Elastomeric composition, sealing material and method for manufacturing a sealing material

Abstract

An embodiment of the present application relates to an elastomer composition, a sealing material, or a manufacturing method of a sealing material, the elastomer composition comprising a cross-linkable fluorine-containing elastomer (A1) other than a perfluoroelastomer having a fluorine content of 69% by mass or more and a cross-linkable fluorine-containing elastomer (A2) other than a perfluoroelastomer having a fluorine content in the range of 55 to 68% by mass, the content of the fluorine-containing elastomer (A1) being 60 to 95% by mass relative to 100 parts by mass of the total of the fluorine-containing elastomers (A1) and (A2).

Description

Technical Field

[0001] One embodiment of the present invention relates to an elastomer composition, a sealing material, or a method of manufacturing a sealing material. Background Technology

[0002] Sealing materials have long been widely used for various purposes. Among these applications, one example of the application that places the greatest load on sealing materials is the sealing materials used in semiconductor manufacturing equipment.

[0003] In order to obtain sealing materials with excellent plasma resistance or free radical resistance, cross-linked fluorinated elastomers such as fluorinated elastomers (FKM) and perfluorinated elastomers (FFKM) are used as such sealing materials.

[0004] For example, Patent Document 1 discloses a sealing material characterized by containing a specified amount of FFKM and FKM.

[0005] Sealing materials made from the aforementioned cross-linked fluorinated elastomers typically use an elastomer composition obtained by incorporating cross-linking agents, cross-linking aids, and other additives into the cross-linked fluorinated elastomer. This elastomer composition is then molded and cross-linked to be used as a sealing material.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent No. 4628814 Summary of the Invention

[0009] The technical problem that the invention aims to solve

[0010] As described above, when an elastomer composition is formed by incorporating additives into a crosslinked fluorinated elastomer, it is necessary to mix the components of the elastomer composition evenly in order to manufacture a sealing material exhibiting the desired physical properties from the elastomer composition.

[0011] However, when using existing cross-linked fluorinated elastomers, especially when using liquid or oily components, the preparation of such a homogeneous elastomer composition takes a long time, and there is room for improvement in this respect.

[0012] Furthermore, when forming sealing materials from manufactured elastomer compositions at high productivity, the elastomer composition is typically formed into sheets through a pressing process. This pressing process usually involves passing the elastomer composition between rollers. However, with existing elastomer compositions, the composition sometimes fails to be gripped between the rollers or cannot be smoothly wound onto the rollers, making it difficult to form sheets (poor pressing properties). Therefore, there is still room for improvement in the formability of existing elastomer compositions.

[0013] Furthermore, as a sealing material formed from existing elastomer compositions, especially for applications where particle generation is a problem, there is still room for improvement in terms of tensile stress (100% Mo) at 100% elongation, where no or minimal filler material is added.

[0014] One embodiment of the present invention can be formed into a uniform elastomer composition in a short time, providing an elastomer composition with excellent formability, which can form a sealing material with high tensile stress (100% Mo) at 100% elongation.

[0015] Technical solutions adopted to solve technical problems

[0016] In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved by the following configuration example, thereby completing the present invention.

[0017] The structure of the present invention is described below.

[0018] [1] An elastomer composition comprising a crosslinked fluorinated elastomer (A1) other than a perfluorinated elastomer with a fluorine content of 69% by mass or more and a crosslinked fluorinated elastomer (A2) other than a perfluorinated elastomer with a fluorine content in the range of 55% to 68% by mass, wherein the content of the fluorinated elastomer (A1) is 60 to 95% by mass relative to a total of 100 parts by mass of the fluorinated elastomers (A1) and (A2).

[0019] [2] The elastomer composition as described in [1], wherein the fluorinated elastomers (A1) and (A2) are peroxide-crosslinkable fluorinated elastomers.

[0020] [3] The elastomer composition as described in [1] or [2], wherein it comprises at least one compound (B) containing an olefinically unsaturated bond selected from compounds having a perfluorinated skeleton with an olefinically unsaturated bond and compounds having a siloxane skeleton with an olefinically unsaturated bond.

[0021] [4] The elastomer composition as described in any one of [1] to [3], wherein it comprises a crosslinking agent.

[0022] [5] The elastomer composition as described in any one of [1] to [4], wherein the content of filler material is 5 parts by mass or less relative to a total of 100 parts by mass of the fluorinated elastomers (A) and (A2).

[0023] [6] A sealing material obtained from any one of the elastomer compositions described in [1] to [5].

[0024] [7] A method for manufacturing a sealing material, comprising a step of crosslinking the elastomer composition described in any one of [1] to [5].

[0025] Invention Effects

[0026] According to one embodiment of the present invention, it is possible to provide an elastic composition with excellent formability, particularly compressibility, that can be formed into a uniform elastomer composition in a short time.

[0027] Furthermore, according to one embodiment of the present invention, by using this elastomer composition, a sealing material with high tensile stress (100% Mo) at 100% elongation can be formed, and in particular, a sealing material exhibiting excellent hardness, tensile strength, elongation at break and 100% Mo with good balance can be obtained.

[0028] Furthermore, according to one embodiment of the present invention, a sealing material with excellent plasma resistance (free radical resistance), crack resistance, and compression set can be obtained. Therefore, this sealing material is suitable for use as a sealing material for semiconductor manufacturing apparatuses and plasma processing apparatuses. Detailed Implementation

[0029] Elastomer Compositions

[0030] An elastomer composition according to one embodiment of the present invention (hereinafter also referred to as "the composition") comprises a crosslinked fluorinated elastomer (A1) other than a perfluorinated elastomer with a fluorine content of 69% by mass or more and a crosslinked fluorinated elastomer (A2) other than a perfluorinated elastomer with a fluorine content in the range of 55% to 68% by mass, wherein the content of the fluorinated elastomer (A1) is 60 to 95% by mass relative to a total of 100 parts by mass of the fluorinated elastomer (A1) and (A2).

[0031] In this invention, "elastomer" and "rubber" are synonymous and are not distinguished in any particular way.

[0032] <Cross-linked fluorinated elastomers (A1) and (A2)>

[0033] Crosslinked fluorinated elastomers (A1) are not particularly limited as long as they are crosslinked fluorinated elastomers other than perfluorinated elastomers with a fluorine content of 69% by mass or more. Crosslinked fluorinated elastomers (A2) are not particularly limited as long as they are crosslinked fluorinated elastomers other than perfluorinated elastomers with a fluorine content in the range of 55% to 68% by mass.

[0034] As long as the fluorine content of the cross-linked fluorinated elastomer (A1) and the cross-linked fluorinated elastomer (A2) is within the aforementioned range, the types of structural units constituting these elastomers can be the same or different.

[0035] The fluorinated elastomer (A1) contained in this composition may be one type or two or more types. Additionally, the fluorinated elastomer (A2) contained in this composition may be one type or two or more types.

[0036] Hereinafter, cross-linked fluorinated elastomers (A1) and cross-linked fluorinated elastomers (A2) will be collectively referred to as cross-linked fluorinated elastomers (A).

[0037] Crosslinked fluorinated elastomers (A), also known as uncured fluorinated rubber, include various crosslinking types such as peroxide crosslinking, polyol crosslinking, amine crosslinking, and radiation crosslinking. Among these, peroxide crosslinkable fluorinated elastomers are preferred from the perspective of not requiring the use of acid absorbers that become particle generation sources in plasma atmospheres, and ensuring that the resulting sealing material does not pose a risk of particle generation during use.

[0038] As specific examples of crosslinked fluorinated elastomers (A), examples include fluorinated elastomers (FKM), tetrafluoroethylene-propylene elastomers (FEPM), and fluorinated thermoplastic elastomers (e.g., elastomers comprising at least one elastomeric polymer segment and at least one non-elastomeric polymer segment, wherein at least one of them is a fluorinated polymer segment).

[0039] As a crosslinked fluorinated elastomer (A1), an elastomer that can produce a sealing material resistant to plasma (plasma etching) used in various semiconductor dry processes is preferred, and FKM, which has good plasma resistance and excellent sealing performance, is even more preferred. In addition, FKM is also preferred in terms of low cost and versatility.

[0040] As a crosslinked fluorinated elastomer (A2), FKM and FEPM are preferred, and FKM is more preferred for the same reasons as the crosslinked fluorinated elastomer (A1).

[0041] As the crosslinkable fluorinated elastomer (A), products synthesized by conventionally known methods can be used, as well as commercially available products. Examples of such commercially available products include "DAI-EL" manufactured by Daikin Industries, Ltd., "Viton" manufactured by Chemours, "Dyneon" manufactured by 3M, and "Technoflon" manufactured by Solvay.

[0042] The crosslinked fluorinated elastomer (A1) has a fluorine content of 69% by mass or more, preferably 70% by mass or more, preferably 73% by mass or less, and more preferably 71% by mass or less.

[0043] The fluorine content of the crosslinked fluorinated elastomer (A2) is 55-68% by mass, preferably 60-68% by mass, more preferably 63-68% by mass, and even more preferably 65-68% by mass.

[0044] By using at least two crosslinked fluorinated elastomers with fluorine content within the above range, a uniform elastomer composition can be obtained in a short time, and an elastomer composition with excellent formability can be easily obtained. Sealing materials with 100% Mo content, exhibiting excellent hardness, tensile strength, elongation at break, and 100% Mo content, can be easily obtained.

[0045] The fluorine content can be determined by using... 19 F-NMR, 1 Fluorine elemental analysis such as H-NMR or mass spectrometry (MS) is used for determination and calculation.

[0046] The fluorine content in this invention is a value obtained by rounding to the nearest whole number.

[0047] The Mooney viscosity of the crosslinked fluorinated elastomer (A) is preferably 10 or more, more preferably 15 or more, even more preferably 18 or more, preferably 140 or less, more preferably 120 or less, even more preferably 80 or less, and particularly preferably 60 or less.

[0048] If the Mooney viscosity of the crosslinked fluorinated elastomer (A) is within the above range, an elastomer composition with excellent formability, especially excellent compressibility, can be easily obtained.

[0049] Additionally, the Mooney viscosity in this specification refers to the Mooney viscosity (ML1+10) at 121°C as measured according to ASTM D 1646.

[0050] As an example of a crosslinked fluorinated elastomer (A1), it is preferable to use a crosslinked fluorinated elastomer (A1-1) with a Mooney viscosity preferably in the range of 40 to 140, more preferably 40 to 120, and even more preferably 40 to 60, and a crosslinked fluorinated elastomer (A1-2) with a Mooney viscosity preferably 10 or more and less than 40, more preferably in the range of 10 to 30.

[0051] By using cross-linked fluorinated elastomers (A1-1) and (A1-2), it is possible to exhibit the conventional physical properties, formability, and especially the sheeting properties of elastomer compositions of sealing materials such as 100% Mo with better balance, including excellent hardness, tensile strength, elongation at break, and other properties.

[0052] When using crosslinked fluorinated elastomers (A1-1) and (A1-2) as the crosslinked fluorinated elastomer (A1), the content of crosslinked fluorinated elastomer (A1-1) is preferably 20 to 80% by mass relative to its total 100% mass.

[0053] If the content of crosslinked fluorinated elastomer (A1-1) is within the above range, it can exhibit excellent hardness, tensile strength, elongation at break, and conventional physical properties and formability, especially sheeting properties, of the sealing material obtained from 100% Mo, and is therefore preferred.

[0054] The content of crosslinked fluorinated elastomer (A1) in the solid component of this composition is preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 95% by mass or less, and even more preferably 85% by mass or less.

[0055] If the content of cross-linked fluorinated elastomer (A1) is within the above range, it is easy to obtain a sealing material with excellent chemical resistance, such as plasma resistance and chemical resistance.

[0056] In this specification, solid components refer to components other than solvents.

[0057] The content of crosslinked fluorinated elastomer (A2) in the solid component of this composition is preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0058] If the content of crosslinked fluorinated elastomer (A2) is within the above range, a sealing material exhibiting excellent formability and chemical resistance with good balance can be easily obtained.

[0059] The content of crosslinked fluorinated elastomer (A1) is 60% by mass or more, preferably 65% ​​by mass or more, and 95% by mass or less, preferably 90% by mass or less, relative to the total content of crosslinked fluorinated elastomers (A1) and (A2) in the composition.

[0060] If the mass ratio of the crosslinked fluorinated elastomers (A1) and (A2) is within the above range, a uniform elastomer composition can be obtained in a short time, and an elastomer composition with excellent formability can be easily obtained. A sealing material with 100% Mo high content, especially exhibiting excellent hardness, tensile strength, elongation at break and good balance, can be easily obtained.

[0061] [FKM]

[0062] There are no particular limitations on FKM, but examples can be given of polymers that contain hydrogen atoms (carbon-hydrogen bonds) in the polymer backbone. Specifically, it is preferred to include structural units derived from vinylidene fluoride.

[0063] There are no specific limitations on FKM. For example, we can cite polymers based on vinylidene fluoride-hexafluoropropylene, polymers based on vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene, polymers based on vinylidene fluoride-propylene-tetrafluoroethylene, polymers based on ethylene-tetrafluoroethylene-perfluoroalkyl vinyl ether, and polymers based on vinylidene fluoride-tetrafluoroethylene-perfluoroalkyl vinyl ether.

[0064] As a preferred example of the perfluoroalkyl vinyl ether, perfluoromethyl vinyl ether can be cited.

[0065] Among them, considering the superior plasma resistance, heat resistance, and chemical resistance, ternary polymers are preferred, and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene polymers are even more preferred.

[0066] Fluorinated elastomers that can be crosslinked by peroxides preferably have functional groups such as iodine, bromine, cyano, peroxy, and unsaturated groups. From the perspective of the ease of introducing functional groups, iodine and bromine groups are more preferred.

[0067] Fluorinated elastomers having iodine and / or bromine groups can be obtained, for example, by using one or more saturated or unsaturated iodine and / or bromine-containing compounds during the synthesis of the elastomer.

[0068] Examples of iodine- and / or bromine-containing compounds include, for example, compounds represented by formula (1) or (2).

[0069] Fluorinated elastomers having iodine and / or bromine groups on the side chains can be synthesized by using compounds represented by formula (1), and fluorinated elastomers having iodine and / or bromine groups at the ends can be synthesized by using compounds represented by formula (2).

[0070] CY 1 2 = CY 2 RfX (1)

[0071] [Y 1 and Y 2 Each of the following is independently a fluorine atom, a hydrogen atom, or a methyl group; Rf is a straight-chain or branched fluorinated alkylene group in which some or all hydrogen atoms are replaced by fluorine atoms, or a group in which a portion of the fluorinated alkylene group contains an ether bond; X is an iodine atom or a bromine atom.

[0072] As a specific example of a compound represented by the above formula (1), the compound described in International Publication No. 2009 / 119409 can be cited.

[0073] I n Br m R(2)

[0074] [R is a fluoroalkyl group with 1 to 12 carbon atoms, n and m are each independent integers from 0 to 2, and n+m is 1 or 2.]

[0075] As specific examples of compounds represented by the above formula (2), compounds described in Japanese Patent Application Publication No. 2002-97329 or Japanese Patent Application Publication No. 2008-56739 may be cited.

[0076] <Compounds containing olefinic unsaturated bonds (B)>

[0077] From the viewpoint that non-adhesive sealing materials with excellent plasma resistance can be readily obtained, this composition preferably uses a compound (B) containing olefinic unsaturated bonds.

[0078] Compound (B) is at least one compound selected from compounds (B1) having a perfluorinated skeleton with olefinic unsaturated bonds and compounds (B2) having a siloxane skeleton with olefinic unsaturated bonds. From the viewpoint of readily obtaining sealing materials with superior plasma resistance, compound (B) preferably includes compound (B1).

[0079] Examples of alkenyl unsaturated bonds include, for example, vinyl, methyl vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, heptenyl, and other alkenyl groups with 2 to 8 carbon atoms, as well as vinylphenyl, (meth)acryloyl, allyloxy, styryl, and propargyl. Among these, alkenyl groups are preferred, alkenyl groups with 2 to 4 carbon atoms are more preferred, and vinyl groups are particularly preferred.

[0080] Compound (B) may have two or more olefinic unsaturated bonds.

[0081] Compound (B) can be synthesized by conventionally known methods or is a commercially available product. An example of such a commercially available product is "SIFEL" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0082] As commercially available products containing compound (B), including both single-component and two-component commercially available products, any one of them may be used. Furthermore, as commercially available products containing compound (B), including liquid, paste, oil, and mirable types, any one of them may be used.

[0083] When a commercially available product is used as compound (B), the product may sometimes contain additives such as reactive organosilicon compounds having two or more hydrosilyl groups within their molecules (e.g., organosilicon compounds described in Japanese Patent Application Publication No. 2003-183402, Japanese Patent Application Publication No. 11-116684, etc.), catalysts (e.g., catalysts described in Japanese Patent Application Publication No. 2003-183402, Japanese Patent Application Publication No. 11-116684, etc.), and filler materials (e.g., silica). Compounds containing these additives may also be used as compound (B).

[0084] When this composition contains compound (B), from the viewpoint that a uniform elastomer composition can be obtained in a shorter time and a sealing material with better plasma resistance can be easily obtained, the content of compound (B) in this composition relative to 100 parts by mass of crosslinked fluorinated elastomer (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, preferably 50 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 10 parts by mass or less.

[0085] When this composition contains compound (B) and the crosslinking agent described below, from the viewpoint that sealing materials with excellent plasma resistance can be easily obtained, the mass ratio of the content of compound (B) to the content of crosslinking agent (content of compound (B) / content of crosslinking agent) in this composition is preferably 0.5 or more, more preferably 1 or more, more preferably 20 or less, and more preferably 10 or less.

[0086] [Compound (B1)]

[0087] Compound (B1) is a compound other than cross-linked fluorinated elastomer (A).

[0088] Examples of compounds (B1) include compounds with a perfluoropolyether structure having an olefin unsaturated bond and compounds with a perfluoroalkylene structure having an olefin unsaturated bond. Among these, compounds with a perfluoropolyether structure having an olefin unsaturated bond are preferred (hereinafter also referred to as "compound (B1-1)").

[0089] When the composition contains compound (B1), the compound (B1) contained in the composition may be one or more.

[0090] Compound (B1-1)

[0091] The compound (B1-1) is preferably a perfluoropolyether having two or more olefinic unsaturated bonds within one molecule.

[0092] Preferred examples of compound (B1-1) include the compounds described in Japanese Patent Application Publication No. 2003-183402, Japanese Patent Application Publication No. 11-116684, Japanese Patent Application Publication No. 11-116685 and Japanese Patent Application Publication No. 2015-67737.

[0093] As a compound (B1-1), examples of compounds represented by the following formula (1) can be cited.

[0094] Z 1 -(X) p -(Rf-Q) a -Rf-(X) p -Z 2 ...(1)

[0095] X can be independently -CH2-, -CH2O-, -CH2OCH2-, or *-Si(R) 2 )2-Ph-(Ph: phenylene), *-Y-NR 1 SO2- or *-Y-NR 1 -CO-(where Y is -CH2- or *-Si(R) 2 )2-Ph-, the * part is related to Z 1 or Z 2 (bonding).

[0096] Rf stands for divalent perfluoropolyether (divalent perfluorooxyolefin).

[0097] p is independently 0 or 1; a is an integer greater than or equal to 0, preferably an integer from 0 to 10, and more preferably an integer from 0 to 6.

[0098] Q is a group represented by formula (2), (3) or (4).

[0099] R 2These are monovalent hydrocarbon groups with 1 to 10 carbon atoms, especially 1 to 8 carbon atoms, and are either substituted or unsubstituted, such as alkyl groups like methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, etc.; cycloalkyl groups like cyclopentyl, cyclohexyl, cycloheptyl, etc.; alkenyl groups like vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, etc.; aryl groups like phenyl, tolyl, xylyl, naphthyl, etc.; and aralkyl groups like benzyl, phenethyl, phenylpropyl, etc., where some or all of the hydrogen atoms of these groups are substituted by halogen atoms (e.g., fluorosubstituted alkyl groups like chloromethyl, chloropropyl, bromoethyl, 3,3,3-trifluoropropyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl).

[0100] R 1 It is a hydrogen atom or related to the above as R 2 Examples of substituted or unsubstituted monovalent hydrocarbon groups with the same number of carbons (1-10), particularly 1-8, include hydrogen atoms or groups with the same number of carbons as R. 2 The same group, such as alkyl such as methyl, ethyl, propyl, isopropyl, cyclohexyl, alkenyl such as vinyl, allyl, aryl such as phenyl, tolyl, etc., groups in which some or all of the hydrogen atoms are replaced by halogen atoms (e.g., fluorosubstituted alkyl such as chloromethyl, chloropropyl, 3,3,3-trifluoropropyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl).

[0101] Z 1 and Z 2 Each can be an independent group containing an olefinic unsaturated bond, and can be -Si (a group containing an olefinic unsaturated bond) (R')2.

[0102] The group containing the alkene unsaturated bond is preferably a monovalent alkenyl group, more preferably a monovalent alkenyl group with 2 to 4 carbon atoms, and particularly preferably a monovalent vinyl group.

[0103] R′ can be a substituted or unsubstituted monovalent hydrocarbon group, specifically alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, and hexyl; aryl groups such as phenyl, tolyl, and xylyl; and haloalkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl. Alkyl groups with 1 to 5 carbon atoms are preferred.

[0104] [Chemistry 1]

[0105]

[0106] -(X) p -CH2CH2R 4 CH2CH2-(X) p -.-(3)

[0107]

[0108] In equations (2) to (4), X, p, and R 1 With X, p, R in equation (1) above 1 Same definition. R 3 and R 4 Each is independently a divalent hydrocarbon group, optionally selected from oxygen, nitrogen, silicon, and sulfur atoms, with one or more substituted or unsubstituted groups inserted in the middle of the bond, R in formula (2) 3 and R in equation (3) 4 Each can be a group represented independently by formula (5) or (6).

[0109] [Chemistry 2]

[0110]

[0111] In equations (5) and (6), R 5 For substituted or unsubstituted monovalent hydrocarbon groups, R 6 It contains one or more groups selected from carbon, oxygen, nitrogen, silicon and sulfur atoms.

[0112] R 3 and R 4 Any substituted or unsubstituted divalent hydrocarbon group is acceptable, with no particular limitation. Preferred divalent hydrocarbon groups have 1 to 20 carbon atoms, especially 2 to 12. Examples include alkylene groups such as methylene, ethylene, propylene, methyl ethylene, butylene, and hexamethylene; cyclohexylene groups such as cyclohexylene; and aryl groups such as phenylene, tolylene, xylene, naphthylene, and biphenylene. Groups in which some hydrogen atoms of these groups are replaced by halogen atoms, as well as combinations of these substituted or unsubstituted alkylene and aryl groups.

[0113] Preferred - (X) p -(Rf-Q) a -Rf-(X) p -for-(OR) 7 ) n -[R 7 Represents a perfluoroalkyl dimethyl group, where n represents an integer greater than or equal to 2. Multiple existing R groups... 7 They can be the same or different.

[0114] As a result of R 7 The perfluoroalkyl dimethyl group represented can be exemplified by C m F 2m The group represented by (m is an integer of 2 or more) can be linear or branched. The number of carbons (i.e., m) of the perfluoroalkyl diester is, for example, 1 to 10, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 to 3.

[0115] n can be 2 or more, for example, 10 or more, preferably 40 or more, and more preferably 70 or more. Alternatively, n can be 300 or less, preferably 200 or less, and more preferably 150 or less.

[0116] -(OR 7 ) n - It can be the same group as Rf below.

[0117] The compound represented by formula (1) above is preferably the compound represented by formula (1-1) below.

[0118] CH2=CH-(X) p -(Rf-Q) a -Rf-(X) p -CH=CH2···(1-1)

[0119] [The definitions of the symbols in equation (1-1) are the same as those in equation (1).]

[0120] Furthermore, the compound represented by the above formula (1-1) is preferably a compound in which a is 0, in which case it is represented by the following formula (1-1-1).

[0121] CH2=CH-(X) p -Rf-(X) p -CH=CH2···(1-1-1)

[0122] [The definitions of the symbols in equation (1-1-1) are the same as those in equation (1).]

[0123] Specific examples of Rf can be cited from the following groups.

[0124] -[CF(Z)OCF2] p -(CF2) r -[CF2OCF(Z)] q -

[0125] (Z is a fluorine atom or -CF3, p, q, r are integers satisfying p≥1, q≥1, 2≤p+q≤200, preferably 2≤p+q≤110, 0≤r≤6)

[0126] -CF2CF2OCF2-(CF(CF3)OCF2) s -(CF2) r -(CF2OCF(CF3)) t -CF2OCF2CF2-

[0127] (r, s, and t are integers that satisfy 0 ≤ r ≤ 6, s ≥ 0, t ≥ 0, 0 ≤ s + t ≤ 200, preferably 2 ≤ s + t ≤ 110).

[0128] -CF(Z)-(OCF(Z)CF2) u -(OCF2) v -OCF(Z)-

[0129] (Z is a fluorine atom or -CF3, u and v are integers satisfying 1≤u≤100 and 1≤v≤50),

[0130] -CF2CF2-[OCF2CF2CF2] w -OCF2CF2-

[0131] (w is an integer that satisfies 1≤w≤100).

[0132] [Compound (B2)]

[0133] Compound (B2) is preferably a polysiloxane having two or more olefinic unsaturated bonds per molecule, and more preferably an organopolysiloxane having two or more olefinic unsaturated bonds per molecule and whose organic groups are bonded to silicon atoms. There are no particular limitations on the bonding positions of the olefinic unsaturated bonds.

[0134] When the composition contains compound (B2), the compound (B2) contained in the composition may be one or more.

[0135] Examples of organic groups that bond with silicon atoms include, for example, olefinic unsaturated bonds, straight-chain alkyl groups, branched alkyl groups, cyclic alkyl groups, aryl groups, aralkyl groups, and haloalkyl groups.

[0136] Examples of straight-chain alkyl groups include methyl, ethyl, propyl, hexyl, octyl, decyl, and other groups with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

[0137] Examples of branched alkyl groups include isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, and other groups with 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.

[0138] Examples of cycloalkyl groups include cyclopentyl and cyclohexyl groups with 3 to 20 carbon atoms.

[0139] Examples of aryl groups include phenyl, tolyl, and other groups with 6 to 20 carbon atoms.

[0140] Examples of aralkyl groups include benzyl, 2-phenylethyl, 2-methyl-2-phenylethyl, and other groups with 7 to 20 carbon atoms.

[0141] Examples of haloalkyl groups include 3,3,3-trifluoropropyl, 2-(nonafluorobutyl)ethyl, 2-(heptadecylfluorooctyl)ethyl, etc., which have 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.

[0142] The organic groups bonded to silicon atoms are preferably straight-chain alkyl, alkenyl, or aryl groups, more preferably straight-chain alkyl, alkenyl, or aryl groups having 1 to 6 carbon atoms, and particularly preferably methyl, vinyl, or phenyl groups.

[0143] There are no particular limitations on the molecular structure of compound (B2). Examples include linear, branched, partially branched linear, and dendritic structures, with linear and partially branched linear structures being preferred. Compound (B2) can be a homopolymer having these molecular structures, a copolymer having these molecular structures, or a mixture of two or more of these polymers.

[0144] Examples of compounds (B2) include dimethyl polysiloxanes whose molecular chains are capped at both ends by dimethylvinylsiloxy groups, dimethyl polysiloxanes whose molecular chains are capped at both ends by methylphenylvinylsiloxy groups, dimethyl siloxane-methylphenyl siloxane copolymers whose molecular chains are capped at both ends by dimethylvinylsiloxy groups, dimethyl siloxane-methylvinyl siloxane copolymers whose molecular chains are capped at both ends by dimethylvinylsiloxy groups, dimethyl siloxane-methylvinyl siloxane-methylphenyl siloxane copolymers whose molecular chains are capped at both ends by silanol groups, dimethyl siloxane-methylvinyl siloxane-methylphenyl siloxane copolymers whose molecular chains are capped at both ends by silanol groups, dimethyl siloxane-methylvinyl siloxane-methylphenyl siloxane copolymers whose molecular chains are capped at both ends by trimethylsiloxy groups, methyl (3,3,3-trifluoropropyl) polysiloxanes whose molecular chains are capped at both ends by dimethylvinylsiloxy groups, and polysiloxanes of the formula (CH3)3SiO 1 / 2 The siloxane unit and formula represented are: (CH3)2(CH2=CH)SiO 1 / 2 The siloxane unit and formula represented by: CH3SiO 3 / 2 The siloxane unit and formula represented by: (CH3)2SiO 2 / 2 Organosiloxane copolymers composed of siloxane units, and compounds represented by the following formula (7).

[0145] [Chemistry 3]

[0146]

[0147] In equation (7), each R 1 Each is an independent monovalent hydrocarbon group, either unsubstituted or substituted, and each R 2 Independently, it is alkyl, alkoxyalkyl, alkenyl, or acyl, b is an integer from 2 to 100, and a is an integer from 1 to 3. R in formula (7) 1 and R 2 At least two of them contain the olefinic unsaturated bonds.

[0148] In equation (7), R 1Each group is independently unsubstituted or substituted, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of such groups are the same as those exemplified above as organic groups bonded to silicon atoms. Among these, monovalent hydrocarbon groups having 1 to 6 carbon atoms are preferred, and alkenyl, aryl, and alkyl groups having 1 to 3 carbon atoms are more preferred.

[0149] As R in equation (7) 2 Alkyl and alkenyl groups, for example, are the same straight-chain alkyl, branched alkyl, cyclic alkyl, and alkenyl groups as those exemplified above as organic groups bonded to silicon atoms.

[0150] As R in equation (7) 2 Alkoxyalkyl groups, for example, methoxyethyl, methoxypropyl, etc., are groups with 2 to 10 carbon atoms.

[0151] As R in equation (7) 2 Acyl groups, for example, are groups with 2 to 10 carbon atoms, such as acetyl and octanoyl.

[0152] In formula (7), b is preferably an integer from 10 to 50, and a is preferably 3.

[0153] Crosslinking agent

[0154] The crosslinked fluorinated elastomer (A) can be crosslinked even without the use of a crosslinking agent. From the viewpoint that it is possible to obtain a sealing material that exhibits excellent hardness, tensile strength, elongation at break and 100% Mo with good balance by fully crosslinking, this composition preferably contains a crosslinking agent corresponding to the type of crosslinked fluorinated elastomer (A) used.

[0155] When the composition contains a crosslinking agent, the crosslinking agent contained in the composition may be one or more.

[0156] As the crosslinking agent, any existing crosslinking agent can be used without any restrictions. It can be appropriately selected according to the type of crosslinked fluorinated elastomer (A) used. For example, when using FKM, peroxide crosslinking agents, polyamine crosslinking agents, polyol crosslinking agents, triazine crosslinking agents, etc., can be used.

[0157] From the viewpoint that there is no need to incorporate acid absorbers such as magnesium oxide and calcium hydroxide, which can become particle generation sources in plasma atmospheres, into the composition, and that the resulting sealing material does not pose a risk of particle generation during use, peroxide-based crosslinking agents are preferred.

[0158] Examples of peroxide-based crosslinking agents include 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, tert-butyldicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-(tert-butylperoxide)-3-hexyne, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, α,α'-bis(tert-butylperoxide-m-isopropyl) α,α-bis(tert-butylperoxyisopropyl)carbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, p-chlorobenzoyl peroxide, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, α,α-bis(tert-butylperoxy)-p-diisopropylbenzene, tert-butylperoxybenzene, tert-butyl maleate peroxide.

[0159] Preferably, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, 2,4-dichlorobenzoyl peroxide, diisopropylbenzene peroxide, benzoyl peroxide, and α,α'-bis(tert-butylperoxide-m-isopropyl)benzene are used, and more preferably 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane are used.

[0160] When this composition contains a crosslinking agent, from the viewpoint that a sealing material exhibiting excellent hardness, tensile strength, elongation at break, and 100% Mo can be easily obtained with a good balance when the crosslinking reaction is fully carried out, the content of the crosslinking agent in this composition is preferably 0.2 to 4 parts by mass relative to 100 parts by mass of the crosslinked fluorinated elastomer (A), more preferably 0.2 to 2.5 parts by mass.

[0161] Crosslinking aids

[0162] In this composition, the crosslinking agent can be used alone, but when using a crosslinking agent, it is preferable to use a crosslinking aid. As the crosslinking aid, a known crosslinking aid can be selected depending on the type of crosslinking agent.

[0163] When the composition contains a crosslinking aid, the crosslinking aid contained in the composition may be one or more crosslinking aids.

[0164] For example, examples of crosslinking aids used when using peroxide-based crosslinking agents include: triallyl isocyanurate; triallyl cyanurate; trimethylallyl isocyanurate; triallyl formaldehyde; triallyl trimellitate; N,N'-m-phenylene bismaleimide; diacetylacetate; diallyl phthalate; tetraallyl terephthalamide; ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and other multifunctional (meth)acrylates that can be co-crosslinked by free radicals (multifunctional monomers): higher carboxylic acid metal salts; polyol (meth)acrylates; (meth)acrylate metal salts.

[0165] Triallyl isocyanurate is preferred because it exhibits excellent reactivity and heat resistance, and can easily be used to obtain high-modulus sealing materials with high hardness.

[0166] When this composition contains a crosslinking aid, from the viewpoint that a sealing material exhibiting excellent hardness, tensile strength, elongation at break, and 100% Mo can be easily obtained with a good balance when the crosslinking reaction is fully carried out, the content of the crosslinking aid in this composition relative to 100 parts by weight of the crosslinked fluorinated elastomer (A) is preferably 1 part by weight or more, more preferably 2 parts by weight or more, even more preferably 4 parts by weight or more, preferably 10 parts by weight or less, more preferably 7 parts by weight or less, and even more preferably 6 parts by weight or less.

[0167] In particular, to suppress cracking of the sealing material that may occur in a plasma atmosphere, a radioactively cross-linked sealing material (radiation-treated material) is preferred. In this case, from the viewpoint that a sealing material with higher hardness and higher modulus can be easily obtained even without using the filler material described later, the content of the cross-linking aid in this composition is preferably 2 parts by mass or more, more preferably 4 parts by mass or more, more preferably 7 parts by mass or less, and more preferably 6 parts by mass or less, relative to 100 parts by mass of the cross-linked fluorinated elastomer (A).

[0168] From the viewpoint that the crosslinking agent reaction is just right, so that a sealing material exhibiting the desired physical properties can be easily obtained, and especially that a sealing material with higher hardness and higher modulus can be easily obtained even without the use of the filler material described later, the mass ratio of the crosslinking aid content to the crosslinking agent content in this composition (crosslinking aid content / crosslinking agent content) is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, more preferably 30 or less, and even more preferably 20 or less.

[0169] <Other Ingredients>

[0170] In addition to the components described above, this composition may, without impairing the effects of the present invention, contain other conventionally known components incorporated into the sealing material as needed. Examples of such other components include: reactive organosilicon compounds having two or more silane groups within their molecules; catalysts; polyol compounds; acid scavengers such as magnesium oxide and calcium hydroxide; anthraquinone pigments, perylene pigments, and dioxin pigments. Organic pigments such as azinoid pigments; plasticizers; processing aids; vulcanization accelerators; anti-aging agents; antioxidants; inorganic fillers; organic fillers.

[0171] The other ingredients may be used in single or multiple forms.

[0172] [Reactive organosilicon compounds]

[0173] Examples of the reactive organosilicon compounds include compounds similar to those described in Japanese Patent Application Publication No. 2003-183402 and Japanese Patent Application Publication No. 11-116684.

[0174] [catalyst]

[0175] As the catalyst, examples preferably include catalysts similar to those described in Japanese Patent Application Publication No. 2003-183402 and Japanese Patent Application Publication No. Hei 11-116684.

[0176] [Polyol compounds]

[0177] By using the aforementioned polyol compounds, sealing materials with excellent crack resistance in plasma environments can be easily formed without compromising their performance as sealing materials.

[0178] While conventionally known compounds can be widely used as polyols, bisphenols are preferred from the viewpoint of easily obtaining sealing materials with excellent crack resistance.

[0179] Examples of bisphenols include 2,2-bis(4-hydroxyphenyl)perfluoropropane (bisphenol AF), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), and bis(4-hydroxyphenyl)sulfone (bisphenol S). Salts of these compounds, such as alkali metal salts and alkaline earth metal salts, can also be used. Among these, bisphenol AF and bisphenol A are preferred, and bisphenol AF is more preferred from the viewpoint that it is easier to obtain sealing materials with particularly excellent crack resistance.

[0180] When this composition contains polyol compounds, from the viewpoint that sealing materials with excellent crack resistance, low compression set, and fast vulcanization speed can be easily obtained, the content of polyol compounds in this composition relative to 100 parts by weight of crosslinked fluorinated elastomer (A) is preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and even more preferably 0.1 to 1 part by weight.

[0181] [Organic Pigments]

[0182] As the organic pigment, examples preferably include organic pigments that are the same as those described in International Patent Publication No. 2016 / 043100, Japanese Patent No. 4720501, and International Patent Publication No. 2004 / 094527.

[0183] [Filling Material]

[0184] The inorganic and organic fillers (hereinafter collectively referred to as "fillers") are granular (powder) components other than compound (B), crosslinking agent and crosslinking aid.

[0185] Examples of inorganic filler materials include carbon black, silicon dioxide, barium sulfate, titanium dioxide, and aluminum oxide.

[0186] Examples of organic filler materials include fluoropolymers such as PTFE, PFA, FEP, ETFE, and PVDF, polyethylene resins, polyimide resins, silicone resins, and melamine resins.

[0187] When this composition is used to manufacture a sealing material in which particle generation becomes a problem in plasma atmospheres, the content of the filler material relative to 100 parts by weight of the crosslinked fluorinated elastomer (A) is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and most preferably 0 parts by weight.

[0188] <Method for manufacturing this composition>

[0189] This composition can be manufactured by mixing (kneading) a specified amount of crosslinked fluorinated elastomer (A1) and crosslinked fluorinated elastomer (A2), preferably by mixing (kneading) the elastomers (A1) and (A2), compound (B), crosslinking agent, crosslinking aid, and other components as needed.

[0190] There is no particular limitation on the mixing order of elastomers (A1) and (A2), compound (B), crosslinking agent, crosslinking aid, other components and other additives. They can be mixed (kneaded) in any order or all at once. It is preferred to mix (knead) them in order to make the components uniform.

[0191] The mixing (kneading) process can use conventionally known mixing (kneading) machines, such as open roller presses, Banbury mixers, twin-spindle roller presses, and kneaders.

[0192] In addition, during the mixing (kneading) process, depending on the type of mixing (kneading) machine, mixing (kneading) can be carried out under heating or cooling conditions as needed.

[0193] Sealing Materials

[0194] The sealing material of one embodiment of the present invention (hereinafter also referred to as "the sealing material") is a sealing material obtained from the present composition.

[0195] This sealing material is obtained from the aforementioned composition, and therefore exhibits excellent balance in terms of hardness, tensile strength, elongation at break and 100% Mo, as well as excellent resistance to plasma (free radicals), cracking, and compression set.

[0196] This sealing material can be used, for example, as gaskets or seals for various components. In particular, due to the aforementioned effects, it is suitable for use in semiconductor manufacturing equipment and plasma processing equipment, and is especially suitable for drive units, such as gate valves used in the openings of plasma processing chamber units.

[0197] The shape and other properties of this sealing material can be appropriately selected according to the intended use.

[0198] When this sealing material is manufactured through the following radiation irradiation process, this sealing material may be a sealing material that does not contain filler material but has the following physical properties.

[0199] According to JIS K 6251:2017, the 100% Mo of this sealing material is preferably 4 MPa or higher.

[0200] The Shore A hardness (type A hardness tester hardness) of this sealing material, as measured according to JIS K 6253:2012, is preferably 60 or higher.

[0201] The tensile strength of this sealing material, as determined according to JIS K 6251:2017, is preferably 7 MPa or higher, and more preferably 9 MPa or higher.

[0202] The elongation at break of this sealing material, as measured according to JIS K 6251:2017, is preferably 120% or more, and more preferably 130% or more.

[0203] If this sealing material is manufactured without undergoing the following radiation irradiation process, this sealing material may be a sealing material that does not contain filler material but has the following physical properties.

[0204] The preferred strength for 100% Mo, as determined by JIS K 6251:2017, is 1.3 MPa or higher.

[0205] The Shore A hardness (type A hardness tester hardness) of this sealing material, as measured according to JIS K 6253:2012, is preferably 55 or higher.

[0206] The tensile strength of this sealing material, as determined by JIS K 6251:2017, is preferably 10 MPa or higher.

[0207] The elongation at break of this sealing material, as determined by JIS K 6251:2017, is preferably 180% or more.

[0208] <Manufacturing method of this sealing material>

[0209] Specifically, this sealing material can be manufactured by molding this composition. From the viewpoint that it is possible to easily obtain sealing materials with superior plasma resistance (free radical resistance), crack resistance, non-adhesion, etc., and exhibiting excellent hardness, tensile strength, elongation at break and 100% Mo with a good balance, it is preferable to obtain a cross-linked product by a method including a process of cross-linking this composition (cross-linking process).

[0210] When forming a sealing material from this composition, a tableting process is preferred from the viewpoint of improving the efficiency of the forming operation and reducing the defect rate. This tableting process is usually carried out using rollers or the like, and is typically a process in which the composition is pre-formed into a sheet shape.

[0211] The sheet obtained by the pressing process is preferably pre-formed into the desired sealing material shape before the crosslinking process.

[0212] In this preforming process, the sheet obtained in the tableting process can be directly formed into the desired sealing material shape, or the sheet obtained in the tableting process can be formed into a rope shape (the same meaning applies to strips, noodles, etc.) by cutting or extrusion molding, and then the resulting rope shape can be formed into the desired sealing material shape.

[0213] The crosslinking process more preferably includes a primary crosslinking process and a secondary crosslinking process.

[0214] The crosslinking process is preferably performed using the desired sealing material shape obtained through the preforming.

[0215] The preferred cross-linking process is a process of heating and pressurizing the desired sealing material shape obtained by the preforming. Specifically, examples include placing the preformed material into a mold and using a hot press or similar device to perform a cross-linking process at a pressure of about 2 to 15 MPa and a temperature of, for example, 150 to 200°C for about 5 to 20 minutes.

[0216] The secondary crosslinking process is preferably a process of heating the molded body obtained in the primary crosslinking process. Specifically, examples include heating at a temperature of 150 to 300°C for 1 to 24 hours, preferably 3 to 24 hours, using various ovens under normal to reduced pressure, preferably using a vacuum oven.

[0217] This secondary crosslinking process promotes crosslinking, and even if unreacted components remain after the primary crosslinking process, these unreacted components can be decomposed and volatilized, resulting in a sealing material that releases less gas.

[0218] In the manufacturing method of this sealing material, from the viewpoint of more easily suppressing cracks in the sealing material in plasma atmospheres, a radiation irradiation process (radiation irradiation process) can be performed after the crosslinking process. The sealing material obtained by this radiation irradiation process can be referred to as a radiation-treated material.

[0219] The radiation used in the radiation irradiation process is not particularly limited as long as it can crosslink the crosslinked fluorinated elastomer (A). Examples include X-rays, gamma rays, electron beams, proton beams, neutron beams, heavy particle beams, alpha rays, and beta rays, with gamma rays and electron beams being preferred.

[0220] The radiation used for irradiation can be a single type or two or more types.

[0221] When irradiating with radiation, it is preferable to irradiate with an absorbed radiation dose of 1 to 120 kGy, more preferably 20 to 100 kGy. By irradiating with this dose, unreacted components that may become particles or release gases can be reduced, and sealing materials with excellent plasma resistance and crack resistance can be easily obtained while preventing the molecular weight of the crosslinked fluorinated elastomer (A) from being too low.

[0222] The radiation irradiation process can be carried out in two or more stages by changing the conditions.

[0223] While irradiation can occur in air, the presence of oxygen during the process hinders the cross-linking reaction, reduces the mechanical strength of the sealing material, and may cause the surface of the sealing material to become sticky. Therefore, the irradiation process is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0224] Example

[0225] The present invention will now be described in more detail with reference to embodiments, but the invention is not limited thereto.

[0226] <Crosslinked Fluorinated Elastomers>

[0227] The crosslinked fluorinated elastomers used in the following examples and comparative examples are as follows.

[0228] • Crosslinked fluorinated elastomer (A1-a): Tecnoflon P959 (manufactured by Solvay, fluorine content: 70% by mass)

[0229] • Crosslinked fluorinated elastomer (A1-b): Tecnoflon P459 (manufactured by Solvay, fluorine content: 70% by mass)

[0230] • Crosslinked fluorinated elastomer (A1-c): DAI-EL G912 (manufactured by Daikin Industries, Ltd., fluorine content: 71% by mass)

[0231] • Crosslinked fluorinated elastomer (A1-d): DAI-EL G902 (manufactured by Daikin Industries, Ltd., fluorine content: 71% by mass)

[0232] • Crosslinked fluorinated elastomer (A2-a): Tecnoflon P757 (manufactured by Solvay, fluorine content: 67% by mass)

[0233] • Crosslinked fluorinated elastomer (A2-b): Tecnoflon P457 (manufactured by Solvay, fluorine content: 67% by mass)

[0234] • Crosslinked fluorinated elastomer (A2-c): DAI-EL G801 (manufactured by Daikin Industries, Ltd., fluorine content: 66% by mass)

[0235] • Crosslinked fluorinated elastomer (A2-d): Tecnoflon PL855 (manufactured by Solvay, fluorine content: 64% by mass)

[0236] • Crosslinked fluorinated elastomer (A2-e): DAI-EL LT302 (manufactured by Daikin Industries, Ltd., fluorine content: 65% by mass)

[0237] • Crosslinked fluorinated elastomer (A2-f): AFLAS 100S (manufactured by AGC Corporation, fluorine content: 57% by mass)

[0238] [Example 1]

[0239] 70 parts by weight of crosslinked fluorinated elastomer (A1-a), 30 parts by weight of crosslinked fluorinated elastomer (A2-a), 1.0 part by weight of SIFEL8070A (manufactured by Shin-Etsu Chemical Co., Ltd.), 1.0 part by weight of SIFEL 8070B (manufactured by Shin-Etsu Chemical Co., Ltd.), 6.0 parts by weight of TAIC (manufactured by Mitsubishi Chemical Corporation, triallyl isocyanurate), and 0.5 parts by weight of Perhexa 25B (manufactured by Nippon Oil Co., Ltd.) were sequentially added to a kneader and mixed until the current value stabilized, thereby obtaining a block elastomer composition.

[0240] At least one of SIFEL 8070A and SIFEL 8070B comprises a compound having a perfluorinated skeleton with olefinic unsaturated bonds.

[0241] Kneading time is defined as the total time from the initial addition of the component to the time when the current value stabilizes after the final component is added. The results are shown in Table 1.

[0242] Generally speaking, when using a kneader for mixing, the current value will stabilize if all added ingredients are mixed evenly. Therefore, the stabilization of the current value is often used as the standard for completion of mixing to determine that a homogeneous composition has been obtained.

[0243] The obtained block elastomer composition is subjected to a tableting process (sheet forming process) using rollers (roller gap: 8 mm, temperature: 50 °C).

[0244] At this point, if the block-shaped elastomer composition can be formed into a sheet, the compressibility is "OK"; if the elastomer composition is not gripped between the rollers or has poor adhesion to the rollers and fails to achieve good compressibility, the compressibility is "NG". The results are shown in Table 1.

[0245] The sheet obtained in the above tableting process was pressurized at 170°C for 10 minutes under a pressure of 5 MPa using a vacuum press (first crosslinking). Then, the pressurized sheet was placed in a vacuum oven (vacuum degree: 50 Pa) and heated at 200°C for 16 hours under reduced pressure (second crosslinking). Finally, the second crosslinked sheet was irradiated with radiation at an absorbed linear intensity of 80 kGy to obtain the molded body.

[0246] The following conventional physical properties were measured on the resulting molded articles. The results are shown in Table 1.

[0247] <Common Physical Properties>

[0248] As standard physical properties, Shore A hardness was determined according to JIS K 6253:2012, and tensile strength, elongation at break, and tensile stress at 100% elongation (100% Mo) were determined according to JIS K6251:2017.

[0249] [Examples 2-5 and Comparative Examples 1-2]

[0250] Except that the crosslinked fluorinated elastomers shown in Table 1 were used in the amounts shown in Table 1, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[0251] [Table 1]

[0252]

[0253] In Examples 1-5, the time required to produce a uniform elastomer composition was short, and the elastomer compositions obtained in Examples 1-5 had excellent compressibility (sheet forming properties).

[0254] In Comparative Examples 1 and 2, it took a long time to obtain a uniform elastomer composition, and the elastomer compositions obtained in Comparative Examples 1 and 2 had poor compressibility, specifically, the elastomer composition was not bitten between the rollers or was not smoothly wound onto the rollers, thus failing to form a good sheet.

[0255] [Examples 6-11 and Comparative Examples 3-4]

[0256] Except for using the crosslinked fluorinated elastomers shown in Table 2 in the amounts shown in Table 2, the bulk elastomer composition was obtained in the same manner as in Example 1.

[0257] In Examples 9 and 10, the amount of TAIC used was 5.5 parts by weight. In Example 11, the amount of SIFEL 8070A was 2.0 parts by weight, the amount of SIFEL 8070B was 2.0 parts by weight, the amount of TAIC was 5.0 parts by weight, and the amount of Perhexa 25B was 1.0 part by weight.

[0258] The obtained block elastomer composition was filled into a mold and pressurized at 170°C for 10 minutes under a pressure of 5 MPa using a compression vacuum press (first crosslinking). The pressurized sheet was then placed in a vacuum oven (vacuum degree: 50 Pa) and heated at 200°C for 16 hours under reduced pressure (second crosslinking). The second crosslinked sheet was then irradiated with radiation at an absorption linearity of 80 kGy to obtain the molded body.

[0259] The obtained molded articles were tested for the above-mentioned conventional physical properties. The results are shown in Table 2.

[0260] [Table 2]

[0261]

[0262] [Example 12]

[0263] 70 parts by weight of crosslinked fluorinated elastomer (A1-c), 30 parts by weight of crosslinked fluorinated elastomer (A2-a), 2 parts by weight of SIFEL3590-N (manufactured by Shin-Etsu Chemical Industry Co., Ltd., a compound containing a perfluorinated skeleton with olefinic unsaturated bonds, single-liquid type), 6 parts by weight of TAIC, and 1 part by weight of Perhexa 25B1 were sequentially added to a kneader and mixed until the current value stabilized to obtain a block elastomer composition.

[0264] Using the obtained block elastomer composition, the molded body was obtained in the same manner as in Example 6.

[0265] The conventional physical properties of the resulting molded articles and the plasma resistance 1 were measured. The results are shown in Table 3.

[0266] [Example 13]

[0267] 70 parts by weight of crosslinked fluorinated elastomer (A1-c), 30 parts by weight of crosslinked fluorinated elastomer (A2-a), 10 parts by weight of SIFEL3590-N, 6 parts by weight of TAIC, and 1 part by weight of Perhexa 25B were sequentially added to a kneader and mixed until the current value stabilized to obtain a block-shaped elastomer composition.

[0268] Using the obtained block elastomer composition, the molded body was obtained in the same manner as in Example 6.

[0269] The conventional physical properties of the resulting molded articles and the plasma resistance 1 were measured. The results are shown in Table 3.

[0270] [Example 14]

[0271] 70 parts by weight of crosslinked fluorinated elastomer (A1-c), 30 parts by weight of crosslinked fluorinated elastomer (A2-a), 2 parts by weight of KE-1830 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., a compound containing a siloxane skeleton with olefinic unsaturated bonds, single-liquid type), 6 parts by weight of TAIC, and 0.5 parts by weight of Perhexa 25B were sequentially added to a kneader and kneaded until the current value stabilized to obtain a block elastomer composition.

[0272] Using the obtained block elastomer composition, the molded body was obtained in the same manner as in Example 6.

[0273] The conventional physical properties of the resulting molded articles and the plasma resistance 1 were measured. The results are shown in Table 3.

[0274] <Plasma Resistance 1>

[0275] The plasma resistance (mass reduction rate) of the obtained molded body was measured. The specific measurements are as follows.

[0276] Using a flat plasma treatment device with an electrode diameter of φ300mm and an electrode spacing of 50mm, the obtained shaped body was irradiated with plasma for 3 hours under the conditions of RF500W, CF4 gas flow rate of 50sccm, O2 gas flow rate of 150sccm, and vacuum degree of 1tor.

[0277] The resulting molded body was placed 6 cm from the plasma electrode. Next, the mass of the molded body before and after the test was measured, and the mass reduction rate (%) was calculated using the following formula to evaluate plasma resistance. It can be said that the smaller the mass reduction rate, the better the plasma resistance.

[0278] Mass reduction rate (%) = [(mass of molded part before test - mass of molded part after test) / mass of molded part before test] × 100

[0279] [Table 3]

[0280] [Examples 15-18 and Comparative Examples 5-7]

[0281] Except that the crosslinked fluorinated elastomers shown in Table 4 are used in the amounts shown in Table 4, the same procedure as in Example 1 is followed to obtain a block-shaped elastomer composition.

[0282] In Example 18, the amount of SIFEL 8070A used was 3 parts by weight, and the amount of SIFEL 8070B used was 3 parts by weight.

[0283] The obtained block elastomer composition was filled into a mold and pressurized at 170°C for 10 minutes under a pressure of 5 MPa using a compression vacuum press (first crosslinking). The pressurized sheet was then placed in a vacuum oven (vacuum degree: 50 Pa) and heated at 200°C for 16 hours under reduced pressure (second crosslinking).

[0284] The obtained molded articles were tested for the above-mentioned conventional physical properties and the following plasma resistance. The results are shown in Table 4.

[0285] <Plasma Resistance 2>

[0286] The plasma resistance (mass reduction rate) of the obtained molded body was measured. The specific measurements are as follows.

[0287] Using a flat plasma processing device with an electrode diameter of φ300mm and an electrode spacing of 50mm, the obtained shaped body was irradiated with plasma for 3 hours under the conditions of RF1000W, O2 gas and CF4 gas flow ratio (O2:CF4) 190:10, gas flow rate 200sccm, and vacuum degree 1torr.

[0288] The resulting molded body was placed 6 cm from the plasma electrode. Next, the mass of the molded body before and after the test was measured, and the mass reduction rate (%) was calculated using the following formula to evaluate plasma resistance. It can be said that the smaller the mass reduction rate, the better the plasma resistance.

[0289] Mass reduction rate (%) = [(mass of molded part before test - mass of molded part after test) / mass of molded part before test] × 100

[0290] [Table 4]

[0291]

[0292] [Example 19 and Comparative Example 8]

[0293] Except for using the crosslinked fluorinated elastomers shown in Table 5 in the amounts shown in Table 5, with 2.0 parts by weight of SIFEL 8070A and B, 4.0 parts by weight of TAIC, 2.0 parts by weight of Perhexa 25B, and 0.5 parts by weight of bisphenol AF (manufactured by Tokyo Chemical Industry Co., Ltd.), the block elastomer composition was obtained by the same operation as in Example 1.

[0294] Using the obtained block elastomer composition, the molded article was obtained in the same manner as in Example 15.

[0295] The conventional physical properties and plasma resistance of the obtained molded articles were measured. The results are shown in Table 5.

[0296] [Table 5]

[0297]

[0298] [Example 20]

[0299] 70 parts by weight of crosslinked fluorinated elastomer (A1-c), 30 parts by weight of crosslinked fluorinated elastomer (A2-a), 2 parts by weight of SIFEL3590-N, 6 parts by weight of TAIC, and 0.5 parts by weight of Perhexa 25B were sequentially added to a kneader and mixed until the current value stabilized to obtain a block-shaped elastomer composition.

[0300] Using the obtained block elastomer composition, the molded article was obtained in the same manner as in Example 15.

[0301] The conventional physical properties and plasma resistance of the obtained molded articles were measured. The results are shown in Table 6.

[0302] [Example 21]

[0303] Except that 2 parts by mass of KE-1830 were used instead of 2 parts by mass of SIFEL 3590-N in Example 20, the same procedure as in Example 20 was followed to obtain a block-shaped elastomer composition.

[0304] Using the obtained block elastomer composition, the molded article was obtained in the same manner as in Example 15.

[0305] The conventional physical properties and plasma resistance of the obtained molded articles were measured. The results are shown in Table 6.

[0306] [Example 22]

[0307] Except that SIFEL 3590-N was not used, the procedure was the same as in Example 20 to obtain a block-shaped elastomer composition.

[0308] Using the obtained block elastomer composition, the molded article was obtained in the same manner as in Example 15.

[0309] The conventional physical properties and plasma resistance of the obtained molded articles were measured. The results are shown in Table 6.

[0310] [Table 6]

[0311]

Claims

1. An elastomer composition comprising Crosslinked fluorinated elastomers other than perfluorinated elastomers with a fluorine content of 69% by mass or more (A1) Crosslinked fluorinated elastomers other than perfluorinated elastomers with a fluorine content in the range of 55-68% by mass (A2) The compound (B) is selected from at least one compound containing an olefinic unsaturated bond, which is a compound with a perfluorinated skeleton having an olefinic unsaturated bond and a siloxane skeleton having an olefinic unsaturated bond. The content of the fluorinated elastomer (A1) relative to 100 parts by mass of the total fluorinated elastomers (A1) and (A2) is 65% to 95% by mass. The content of compound (B) relative to a total of 100 parts by mass of the fluorinated elastomers (A1) and (A2) is 0.5 parts by mass or more and 25 parts by mass or less.

2. The elastomer composition of claim 1, wherein, The fluorinated elastomers (A1) and (A2) are peroxide-crosslinkable fluorinated elastomers.

3. The elastomer composition according to claim 1 or 2, wherein, It contains a crosslinking agent.

4. The elastomer composition according to claim 1 or 2, wherein, The content of filler material is less than 5 parts by mass relative to a total of 100 parts by mass of the fluorinated elastomers (A1) and (A2).

5. A sealing material obtained from the elastomeric composition according to any one of claims 1 to 4.

6. A method for manufacturing sealing materials, wherein, The process includes a step of crosslinking the elastomer composition according to any one of claims 1 to 4.

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