WO2002079280A1

WO2002079280A1 - Fluoroolefin polymer particle

Info

Publication number: WO2002079280A1
Application number: PCT/JP2002/002883
Authority: WO
Inventors: Sadashige Irie; Kazuyoshi Mimura; Hirofumi Nishibayashi; Hiroyuki Tanaka; Tsuyoshi Noguchi; Mitsuru Kishine
Original assignee: Daikin Industries, Ltd.
Priority date: 2001-03-28
Filing date: 2002-03-26
Publication date: 2002-10-10
Also published as: JP2002293831A; JP5044800B2

Abstract

Fluororesin particles which have a melting point of 230 to 300°C, cannot be melt-proceeded, and have an average particle diameter of 100 nm or smaller and a melt flow rate, as measured in accordance with ASTM D3307 at 327°C under a load of 5 kg, of 0.005 to 0.1 g/10 min; and a composition which comprises the particles and either a fluoroelastomer or a melt-processable fluororesin. The composition gives a molding excellent in heat resistance, mechanical strength, transparency, etc.

Description

Akira Itoda Fluorine-containing olefin polymer particles-Technical Field

The present invention relates to a fluororesin particle to be filled in an elastomer or a resin molded product, which is particularly preferably used for a sealing part such as a ring or a gasket of a semiconductor manufacturing apparatus. Such a filler imparts cleanliness, heat resistance, and strength to the obtained sealing material. Background art

It has been conventionally used to add fluororesin particles as a filler to a fluorine-containing elastomer to improve the wear resistance of a molded product or to lower the friction coefficient. In recent years, such molded products have been used for sealing parts (such as rings and gaskets) in semiconductor manufacturing equipment by utilizing the chemical resistance and heat resistance of fluoroplastics.

For example, WO 97/0823 pamphlet indicates that a composition containing 5 to 50 parts by weight of a fluororesin powder can provide a particularly clean material as a sealing material for an etching apparatus of a semiconductor manufacturing apparatus. WO 95/02634 describes that a composition in which 2 to 50 parts by weight of a fluororesin powder is blended with 100 parts by weight of a rubber component provides a clean environment as a sealing material for a semiconductor jet process device. Have been. Further, JP-A-2000-239321 and JP-A-2000-239470 disclose that a fluorocarbon rubber and a fluororesin are nanocomposited (finely dispersed) to achieve high strength, to further improve engine oil resistance and to improve surface smoothness. Is being improved. However, even with the nanocomposite, the heat resistance of the fluororesin melts at a temperature near the melting point of the finely dispersed fluororesin, and there is no merit of the nanocomposite, so it is difficult to use for heat resistant applications. There is a problem that there is. Disclosure of the invention

The present invention provides a fluororesin particle to be filled in a fluorine-containing elastomer or a resin, and which can impart good properties to the elastomer-vulcanized product even at a temperature exceeding the melting point of the fluororesin particle. It is intended to provide.

That is, the present invention relates to a fluororesin particle having a melting point of 230 to 300 ° C and an average particle size of 100 nm or less which cannot be melt-processed, and has a melt flow rate of 327 measured according to ASTM D 3307 at a load of 5 kg. It relates to a fluororesin particle having a rate (MFR) of 0.005 to 0.1 gZl Omin. As the fluororesin particles, a fluorocopolymer of tetrafluoroethylene (TFE) and a perfluororefin other than TFE, particularly a fluororesin particle containing 90 mol% or more of TFE units is preferable.

The content of perfluoroethylene units other than TFE is preferably 2 to 9 mol%, and the perfluoroolefin to be copolymerized with TFE is preferably perfluoro (alkyl vinyl ether) (PAVE), particularly preferably perfluoro (methyl vinyl ether). Can be

The present invention also relates to an aqueous fluororesin particle dispersion in which these fluororesin particles are dispersed in water.

The present invention also relates to a fluoroelastomer composition comprising these specific fluororesin particles and a fluoroelastomer, or a fluororesin composition comprising the specific fluororesin particles and a melt-moldable fluororesin. Fluorine-containing As the elastomer, a perfluoroelastomer is preferable, and as the melt-processable fluororesin, a perfluoro resin is preferable.

The present invention also relates to a sealing part for a semiconductor manufacturing apparatus obtained by molding from these elastomer compositions. BEST MODE FOR CARRYING OUT THE INVENTION The fluororesin particles of the present invention have a melting point of 230 to 300 ° C, but have a low fluidity of the resin even at a temperature higher than the melting point, and have a high molecular weight and crystallinity that cannot be melt processed. Fluororesin particles.

Specifically, it has a melting point of 230-300 ° C, more preferably 250-29 O: and an MFR at 372 above the melting point of 0.005-0.1 g gZl 0 min, more preferably 0.01-1-0 . 05 gZl Omin, small (hard to flow) fluororesin particles.

With a melting point of 230 to 300, the property of heat resistance can be imparted, and due to the low melt fluidity (MFR) at high temperatures above the melting point, the properties as a filler even at temperatures above the melting point can be improved. There is no significant loss.

If the MFR (372) is smaller than 0.005 g / 1 Omin, only TFE homopolymer PTFE itself exists, causing fibrillation when finely dispersed in a matrix polymer, resulting in extremely fine dispersion. It becomes difficult. If it exceeds 0.1 gZl Omin, it becomes difficult to impart heat resistance.

As such a fluororesin, a TFE copolymer containing at least 90 mol% of a TFE unit which is relatively inexpensive, has high reactivity, is easy to increase in molecular weight, and gives a homopolymer having high crystallinity is most suitable. Any copolymerizable component may be used as long as it is a monomer copolymerizable with TFE. However, from the viewpoint of achieving a high melting point (heat resistance), a powder other than TFE such as PAVE or hexafluoropropylene (HFP) is used. —Fluororefin is preferred. PAVE, especially perfluoro (methylvinyl ether) (PMVE), is preferred because it is relatively inexpensive and has good copolymerizability with TFE. It is preferred that these comonomer units are contained in an amount of 10 mol% or less, particularly 2 to 9 mol% (TFE is 91 to 98 mol%). However, the resulting copolymer must be one that cannot be melt processed. When the content of the comonomer unit is low, fibrillation occurs at the time of dispersion processing as in the case of PTFE, and fine dispersion becomes difficult. If the amount is too large, the melting point will be lowered, so that heat resistance cannot be imparted even if the molecular weight is increased, and the MFR (372 ° C) will increase, making the resin melt-processable and unsuitable as a heat-resistant filler.

The fluororesin particles for the filler of the present invention have a mean particle size of 100 nm or less, preferably 20 to 60 nm. By using these fine particles, high strength can be imparted to the molded article. In particular, when an elastomer or resin having excellent transparency is used as the matrix polymer, a transparent molded product can be provided. On the other hand, when the average particle size is large, it becomes difficult to finely disperse the particles in the matrix polymer.

The specific fluororesin particles of the present invention can be produced by a usual emulsion polymerization method, and the resulting polymerization reaction product, an emulsion, can be used as it is or by adjusting an appropriate concentration to obtain an aqueous dispersion. . Alternatively, they may be dried once and then re-emulsified and dispersed. Generally, the particle size increases when re-emulsifying, so adjust the particle size after re-emulsification to 100 nm or less.

The present invention also relates to an aqueous dispersion in which the specific fluororesin particles are dispersed in water.

Furthermore, the present invention also relates to a composition comprising the above-mentioned specific fluororesin particles as a filler in a matrix polymer such as a fluorine-containing elastomer or a melt-processable fluororesin. The matrix elastomer used in the composition of the present invention may be any elastomer that can form an emulsion in the form of particles and has compatibility with fluororesin particles. From this point, fluorine-containing elastomers are preferred.

When a fluorine-containing elastomer is used as the matrix polymer, when the fluororesin particles of the present invention are filled, the properties as a filler are not significantly impaired even in kneading or vulcanization at a high temperature.

As a fluorine-containing elastomer, for example, the formula (1):

I

OR _f

(Wherein, mZn = 95-50 / 5-50 (mol%; the same applies hereinafter), R _f is charcoal

.8 perfluoroalkyl group) (tetrafluoroethylene (TFE) perfluoro (alkyl vinyl ether) (PAVE) elastomer)

Equation (2):

~ CF ₂ — CF ₂ r ^ CF ₂ — CF) ^ CF ₂ — CF t

I I

CF ₃ OR _f

(Wherein 1 / m / n = 95-35Z0-30-5-35, R _f is a perfluoroalkyl group having 1-8 carbon atoms) A terpolymer elastomer (TFE / Xafluoropropylene (HF P) ZPAVE-based elastomer)

Equation (3):

CF 3 (Wherein, m / n = 85 to 60, 15 to 40), a binary copolymer elastomer represented by

Equation (4):

-CH, -CF ₂ -r- (CF _? .-CF 2 _z ^ ^J m- CF, -CF)

CF ₃

(Wherein, lZm / n = 85 to 200/40/15 to 40) A terpolymer elastomer represented by the formula:

Equation (5):

HZ ¹

I I

F ₂ _ CF ₂ r ^ C— C) ^ ~ CF ₂ _ C

I I I

Z ² Z ³ OR _f

(Wherein, 1 / m / n = 9 5~45Z0~1 0 / 5~4 5, ZZ 2 and Z ³ are each independently a fluorine atom or a hydrogen atom, R _f is from 1 to 8 carbon Terpolymer elastomers represented by the following formula:

(1 / m2 20-80Z80-20),

(1 / m = 80 ~ 50/20 ~ 50). CF ₃

I

CH ₂ _ CH ₂ ^ "(CF ₂ CF CH ₂ _ CF ₂ ^ ~

(1 / m / n = 10-65 / 15-45Z0.45),

-^ CH ₂ -CH ₂ - _T -CF ₂ CF ₂ - _S -CF ₂ CF) ^

I

OR _f

(1 / mZn = 1 to 80/0 to 80/10 to 50, R _f is the same as described above).

More specifically, TFEZPAVE copolymer elastomer, vinylidene fluoride (VdF) / hexafluoropropylene (HFP) copolymer elastomer, VdFZHFPZTFE copolymer elastomer, VdFZ TFE / PAVE copolymer elastomer These elastomers may be further copolymerized with a small amount of a monomer containing a crosslinkable reactive group. Examples of the crosslinkable reactive group include an iodine atom, a bromine atom, a nitryl group, a propyloxyl group, an unsaturated double bond, a hydroxyl group, and the like. These fluorinated elastomers can be produced by a usual emulsion polymerization method, and the resulting polymerization reaction product, emulsion, can be used as it is or after adjusting the concentration as appropriate for coagulation described below. . Alternatively, they may be dried once and then re-emulsified and dispersed.

Examples of the elastomer other than the fluorine-containing elastomer include hydrogenated nitrile butadiene rubber, acrylic rubber, and silicone rubber.

The average particle size of the elastomer particles in the emulsion is not particularly limited, and is, for example, 10 to 80011111, preferably 20 to 500 nm. However, if it is smaller than 10 nm, it will be difficult to coagulate, and it will be larger than 800 nm. And the emulsion becomes unstable, making it difficult to co-coagulate.

The mixing ratio of the fluorinated elastomer to the specific fluororesin particles may be appropriately selected depending on the properties to be imparted to the molded article, but the fluororesin particles have a reinforcing effect on 100 parts by weight of the fluorinated elastomer. 1 part by weight or more, preferably 5 parts by weight or more, and 150 parts by weight or less, preferably 100 parts by weight or less, more preferably 50 parts by weight from the viewpoint of easy rubber processing of the obtained crosslinked product. Parts or less.

The combination of the elastomer and the fluororesin particles should be selected according to the intended function, taking into account whether or not the coagulation properties are similar and whether or not they have an affinity as a polymer. I just need. Since a copolymer mainly composed of TFE is preferred as the fluororesin particles, the fluorine-containing elastomer is also preferably an elastomer containing TFE. Examples include, but are not limited to, TFE / PAVE elastomers, or TFE / HFPZPAVE elastomers obtained by further copolymerizing at least one fluoromonomer.

The elastomer composition of the present invention can be produced by mixing the above-mentioned emulsion of the elastomer particles and the emulsion of the fluororesin particles and co-coagulating them. Co-coagulation can be performed according to a known coagulation method. For example, a method of dropping a mixed liquid obtained by mixing an emulsion of elastomer particles and an emulsion of fluororesin particles into a coagulation liquid, or a method of dropping a coagulation liquid into an emulsion mixed liquid can be employed.

The concentration of the mixed emulsion may be appropriately determined depending on the productivity and the like, and is not particularly limited, but is usually 5 to 50% by weight, preferably 10 to 30% by weight. For coagulation, it is also possible to dilute with pure water 2- to 10-fold.

Specific examples of the co-coagulation method include a salting-out method, an acid coagulation method, a freeze coagulation method, and a method of coagulating by applying a mechanical shear force. As the coagulant, for example, acids such as nitric acid, hydrochloric acid, and sulfuric acid; metal salts such as aluminum nitrate and aluminum sulfate can be used. Of these, the acid is used in order to keep the polymer clean; Therefore, metal salts are preferred. The coagulated product obtained by co-coagulation can be used as a base material for molding by washing it if necessary and then drying it in a hot air oven or vacuum dryer. When the fluorinated elastomer composition of the present invention is used as a base material, the resulting molded article can be provided with excellent heat resistance, mechanical strength, abrasion resistance, transparency, moldability, and the like. .

By mixing a crosslinking agent and a crosslinking accelerator to the fluorinated elastomer composition of the present invention, a crosslinkable fluorinated elastomer composition can be obtained.

As the cross-linking system, a cross-linking system generally used for fluorine-containing elastomers can be applied.For example, oxazole cross-linking system, imidazole cross-linking system, thiazole cross-linking system, triazine cross-linking system, peroxide cross-linking system, polyol cross-linking system, polyamine cross-linking System. Crosslinking by radiation, electron beam, ultraviolet light, etc. is also possible.

Examples of the crosslinking agent used in the oxazole crosslinking system, the imidazole crosslinking system, and the thiazole crosslinking system include, for example, a compound represented by the formula (I):

(Wherein, R ¹ is one of S 0 ₂ _, _〇—, one CO—, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms or a bond. , R ² and R ³ are one NH ₂ and the other is —NH ₂ , —〇H or 1 SH), a bisamino (thio) phenol crosslinker or a tetraamine crosslinker represented by the formula (Π) ):

(Wherein, R ¹ is the same as above, R ⁴ is

ΝΗ

C

または. Or

ΝΟΗ

— C

ΝΗ ₉

A) a bisamidrazone-based crosslinking agent represented by the formula (III) or (IV):

ΝΗ ΝΗ

H _? NHN-CR _f ² -C-NHNH _? (III)

(Wherein, R _f ² is a perfluoroalkylene group having 1 to 10 carbon atoms)

NH. NH.

HON = C- (CF ₂ ^ C = NOH (IV)

(Wherein, n is an integer of 1 to 10).

Further, a crosslinking accelerator may be used in combination as needed.

The amount of the crosslinking agent is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, and the crosslinking accelerator is 0.1 to 10 parts by weight, preferably 100 parts by weight, per 100 parts by weight of the fluorine-containing elastomer. 0.2 to 5 parts by weight.

Examples of the crosslinking agent used in the peroxide crosslinking system include 1,1-bis (t-butylpropyl) -1,3,5,5- 2,5_dimethylhexane-1,2,5-dihydroperoxide, di-tert-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, a, α-bis (t-butylperoxy) -p-diisopropylpropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -1-hexyne-1, benzoyl peroxide, t-butylperoxide Oxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxymaleic acid, tert-butylperoxyisopropyl phenol, etc. .

In the case of a peroxide crosslinking system, it is desirable to use a crosslinking accelerator. Examples of the crosslinking accelerator include triallyl cyanurate, triallyl isocyanurate, triallyl formal, triallyl trimellitate, N, N '1 m-phenylenebismaleimide, dipropargyl terephthalate, diaryl phthalate, Tetraaryl terephthalate amide, triallyl phosphate and the like.

The amount of the crosslinking agent is 0.05 to 10 parts by weight, preferably 1.0 to 5 parts by weight, and the crosslinking accelerator is 0.1 to 10 parts by weight based on 100 parts by weight of the elastomer. Parts by weight, preferably 0.5 to 5 parts by weight.

In the case where the vulcanized product does not need to use inorganic fillers for cross-linking and does not develop color due to cross-linking, as in a peroxide cross-linking system, and the vulcanized product shows transparency with a so-called pure rubber compound, a transparent elastomer molded article Can be provided. The transparent crosslinked elastomer molded article obtained by the present invention has a haze value of 50% or less, preferably 40% or less, particularly 30% or less. As the crosslinking agent used in the polyol crosslinking system, generally used polyhydroxy aromatic compounds can be used. For example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A), 2,2-bis ( Four (Hydroxyphenyl) perfluoropropane (so-called bisphenol AF), resorcinol, 1,3,5-trihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4, 4 'dihydroxydiphenyl, 4, 4'-dihydroxystilpene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (so-called bisphenol B) , 4,4-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorochloropropane, 4,4'-dihydroxydiphenylsulfone, 4,4'- Dihydroxydiphenylketone, tri (4-hydroxyphenyl) methane, 3,3 ', 5,5'-tetrachlorobisphenol, 3 3 ', 5, 5' - Tetorabu Romo bisphenol A or the like alkali metal salts thereof or alkaline earth metal salts, and the like.

It is preferable to use a crosslinking accelerator together in the polyol crosslinking system. Examples of the crosslinking accelerator include an ammonium compound, a phosphonium compound, an oxonium compound, a sulfonium compound and the like, and a quaternary ammonium salt and a quaternary phosphonium salt are particularly preferable.

The amount of the crosslinking agent is 0.5 to 5 parts by weight per 100 parts by weight of the elastomer, and the crosslinking accelerator is 5 to 400 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight of the crosslinking agent. Parts by weight.

Examples of the crosslinking agent used in the polyamine crosslinking system include a polyamine compound. The polyamine compound is a primary amine or a secondary amine which binds two or more basic nitrogens in the molecule.In many cases, these are formed in the form of a salt to adjust the reactivity to be mild. use. Specific examples include, for example, ethylenediaminecarbamate, hexamethylenediaminecarbamate, and 4,4'diaminocyclohexylmethanecarbamate. Alkylene diamines such as salts are relatively often used. Also, N-salt can be used. In addition, it can be preferably used in combination with other basic compounds such as polyamine aromatic compounds having poor basicity. Other basic compounds include, for example, diphenyldananidin, di-0-triguanidine, diphenylthiodiarea, 2-mercaptoimidazoline, and the like. Compounds having ₂ and / or 1 NH—, or divalent metal hydroxides and the like can be mentioned. The amount of the crosslinking agent is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the elastomer.

Examples of other additives include known additives such as a filler other than the fluororesin particles of the present invention, a pigment, an ultraviolet absorber, and an antioxidant.

Other fillers include, for example, inorganic fillers such as carbon black (particularly graphitizable carbon black, gay oxide, titanium oxide, and alumina); and organic fillers such as polyimide. The amount is 100 parts by weight or less, preferably 1 to 50 parts by weight, based on 100 parts by weight.

The cross-linking agent, the cross-linking accelerator, and other additives such as organic and inorganic fillers may be added at the time of the co-coagulation, if possible, but the composition of the elastomer and the fluorine resin fine particles is produced. After that, they may be mixed. The mixing method may be a kneading method using a conventionally known roll.

The crosslinkable elastomer composition in which the fluororesin fine particles thus obtained are finely dispersed is kneaded and crosslinked to produce a crosslinked molded product. As a kneading method, a usual method, for example, roll kneading, kneading, or the like can be adopted. As a molding method, a usual compression molding method, injection molding method, extrusion molding method, transfer molding method, or the like can be adopted. The molding conditions may be the same as the conventional conditions. The resulting cross-linked molding, if free of other fillers, If the box is a transparent elastomer, it maintains its transparency. Although the transparency may slightly decrease, the visible light transmittance of the elastomer alone is maintained at 20% or more.

The molded article of the present invention is excellent in heat resistance, mechanical strength, post-processability, plasma resistance, and gas barrier uniformity. Further, since the finely dispersed fluororesin fine particles are hard to fall off from the elastomer of the matrix, there is little possibility that particles are generated even when used as a sealing part of a semiconductor manufacturing apparatus, for example. The fluorine-containing elastomer composition of the present invention is suitable as molded articles shown in the following Tables 1, 2 and 3 by utilizing its excellent properties.

Industry Fields Final products Final products Mouth Michido Tsutomu Tsutomu; notices, monthly reports,

Liquid crystal LCD panel,, nel iS; notice: Qi k, lancho, lan, kin, tonko, lan, lan, plasma panel manufacturing equipment wet etching equipment material, tube, mouth oxidation diffusion equipment, coating sputtering Equipment K, Lining, Atshing equipment Gasket, Die

Ano Funorano 8, ■ ノ + ヽ： -F Ion implanter

Transport vehicles Automobiles Engines and peripheral equipment Gaskets, shaft seals, valve stem seals, Ichino, Pef-Ninma, Nokisonon, Noube, packing, valve cores, hoses, sealants The diaphragm aircraft aircraft fuel system diaphragm, ο (

1)) Reb 1,000-Bupa, Sokin, Ho '~' 乂 Seal material Rocket Rocket Fuel system Same ship Vessel Ship fuel system Same 'Chemical chemicals Pharmaceuticals, pesticides, paints , Tree inning, zo j resin, etc., chemical manufacturing process, packing, mouth, hose, diaphragm, o (square

) Rings, tubes, sealing materials

(Oil)

Medicine medicine medicine stopper

Machine Photo Developing machine Film developing machine Roll

X-ray film developing machine roll

Printing printing machine printing roll roll

Painting equipment Painting roll Roll

Analytical 'Rika ^! Tube Food Food manufacturing process Lining, Zoleb, Packing, Mouth, Hose, Diaphragm, 0 (square

) Rings, tubes, sealing materials Iron and steel Sheet metal processing equipment Sheet metal processing rolls Rolls Table 2

Industry Basic Needs

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

Transportation ΚΒίHeat 'f raw, »/ ¾ ノ' te

Machine

Heat resistance, amine resistance

Fuel resistance, fuel permeability, heat resistance Fuel resistance, fuel permeability, heat resistance

Fuel resistance, fuel permeability, heat resistance

Chemical Chemical resistance, solvent resistance, heat resistance

Chemical resistance, solvent resistance, heat resistance

Cleanliness

Machine chemical resistance

chemical resistance

Solvent resistance

Solvent resistance Foods Chemical resistance, solvent resistance, heat resistance

Metal Heat resistance, acid resistance Table 3

Concrete name

O-ring and sealing material for gate valve of applicable manufacturing equipment O-ring and sealing material for quartz window of applicable manufacturing equipment O-ring and sealing material for champ of applicable manufacturing equipment O-ring and sealing material for gate of applicable manufacturing equipment

O-ring and sealing material of bell jar of applicable manufacturing equipment O-ring and sealing material of power coupling of applicable manufacturing equipment

I O-ring and seal material of the pump of the relevant manufacturing equipment

O-ring and sealing material for semiconductor gas control device of applicable manufacturing equipment O-ring and sealing material for resist developer and stripper Liquid o-ring and sealing material for wafer cleaning liquid

Diaphragm of pump of applicable manufacturing equipment

Hose for resist developer and stripper

Hose and tube for wafer cleaning solution

Roll for wafer transfer

Lining of resist developer bath, stripper bath, coating Wafer cleaning bath lining, coating

Lining of wet etching tank, coating Engine head gasket

Metal gasket

Crankshaft seal

Camshaft seal

Valve stem seal

Manifold packing

Oil hose

AT F hose

Injector O-ring

Injector packing

Fuel pump 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 Food In particular, it can be used by being incorporated in the following semiconductor manufacturing apparatus.

(1) Etching equipment Plasma etching equipment

Reactive ion etching equipment

Reactive ion beam etching equipment Ion beam etching equipment

ゥ Etching equipment

(2) Cleaning device

Dry etching cleaning equipment

uvzo ₃ cleaning equipment

Ion beam cleaning equipment

Laser beam cleaning equipment

Plasma cleaning equipment

Gas etching cleaning equipment

Extraction washing device

Soxhlet extraction cleaning equipment

High temperature and high pressure extraction and cleaning equipment

Microwave extraction cleaning equipment

Supercritical extraction cleaning equipment

(3) Exposure equipment

Stepper

Overnight (4) Polishing equipment

CMP equipment

(5) Film forming equipment

CVD equipment

(6) Diffusion ion implantation equipment

Oxidation diffusion device

Ion implanter

When a melt-processable fluororesin is used as the matrix polymer, excellent properties such as high strength and improved chemical resistance can be imparted to the molded product in a well-balanced manner.

PFA, FEP, ETFE, PCTFE, E CTF E, etc., can be used as the melt-processable fluororesin used as the matrix polymer. The 1 ^ 1 value (372, 5 kg) is 0.1 to 50 g / 1 Omin And preferably 5 to 30 gZl Omin.

Among them, perfluoro resins are preferred because of their excellent heat resistance and chemical resistance. Specifically, for example, TFEZHFP (HFP content 5 to 15 mol%), TFE / HFP / PAVE (HFP content 5 to 15 mol%, PAVE content 0.5 to 3 mol%), TFE / PAVE (PAVE content 0.5 to 8 mol%).

As a method of uniformly mixing and finely dispersing specific fluororesin particles as a filler in a melt-processable fluororesin as a matrix polymer, the co-coagulation method described in the above-mentioned fluoroelastomer composition can be preferably employed. . The amount of the fluororesin particles that cannot be melt-processed as a filler is preferably 1 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, per 100 parts by weight of the matrix polymer (the melt-processable fluororesin). In addition, it is described in terms of a fluorine-containing elastomer composition. The various additives mentioned can likewise be used.

Such fluororesin compositions utilize heat resistance, non-contamination adhesion prevention properties, chemical resistance, cleanliness, etc., and are used to cover electric wires, chemical solution containers, tubes and hoses, pump lining materials, etching carriers, etc. It is suitable for the production of molded articles.

Next, the present invention will be described with reference to Synthesis Examples and Examples, but the present invention is not limited only to such Synthesis Examples and Examples.

Synthesis Example 1 (Production of emulsion of fluororesin fine particles)

In a 6 liter stainless steel autoclave with no ignition source, 3 liters of pure water and C ₃ F ₇ OCF (CF ₃ ) CF ₂ 〇CF (CF ₃ ) C〇〇NH ₄ as emulsifier 30 g, 0.27 g of disodium hydrogen phosphate '12 hydrate was added as a pH adjuster, and the system was sufficiently purged with nitrogen gas and degassed.Then, the mixture was raised to 80 while stirring at 600 rpm. After heating, a mixed gas of tetrafluoroethylene (TFE) and perfluoro (methyl vinyl ether) (PMVE) (TFE / PMVE = 88, 12 molar ratio) was charged so that the internal pressure became 0.20 MPa. Next, 4 ml of a 2.5 mg / ml aqueous solution of ammonium persulfate (APS) was injected under nitrogen pressure to start the reaction.

When the internal pressure dropped to 0.15 MPa due to the progress of polymerization, a mixed gas of TFE ZPMVE (TFE / PMVE = 955 molar ratio) was injected with nitrogen gas so that the internal pressure became 0.20 MPa. . Thereafter, a TFEZPMVE mixed gas (95/5 molar ratio) was similarly injected with the progress of the reaction, and the pressure was repeatedly increased and decreased between 0.15 and 0.2 OMPa.

4.5 hours after the start of the polymerization reaction, when the total charged amount of TFE and PMVE reached 331 g, the autoclave was cooled, unreacted monomers were released, and the solid content concentration was 9.7% by weight of fluorine. Resin fine particles (Average particle size: 44 nm). The average particle size was obtained by mixing 12 Omg of the emulsion with 4.4 g of dimethyl sulfoxide, and using a? It was measured at 8,300,3100.

A part of this emulsion was taken out, coagulated by adding nitric acid, and the precipitate was washed and dried to obtain white fluororesin fine particles. This product had a composition ratio of TFE / PMVE-94.5 / 5.5.5 (mol%) by ¹⁹ F-NMR analysis.

The fluorine resin particles Merutofu opening one rate (MFR) is 0. 01 g / 1 Offlin under the conditions of holding load 5 kg, 3 72 ° C 5 minutes initial measured by DSC (l ^st run) melt temperature It is 290 ° C, a melting point (2 ^nd run) was 264 ° C.

Synthesis Example 2 (Production of emulsion of fluororesin fine particles)

In Synthesis Example 1, the initial monomer charge composition was changed to TFEZPMVE = 88 /

An emulsion of fluororesin particles having an average particle diameter of 56 nm was produced in the same manner except that the molar ratio was set to 12 and the additional monomer composition was set to TFE / PMVE-98 / 2 (mol ratio). It has a composition ratio of T by ¹⁹ F-NMR analysis.

FE / PMVE = 97.5 / 2.5 (mol%).

The melt flow rate (MFR) of the fluororesin particles was 5 kg, 3

72 0.01 g / 10 min or less under the condition of holding for 5 minutes, the initial ( ^lst run) melting temperature measured by DSC is 314 ° C, and the melting point (2 ^Bd run) is 29

It was 0 ° C.

Synthesis Example 3 (Production of emulsion of fluororesin fine particles)

The average particle size was the same as in Synthesis Example 1, except that the initial monomer charge composition was TFEZPMVE = 82/18 (molar ratio) and the additional monomer composition was TFE / PMVE = 988 (molar ratio). An emulsion of fluororesin particles having a diameter of 46 nm was produced. It has a composition ratio of T by ¹⁹ F-NMR analysis. FE / PMVE = 91.7 / 8 (mol%).

Melt flow rate of the fluorine resin particles (MFR) is 0. 1 g "1 Omin at the conditions of holding load 5 kg, 3 72 ° C5 min, initial (l ^st run) melting temperature measured by DSC 262 ° C and the melting point (^ run) was 236 ° C.

Synthesis Example 4 (Production of emulsion of fluorine-containing elastomer particles)

In a 3 liter stainless steel autoclave with no ignition source, 1 liter of pure water and C ₃ F ₇ 〇CF (CF ₃ ) CF ₂ 〇CF (CF ₃ ) C〇〇NH _{4 as} emulsifier And 10 g of disodium hydrogen phosphate / 12 dehydrate as a pH adjuster, sufficiently purge the system with nitrogen gas, degas, and then raise to 53 while stirring at 600 rpm. After heating, a mixed gas of tetrafluoroethylene (TFE) and perfluoro (methyl vinyl ether) (PMVE) (TFE / PMVE = 25/75 molar ratio) was charged so that the internal pressure became 0.78 MPa. Next, 20 ml of an aqueous solution of ammonium persulfate (APS) having a concentration of 264 mgZml was injected under nitrogen pressure to start the reaction.

When the internal pressure dropped to 0.69 MPa due to the progress of polymerization, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN (CNVE) was injected under a nitrogen pressure of 2.2 g. Then, 4.7 g of TFE and 5.3 g of PMVE were respectively injected under their own pressures so that the pressure became 0.78 MPa. Thereafter, TFE and PMVE were similarly injected as the reaction progressed, and the pressure was repeatedly increased and decreased between 0.69 and 0.78 MPa, and CNVE was injected when the total amount of TFE and PMVE reached 70 g. 2. Press-fit with 2 g nitrogen pressure. Six hours after the start of the polymerization reaction, when the total charged amount of TFE and PMVE reached 130 g, the autoclave was cooled, unreacted monomers were discharged, and the solid content concentration was 11.3% by weight of fluorine-containing. Emulsions of elastomer particles (A-2) 1160 g was obtained.

100 g of this emulsion was diluted with 300 g of water, and slowly added to 280 g of a 3.5% by weight hydrochloric acid aqueous solution while stirring. After the addition, the mixture was further stirred for 5 minutes, and the obtained coagulated product was separated by filtration. The obtained elastomer particles were further washed with 200 g of HCFC-141b and filtered. Washing with HC FC-141b and filtration were repeated four times, and then vacuum-dried at 60 ° C. for 72 hours to obtain 11.2 g of a fluorine-containing elastomer.

When the composition ratio of this fluorine-containing elastomer was determined by ¹⁹ F-NMR analysis, it was TFE / PMVE / CNVE = 60.4 / 38.9 / 0.7 (mol%).

Examples 1-3

The emulsion of the fluorinated elastomer particles obtained in Synthesis Example 4 and the emulsion of the fluorinated resin fine particles obtained in Synthesis Examples 1 to 3 were mixed (solid content ratio: fluorinated elastomer / fluorinated resin = 85 to 15 wt. The ratio was dropped into a stirring 9% aqueous nitric acid solution over 10 minutes to perform co-coagulation. The obtained co-coagulated product was washed with water and dried to obtain an elastomer composition in which fluororesin fine particles were finely dispersed in a fluorine-containing elastomer.

Then, 100 parts by weight of the obtained elastomer composition was used as a cross-linking agent for 2,2-bis-[(3-amino-4-phenylamino) phenyl] hexafluo propane. 20, Synthesized by the method described in Vol. 20, 2381-2393 (1982)) 1. 75 parts by weight were mixed and kneaded with an open roll at 40 ° C. to obtain a crosslinkable elastomer composition. Was. The winding property on the roll was observed on the basis described later during the kneading. Table 4 shows the results.

Further, the crosslinkable elastomer composition was press-crosslinked at 170 ^ for 15 minutes, and then oven-crosslinked at 204 ° C for 18 hours and then at 288 ° C for 18 hours. A crosslinked product was obtained. The physical properties of the crosslinked product under normal conditions were measured. O-rings (P-24) were manufactured under the same crosslinking conditions, and compression set (CS) was measured. Table 4 shows the results.

(Roll winding property)

〇: Sufficiently wound around the roll at a roll surface temperature of room temperature.

Δ: Rolling occurs when the roll surface temperature is 50 ° C.

X: No winding even when the roll surface temperature is 5 O :.

(Normal physical properties)

The 100% modulus, tensile strength, tensile elongation, and hardness (JISA hardness) under normal conditions (25) are measured according to JIS K6301.

(Compression set)

Measure the permanent compression set (%) after 70 hours at 27 ° C and 25% compression according to JIS K6301. Table 4

As shown in Table 4, when the specific fluororesin particles of the present invention are blended as a filler, they must have excellent mechanical properties in a well-balanced manner and give a small value of compression set even at a high temperature of 275 ° C. Can be. Example 4

What can be melted? Perfluoro (propyl pinyl ether) (= 87.5 / 11.5 / 1.0 mole ratio) Emulsion of particles and synthesis of emulsion of fluororesin fine particles obtained in Example 1 were mixed (solid content ratio: FEPZ fluororesin = 70Z30 weight ratio) was dropped into a stirring 9% aqueous nitric acid solution over 10 minutes to perform co-coagulation. The obtained co-coagulated product was washed with water and dried to obtain a fluororesin composition in which fluororesin fine particles were finely dispersed in FEP. This fluororesin composition was press-molded at 372 ° to produce a sheet (thickness: lmm). When the mechanical strength UIS K6891) of this sheet was measured, the tensile strength was 32.8 MPa and the tensile elongation was 291%. Then, after heating this sheet at a temperature of 250 ° C for 100 hours, the mechanical strength was measured. The tensile strength was 33. IMP a, and the tensile elongation was 300%. Was. Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, the composition which can provide the molded article excellent in heat resistance, mechanical strength, and also transparency can be provided.

Claims

Scope of word blue

1. Fluororesin particles having a melting point of 230 to 300 t and an average particle size of 100 nm or less that cannot be melt-processed. Fluororesin particles having a melt mouth opening rate of 0.05 to 0.1 g / 1 O min measured under a kg load.

2. The fluororesin particles according to claim 1, wherein the fluororesin particles are fluorine-containing copolymer particles of tetrafluoroethylene and a non-tetrafluoroethylene derivative.

3. The fluororesin particles according to claim 2, wherein the fluorocopolymer particles contain 90 mol% or more of tetrafluoroethylene units.

4. The fluororesin particles according to claim 2, wherein the content of perfluoroethylene units other than tetrafluoroethylene is 2 to 9 mol%.

5. The fluororesin particles according to any one of claims 2 to 4, wherein the perfluoroolefin copolymerized with tetrafluoroethylene is perfluoro (alkyl vinyl ether).

6. An aqueous dispersion of fluororesin particles, wherein the fluororesin particles according to any one of claims 1 to 5 are dispersed in water.

7. A fluorinated elastomer composition comprising the fluorinated elastomer and the fluororesin particles according to claims 1 to 5.

8. The fluorine-containing elastomer composition according to claim 7, wherein the fluorine-containing elastomer is a perfluoroelastomer.

9. A sealing part for a semiconductor manufacturing apparatus obtained by molding from the elastomer composition according to claim 7 or 8.

10. Fluororesin that can be melt-processed and the fluororesins of claims 1 to 5 A fluorine-containing resin composition comprising particles.

11. The fluororesin composition according to claim 10, wherein the melt-processable fluororesin is a perfluoro resin.