WO2024128165A1 - Millable silicone rubber composition - Google Patents
Millable silicone rubber composition Download PDFInfo
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- WO2024128165A1 WO2024128165A1 PCT/JP2023/044089 JP2023044089W WO2024128165A1 WO 2024128165 A1 WO2024128165 A1 WO 2024128165A1 JP 2023044089 W JP2023044089 W JP 2023044089W WO 2024128165 A1 WO2024128165 A1 WO 2024128165A1
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- silicone rubber
- rubber composition
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 74
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 21
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical class [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000004438 BET method Methods 0.000 claims abstract description 13
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 claims description 4
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 3
- ZICNIEOYWVIEQJ-UHFFFAOYSA-N (2-methylbenzoyl) 2-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1C ZICNIEOYWVIEQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- -1 β-phenylpropyl groups Chemical group 0.000 description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 125000005372 silanol group Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003058 platinum compounds Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000007706 flame test Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 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 1
- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- KKFPIBHAPSRIPB-UHFFFAOYSA-N cerium(3+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Ce+3].[Ce+3] KKFPIBHAPSRIPB-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Definitions
- the present invention relates to a millable type silicone rubber composition.
- the main skeleton of silicone rubber is made of siloxane bonds, and compared to ordinary organic rubber, it has a lower ratio of organic components (hydrocarbon components) and is resistant to combustion.
- silicone rubber will ignite and burn.
- Patent Document 1 it is known to blend a platinum compound or a reaction product of a platinum compound with a compound having an alkynyl group and an alcoholic hydroxyl group, and a triazole-based compound as a flame retardant to the silicone rubber composition.
- Patent Document 2 A method has also been proposed in which titanium dioxide with an average particle size of 0.10 to 0.50 ⁇ m is added to a silicone rubber composition (Patent Document 2), but in either case the heat resistance of the resulting cured silicone rubber is reduced.
- Patent Document 3 describes how adding 0.1 mass % or more of titanium oxide and iron oxide (particularly diferric oxide) to a silicone rubber composition can improve the heat resistance of the silicone rubber, but the effect of the iron oxide reduces flame retardancy.
- Patent Document 4 describes that adding cerium oxide hydrate and/or zirconium oxide hydrate to a silicone rubber composition improves the heat resistance of the silicone rubber, and measures the physical properties after placing the composition in a dryer at 225°C for 72 hours. However, heat resistance at higher temperatures is insufficient.
- Patent Document 5 and Patent Document 6 describe titanium oxide doped with metal ions (metal salts) of transition metals and the like.
- the method of adding titanium oxide doped with metal ions (metal salts) to a silicone rubber composition improves high-temperature heat resistance but reduces flame retardancy.
- Patent Document 7 describes an addition reaction curing organopolysiloxane composition containing yellow iron oxide fine powder, preferably yellow iron oxide solid-dissolved with aluminic acid or aluminate. It describes that the composition cures by addition reaction to provide a cured product with excellent heat resistance in the high temperature range of 280°C or higher. However, the addition of yellow iron oxide significantly reduces flame retardancy.
- the object of the present invention is therefore to provide a millable silicone rubber composition that produces a silicone rubber (cured product) that has excellent heat resistance at high temperatures of 200°C or higher, particularly 300°C, and also has excellent flame retardancy.
- the present invention provides the following millable type silicone rubber composition.
- the millable silicone rubber composition of the present invention can provide silicone rubber with excellent flame retardancy and heat resistance.
- the cured product (silicone rubber) of the millable silicone rubber composition of the present invention exhibits excellent heat resistance at temperatures of 200°C or higher, particularly at high temperatures of 300°C.
- the cured product exhibits good flame retardancy equivalent to V-0 in a flame test according to the UL-94 test method.
- the millable composition refers to a highly viscous, non-liquid composition that does not have self-flowing properties at room temperature (25°C) and can be kneaded uniformly under shear stress using a kneading machine such as a roll mill (e.g., two-roll or three-roll).
- Component (A) is an organopolysiloxane that is the main component (base polymer) of the composition, and has at least two alkenyl groups bonded to silicon atoms in each molecule, and preferably has from 2 to 50 alkenyl groups bonded to silicon atoms. It is preferable that there is at least one alkenyl group at each of the ends of the molecular chain, and it is even more preferable that there are alkenyl groups in the side chains of the molecular chain.
- Component (A) has an average degree of polymerization of 100 or more, preferably in the range of 1,000 to 100,000, more preferably in the range of 3,000 to 50,000, and particularly preferably in the range of 4,000 to 20,000. If the average degree of polymerization is less than 100, the millable silicone rubber composition of the present invention will no longer satisfy the properties required for millable rubber, and roll kneading properties and the like will be significantly deteriorated, which is not preferable.
- This average degree of polymerization is determined from the weight average molecular weight in terms of polystyrene in GPC (gel permeation chromatography) analysis measured under the following conditions.
- component (A) is preferably a non-liquid organopolysiloxane gum that has a high degree of polymerization (high viscosity) and no self-flowing properties at room temperature (25°C).
- the (A) component may be any alkenyl-containing organopolysiloxane that satisfies the above average degree of polymerization.
- alkenyl group examples include vinyl, allyl, butenyl, and hexenyl groups.
- Alkenyl groups having 2 to 8 carbon atoms are preferred, vinyl or allyl groups are more preferred, and vinyl groups are even more preferred.
- the substituents bonded to silicon atoms other than the alkenyl groups are monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
- Examples of the monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups such as ⁇ -phenylpropyl groups.
- Some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms, such as 3,3,3-trifluoropropyl groups.
- methyl groups, phenyl groups, and trifluoropropyl groups are preferred, and methyl groups are more preferred.
- 50% or more of the total substituents of the alkenyl-containing organopolysiloxane are methyl groups, more preferably 80% or more are methyl groups, and even more preferably that all of the substituents other than the alkenyl groups are methyl groups.
- the alkenyl group-containing organopolysiloxane is preferably linear or branched, more preferably linear.
- it is preferably a linear diorganopolysiloxane whose main chain is composed of repeated diorganosiloxane units and whose molecular chain ends are blocked with triorganosiloxy groups. With such a structure, the resulting cured product exhibits sufficient rubber elasticity.
- both molecular chain ends are blocked with trimethylsiloxy groups, dimethylvinylsiloxy groups, dimethylhydroxysiloxy groups, methyldivinylsiloxy groups, trivinylsiloxy groups, etc., and in particular, it is preferable that the molecular chain ends are blocked with triorganosiloxy groups having one or more vinyl groups.
- These organopolysiloxanes may be used alone or in combination of two or more types having different degrees of polymerization or molecular structures.
- the content of component (A) is preferably 43 to 96 mass%, more preferably 50 to 90 mass%, and even more preferably 60 to 80 mass%.
- (B) reinforcing silica is a filler that imparts excellent mechanical properties to the resulting silicone rubber.
- the reinforcing silica may be precipitated silica (wet silica) or fumed silica (dry silica), and has a large number of silanol (hydroxysilyl) groups on its surface.
- (B) reinforcing silica in the present invention must have a specific surface area of 50 m 2 /g or more as measured by the BET method. There is no particular upper limit to the specific surface area, but it should be 400 m 2 /g or less, and is preferably 100 to 400 m 2 /g. If the specific surface area is less than 50 m 2 /g, the reinforcing effect of the silicone rubber imparted by component (B) may be insufficient.
- the reinforcing silica (B) may be used in an untreated state, or may be a reinforcing surface-treated silica that has been surface-treated with an organosilicon compound (surface treatment agent) such as organopolysiloxane, organopolysilazane, chlorosilane, or alkoxysilane, as necessary.
- organosilicon compound surface treatment agent
- the reinforcing surface-treated silica may be treated with one type of surface treatment agent, or may be treated with two or more types of surface treatment agents.
- This organosilicon compound (surface treatment agent) differs from the dispersant for fillers (H) described below in that it does not have a silanol group in one molecule.
- the reinforcing silica of component (B) may be used alone or in combination of two or more types.
- the amount of reinforcing silica (B) is 5 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 70 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If the amount of component (B) is less than 5 parts by mass or more than 100 parts by mass per 100 parts by mass of component (A), not only will the processability of the resulting millable silicone rubber composition decrease, but the mechanical properties of the silicone rubber cured product obtained by curing the silicone rubber composition, such as tensile strength and tear strength, may become insufficient.
- platinum-based compounds examples include platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate.
- the amount of platinum-based compound is 0.5 to 1,000 ppm, particularly 1 to 500 ppm, of platinum (by mass) relative to the amount of component (A). If it is less than 0.5 ppm, the flame retardancy is insufficient, and if it is more than 1,000 ppm, it is not economical and the flame retardancy may decrease.
- Component (D) is one or more cerium compounds selected from cerium oxide and cerium hydroxide. When used in combination with magnesium ferrite (F), which will be described later, either of these compounds significantly improves the heat resistance of the silicone rubber.
- cerium oxide products include Showrox FL-2 (manufactured by Showa Denko K.K.), SN-2 (manufactured by Nikki Co., Ltd.), and Cerium Oxide S (manufactured by Anan Kasei Co., Ltd.).
- cerium hydroxide products include cerium hydroxide (manufactured by Nikki Co., Ltd.) and Cerhydrate 90 (manufactured byDeutschach Industrie AG).
- the amount of component (D) added is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If the amount is less than 0.01 per 100 parts by mass of component (A), the heat resistance of the silicone rubber will not improve, and if more than 10 parts by mass is added, the mechanical properties of the silicone rubber may be significantly reduced.
- Cerium oxide and cerium hydroxide may each be used alone or in combination of two or more types. Of these, it is preferable to use cerium oxide alone. If cerium oxide and cerium hydroxide are used in combination, the total amount should be within the above range.
- (E) Fumed titanium oxide is titanium oxide produced by a dry method, and has a specific surface area measured by the BET method of 5 to 200 m2 /g, preferably 20 to 100 m2 /g.
- the crystal structure may be either rutile or anatase, or the two may be mixed.
- the amount of component (E) added is 1.0 to 20 parts by weight, and preferably 3.0 to 10 parts by weight, per 100 parts by weight of the organopolysiloxane of component (A). If the amount is less than 1.0 part by mass per 100 parts by mass of component (A), the flame retardancy of the silicone rubber will not improve, whereas if more than 20 parts by mass is added, the mechanical properties of the silicone rubber may decrease significantly.
- the (F) magnesium ferrite has an oil absorption of 20 to 40 g/100 g as measured by a kneading method.
- the amount of component (F) added is 0.5 to 30 parts by mass, and preferably 1.0 to 20 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If less than 0.5 parts by mass is added per 100 parts by mass of component (A), the heat resistance of the silicone rubber will not improve, and if more than 30 parts by mass is added, the mechanical properties (e.g., elongation at break (%)) of the silicone rubber may be significantly reduced. Note that diiron trioxide and yellow iron oxide are not preferred as they deteriorate the flame retardancy.
- Commercially available magnesium ferrite products include TAROX T-20 manufactured by Titan Kogyo Co., Ltd.
- the organic peroxide is a curing agent capable of curing the millable type silicone rubber composition of the present invention.
- organic peroxides examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-butyl peroxide, t-butyl perbenzoate, and 1,6-hexanediol-bis-t-butylperoxycarbonate.
- the amount of organic peroxide to be added is 0.1 to 10 parts by mass, and preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (A).
- the amount added is less than 0.1 part by mass per 100 parts by mass of component (A), curing may be insufficient, while if more than 10 parts by mass is added, the decomposition residue of the organic peroxide may cause discoloration of the cured silicone rubber.
- the millable silicone rubber composition of the present invention may further contain a dispersant for fillers, particularly a dispersant for inorganic fillers or silica, and is preferably a dispersant for silica.
- a dispersant for fillers particularly a dispersant for inorganic fillers or silica
- the reinforcing silica described above can be well dispersed in the composition.
- the dispersant is characterized by having one or more silanol groups in one molecule, and examples thereof include low molecular weight organosilicon compounds having silanol groups and alkoxy groups, and hydrolysates thereof.
- examples include various alkoxysilanes, particularly hydrolysates of alkoxysilanes containing phenyl groups, diphenylsilanediol, silanol group-containing carbon functional silanes, and silanol group-containing low molecular weight siloxanes (e.g., organopolysiloxanes blocked with silanol groups at both ends).
- diphenylsilanediol is preferred because it further improves the heat resistance of the silicone rubber.
- diphenylsilanediol is more preferred because it further improves the dispersibility of the reinforcing silica.
- component (H) differs from the organosilicon compound for surface treating the reinforcing silica (B) in that component (H) has one or more silanol groups in each molecule.
- the amount of component (H) is preferably 0.1 to 50 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of component (A). If the amount of component (H) is too small, the effect of adding it will not be seen, and if the amount is too large, the plasticity of the composition will be too low, and roll adhesion will occur in kneading means such as a roll mill, which may deteriorate roll workability.
- the millable silicone rubber composition used in the present invention may contain other known fillers and additives in heat-curable silicone rubber compositions as necessary, within the scope of not impairing the effects of the present invention.
- fillers other than the (B) component and the (H) component crushed quartz, diatomaceous earth, calcium carbonate, etc.
- colorants pigments
- tear strength improvers flame retardant improvers
- acid acceptors thermal conductivity improvers (alumina, boron nitride, etc.), release agents, etc.
- the other components may be used alone or in combination of two or more.
- the blending amount may be appropriately adjusted within the scope of not impairing the effects of the present invention.
- the millable type silicone rubber composition of the present invention can be obtained by mixing the above-mentioned components with a known kneading machine such as a kneader, a Banbury mixer, or a two-roll mill.
- a known kneading machine such as a kneader, a Banbury mixer, or a two-roll mill.
- a composition containing the above-mentioned components (A) to (G) it is preferable to mix (A) organopolysiloxane, (B) reinforcing silica, (C) platinum compound, (D) cerium oxide or cerium hydroxide, (E) titanium oxide, and (F) magnesium ferrite, and then add (G) organic peroxide to the resulting mixture.
- component (H) when other components are included, it is preferable to mix (A), (B), (C), (D), (E), and (F) with the other components, and then add (G) organic peroxide to the resulting mixture. Furthermore, when component (H) is contained, it is preferable to prepare a mixture of components (A), (B), and (H), mix the mixture with components (C), (D), (E), and (F), and, if necessary, other components, and then add component (G) to the mixture obtained.
- the millable silicone rubber composition may be molded by a known molding method according to the shape and size of the desired molded product.
- molding methods include casting, compression molding, injection molding, calendar molding, and extrusion molding.
- the curing conditions for the millable silicone rubber composition may be those known for the molding method used, and the millable silicone rubber composition is generally heated for a period of several seconds to a day at a temperature of 60 to 450° C.
- a post cure may be performed in an oven at 200° C. or higher, preferably 200 to 250° C., for 1 hour or more, preferably 1 to 70 hours, and more preferably 1 to 10 hours.
- heat resistance tests and flame retardancy tests were carried out as follows. [Heat-resistant] Using a test sheet prepared by curing the millable type silicone rubber composition, the hardness (Durometer A) and initial value of elongation at break (%) were measured according to JIS K 6249: 2003. The test sheet was placed in a dryer at 300°C for 3 days, after which the hardness and elongation at break were measured. The results are shown in Table 1.
- B Reinforcing Silica
- B-1 Fumed silica having a specific surface area of 200 m 2 /g measured by the BET method (product name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.)
- B-2) Reinforcing Surface-Treated Silica Reinforcing surface-treated silica was produced by the following method. 200g of fumed silica (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 200m2 /g measured by the BET method was charged into a high-speed mixer (volume 10L) and operated at a rotation speed of 1,500 rpm.
- C Platinum-based compound (C-1) 2-ethylhexanol solution of chloroplatinic acid hexahydrate (platinum concentration of 2% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)
- D Cerium oxide and cerium hydroxide (D-1) Cerium oxide (product name: SN-2, manufactured by Nikki Co., Ltd.)
- D-2 Cerium hydroxide (product name: Cerhydrate 90, manufactured by Treibach Industry AG)
- E Fumed titanium oxide (E-1) Titanium oxide (product name: AEROXIDE TiO 2 P25, manufactured by Nippon Aerosil Co., Ltd.) (specific surface area: 50 m 2 /g by BET method)
- F Magnesium ferrite (F-1) Magnesium ferrite (product name: TAROX T-20, manufactured by Titan Kogyo Co., Ltd.) (oil absorption: 30 g/100 g)
- F'-1) Red iron oxide product name: BAY
- Example 1 100 parts by mass of (A-1), 40 parts by mass of (B-1), 5 parts by mass of (H-1), and 2 parts by mass of (H-2) were added, and the mixture was heated at 170° C. for 2 hours while being mixed in a kneader, and then a base compound (1) was prepared.
- Examples 2 to 7, Comparative Examples 1 to 8 Silicone rubber compositions were prepared using the formulations shown in Table 1 in the same manner as in Example 1, and the resulting cured products were subjected to heat resistance tests and flame retardancy tests in the same manner as in Example 1. The results are shown in Table 1.
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Abstract
Provided is a millable silicone rubber composition that constitutes silicone rubber (cured product) having excellent heat resistance and flame resistance. The millable silicone rubber composition contains: (A) 100 parts by mass of organopolysiloxane that includes, per molecule, at least two alkenyl groups bound to silicon atoms, and that has an average degree of polymerization of at least 100; (B) 5-100 parts by mass of reinforcing silica that has a specific surface area of at least 50 m2/g based on the BET method; (C) 0.5-1,000 ppm of platinum-based compound with respect to the total mass of the component (A); (D) 0.01-10 parts by mass of at least one type selected from cerium oxides and cerium hydroxides; (E) 1.0-20 parts by mass of fumed titanium oxide that has a specific surface area of 5-200 m2/g based on the BET method; (F) 0.5-30 parts by mass of magnesium ferrite that has an oil absorption amount of 20-40 g/100 g; and (G) 0.1-10 parts by mass of organic peroxide.
Description
本発明はミラブル型シリコーンゴム組成物に関する。
The present invention relates to a millable type silicone rubber composition.
シリコーンゴムは主骨格がシロキサン結合からできており、通常の有機ゴムに比べて有機成分（炭化水素成分）の割合が低く、燃えにくい性質がある。しかしながら、直に炎に接するなどの過酷な条件下では、シリコーンゴムに引火し燃焼してしまう。上記の問題を解決するために、シリコーンゴム組成物に、難燃性付与剤として、白金化合物又は白金化合物とアルキニル基とアルコール性水酸基を有する化合物との反応物、及び、トリアゾール系化合物を配合することが知られている（特許文献１）。
The main skeleton of silicone rubber is made of siloxane bonds, and compared to ordinary organic rubber, it has a lower ratio of organic components (hydrocarbon components) and is resistant to combustion. However, under harsh conditions such as direct contact with flame, silicone rubber will ignite and burn. To solve the above problem, it is known to blend a platinum compound or a reaction product of a platinum compound with a compound having an alkynyl group and an alcoholic hydroxyl group, and a triazole-based compound as a flame retardant to the silicone rubber composition (Patent Document 1).
また、平均粒子径が０．１０～０．５０μｍの二酸化チタンをシリコーンゴム組成物に添加する方法（特許文献２）も提案されているが、いずれの場合も得られるシリコーンゴム硬化物の耐熱性が低下してしまう。
A method has also been proposed in which titanium dioxide with an average particle size of 0.10 to 0.50 μm is added to a silicone rubber composition (Patent Document 2), but in either case the heat resistance of the resulting cured silicone rubber is reduced.
シリコーンゴムの耐熱性を向上させるため、酸化セリウム、水酸化セリウム、酸化鉄、カーボンブラック等の添加剤をシリコーンゴム組成物に配合することは知られている。しかし、２５０℃以上の高温条件下でのシリコーンゴムの耐熱性は十分ではない。
It is known that additives such as cerium oxide, cerium hydroxide, iron oxide, and carbon black are blended into silicone rubber compositions to improve the heat resistance of silicone rubber. However, the heat resistance of silicone rubber under high temperature conditions of 250°C or higher is insufficient.
特許文献３には、シリコーンゴム組成物に０．１質量％以上の酸化チタンと酸化鉄（特には三酸化二鉄）を添加することでシリコーンゴムの耐熱性を向上させることが記載されているが、酸化鉄の影響で難燃性が低下してしまう。
Patent Document 3 describes how adding 0.1 mass % or more of titanium oxide and iron oxide (particularly diferric oxide) to a silicone rubber composition can improve the heat resistance of the silicone rubber, but the effect of the iron oxide reduces flame retardancy.
特許文献４には、シリコーンゴム組成物に含水酸化セリウムおよび／または含水酸化ジルコニウムを添加するとシリコーンゴムの耐熱性が向上することが記載されており、２２５℃の乾燥機に７２時間入れた後の物性を測定している。しかし、より高温での耐熱性は十分ではない。
Patent Document 4 describes that adding cerium oxide hydrate and/or zirconium oxide hydrate to a silicone rubber composition improves the heat resistance of the silicone rubber, and measures the physical properties after placing the composition in a dryer at 225°C for 72 hours. However, heat resistance at higher temperatures is insufficient.
特許文献５や特許文献６には、遷移金属などの金属イオン（金属塩）を酸化チタンにドープしたものが記載されている。しかし、金属イオン（金属塩）をドープした酸化チタンをシリコーンゴム組成物に添加する方法では高温の耐熱性は向上するが、難燃性が低下する。
Patent Document 5 and Patent Document 6 describe titanium oxide doped with metal ions (metal salts) of transition metals and the like. However, the method of adding titanium oxide doped with metal ions (metal salts) to a silicone rubber composition improves high-temperature heat resistance but reduces flame retardancy.
特許文献７には、黄色酸化鉄微粉末、好ましくはアルミン酸若しくはアルミン酸塩を固溶した黄色酸化鉄を配合した付加反応硬化型オルガノポリシロキサン組成物の記載がある。該組成物は付加反応により硬化して２８０℃以上の高温度領域において優れた耐熱性を有する硬化物を提供すると記載されている。しかし、黄色酸化鉄の添加により、難燃性が大きく低下してしまう。
Patent Document 7 describes an addition reaction curing organopolysiloxane composition containing yellow iron oxide fine powder, preferably yellow iron oxide solid-dissolved with aluminic acid or aluminate. It describes that the composition cures by addition reaction to provide a cured product with excellent heat resistance in the high temperature range of 280°C or higher. However, the addition of yellow iron oxide significantly reduces flame retardancy.
現在、シリコーンゴムの需要は益々高まっており、耐熱性に優れ、且つ優れた難燃性を有するシリコーンゴムの開発が望まれている。
Currently, the demand for silicone rubber is increasing, and there is a need to develop silicone rubber that has excellent heat resistance and flame retardancy.
したがって、本発明は、２００℃以上、特に３００℃という高温での耐熱性に優れ、且つ優れた難燃性を有するシリコーンゴム（硬化物）となるミラブル型シリコーンゴム組成物を提供することを目的とする。
The object of the present invention is therefore to provide a millable silicone rubber composition that produces a silicone rubber (cured product) that has excellent heat resistance at high temperatures of 200°C or higher, particularly 300°C, and also has excellent flame retardancy.
本発明者らは、上記目的を達成するために鋭意研究した結果、白金系化合物、酸化チタン、酸化セリウム及びマグネシウムフェライトをシリコーンゴム組成物に配合することにより、このシリコーンゴム組成物の硬化物が、難燃性に優れ、且つ高温での耐熱性に優れることを知見し、本発明をなすに至ったものである。
すなわち、本発明は、以下のようなミラブル型シリコーンゴム組成物を提供する。 As a result of intensive research conducted by the inventors in order to achieve the above-mentioned object, they discovered that by blending a platinum-based compound, titanium oxide, cerium oxide and magnesium ferrite into a silicone rubber composition, the cured product of this silicone rubber composition has excellent flame retardancy and excellent heat resistance at high temperatures, which led to the creation of the present invention.
That is, the present invention provides the following millable type silicone rubber composition.
すなわち、本発明は、以下のようなミラブル型シリコーンゴム組成物を提供する。 As a result of intensive research conducted by the inventors in order to achieve the above-mentioned object, they discovered that by blending a platinum-based compound, titanium oxide, cerium oxide and magnesium ferrite into a silicone rubber composition, the cured product of this silicone rubber composition has excellent flame retardancy and excellent heat resistance at high temperatures, which led to the creation of the present invention.
That is, the present invention provides the following millable type silicone rubber composition.
［１］
（Ａ）ケイ素原子に結合したアルケニル基を１分子中に２個以上有する、平均重合度が１００以上のオルガノポリシロキサン：１００質量部、
（Ｂ）ＢＥＴ法による比表面積が５０ｍ2／ｇ以上である補強性シリカ：５～１００質量部、
（Ｃ）白金系化合物：（Ａ）成分の合計質量に対し、０．５～１，０００ｐｐｍ、
（Ｄ）酸化セリウム及び水酸化セリウムから選ばれる１種以上：０．０１～１０質量部、
（Ｅ）ＢＥＴ法による比表面積が５～２００ｍ2／ｇのヒュームド酸化チタン：１．０～２０質量部、
（Ｆ）吸油量が２０～４０ｇ／１００ｇのマグネシウムフェライト：０．５～３０質量部、及び、
（Ｇ）有機過酸化物：０．１～１０質量部
を含有するミラブル型シリコーンゴム組成物。
［２］
（Ａ）成分が直鎖状オルガノポリシロキサンである、［１］に記載のミラブル型シリコーンゴム組成物。
［３］
（Ａ）成分が平均重合度１，０００～１００，０００を有する、［１］又は［２］に記載のミラブル型シリコーンゴム組成物。
［４］
（Ｇ）成分が、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｐ－メチルベンゾイルパーオキサイド又はｏ－メチルベンゾイルパーオキサイドである［１］～［３］のいずれか１項に記載のミラブル型シリコーンゴム組成物。
［５］
さらに（Ａ）成分１００質量部に対して（Ｈ）充填材用分散剤を０．１～５０質量部含有する、［１］～［４］のいずれか１項に記載のミラブル型シリコーンゴム組成物。
［６］
［１］～［５］のいずれか１項に記載のミラブル型シリコーンゴム組成物の硬化物。
[1]
(A) 100 parts by mass of an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in each molecule and having an average degree of polymerization of 100 or more,
(B) reinforcing silica having a specific surface area of 50 m 2 /g or more as measured by the BET method: 5 to 100 parts by mass,
(C) Platinum-based compound: 0.5 to 1,000 ppm based on the total mass of component (A),
(D) one or more selected from cerium oxide and cerium hydroxide: 0.01 to 10 parts by mass,
(E) fumed titanium oxide having a specific surface area measured by the BET method of 5 to 200 m 2 /g: 1.0 to 20 parts by mass,
(F) magnesium ferrite having an oil absorption of 20 to 40 g/100 g: 0.5 to 30 parts by mass, and
(G) A millable type silicone rubber composition containing an organic peroxide: 0.1 to 10 parts by mass.
[2]
The millable silicone rubber composition according to [1], wherein component (A) is a linear organopolysiloxane.
[3]
The millable type silicone rubber composition according to [1] or [2], wherein component (A) has an average degree of polymerization of 1,000 to 100,000.
[4]
The millable type silicone rubber composition according to any one of [1] to [3], wherein component (G) is benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide or o-methylbenzoyl peroxide.
[5]
The millable type silicone rubber composition according to any one of [1] to [4], further comprising 0.1 to 50 parts by mass of a dispersant for fillers (H) per 100 parts by mass of component (A).
[6]
A cured product of the millable type silicone rubber composition according to any one of [1] to [5].
（Ａ）ケイ素原子に結合したアルケニル基を１分子中に２個以上有する、平均重合度が１００以上のオルガノポリシロキサン：１００質量部、
（Ｂ）ＢＥＴ法による比表面積が５０ｍ2／ｇ以上である補強性シリカ：５～１００質量部、
（Ｃ）白金系化合物：（Ａ）成分の合計質量に対し、０．５～１，０００ｐｐｍ、
（Ｄ）酸化セリウム及び水酸化セリウムから選ばれる１種以上：０．０１～１０質量部、
（Ｅ）ＢＥＴ法による比表面積が５～２００ｍ2／ｇのヒュームド酸化チタン：１．０～２０質量部、
（Ｆ）吸油量が２０～４０ｇ／１００ｇのマグネシウムフェライト：０．５～３０質量部、及び、
（Ｇ）有機過酸化物：０．１～１０質量部
を含有するミラブル型シリコーンゴム組成物。
［２］
（Ａ）成分が直鎖状オルガノポリシロキサンである、［１］に記載のミラブル型シリコーンゴム組成物。
［３］
（Ａ）成分が平均重合度１，０００～１００，０００を有する、［１］又は［２］に記載のミラブル型シリコーンゴム組成物。
［４］
（Ｇ）成分が、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｐ－メチルベンゾイルパーオキサイド又はｏ－メチルベンゾイルパーオキサイドである［１］～［３］のいずれか１項に記載のミラブル型シリコーンゴム組成物。
［５］
さらに（Ａ）成分１００質量部に対して（Ｈ）充填材用分散剤を０．１～５０質量部含有する、［１］～［４］のいずれか１項に記載のミラブル型シリコーンゴム組成物。
［６］
［１］～［５］のいずれか１項に記載のミラブル型シリコーンゴム組成物の硬化物。
[1]
(A) 100 parts by mass of an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in each molecule and having an average degree of polymerization of 100 or more,
(B) reinforcing silica having a specific surface area of 50 m 2 /g or more as measured by the BET method: 5 to 100 parts by mass,
(C) Platinum-based compound: 0.5 to 1,000 ppm based on the total mass of component (A),
(D) one or more selected from cerium oxide and cerium hydroxide: 0.01 to 10 parts by mass,
(E) fumed titanium oxide having a specific surface area measured by the BET method of 5 to 200 m 2 /g: 1.0 to 20 parts by mass,
(F) magnesium ferrite having an oil absorption of 20 to 40 g/100 g: 0.5 to 30 parts by mass, and
(G) A millable type silicone rubber composition containing an organic peroxide: 0.1 to 10 parts by mass.
[2]
The millable silicone rubber composition according to [1], wherein component (A) is a linear organopolysiloxane.
[3]
The millable type silicone rubber composition according to [1] or [2], wherein component (A) has an average degree of polymerization of 1,000 to 100,000.
[4]
The millable type silicone rubber composition according to any one of [1] to [3], wherein component (G) is benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide or o-methylbenzoyl peroxide.
[5]
The millable type silicone rubber composition according to any one of [1] to [4], further comprising 0.1 to 50 parts by mass of a dispersant for fillers (H) per 100 parts by mass of component (A).
[6]
A cured product of the millable type silicone rubber composition according to any one of [1] to [5].
本発明のミラブル型シリコーンゴム組成物は、難燃性、耐熱性に優れたシリコーンゴムを提供することができる。すなわち、本発明のミラブル型シリコーンゴム組成物の硬化物（シリコーンゴム）は、２００℃以上、特に３００℃もの高温下で、優れた耐熱性を示す。また、該硬化物は、ＵＬ－９４試験法による燃焼試験におけるＶ－０と同程度の良好な難燃性を示す。
The millable silicone rubber composition of the present invention can provide silicone rubber with excellent flame retardancy and heat resistance. In other words, the cured product (silicone rubber) of the millable silicone rubber composition of the present invention exhibits excellent heat resistance at temperatures of 200°C or higher, particularly at high temperatures of 300°C. In addition, the cured product exhibits good flame retardancy equivalent to V-0 in a flame test according to the UL-94 test method.
本明細書中において、比表面積はＢＥＴ法により測定された値である。なお、ミラブル型組成物とは、室温（２５℃）において自己流動性のない高粘度で非液状の組成物であって、ロールミル（例えば、二本ロールや三本ロール）などの混練機で剪断応力下に均一に混練することが可能な組成物を意味する。
In this specification, the specific surface area is a value measured by the BET method. The millable composition refers to a highly viscous, non-liquid composition that does not have self-flowing properties at room temperature (25°C) and can be kneaded uniformly under shear stress using a kneading machine such as a roll mill (e.g., two-roll or three-roll).
［（Ａ）オルガノポリシロキサン］
（Ａ）成分は、本組成物の主剤（ベースポリマー）であるオルガノポリシロキサンであり、ケイ素原子に結合したアルケニル基を１分子中に２個以上有し、好ましくは、ケイ素原子に結合したアルケニル基を２～５０個有する。アルケニル基は分子鎖の両末端にそれぞれ１個以上有していることが好ましく、さらに分子鎖の側鎖にもアルケニル基を有していることが、より好ましい。 [(A) Organopolysiloxane]
Component (A) is an organopolysiloxane that is the main component (base polymer) of the composition, and has at least two alkenyl groups bonded to silicon atoms in each molecule, and preferably has from 2 to 50 alkenyl groups bonded to silicon atoms. It is preferable that there is at least one alkenyl group at each of the ends of the molecular chain, and it is even more preferable that there are alkenyl groups in the side chains of the molecular chain.
（Ａ）成分は、本組成物の主剤（ベースポリマー）であるオルガノポリシロキサンであり、ケイ素原子に結合したアルケニル基を１分子中に２個以上有し、好ましくは、ケイ素原子に結合したアルケニル基を２～５０個有する。アルケニル基は分子鎖の両末端にそれぞれ１個以上有していることが好ましく、さらに分子鎖の側鎖にもアルケニル基を有していることが、より好ましい。 [(A) Organopolysiloxane]
Component (A) is an organopolysiloxane that is the main component (base polymer) of the composition, and has at least two alkenyl groups bonded to silicon atoms in each molecule, and preferably has from 2 to 50 alkenyl groups bonded to silicon atoms. It is preferable that there is at least one alkenyl group at each of the ends of the molecular chain, and it is even more preferable that there are alkenyl groups in the side chains of the molecular chain.
（Ａ）成分は、平均重合度１００以上を有し、特に１，０００～１００，０００の範囲であることが好ましく、３，０００～５０，０００の範囲であることがより好ましく、４，０００～２０，０００の範囲であることが特に好ましい。平均重合度が１００未満では、本発明のミラブル型シリコーンゴム組成物がミラブルゴムとしての性状を満たさなくなり、ロール混練性等が著しく悪化してしまうため好ましくない。なお、この平均重合度は、下記条件で測定したＧＰＣ（ゲルパーミエーションクロマトグラフィ）分析におけるポリスチレン換算の重量平均分子量から、平均重合度として求められる。
Component (A) has an average degree of polymerization of 100 or more, preferably in the range of 1,000 to 100,000, more preferably in the range of 3,000 to 50,000, and particularly preferably in the range of 4,000 to 20,000. If the average degree of polymerization is less than 100, the millable silicone rubber composition of the present invention will no longer satisfy the properties required for millable rubber, and roll kneading properties and the like will be significantly deteriorated, which is not preferable. This average degree of polymerization is determined from the weight average molecular weight in terms of polystyrene in GPC (gel permeation chromatography) analysis measured under the following conditions.
［測定条件］
・展開溶媒：トルエン
・流量：１ｍＬ／ｍｉｎ
・検出器：示差屈折率検出器（ＲＩ）
・カラム：ＫＦ－８０５Ｌ×２本（Ｓｈｏｄｅｘ社製）
・カラム温度：２５℃
・試料注入量：３０μＬ（濃度０．２質量％のトルエン溶液） [Measurement condition]
Developing solvent: toluene Flow rate: 1 mL/min
Detector: Refractive index detector (RI)
Column: KF-805L x 2 (Shodex)
Column temperature: 25°C
Sample injection volume: 30 μL (toluene solution with a concentration of 0.2% by mass)
・展開溶媒：トルエン
・流量：１ｍＬ／ｍｉｎ
・検出器：示差屈折率検出器（ＲＩ）
・カラム：ＫＦ－８０５Ｌ×２本（Ｓｈｏｄｅｘ社製）
・カラム温度：２５℃
・試料注入量：３０μＬ（濃度０．２質量％のトルエン溶液） [Measurement condition]
Developing solvent: toluene Flow rate: 1 mL/min
Detector: Refractive index detector (RI)
Column: KF-805L x 2 (Shodex)
Column temperature: 25°C
Sample injection volume: 30 μL (toluene solution with a concentration of 0.2% by mass)
本発明において（Ａ）成分は、高重合度（高粘度）であって、室温（２５℃）において自己流動性のない非液状のオルガノポリシロキサン生ゴムであるのが好ましい。
In the present invention, component (A) is preferably a non-liquid organopolysiloxane gum that has a high degree of polymerization (high viscosity) and no self-flowing properties at room temperature (25°C).
該（Ａ）成分は、上記平均重合度を満たすアルケニル基含有オルガノポリシロキサンであればよい。
The (A) component may be any alkenyl-containing organopolysiloxane that satisfies the above average degree of polymerization.
上記アルケニル基としては、具体的には、ビニル基、アリル基、ブテニル基、ヘキセニル基等が挙げられる。好ましくは、炭素数２～８のアルケニル基であり、より好ましくはビニル基、またはアリル基であり、さらに好ましくはビニル基である。
Specific examples of the alkenyl group include vinyl, allyl, butenyl, and hexenyl groups. Alkenyl groups having 2 to 8 carbon atoms are preferred, vinyl or allyl groups are more preferred, and vinyl groups are even more preferred.
上記アルケニル基以外のケイ素原子に結合する置換基としては、炭素原子数１～１０、好ましくは１～８、より好ましくは１～６の１価炭化水素基である。該１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基等のアリール基、β－フェニルプロピル基等のアラルキル基等が挙げられる。なお、これらの基の炭素原子に結合した水素原子の一部若しくは全部がハロゲン原子で置換されていてもよく、例えば３，３，３－トリフルオロプロピル基等が挙げられる。これらの中では、メチル基フェニル基及びトリフルオロプロピル基が好ましく、より好ましくは、メチル基である。これらの中でも好ましくは、アルケニル基含有オルガノポリシロキサンの全置換基中、５０％以上がメチル基であり、より好ましくは８０％以上がメチル基であり、更に好ましくはアルケニル基以外の全ての置換基がメチル基であるのがよい。
The substituents bonded to silicon atoms other than the alkenyl groups are monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups such as β-phenylpropyl groups. Some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms, such as 3,3,3-trifluoropropyl groups. Of these, methyl groups, phenyl groups, and trifluoropropyl groups are preferred, and methyl groups are more preferred. Of these, it is preferred that 50% or more of the total substituents of the alkenyl-containing organopolysiloxane are methyl groups, more preferably 80% or more are methyl groups, and even more preferably that all of the substituents other than the alkenyl groups are methyl groups.
上記アルケニル基含有オルガノポリシロキサンは、直鎖状、または分岐状であることが好ましく、直鎖状であることがより好ましい。特に、主鎖がジオルガノシロキサン単位の繰り返しからなり、分子鎖両末端がトリオルガノシロキシ基で封鎖された、直鎖状のジオルガノポリシロキサンであることが好ましい。このような構造であれば、得られる硬化物は十分なゴム弾性を示す。分子鎖両末端が、トリメチルシロキシ基、ジメチルビニルシロキシ基、ジメチルヒドロキシシロキシ基、メチルジビニルシロキシ基、トリビニルシロキシ基等で封鎖されたものが好ましく、特に、１つ以上のビニル基を有するトリオルガノシロキシ基で封鎖されたものが好適である。これらのオルガノポリシロキサンは、１種単独で用いてもよく、重合度や分子構造の異なる２種以上を組み合わせて用いてもよい。
The alkenyl group-containing organopolysiloxane is preferably linear or branched, more preferably linear. In particular, it is preferably a linear diorganopolysiloxane whose main chain is composed of repeated diorganosiloxane units and whose molecular chain ends are blocked with triorganosiloxy groups. With such a structure, the resulting cured product exhibits sufficient rubber elasticity. It is preferable that both molecular chain ends are blocked with trimethylsiloxy groups, dimethylvinylsiloxy groups, dimethylhydroxysiloxy groups, methyldivinylsiloxy groups, trivinylsiloxy groups, etc., and in particular, it is preferable that the molecular chain ends are blocked with triorganosiloxy groups having one or more vinyl groups. These organopolysiloxanes may be used alone or in combination of two or more types having different degrees of polymerization or molecular structures.
本発明のミラブル型シリコーンゴム組成物中、（Ａ）成分の含有量は４３～９６質量％であることが好ましく、５０～９０質量％であることがより好ましく、６０～８０質量％であることがさらに好ましい。
In the millable silicone rubber composition of the present invention, the content of component (A) is preferably 43 to 96 mass%, more preferably 50 to 90 mass%, and even more preferably 60 to 80 mass%.
［（Ｂ）補強性シリカ］
（Ｂ）補強性シリカは、得られるシリコーンゴムに対して優れた機械的特性を付与する充填材である。該補強性シリカは、沈降シリカ（湿式シリカ）でもヒュームドシリカ（乾式シリカ）でもよく、表面に多数のシラノール（ヒドロキシシリル）基が存在しているものである。本発明において（Ｂ）補強性シリカは、ＢＥＴ法による比表面積５０ｍ2／ｇ以上を有することが必要である。比表面積の上限は特に制限されないが４００ｍ2／ｇ以下であればよく、好ましくは１００～４００ｍ2／ｇである。比表面積が５０ｍ2／ｇ未満であると、（Ｂ）成分により付与されるシリコーンゴムの補強効果が不十分となる場合がある。 [(B) Reinforcing Silica]
(B) reinforcing silica is a filler that imparts excellent mechanical properties to the resulting silicone rubber. The reinforcing silica may be precipitated silica (wet silica) or fumed silica (dry silica), and has a large number of silanol (hydroxysilyl) groups on its surface. (B) reinforcing silica in the present invention must have a specific surface area of 50 m 2 /g or more as measured by the BET method. There is no particular upper limit to the specific surface area, but it should be 400 m 2 /g or less, and is preferably 100 to 400 m 2 /g. If the specific surface area is less than 50 m 2 /g, the reinforcing effect of the silicone rubber imparted by component (B) may be insufficient.
（Ｂ）補強性シリカは、得られるシリコーンゴムに対して優れた機械的特性を付与する充填材である。該補強性シリカは、沈降シリカ（湿式シリカ）でもヒュームドシリカ（乾式シリカ）でもよく、表面に多数のシラノール（ヒドロキシシリル）基が存在しているものである。本発明において（Ｂ）補強性シリカは、ＢＥＴ法による比表面積５０ｍ2／ｇ以上を有することが必要である。比表面積の上限は特に制限されないが４００ｍ2／ｇ以下であればよく、好ましくは１００～４００ｍ2／ｇである。比表面積が５０ｍ2／ｇ未満であると、（Ｂ）成分により付与されるシリコーンゴムの補強効果が不十分となる場合がある。 [(B) Reinforcing Silica]
(B) reinforcing silica is a filler that imparts excellent mechanical properties to the resulting silicone rubber. The reinforcing silica may be precipitated silica (wet silica) or fumed silica (dry silica), and has a large number of silanol (hydroxysilyl) groups on its surface. (B) reinforcing silica in the present invention must have a specific surface area of 50 m 2 /g or more as measured by the BET method. There is no particular upper limit to the specific surface area, but it should be 400 m 2 /g or less, and is preferably 100 to 400 m 2 /g. If the specific surface area is less than 50 m 2 /g, the reinforcing effect of the silicone rubber imparted by component (B) may be insufficient.
（Ｂ）補強性シリカは、未処理の状態で使用しても、必要に応じて、オルガノポリシロキサン、オルガノポリシラザン、クロロシラン、アルコキシシラン等の有機ケイ素化合物（表面処理剤）で表面処理した補強性表面処理シリカであってもよい。また、補強性表面処理シリカは、１種類の表面処理剤で処理されてもよいし、２種以上の表面処理剤で処理されてもかまわない。なお、この有機ケイ素化合物（表面処理剤）は、後述の（Ｈ）充填材用分散剤とは、１分子中にシラノール基を有さないという点で異なるものである。（Ｂ）成分の補強性シリカは、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The reinforcing silica (B) may be used in an untreated state, or may be a reinforcing surface-treated silica that has been surface-treated with an organosilicon compound (surface treatment agent) such as organopolysiloxane, organopolysilazane, chlorosilane, or alkoxysilane, as necessary. The reinforcing surface-treated silica may be treated with one type of surface treatment agent, or may be treated with two or more types of surface treatment agents. This organosilicon compound (surface treatment agent) differs from the dispersant for fillers (H) described below in that it does not have a silanol group in one molecule. The reinforcing silica of component (B) may be used alone or in combination of two or more types.
（Ｂ）補強性シリカの配合量は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して５～１００質量部であり、好ましくは１０～８０質量部、より好ましくは２０～７０質量部である。（Ｂ）成分の配合量が（Ａ）成分１００質量部に対して、５質量部未満又は１００質量部超では、得られるミラブル型シリコーンゴム組成物の加工性が低下するだけでなく、該シリコーンゴム組成物を硬化して得られるシリコーンゴム硬化物の引張り強度や引き裂き強度等の機械的特性が不十分なものとなる場合がある。
The amount of reinforcing silica (B) is 5 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 70 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If the amount of component (B) is less than 5 parts by mass or more than 100 parts by mass per 100 parts by mass of component (A), not only will the processability of the resulting millable silicone rubber composition decrease, but the mechanical properties of the silicone rubber cured product obtained by curing the silicone rubber composition, such as tensile strength and tear strength, may become insufficient.
［（Ｃ）白金系化合物］
（Ｃ）成分の白金系化合物としては、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系化合物が挙げられる。 [(C) Platinum-based compounds]
Examples of the platinum-based compound of component (C) include platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate.
（Ｃ）成分の白金系化合物としては、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系化合物が挙げられる。 [(C) Platinum-based compounds]
Examples of the platinum-based compound of component (C) include platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate.
なお、この白金系化合物の配合量は、白金（質量換算）として、（Ａ）成分の量に対し、０．５～１，０００ｐｐｍであり、特に１～５００ｐｐｍである。０．５ｐｐｍより少ないと難燃性が不十分であり、１，０００ｐｐｍより多いと、経済的でなく、また、難燃性が低下する場合がある。
The amount of platinum-based compound is 0.5 to 1,000 ppm, particularly 1 to 500 ppm, of platinum (by mass) relative to the amount of component (A). If it is less than 0.5 ppm, the flame retardancy is insufficient, and if it is more than 1,000 ppm, it is not economical and the flame retardancy may decrease.
［（Ｄ）酸化セリウム及び／又は水酸化セリウム］
（Ｄ）成分は、酸化セリウム及び水酸化セリウムから選ばれる１種以上のセリウム化合物である。いずれも、後述する（Ｆ）マグネシウムフェライトと併用すると、シリコーンゴムの耐熱性が著しく向上する。 [(D) Cerium oxide and/or cerium hydroxide]
Component (D) is one or more cerium compounds selected from cerium oxide and cerium hydroxide. When used in combination with magnesium ferrite (F), which will be described later, either of these compounds significantly improves the heat resistance of the silicone rubber.
（Ｄ）成分は、酸化セリウム及び水酸化セリウムから選ばれる１種以上のセリウム化合物である。いずれも、後述する（Ｆ）マグネシウムフェライトと併用すると、シリコーンゴムの耐熱性が著しく向上する。 [(D) Cerium oxide and/or cerium hydroxide]
Component (D) is one or more cerium compounds selected from cerium oxide and cerium hydroxide. When used in combination with magnesium ferrite (F), which will be described later, either of these compounds significantly improves the heat resistance of the silicone rubber.
酸化セリウムの市販品としては、ショウロックスＦＬ－２（昭和電工株式会社製）、ＳＮ－２（ニッキ株式会社製）、酸化セリウムＳ（阿南化成株式会社製）等が挙げられる。
水酸化セリウムの市販品としては、水酸化セリウム（ニッキ株式会社製）、Ｃｅｒｈｙｄｒａｔｅ９０（トライバッハ インダストリ エージー社製）等が挙げられる。 Commercially available cerium oxide products include Showrox FL-2 (manufactured by Showa Denko K.K.), SN-2 (manufactured by Nikki Co., Ltd.), and Cerium Oxide S (manufactured by Anan Kasei Co., Ltd.).
Commercially available cerium hydroxide products include cerium hydroxide (manufactured by Nikki Co., Ltd.) and Cerhydrate 90 (manufactured by Treibach Industrie AG).
水酸化セリウムの市販品としては、水酸化セリウム（ニッキ株式会社製）、Ｃｅｒｈｙｄｒａｔｅ９０（トライバッハ インダストリ エージー社製）等が挙げられる。 Commercially available cerium oxide products include Showrox FL-2 (manufactured by Showa Denko K.K.), SN-2 (manufactured by Nikki Co., Ltd.), and Cerium Oxide S (manufactured by Anan Kasei Co., Ltd.).
Commercially available cerium hydroxide products include cerium hydroxide (manufactured by Nikki Co., Ltd.) and Cerhydrate 90 (manufactured by Treibach Industrie AG).
（Ｄ）成分の添加量は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して０．０１～１０質量部であり、好ましくは０．１～５質量部である。（Ａ）成分１００質量部に対して、０．０１未満では、シリコーンゴムの耐熱性が向上せず、１０質量部超を添加すると、シリコーンゴムの機械特性が著しく低下するおそれがある。なお、酸化セリウム及び水酸化セリウムは、それぞれ、１種単独で用いてもよく、２種以上を併用してもよい。中でも酸化セリウム単独で用いることが好ましい。なお、酸化セリウム及び水酸化セリウムを併用する場合は、その総量が上記範囲を満たせばよい。
The amount of component (D) added is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If the amount is less than 0.01 per 100 parts by mass of component (A), the heat resistance of the silicone rubber will not improve, and if more than 10 parts by mass is added, the mechanical properties of the silicone rubber may be significantly reduced. Cerium oxide and cerium hydroxide may each be used alone or in combination of two or more types. Of these, it is preferable to use cerium oxide alone. If cerium oxide and cerium hydroxide are used in combination, the total amount should be within the above range.
［（Ｅ）ヒュームド酸化チタン］
（Ｅ）ヒュームド酸化チタンは、乾式法で作られた酸化チタンであって、ＢＥＴ法による比表面積が５～２００ｍ2／ｇであり、好ましくは２０～１００ｍ2／ｇである。また、結晶構造はルチル型でもアナターゼ型でもよく、これら２種が混在していてもよい。
（Ｅ）成分の添加量は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して、１．０～２０質量部であり、好ましくは３．０～１０質量部である。
（Ａ）成分１００質量部に対して、１．０質量部未満では、シリコーンゴムの難燃性が向上せず、２０質量部超を添加すると、シリコーンゴムの機械特性が著しく低下するおそれがある。 [(E) Fumed titanium oxide]
(E) Fumed titanium oxide is titanium oxide produced by a dry method, and has a specific surface area measured by the BET method of 5 to 200 m2 /g, preferably 20 to 100 m2 /g. The crystal structure may be either rutile or anatase, or the two may be mixed.
The amount of component (E) added is 1.0 to 20 parts by weight, and preferably 3.0 to 10 parts by weight, per 100 parts by weight of the organopolysiloxane of component (A).
If the amount is less than 1.0 part by mass per 100 parts by mass of component (A), the flame retardancy of the silicone rubber will not improve, whereas if more than 20 parts by mass is added, the mechanical properties of the silicone rubber may decrease significantly.
（Ｅ）ヒュームド酸化チタンは、乾式法で作られた酸化チタンであって、ＢＥＴ法による比表面積が５～２００ｍ2／ｇであり、好ましくは２０～１００ｍ2／ｇである。また、結晶構造はルチル型でもアナターゼ型でもよく、これら２種が混在していてもよい。
（Ｅ）成分の添加量は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して、１．０～２０質量部であり、好ましくは３．０～１０質量部である。
（Ａ）成分１００質量部に対して、１．０質量部未満では、シリコーンゴムの難燃性が向上せず、２０質量部超を添加すると、シリコーンゴムの機械特性が著しく低下するおそれがある。 [(E) Fumed titanium oxide]
(E) Fumed titanium oxide is titanium oxide produced by a dry method, and has a specific surface area measured by the BET method of 5 to 200 m2 /g, preferably 20 to 100 m2 /g. The crystal structure may be either rutile or anatase, or the two may be mixed.
The amount of component (E) added is 1.0 to 20 parts by weight, and preferably 3.0 to 10 parts by weight, per 100 parts by weight of the organopolysiloxane of component (A).
If the amount is less than 1.0 part by mass per 100 parts by mass of component (A), the flame retardancy of the silicone rubber will not improve, whereas if more than 20 parts by mass is added, the mechanical properties of the silicone rubber may decrease significantly.
［（Ｆ）マグネシウムフェライト］
（Ｆ）マグネシウムフェライトは、練り合わせ法による吸油量が２０～４０ｇ／１００ｇのものである。（Ｆ）成分の添加量は（Ａ）成分のオルガノポリシロキサン１００質量部に対して、０．５～３０質量部であり、好ましくは１．０～２０質量部である。（Ａ）成分１００質量部に対して、０．５質量部未満では、シリコーンゴムの耐熱性が向上せず、３０質量部超を添加すると、シリコーンゴムの機械特性（例えば、切断時伸び（％））が著しく低下するおそれがある。なお、三酸化二鉄や黄色酸化鉄は、難燃性が悪化するため好ましくない。
マグネシウムフェライトの市販品としては、ＴＡＲＯＸ Ｔ－２０、チタン工業（株）製等が挙げられる。 [(F) Magnesium ferrite]
The (F) magnesium ferrite has an oil absorption of 20 to 40 g/100 g as measured by a kneading method. The amount of component (F) added is 0.5 to 30 parts by mass, and preferably 1.0 to 20 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If less than 0.5 parts by mass is added per 100 parts by mass of component (A), the heat resistance of the silicone rubber will not improve, and if more than 30 parts by mass is added, the mechanical properties (e.g., elongation at break (%)) of the silicone rubber may be significantly reduced. Note that diiron trioxide and yellow iron oxide are not preferred as they deteriorate the flame retardancy.
Commercially available magnesium ferrite products include TAROX T-20 manufactured by Titan Kogyo Co., Ltd.
（Ｆ）マグネシウムフェライトは、練り合わせ法による吸油量が２０～４０ｇ／１００ｇのものである。（Ｆ）成分の添加量は（Ａ）成分のオルガノポリシロキサン１００質量部に対して、０．５～３０質量部であり、好ましくは１．０～２０質量部である。（Ａ）成分１００質量部に対して、０．５質量部未満では、シリコーンゴムの耐熱性が向上せず、３０質量部超を添加すると、シリコーンゴムの機械特性（例えば、切断時伸び（％））が著しく低下するおそれがある。なお、三酸化二鉄や黄色酸化鉄は、難燃性が悪化するため好ましくない。
マグネシウムフェライトの市販品としては、ＴＡＲＯＸ Ｔ－２０、チタン工業（株）製等が挙げられる。 [(F) Magnesium ferrite]
The (F) magnesium ferrite has an oil absorption of 20 to 40 g/100 g as measured by a kneading method. The amount of component (F) added is 0.5 to 30 parts by mass, and preferably 1.0 to 20 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If less than 0.5 parts by mass is added per 100 parts by mass of component (A), the heat resistance of the silicone rubber will not improve, and if more than 30 parts by mass is added, the mechanical properties (e.g., elongation at break (%)) of the silicone rubber may be significantly reduced. Note that diiron trioxide and yellow iron oxide are not preferred as they deteriorate the flame retardancy.
Commercially available magnesium ferrite products include TAROX T-20 manufactured by Titan Kogyo Co., Ltd.
［（Ｇ）有機過酸化物］
（Ｇ）有機過酸化物は、本発明のミラブル型シリコーンゴム組成物を硬化させ得る硬化剤である。 [(G) Organic Peroxide]
(G) The organic peroxide is a curing agent capable of curing the millable type silicone rubber composition of the present invention.
（Ｇ）有機過酸化物は、本発明のミラブル型シリコーンゴム組成物を硬化させ得る硬化剤である。 [(G) Organic Peroxide]
(G) The organic peroxide is a curing agent capable of curing the millable type silicone rubber composition of the present invention.
有機過酸化物としては、例えば、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｐ－メチルベンゾイルパーオキサイド、ｏ－メチルベンゾイルパーオキサイド、２，４－ジクミルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルパーベンゾエート、１，６－ヘキサンジオール－ビス－ｔ－ブチルパーオキシカーボネート等が挙げられる。
有機過酸化物の配合量は（Ａ）成分１００質量部に対して０．１～１０質量部であり、０．２～５質量部が好ましい。配合量が（Ａ）成分１００質量部に対して、０．１質量部未満では、硬化が不十分となる場合があり、１０質量部超を添加すると、有機過酸化物の分解残渣によりシリコーンゴム硬化物が変色する場合がある。 Examples of organic peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-butyl peroxide, t-butyl perbenzoate, and 1,6-hexanediol-bis-t-butylperoxycarbonate.
The amount of organic peroxide to be added is 0.1 to 10 parts by mass, and preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (A). If the amount added is less than 0.1 part by mass per 100 parts by mass of component (A), curing may be insufficient, while if more than 10 parts by mass is added, the decomposition residue of the organic peroxide may cause discoloration of the cured silicone rubber.
有機過酸化物の配合量は（Ａ）成分１００質量部に対して０．１～１０質量部であり、０．２～５質量部が好ましい。配合量が（Ａ）成分１００質量部に対して、０．１質量部未満では、硬化が不十分となる場合があり、１０質量部超を添加すると、有機過酸化物の分解残渣によりシリコーンゴム硬化物が変色する場合がある。 Examples of organic peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-butyl peroxide, t-butyl perbenzoate, and 1,6-hexanediol-bis-t-butylperoxycarbonate.
The amount of organic peroxide to be added is 0.1 to 10 parts by mass, and preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (A). If the amount added is less than 0.1 part by mass per 100 parts by mass of component (A), curing may be insufficient, while if more than 10 parts by mass is added, the decomposition residue of the organic peroxide may cause discoloration of the cured silicone rubber.
［（Ｈ）充填材用分散剤］
本発明のミラブル型シリコーンゴム組成物は、前記（Ａ）～（Ｇ）成分に加えて、充填材用分散剤、特には無機充填材又はシリカ用の分散剤をさらに含んでもよく、好ましくはシリカ用分散剤である。当該分散剤を更に含むことで上述した補強性シリカを組成物中に良好に分散することができる。当該分散剤としては、１分子中にシラノール基を１個以上有することを特徴とし、例えば、シラノール基及びアルコキシ基等を有する低分子有機ケイ素化合物及びその加水分解物が挙げられる。より詳細には、各種アルコキシシラン、特にフェニル基含有アルコキシシランの加水分解物、ジフェニルシランジオール、シラノール基含有カーボンファンクショナルシラン、シラノール基含有低分子シロキサン（例えば、両末端シラノール基封鎖オルガノポリシロキサン）等が挙げられる。中でも、ジフェニルシランジオールを用いると、シリコーンゴムの耐熱性がさらに向上するため好ましい。また、ジフェニルシランジオールをアルキルアルコキシシランまたはその加水分解物と併用することで、補強性シリカの分散性がさらに向上するため、より好ましい。なお、上述した通り、（Ｈ）成分は、前記（Ｂ）補強性シリカを表面処理するための有機ケイ素化合物とは、１分子中にシラノール基を１個以上有するという点で異なる。 [(H) Dispersant for Filler]
In addition to the components (A) to (G), the millable silicone rubber composition of the present invention may further contain a dispersant for fillers, particularly a dispersant for inorganic fillers or silica, and is preferably a dispersant for silica. By further containing the dispersant, the reinforcing silica described above can be well dispersed in the composition. The dispersant is characterized by having one or more silanol groups in one molecule, and examples thereof include low molecular weight organosilicon compounds having silanol groups and alkoxy groups, and hydrolysates thereof. More specifically, examples include various alkoxysilanes, particularly hydrolysates of alkoxysilanes containing phenyl groups, diphenylsilanediol, silanol group-containing carbon functional silanes, and silanol group-containing low molecular weight siloxanes (e.g., organopolysiloxanes blocked with silanol groups at both ends). Among them, diphenylsilanediol is preferred because it further improves the heat resistance of the silicone rubber. In addition, it is more preferred to use diphenylsilanediol in combination with an alkylalkoxysilane or its hydrolysate, because it further improves the dispersibility of the reinforcing silica. As described above, component (H) differs from the organosilicon compound for surface treating the reinforcing silica (B) in that component (H) has one or more silanol groups in each molecule.
本発明のミラブル型シリコーンゴム組成物は、前記（Ａ）～（Ｇ）成分に加えて、充填材用分散剤、特には無機充填材又はシリカ用の分散剤をさらに含んでもよく、好ましくはシリカ用分散剤である。当該分散剤を更に含むことで上述した補強性シリカを組成物中に良好に分散することができる。当該分散剤としては、１分子中にシラノール基を１個以上有することを特徴とし、例えば、シラノール基及びアルコキシ基等を有する低分子有機ケイ素化合物及びその加水分解物が挙げられる。より詳細には、各種アルコキシシラン、特にフェニル基含有アルコキシシランの加水分解物、ジフェニルシランジオール、シラノール基含有カーボンファンクショナルシラン、シラノール基含有低分子シロキサン（例えば、両末端シラノール基封鎖オルガノポリシロキサン）等が挙げられる。中でも、ジフェニルシランジオールを用いると、シリコーンゴムの耐熱性がさらに向上するため好ましい。また、ジフェニルシランジオールをアルキルアルコキシシランまたはその加水分解物と併用することで、補強性シリカの分散性がさらに向上するため、より好ましい。なお、上述した通り、（Ｈ）成分は、前記（Ｂ）補強性シリカを表面処理するための有機ケイ素化合物とは、１分子中にシラノール基を１個以上有するという点で異なる。 [(H) Dispersant for Filler]
In addition to the components (A) to (G), the millable silicone rubber composition of the present invention may further contain a dispersant for fillers, particularly a dispersant for inorganic fillers or silica, and is preferably a dispersant for silica. By further containing the dispersant, the reinforcing silica described above can be well dispersed in the composition. The dispersant is characterized by having one or more silanol groups in one molecule, and examples thereof include low molecular weight organosilicon compounds having silanol groups and alkoxy groups, and hydrolysates thereof. More specifically, examples include various alkoxysilanes, particularly hydrolysates of alkoxysilanes containing phenyl groups, diphenylsilanediol, silanol group-containing carbon functional silanes, and silanol group-containing low molecular weight siloxanes (e.g., organopolysiloxanes blocked with silanol groups at both ends). Among them, diphenylsilanediol is preferred because it further improves the heat resistance of the silicone rubber. In addition, it is more preferred to use diphenylsilanediol in combination with an alkylalkoxysilane or its hydrolysate, because it further improves the dispersibility of the reinforcing silica. As described above, component (H) differs from the organosilicon compound for surface treating the reinforcing silica (B) in that component (H) has one or more silanol groups in each molecule.
（Ｈ）成分の配合量は、上記（Ａ）成分１００質量部に対して０．１～５０質量部が好ましく、特に１～２０質量部が好ましい。（Ｈ）成分の配合量が少なすぎると、添加した効果が見られず、多すぎると組成物の可塑度が低くなりすぎ、ロールミル等の混練手段においてロール粘着が発生してロール作業性が悪化することがある。
The amount of component (H) is preferably 0.1 to 50 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of component (A). If the amount of component (H) is too small, the effect of adding it will not be seen, and if the amount is too large, the plasticity of the composition will be too low, and roll adhesion will occur in kneading means such as a roll mill, which may deteriorate roll workability.
［その他の成分］
本発明で用いるミラブル型シリコーンゴム組成物には、本発明の効果を損なわない範囲において、上記成分に加え、必要に応じて、その他の、熱硬化型シリコーンゴム組成物における公知の充填材及び添加剤を含んでよい。例えば、（Ｂ）成分及び（Ｈ）成分以外の充填材（粉砕石英、珪藻土、炭酸カルシウム等）、着色剤（顔料）、引き裂き強度向上剤、難燃性向上剤、受酸剤、熱伝導率向上剤（アルミナ、窒化硼素等）、離型剤等が挙げられる。その他の成分は１種単独で用いてもよく、２種以上を併用してもよい。また配合量は、本発明の効果を損ねない範囲において適宜調整されればよい。 [Other ingredients]
In addition to the above components, the millable silicone rubber composition used in the present invention may contain other known fillers and additives in heat-curable silicone rubber compositions as necessary, within the scope of not impairing the effects of the present invention. For example, fillers other than the (B) component and the (H) component (crushed quartz, diatomaceous earth, calcium carbonate, etc.), colorants (pigments), tear strength improvers, flame retardant improvers, acid acceptors, thermal conductivity improvers (alumina, boron nitride, etc.), release agents, etc. may be mentioned. The other components may be used alone or in combination of two or more. The blending amount may be appropriately adjusted within the scope of not impairing the effects of the present invention.
本発明で用いるミラブル型シリコーンゴム組成物には、本発明の効果を損なわない範囲において、上記成分に加え、必要に応じて、その他の、熱硬化型シリコーンゴム組成物における公知の充填材及び添加剤を含んでよい。例えば、（Ｂ）成分及び（Ｈ）成分以外の充填材（粉砕石英、珪藻土、炭酸カルシウム等）、着色剤（顔料）、引き裂き強度向上剤、難燃性向上剤、受酸剤、熱伝導率向上剤（アルミナ、窒化硼素等）、離型剤等が挙げられる。その他の成分は１種単独で用いてもよく、２種以上を併用してもよい。また配合量は、本発明の効果を損ねない範囲において適宜調整されればよい。 [Other ingredients]
In addition to the above components, the millable silicone rubber composition used in the present invention may contain other known fillers and additives in heat-curable silicone rubber compositions as necessary, within the scope of not impairing the effects of the present invention. For example, fillers other than the (B) component and the (H) component (crushed quartz, diatomaceous earth, calcium carbonate, etc.), colorants (pigments), tear strength improvers, flame retardant improvers, acid acceptors, thermal conductivity improvers (alumina, boron nitride, etc.), release agents, etc. may be mentioned. The other components may be used alone or in combination of two or more. The blending amount may be appropriately adjusted within the scope of not impairing the effects of the present invention.
組成物の製造方法
本発明のミラブル型シリコーンゴム組成物は、上述した各成分をニーダー、バンバリーミキサー、二本ロール等の公知の混練機で混合することにより得ることができる。たとえば、上記（Ａ）～（Ｇ）成分を含有する組成物を調製する場合、（Ａ）オルガノポリシロキサンと（Ｂ）補強性シリカと（Ｃ）白金系化合物と（Ｄ）酸化セリウム又は水酸化セリウムと（Ｅ）酸化チタンと（Ｆ）マグネシウムフェライトを混合した後、得られた混合物に（Ｇ）有機過酸化物を添加することが好ましい。また、その他の成分を含む場合には、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、（Ｅ）成分及び（Ｆ）成分と、その他の成分とを混合した後、得られた混合物に（Ｇ）有機過酸化物を添加することが好ましい。更に、（Ｈ）成分を含む場合、（Ａ）成分と（Ｂ）成分と（Ｈ）成分との混合物を調製し、該混合物と、（Ｃ）成分、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分、必要に応じてその他の成分とを混合した後、得られた混合物に（Ｇ）成分を添加することが好ましい。 Manufacturing method of the composition The millable type silicone rubber composition of the present invention can be obtained by mixing the above-mentioned components with a known kneading machine such as a kneader, a Banbury mixer, or a two-roll mill. For example, when preparing a composition containing the above-mentioned components (A) to (G), it is preferable to mix (A) organopolysiloxane, (B) reinforcing silica, (C) platinum compound, (D) cerium oxide or cerium hydroxide, (E) titanium oxide, and (F) magnesium ferrite, and then add (G) organic peroxide to the resulting mixture. In addition, when other components are included, it is preferable to mix (A), (B), (C), (D), (E), and (F) with the other components, and then add (G) organic peroxide to the resulting mixture. Furthermore, when component (H) is contained, it is preferable to prepare a mixture of components (A), (B), and (H), mix the mixture with components (C), (D), (E), and (F), and, if necessary, other components, and then add component (G) to the mixture obtained.
本発明のミラブル型シリコーンゴム組成物は、上述した各成分をニーダー、バンバリーミキサー、二本ロール等の公知の混練機で混合することにより得ることができる。たとえば、上記（Ａ）～（Ｇ）成分を含有する組成物を調製する場合、（Ａ）オルガノポリシロキサンと（Ｂ）補強性シリカと（Ｃ）白金系化合物と（Ｄ）酸化セリウム又は水酸化セリウムと（Ｅ）酸化チタンと（Ｆ）マグネシウムフェライトを混合した後、得られた混合物に（Ｇ）有機過酸化物を添加することが好ましい。また、その他の成分を含む場合には、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、（Ｅ）成分及び（Ｆ）成分と、その他の成分とを混合した後、得られた混合物に（Ｇ）有機過酸化物を添加することが好ましい。更に、（Ｈ）成分を含む場合、（Ａ）成分と（Ｂ）成分と（Ｈ）成分との混合物を調製し、該混合物と、（Ｃ）成分、（Ｄ）成分、（Ｅ）成分、（Ｆ）成分、必要に応じてその他の成分とを混合した後、得られた混合物に（Ｇ）成分を添加することが好ましい。 Manufacturing method of the composition The millable type silicone rubber composition of the present invention can be obtained by mixing the above-mentioned components with a known kneading machine such as a kneader, a Banbury mixer, or a two-roll mill. For example, when preparing a composition containing the above-mentioned components (A) to (G), it is preferable to mix (A) organopolysiloxane, (B) reinforcing silica, (C) platinum compound, (D) cerium oxide or cerium hydroxide, (E) titanium oxide, and (F) magnesium ferrite, and then add (G) organic peroxide to the resulting mixture. In addition, when other components are included, it is preferable to mix (A), (B), (C), (D), (E), and (F) with the other components, and then add (G) organic peroxide to the resulting mixture. Furthermore, when component (H) is contained, it is preferable to prepare a mixture of components (A), (B), and (H), mix the mixture with components (C), (D), (E), and (F), and, if necessary, other components, and then add component (G) to the mixture obtained.
ミラブル型シリコーンゴム組成物は、目的とする成形品の形状及び大きさにあわせて公知の成形方法により成形されればよい。成形方法としては、例えば、注入成形、圧縮成形、射出成形、カレンダー成形、及び押出成形などが挙げられる。
The millable silicone rubber composition may be molded by a known molding method according to the shape and size of the desired molded product. Examples of molding methods include casting, compression molding, injection molding, calendar molding, and extrusion molding.
硬化物
ミラブル型シリコーンゴム組成物の硬化条件は、用いる成形方法における公知の条件でよく、ミラブル型シリコーンゴム組成物を一般的に６０～４５０℃の温度で数秒～１日程度加熱する。また、得られる硬化物の圧縮永久歪の低下、得られるシリコーンゴム中に残存している低分子シロキサン成分の低減、該シリコーンゴム中の有機過酸化物の分解物の除去等の目的で、２００℃以上、好ましくは２００～２５０℃のオーブン内等で１時間以上、好ましくは１～７０時間程度、より好ましくは１～１０時間のポストキュア（２次キュア）を行ってもよい。 The curing conditions for the millable silicone rubber composition may be those known for the molding method used, and the millable silicone rubber composition is generally heated for a period of several seconds to a day at a temperature of 60 to 450° C. In addition, for the purposes of lowering the compression set of the obtained cured product, reducing the low molecular weight siloxane components remaining in the obtained silicone rubber, and removing decomposition products of organic peroxides in the silicone rubber, a post cure (secondary cure) may be performed in an oven at 200° C. or higher, preferably 200 to 250° C., for 1 hour or more, preferably 1 to 70 hours, and more preferably 1 to 10 hours.
ミラブル型シリコーンゴム組成物の硬化条件は、用いる成形方法における公知の条件でよく、ミラブル型シリコーンゴム組成物を一般的に６０～４５０℃の温度で数秒～１日程度加熱する。また、得られる硬化物の圧縮永久歪の低下、得られるシリコーンゴム中に残存している低分子シロキサン成分の低減、該シリコーンゴム中の有機過酸化物の分解物の除去等の目的で、２００℃以上、好ましくは２００～２５０℃のオーブン内等で１時間以上、好ましくは１～７０時間程度、より好ましくは１～１０時間のポストキュア（２次キュア）を行ってもよい。 The curing conditions for the millable silicone rubber composition may be those known for the molding method used, and the millable silicone rubber composition is generally heated for a period of several seconds to a day at a temperature of 60 to 450° C. In addition, for the purposes of lowering the compression set of the obtained cured product, reducing the low molecular weight siloxane components remaining in the obtained silicone rubber, and removing decomposition products of organic peroxides in the silicone rubber, a post cure (secondary cure) may be performed in an oven at 200° C. or higher, preferably 200 to 250° C., for 1 hour or more, preferably 1 to 70 hours, and more preferably 1 to 10 hours.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記の実施例に制限されるものではない。
The present invention will be explained in more detail below with examples and comparative examples, but the present invention is not limited to the following examples.
実施例及び比較例において耐熱性試験、難燃性試験は下記に従い行った。
［耐熱性］
ミラブル型シリコーンゴム組成物を硬化して作製した試験用シートを用い、ＪＩＳ Ｋ ６２４９：２００３に準拠して硬さ（デュロメーターＡ）、及び切断時伸び（％）の初期値を測定した。該試験用シートを３００℃の乾燥機に３日間入れた後に、硬さ、切断時伸びを測定した。結果を表１に示す。
［難燃性］
ミラブル型シリコーンゴム組成物を硬化して作製した試験用シートを用い、ＵＬ９４の２０ｍｍ垂直燃焼試験に規定する方法に従って、５枚の１ｍｍ厚のシリコーンゴムシートを用い、残炎時期間Ｔ１及びＴ２、並びに、全ての処理による各組の残炎時間の合計（５枚のシリコーンゴムシートのＴ１＋Ｔ２の合計）を測定した。Ｔ１とは第１回接炎後の残炎時間、Ｔ２とは第２回接炎後の残炎時間を表す。
結果を表１に示す。
In the examples and comparative examples, heat resistance tests and flame retardancy tests were carried out as follows.
[Heat-resistant]
Using a test sheet prepared by curing the millable type silicone rubber composition, the hardness (Durometer A) and initial value of elongation at break (%) were measured according to JIS K 6249: 2003. The test sheet was placed in a dryer at 300°C for 3 days, after which the hardness and elongation at break were measured. The results are shown in Table 1.
[Flame retardance]
Using test sheets prepared by curing the millable type silicone rubber composition, five 1 mm thick silicone rubber sheets were used according to the method specified in the UL94 20 mm vertical flame test to measure the afterflame time periods T1 and T2, as well as the total afterflame time for each set of all treatments (the total of T1+T2 for the five silicone rubber sheets). T1 represents the afterflame time after the first contact with the flame, and T2 represents the afterflame time after the second contact with the flame.
The results are shown in Table 1.
［耐熱性］
ミラブル型シリコーンゴム組成物を硬化して作製した試験用シートを用い、ＪＩＳ Ｋ ６２４９：２００３に準拠して硬さ（デュロメーターＡ）、及び切断時伸び（％）の初期値を測定した。該試験用シートを３００℃の乾燥機に３日間入れた後に、硬さ、切断時伸びを測定した。結果を表１に示す。
［難燃性］
ミラブル型シリコーンゴム組成物を硬化して作製した試験用シートを用い、ＵＬ９４の２０ｍｍ垂直燃焼試験に規定する方法に従って、５枚の１ｍｍ厚のシリコーンゴムシートを用い、残炎時期間Ｔ１及びＴ２、並びに、全ての処理による各組の残炎時間の合計（５枚のシリコーンゴムシートのＴ１＋Ｔ２の合計）を測定した。Ｔ１とは第１回接炎後の残炎時間、Ｔ２とは第２回接炎後の残炎時間を表す。
結果を表１に示す。
In the examples and comparative examples, heat resistance tests and flame retardancy tests were carried out as follows.
[Heat-resistant]
Using a test sheet prepared by curing the millable type silicone rubber composition, the hardness (Durometer A) and initial value of elongation at break (%) were measured according to JIS K 6249: 2003. The test sheet was placed in a dryer at 300°C for 3 days, after which the hardness and elongation at break were measured. The results are shown in Table 1.
[Flame retardance]
Using test sheets prepared by curing the millable type silicone rubber composition, five 1 mm thick silicone rubber sheets were used according to the method specified in the UL94 20 mm vertical flame test to measure the afterflame time periods T1 and T2, as well as the total afterflame time for each set of all treatments (the total of T1+T2 for the five silicone rubber sheets). T1 represents the afterflame time after the first contact with the flame, and T2 represents the afterflame time after the second contact with the flame.
The results are shown in Table 1.
本発明の実施例、比較例で用いた各成分は、以下の通りである。
（Ａ）アルケニル基含有オルガノポリシロキサン
（Ａ－１）ジメチルシロキサン単位９９．８５モル％、メチルビニルシロキサン単位０．１２５モル％、及びジメチルビニルシロキシ単位０．０２５モル％からなり（１分子中のビニル基の個数：１０個）、平均重合度が６，０００であるオルガノポリシロキサン生ゴム
（Ｂ）補強性シリカ
（Ｂ－１）ＢＥＴ法で測定した比表面積が２００ｍ2／ｇのヒュームドシリカ（商品名：アエロジル２００、日本アエロジル（株）製）
（Ｂ－２）補強性表面処理シリカ
補強性表面処理シリカは以下の方法で製造した。
ＢＥＴ法で測定した比表面積が２００ｍ2／ｇのヒュームドシリカ（商品名：アエロジル２００、日本アエロジル（株）製）２００ｇを、高速ミキサー（容量１０Ｌ）に仕込み、回転数１，５００ｒｐｍで運転した。回転が安定したところで、表面処理剤（疎水化剤）として、両末端シラノール基を有し、平均重合度４、２５℃における粘度が１５ｍＰａ・ｓであるジメチルポリシロキサン２０ｇと、ビニルトリメトキシシラン１．２ｇとの混合物を２０秒間で噴霧し、湿潤シリカを得た。この湿潤シリカ１００ｇを２Ｌフラスコに仕込み、２５０℃で２．５時間加熱し、ＢＥＴ法で測定した比表面積が２００ｍ2／ｇの補強性表面処理シリカを作製した。
（Ｃ）白金系化合物
（Ｃ－１）塩化白金酸６水和物の２－エチルヘキサノール溶液（質量換算での白金濃度２質量％、信越化学工業（株）製）
（Ｄ）酸化セリウム及び水酸化セリウム
（Ｄ－１）酸化セリウム（商品名：ＳＮ－２、ニッキ（株）製）
（Ｄ－２）水酸化セリウム（商品名：Ｃｅｒｈｙｄｒａｔｅ９０、トライバッハ インダストリ エージー社製）
（Ｅ）ヒュームド酸化チタン
（Ｅ－１）酸化チタン（商品名：ＡＥＲＯＸＩＤＥ ＴｉＯ2Ｐ２５、日本アエロジル（株）製）（比表面積：ＢＥＴ法で５０ｍ2／ｇ）
（Ｆ）マグネシウムフェライト
（Ｆ－１）マグネシウムフェライト（商品名：ＴＡＲＯＸ Ｔ－２０、チタン工業（株）製）（吸油量：３０ｇ／１００ｇ）
（Ｆ’－１）赤色酸化鉄（商品名：ＢＡＹＦＥＲＲＯＸ １３０Ｍ、ランクセス（株）製）［比較例用］
（Ｆ’－２）黄色酸化鉄（商品名：ＴＡＲＯＸ－ＬＬ－ＸＬＯ、チタン工業（株）製）［比較例用］
（Ｆ’－３）３質量％の酸化鉄をドープした酸化チタン（商品名：ＡＥＲＯＸＩＤＥ ＴｉＯ2 ＰＦ２、日本アエロジル（株）製）［比較例用］
（Ｆ’－４）酸化チタン（商品名：タイペークＲ－８２０、石原産業（株）製）［比較例用］
（Ｇ）有機過酸化物
（Ｇ－１）ｐ－メチルベンゾイルパーオキサイド
（Ｈ）充填材用分散剤
（Ｈ－１）ジフェニルシランジオール
（Ｈ－２）両末端シラノール基含有ジメチルポリシロキサン（平均重合度：４、粘度（２５℃）：１５ｍＰａ・ｓ）
The components used in the examples and comparative examples of the present invention are as follows.
(A) Alkenyl Group-Containing Organopolysiloxane (A-1) An organopolysiloxane gum consisting of 99.85 mol % dimethylsiloxane units, 0.125 mol % methylvinylsiloxane units, and 0.025 mol % dimethylvinylsiloxy units (number of vinyl groups per molecule: 10) and having an average degree of polymerization of 6,000.
(B) Reinforcing Silica (B-1): Fumed silica having a specific surface area of 200 m 2 /g measured by the BET method (product name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.)
(B-2) Reinforcing Surface-Treated Silica Reinforcing surface-treated silica was produced by the following method.
200g of fumed silica (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 200m2 /g measured by the BET method was charged into a high-speed mixer (volume 10L) and operated at a rotation speed of 1,500 rpm. When the rotation was stabilized, a mixture of 20g of dimethylpolysiloxane having silanol groups at both ends, an average degree of polymerization of 4, and a viscosity of 15mPa·s at 25°C as a surface treatment agent (hydrophobizing agent), and 1.2g of vinyltrimethoxysilane was sprayed for 20 seconds to obtain wet silica. 100g of this wet silica was charged into a 2L flask and heated at 250°C for 2.5 hours to prepare a reinforcing surface-treated silica having a specific surface area of 200m2 /g measured by the BET method.
(C) Platinum-based compound (C-1) 2-ethylhexanol solution of chloroplatinic acid hexahydrate (platinum concentration of 2% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)
(D) Cerium oxide and cerium hydroxide (D-1) Cerium oxide (product name: SN-2, manufactured by Nikki Co., Ltd.)
(D-2) Cerium hydroxide (product name: Cerhydrate 90, manufactured by Treibach Industry AG)
(E) Fumed titanium oxide (E-1) Titanium oxide (product name: AEROXIDE TiO 2 P25, manufactured by Nippon Aerosil Co., Ltd.) (specific surface area: 50 m 2 /g by BET method)
(F) Magnesium ferrite (F-1) Magnesium ferrite (product name: TAROX T-20, manufactured by Titan Kogyo Co., Ltd.) (oil absorption: 30 g/100 g)
(F'-1) Red iron oxide (product name: BAYFERROX 130M, manufactured by LANXESS AG) [for comparison]
(F'-2) Yellow iron oxide (product name: TAROX-LL-XLO, manufactured by Titan Kogyo Co., Ltd.) [for comparison]
(F'-3) Titanium oxide doped with 3% by mass of iron oxide (product name: AEROXIDE TiO 2 PF2, manufactured by Nippon Aerosil Co., Ltd.) [for comparison]
(F'-4) Titanium oxide (product name: Tipaque R-820, manufactured by Ishihara Sangyo Kaisha, Ltd.) [for comparison]
(G) Organic Peroxide (G-1) p-Methylbenzoyl Peroxide
(H) Dispersant for fillers (H-1) Diphenylsilanediol (H-2) Dimethylpolysiloxane containing silanol groups at both ends (average degree of polymerization: 4, viscosity (25°C): 15 mPa·s)
（Ａ）アルケニル基含有オルガノポリシロキサン
（Ａ－１）ジメチルシロキサン単位９９．８５モル％、メチルビニルシロキサン単位０．１２５モル％、及びジメチルビニルシロキシ単位０．０２５モル％からなり（１分子中のビニル基の個数：１０個）、平均重合度が６，０００であるオルガノポリシロキサン生ゴム
（Ｂ）補強性シリカ
（Ｂ－１）ＢＥＴ法で測定した比表面積が２００ｍ2／ｇのヒュームドシリカ（商品名：アエロジル２００、日本アエロジル（株）製）
（Ｂ－２）補強性表面処理シリカ
補強性表面処理シリカは以下の方法で製造した。
ＢＥＴ法で測定した比表面積が２００ｍ2／ｇのヒュームドシリカ（商品名：アエロジル２００、日本アエロジル（株）製）２００ｇを、高速ミキサー（容量１０Ｌ）に仕込み、回転数１，５００ｒｐｍで運転した。回転が安定したところで、表面処理剤（疎水化剤）として、両末端シラノール基を有し、平均重合度４、２５℃における粘度が１５ｍＰａ・ｓであるジメチルポリシロキサン２０ｇと、ビニルトリメトキシシラン１．２ｇとの混合物を２０秒間で噴霧し、湿潤シリカを得た。この湿潤シリカ１００ｇを２Ｌフラスコに仕込み、２５０℃で２．５時間加熱し、ＢＥＴ法で測定した比表面積が２００ｍ2／ｇの補強性表面処理シリカを作製した。
（Ｃ）白金系化合物
（Ｃ－１）塩化白金酸６水和物の２－エチルヘキサノール溶液（質量換算での白金濃度２質量％、信越化学工業（株）製）
（Ｄ）酸化セリウム及び水酸化セリウム
（Ｄ－１）酸化セリウム（商品名：ＳＮ－２、ニッキ（株）製）
（Ｄ－２）水酸化セリウム（商品名：Ｃｅｒｈｙｄｒａｔｅ９０、トライバッハ インダストリ エージー社製）
（Ｅ）ヒュームド酸化チタン
（Ｅ－１）酸化チタン（商品名：ＡＥＲＯＸＩＤＥ ＴｉＯ2Ｐ２５、日本アエロジル（株）製）（比表面積：ＢＥＴ法で５０ｍ2／ｇ）
（Ｆ）マグネシウムフェライト
（Ｆ－１）マグネシウムフェライト（商品名：ＴＡＲＯＸ Ｔ－２０、チタン工業（株）製）（吸油量：３０ｇ／１００ｇ）
（Ｆ’－１）赤色酸化鉄（商品名：ＢＡＹＦＥＲＲＯＸ １３０Ｍ、ランクセス（株）製）［比較例用］
（Ｆ’－２）黄色酸化鉄（商品名：ＴＡＲＯＸ－ＬＬ－ＸＬＯ、チタン工業（株）製）［比較例用］
（Ｆ’－３）３質量％の酸化鉄をドープした酸化チタン（商品名：ＡＥＲＯＸＩＤＥ ＴｉＯ2 ＰＦ２、日本アエロジル（株）製）［比較例用］
（Ｆ’－４）酸化チタン（商品名：タイペークＲ－８２０、石原産業（株）製）［比較例用］
（Ｇ）有機過酸化物
（Ｇ－１）ｐ－メチルベンゾイルパーオキサイド
（Ｈ）充填材用分散剤
（Ｈ－１）ジフェニルシランジオール
（Ｈ－２）両末端シラノール基含有ジメチルポリシロキサン（平均重合度：４、粘度（２５℃）：１５ｍＰａ・ｓ）
The components used in the examples and comparative examples of the present invention are as follows.
(A) Alkenyl Group-Containing Organopolysiloxane (A-1) An organopolysiloxane gum consisting of 99.85 mol % dimethylsiloxane units, 0.125 mol % methylvinylsiloxane units, and 0.025 mol % dimethylvinylsiloxy units (number of vinyl groups per molecule: 10) and having an average degree of polymerization of 6,000.
(B) Reinforcing Silica (B-1): Fumed silica having a specific surface area of 200 m 2 /g measured by the BET method (product name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.)
(B-2) Reinforcing Surface-Treated Silica Reinforcing surface-treated silica was produced by the following method.
200g of fumed silica (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 200m2 /g measured by the BET method was charged into a high-speed mixer (volume 10L) and operated at a rotation speed of 1,500 rpm. When the rotation was stabilized, a mixture of 20g of dimethylpolysiloxane having silanol groups at both ends, an average degree of polymerization of 4, and a viscosity of 15mPa·s at 25°C as a surface treatment agent (hydrophobizing agent), and 1.2g of vinyltrimethoxysilane was sprayed for 20 seconds to obtain wet silica. 100g of this wet silica was charged into a 2L flask and heated at 250°C for 2.5 hours to prepare a reinforcing surface-treated silica having a specific surface area of 200m2 /g measured by the BET method.
(C) Platinum-based compound (C-1) 2-ethylhexanol solution of chloroplatinic acid hexahydrate (platinum concentration of 2% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.)
(D) Cerium oxide and cerium hydroxide (D-1) Cerium oxide (product name: SN-2, manufactured by Nikki Co., Ltd.)
(D-2) Cerium hydroxide (product name: Cerhydrate 90, manufactured by Treibach Industry AG)
(E) Fumed titanium oxide (E-1) Titanium oxide (product name: AEROXIDE TiO 2 P25, manufactured by Nippon Aerosil Co., Ltd.) (specific surface area: 50 m 2 /g by BET method)
(F) Magnesium ferrite (F-1) Magnesium ferrite (product name: TAROX T-20, manufactured by Titan Kogyo Co., Ltd.) (oil absorption: 30 g/100 g)
(F'-1) Red iron oxide (product name: BAYFERROX 130M, manufactured by LANXESS AG) [for comparison]
(F'-2) Yellow iron oxide (product name: TAROX-LL-XLO, manufactured by Titan Kogyo Co., Ltd.) [for comparison]
(F'-3) Titanium oxide doped with 3% by mass of iron oxide (product name: AEROXIDE TiO 2 PF2, manufactured by Nippon Aerosil Co., Ltd.) [for comparison]
(F'-4) Titanium oxide (product name: Tipaque R-820, manufactured by Ishihara Sangyo Kaisha, Ltd.) [for comparison]
(G) Organic Peroxide (G-1) p-Methylbenzoyl Peroxide
(H) Dispersant for fillers (H-1) Diphenylsilanediol (H-2) Dimethylpolysiloxane containing silanol groups at both ends (average degree of polymerization: 4, viscosity (25°C): 15 mPa·s)
［実施例１］
（Ａ－１）１００質量部、（Ｂ－１）４０質量部、（Ｈ－１）５質量部、及び、（Ｈ－２）２質量部を添加し、１７０℃で２時間、ニーダーにより混合下で加熱した後、ベースコンパウンド（１）を調製した。 [Example 1]
100 parts by mass of (A-1), 40 parts by mass of (B-1), 5 parts by mass of (H-1), and 2 parts by mass of (H-2) were added, and the mixture was heated at 170° C. for 2 hours while being mixed in a kneader, and then a base compound (1) was prepared.
（Ａ－１）１００質量部、（Ｂ－１）４０質量部、（Ｈ－１）５質量部、及び、（Ｈ－２）２質量部を添加し、１７０℃で２時間、ニーダーにより混合下で加熱した後、ベースコンパウンド（１）を調製した。 [Example 1]
100 parts by mass of (A-1), 40 parts by mass of (B-1), 5 parts by mass of (H-1), and 2 parts by mass of (H-2) were added, and the mixture was heated at 170° C. for 2 hours while being mixed in a kneader, and then a base compound (1) was prepared.
該ベースコンパウンド（１）に、（Ｃ－１）０．１質量部、（Ｄ－１）１．５質量部、（Ｅ－１）５．０質量部、（Ｆ－１）０．５質量部を二本ロールで添加してコンパウンド（Ａ）を調製した。
0.1 parts by mass of (C-1), 1.5 parts by mass of (D-1), 5.0 parts by mass of (E-1), and 0.5 parts by mass of (F-1) were added to the base compound (1) using a two-roll mill to prepare compound (A).
該コンパウンド（Ａ）に、（Ｇ－１）０．７質量部を加え、二本ロールで均一に混合してミラブル型シリコーンゴム組成物を得た。
該シリコーンゴム組成物を１２０℃、７０ｋｇｆ／ｃｍ2の条件で１０分間プレスキュアし、耐熱試験用２ｍｍ厚の試験用シート、難燃試験用１ｍｍ厚の試験用シートそれぞれを作製した。次いで該試験用シートを１５０℃のオーブンで１時間ポストキュアした。得られた硬化物について、上述した耐熱性試験、難燃性試験を行った。結果を表１に記載した。 To the compound (A) was added 0.7 parts by mass of (G-1), and the mixture was mixed uniformly using a twin roll mill to obtain a millable type silicone rubber composition.
The silicone rubber composition was press-cured for 10 minutes at 120°C and 70 kgf/ cm2 to prepare a 2 mm thick test sheet for a heat resistance test and a 1 mm thick test sheet for a flame retardancy test. The test sheets were then post-cured in an oven at 150°C for 1 hour. The cured products obtained were subjected to the above-mentioned heat resistance test and flame retardancy test. The results are shown in Table 1.
該シリコーンゴム組成物を１２０℃、７０ｋｇｆ／ｃｍ2の条件で１０分間プレスキュアし、耐熱試験用２ｍｍ厚の試験用シート、難燃試験用１ｍｍ厚の試験用シートそれぞれを作製した。次いで該試験用シートを１５０℃のオーブンで１時間ポストキュアした。得られた硬化物について、上述した耐熱性試験、難燃性試験を行った。結果を表１に記載した。 To the compound (A) was added 0.7 parts by mass of (G-1), and the mixture was mixed uniformly using a twin roll mill to obtain a millable type silicone rubber composition.
The silicone rubber composition was press-cured for 10 minutes at 120°C and 70 kgf/ cm2 to prepare a 2 mm thick test sheet for a heat resistance test and a 1 mm thick test sheet for a flame retardancy test. The test sheets were then post-cured in an oven at 150°C for 1 hour. The cured products obtained were subjected to the above-mentioned heat resistance test and flame retardancy test. The results are shown in Table 1.
［実施例２～７、比較例１～８］
表１に記載した配合で、実施例１と同様の方法で、シリコーンゴム組成物を調製し、得られた硬化物について、実施例１と同様に耐熱性試験、難燃性試験を行った。結果を表１に記載した。 [Examples 2 to 7, Comparative Examples 1 to 8]
Silicone rubber compositions were prepared using the formulations shown in Table 1 in the same manner as in Example 1, and the resulting cured products were subjected to heat resistance tests and flame retardancy tests in the same manner as in Example 1. The results are shown in Table 1.
表１に記載した配合で、実施例１と同様の方法で、シリコーンゴム組成物を調製し、得られた硬化物について、実施例１と同様に耐熱性試験、難燃性試験を行った。結果を表１に記載した。 [Examples 2 to 7, Comparative Examples 1 to 8]
Silicone rubber compositions were prepared using the formulations shown in Table 1 in the same manner as in Example 1, and the resulting cured products were subjected to heat resistance tests and flame retardancy tests in the same manner as in Example 1. The results are shown in Table 1.
Claims (6)
- （Ａ）ケイ素原子に結合したアルケニル基を１分子中に２個以上有する、平均重合度が１００以上のオルガノポリシロキサン：１００質量部、
（Ｂ）ＢＥＴ法による比表面積が５０ｍ2／ｇ以上である補強性シリカ：５～１００質量部、
（Ｃ）白金系化合物：（Ａ）成分の合計質量に対し、０．５～１，０００ｐｐｍ、
（Ｄ）酸化セリウム及び水酸化セリウムから選ばれる１種以上：０．０１～１０質量部、
（Ｅ）ＢＥＴ法による比表面積が５～２００ｍ2／ｇのヒュームド酸化チタン：１．０～２０質量部、
（Ｆ）吸油量が２０～４０ｇ／１００ｇのマグネシウムフェライト：０．５～３０質量部、及び、
（Ｇ）有機過酸化物：０．１～１０質量部
を含有するミラブル型シリコーンゴム組成物。 (A) 100 parts by mass of an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in each molecule and having an average degree of polymerization of 100 or more,
(B) reinforcing silica having a specific surface area of 50 m 2 /g or more as measured by the BET method: 5 to 100 parts by mass,
(C) Platinum-based compound: 0.5 to 1,000 ppm based on the total mass of component (A),
(D) one or more selected from cerium oxide and cerium hydroxide: 0.01 to 10 parts by mass,
(E) fumed titanium oxide having a specific surface area measured by the BET method of 5 to 200 m 2 /g: 1.0 to 20 parts by mass,
(F) magnesium ferrite having an oil absorption of 20 to 40 g/100 g: 0.5 to 30 parts by mass, and
(G) A millable type silicone rubber composition containing an organic peroxide: 0.1 to 10 parts by mass. - （Ａ）成分が直鎖状オルガノポリシロキサンである、請求項１に記載のミラブル型シリコーンゴム組成物。 The millable silicone rubber composition according to claim 1, in which component (A) is a linear organopolysiloxane.
- （Ａ）成分が平均重合度１，０００～１００，０００を有する、請求項１に記載のミラブル型シリコーンゴム組成物。 The millable silicone rubber composition according to claim 1, in which component (A) has an average degree of polymerization of 1,000 to 100,000.
- （Ｇ）成分が、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｐ－メチルベンゾイルパーオキサイド又はｏ－メチルベンゾイルパーオキサイドである請求項１に記載のミラブル型シリコーンゴム組成物。 The millable silicone rubber composition according to claim 1, in which component (G) is benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, or o-methylbenzoyl peroxide.
- さらに（Ａ）成分１００質量部に対して（Ｈ）充填材用分散剤を０．１～５０質量部含有する、請求項１に記載のミラブル型シリコーンゴム組成物。 The millable silicone rubber composition according to claim 1 further contains 0.1 to 50 parts by mass of (H) a dispersant for fillers per 100 parts by mass of component (A).
- 請求項１～５のいずれか１項に記載のミラブル型シリコーンゴム組成物の硬化物。 A cured product of the millable type silicone rubber composition according to any one of claims 1 to 5.
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| JP2022198532A JP2024084326A (en) | 2022-12-13 | 2022-12-13 | Millable silicone rubber composition |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4967933A (en) * | 1972-10-31 | 1974-07-02 | ||
| JPS5245655A (en) * | 1975-10-09 | 1977-04-11 | Toshiba Silicone Co Ltd | Cold curing polysiloxane compositions |
| JPS5358557A (en) * | 1976-11-08 | 1978-05-26 | Toshiba Silicone | Heat resistant polyorganosiloxane composition |
| JPH09194730A (en) * | 1996-01-16 | 1997-07-29 | Shin Etsu Chem Co Ltd | Flame-retardant silicone rubber composition |
| JPH09208824A (en) * | 1995-12-01 | 1997-08-12 | General Electric Co <Ge> | Improved thermosetting rubber |
| WO2021033545A1 (en) * | 2019-08-21 | 2021-02-25 | 信越化学工業株式会社 | Millable silicone rubber composition, silicone rubber cured product, and electrically-insulating member for power cable connection |
-
2022
- 2022-12-13 JP JP2022198532A patent/JP2024084326A/en active Pending
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2023
- 2023-12-08 WO PCT/JP2023/044089 patent/WO2024128165A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4967933A (en) * | 1972-10-31 | 1974-07-02 | ||
| JPS5245655A (en) * | 1975-10-09 | 1977-04-11 | Toshiba Silicone Co Ltd | Cold curing polysiloxane compositions |
| JPS5358557A (en) * | 1976-11-08 | 1978-05-26 | Toshiba Silicone | Heat resistant polyorganosiloxane composition |
| JPH09208824A (en) * | 1995-12-01 | 1997-08-12 | General Electric Co <Ge> | Improved thermosetting rubber |
| JPH09194730A (en) * | 1996-01-16 | 1997-07-29 | Shin Etsu Chem Co Ltd | Flame-retardant silicone rubber composition |
| WO2021033545A1 (en) * | 2019-08-21 | 2021-02-25 | 信越化学工業株式会社 | Millable silicone rubber composition, silicone rubber cured product, and electrically-insulating member for power cable connection |
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