WO1995015995A1 - Peroxide-crosslinkable, low-hardness, fluorine rubber composition - Google Patents
Peroxide-crosslinkable, low-hardness, fluorine rubber composition Download PDFInfo
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- WO1995015995A1 WO1995015995A1 PCT/US1994/014093 US9414093W WO9515995A1 WO 1995015995 A1 WO1995015995 A1 WO 1995015995A1 US 9414093 W US9414093 W US 9414093W WO 9515995 A1 WO9515995 A1 WO 9515995A1
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- Prior art keywords
- weight
- fluoroelastomer
- parts
- peroxide
- hardness
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 title description 8
- 229920001971 elastomer Polymers 0.000 title description 5
- 239000011737 fluorine Substances 0.000 title description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 4
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 30
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 8
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004971 Cross linker Substances 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920006027 ternary co-polymer Polymers 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- -1 Austin black Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
Definitions
- the present invention relates to a novel vulcanization composition containing a fluoroelastomer. More specifically, the present invention is directed to a peroxide-vulcanizable fluoroelastomer composition which permits achievement of low hardness and excellent chemical resistance. BACKGROUND OF THE INVENTION
- Fluoroelastomers have excellent heat resistance and oil resistance. Therefore, they are used for O-rings, gaskets, oil seals, diaphragms, hoses, rolls, sheet materials, and the like in a variety of industrial fields, such as those involving automobiles, ships, aircraft, and hydraulic devices; the chemical industry and general appliances industry; and pollution-related fields.
- Peroxide-vulcanizable fluoroelastomer products have exceptional acid and chemical resistance and are used for office equipment, in the fields of medical drugs and medical treatment, and in food product-related applications. Peroxide-vulcanized fluoroelastomer products having a low degree of hardness are desirable for applications which require acid or chemical resistance as well as good sealing properties with low tightening force in glass or plastic vessels. However, there are no examples of any such products which are satisfactory in terms of practical performance with a hardness of 50 or less.
- the present invention is a peroxide-vulcanizable fluoroelastomer composition which allows a molded article with a hardness of 50 or less to be obtained, which composition comprises a) a peroxide-vulcanizable bromine-containing fluoroelastomer or iodine-containing fluoroelastomer, said fluoroelastomer having i) at least 20% by weight of a fraction having molecular weight of no more than 50,000, and ii) no more than 1% by weight of a fraction having molecular weight of 1,000,000 or more; b) 0.1 to 5 parts by weight of an organic peroxide per 100 parts by weight of a); and c) 0.1 to 5 parts by weight of a poly functional co-crosslinker per 100 parts by weight of a).
- the present invention provides a peroxide-vulcanizable fluoroelastomer composition which permits a molded article with a hardness of 50 or less to be obtained without impairing the kneading workability and without sacrificing the heat resistance, oil resistance, acid resistance, and chemical resistance which are characteristic of conventional peroxide-vulcanizable fluoroelastomers.
- component a) of the present invention examples include binary copolymers having interpolymerized units of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), or ternary copolymers having interpolymerized units of VDF, HFP, and tetrafluoroethylene (TFE), either of which copolymers contain bromine and/or iodine in the polymer chain or polymer terminals.
- VDF vinylidene fluoride
- HFP hexafluoropropylene
- TFE tetrafluoroethylene
- binary and ternary refer to principal constituent monomers which do not include interpolymerized units of bromine-containing or iodine-containing monomers.
- Component b) of the present invention is an organic peroxide that produces peroxide radicals at the vulcanization temperature, for example, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- di-(t-butylperoxy) hexane, and 2,5-dimethyl-2,5-2,5-di-(t-butylperoxy) hexane-3.
- Component c) is a polyfunctional co-crosslinker.
- Examples of component c) of the present invention include triallylcyanurate, triallylisocyanurate, and trimethallylisocyanurate.
- the ratio in which component b) is used is 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight, per 100 parts by weight of component a) of the present invention.
- Component c) is used in a ratio of 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight per 100 parts by weight of component a).
- Use of less than 0.1 weight part of component b) does not permit the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 parts by weight does not permit a hardness of 50 or less to be achieved.
- Use of less than 0.1 parts by weight of component c) does not allow the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 weight parts makes it difficult to achieve a hardness of 50 or less.
- the molecular weight distribution of component a) is stipulated within the aforementioned range because less than 20% by weight of the M50 fraction does not allow a hardness of 50 or less to be achieved. Similarly, more than 1% by weight of the Ml 000 fraction also does not allow a hardness of 50 or less to be achieved.
- Other components such as carbon black, Austin black, graphite, silica, clay, diatomaceous earth, talc, calcium carbonate, calcium silicate, calcium sulfate, fatty acid calcium, fatty acid amides, low molecular weight polyethylene, silicone oil, silicone grease, metal soap, stearic acid, fatty amines, titanium oxide, red iron oxide, and other such fillers, working adjuvants, plasticizers, coloring agents, and the like can be blended as needed into the fluoroelastomer composition of the present invention.
- Acid-absorbers such as magnesium oxide, zinc oxide, calcium oxide, and calcium hydroxide, may also be added.
- Methods for vulcanizing the fluoroelastomer composition thus obtained include methods in which the material is kneaded using an open-type mixing roll or closed-type kneading roll (such as a Banbury mixer or a pressure kneader), and the material is then introduced into a heated mold and compressed to effect primary vulcanization, followed by secondary vulcanization.
- an open-type mixing roll or closed-type kneading roll such as a Banbury mixer or a pressure kneader
- the conditions for the primary vulcanization include a temperature of 120° to 200°C, a time of 1 to 80 minutes, and a pressure of 20 to 150 kg/cm 2
- the conditions for the secondary vulcanization include a temperature of 120° to 250°C, and a time of 0 to 48 hours.
- Other vulcanization means which can be used include methods in which a preform is fashioned by injection or extrusion or the like, followed by vulcanization, or methods in which one or more ketones, ethers, or the like are used as media to prepare a solution or dispersion, which is then used to coat the surface of paper, fiber, film, sheets, plates, tubes, pipes, tanks, large-scale containers, or other molded articles, followed by vulcanization.
- Liquid chromatograph model LC-3A (Shimadzu Seisakusho) Columns: KF-80 M (two) & KF-800 P (precolumn) (Showa Denko) Detector: ERC-7510 S (Elmer Optical)
- Polymer serving as standard for molecular weight detection lines various types of monodisperse polystyrene (Toyo Soda) Concentration: 0.1 wt%
- Fluoroelastomer FR-6150 (100 parts by weight, 34% by weignt M50 fraction and 0% Ml 000 fraction) manufactured by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol% HFP, 17.4 mol% TFE, 68.0 wt% F content, and 5200 ppm I content) was wound on an open-type mixing roll. Carbon black (3 parts by weight, Thermax N-990 from Cancarb), 1 part by weight lead oxide (Litharge No.
- Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1 part by weight and the amount of TAIC used was 2 parts by weight. The various tests were conducted, and the results are shown in Table 1.
- Example 3 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1.5 parts by weight and the amount of TAIC used was 3 parts by weight. The various tests were conducted, and the results are shown in Table 1.
- Comparative Example 1 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by FR-6350 (containing 13% M50 and 0% M1000) by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol % HFP, 17.4 mol % TFE, 68.0% F content, and 3000 ppm I content). The various tests were conducted. The results are shown in Table 1.
- Comparative Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by G-902 (containing 21% M50 and 1.5% Ml 000) by Daikin Industries (54.7 mol% VDF, 23.6 mol% HFP, 21.7 mol% TFE, 69.7% F content, and 2200 ppm I content). The various tests were conducted. The results are shown in Table 1.
- Vulcanizability (g). 160°C Optimal time (min) 10.8 11.0 11.5 12.5 11.8
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Peroxide-vulcanizable fluoroelastomer compositions yield molded articles with a hardness of 50 or less.
Description
TITLE
PEROXIDE-CROSSLINKABLE, LOW-HARDNESS,
FLUORINE RUBBER COMPOSITION
FIELD OF THE INVENTION The present invention relates to a novel vulcanization composition containing a fluoroelastomer. More specifically, the present invention is directed to a peroxide-vulcanizable fluoroelastomer composition which permits achievement of low hardness and excellent chemical resistance. BACKGROUND OF THE INVENTION
Fluoroelastomers have excellent heat resistance and oil resistance. Therefore, they are used for O-rings, gaskets, oil seals, diaphragms, hoses, rolls, sheet materials, and the like in a variety of industrial fields, such as those involving automobiles, ships, aircraft, and hydraulic devices; the chemical industry and general appliances industry; and pollution-related fields.
Peroxide-vulcanizable fluoroelastomer products have exceptional acid and chemical resistance and are used for office equipment, in the fields of medical drugs and medical treatment, and in food product-related applications. Peroxide-vulcanized fluoroelastomer products having a low degree of hardness are desirable for applications which require acid or chemical resistance as well as good sealing properties with low tightening force in glass or plastic vessels. However, there are no examples of any such products which are satisfactory in terms of practical performance with a hardness of 50 or less.
There have been studies directed to lowering the hardness of peroxide-vulcanizable fluoroelastomers. In the method disclosed in Japanese Laid-Open Patent Application 62-277456, for example, a liquid fluorine rubber is blended in a solid fluorine rubber in a ratio of 100:10 to 100: 100 to effect peroxide vulcanization so as to obtain a molded article having a hardness of 53 to 57. The addition of large amounts of the liquid fluorine rubber in this method, however, results in poor kneading workability, and it is still not possible to obtain a molded article with a hardness of 50 or less.
SUMMARY OF THE INVENTION
The present invention is a peroxide-vulcanizable fluoroelastomer composition which allows a molded article with a hardness of 50 or less to be obtained, which composition comprises a) a peroxide-vulcanizable bromine-containing fluoroelastomer or iodine-containing fluoroelastomer, said fluoroelastomer having i) at least 20% by weight of a fraction having molecular weight of no more than 50,000, and ii) no more than 1% by weight of a fraction having molecular weight of 1,000,000 or more; b) 0.1 to 5 parts by weight of an organic peroxide per 100 parts by weight of a); and c) 0.1 to 5 parts by weight of a poly functional co-crosslinker per 100 parts by weight of a). DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a peroxide-vulcanizable fluoroelastomer composition which permits a molded article with a hardness of 50 or less to be obtained without impairing the kneading workability and without sacrificing the heat resistance, oil resistance, acid resistance, and chemical resistance which are characteristic of conventional peroxide-vulcanizable fluoroelastomers. It has been discovered that the aforementioned objectives can be achieved by provision of a composition obtained by blending a prescribed amount of an organic peroxide and a prescribed amount of a polyfunctional co-crosslinker with a peroxide-vulcanizable fluoroelastomer containing at least 20% by weight of a fraction having molecular weight of no more than 50,000 (hereinafter abbreviated as M50) and no greater than 1% by weight of a fraction having molecular weight of 1,000,000 or more (hereinafter abbreviated as Ml 000). It can thus be used in applications in the fields of office equipment, food products, medical drugs, and medical treatment instruments.
Examples of component a) of the present invention include binary copolymers having interpolymerized units of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), or ternary copolymers having interpolymerized units of VDF, HFP, and tetrafluoroethylene (TFE),
either of which copolymers contain bromine and/or iodine in the polymer chain or polymer terminals. As used herein, "binary" and "ternary" refer to principal constituent monomers which do not include interpolymerized units of bromine-containing or iodine-containing monomers. Iodine or bromine is introduced into the polymer chain either by use of chain transfer agents or by copolymerization of bromine- or iodine-containing olefin monomers. Methods for manufacture of such polymers have been disclosed, for example, in Japanese Patent Application 59-7513. Component b) of the present invention is an organic peroxide that produces peroxide radicals at the vulcanization temperature, for example, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- di-(t-butylperoxy) hexane, and 2,5-dimethyl-2,5-2,5-di-(t-butylperoxy) hexane-3.
Component c) is a polyfunctional co-crosslinker. Examples of component c) of the present invention include triallylcyanurate, triallylisocyanurate, and trimethallylisocyanurate.
The ratio in which component b) is used is 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight, per 100 parts by weight of component a) of the present invention. Component c) is used in a ratio of 0.1 to 5 parts by weight, and preferably 0.3 to 3 parts by weight per 100 parts by weight of component a). Use of less than 0.1 weight part of component b) does not permit the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 parts by weight does not permit a hardness of 50 or less to be achieved. Use of less than 0.1 parts by weight of component c) does not allow the necessary degree of crosslinking to be achieved, whereas an amount in excess of 5 weight parts makes it difficult to achieve a hardness of 50 or less.
The molecular weight distribution of component a) is stipulated within the aforementioned range because less than 20% by weight of the M50 fraction does not allow a hardness of 50 or less to be achieved. Similarly, more than 1% by weight of the Ml 000 fraction also does not allow a hardness of 50 or less to be achieved.
Other components, such as carbon black, Austin black, graphite, silica, clay, diatomaceous earth, talc, calcium carbonate, calcium silicate, calcium sulfate, fatty acid calcium, fatty acid amides, low
molecular weight polyethylene, silicone oil, silicone grease, metal soap, stearic acid, fatty amines, titanium oxide, red iron oxide, and other such fillers, working adjuvants, plasticizers, coloring agents, and the like can be blended as needed into the fluoroelastomer composition of the present invention. Acid-absorbers, such as magnesium oxide, zinc oxide, calcium oxide, and calcium hydroxide, may also be added. One or two conventionally known vulcanization agents or vulcanization promoters may also be added, provided that the essence of the present invention is not thereby compromised. Methods for vulcanizing the fluoroelastomer composition thus obtained include methods in which the material is kneaded using an open-type mixing roll or closed-type kneading roll (such as a Banbury mixer or a pressure kneader), and the material is then introduced into a heated mold and compressed to effect primary vulcanization, followed by secondary vulcanization. The conditions for the primary vulcanization include a temperature of 120° to 200°C, a time of 1 to 80 minutes, and a pressure of 20 to 150 kg/cm2, and the conditions for the secondary vulcanization include a temperature of 120° to 250°C, and a time of 0 to 48 hours. Other vulcanization means which can be used include methods in which a preform is fashioned by injection or extrusion or the like, followed by vulcanization, or methods in which one or more ketones, ethers, or the like are used as media to prepare a solution or dispersion, which is then used to coat the surface of paper, fiber, film, sheets, plates, tubes, pipes, tanks, large-scale containers, or other molded articles, followed by vulcanization.
EXAMPLES The present invention is described in further detail below with reference to certain preferred embodiments wherein all parts are by weight unless otherwise specified. The molecular weight distribution of the fluoroelastomer and the physical properties, etc., of the vulcanized composition were determined using the following methods.
1) Molecular weight distribution:
Liquid chromatograph: model LC-3A (Shimadzu Seisakusho) Columns: KF-80 M (two) & KF-800 P (precolumn) (Showa Denko) Detector: ERC-7510 S (Elmer Optical)
Integrator: 7000 A (System Instruments) Developing solvent: tetrahydrofuran
Polymer serving as standard for molecular weight detection lines: various types of monodisperse polystyrene (Toyo Soda) Concentration: 0.1 wt%
Temperature: 35°C (2) Physical properties of the vulcanized product: Hardness measured according to JIS A.
100% tensile stress, tensile strength, elongation, and compression set measured according to JIS K 6301.
Example 1
Fluoroelastomer FR-6150 (100 parts by weight, 34% by weignt M50 fraction and 0% Ml 000 fraction) manufactured by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol% HFP, 17.4 mol% TFE, 68.0 wt% F content, and 5200 ppm I content) was wound on an open-type mixing roll. Carbon black (3 parts by weight, Thermax N-990 from Cancarb), 1 part by weight lead oxide (Litharge No. 1 Canary Yellow from Nippon Chemical Industry), 0.5 part by weight 2,5-dimethyl-2,5- di (t-butylperoxy) hexane (Perhexa 2,5 B, from Nippon Oil & Fats), and 1 part by weight triallylisocyanurate (TAIC, from Nippon Chemical Industry) were kneaded and then allowed to age overnight.
The material was kneaded again, introduced into a mold, and press cured for 15 minutes at a temperature of 160°C for molded sheet or press cured for 20 minutes at a temperature of 160°C for molded JIS cylinder. The material was removed from the mold and heated for four hours in a circulating air oven at a temperature of 180°C to complete the secondary vulcanization, and the various tests were conducted. The results are shown in Table 1.
Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1 part by weight and the amount of TAIC used was 2 parts by weight. The various tests were conducted, and the results are shown in Table 1.
Example 3 Vulcanized molded material was prepared in the same manner as in Example 1 except that the amount of Perhexa 2,5 B used was 1.5 parts by weight and the amount of TAIC used was 3 parts by weight. The various tests were conducted, and the results are shown in Table 1.
Comparative Example 1 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by FR-6350 (containing 13% M50 and 0% M1000) by Asahi Chemical Industry (64.4 mol% VDF, 18.2 mol % HFP, 17.4 mol % TFE, 68.0% F content, and 3000 ppm I content). The various tests were conducted. The results are shown in Table 1.
Comparative Example 2 Vulcanized molded material was prepared in the same manner as in Example 1 except that the FR-6150 was replaced by G-902 (containing 21% M50 and 1.5% Ml 000) by Daikin Industries (54.7 mol% VDF, 23.6 mol% HFP, 21.7 mol% TFE, 69.7% F content, and 2200 ppm I content). The various tests were conducted. The results are shown in Table 1.
Table 1. Summary of Formulations and Results
Comp. Comp.
Ex- . Ex. 2 Ex. 3 Ex. 1 Ex. 2
Blend
Ex. 1 Polymer 100 100 100
Comp. Ex. 1 Polymer 100
Comp. Ex. 2 Polymer 100
Thermax N-990 3 3 3 3 3
Litharge No. 1 Yellow 1 1 1 1 1
TAIC 1 2 3 1 1
Perhexa 2,5 B 0.5 1 1.5 0.5 0.5
Vulcanizability (g). 160°C Optimal time (min) 10.8 11.0 11.5 12.5 11.8
Physical Properties (g). 23 °C Hardness (points) 47 48 49 52 53 100% Tensile Stress (kgff cm2) 9 10 11 10 12 Tensile Strength (kgfTcm2) 138 142 145 130 135 Elongation (%) 600 550 500 570 590
Compression Set
25% compression, 150°C, 70 hr 28 23 20 33 30
Claims
1. A vulcanizable fluoroelastomer composition, which comprises a) a peroxide-vulcanizable bromine-containing fluoroelastomer or iodine-containing fluoroelastomer, said fluoroelastomer having i) at least 20% by weight of a fraction having molecular weight of no more than 50,000 and ii) no more than 1% by weight of a fraction having molecular weight of 1,000,000 or more; b) 0.1 to 5 parts by weight of an organic peroxide per 100 parts by weight of a); and c) 0.1 to 5 parts by weight of a polyfunctional co-crosslinker per 100 parts by weight of a).
2. The vulcanizable fluoroelastomer composition of Claim 1 , wherein the bromine-containing fluoroelastomer or iodine- containing fluoroelastomer is a binary copolymer having interpolymerized units of vinylidene fluoride and hexafluoropropylene.
3. The vulcanizable fluoroelastomer composition of Claim 1, wherein the bromine-containing fluoroelastomer or iodine- containing fluoroelastomer is a ternary copolymer having interpolymerized units of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene.
4. The vulcanizable fluoroelastomer composition of Claim 1, wherein component b) is present in an amount of 0.3 to 3 parts by weight.
5. The vulcanizable fluoroelastomer composition of Claim 1, wherein the amount of component c) is 0.3 to 3 parts by weight..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95904842A EP0733085A1 (en) | 1993-12-07 | 1994-12-06 | Peroxide-crosslinkable, low-hardness, fluorine rubber composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP93/306,574 | 1993-12-07 | ||
| JP30657493A JPH07196878A (en) | 1993-12-07 | 1993-12-07 | Low-hardness fluororubber vulcanizing composition crosslinkable by peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1995015995A1 true WO1995015995A1 (en) | 1995-06-15 |
Family
ID=17958702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1994/014093 WO1995015995A1 (en) | 1993-12-07 | 1994-12-06 | Peroxide-crosslinkable, low-hardness, fluorine rubber composition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0733085A1 (en) |
| JP (1) | JPH07196878A (en) |
| WO (1) | WO1995015995A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001016234A1 (en) * | 1999-08-31 | 2001-03-08 | Daikin Industries, Ltd. | Polymer composition crosslinkable with ultraviolet |
| US6911498B2 (en) * | 1997-04-15 | 2005-06-28 | Daikin Industries Ltd. | Composition for vulcanizing fluororubbers and fluororubber moldings |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2805705B1 (en) | 2013-05-23 | 2016-11-09 | IP Gesellschaft für Management mbH | Packaging with one or more administration units comprising a sodium salt of (R)-3-[6-amino-pyridin-3-yl]-2-(1-cyclohexyl-1 H-imidazol-4-yl)-propionic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340786A1 (en) * | 1988-05-06 | 1989-11-08 | E.I. Du Pont De Nemours And Company | Peroxide curable fluoroelastomer compositions containing a tetraalkylammonium halide and coagent |
| EP0600090A1 (en) * | 1992-05-11 | 1994-06-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Fluoroelastomer composition and molding produced therefrom |
-
1993
- 1993-12-07 JP JP30657493A patent/JPH07196878A/en active Pending
-
1994
- 1994-12-06 EP EP95904842A patent/EP0733085A1/en not_active Withdrawn
- 1994-12-06 WO PCT/US1994/014093 patent/WO1995015995A1/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340786A1 (en) * | 1988-05-06 | 1989-11-08 | E.I. Du Pont De Nemours And Company | Peroxide curable fluoroelastomer compositions containing a tetraalkylammonium halide and coagent |
| EP0600090A1 (en) * | 1992-05-11 | 1994-06-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Fluoroelastomer composition and molding produced therefrom |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6911498B2 (en) * | 1997-04-15 | 2005-06-28 | Daikin Industries Ltd. | Composition for vulcanizing fluororubbers and fluororubber moldings |
| WO2001016234A1 (en) * | 1999-08-31 | 2001-03-08 | Daikin Industries, Ltd. | Polymer composition crosslinkable with ultraviolet |
| US6974845B1 (en) | 1999-08-31 | 2005-12-13 | Daikin Industries, Ltd. | Polymer composition crosslinkable with ultraviolet |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0733085A1 (en) | 1996-09-25 |
| JPH07196878A (en) | 1995-08-01 |
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