WO2020059437A1 - Composition de caoutchouc de silicone et corps réticulé en caoutchouc de silicone - Google Patents

Composition de caoutchouc de silicone et corps réticulé en caoutchouc de silicone Download PDF

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WO2020059437A1
WO2020059437A1 PCT/JP2019/033338 JP2019033338W WO2020059437A1 WO 2020059437 A1 WO2020059437 A1 WO 2020059437A1 JP 2019033338 W JP2019033338 W JP 2019033338W WO 2020059437 A1 WO2020059437 A1 WO 2020059437A1
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silicone rubber
rubber composition
group
phenyl group
phthalocyanine
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PCT/JP2019/033338
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English (en)
Japanese (ja)
Inventor
竜介 山岡
安紀 二村
早崎　康行
泰 村上
小林　正美
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住友理工株式会社
国立大学法人信州大学
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Publication of WO2020059437A1 publication Critical patent/WO2020059437A1/fr

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    • 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
    • C08K3/16—Halogen-containing compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • 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 silicone rubber composition and a crosslinked silicone rubber having excellent heat resistance.
  • Silicone rubber is superior in heat resistance to general organic synthetic rubber and natural rubber, and is used for applications requiring heat resistance.
  • Various studies have been made for the purpose of further improving the heat resistance of silicone rubber.
  • Patent Document 1 describes that in an addition-curable silicone rubber composition, heat resistance is improved by adding an organosilicon compound having an alkoxy group and an epoxy group together with iron sesquioxide.
  • Patent Literature 2 describes that in a condensation-curable silicone rubber composition, the heat resistance is improved by adding a metal phthalocyanine complex.
  • the problem to be solved by the present invention is to provide a silicone rubber composition and a crosslinked silicone rubber having excellent heat resistance.
  • the silicone rubber composition according to the present invention comprises (a) an organopolysiloxane having at least two alkenyl groups in one molecule, (b) a hydrosilyl crosslinking agent, (c) a hydrosilylation catalyst,
  • the gist of the invention is that it contains d) a phthalocyanine compound and (e) a phenyl group-containing organopolysiloxane.
  • the siloxane unit of (e) is preferably composed of diphenylsiloxane (e1) and dialkylsiloxane (e2).
  • the siloxane unit of (e) may be composed of methylphenylsiloxane (e3) and dialkylsiloxane (e2).
  • the ratio of the number of moles of siloxane units not containing a phenyl group to the number of moles of siloxane units containing a phenyl group is preferably 5 or more.
  • the above (e) is preferably a periodic copolymer or a block copolymer.
  • the number of repeating units of a phenyl group-containing siloxane unit in one cycle of the periodic copolymer or the number of repeating units of a phenyl group-containing siloxane unit in the block copolymer is 1 to 3. Is preferred.
  • the gist of the crosslinked silicone rubber of the present invention is that it is a crosslinked product of the silicone rubber composition of the present invention.
  • silicone rubber composition of the present invention (a) an organopolysiloxane having at least two alkenyl groups in one molecule, (b) a hydrosilyl crosslinking agent, (c) a hydrosilylation catalyst, and (d) a phthalocyanine-based compound Since it contains the compound, (e) a phenyl group-containing organopolysiloxane, the crosslinked product is excellent in heat resistance.
  • the crosslinked silicone rubber composition of the present invention is excellent in heat resistance.
  • the silicone rubber composition according to the present invention comprises (a) an organopolysiloxane having at least two alkenyl groups in one molecule, (b) a hydrosilyl crosslinking agent, (c) a hydrosilylation catalyst, (d) a phthalocyanine compound, (E) a phenyl group-containing organopolysiloxane.
  • (A) is used as a main raw material of an addition-curable silicone rubber composition. Since (a) has at least two alkenyl groups in one molecule, it is crosslinked by (b) a hydrosilyl crosslinking agent by an addition reaction with (b) a hydrosilyl crosslinking agent.
  • alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • (A) has an organic group other than an alkenyl group in addition to the alkenyl group.
  • the organic group is a monovalent substituted or unsubstituted hydrocarbon group.
  • the unsubstituted hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group, an aryl group such as a phenyl group, a ⁇ -phenylethyl group, and a ⁇ -phenylpropyl group.
  • an aralkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group
  • an aryl group such as a phenyl group, a ⁇ -phenylethyl group, and a ⁇ -phenylpropyl
  • Examples of the substituted hydrocarbon group include a chloromethyl group and a 3,3,3-trifluoropropyl group.
  • the organopolysiloxane generally, those having a methyl group as an organic group are frequently used because of ease of synthesis and the like.
  • the organopolysiloxane is preferably linear, but may be branched or cyclic.
  • (A) has no hydrosilyl group because of the relationship with (b).
  • (A) may have a phenyl group or may not have a phenyl group.
  • (A) may be a liquid type or a millable type.
  • the viscosity at 25 ° C. is from 300 to 300 from the viewpoints of improving the dispersibility of (d) the phthalocyanine compound, (e) the phenyl group-containing organopolysiloxane, and improving the mechanical properties of the crosslinked product.
  • it is 100,000 cs (centistokes). More preferably, it is 400 to 10,000 cs.
  • the viscosity can be measured with a B-type viscometer.
  • the degree of polymerization is preferably from 3,000 to 10,000 from the viewpoint of improving the mechanical properties of the crosslinked product.
  • the hydrosilyl crosslinking agent is used as a crosslinking agent for an addition-curable silicone rubber composition, and is a crosslinking agent for crosslinking (a).
  • the hydrosilyl crosslinking agent has a hydrosilyl group (SiH group) in its molecular structure.
  • the hydrosilyl crosslinking agent is a hydrosilyl group-containing organopolysiloxane (organohydrogenpolysiloxane).
  • the number of hydrosilyl groups in the molecular structure is not particularly limited, but is preferably in the range of 2 to 50 from the viewpoint of excellent curing speed and excellent stability. Further, from the viewpoint of crosslinkability and the like, it is preferably in the range of 3 to 50.
  • the hydrosilyl groups are preferably present in different Si.
  • the polysiloxane may be a chain or a cyclic one.
  • the hydrosilyl group-containing organopolysiloxane preferably has at least two hydrosilyl groups in one molecule.
  • the hydrosilyl crosslinking agent preferably has a number average molecular weight in the range of 200 to 30,000 from the viewpoint of excellent handleability.
  • (B) has no alkenyl group because of the relationship with (a).
  • (B) may have a phenyl group or may not have a phenyl group.
  • hydrosilyl group-containing organopolysiloxane examples include methylhydrogenpolysiloxane having trimethylsiloxy groups at both ends and dimethylsiloxane / methylhydrogensiloxane copolymer having trimethylsiloxy groups at both ends.
  • the amount of the hydrosilyl crosslinking agent (b) is not particularly limited, but is usually in the range of 0.1 to 40 parts by mass with respect to 100 parts by mass of (a).
  • the hydrosilylation catalyst is a catalyst that promotes the crosslinking reaction of (a) by the (b) hydrosilyl crosslinking agent.
  • Examples of the hydrosilylation catalyst include a platinum catalyst, a ruthenium catalyst, and a rhodium catalyst.
  • Examples of the platinum catalyst include fine particles of platinum, platinum black, activated carbon carrying platinum, silica carrying platinum, chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, and alkenylsiloxane complexes of platinum. These may be used alone or in combination of two or more.
  • the hydrosilylation catalyst may be microencapsulated using a resin.
  • the microencapsulated catalyst (microencapsulated catalyst) is composed of resin fine particles containing a hydrosilylation catalyst.
  • the resin fine particles containing the hydrosilylation catalyst are preferably solid at least at room temperature and have an average particle diameter of 30 ⁇ m or less.
  • the average particle size is measured by a laser microscope.
  • the average particle diameter of the resin fine particles containing the hydrosilylation catalyst is preferably 10 ⁇ m or less from the viewpoint of enhancing the dispersibility of the hydrosilylation catalyst. More preferably, it is 7.0 ⁇ m or less.
  • the thickness is preferably 0.1 ⁇ m or more. It is more preferably at least 2.0 ⁇ m.
  • the resin of the microcapsule type catalyst may be either a thermoplastic resin or a thermosetting resin.
  • the resin of the microcapsule type catalyst is more preferably a thermosetting resin from the viewpoint that a reduction in compression set can be suppressed by being crosslinked.
  • Examples of the resin of the microcapsule type catalyst include epoxy resin, acrylic resin, polyvinyl butyral resin, styrene-based polymer, polycarbonate resin, unsaturated polyester resin, alkyd resin, urea resin, melamine resin, vinyl chloride resin, polyurethane resin, and polyether.
  • Examples include a sulfone resin, a polysulfone resin, a polyphenylene sulfide resin, a phenol resin, a diallyl phthalate resin, a polyvinyl alcohol resin, a hydrogenated terpene resin, and a silicone resin. These may be used alone as a resin of the microcapsule type catalyst, or may be used in combination of two or more.
  • thermosetting resin examples include polyvinyl butyral resin, epoxy resin, unsaturated polyester resin, phenol resin, resol resin, alkyd resin, urea resin, melamine resin, polyurethane resin, diallyl phthalate resin, and acrylic resin.
  • an epoxy resin, an acrylic resin, a polyvinyl butyral resin, and an unsaturated polyester resin are more preferable from the viewpoint of particularly excellent storage stability of the material before curing.
  • the resin (coating resin) of the microcapsule catalyst is preferably a solubility parameter that largely deviates from the solubility parameter of the organopolysiloxane (a) from the viewpoint of storage stability and the like.
  • the solubility parameter (SP value) is preferably 7.9 or more. It is more preferably 8.3 or more, and still more preferably 9.0 or more.
  • the upper limit of the solubility parameter of the resin of the microcapsule catalyst is not particularly limited, and may be, for example, 20 or less.
  • the solubility parameter can be calculated from the molecular structure by Small's calculation method.
  • the resin of the microcapsule type catalyst preferably has a glass transition temperature (Tg) of 40 to 145 ° C from the viewpoints of improvement in crosslinking reactivity due to an increase in the diffusion amount of the crosslinking catalyst and storage stability.
  • the temperature is more preferably from 45 to 100 ° C, and even more preferably from 50 to 85 °.
  • the glass transition temperature (Tg) of the thermosetting resin is a value before thermosetting.
  • the glass transition temperature can be measured by DSC (differential scanning calorimetry).
  • the resin of the microcapsule-type catalyst has a thermal conductivity of 0.16 W / m ⁇ K or more, a thermal conductivity of 0.17 W / m ⁇ K or more, from the viewpoint of improving the crosslinking reactivity by increasing the diffusion amount of the crosslinking catalyst. Is preferably 0.20 W / m ⁇ K or more.
  • the thermal conductivity can be measured according to ASTM C177.
  • the microcapsule type catalyst can be produced by a conventionally known method. From the viewpoints of productivity, sphericity, and the like, a suspension polymerization method, an emulsion polymerization method, a spray dryer method, a submerged drying method, and the like are preferable.
  • the amount of the hydrosilylation catalyst (c) is usually in the range of 1 ppm to 1.0 part by mass, based on 100 parts by mass of the metal (a).
  • the phthalocyanine-based compound has the effect of improving the heat resistance of the silicone rubber by being added to the silicone rubber composition. This is presumed to be due to the radical trapping action of the phthalocyanine compound (d) under a high temperature environment.
  • the phthalocyanine-based compound is a compound having a phthalocyanine ring, and includes phthalocyanine, a phthalocyanine derivative, a metal phthalocyanine, and a metal phthalocyanine derivative.
  • the phthalocyanine-based compound may or may not contain a metal.
  • the metal phthalocyanine is represented by the following general formula (1).
  • Metal phthalocyanine has a structure in which a metal is coordinated at the center of a phthalocyanine ring.
  • M represents a metal element, preferably one selected from Cu, Fe, Co, Mn, Ni, Cr, Zn, Pb, Ti, Pt, Pd, Ru, Ce, and V That is all.
  • the phthalocyanine ring has one or more substituents on one or more of the four benzene rings. It may be something.
  • the substituent include a halogen group, a hydroxyl group, an alkyl group, a nitro group, an amino group, a sulfonic acid group, a carboxy group, and an alkoxy group.
  • the two or more substituents may be the same or different.
  • the substituents on different benzene rings may be the same or different.
  • the phthalocyanine-based compound one or a combination of two or more of copper phthalocyanine, cobalt phthalocyanine, iron phthalocyanine and derivatives thereof is more preferable.
  • copper phthalocyanine and its derivatives include copper phthalocyanine (phthalocyanine blue), chlorinated copper phthalocyanine (phthalocyanine green), and copper phthalocyanine monosulfonic acid.
  • cobalt phthalocyanine and its derivatives include cobalt phthalocyanine, cobalt phthalocyanine amine derivatives, and cobalt phthalocyanine monosulfonic acid.
  • iron phthalocyanine and its derivatives include iron phthalocyanine, iron phthalocyanine tetracarboxylic acid, and iron phthalocyanine monosulfonic acid.
  • the amount of the phthalocyanine compound (d) is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of (a). It is more preferably in the range of 0.5 to 5.0 parts by mass, and even more preferably in the range of 1.0 to 3.0 parts by mass.
  • the phenyl group-containing organopolysiloxane has a polysiloxane skeleton and a phenyl group, thereby improving the dispersibility of the (d) phthalocyanine compound having an aromatic ring in the silicone rubber composition. Thereby, the heat resistance of the silicone rubber is dramatically improved. This is because (d) the phthalocyanine compound has an aromatic ring and the molecules are likely to overlap with each other, and has poor compatibility with the silicone rubber (a). It is inferred that such aggregation is suppressed by the (e) phenyl group-containing organopolysiloxane.
  • the phenyl group-containing organopolysiloxane contains, as siloxane units, diphenylsiloxane (e1) and dialkylsiloxane (e2), methylphenylsiloxane (e3) and dialkylsiloxane (e2), or diphenylsiloxane (e1). ), Methylphenylsiloxane (e3) and dialkylsiloxane (e2).
  • the phenyl group-containing organopolysiloxane may contain a siloxane unit having another functional group in addition to (e1) to (e3), or may contain a siloxane unit having another functional group. It is not necessary.
  • (e) preferably does not have an alkenyl group from the relationship with (a). Further, (e) preferably has no hydrosilyl group in view of the relationship with (b). Further, even when (e) has a hydrosilyl group, the number of hydrosilyl groups is preferably 2 or less in one molecule.
  • the ratio of the number of moles of the siloxane group not containing a phenyl group to the number of moles of the siloxane unit containing a phenyl group is preferably from the viewpoint of excellent compatibility with (a). It is preferably 5.0 or more. More preferably, it is 10 or more. In addition, from the viewpoint of excellent compatibility with (d), it is preferably 500 or less. It is more preferably 300 or less, further preferably 100 or less.
  • the ratio of the number of moles of the siloxane unit not containing a phenyl group to the number of moles of the siloxane unit containing a phenyl group is determined by the molar ratio when the siloxane unit (e) is composed of diphenylsiloxane (e1) and dialkylsiloxane (e2). (E2 / e1), and when the siloxane unit of (e) is composed of methylphenylsiloxane (e3) and dialkylsiloxane (e2), the molar ratio is (e2 / e3).
  • the phenyl group-containing organopolysiloxane may be any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer. Since it is particularly excellent in the effect of improving the heat resistance of the silicone rubber, a periodic copolymer or a block copolymer is preferred.
  • the phenyl group-containing organopolysiloxane may have a viscosity at 25 ° C. of 10 to 6000 cs (centistokes) from the viewpoint of compatibility with the organopolysiloxane (a) and the phthalocyanine compound (d). preferable. More preferably, it is 70 to 500 cs.
  • the viscosity can be measured with a B-type viscometer.
  • the phenyl group-containing organopolysiloxane has, for example, a structure represented by the following general formula (2).
  • R 1 is an alkyl group
  • R 2 is an alkyl group or a phenyl group
  • m, n, and l are 1 or more in the number of repeating units.
  • R 1 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • R 2 is preferably a methyl group, an ethyl group or a phenyl group, more preferably a phenyl group.
  • m is preferably from 8 to 350.
  • n is preferably 1 to 3.
  • l is preferably 1 to 50.
  • the copolymer of the formula (2) may be any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer.
  • the phenyl group may be a phenyl group having a substituent. Examples of the substituent include an alkyl group and an aryl group.
  • the siloxane unit when R 2 is a phenyl group, the siloxane unit is composed of diphenylsiloxane (e1) and dialkylsiloxane (e2). In the formula (2), when R 2 is an alkyl group, the siloxane unit is composed of methylphenylsiloxane (e3) and dialkylsiloxane (e2).
  • the siloxane unit may be composed of diphenylsiloxane (e1) and dialkylsiloxane (e2), or the siloxane unit may be methylphenylsiloxane (e3) and dialkylsiloxane (e2). May be used.
  • the compounding amount of the (e) phenyl group-containing organopolysiloxane is 0.5 parts by mass or more based on 100 parts by mass of (a) from the viewpoint that the effect of improving the dispersibility of (d) is excellent. Is preferred. It is more preferably at least 1.0 part by mass, and even more preferably at least 3.0 parts by mass. In addition, from the viewpoint that the decrease in the curing rate of the silicone rubber and the decrease in the mechanical strength of the crosslinked product are easily suppressed, the amount is preferably 20 parts by mass or less based on 100 parts by mass of (a). More preferably, it is 15 parts by mass or less, further preferably 10 parts by mass or less.
  • the mixing ratio of the (d) phthalocyanine compound and the (e) phenyl group-containing organopolysiloxane is compatible with (a), and is stable when a mixture of (d) and (e) is obtained.
  • additives that can be added to the silicone rubber can be added to the silicone rubber composition within a range that does not impair the present invention.
  • Additives include reinforcing materials, conductive agents, fillers, crosslinking accelerators, crosslinking retarders, crosslinking aids, scorch inhibitors, anti-aging agents, softeners, plasticizers, lubricants, heat stabilizers, flame retardants, flame retardants Examples include a combustion aid, an ultraviolet absorber, a rust inhibitor, and a foaming agent. Further, depending on the foaming method, a thickener, a surfactant, a communication agent, and the like may be added.
  • an electronic conductive agent carbon black, graphite, c-TiO 2 , c-ZnO, c-SnO 2 (c- means conductivity)
  • an ionic conductive agent quaternary ammonium salt
  • Quaternary phosphonium salts Quaternary phosphonium salts, borates, surfactants, etc.
  • a predetermined foaming agent is used depending on the foaming method.
  • the foaming method include emulsion foaming, balloon foaming, mechanical foaming, and chemical foaming.
  • Emulsion foaming is a foaming method in which water is dispersed in an uncured material, the material is cured in the dispersed state, and water is removed from the cured product after curing.
  • Balloon foaming is a foaming method in which a hollow balloon is dispersed in an uncured material, and after curing, the hollow balloon is removed from the cured product, or the hollow balloon is broken to form cells (bubbles).
  • Chemical foaming is a method in which a gas such as carbon dioxide is forcibly mixed into a material from the outside and mechanically stirred and foamed.
  • Chemical foaming is a foaming method in which an organic or inorganic chemical foaming agent is used to foam a material at the time of curing (at the time of molding).
  • the chemical blowing agent include an organic blowing agent such as azodicarbonamide and an inorganic blowing agent such as sodium bicarbonate.
  • Chemical foaming is a method of generating bubbles during curing, and the size of the bubbles tends to be uneven and large.
  • emulsion foaming, balloon foaming, and mechanical foaming are foaming methods in which foam is contained in the material from before the material is cured (before molding), and the foam-containing state is cured as it is. Is easy to make uniform in size. Therefore, emulsion foaming, balloon foaming, and mechanical foaming are preferred from the viewpoint of making the structure containing fine and small variations in air bubbles. Of these, emulsion foaming and balloon foaming are preferred, and emulsion foaming is particularly preferred. Therefore, the foaming agent is preferably water for emulsion foaming, hollow particles for balloon foaming, and gas for mechanical foaming.
  • the balloon-expanded hollow particles are composed of unexpanded or unexpanded, heat-expandable microcapsules (microspheres) containing a low-boiling hydrocarbon in a shell made of a thermoplastic polymer.
  • the heat-expandable microcapsules expand rapidly due to the expansion of the low-boiling hydrocarbons contained therein upon heating and, at the same time, the softening of the shell made of a thermoplastic polymer, resulting in a hollow balloon.
  • the silicone rubber composition can be prepared by blending the above (a) to (e) and, if necessary, additives.
  • the above (a), (b) and (e) are polysiloxanes, and each polysiloxane can be produced by a known polymerization method such as a hydrolysis polymerization method of chlorosilane or a ring-opening polymerization method of cyclic siloxane. .
  • the silicone rubber composition can be formed by, for example, injecting an uncrosslinked conductive silicone rubber composition into a molding die, heating and curing (crosslinking), and then removing the mold. Thereby, a crosslinked silicone rubber comprising the crosslinked product of the silicone rubber composition of the present invention can be obtained.
  • (e) may be immobilized in the skeleton. Thereby, the bleeding of (e) in the silicone rubber crosslinked product is easily suppressed.
  • a hydrosilyl group is contained as a functional group, (e) can be immobilized in a skeleton.
  • the crosslinked silicone rubber may be a non-foamed or foamed material depending on the use or the like.
  • the foam has a plurality of cells (cells) in a base material (solid phase) containing a crosslinked silicone rubber.
  • the foam can be formed by a foaming method such as emulsion foaming, balloon foaming, mechanical foaming, and chemical foaming.
  • the silicone rubber composition having the above constitution, (a) an organopolysiloxane having at least two alkenyl groups in one molecule, (b) a hydrosilyl crosslinking agent, (c) a hydrosilylation catalyst, and (d) a phthalocyanine-based compound Since it contains the compound, (e) a phenyl group-containing organopolysiloxane, the crosslinked product is excellent in heat resistance.
  • the silicone rubber composition according to the present invention has better heat resistance than conventional ones, it is suitable for application to parts requiring high heat resistance.
  • the silicone rubber composition according to the present invention is used, for example, as a component for preventing heat generation of power devices such as SiC, GaN, and Ga 2 O 3, a waterproof seal member for automobiles, and a material for forming a fixing roll for OA equipment. Can be used.
  • Examples 1 to 10 After mixing the liquid silicone rubber (vinyl group-containing dimethylpolysiloxane), fumed silica, hydrosilylation catalyst (platinum catalyst), copper phthalocyanine, and dispersant (phenyl group-containing organopolysiloxane) so as to have the composition shown in Table 2. And a planetary mixer for 30 minutes, and then a hydrosilyl cross-linking agent (hydrosilyl group-containing dimethylpolysiloxane) and a retarder (1-ethynyl-1-cyclohexanol) are further mixed for 30 minutes and defoamed under reduced pressure. Thus, a liquid silicone rubber composition was prepared.
  • a hydrosilyl cross-linking agent hydrosilyl group-containing dimethylpolysiloxane
  • a retarder (1-ethynyl-1-cyclohexanol
  • Example 1 A silicone rubber composition was prepared in the same manner as in Example 1, except that copper phthalocyanine and a dispersant were not used in the preparation of the silicone rubber composition.
  • Example 2 In the preparation of the silicone rubber composition, a silicone rubber composition was prepared in the same manner as in Example 1 except that copper phthalocyanine was added but no dispersant was added.
  • Copper phthalocyanine "Phthalocyanine copper (II) ( ⁇ -type)" manufactured by Tokyo Chemical Industry (E)
  • Component / dispersant A Synthetic product / dispersant B: Synthetic product / dispersant C: Synthetic product / dispersant D: Synthetic product / dispersant E: Dow Toray “SH510-100CS” ⁇ Dispersant F: “KF50-100CS” manufactured by Shin-Etsu Chemical Co., Ltd. ⁇ Dispersant G: “KF50-3000CS” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Dispersant B was obtained in the same manner as in the method for synthesizing dispersant A, except that the polydimethylsiloxane modified with silanol at both ends was changed to "X-21-5841" manufactured by Shin-Etsu Chemical Co., Ltd.
  • Dispersant C was obtained in the same manner as in the method for synthesizing dispersant A, except that the polydimethylsiloxane modified with silanol at both ends was changed to "DMS-S21" manufactured by Gelest.
  • Dispersant D was obtained in the same manner as in the synthesis of Dispersant A, except that the polydimethylsiloxane modified with silanol at both ends was changed to "DMS-S31" manufactured by Gelest.
  • the addition-curable silicone rubber composition contained no phthalocyanine-based compound but a dispersant, and thus had a change in hardness and tensile elongation even at a high temperature of 2 hours at 250 ° C. for 72 hours. Is too large or cannot be evaluated, indicating that the heat resistance is poor.
  • a high temperature of 250 ° C. ⁇ 72 hours is used.
  • the high temperature condition 1 of 285 ° C. ⁇ 72 hours as well as the condition 2 the change in hardness and the change in tensile elongation are small, and it is understood that the heat resistance is excellent.
  • the dispersant is a periodic copolymer, the heat resistance is particularly excellent.

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Abstract

L'invention concerne une composition de caoutchouc de silicone et un corps réticulé en caoutchouc de silicone ayant une excellente résistance à la chaleur. Cette composition de caoutchouc de silicone contient : (a) un organopolysiloxane ayant au moins deux groupes alcényle dans une molécule; (b) un agent de réticulation hydrosilyle; (c) un catalyseur d'hydrosilylation; (d) un composé à base de phtalocyanine; et (e) un organopolysiloxane contenant un groupe phényle. Une unité siloxane de (e) peut comprendre un diphénylsiloxane (e1) et un dialkylsiloxane (e2). De plus, une unité siloxane de (e) peut également comprendre un méthylphénylsiloxane (e3) et un dialkylsiloxane (e2).
PCT/JP2019/033338 2018-09-18 2019-08-26 Composition de caoutchouc de silicone et corps réticulé en caoutchouc de silicone WO2020059437A1 (fr)

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JP2018-173187 2018-09-18
JP2018173187A JP6956697B2 (ja) 2018-09-18 2018-09-18 シリコーンゴム組成物およびシリコーンゴム架橋体

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03146560A (ja) * 1989-10-31 1991-06-21 Toray Dow Corning Silicone Co Ltd 硬化性オルガノポリシロキサンゴム組成物
JP2002294076A (ja) * 2001-04-02 2002-10-09 Dow Corning Toray Silicone Co Ltd 金型成形用シリコーンゲル組成物
JP2014503680A (ja) * 2011-01-26 2014-02-13 ダウ コーニング コーポレーション 高温安定熱伝導性材料
JP2014185229A (ja) * 2013-03-22 2014-10-02 Momentive Performance Materials Inc 付加硬化型シリコーンゴム組成物
JP2014534292A (ja) * 2011-10-06 2014-12-18 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 改善された熱安定性を有するゲル

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03146560A (ja) * 1989-10-31 1991-06-21 Toray Dow Corning Silicone Co Ltd 硬化性オルガノポリシロキサンゴム組成物
JP2002294076A (ja) * 2001-04-02 2002-10-09 Dow Corning Toray Silicone Co Ltd 金型成形用シリコーンゲル組成物
JP2014503680A (ja) * 2011-01-26 2014-02-13 ダウ コーニング コーポレーション 高温安定熱伝導性材料
JP2014534292A (ja) * 2011-10-06 2014-12-18 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 改善された熱安定性を有するゲル
JP2014185229A (ja) * 2013-03-22 2014-10-02 Momentive Performance Materials Inc 付加硬化型シリコーンゴム組成物

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