WO2001053411A1

WO2001053411A1 - Crosslinking composition

Info

Publication number: WO2001053411A1
Application number: PCT/JP2001/000107
Authority: WO
Inventors: Kazuyoshi Kawasaki; Tsuyoshi Itagaki; Katsuhiko Iseki; Takafumi Yamato; Tsuyoshi Noguchi; Mitsuru Kishine
Original assignee: Daikin Industries, Ltd.
Priority date: 2000-01-18
Filing date: 2001-01-12
Publication date: 2001-07-26
Also published as: JP4887595B2

Abstract

A crosslinking composition which comprises (A) a fluoroelastomer comprising tetrafluoroethylene units, perfluoroalkyl vinyl ether units, and olefinic hydrocarbon units and having one or more kinds of crosslinking reactive groups selected from among cyano, carboxyl and alkoxycarbonyl and (B) a crosslinking agent consisting of a compound having at least two functional groups represented by the general formula (I) [wherein R1s are each independently OH, NH¿2?, SH or NH-R?2¿ (wherein R2 is C¿1-10? alkyl which may contain 1 to 4 oxygen atoms and/or a halogen atom, or a phenyl or benzyl group which may have 1 to 5 substituents)]. This composition can give products of crosslinking of fluoroelastomers excellent in heat resistance and chemical resistances including steam resistance, and can provide crosslinkable fluoroelastomer compositions excellent in processability.

Description

Akira Itoda For crosslinking—composition technology

The present invention provides a bridge formed product that excels in chemical resistance such as steam resistance as well as heat resistance, and also excels in workability. The present invention relates to a fluorine-containing elastomer composition for crosslinking. This composition is useful as a seal material for semiconductor production equipment, a seal material for oxygen sensors, and a seal material used in oilfield drilling environments. is there . Background technology

Fluorine-containing elastomers, especially tetrafluoroethylene

(TFE) and a copolymer of perfluoro (alkyl vinyl ether) (PAVE) and a hydrocarbon-based olefin. On the other hand, fluorine-containing elastomers containing an iodine atom, a bromine atom or a nitrile group (CN) are superior in properties such as base resistance and addition resistance. It is used as a sealing material such as a single-ring shaft, etc. after being cross-linked by peroxyside. Japanese Patent Publication No. 7-95043, Japanese Patent Publication No. 7-3101). However, high heat resistance is required for a seal material for an oxygen sensor of a vehicle engine, which is described in Japanese Patent Application Laid-Open No. 8-68787. It was supposed that only those who were self-propelled rosters could be used.

In addition, Japanese Patent No. 25875778 discloses an olefin copolymer containing TFE-PAVE-ethylene-CN. The document states that the elastomer is to be bridged with tetraphenylphenyl tin. However, the use of organic tin is not preferred in terms of safety in the environment, and the bridge obtained with poor workability is also resistant to chemicals. There is a problem.

In addition, the official gazette of Japanese Patent Laid-Open No. 8-1047879 contains a tertiary copolymer with TFE-PAVE-CN-containing monofluorofluorin vis-a-vis It is described that those bridged with a compound or bis (alumino phenol) are superior in compression set when used with a compound or bis (alumino phenol). . In this publication, monomers that can be copolymerized with the aforementioned ternary copolymer include fluorinated olefins, ethylene, and vinyl acetate. Although vinyl monomers are described, there are no specific examples of quaternary copolymers obtained by co-polymerizing them, and they are heat-resistant, chemical-resistant, and so on. Not only is it excellent in workability and workability, but it is also excellent in compression set resistance, which is the purpose of Japanese Utility Model Publication No. 8-1047497. It is not even stated whether or not. In addition, cross-linking requires heavy metal lead oxide as an acid acceptor and expensive crown ether as a bridging aid, which is environmentally friendly. There is room for improvement in terms of cost.

The purpose of the present invention is to provide a fluorine-containing elastomer cross-linked material that is excellent in heat resistance and also in chemical resistance such as steam resistance. Another object of the present invention is to provide a crosslinkable fluorine-containing elastomer composition which is excellent in processability. Disclosure of the invention

In other words, the present invention is based on (A) Tetrafluoroethylene (TFE) units and perfluoro (Alkyl Biertel) (PAVE) Unit, and a hydrocarbon-based olefin unit, and as a crosslinkable reactive group, a nitrile group, a carboxyl group, or an alkyl group. Fluorine-containing elastomers having a hydroxycarbonyl group or two or more of these, and (B) Formula (I):

(Wherein R ¹ is the same or different and OH, NH ₂ , SH or NH—R ² (R ² is 1 to 4 oxygen atoms and / or Alkyl group having 10 alkynes which may contain a logene atom, or phenyl group which may have 1 to 5 substituents or A bridging agent), which is a compound containing at least two functional groups (I) represented by any one of the following: Cross-linking composition

The present invention also relates to a cross-linked molded product obtained by cross-linking the cross-linking composition of the present invention, wherein the formed product is a sealant for a semiconductor manufacturing apparatus, an oxygen sensor. It is suitable for seal materials for use in seals and seal materials used in oil field drilling environments.

In addition, the present invention provides a hydrocarbon-based olefin unit having a TFE unit of 25 to 75 mol%, a PAVE unit of 20 to 45 mol%, and a carbon number of 2 to 4; And a cross-linkable reactive group such as a carboxyl group and a Z or alkoxycarbonyl group. The present invention also relates to a novel fluorine-containing elastomer having a viscosity at 100: of not less than 20. BEST MODE FOR CARRYING OUT THE INVENTION The cross-linking composition of the present invention is a specific cross-linkable fluorine-containing elastomer containing a hydrocarbon-based olefin unit. (A) and a specific cross-linking agent (B) having an amino group. The crosslinkable fluorine-containing elastomer (A) is as described above.

It contains TFE units, PAVE units, and hydrocarbon-based olefin units, and is a cross-linking reactive group such as a nitrile group, a carboxyl group, or an aryl group. It is a fluorine-containing elastomer that has a hydroxyl group.

PAVE includes a perforated mouth (methyl vinyl ether) (PMVE), a perforated mouth (ethyl vinyl ether) (PEVE), Perforated mouths (PPVE) (PPVE), etc., are excellent. Among them, PMVE is preferred because of its excellent cold resistance. .

Examples of hydrocarbon-based olefins include, but are not limited to, ethylene, pyrene, 11-butene, and isobutene. Is it superior to the physical properties of the bridge? ¾ Ash? ^ Hydrocarbon-based olefins of numbers 2 to 4, of which ethylene is preferred.

The content ratio of TFE units, PAVE units, and hydrocarbon-based olefin units (TFE / PAV / hydrogenated ash-based olefins) is mol%, and is 25 to 75/20. ~ 45/1 to 50/50, preferably 30 to 60/25 to 45 /;! ~ 30. In particular, when the amount of TFE decreases, the mechanical properties of the obtained crosslinked product decrease, and when the amount of PAVE decreases, the sealability particularly at low temperatures decreases. When the TFE power increases, the sealability at low temperatures decreases, and when the PAVE increases, the mechanical properties of the obtained crosslinked product decrease. As the amount of hydrocarbon-based olefin increases, the heat resistance decreases. When the amount of hydrogenated hydrocarbons decreases, the cold resistance decreases.

Examples of the cross-linking reactive group that imparts a cross-linking reaction to the fluorine-containing elastomer (A) include a nitrile group, a carboxyl group, and an alkoxy group. It is a carbonyl group or two or more of these. Alkoxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, and propyloxycarbonyl. Nil groups and the like are particularly preferred, especially those having 1 to 3 carbon atoms. The content of these bridging reactive groups is 5 mol% or less, preferably 2 mol% or less from the viewpoint of ensuring the elongation of the cost and the crosslinked product. However, the physical properties of the crosslinked product, in particular, the compression set resistance is preferably at least 0.2 mol%, more preferably at least 0.4 mol%, from the viewpoint of good compression set resistance.

As a method for introducing a cross-linkable reactive group, a cross-linkable reactive group or a monomer having a group that can be converted into a cross-linkable reactive group is copolymerized. There is a method (copolymerization method), a method of converting the polymerization initiator portion of the polymerization terminal into a carboxyl group or the like (terminal group conversion method).

The monomers used in the copolymerization method include:

C F 3

I

CF ₂ = CF (OCF ₂ CF-O — ^-CF ₂ ) _n X ³ (where m is 0 to 5, n is 1 to 8),

CF ₃ -CF-CF ₂ OCF) _n CF ₂ OCF = CF ₂

I I

X ³ CF 3

(n is 1 to 4),

CF ₂ = CFO (CF ₂ ) _n OCF (CF ₃ ) X ³

(n is 2 to 5),

CH ₂ = CFCF ₂ (OCFCF ₂ ) _n OCFX ³

C F 3 C F 3

(n is 0-5),

(n is 1 6)

CF ₂ = CFCFOCFCFO 4 CF-X

C F 3 C F 3

[X ³ is CN, COOH or is Ru Oh in the COOR ^⁵ (R ⁵ is A Le key Lumpur based but it may also be have a full Tsu iodine atom of-carbon number of 1 to 1 0'm free)], or Ha

X = C O O M

(M is NH ₄ or the Ru Oh in A Le force Li Metal)

Monomers, carboxy group-containing monomers, alkoxycarbonyl-group-containing monomers, carboxylate, etc. What are you going to do? Of these, the carbonate can be easily converted to a carboxyl group by the acid treatment described below.

If at least one of these terminal groups is a carboxyl group or an alkoxycarbonyl group, a nitrile group Alternatively, it is preferable to co-polymerize a monomer containing a carboxyl group from the viewpoint of bridge reactivity.

The fluorine-containing elastomer of the present invention can be manufactured by a polymerization method such as an emulsion polymerization method, a suspension polymerization method, and a solution polymerization method.

The polymerization initiator is preferably a carboxyl group or a group that can be converted to a carboxyl group (for example, acid fluoride). , Acid chloride, CF ₂ OH, each of which produces a carboxyl group in the presence of water), or one C〇OM (M is NH ₄ Or Alkali metal) (which produces a carboxyl group in the presence of an acid) at the end of the elastomer. Anything that can be present is used. Specific examples include ammonium persulfate (APS), potassium persulfate (KPS), and the like.

In addition, a chain transfer agent usually used for adjusting the molecular weight may be used, but it is possible to use a hydroxyl group or an alkoxy group introduced into the terminal. Since the proportion of groups that can be converted to carbonyl groups is reduced, it is better not to use them as much as possible. However, this is not a limitation, as long as the chain transfer agent can cause the above-mentioned group to be present at the end of the elastomer. If no chain transfer agent is used, the molecular weight depends on the polymerization being carried out at low pressure, for example below 2 MPa a · G, preferably below IMP a · G. Just adjust it. Other polymerization conditions are not particularly limited, but the polymerization products having a carboxyl group at the terminal end and at the end or in the branched chain will be described later. In order to obtain the compound without using a sour acid treatment, it is preferable that the pH of the polymer is set to a strongly acidic value of 3 or less.

Depending on the polymerization conditions, the polymerized product thus obtained may or may not contain a free calilepoxyl group. By performing the following acid treatment, it can be converted to a free carboxyl group.

One of the important features of the present invention is the acid treatment of the polymer product, and the metal salt of carboxylate present in the polymer product. In some cases, a group such as ammonium salt is converted to a carboxyl group. As the acid treatment method, for example, washing with hydrochloric acid, sulfuric acid, nitric acid, or the like, or the system of the mixture after the polymerization reaction with these acids is adjusted to pH 3 or higher. The method below is appropriate.

This acid treatment is applied as a coagulation means when the polymerized product is isolated from the polymerized reaction mixture by coagulation, which simplifies the process. Preferred from the point of view. Alternatively, acidify the polymer mixture Alternatively, the polymer product may be subsequently isolated by means such as freeze-drying. In addition, methods such as coagulation by supersonic waves and coagulation by mechanical force can be adopted.

It is also possible to introduce a carboxyl group by oxidizing a fluorine-containing elastomer containing iodine or bromine with fuming nitric acid. .

Of the above bridging fluorine-containing elastomers (A), T

FE unit of 25 to 75 mol% and PAVE unit of 20 to 45 mol% and carbon sai 2 to 4 of hydrogenated hydrocarbon unit 0 to 50 mol% It is a copolymer having a hydroxyl group and Z or an alkoxycarbonyl group as a cross-linkable reaction group. A new fluorine-containing elastomer with a viscosity of 20 or more at 0 is a new elastomer

Fluorine-containing elastomers (A) can be used in high energy applications such as bridge methods that do not use cross-linking agents, such as electron beam irradiation, radiation irradiation, and ultraviolet irradiation. Crosslinking can be carried out by the gamma ray irradiation method. However, the bridging composition of the present invention includes a nitrile group, which has a heat resistance and a chemical that improves the chemical resistance. A crosslinking agent (B) having an amino group capable of reacting with a carboxyl group or a alkoxycarbonyl group is to be combined.

The cross-linking agent (B) is used to form the cross-linked structure,

(In the formula, R ¹ is the same force or different, 〇H, NH ₂ , SH or NH—R ² (R ² is 1 to 4 oxygen atoms and Or an alkyl group having 1 to 10 carbon atoms, which may contain a halogen atom, or 1 to 5 substitution groups. At least two, preferably at least 2 to 3, functional groups (I) represented by at least one of an enyl group or a benzyl group). There are two, especially preferably two.

NH cans ability groups (I) - lower A 1-6 In example bets had a as a location substituent R ² Contact only that the R ² in CHCHC 3 H _7, etc.-carbon number of 1 to 1 0 Special of Alkyl group; — CF

C ₂ F ₅ , -CH ₂ F, CH, CFCH, CF, etc., a lower alkyl group containing 1 to 10 carbon atoms, especially 1 to 6 fluorine atoms containing a fluorine atom; perfluoro Alkyl groups containing an oxygen atom such as an alkyl ether group and a perfluoroalkoxy group; a phenyl group; a benzyl group C _fi FCH, CF, etc. A phenyl or benzylyl group in which 1 to 5 hydrogen atoms have been substituted with a fluorine atom of the formula: 1 C ₆ H ₅ — _n (CF 3) _n , -CH 2 C ₆ H ₅ _ _n (CF 3) _n (where n is an integer from 1 to 5) — A CF or ₃ to 5 hydrogen atoms replaced with a hydrogen atom or The benzyl group is removed.

Of these, phenyl has excellent heat resistance, good bridge responsiveness, and is relatively easy to synthesize. The base or CH ₃ is preferred.

Particularly preferred crosslinking agents (B) are of the formula (II):

(Wherein, R ¹ is the same as above. R ³ is _S 0 ₂ —, — 〇 _, — CO —, number of carbons: alkylene group of ~ 6, number of carbon atoms:! ~ ~ The perfluoroalkylene group of 10 is a single bond or a formula (III): CF

Which is a group represented by). Note that the positional relationship between the NH ₂ group and the R ¹ group with respect to the phenyl group in the left and right government function groups (I) may be the same on the left and right or vice versa.

Preferable specific examples of the arylene group which may be substituted for R ³ include, but are not limited to, those having 1 to 6 carbon atoms. An unsubstituted alkylene group or a perfluorinated alkylene group having 1 to 10 carbon atoms, such as a perfluoroalkylene group. Then

C F 3

I

One C one CF 3 and so on. Name you, is this is these R ^3, especially public flat 2 - 5 9 1 7 No. 7 public report, JP open flat 8 - 1 2 0 1 4 6 JP, etc. bi-scan di A Mi Roh off d d It is known as an example of a metal compound.

R ³ may be bonded at any position on the left and right benzene rings, but it is important that the formation is easy and the bridge reaction proceeds easily.ゝet al., it was or NH ₂ groups to join in the jar by ing in Lesゝshift or Ganoderma \ ° La position of the R ¹ group is and this Ru Lesゝnot the good or.

Specific examples include, but are not limited to, a 2,2-bis (3,4-diaminophenyl) hex-a-floor mouth pan , Bis (3, 4 — diaminophenyl) methane, vis (3, 4 — diaminofenyl) ether, 3, 3 '― Bisaminoaminophenyl compounds such as diaminobenzidine, 3,3 ', 4,4'-tetramethylaminobenzophenone; 2,2—Vis [3—Amino 1-41 (N—Methylylamino) phenyl] 2, 2—Vis [3 -4-(N-ethylamino) phenyl] to the fluorophore. , 2, 2-vis [3-ami no 4-(N-propylamino) phenyl] hexafluoropropane, 2, 2 _ vis [3—Amino 1_4_ (N—Fenirile Amino) Fenil] Hexafluoropropane, 2, 2—Visions [3—Amino 1 4 1 (N-North-fluorophenyl) amino] hexafluoropropane, 2, 2—Visions [3—Ami-no-ichi 4 — (N—Benzylamino) phenyl] hexafluoropropane, 3, 3 '—Jamino_4, 4' service (N— Bis-substituted diamino compounds, such as (phenylamine) biphenyl;

2, 2-vis (3-amino 1-hydroxy phenyl) to hexafluoropropane (generic name: vis (amino fueno) ) AF), bis (3-amino 4-hydroxy phenyl) ether, 4,4'-sul honyl bis (2-aminov) Enzymes such as bisaminophenol compounds; 2,2 bis (3 -amino-4-ethylcaptophenyl) Bisaminotinol phenol compounds such as fluoropropane and 3,3'-dimercaptobenzidine can be obtained.

The bridging agent (B) described above has excellent mechanical strength, heat resistance, and chemical resistance, and is particularly excellent in heat resistance and chemical resistance in a good balance. Is given. Compounds in which R ¹ is —NHR ² among the cross-linking agents (B) are known as crosslinking agents. In addition, the formula (IV)

(Wherein, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms), which is a novel compound.

No bisaminophenol crosslinker, bisaminophenol crosslinker or bisaminophenol crosslinker These have previously been used in a bridge system using a nitrile group as a cross-linking point. However, the carboxyl group and the alkoxycarbonyl group have been used. Reacts with the thiol group to form an oxazole ring, a thiazole ring, or an imidazole ring to give a crosslinked product.

The compounding amount of the crosslinking agent (B) is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer. In the crosslinkable composition of the present invention, if necessary, a usual additive, for example, a filler, which is incorporated into a known fluorine-containing elastomer composition, for example, a filler. Agents, processing aids, plasticizers, coloring agents, etc., and may contain one or more conventional cross-linking agents or cross-linking accelerators different from the ones mentioned above. It may be mixed above. In addition, a known fluorine rubber may be mixed within a range that does not impair the effects of the present invention.

The composition of the present invention is capable of converting each of the above components to a usual rubber processing machine, for example, an open roll, a Banbury mixer, or a kneader. It can be prepared by mixing using In addition, it can also be prepared by a method using a closed mixer and a co-coagulation method from an emulsion mixture. The composition of the present invention also contains a perfluoroelastomer known to contain an elastomer having a hydrocarbon-based refin unit. Compared with the main heat-resistant bridge composition (Japanese Patent Publication No. 59-10956 / 46, etc.), it is possible to mix additives such as hydrocarbon compounds. Adjustment is easy.

The method of obtaining a preformed body from the above composition may be a conventional method, such as a method of compressing by heating in a mold or a method of pressing into a heated mold. It can be performed by any known method such as extruding with an extruder. In the case of extruded products such as hoses and electric wires, it is possible to maintain the shape after extrusion, so the extruded parts must be extruded without using a cross-linking agent. You can use the feature as is. Of course, it is also possible to use a preformed body that has been heated and cross-linked by means of a steam or the like using a cross-linking agent. Also, if it is difficult to keep the shape of the molded product such as O-ring in the uncrosslinked state even after demolding, use a crosslinking agent in advance. This can be achieved by using a cross-linked preformed body.

The cross-linking composition of the present invention is compared with the heat-resistant cross-linking composition of a perfluoroelastomer, such as that disclosed in Japanese Patent Application Laid-Open No. 59-094954. It is characterized by its excellent cross-linking properties, such as quick bridges.

In the present invention, when oxazole cross-linking is performed using a cross-linking agent such as bisaminophenol, the usual cross-linking conditions for fluorine rubber are used. You can do it below. For example, put it in a mold and pressurize it under a pressure of 120-250. By holding for up to 60 minutes, press cross-linking is performed, followed by holding in a furnace of 120 to 320 hours for 0 to 48 hours. Therefore, when performing an open bridge, it is possible to obtain a bridge rubber. it can . In addition, the known method of crosslinking fluorine rubber, for example, the blending of a polyamine bridge, a polyol bridge, and a peroxide bridge, requires the use of vis (aminofu). (Enol) It is also possible to cross-link by adding AF or the like.

In addition, imidazole bridges, in which a hydroxyl group or a nitrile group is bridged with a bisaminoaminophenyl-based crosslinking agent, are relatively low. At the crosslinking temperature (for example, 150 to 230, preferably 170 to 200), a cross-linked molded article having good physical properties is provided.

The present invention also relates to the bridge molding thus obtained. The bridge molded product of the present invention is superior in heat resistance, chemical resistance, mechanical strength, workability, and the like. In addition, it has excellent cold resistance compared to cross-linked molded articles with a perforated mouth elastomer elastomer.

The crosslinked molded article of the present invention is useful as various molded articles in the fields shown in Tables 1, 2 and 3 below.

Industry Field Final product Lolo

Semiconductor-related semiconductor manufacturing equipment Equipment (1) to (6) to be described later o (square) ring, packing, sealing material, tube, roll,

LCD panel manufacturing equipment Coating machine, lining, gasket, '/ to, diaphragm, hose Plasma panel manufacturing equipment

Transport vehicles Automobile Engines and peripheral equipment Gaskets, shaft seals, valve stem seals, sealing materials, hoses

AT equipment Hose, sealing material

Fuel system and peripheral equipment o (square) ring, tube, packing, valve core, hose,

N-J wood, tire hum

Aircraft Aircraft Fuel system Tyakhum, ο (square) ring, Half, Chuch, Pakino, Hose, Lumber

Lofture Rocket fes fee system Same as above

Vessel Vessel Fuel system 问 Top

Chemical manufacturing process Brands Pharmaceuticals, pesticides, paints, resins, fins, norirefs, noduccinos, mouth irises, hoses, ta1 / nohum, etc. Chemical manufacturing processes ο (square) link , Tuno, wood

(Ishikuda)

Lolo doctor Lolo stopper

Mouth

Machine Photo Developing machine Film developing machine Roll

Xife film developing machine

Printing printing machine printing roll roll

Painting Painting equipment Painting roll Roll

Analysis

Food Lolo Plant Food Manufacturing Process Lining, Valve, Packing, Roll, Hose, Diaphragm, O (Square) Ring, Tube, Seal

Iron and steel sheet processing equipment Iron sheet processing roll Roll

Table 2

Industry Basic Needs

Electricity Plasma resistance, acid resistance, alkali resistance, amine resistance, ozone resistance, gas resistance, chemical resistance, cleanliness, heat resistance

Transport machine heat resistance, amine resistance

Heat resistance, amine resistance

Fuel resistance, combustion permeability, heat resistance

Chemical resistance to chemicals, solvent resistance, heat resistance

Chemical resistance, solvent resistance, heat resistance

Cleanliness

Machine 1¾ Chemical resistance

chemical resistance

Solvent resistance Solvent resistance

Food era Chemical resistance, solvent resistance, heat resistance

Metal Heat resistance, acid resistance Table 3

Industry Specific name

Metal O-rings, sealing materials, and accessories for the gate valve of the product

O-ring and sealing material of quartz window of applicable product equipment O-ring and sealing material of chamber of applicable product equipment O-ring and sealing material of gate of applicable product equipment

Pelja ring and sealing material of applicable product equipment O-ring and seal material of pump of applicable product equipment

O-ring and sealing material for semiconductor gas control device of applicable product equipment O-ring and sealing material for resist developing solution and stripping solution O-ring and sealing material for wafer cleaning solution

Diaphragm of pump of applicable manufacturing equipment

Hose for resist developer and stripper

Hose and tube for cleaning solution for wafers

Roll for wafer transfer

Lining and coating of resist developer tank and stripper tank Lining and coating of wafer cleaning tank

Lining and coating of wet etching tank Engine gasket for transport engine

Metal gasket

Crankshaft seal

Camshaft seal

Valve stem seal

Manifold packing

Oil hose

AT F hose

Injector O-ring

Injector packing

Fuel pump o-ring, diaphragm

Fuel hose

Chemical machine Developing roll

Development roll

Gravure roll

Guide roll

Gravure roll for magnetic tape production coating line

Guide roll for magnetic tape production coating line

Various coating rolls As a sealant for a semiconductor manufacturing device, a liquid crystal panel manufacturing device, or a plasma panel manufacturing device, specifically, the following devices are used. It can be installed and used.

(1) Evening device

Dragging device

Plasma etching equipment

Reactive ion etching device

Reactive ion beam etching device

Spaghetti etching equipment

Ion beam etching device

Vet-etching device

Fastening equipment

(2) Cleaning equipment

Dry etching cleaning equipment

UV / 〇 ₃ cleaning equipment

Ion beam cleaning equipment

Laser beam cleaning equipment

Plasma cleaning equipment

Gas washing machine

Extraction Wash

Sock slide extraction cleaning device

High pressure extraction cleaning device

Mic mouth Wave extraction Cleaning device

Critical extraction cleaning equipment

(3) Exposure equipment

Stepper

3-Evening-De Beloppa-

(4) Polishing equipment CMP equipment

(5) Film forming equipment

C V D equipment

, Tuttering device

(6) Diffusion / ion injection device

Oxidation diffusion device

Ion injection device

Of these, or in addition to these, the inclusion of hydrocarbon-based olefin units results in better heat resistance and better steam resistance. Because of its excellent chemical resistance, it can be used at relatively high temperatures such as the oxidation process, diffusion process, LP-CVD process, lamp annealing process, and one-step reflow process. Sealing materials for semiconductor manufacturing equipment used in the processing process to be operated; Oxygen sensors for automobile engines; In particular, steam resistance is required. It is suitable as a sealant used in an oil field drilling environment.

Next, the present invention will be described by way of examples, but the present invention is not limited to only such examples.

Example 1

An autoclave made of stainless steel with a volume of 3 liters, which has no ignition source, and 1 liter of pure water and an emulsifier hand

C F 3 C F 3

C ₃ F ₇ 〇 CFCF ₂ 〇 CFCO 〇 NH ₄

10 g, pH adjusted as sodium hydrogen phosphate

2 Charge 0.09 g of water salt, sufficiently replace the inside of the system with nitrogen gas, degas, and raise the temperature to 50 while stirring at 600 rpm. Tetra-fringe mouth (TFE) and perfume The mixed gas (TFEZPMVE = 38Z62 mol ratio) of fluoro (methyl vinyl ether) (PMVE) and the internal pressure became 0.59MPa · G. I was prepared to do it. Then, a reaction was initiated by injecting 10 ml of an aqueous solution of ammonium persulfate (APS) at a concentration of 527 mg Z ml at a nitrogen pressure.

When the internal pressure drops to 0.49 MPa a 'G due to the progress of polymerization, CF ₂ = CF 〇 CF ₂ CF (CF 3) 〇 CF ₂ CF ₂ COOH (CBVE) 2. 8 g was injected with nitrogen pressure. Then, the mixed gas (40.7 / 4 in weight ratio) of TFEZ ethylenno PMVE is self-pressed so that the pressure becomes 0.59 MPa a · G. It was press-fitted. Thereafter, TFE, ethylene, and PMVE are injected in the same manner as the reaction proceeds, and 0.49 to 0.59 MPa a'G is obtained! ^ Therefore, the step-up and step-down are repeated, and the total charge of TFE, ethylene and PMVE is reduced to 46 g, 103 g, 149 g and 196 g. At that time, CBVE was injected with 2.8 g of nitrogen pressure.

After 11 hours from the start of the polymerization reaction, when the total charge of TFE, ethylene and PMVE reaches 24,2 g, an autocure is performed. The reaction mixture was cooled, and the unreacted monomer was discharged to obtain 1,260 g of an aqueous dispersion having a solid content concentration of 19.0% by weight.

One hundred and fifty-five g of this aqueous dispersion was diluted with three hundred and fifty-five g of water, and slowly stirred into three-hundred g of a 3.5% by weight aqueous hydrochloric acid solution with stirring. Was added. After stirring for 5 minutes after the addition, the coagulated product was separated by filtration, and the obtained polymer was further poured into 200 g of water, stirred for 5 minutes, and again. It was filtered off. Thereafter, the operations of washing with water and filtering were repeated four more times, and then the resultant was vacuum-dried at 120 for 48 hours to obtain 235 g of a polymer. As a result of the analysis, the monomer unit composition of this polymer was TF

EZ ethylene / PMVE / CBVE = 44.7 / 2 3.1 / 3 1.1 / 1.1 mol%. In addition, as measured by infrared spectroscopy, the characteristic absorption of the carboxyl group was around 1773 cm- ¹ and the characteristic absorption power of the OH group was 335 cm — ¹ and 390 cm — Near ¹ The Mooney viscosity of this fluorine-containing elastomer was 100 and could not be measured, and the measured value at 140 t was 98.

The resulting cross-linkable fluorine-containing elastomer (A) is crosslinked to 2,2—bis (3,4—diaminophenyl), a bridging agent (B). The weight ratio of Kisa Fluoropropane to the filler Bon Black (Thermax N-990 from Cancarb) is 100/200. , And kneaded in an open roll to prepare a crosslinkable fluorine-containing elastomer composition that can be crosslinked.

The vulcanizability of this crosslinkable composition was examined.

(Vulcanizability measurement method)

For each of the crosslinking compositions, a vulcanization curve was obtained at the temperatures shown in Table 4 using the JSR type Kuraray Messenger Type II, and the lowest viscosity (vmin) and the lowest viscosity were obtained. Determine the high viscosity (max), the induction time (T i) and the optimum vulcanization time (T ₉ ).

Table 4 shows the results.

Then, the crosslinkable composition was pressed at 200 ° C. for 30 minutes to perform crosslinking, and then further in an open at 20 O: at 18 ° C. In the meantime, an open bridge was applied at 288 ° C for 18 hours, and a 2 mm-thick bridge and 〇-ring (AS — 568 A-211) ) Test sample was prepared. The normal physical properties, steam resistance, and permanent compression strain of this bridge It was measured . The results are shown in Table 4.

(Normal characteristics)

100% modulus, tensile strength, tensile elongation and hardness of a 2 mm thick bridge under normal conditions (25) in accordance with JISK 6301 Hardness) is measured.

(Steam resistance)

A bridge of 3 mm X 2 mm X 20 mm was used as a sample to be tested, and after measuring the weight and specific gravity of this sample, a stainless steel sample with an internal volume of 4 m1 was measured. Pour 1 g of water into a steel pressure vessel and seal the pressure vessel tightly. Heat the inside of the pressure vessel to 288, hold it for 1668 hours, return it to room temperature, measure the sample weight and specific gravity, and measure the weight before and after the steam treatment. Volume change

(%) And volume change (%).

(Compression set)

Measure the permanent compression set of the O-ring (AS-568A-2141) after 230: 70 hours in accordance with JISK6301.

Four

Example 1 Composition formulation (parts by weight)

C〇〇H group-containing fluorinated elastomer 100 Crosslinking agent 2 Carbon black 20 Vulcanizability (200)

Minimum viscosity (N) 5.69 Maximum viscosity (N) 39.2 Induction time (min) 0.9 Optimum vulcanization time (min) 14.2 Normal physical properties

100% Modulus (MPa) 7.6 Tensile Strength (MPa) 18.2 Elongation (%) 169 Hardness (JISA) 75 3 "Steam Property

Weight change (%) -0.29 Volume change (%) 4.1 Compression set

2 3 0: X 70 hours (%) 32

Industrial applicability

According to the present invention, it is possible to provide a cross-linked molded article having excellent heat resistance and also excellent chemical resistance such as steam resistance, and also excellent workability. Thus, a fluorine-containing elastomer composition for crosslinking can be provided. This composition is useful as a sealant for semiconductor manufacturing equipment, a sealant for oxygen sensors, and a sealant for use in oilfield drilling environments. is there .

Claims

The scope of the claims

(A) Includes tetrafluoroethylene units, norfluoro (alkyl vinyl ether) units and hydrocarbon-based olefin units. A crosslinkable reactive group such as a nitrile group, a carboxyl group, an alkoxycarbonyl group, or a compound having two or more of these. (B) Formula (I):

(Wherein R ¹ is the same or different and is OH, NH ₂ , SH or NH—R ² (R ² is 1-4 oxygen atoms and Z or halo) An alkyl group having 1 to 10 carbon atoms which may contain a gen atom, or a phenyl group which may have 1 to 5 substituents Is a benzyl group), a cross-linking agent which is a compound containing at least two functional groups represented by:

A cross-linking composition comprising:

2. The fluorine-containing elastomer (A) is composed of 25 to 75 mol% of tetrafluoroethylene units and 0.1% of fluorotetrafluoroethylene. Vinyl ether) unit containing 20 to 45 mol% and a hydrocarbon-based refrain unit of 1 to 50 mol%, forming a bridging reactive group. Claims that are fluorinated elastomers containing a liloxy group, a hydroxyl group, or an alkoxyl group The composition for crosslinking according to claim 1.

3. The crosslinking agent (B) has the formula (II):

(In the formula, R ¹ is the same as the above. R ³ is S 、 ₃ , 0, C〇, carbon number: alkylene group of 6 to 6, carbon atom of 1 to 10) Fluoroalkylene group, single bond or formula (III):

The cross-linking composition according to claim 1 or 2, which is a compound represented by the formula (1) or (2):

4. A bridge molded article obtained by crosslinking the crosslinking composition described in any one of claims 1 to 3 in the scope of the claim.

5. A seal material for a semiconductor manufacturing device obtained by cross-linking the cross-linking composition according to any one of claims 1 to 3.

6. A seal material for an oxygen sensor obtained by crosslinking the bridge composition described in any one of Items 1 to 3 in the scope of the request.

7. Seal material used in an oil field excavation environment obtained by crosslinking the bridge composition described in any one of paragraphs 1 to 3 of the claim .

8. Tetrafluoroethylene unit: 25 to 75 mol% and perfluoro (alkyl vinyl ether) unit: 20 to 45 mol% Is a copolymer of 1 to 50 mol% of a hydrocarbon-based olefin unit having 2 to 4 carbon atoms, and as a crosslinkable reactive group, Fluorine-containing, having a Z- or Z- or alkoxy group, and a Mooney viscosity at 10 O: of 20 or more Tomah.