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 production method of a sealing material, the elastomer composition comprising a cross-linkable fluorine-containing elastomer (A) [the elastomer (A) is a compound not containing a hydrogen silane group] and a composition (B) comprising at least one compound containing an ethylenic unsaturated bond selected from a compound having a perfluorinated skeleton with an ethylenic unsaturated bond [the compound is a compound other than the elastomer (A)] and a compound having a siloxane skeleton with an ethylenic unsaturated bond, and a minimum torque (ML) at 60°C measured with a hot set resin hardening curve tester is 0.5 kgf·cm or more.

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 an uncrosslinked rubber composition comprising a hydrofluoric rubber as a crosslinked fluorinated elastomer and a liquid hydrogen site protectant.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-52226 Summary of the Invention

[0008] The technical problem that the invention aims to solve

[0009] The composition described in Patent Document 1 and other existing uncrosslinked rubber compositions employ liquid or oily components.

[0010] When forming a molded article, such as a sealing material, exhibiting the desired physical properties from this uncrosslinked rubber composition, the components in the composition must be uniformly mixed. However, forming a homogeneous composition from a composition containing a crosslinked fluorinated elastomer and liquid or oily components takes a long time, and there is room for improvement in this regard.

[0011] One embodiment of the present invention provides an elastomer composition that can be formed into a uniform composition in a short time.

[0012] Technical solutions adopted to solve technical problems

[0013] 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.

[0014] The structure of the present invention is described below.

[0015] [1] An elastomer composition comprising a crosslinked fluorinated elastomer (A) [elastomer (A) is a hydrosilyl-free compound] and a composition (B),

[0016] The composition (B) comprises at least one compound containing an olefinic unsaturated bond selected from compounds with a perfluorinated skeleton having olefinic unsaturated bonds [the compound being a compound other than the elastomer (A)] and compounds with a siloxane skeleton having olefinic unsaturated bonds, and the minimum torque (ML) at 60°C, as measured by a thermosetting resin curing curve tester, is 0.5 kgf·cm or more.

[0017] [2] The elastomer composition as described in [1], wherein the elastomer (A) is a peroxide-crosslinkable fluorinated elastomer.

[0018] [3] The elastomer composition as described in [1] or [2], wherein the elastomer (A) is a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene polymer.

[0019] [4] The elastomeric composition as described in any one of [1] to [3], wherein the content of the composition (B) is 0.5 to 100 parts by mass relative to the content of the elastomeric (A) of 100 parts by mass.

[0020] [5] The elastomer composition as described in any one of [1] to [4], wherein it comprises a crosslinking agent (C).

[0021] [6] The elastomer composition as described in any one of [1] to [5], wherein it comprises a crosslinking aid (D).

[0022] [7] The elastomer composition as described in any one of [1] to [6], wherein the content of filler material is 5 parts by mass or less relative to 100 parts by mass of the elastomer (A).

[0023] [8] A sealing material, which is a sealing material obtained from any one of the elastomer compositions described in [1] to [7].

[0024] [9] A method for manufacturing a sealing material, comprising a step of crosslinking the elastomer composition described in any one of [1] to [7].

[0025] Invention Effects

[0026] According to one embodiment of the present invention, a uniform elastomer composition can be obtained in a short time.

[0027] Furthermore, according to one embodiment of the present invention, by employing this elastomer composition, a sealing material exhibiting excellent balance in terms of hardness, tensile strength, elongation at break, and tensile stress (100% Mo) at 100% elongation 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 (A) [elastomer (A) is a hydrosilyl-free compound] and composition (B).

[0031] The composition (B) comprises at least one compound containing an olefinically unsaturated bond selected from compounds with a perfluorinated skeleton having olefinically unsaturated bonds [the compound being a compound other than the elastomer (A)] and compounds with a siloxane skeleton having olefinically unsaturated bonds, and has a minimum torque (ML) of 0.5 kgf·cm or more at 60°C as measured by a thermosetting resin curing curve tester.

[0032] <Cross-linked fluorinated elastomer (A)>

[0033] As for the crosslinked fluorinated elastomer (A), there are no particular limitations as long as it is a compound that does not contain hydrosilyl (-Si-H). Existing crosslinked fluorinated elastomers that are known can be used, and crosslinked fluorinated elastomers other than perfluorinated elastomers are preferred.

[0034] The elastomer (A) contained in this composition may be one type or two or more types.

[0035] In this invention, "elastomer" and "rubber" are synonymous and are not distinguished in any particular way.

[0036] Elastomer (A), also known as uncured fluororubber, can be crosslinked in various ways, including peroxide crosslinking, polyol crosslinking, amine crosslinking, and radiation crosslinking. Among these, fluorinated elastomers that can be crosslinked by peroxides are preferred from the perspective that they do not require the use of acid absorbers that become particle generation sources in plasma atmospheres or the like, and that the resulting sealing material does not pose a risk of particle generation during use.

[0037] As a specific example of elastomer (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).

[0038] As the elastomer (A), products synthesized using 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.

[0039] As the elastomer (A), 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] 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.

[0041] 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.

[0042] As a preferred example of the perfluoroalkyl vinyl ether, perfluoromethyl vinyl ether can be cited.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] Examples of iodine- and / or bromine-containing compounds include, for example, compounds represented by formula (1) or (2).

[0047] 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).

[0048] CY 1 2 = CY 2 RfX (1)

[0049] [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.

[0050] 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.

[0051] I n Br m R(2)

[0052] [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.]

[0053] 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.

[0054] There is no particular limitation on the fluorine content of the elastomer (A). From the viewpoint of being able to easily obtain the desired sealing material, it is preferably 55% by mass or more, more preferably 60% by mass or more, even more preferably 63% by mass or more, particularly preferably 65% ​​by mass or more, more preferably 73% by mass or less, and even more preferably 71% by mass or less.

[0055] 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.

[0056] The fluorine content in this invention is a value obtained by rounding to the nearest whole number.

[0057] The elastomer (A) preferably comprises a cross-linked fluorinated elastomer (A1) with a fluorine content of 69% by mass or more and a cross-linked fluorinated elastomer (A2) with a fluorine content in the range of 55% to 68% by mass.

[0058] By using at least two cross-linked fluorinated elastomers with fluorine content within the above range, a uniform elastomer composition can be obtained in a short time, an elastomer composition with excellent formability can be easily obtained, and a sealing material exhibiting excellent hardness, tensile strength, elongation at break and 100% Mo with good balance can be easily obtained.

[0059] The fluorine content of the elastomer (A1) is preferably 70% by mass or more, preferably 73% by mass or less, and more preferably 71% by mass or less.

[0060] The fluorine content of the elastomer (A2) is preferably 60-68% by mass, more preferably 63-68% by mass, and even more preferably 65-68% by mass.

[0061] The Mooney viscosity of the 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.

[0062] If the Mooney viscosity of the elastomer (A) is within the above range, an elastomer composition with excellent formability, especially excellent compressibility, can be easily obtained.

[0063] Additionally, the Mooney viscosity in this specification refers to the Mooney viscosity (ML1+10) at 121°C as measured according to ASTM D 1646.

[0064] The content of elastomer (A) 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 93% by mass or less.

[0065] If the content of elastomer (A) is within the above range, it is easy to obtain a sealing material with excellent chemical resistance such as plasma resistance and chemical resistance, and exhibiting excellent hardness, tensile strength, elongation at break and 100% Mo in a good balance.

[0066] In this specification, solid components refer to components other than solvents.

[0067] The content of 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.

[0068] If the content of 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.

[0069] The content of 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.

[0070] If the content of elastomer (A2) is within the above range, a sealing material exhibiting excellent formability and chemical resistance with good balance can be easily obtained.

[0071] The content of elastomer (A1) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, more preferably 95% by mass or less, and more preferably 90% by mass or less, relative to the total content of elastomer (A1) and (A2) in the composition.

[0072] If the mass ratio of the contents of 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 exhibiting excellent hardness, tensile strength, elongation at break and 100% Mo with good balance can be easily obtained.

[0073] <Composition (B)>

[0074] This composition comprises a composition (B) containing a compound with olefinic unsaturated bonds and having a minimum torque (ML) of 0.5 kgf·cm or more at 60°C as measured by a thermosetting resin curing curve tester. The compound with olefinic unsaturated bonds is selected from at least one of compounds having a perfluorinated skeleton with olefinic unsaturated bonds [the compound is a compound other than the elastomer (A)] and compounds having a siloxane skeleton with olefinic unsaturated bonds.

[0075] By using composition (B), a non-adhesive sealing material with excellent plasma resistance can be easily obtained. Furthermore, by using composition (B), a sealing material exhibiting excellent balance of hardness, tensile strength, elongation at break, and 100% Mo can be easily obtained.

[0076] The composition (B) contained in this composition may be one or more. The inclusion of composition (B) in this composition means that composition (B) is used as a raw material in the preparation of this composition. When the composition (B) contained in this composition is two or more, it means that two or more compositions (B) are used as raw materials in the preparation of this composition.

[0077] The minimum torque (ML) at 60°C measured by a thermosetting resin curing curve tester is above 0.5 kgf·cm, which is synonymous with the abrasion-resistant (mirable) type commonly used in this field. Specifically, composition (B) refers to a solid composition such as synthetic rubber, which is different from liquid (paste) or oily compositions. It is an uncured composite rubber whose state before curing is similar to that of natural rubber or ordinary synthetic rubber, and can be plasticized and mixed using a mixing mill or closed mixer.

[0078] Furthermore, this refers to the minimum torque (ML) of the composition (B) before it is mixed with the elastomer (A) and the following crosslinking agent (C), crosslinking aid (D), and other components, within the specified range.

[0079] The minimum torque (ML) is specifically determined by the method described in the following embodiments.

[0080] Composition (B) typically comprises the compound (b) and a filler such as silica. The compound (b) contained in composition (B) may be one or more, and the filler contained in composition (B) may be one or more.

[0081] In addition, composition (B) may also contain additives such as reactive organosilicon compounds having two or more hydrosilyl groups in 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.).

[0082] As composition (B), depending on the type of compound (b), examples include peroxide crosslinking type, which is crosslinked by free radicals generated by peroxide decomposition, and addition crosslinking type, which is crosslinked by reacting olefinic unsaturated bonds and hydrosilyl groups using a catalyst. This composition can use either of these, but the peroxide crosslinking type is preferred.

[0083] When using the peroxide crosslinking composition (B), the following peroxide crosslinking agents are preferred.

[0084] From the viewpoint that non-adhesive sealing materials with excellent plasma resistance can be easily obtained, the content of compound (b) in composition (B) is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 90% by mass or less, and more preferably 80% by mass or less.

[0085] Furthermore, from the viewpoint that a wear-resistant composition can be formed and a uniform elastomer composition can be obtained in a shorter time, the filler content in composition (B) is preferably 10% by mass or more, more preferably 20% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.

[0086] Composition (B) may be a commercially available product. An example of such a commercially available product is "SIFEL" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0087] Commercially available products of composition (B) include single-component and two-component commercially available products, and any one of them may be used.

[0088] From the viewpoint that a uniform elastomer composition can be obtained in a shorter time and that a sealing material with better plasma resistance can be easily obtained, the content of composition (B) in this composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 25 parts by mass or less, relative to 100 parts by mass of elastomer (A).

[0089] From the viewpoint that sealing materials with superior plasma resistance can be easily obtained, the mass ratio of composition (B) content to crosslinking agent (C) content (content of composition (B) / content of crosslinking agent (C)) in this composition is preferably 0.5 or more, more preferably 1 or more, more preferably 50 or less, and more preferably 20 or less.

[0090] <Compound (b)>

[0091] Compound (b) is at least one compound selected from compounds with a perfluorinated skeleton having olefinic unsaturated bonds (hereinafter also referred to as "compound (b1)") and compounds with a siloxane skeleton having olefinic unsaturated bonds (hereinafter also referred to as "compound (b2)"). Among these, from the viewpoint that sealing materials with better plasma resistance can be readily obtained, it is preferred that compound (b) includes compound (b1).

[0092] 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.

[0093] Compound (b) may have more than two types of olefinic unsaturated bonds.

[0094] [Compound (b1)]

[0095] Compound (b1) is a compound with a perfluorinated skeleton having olefinic unsaturated bonds and is a compound other than the elastomer (A).

[0096] 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)").

[0097] Compound (b1-1)

[0098] The compound (b1-1) is preferably a perfluoropolyether having two or more olefinic unsaturated bonds within one molecule.

[0099] Preferred examples of compound (b1-1) include 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.

[0100] As a compound (b1-1), examples of compounds represented by the following formula (1) can be cited.

[0101] Z 1 -(X) p -(Rf-Q) a -Rf-(X) p -Z 2 ...(1)

[0102] 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).

[0103] Rf stands for divalent perfluoropolyether (divalent perfluorooxyolefin).

[0104] 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.

[0105] Q is a group represented by formula (2), (3) or (4).

[0106] 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).

[0107] 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 groups like methyl, ethyl, propyl, isopropyl, etc., cycloalkyl groups like cyclohexyl, alkenyl groups like vinyl, allyl, etc., aryl groups like phenyl, tolyl, etc., groups in which some hydrogen atoms are replaced by halogen atoms, etc. (e.g., fluorosubstituted alkyl groups like chloromethyl, chloropropyl, 3,3,3-trifluoropropyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl).

[0108] 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.

[0109] 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.

[0110] 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.

[0111] [Chemistry 1]

[0112]

[0113] -(X) p -CH2CH2R 4 CH2CH2-(X) p - -(3)

[0114]

[0115] 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).

[0116] [Chemistry 2]

[0117]

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] -(OR 7 ) n - It can be the same group as Rf below.

[0124] The compound represented by formula (1) above is preferably the compound represented by formula (1-1) below.

[0125] CH2=CH-(X) p -(Rf-Q) a -Rf-(X) p -CH=CH2···(1-1)

[0126] [The definitions of the symbols in equation (1-1) are the same as those in equation (1).]

[0127] 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).

[0128] CH2=CH-(X) p -Rf-(X) p -CH=CH2···(1-1-1)

[0129] [The definitions of the symbols in equation (1-1-1) are the same as those in equation (1).]

[0130] Specific examples of Rf can be cited from the following groups.

[0131] -[CF(Z)OCF2] p -(CF2) r -[CF2OCF(Z)] q -

[0132] (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)

[0133] -CF2CF2OCF2-(CF(CF3)OCF2) s -(CF2) r -(CF2OCF(CF3)) t -CF2OCF2CF2-

[0134] (r, s, and t are integers that satisfy 0 ≤ r ≤ 6, s ≥ 0, t ≥ 0, 0 ≤ s + t ≤ 200, preferably 2 ≤ s + t ≤ 110).

[0135] -CF(Z)-(OCF(Z)CF2) u -(OCF2) v -OCF(Z)-

[0136] (Z is a fluorine atom or -CF3, u and v are integers satisfying 1≤u≤100 and 1≤v≤50),

[0137] -CF2CF2-[OCF2CF2CF2] w -OCF2CF2-

[0138] (w is an integer that satisfies 1≤w≤100).

[0139] [Compound (b2)]

[0140] Compound (b2) is a siloxane skeleton having olefinic unsaturated bonds, 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 organic groups bonded to silicon atoms. There are no particular limitations on the bonding positions of the olefinic unsaturated bonds.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] Examples of cycloalkyl groups include cyclopentyl and cyclohexyl groups with 3 to 20 carbon atoms.

[0145] Examples of aryl groups include phenyl, tolyl, and other groups with 6 to 20 carbon atoms.

[0146] Examples of aralkyl groups include benzyl, 2-phenylethyl, 2-methyl-2-phenylethyl, and other groups with 7 to 20 carbon atoms.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] Examples of compounds (b2) include dimethyl polysiloxanes whose molecular chains are capped at both ends by dimethyl vinylsiloxy groups, dimethyl polysiloxanes whose molecular chains are capped at both ends by methylphenyl vinylsiloxy groups, dimethyl siloxane-methylphenyl siloxane copolymers whose molecular chains are capped at both ends by dimethyl vinylsiloxy groups, dimethyl siloxane-methyl vinylsiloxane copolymers whose molecular chains are capped at both ends by dimethyl vinylsiloxy groups, dimethyl siloxane-methyl vinylsiloxane-methylphenyl siloxane copolymers whose molecular chains are capped at both ends by silanol groups, dimethyl siloxane-methyl vinylsiloxane-methylphenyl siloxane copolymers whose molecular chains are capped at both ends by silanol groups, dimethyl siloxane-methyl vinylsiloxane-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 dimethyl vinylsiloxy 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).

[0151] [Chemistry 3]

[0152]

[0153] 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.

[0154] 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.

[0155] 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.

[0156] As R in equation (7) 2 Alkoxyalkyl groups, for example, methoxyethyl, methoxypropyl, etc., are groups with 2 to 10 carbon atoms.

[0157] As R in equation (7) 2 Acyl groups, for example, are groups with 2 to 10 carbon atoms, such as acetyl and octanoyl.

[0158] In formula (7), b is preferably an integer from 10 to 50, and a is preferably 3.

[0159] <Crosslinking agent (C)>

[0160] The elastomer (A) can be crosslinked even without the use of a crosslinking agent (C). From the viewpoint that sufficient crosslinking can easily yield a sealing material exhibiting excellent balance of hardness, tensile strength, elongation at break, and 100% Mo, this composition preferably contains a crosslinking agent (C) corresponding to the type of elastomer (A) used.

[0161] When the composition contains a crosslinking agent (C), the crosslinking agent (C) contained in the composition may be one or more.

[0162] As the crosslinking agent (C), any existing crosslinking agent can be used without any restrictions. As long as it is appropriately selected according to the type of elastomer (A) used, for example, in the case of using FKM, peroxide crosslinking agents, polyamine crosslinking agents, polyol crosslinking agents, triazine crosslinking agents, etc. can be used.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] When the composition contains a crosslinking agent (C), from the viewpoint that a sealing material exhibiting excellent hardness, tensile strength, elongation at break, and 100% Mo can be easily obtained with sufficient crosslinking reaction, the content of the crosslinking agent (C) in the composition is preferably 0.2 to 4 parts by mass relative to 100 parts by mass of elastomer (A), more preferably 0.2 to 2.5 parts by mass.

[0167] <Crosslinking aid (D)>

[0168] In this composition, the crosslinking agent (C) can be used alone, but it is preferable to use a crosslinking aid (D) when using the crosslinking agent (C). As the crosslinking aid (D), any existing and known crosslinking aid can be selected according to the type of crosslinking agent (C).

[0169] When the composition contains a crosslinking aid (D), the crosslinking aid (D) contained in the composition may be one type or two or more types.

[0170] 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.

[0171] 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.

[0172] When the composition contains a crosslinking aid (D), 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 (D) in the composition relative to 100 parts by mass of elastomer (A) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 4 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 6 parts by mass or less.

[0173] In particular, to suppress cracking of the sealing material that may occur in a plasma atmosphere or the like, a radioactively cross-linked sealing material (radiation-treated material) is preferred. In this case, from the viewpoint that a sealing material with higher modulus and the like can be easily obtained with higher hardness, the content of the cross-linking aid (D) 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 elastomer (A).

[0174] From the viewpoint that the reaction of the crosslinking agent (C) is just right, so that a sealing material exhibiting the desired physical properties can be easily obtained, especially a sealing material with higher modulus and higher hardness can be easily obtained, the mass ratio of the content of the crosslinking aid (D) to the content of the crosslinking agent (C) in this composition (content of crosslinking aid (D) / content of crosslinking agent (C)) is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, preferably 30 or less, and more preferably 20 or less.

[0175] <Other Ingredients>

[0176] In addition to the aforementioned components, this composition may, as needed and without impairing the effects of the invention, contain other conventionally known components incorporated into the sealing material. Examples of such other components include: reactive organosilicon compounds having two or more hydrosilyl groups in their molecules; catalysts; polyol compounds; acid scavengers such as magnesium oxide and calcium hydroxide; organic pigments such as anthraquinone pigments, perylene pigments, and dioxazine pigments; plasticizers; processing aids; vulcanization accelerators; anti-aging agents; antioxidants; inorganic fillers; and organic fillers.

[0177] The other ingredients may be used in single or multiple forms.

[0178] [Reactive organosilicon compounds]

[0179] 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.

[0180] [catalyst]

[0181] 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.

[0182] [Polyol compounds]

[0183] 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.

[0184] While conventionally known compounds can be widely used as polyols, bisphenols are particularly preferred from the viewpoint of easily obtaining sealing materials with excellent crack resistance.

[0185] 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.

[0186] 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 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.

[0187] [Organic Pigments]

[0188] 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.

[0189] [Filling Material]

[0190] The inorganic and organic fillers (hereinafter collectively referred to as "fillers") are granular (powder) components other than the composition (B), crosslinking agent (C), and crosslinking aid (D).

[0191] Examples of inorganic filler materials include carbon black, silicon dioxide, barium sulfate, titanium dioxide, and aluminum oxide.

[0192] Examples of organic filler materials include, for example, PTFE, PFA, FEP, ETFE, and...

[0193] Fluoropolymers such as PVDF, polyethylene resin, polyimide resin, silicone resin, and melamine resin.

[0194] 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 is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of elastomer (A).

[0195] <Method for manufacturing this composition>

[0196] This composition can be manufactured by mixing (kneading) the elastomer (A) and the composition (B), preferably by mixing (kneading) the elastomer (A), the composition (B), the crosslinking agent (C) and the crosslinking aid (D), as well as other components used as needed.

[0197] There is no particular limitation on the mixing order of the elastomer (A), composition (B), crosslinking agent (C), crosslinking aid (D), and other additives. They can be mixed (kneaded) in any order or all at once. It is preferred to mix (knead) them sequentially to make the components uniform.

[0198] The mixing (kneading) process can use conventionally known mixing (kneading) machines, such as open roller presses, Banbury mixers, twin-spindle roller presses, and kneaders.

[0199] 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.

[0200] Sealing Materials

[0201] 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.

[0202] This sealing material is obtained from the aforementioned composition, and therefore exhibits excellent hardness, tensile strength, elongation at break and 100% Mo with a good balance, as well as excellent plasma resistance (free radical resistance), crack resistance and compression set.

[0203] 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.

[0204] The shape and other properties of this sealing material can be appropriately selected according to the intended use.

[0205] <Manufacturing method of this sealing material>

[0206] 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).

[0207] 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.

[0208] The sheet obtained by the pressing process is preferably pre-formed into the desired sealing material shape before the crosslinking process.

[0209] 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.

[0210] More preferably, the crosslinking process includes a primary crosslinking process and a secondary crosslinking process.

[0211] The crosslinking process is preferably performed using the desired sealing material shape obtained through the preforming.

[0212] The preferred cross-linking process is to heat and pressurize the desired sealing material shape obtained by the preforming. Specifically, examples include placing the preformed material into a mold and cross-linking it for about 5 to 20 minutes at a pressure of about 2 to 15 MPa and a temperature of about 150 to 200°C using a hot press or the like.

[0213] 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, for example, 150 to 300°C for 1 to 24 hours, preferably at atmospheric pressure to reduced pressure, using various ovens, preferably vacuum ovens, for about 3 to 24 hours.

[0214] 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.

[0215] 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.

[0216] The radiation used in the radiation irradiation process is not particularly limited as long as it can crosslink the 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.

[0217] The radiation used for irradiation can be a single type or two or more types.

[0218] When irradiating with radiation, it is preferable to irradiate with an absorption dose of 1 to 120 kGy, more preferably 20 to 100 kGy. By irradiating with this amount of radiation, 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 elastomer (A) from being too low.

[0219] The radiation irradiation process can be carried out in two or more stages by changing the conditions.

[0220] 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.

[0221] Example

[0222] The present invention will now be described in more detail with reference to embodiments, but the invention is not limited thereto.

[0223] [Example 1]

[0224] 100 parts by weight of DAI-EL G912 (manufactured by Daikin Industries, Ltd., fluorine content: 71% by weight, hereinafter also referred to as "crosslinked fluorinated elastomer 1") were wound and mixed on a 6-inch roller with a roller temperature set to 60°C at a rotation speed of 20 ppm, and the process was repeated. 2 parts by weight of X-71-906 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., a wear-resistant compound containing a perfluorinated skeleton with olefinic unsaturated bonds, hereinafter also referred to as "composition B1") were added and mixed until a uniform appearance was achieved.

[0225] The minimum torque (ML) of composition B1 was determined under the following conditions using a Curastometer TYPE (for rubber) manufactured by JSR Trading Co., Ltd., and the result was 3.74 kgf·cm.

[0226] Sample: 10g

[0227] Temperature: 60℃

[0228] Amplitude angle: ±3°

[0229] Measurement time: 10 minutes

[0230] [Example 2]

[0231] Composition B2 was obtained by compounding 100 parts by weight of X-71-906 and 25 parts by weight of KE-1830 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., a compound containing a siloxane skeleton having olefinic unsaturated bonds). The minimum torque (ML) of the obtained composition B2 was measured in the same manner as above, and the result was 2.43 kgf·cm.

[0232] Except that the resulting composition B2 is used instead of composition B1 in Example 1, the mixture is kneaded in the same manner as in Example 1 until the appearance becomes uniform.

[0233] [Comparative Example 1]

[0234] Except that SIFEL 3590-N (manufactured by Shin-Etsu Chemical Industry Co., Ltd., a compound containing a perfluorinated skeleton with olefinic unsaturated bonds, single-liquid type) was used instead of composition B1, the mixture was kneaded in the same manner as in Example 1 until the appearance became uniform.

[0235] [Comparative Example 2]

[0236] Except that 1 part by weight of SIFEL 8070A (manufactured by Shin-Etsu Chemical Industry Co., Ltd., oily type) and 1 part by weight of SIFEL 8070B (manufactured by Shin-Etsu Chemical Industry Co., Ltd., oily type) were used instead of 2 parts by weight of composition B1, the mixture was kneaded in the same manner as in Example 1 until the appearance became uniform.

[0237] At least one of SIFEL 8070A and SIFEL 8070B comprises a compound having a perfluorinated skeleton with olefinic unsaturated bonds.

[0238] In Examples 1-2 and Comparative Examples 1-2, the time required for mixing until the appearance became uniform was measured, and the results were evaluated according to the following criteria. The results are shown in Table 1.

[0239] ○: The time required for mixing until the appearance becomes uniform should be within 10 minutes.

[0240] △: The time required to mix until the appearance becomes uniform is more than 10 minutes but less than 30 minutes.

[0241] ×: The time required to mix until the mixture becomes uniform in appearance exceeds 30 minutes.

[0242] [Table 1]

[0243] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Crosslinked fluorinated elastomer 1 100 100 100 100 Composition B1 2 Composition B2 2 SIFEL 3590-N 2 SIFEL 8070A+B 2 evaluate ○ ○ △ ×

[0244] [Example 3]

[0245] 100 parts by weight of crosslinked fluorinated elastomer 1 were wound and kneaded on a 6-inch roller with a roller temperature set to 60°C at a rotation speed of 20 ppm, and the process was repeated. 2 parts by weight of composition B1 were added and kneaded until uniform in appearance. Then, the process was repeated, and 6 parts by weight of TAIC (manufactured by Mitsubishi Chemical Corporation, triallyl isocyanurate) were added and kneaded until uniform in appearance. Next, 1 part by weight of Perhexa 25B (manufactured by Nippon Oil Co., Ltd.) was added and kneaded until uniform in appearance.

[0246] Even with 100 parts by weight of composition B1, it can be compounded relative to 100 parts by weight of crosslinked fluorinated elastomer 1.

[0247] [Example 4]

[0248] Except that the composition B1 of Example 3 was replaced with composition B2 obtained by the same operation as in Example 2, the mixture was kneaded in the same operation as in Example 3 until the appearance was uniform.

[0249] [Comparative Example 3]

[0250] Except for replacing composition B1 with SIFEL 3590-N, the mixture was kneaded in the same manner as in Example 3 until a uniform appearance was achieved.

[0251] When using SIFEL 3590-N, the maximum amount of SIFEL 3590-N that can be compounded is 50 parts by mass relative to 100 parts by mass of crosslinked fluorinated elastomer 1.

[0252] [Comparative Example 4]

[0253] Except that 1 part by weight of SIFEL 8070A and 1 part by weight of SIFEL 8070B are used to replace 2 parts by weight of composition B1, the mixture is kneaded in the same manner as in Example 3 until the appearance is uniform.

[0254] When using SIFEL 8070A and B, the maximum total amount of SIFEL 8070A and B that can be compounded is 10 parts by mass relative to 100 parts by mass of crosslinked fluorinated elastomer 1.

[0255] In Examples 3-4 and Comparative Examples 3-4, the time required for mixing until the appearance became uniform was measured, and the results were evaluated according to the following criteria. The results are shown in Table 2.

[0256] ○: The time required for mixing until the appearance becomes uniform should be within 60 minutes.

[0257] △: The time required to mix until the appearance becomes uniform is more than 60 minutes but less than 90 minutes.

[0258] ×: The time required for mixing until the appearance becomes uniform exceeds 90 minutes.

[0259] [Table 2]

[0260] Example 3 Example 4 Comparative Example 3 Comparative Example 4 Crosslinked fluorinated elastomer 1 100 100 100 100 Composition B1 2 Composition B2 2 SIFEL 3590-N 2 SIFEL 8070A+B 2 TAIC 6 6 6 6 Perhexa 25B 1 1 1 1 evaluate ○ ○ △ ×

[0261] [Example 5]

[0262] The cross-linked fluorinated elastomer 1, 30 parts by weight of Tecnoflon P757 (manufactured by Solvay, fluorine content: 67% by weight, hereinafter also referred to as "cross-linked fluorinated elastomer 2"), 2 parts by weight of composition B1, 6 parts by weight of TAIC and 1 part by weight of Perhexa 25B are uniformly mixed using a roller to obtain a block elastomer composition.

[0263] The obtained block elastomer composition was put into a mold and pressurized at 170°C for 10 minutes under a pressure of 5 MPa using a compression 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).

[0264] The following conventional physical properties were measured on the resulting molded articles. The results are shown in Table 3.

[0265] <Common Physical Properties>

[0266] 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 K 6251:2017.

[0267] [Examples 6-9]

[0268] Except for varying the amount of composition B1 as shown in Table 3, various evaluations were performed in the same manner as in Example 5. The results are shown in Table 3.

[0269] [Table 3]

[0270]

[0271] [Examples 10-14]

[0272] Except for varying the amount of composition B1 as shown in Table 4, the same procedure as in Example 5 was followed to obtain a block elastomer composition.

[0273] 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.

[0274] The obtained molded articles were tested for the above-mentioned conventional physical properties. The results are shown in Table 4.

[0275] Plasma Resistance

[0276] The plasma resistance (mass reduction rate) of the obtained molded body was measured. The specific measurements are as follows.

[0277] 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.

[0278] 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.

[0279] Mass reduction rate (%) = [(mass of molded part before test - mass of molded part after test) / mass of molded part before test] × 100

[0280] [Table 4]

[0281]

[0282] [Example 15]

[0283] Except for changing the amount of Perhexa 25B used in Example 10 to 0.5 parts by weight, the same procedure as in Example 10 was followed to obtain the molded article.

[0284] The conventional physical properties and plasma resistance of the obtained molded articles were measured, and the results are shown in Table 5.

[0285] [Comparative Example 5]

[0286] Except that composition B1 was not used, the same procedure as in Example 15 was followed to obtain the molded article.

[0287] The conventional physical properties and plasma resistance of the obtained molded articles were measured, and the results are shown in Table 5.

[0288] [Table 5]

[0289]

Claims

1. An elastomer composition comprising a crosslinked fluorinated elastomer (A) and a composition (B), wherein the crosslinked fluorinated elastomer (A) is a hydrosilyl-free compound. The composition (B) comprises a compound having a perfluorinated skeleton with olefinic unsaturated bonds, and the minimum torque (ML) at 60°C, measured using a thermosetting resin curing curve tester, is greater than or equal to 0.5 kgf·cm. The compound with a perfluorinated skeleton having olefinic unsaturated bonds is a compound other than the elastomer (A). The content of the composition (B) is 0.5 to 50 parts by mass relative to 100 parts by mass of the crosslinked fluorinated elastomer (A).

2. The elastomer composition of claim 1, wherein, The elastomer (A) is a peroxide-crosslinkable fluorinated elastomer.

3. The elastomer composition of claim 1, wherein, The elastomer (A) is a polymer based on vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene.

4. The elastomer composition according to any one of claims 1 to 3, wherein, Contains crosslinking agent (C).

5. The elastomer composition according to any one of claims 1 to 3, wherein, Contains crosslinking aid (D).

6. The elastomer composition according to any one of claims 1 to 3, wherein, The content of filler material is less than 5 parts by mass relative to 100 parts by mass of the elastomer (A).

7. A sealing material, which is a sealing material obtained from the elastomeric composition according to any one of claims 1 to 6.

8. 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 6.

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