for wind tunnels; chemical devices such as reactors and stirrers, analytical instruments and instruments, chemical pumps, pump housings, valves, tachometers, etc. O-ring for mechanical seal, O-ring for compressor sealing; high-temperature vacuum dryer, gas chromatography and p Packing used for tube connection parts of meters, glass cooler packing of sulfuric acid production equipment; Diaphragms used for diaphragm pumps, analytical instruments and physics and chemistry instruments; Gaskets used for analytical instruments and instruments; Analytical instruments and instruments Ferrules used in the field; valve seats; U cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc., corrosion resistant linings in anodized processing tanks; coating of masking jigs for plating; valves for analytical instruments and physics and chemistry instruments Parts; Expansion joints of flue gas desulfurization plants; Acid-resistant hoses for concentrated sulfuric acid, chlorine gas transfer hoses, oil-resistant hoses, rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubes used for analytical instruments and physics and chemistry instruments Medical tube; anti-trick for textile dyeing Down roll and dyeing roll; pharmaceutical Kusurisen; rubber stopper for medical, chemical bottle, chemical tank, bags, drug containers; Resistant acid, and the like protection gloves and boots, etc. solvent.

In the photographic field such as the developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, it can be used as a roll, a belt, a seal, a valve part, etc. of a dry copying machine.
Specific usage forms in the photographic field, printing field, and painting field include a surface layer of a transfer roll of a copying machine, a cleaning blade of a copying machine, a belt of a copying machine; for OA equipment such as a copying machine, a printer, and a facsimile machine. Rolls (for example, fixing rolls, pressure rolls, pressure rolls, etc.), belts; rolls for PPC copiers, roll blades, belts; rolls for film developing machines and X-ray film developing machines; printing rolls for printing machines , Scrapers, tubes, valve parts, belts; printer ink tubes, rolls, belts; coating, painting equipment coating rolls, scrapers, tubes, valve parts; development rolls, gravure rolls, guide rolls, magnetic tape production coating lines Guide rolls, gravure rolls for magnetic tape production coating lines, coating lows And the like.

In the field of food equipment including the above-mentioned food plant equipment and household goods, it can be used for food production processes, food transporters or food reservoirs.
Specific uses in the food equipment field include plate heat exchanger seals, vending machine solenoid valve seals, jar pot packing, sanitary pipe packing, pressure cooker packing, water heater seals, heat exchange. Gaskets for equipment, diaphragms and packing for food processing equipment, rubber materials for food processing equipment (for example, heat exchanger gaskets, diaphragms, O-rings and other seals, piping, hoses, sanitary packing, valve packing, when filling And packing for use as a joint between a mouth such as a bottle and a filler. Moreover, packing, a gasket, a tube, a diaphragm, a hose, a joint sleeve etc. which are used for products, such as alcoholic beverages and soft drinks, a filling apparatus, a food sterilization apparatus, a brewing apparatus, a water heater, various automatic food vending machines, etc. are mentioned.

In the nuclear plant equipment field, it can be used as a check valve, a pressure reducing valve, a seal of a uranium hexafluoride concentrator, etc. around the reactor.

Specific usage forms in the general industrial field include: sealing materials for hydraulic equipment such as machine tools, construction machines, hydraulic machines; seals and bearing seals for hydraulic and lubrication machines; sealing materials used for mandrels, etc .; dry cleaning equipment Seals used for windows, etc .; cyclotron seals, (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms and snakes for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in the air Pump lining, printing press rolls and belts, transport belts (conveyor belts), pickling rolls for pickling iron plates, robot cables, solvent rolling rolls such as aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials , Dust seals and lip rubber on sliding parts of cutting machines, garbage incinerators Basket, friction materials, and metal or rubber coating material. Also, pre-coating obtained by applying primer treatment to gaskets and sealants for equipment used in the papermaking process, sealants for clean room filter units, sealants for construction, fuel containers such as small generators and lawn mowers, and metal plates It can also be used as metal.

Specific examples of usage in the steel field include iron plate processing rolls for iron plate processing equipment.

Specific usage forms in the electrical field include: Shinkansen insulating oil caps, liquid-sealed transformer benching seals, transformer seals, oil well cable jackets, electric furnace oven oven seals, microwave oven window frames, etc. Used for sealing, sealing materials used when bonding CRT wedges and necks, halogen lamp sealing materials, electrical component fixing agents, sheathing heater end treatment sealing materials, electrical equipment lead wire terminals Sealing materials that can be used. Also used for coating materials such as oil and heat resistant wires, high heat resistant wires, chemical resistant wires, high insulating wires, high voltage transmission lines, cables, wires used in geothermal power generation equipment, wires used around automobile engines, etc. You can also. It can also be used for oil seals and shaft seals for vehicle cables. Furthermore, electrical insulating materials (for example, insulating spacers for various electrical equipment, insulating tapes used for cable joints and terminals, materials used for heat-shrinkable tubes, etc.) It can also be used for electronic equipment materials (for example, lead wire materials for motors, wire materials around high-temperature furnaces).

In the above fuel cell field, sealing materials between electrodes, electrode-separators, piping seals, packings, separators for hydrogen, oxygen, produced water, etc., in polymer electrolyte fuel cells, phosphate fuel cells, etc. It can be used as such.

In the electronic component field, it can be used as a heat radiating material, an electromagnetic shielding material, a gasket for a computer hard disk drive (magnetic recording device), and the like. In addition, shock absorbers for hard disk drives (crash stoppers), sealing agents, optical fiber quartz coatings, optical fiber coatings and other films and sheets, electronic components, anti-scattering materials for light bulbs, computer gaskets, large computer cooling hoses It is also used as a gasket for secondary batteries, particularly lithium secondary batteries, packing such as O-rings, connectors, dampers and the like.

In the chemical transport equipment field, it can be used as a safety valve or a shipping valve for trucks, trailers, tank trucks, ships, etc.

In the field of parts for exploring and mining energy resources such as oil and gas, they are used as various sealing materials used in the mining of oil and natural gas, boots for electrical connectors used in oil wells, and the like.
Specific uses in the energy resource search and mining equipment parts field include drill bit seals, pressure adjustment diaphragms, horizontal drilling motor (stator) seals, stator bearing (shaft) seals, and blowout prevention devices (BOP). Sealing material, sealing material used for rotation blowout prevention device (pipe wiper), sealing material used for MWD (real-time excavation information detection system), gas-liquid connector, logging used for logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packing, gas-liquid connectors, boots, etc.), inflatable packers and completion packers, packer seals used in them, seals and packings used in cementing devices, perforators (perforators) ) Seals, seals used for mud pumps, packing, motor lining, underground detector covers, U cups, composition seating cups, rotating seals, laminated elastomeric bearings, flow control seals, sand control seals, safety valves Seals, hydraulic fracturing equipment (fracturing equipment) seals, linear packer and linear hanger seals and packing, wellhead seals and packing, choke and valve seals and packing, LWD (logging during logging), Diaphragms used in oil exploration and oil drilling applications (for example, diaphragms for supplying lubricating oil such as oil drilling pits), gate valves, electronic boots, drill gun seal elements, and the like.

In addition, joint seals for kitchens, bathrooms, toilets, etc .; outdoor tent pulling cloth; seals for printing materials; rubber heat hoses for gas heat pumps, refractory rubber hoses; agricultural films, linings, weatherproof covers; It can also be used for tanks such as laminated steel plates used in the above.

Furthermore, it can be used as an article combined with a metal such as aluminum. Examples of such usage include door seals, gate valves, pendulum valves, and solenoid tips, as well as metal rubber parts combined with metals such as piston seals, diaphragms, and metal gaskets combined with metals.
It can also be used for rubber parts, brake shoes, brake pads, etc. in bicycles.

Moreover, a belt is mentioned as one of the forms of the molded object of this invention. Such a belt is also one aspect of the present invention.
The following are illustrated as said belt. Power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.) and conveyor belts (conveyor belts), such as parts around the engine of agricultural machinery, machine tools, industrial machinery, etc. Flat belts used in slabs; conveyor belts for transporting loose and granular materials such as coal, crushed stone, earth and sand, ore, and wood chips in a high-temperature environment; conveyor belts used in steelworks such as blast furnaces; precision Conveyor belts in applications exposed to high temperatures in equipment assembly factories, food factories, etc .; agricultural machinery, general equipment (eg, OA equipment, printing machines, commercial dryers, etc.), V belts for automobiles, etc. V-ribbed belts; Transmission belts for conveyor robots; Toothed belts for food machines and machine tools; Used in automobiles, OA equipment, medical devices, printing machines, etc. Such as a toothed belt to be like.
In particular, a timing belt is typical as a toothed belt for automobiles.

The belt may have a single layer structure or a multilayer structure.
In the case of a multilayer structure, the belt of the present invention may be composed of a layer made of the molded body and a layer made of another material.
In the multilayer belt, examples of the layer made of another material include a layer made of other rubber, a layer made of a thermoplastic resin, various fiber reinforcing layers, a canvas, and a metal foil layer.

The molded product of the present invention can also be used for industrial vibration-proof pads, vibration-proof mats, railway slab mats, pads, automobile vibration-proof rubbers, and the like. Anti-vibration rubbers for automobiles include anti-vibration rubbers for engine mount, motor mount, member mount, strut mount, bush, damper, muffler hanger, and center bearing.

Other usage forms include joint members such as flexible joints and expansion joints, boots, grommets, and the like. If it is a ship field, a marine pump etc. will be mentioned, for example.
A joint member is a joint used for piping and piping equipment. It prevents vibration and noise generated from the piping system, absorbs expansion and contraction due to temperature changes and pressure changes, absorbs dimensional fluctuations, earthquakes, and subsidence. It is used for applications such as mitigating and preventing the effects of
Flexible joints and expansion joints are preferably used as complex shaped molded bodies for shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering / water supply piping, automobiles, etc. it can.
Boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, piston boots and other automobile boots, agricultural machinery boots, industrial vehicle boots, building machinery boots, hydraulic machinery boots, empty It can be preferably used as a compact shaped article such as various industrial boots such as pressure machine boots, centralized lubricator boots, liquid transfer boots, fire fighting boots and various liquefied gas transfer boots.

The molded body of the present invention can also be used for filter press diaphragms, blower diaphragms, water supply diaphragms, liquid storage tank diaphragms, pressure switch diaphragms, accumulator diaphragms, diaphragms for air springs such as suspensions, and the like.

In addition, the molded body of the present invention can be used as a cushion material for hot press molding in the production of decorative plywood, printed circuit boards, electrical insulating boards, rigid polyvinyl chloride laminates, etc. made of melamine resin, phenol resin, epoxy resin, etc. Can also be used.

In addition, the molded article of the present invention can also contribute to impermeability of various supports such as weapon-related sealing gaskets and protective clothing against contact with invasive chemical agents.

Lubricating oils (engine oil, mission oil, gear oil, etc.) containing amine additives (especially amine additives used as antioxidants and detergent dispersants) used in automobiles, ships and other transportation systems O-Ring, V-Ring, X-Ring, Packing, Gasket, Diaphragm, Oil Seal, Bearing Seal, Lip Seal used for sealing and sealing oil, fuel oil and grease (especially urea grease) Can be used for plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals and other various sealing materials, etc., tube, hose, various rubber rolls, coatings, belts, valve discs It can also be used as such. It can also be used as a laminating material and a lining material.

Coating materials for heat and oil resistant wires used for lead wires of sensors that detect the oil temperature and / or oil pressure when contacting with the oil and / or engine oil of an internal combustion engine such as an automobile, as well as for automatic transmissions and engines It can also be used in a high temperature oil atmosphere such as in an oil pan.

In addition, a vulcanized film may be formed on the molded article of the present invention. Specifically, non-adhesive oil-resistant rolls for copiers, weather strips for weathering and anti-icing, infusion rubber stoppers, vial rubber stoppers, release agents, non-adhesive light transport belts, and anti-adhesion coatings on automobile engine mount play gaskets Applications include synthetic fiber coating, bolt members or joints having a thin packing coating layer, and the like.

In addition, about the automotive-related parts use of the molded object of this invention, the parts use of the motorcycle of the same structure is also included.
Examples of the fuel for the automobile include light oil, gasoline, diesel engine fuel (including biodiesel fuel), and the like.
The molded body of the present invention is particularly suitable as a sealing material, a sliding member or a non-adhesive member, among others.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Various characteristics in this specification were measured by the following methods.

(1) Coefficient of dynamic friction Measured with a friction player FPR2000 manufactured by Reska Corporation at a load of 20 g, a rotation mode, a rotation speed of 120 rpm, and a rotation radius of 10 mm. The numerical value was taken as the dynamic friction coefficient.

(2) Non-adhesive (tack value)
Adhesion in the process of pressing and pulling a measurement probe (cylindrical type φ5.0 mm, SUS304) controlled under the following conditions to a molded sheet with a surface temperature of 40 ° C., using a Reska-made tacking tester (TAC-II) The force was measured.
・ Entry speed 120mm / min ・ Pressure force 500gf
・ Pressurization time: 10 seconds ・ Peeling speed: 600 mm / min

(3) Shape of convex portion Using a color 3D laser microscope (VK-9700) manufactured by Keyence Corporation, an arbitrary region (200 μm × 280 μm) on the surface of the molded product was observed to confirm the presence or absence of a linear convex portion. .

(4) Infrared spectroscopy (IR) analysis Using a Fourier transform infrared spectrometer (FT-IR NICOLET6700) manufactured by Thermo Fisher Scientific Co., Ltd. irradiated with light, the reflected light (or transmitted light) of the spectrum obtained by spectroscopy of the intensity of the absorption position 1097Cm ^-1, the intensity of the absorption position 1395Cm ^-1 measured intensity ratio X and Y ( (Intensity at absorption position 1097 cm ⁻¹ ) / (Intensity at absorption position 1395 cm ⁻¹ ) was calculated (X is an intensity ratio when the surface of the molded body was measured, and Y was an intensity ratio when the inside of the molded body was measured. Is).
The IR analysis inside the molded body was performed using a cross section inside the test piece obtained by cutting the obtained molded body with a cutter or the like.

(5) Shore A hardness Measured according to JISK6253. The peak value was used for the numerical value.

(6) Indentation hardness Using an ultra-fine indentation hardness tester (ENT-2100, manufactured by Elionix), the measurement was performed under the following measurement conditions.
Number of load splits: 500
Load step interval: 20 [msec]
Maximum load holding time: 5000 [msec]
Maximum number of measurements when holding: 250
Unloading start load: 10 [uN]
Unloading end load: 0 [uN]
Unloading division number: 500
Unloading step interval: 20 [msec]

The materials used in Table 1 and the specification are as follows.

Fluoro rubber (A1)
Daikin Industries, Ltd. (binary crosslinkable fluororubber, VdF / HFP copolymer, fluorine content 66 mass%)
Fluoro rubber (A2)
Daikin Industries, Ltd. (binary fluorine rubber dispersion, VdF / HFP copolymer, fluorine content 66 mass%)

Fluororesin FEP (TFE / HFP copolymer) aqueous dispersion (solid content concentration 21% by mass, melting point 215 ° C.) (Fluororesin dispersion (FEP aqueous dispersion) (B1))

Filler carbon black (N990)

Crosslinker 2,2-bis (4-hydroxyphenyl) perfluoropropane

Cross-linking accelerator N-8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride

Acid acceptor magnesium oxide (high activity)
Magnesium oxide (low activity)
Calcium hydroxide

Silicon dioxide compound Silica metasilicate sodium nonahydrate No.1 Sodium silicate No.1 Potassium silicate

Example 1
The predetermined compound shown in Table 1 was mixed with fluororubber with an open roll to obtain a crosslinkable composition (fluororubber composition).
Then, it shape | molded in the shaping die and obtained the crosslinked molded product. The obtained cross-linked molded product was placed in a heating furnace maintained at 230 ° C. for 24 hours and subjected to heat treatment to obtain a molded product. FIG. 5 shows a 3D image obtained by observing the surface of the molded body obtained in Example 1 with a laser microscope.

Examples 2-9 and Comparative Examples 1-10
A cross-linkable composition, a cross-linked molded article, and a molded body subjected to heat treatment were obtained in the same manner as in Example 1 except that the blending amounts shown in Table 1 or Table 2 were used. 3D images observed with a laser microscope are shown in FIGS. 6 to 18 by taking the surfaces of the molded bodies obtained in Examples 2 to 6 and Comparative Examples 1 to 8 as examples.

Examples 10-12
In a vacuum emulsifier, an aqueous solution in which 2000 cc of water and 12 g of aluminum sulfate are mixed in advance, an FEP aqueous dispersion (B1) and a dispersion of fluororubber (A2), so that the solid content becomes a mass ratio shown in Table 1. 810 g of a premixed solution was added to the mixture, mixed at 4000 rpm for 3 minutes, and co-coagulated. After co-coagulation, the solid content was taken out and dried in a drying furnace at 100 ° C. for 24 hours.
A predetermined composition shown in Table 1 was mixed with the co-coagulated product with an open roll to obtain a crosslinkable composition (fluororubber composition).
Then, it shape | molded in the shaping die and obtained the crosslinked molded product. The obtained cross-linked molded product was placed in a heating furnace maintained at 250 ° C. for 24 hours and subjected to heat treatment to obtain a molded product. 20 and 21 show 3D images obtained by observing the surfaces of the molded bodies obtained in Examples 10 and 11 with a laser microscope.

11: convex part 12: concave part 13: top part 14: inclined surface 15: branching part

Claims (6)

Rubber (A) ,
0.1 to 100 parts by mass of the silicon dioxide-containing compound (B) with respect to 100 parts by mass of the rubber (A),
0.1 to 2.5 parts by mass of highly active magnesium oxide with respect to 100 parts by mass of rubber (A) or 0.1 to 4.5 parts by mass of low activity with respect to 100 parts by mass of rubber (A) Of magnesium oxide,
A molded body comprising a composition comprising
Shore A hardness is 95 or less,
Push der indentation hardness measured is 400 N / mm ² or more loads as 10μN is,
The molded article characterized in that the rubber (A) is fluororubber . Ratio below X and Y [X / Y] is, the molded body according to claim 1, wherein at least 2.0.
X: Ratio of the intensity (bX) at the absorption position 1097 cm ^{−1 and} the intensity (aX) at the absorption position 1395 cm ⁻¹ , which was measured by infrared spectroscopic analysis of the surface of the molded body [intensity (bX) / intensity (aX )]
Y: Ratio of the intensity (bY) at the absorption position 1097 cm ⁻¹ and the intensity (aY) at the absorption position 1395 cm ⁻¹ , which was measured by infrared spectroscopic analysis of the inside of the molded body [intensity (bY) / intensity (aY )] The molded article according to claim 1 or 2 , wherein the composition further contains a fluororesin (C). The molded article according to claim 3 , wherein the volume ratio of the rubber (A) to the fluororesin (C) is 60/40 to 99/1. The molded article according to claim 1, 2, 3, or 4 , wherein the molded article has a linear protrusion on the surface. The molded article according to claim 1, 2, 3, 4 or 5, which is a sealing material, a sliding member or a non-adhesive member.