TW201249913A - Perfluoroelastomer composition and molded product thereof - Google Patents

Abstract

A perfluoroelastomer composition includes a perfluoroelstomer component, and carbon black having a DBP absorption (method A) of 90 to 600 cm<SP>3</SP>/100g. The perfluoroelastomer composition and a molded product thereof exhibit excellent resistance to a fluorine decomposition product.

Description

201249913 VI. Description of the Invention: [Technical Field of the Invention] The present invention is suitable as a molded body such as a sealing or plasma CVD step of a device used in *. $, the full-gas elastomer composition of the sealing material and [prior art] The perfluoroelastomer forming system is used for semi-conducting (four) a large number of heat-resistant furnaces or electricity; ==:= is used in general, The whole _ bio-forming system is constructed by the second, part (10) copolymerization of the line "the stability of the unit and the non-existence: excellent chemical resistance, heat resistance" can be used by the main use and the common father The peroxide cross (IV) obtains the domain heterosome composition. Further, the king fluoroelastomer molded body can be improved in mechanical properties by blending carbon black as a filler. [PRIOR ART DOCUMENT] [Patent Document] Patent Document 1. International Publication No. WO2000/000054 Patent Document 2. Japanese Patent Laid-Open No. 2011-32465 (Summary of the Invention) In the thermal diffusion step or the electric-grade CVD step, decomposition of fluorine 101116814 201249913 occurs, and the decomposition products may be used for a device such as a thermal diffusion furnace and a peripheral device connected to the device, such as an exhaust device. The impact is caused by problems such as deterioration of the sealing material. In addition, the present invention discloses an elastomer molded article which comprises a carbon black filler having an impurity metal content of 300 ppm or less and an average particle diameter of 700 μm or less by an ashing analysis method. The crosslinkable elastomer composition of the crosslinkable elastomer component is obtained by cross-linking molding, wherein the content of the impurity metal in the molded article by the ashing analysis method is 100 ppm or less, and the particles irradiated by the oxygen plasma are increased. The rate is below 500%. Further, it is described that the carbon black filler to be blended in the crosslinkable elastomer composition preferably has a specific surface area of 3 m 2 /g or more and a DBP oil absorption of I5 ml/100 g or more from the viewpoint of workability. However, the elastomer molded article described in WO2000/042093 is used to suppress the generation of particles (impurity fine particles) from the elastomer molded article in a dry step such as plasma etching in the semiconductor manufacturing step, or to solve the problem. The problem of metal dissolution of the elastomer molded article used in the wet process such as washing is not the case of solving the resistance to the fluorine decomposition product. In addition, Japanese Laid-Open Patent Publication No. 2011-32465 discloses that 5 to 60 parts by mass of the vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene-based copolymer rubber is blended in an amount of 5 to 60 parts by mass. A rubber member in which a rubber composition of carbon black is crosslinked and formed. The carbon black system preferably has a nitrogen specific surface area of 5 to 80 m 2 /g and a DBP oil absorption amount from the viewpoint of mixing workability and formability.

101116814 S 201249913 150ml/100g or less. However, the rubber member of Japanese Laid-Open Patent Publication No. 2011-32465 is one in which the abrasive powder generated from the rubber member is less resistant to adhesion to the conveyed material and superior in resistance to phosphoric acid, hydrochloric acid, nitric acid, etc., and is not solved for the fluorine decomposition product. Tolerant. Accordingly, an object of the present invention is to provide a perfluoroelastomer composition which exhibits excellent chemical properties for a fluorine-decomposed product and a molded article thereof. (Means for Solving the Problem) According to the above-mentioned actual situation, the inventors of the present invention have carefully studied and found that 'if it is an elastomer molded product obtained by cross-linking a perfluoroelastic composition having a specific carbon black. The superior resistance to decomposition of fluorine generated in the thermal diffusion step or the plasma CVD step is shown, thereby completing the present invention. That is, the present invention provides a whole-physical composition containing all of the bio-components and the amount of the raw material (A^9 (above, more than 600 cm3/100 g of carbon black. Further, the present invention is Provided is a lacquer body, which is obtained by forming a parent-linked composite of the above-mentioned perfluoroelastomer composition. (Effect of the invention) Ten Γ月性形形系 shows a decomposition product of fluorine Superiority = Electricity: ': The use of the elastomer molded article of the present invention as a continuation, which can be applied to a long phase dense (four) material 101116814 丨 from 14 201249913 [Embodiment] The perfluoroelastomer composition of the present invention (hereinafter, Simply referred to as ".""" contains all-IL elastomer components. Quandon elastomer component is tetrafluoroethylene, (b) all l (C "C5 silk Ethyl (4) and / or perfluoro = (4) alkane Ethoxyalkyl vinyl ether), (c) a copolymer of a hardening site monomer. 3-Cl1 (b) component perfluoro(crc5-hospitable vinyl group) is a perfluoro group after the burning of 1 The base is fine, specifically, perfluoromethyl b = ether, perfluoroethyl vinyl fluorene, all I propyl acetylene, etc.曰 Difluorodecyl vinyl ether. '&amp;All again' (b) component of all l (CrCn morphine oxyalkylene group) is a side chain of the total carbon number of 3 to 11 perfluoroalkoxy The alkylalkyl vinyl ether, that is, the alkoxy group and the leuco group have a total carbon number of 3 to 11 and a total of a neooxyalkyl group (10) group. Specifically, CF2=CFOCF2CF(CF3)OCnF2n+1 is exemplified. (n: Bu 5),,, CF2=CFO(CF2)3〇CnF2n+i(n : 1~5) &gt; CF2=CF0CF2CF(CF3)0(CF20)mCnF2n+1(n: Bu 5,m : K3), CF2=CFO(CF2)2OCnF2n+1 (n: 1 to 5), etc. These (8) components can be used alone or in combination of two or more. As the (C) hardening site monomer, iodine is mentioned. Or a hardening site monomer of bromine or a hardening site monomer containing a cyano group. As a hardening site monomer containing iodine or bromine, CF2=CF(CF2)nI, CF2=CF(CF2)nBr, 1 („2) 〇1, etc. Further, examples of the hardening site monomer containing a cyano group include a perfluoroethylene group containing a cyano group, and for example,

J01116814 6 S 201249913 CF2=CFO(CF2)nOCF(CF3)CN(n : 2~4), CF2=CFO(CF2)nCN(n : 2~12), CF2=CF0[CF2CF(CF3)0]m( CF2)nCN(n : 2,m : K5), CF2=CF0[CF2CF(CF3)0]m(CF2)nCN(n : 1 〜4,m . , Λ, ΐ·ίΐ · i 〜2), CFfCFOtChCFfFJOLChCFKFdCNdi : 〇~4)f. Among them, perfluoro(8-cyano-5-fluorenyl-3,6-diη, etc.) is preferred. Further, the blending ratio is (a) tetrafluoroethylene of 50 to 75 mol%, preferably 6 to 75 mol%; (b) perfluoro(CrC5 alkyl vinyl ether) and/or perfluoro( C3_c &quot;alkoxyalkyl vinyl ether) is 49.8 to 25 mol%, preferably 39 8 to 25 mol%; (c) the hardening site monomer is 0.2 to 5 mol%, preferably 〇 5~3 mol%. The amount of the carbon black-based DBp oil to be blended in the elastomer composition is preferably 90 cm 3 /100 g or more and _cmV 10 g or less, particularly preferably 95 cm 3 /1 〇〇 g or more and 400 cm 3 /l 〇〇 g or less. Preferably, it is 95 cm 3 /1 〇〇 g or more and 200 cm 3 /100 g or less. If the DBp oil absorption of the carbon black is less than 9 〇 cm 3 / 1 〇〇 g, the surface of the elastomer formed body is easily dissolved when exposed to a fluorine gas heated to a high temperature. The DBP oil absorption refers to the amount of DBP (dibutylphthalic acid) absorbed by the carbon black i〇〇g (jIS K6221). The carbon black nitrogen adsorption specific surface area to be blended in the elastomer composition is 50 m 2 /g or more and 13 〇〇 m 2 /g or less, preferably 6 〇 m 2 /g or more and 1000 m 2 /g or less, and particularly preferably 65 m 2 . /g or more and 2〇〇m2/g or less. If the nitrogen specific surface area of the carbon black is less than 50 m2/g, the surface becomes easily dissolved when the elastomer shaped body is exposed to a fluorine gas heated to a high temperature by 101116814 7 201249913. Further, the nitrogen adsorption specific surface area refers to a specific surface area (JIS K 6217) obtained from the nitrogen adsorption amount by the S-ΒΕΤ formula. Examples of such carbon black include furnace black or acetylene black such as SAF carbon black, ISAF carbon black, HAF carbon black, and FEF carbon black. Among them, acetylene black is preferred from the viewpoint of excellent resistance to fluorine gas. The carbon black is blended in an amount of 5 parts by weight or more (more preferably 10 parts by weight or more) or 30 parts by weight or less, and particularly preferably 12 parts by weight or more and 25 parts by weight or less based on 100 parts by weight of the perfluoroelastomer component. More preferably, it is 14 parts by weight or more and 20 parts by weight or less. When the amount of carbon black is less than 5 parts by weight based on 100 parts by weight of the perfluoroelastomer component, the surface of the elastomer formed body is easily dissolved when exposed to a fluorine gas heated to a high temperature. In the elastomer composition of the present invention, as the optional component, various additives corresponding to the requirements of the application can be formulated. As such various additives, for example, a stabilizer, a plasticizer, a lubricant, a processing aid, and the like can be given. Further, the blending amount of each of the additives can be appropriately determined within a range that does not impair the effects of the present invention. The elastomer composition of the present invention contains a crosslinking agent. The crosslinking agent to be formulated in the elastomer composition of the present invention can be appropriately selected depending on the kind of the crosslinking group of the elastomer. Examples of the crosslinking reaction include, for example, all-oxide cross-linking, polyol cross-linking, polyamine cross-linking, three-plowing cross-linking, sirolimus cross-linking, imidazole cross-linking, ° plug-in-sitting contact, and radiation cross-linking. The contact.

101116814 8 S 201249913 The amount of the crosslinking agent is usually 0.05 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the perfluoroelastomer component. When the amount of the crosslinking agent is less than 0.05 part by weight, the elastomer is not sufficiently crosslinked, and when it exceeds 10 parts by weight, the physical properties of the crosslinked product are deteriorated. The elastomer composition of the present invention is useful as a molding material for various molded articles. Further, the elastomer composition of the present invention can be used in particular in the case of a molded article for sealing in a thermal diffusion furnace of a semiconductor wafer. The elastomer composition of the present invention may be a general kneading machine for an elastomer, for example, a hot-melt roll, a Bancher mixer, a kneader, or the like, and the above components such as a perfluoroelastomer component, the carbon black, and a crosslinking agent. It is mixed and prepared. The elastomer molding system of the present invention is obtained by cross-linking an elastomer composition. In other words, the obtained kneaded material is formed into a predetermined shape, for example, a ring of 0 or the like, and heated to be crosslinked, whereby the perfluoroelastomer molded body of the present invention can be obtained. The crosslinking conditions may be in accordance with a known method. For example, it may be placed in a mold and held under pressure at 120 to 220 ° C for 1 to 60 minutes to carry out press crosslinking, followed by 120 to 260. The furnace of °C is kept for 0.5 to 50 hours, thereby performing the method of crosslinking the hot furnace. When the elastomer molded article of the present invention is used as a sealing material for sealing (e.g., an ankle ring) as a thermal diffusion furnace for a semiconductor wafer, the effects of the present invention can be remarkably exhibited. A thermal diffusion furnace for a semiconductor wafer is used for the thermal diffusion of impurities into a wafer during the manufacturing process of the semiconductor wafer, and is, for example, an impurity diffusion device of Japanese Laid-Open Patent Publication No. Hei 6-45294. Further, thermal diffusion of the semiconductor wafer 101116814 9 201249913 The furnace system includes, for example, an exhaust device around the thermal diffusion furnace. When the molded article of the present invention is used as a material for the thermal diffusion furnace as, for example, an anthracene ring, even if it is exposed to a high-temperature gas generated by a thermal diffusion furnace, the surface of the anthracene ring is not dissolved. Damage, so it can show a stable sealing function after a long time. (Embodiment) Next, the present invention will be specifically described by exemplifying the embodiment, and the present invention is not intended to limit the inventors. (Example 1) (Production of Elastomer) Base water 2 was added to a stainless steel high-pressure steel having a capacity of 5 〇〇 ml. _, all = ampere 2.5g * Na2HP 〇 4 · 12H2 〇 4 吆, after the internal substitution, followed by decompression. After cooling the high temperature town, •tt PTFE is called, all I 曱 乙 乙 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , (4) 75 g and persulfate recorded 3.75 g and used as an aqueous solution of μ. After the polymerization was continued for 2 hours, the unreacted gas was subjected to water-solubilization = the aqueous latex was taken out, and after salting out of the sodium hydride, it was dried to obtain a ternary copolymerized gas in the form of a crumb rubber. According to the material, (4) the silk of the analysis, the ternary mixture has tetracyano group / ear %, perfluoromethyl ethylene fine 37 mole % and all said 3,6-di + octyl (cyano) The characteristic absorption 2 fine (10) 101116814 201249913 The molar composition of the molar %. (Manufacturing of the anthracene ring) 100 parts by weight of the elastomer obtained by the above production method, the crosslinking agent 2, 2 by using an open roll - 1 part by weight of bis(3-amino-4-hydroxyphenyl)hexafluoropropanone, and 5 parts by weight of the following "carbon black A" were kneaded, and then heat-treated at 190 ° C for 30 minutes, and One cross-linking was carried out, followed by heat treatment at 240 C for 48 hours, and secondary cross-linking was carried out to form. The shape of the formed body was changed to 0 ring (AS568B-214). In addition, the carbon black was JIS K 6217 ( 1997) Calculated DBP oil absorption and nitrogen adsorption specific surface area as the benchmark's value is the manufacturer's type record value. The obtained 0 ring system is subjected to the following fluorine gas exposure test, and it is resistant to high temperature fluorine gas. The evaluation is carried out. The results are shown in Table 1. "Carbon Black A"; "DENKABLACK" (Electrical Chemical Industry Company) ; acetylene black) DBP oil absorption 190cm3 / 100g, nitrogen adsorption specific surface area 69m2 / g (fluorine gas exposure test) The eight 85683-214 size (diameter 3.5 is 3.53111111) 〇 ring cut, made into a circular section For the linear body, a test piece (see Fig. 1) in which the length L was cut out by 1 mm was obtained. Then, the test piece was set in a chamber to introduce a fluorine gas (80% nitrogen) at a concentration of 20%. After the pressure was changed to 5 〇〇t〇rr, the chamber was heated to 250 ° C for 2 hours. (Evaluation method) 101116814 201249913 Observing the surface of the 〇 ring of the four high-temperature fluorine gas after the fluorine gas exposure test And the end face. In the same way, at the corner of the end face of the ring; raw, with = as shown in Figure 2 (8), the end face gradually approaches the spherical surface (four) and continues

Ujtt*, by measuring the radius R of the 0-ring, and evaluating the corner radius R of the high-temperature fluorine gas = the half-photograph of the ankle ring along the corner after the test, and cutting by the shadow line The profile is obtained by processing Tian Tian ~ image processing. Therefore, the larger the resistance to high-temperature fluorine gas is, the better the selectivity of the gamma-containing (_) warm fluorine gas becomes. (4) Small's is high (Example 2) A ring of 0 is produced in the same manner as in Example 1 except that the following "carbon black" is used instead of "carbon black Aj". In addition, the carbon black is calculated based on JIS and K 6217 (199η), and the value of the fuel absorption and the gas adsorption specific surface area are calculated. This value is the manufacturer's Wei value. The Q-ring system of the company is similarly evaluated and gas-filled. The results are shown in Table 3. Further, the image of the radius of the end face corner portion of the test body after the fluorine gas exposure test is shown in Fig. 3. In Fig. 3, the white portion of the 'black portion is the test body' is The circular shape is added to the image with the radius of the corner. "Carbon black B"; "SHIYOUBLACKIP1500" (SAF carbon black) (Cab〇t company) DBP oil absorption 123cm3/100g, gas adsorption specific surface area i8〇m2 /g (Example 3)

101116814 S 201249913 An anthracene ring was produced in the same manner as in Example 1 except that the following "carbon black C" was used instead of "carbon black A". Further, the carbon black is calculated based on JIS K 6217 (1997), and the DBP oil absorption amount and the nitrogen adsorption specific surface area are calculated, and this value is a manufacturer type record value. The obtained 0 ring system was similarly evaluated for fluorine gas resistance. The results are shown in Table 1. Further, an image of the radius of the corner portion of the end face of the test body after the fluorine gas exposure test was obtained is shown in Fig. 4. In Fig. 4, the black portion is a test body, and the white portion is a circular shape attached by image processing having a radius of a corner portion. "Carbon black C"; "Asa #70" (HAF carbon black) (manufactured by Asahi Carbon Co., Ltd.) DBP oil absorption 101cm3/100g, nitrogen adsorption specific surface area 77m2/g (Example 4) In addition to replacing "carbon black A" 5 weight An anthracene ring was prepared in the same manner as in Example 1 except that 15 parts by weight of "carbon black A" was used. The obtained anthracene ring system was similarly evaluated for fluorine-resistant gas resistance. The results are shown in Table 1. Further, an image of the radius of the corner portion of the end face of the test body after the fluorine gas exposure test was obtained is shown in Fig. 5. (Example 5) An anthracene ring was produced in the same manner as in Example 2 except that 15 parts by weight of "carbon black B" was used instead of 5 parts by weight of "carbon black B". The obtained anthracene ring system was similarly evaluated for fluorine-resistant gas resistance. The results are shown in Table 1. Further, it is used to obtain a shadow of the radius of the end face portion of the test body after the fluorine gas exposure test. 101116814 13 201249913 The image is shown in Fig. 6. (Example 6) An oxime was produced in the same manner as in Example 3 except that 5 parts by weight of "carbon black C" was used instead of 15 parts by weight of "carbon black C". The obtained anthracene ring system was similarly evaluated for fluorine-resistant gas resistance. The results are not shown in Table 1. Further, an image of the radius of the corner portion of the end face of the test body after the fluorine gas exposure test was obtained is shown in Fig. 7. In Fig. 7, the black portion is a test body, and the white portion is a circle attached by image processing having a corner radius. (Comparative Example 1) An anthracene ring was produced in the same manner as in Example 1 except that the following "carbon black D" was used instead of "carbon black A". In addition, the carbon black system calculates the DBP oil absorption and nitrogen, and the specific surface area based on jis &amp; 6217 (1997). This value is manufactured by the manufacturer. The Lai's ring system is similarly evaluated for fluorine gas. The results are shown in the table, and the radius of the end portion of the test body after the I gas exposure test is obtained. In Fig. 8, the two circles are attached by a process having a corner half-length image. "Carbon Black D"; "Asa #50" (SRF-HS-HM carbon black) (made by Asahi Carbon Co., Ltd.) DBP oil absorption 63cm3/1〇〇g, nitrogen adsorption specific surface area (Comparative Example 2) g In addition to replacing "carbon In the same manner as in Example 1, except that the amount of the black A" was 5 parts by weight, the same procedure as in Example 1 was carried out, except that the following "俨 展 E" 15 weights 101116814 201249913 parts were used. Further, the carbon black system calculates the DBP oil absorption amount and the nitrogen adsorption specific surface area based on JIS κ 6217 (1997), and this value is a manufacturer type record value. The obtained anthracene ring system was similarly evaluated for fluorine-resistant gas. The results are shown in Table 1. Further, an image of the radius of the corner portion of the end face of the test body after the fluorine gas exposure test was obtained is shown in Fig. 9. In Fig. 9, the two circles are attached by image processing having a corner radius. ~Carbon black Ε"; "SurmaxMT N990" (MT carbon black) (manufactured by Cancarb) DBP oil absorption 43cm3/100g, nitrogen adsorption specific surface area l〇m2/g [Table 1]

DBP oil absorption amount fcm3/100gl N-2 specific surface area fm2/gl Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 - fluorine-depleted elastomer 100 100 100 100 100 100 100 100 基策某3·月女基-4-3⁄4 六气丙坑1 1 1 1 1 1 1 1 JL, A 190 69 5 a 15 He 123 180 a 5 a 15 101 77 _ a 5 a 15 ___ ~^黑D 63 23一一一__ 5一43 10 —一一— _ The results of the rolling taming test (the corner of the section - semi-circumferential : mm) 0.40 ~ 0.90 0.86 1.11 0 0 0.19 1.52 1.2 ---J As shown in Table 1 and Fig. 5 to Fig. 7, the weight of the carbon black having a DBP oil absorption of 9 〇cm3/1 〇〇g or more is contained in an amount of 100 parts by weight or more based on 100 parts by weight of the elastomer component. The molding systems of Examples 4 to 6 obtained from the fluoroelastomer composition hardly observed the dissolution phenomenon even when exposed to a temperature of a fluorine gas atmosphere for a predetermined period of time. This system can be considered as 101116814 15 201249913 with DBP oil absorption of 9〇cm3/100g or more. Because of its well-developed structure, it has strong interaction with all (four) sexual bodies, so even if it is exposed to ... fluorine gas, it can stop the elasticity. (4). In addition, as shown in Table 3 and Figure 4, &amp; 3*: Α 吓 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 吓 吓 DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB DB The molding system of Examples ～3 obtained by the above carbon absorbing and 5 parts by weight of the total (four) morphological composition did not observe a large amount of dissolution even when exposed to the same gas/gas content. On the other hand, the molding systems of Comparative Examples 1 and 2 obtained by the fluoroelastomer composition containing the DBp oil absorption amount of the fine 3 chest g or 6 W/i〇〇g, FIG. 8 and FIG. 9 As shown in the figure, a large amount of dissolution phenomenon can be observed. (Industrial Applicability) The elastomer molded article of the present invention can be suitably used as a decomposition product because it exhibits superiority to the decomposition product of 1. Sealing material for sealing of a thermal diffusion furnace of a semiconductor wafer. [Simplified description of the drawings] Fig. 1 is a view showing a shape of a test body supplied to a fluorine gas exposure test, and (A) is a front view of a perspective view (B). (C) is a side view. Fig. 2 is a view showing the shape of the test body after the fluorine gas exposure test of Comparative Example, (A) is a front view, and (B) is a view along the χ_χ line in Fig. 2(A) Fig. 3 is a process image for obtaining the radius of the corner portion of the cross section of Embodiment 2. Fig. 4 is a process image for obtaining the radius of the corner portion of the cross section of Embodiment 3. Fig. 5 is for obtaining an embodiment. 4 processed image of the corner radius of the section. Figure 6 is used to obtain the section corner of the embodiment 5. Image processing radius.

S 101116814 201249913 FIG. 7 is a processed image for obtaining the radius of the corner portion of the cross section of Example 6. Fig. 8 is a process image for obtaining the radius of the corner portion of the cross section of Comparative Example 1. Fig. 9 is a process image for obtaining the radius of the corner portion of the scraping surface of Comparative Example 2. [Description of main component symbols] D Diameter of test body L Length of test body R Radius of the corner where it is dissolved 101116814 17

Claims (1)

201249913 VII. Patent application scope: 1. A perfluoroelastomer composition containing a perfluoroelastomer component and a carbon black having a DBP oil absorption amount (A method) of 90 cm 3 /100 g or more and 600 cm 3 /100 g or less. 2. The perfluoroelastomer composition of claim 1, wherein the carbon black is acetylene black. 3. The perfluoroelastomer composition according to the first or second aspect of the invention, wherein the carbon black is contained in an amount of 10 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the perfluoroelastomer component. An elastomer molded body obtained by cross-linking a perfluoroelastomer composition according to any one of claims 1 to 3. 101116814