WO2021014968A1 - 室温硬化性オルガノポリシロキサン組成物及び自動車ロングライフクーラントシール材 - Google Patents

室温硬化性オルガノポリシロキサン組成物及び自動車ロングライフクーラントシール材 Download PDF

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WO2021014968A1
WO2021014968A1 PCT/JP2020/026628 JP2020026628W WO2021014968A1 WO 2021014968 A1 WO2021014968 A1 WO 2021014968A1 JP 2020026628 W JP2020026628 W JP 2020026628W WO 2021014968 A1 WO2021014968 A1 WO 2021014968A1
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group
mass
parts
room temperature
organopolysiloxane composition
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PCT/JP2020/026628
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English (en)
French (fr)
Japanese (ja)
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晃 打它
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信越化学工業株式会社
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Priority to JP2021533922A priority Critical patent/JP7509146B2/ja
Publication of WO2021014968A1 publication Critical patent/WO2021014968A1/ja

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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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • 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
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention relates to a room temperature curable organopolysiloxane composition, particularly a room temperature curable organopolysiloxane composition for an automobile LLC seal, which is suitably used as an automobile long life coolant (LLC) sealing material. ..
  • the present invention particularly relates to a room temperature curable organopolysiloxane composition for an automobile LLC seal and an automobile long life coolant sealing material, which are excellent in LLC resistance and heat resistance and also provide good adhesiveness and curability.
  • gaskets and packing materials made of cork, organic rubber, asbestos, etc. have been used as sealing materials around LLC of automobiles.
  • these conventional gaskets and packing materials have a disadvantage that inventory management and work processes are complicated, and further, they have a drawback that their sealing performance is not reliable. Therefore, in the use of LLC seals, a Formed In Place Gasket (FIPG) method using a room temperature curable organopolysiloxane composition is adopted as a liquid gasket.
  • FIPG Formed In Place Gasket
  • LLC is basically used by mixing with water. Therefore, the automotive LLC sealant needs to withstand high temperature conditions in the presence of a chemical that is highly aggressive against FIPG, which is a mixture of LLC and water.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-226708
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2016-199687
  • the LLC resistance can be improved by adding an organopolysiloxane resin having a three-dimensional network structure dissolved in an organic solvent to the composition.
  • an organopolysiloxane resin having a three-dimensional network structure dissolved in an organic solvent
  • the residual silanol groups undergo a condensation reaction, so that the elongation rate of the rubber inevitably decreases when exposed to a high temperature environment.
  • a material containing volatile organic chemical substances Volatile Organic Compounds, hereinafter referred to as VOC
  • the present invention has been made in view of the above circumstances, and particularly relates to a room temperature curable organopolysiloxane composition preferably used as an automobile LLC seal.
  • the present invention has excellent LLC resistance and heat resistance, provides good adhesiveness and curability, and has a reduced VOC content, and is suitable as a material for FIPG, and has room temperature curability for automobile LLC seals. It is an object of the present invention to provide an organopolysiloxane composition and an automobile long life coolant sealing material.
  • the present inventor has deacetone having a silethylene (-Si-CH 2 CH 2- Si-) bond in the molecule as a cross-linking component of the condensation-curing composition. It has been found that the LLC resistance and the curability are significantly improved by using the type of polyfunctional curing agent. Further, in the present invention, sufficient LLC resistance can be obtained without using an organopolysiloxane resin (so-called silicone resin) having a three-dimensional network structure, and heat resistance (decrease in elongation rate at high temperature exposure) is also greatly improved.
  • organopolysiloxane resin so-called silicone resin
  • the present invention provides the following room temperature curable organopolysiloxane composition and automobile long life coolant sealing material.
  • 1. Organopolysiloxane having a viscosity of 2,000 mPa ⁇ s or more at 23 ° C. represented by the following general formula (1): 100 parts by mass, HO- (SiR 1 2 O) a- H (1)
  • R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and each R 1 may be the same group or a different group from each other.
  • A is 100.
  • N indicates an integer of 0 to 50.
  • R 4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms having at least one atom of any one or more selected from a nitrogen atom, a sulfur atom and an oxygen atom
  • R 5 Is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms
  • X is a hydrolyzable group
  • d is 0, 1 or 2
  • a room temperature curable organopolysiloxane composition containing up to 20 parts by mass 2. 2. 2. The room temperature according to 1, wherein the inorganic filler of the component (B) is at least one selected from calcium carbonate, aerosol silica, precipitated silica, carbon black and aluminum oxide hydrophobized with a surface treatment agent. Curable organopolysiloxane composition. 3. 3. The room temperature curable organopolysiloxane composition according to 1 or 2, wherein the residual amount of VOC in the composition is 5,000 ppm or less. 4.
  • the rate of change in tensile strength and elongation during cutting after the LLC resistance test of immersing in automobile long life coolant at 120 ° C for 240 hours is -50% or more and 100% or less, and 120 ° C, 1,
  • the room temperature curable organopolysiloxane composition according to any one of 1 to 3, which gives a cured product in which the tensile strength after a heat resistance test for 000 hours and the rate of change in elongation at the time of cutting are -50% or more and 20% or less. Stuff. 5.
  • the automobile long-life coolant sealant which is a cured product of the room temperature curable organopolysiloxane composition for the automobile long-life coolant seal according to 5.
  • the composition of the present invention is particularly suitable for an automobile long-life coolant seal in which a cured product (silicone rubber) having excellent LLC resistance and heat resistance performance and good adhesiveness and curability is provided and the VOC content is suppressed. It is a room temperature curable organopolysiloxane composition.
  • the room temperature curable organopolysiloxane composition according to the present invention contains the following components (A) to (E).
  • the room temperature means 25 ° C. ⁇ 10 ° C., preferably 20 to 25 ° C.
  • the component (A) of the room temperature curable organopolysiloxane composition used in the present invention is represented by the following general formula (1).
  • HO- (SiR 1 2 O) a- H (1) (In the formula (1), R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and each R 1 may be the same group or a different group from each other. A is 100. The above integers.)
  • the component (A) has a main chain consisting of repeating diorganosiloxane units, and both ends of the molecular chain are sealed with a hydroxyl group (silanol group) bonded to a silicon atom at 23 ° C. It is a linear diorganopolysiloxane having a viscosity of 2,000 mPa ⁇ s or more, and acts as a main agent (base polymer) of the composition of the present invention.
  • R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group.
  • Alkyl group such as group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, octyl group, 2-ethylhexyl group; cycloalkyl group such as cyclohexyl group; vinyl group, allyl group, propenyl group, isopropenyl group , Alkenyl groups such as butenyl group and hexenyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group.
  • R 1 a group in which the hydrogen atom of these hydrocarbon groups is partially substituted with a halogen atom such as chlorine, fluorine or bromine, for example, a trifluoropropyl group or the like can be mentioned.
  • a halogen atom such as chlorine, fluorine or bromine
  • R 1 a group in which the hydrogen atom of these hydrocarbon groups is partially substituted with a halogen atom such as chlorine, fluorine or bromine, for example, a trifluoropropyl group or the like.
  • a halogen atom such as chlorine, fluorine or bromine
  • a trifluoropropyl group or the like a group in which the hydrogen atom of these hydrocarbon groups is partially substituted with a halogen atom such as chlorine, fluorine or bromine, for example, a trifluoropropyl group or the like.
  • R 1 may be the same group or a different group.
  • a indicating the number of repetitions (or degree of polymerization) of the bifunctional diorganosiloxane unit (SiR 1 2 O 2/2 ) constituting the main chain may be an integer of 100 or more. It is preferably an integer of 100 to 2,000, more preferably an integer of 150 to 1,000, and particularly preferably an integer of 200 to 800.
  • the viscosity of the component (A) organopolysiloxane at 23 ° C. is 2,000 mPa ⁇ s or more, preferably in the range of 2,000 to 500,000 mPa ⁇ s, and more preferably in the range of 3,000 to 500,000 mPa ⁇ s. Preferably, the range of 5,000 to 100,000 mPa ⁇ s is particularly preferable.
  • the viscosity is a value measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, etc.).
  • the degree of polymerization is, for example, the polystyrene-equivalent number average degree of polymerization (or number average molecular weight) in gel permeation chromatography (GPC) analysis using toluene, tetrahydrofuran (THF) or the like as a developing solvent. ) Etc. can be obtained.
  • the organopolysiloxane of the component (A) may be used alone or in combination of two or more.
  • the inorganic filler as the component (B) is a reinforcing filler or a non-reinforcing filler for imparting excellent rubber physical characteristics to the room temperature curable organopolysiloxane composition of the present invention.
  • Examples of the inorganic filler of the component (B) include a surface-treated (hydrophobicized) or surface-untreated inorganic filler. That is, silica-based fillers such as calcined silica, dry silica such as fuming silica (fumed silica), precipitated silica, and wet silica such as sol-gel method silica; carbon black, talc, bentonite, calcium carbonate, zinc carbonate. , Magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, aluminum hydroxide and the like are exemplified.
  • silica-based fillers such as calcined silica, dry silica such as fuming silica (fumed silica), precipitated silica, and wet silica such as sol-gel method silica
  • carbon black, talc, bentonite calcium carbonate, zinc carbonate.
  • the surface of the inorganic filler is hydrophobized with a surface treatment agent, and calcium carbonate, fumes silica, and precipitated silica are treated.
  • a surface treatment agent calcium carbonate, fumes silica, and precipitated silica are treated.
  • Carbon black, aluminum oxide it is preferable that these inorganic fillers have a small amount of water.
  • the type, amount, treatment method, etc. of the surface treatment agent are not particularly limited, but typically, organosilicon compounds such as chlorosilane, alkoxysilane, and organosilazane, fatty acids, paraffin, silane coupling agents, and titanium are used.
  • a known treatment method using a treatment agent such as a coupling agent can be applied.
  • the inorganic filler of the component (B) may be used alone or in combination of two or more.
  • the blending amount of the component (B) is in the range of 1 to 500 parts by mass, preferably in the range of 20 to 300 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount of the component (B) is less than 1 part by mass, the obtained room temperature curable organopolysiloxane composition cannot obtain sufficient rubber strength, which causes a problem that it is not suitable for use for automobile LLC seals. On the other hand, if it exceeds 500 parts by mass, the discharge from the cartridge is deteriorated, the storage stability is lowered, and the mechanical characteristics of the obtained rubber physical properties are also lowered.
  • Component (C) A hydrolyzable organosilicon compound having a silethylene bond in the molecule and having three or more isopropenoxy groups bonded to a silicon atom in the molecule and / or a partially hydrolyzed condensate thereof]
  • the hydrolyzable organosilicon compound (hydrolyzable organosilane compound or organosiloxane compound) which is the component (C) of the present invention functions as a cross-linking agent and is a component generally called a curing agent.
  • the component (C) imparts good storage stability to the obtained room temperature curable organopolysiloxane composition under closed conditions, and air the room temperature curable organopolysiloxane composition after opening or in a non-sealed state. It reacts with the moisture (moisture) inside to make it rubber (three-dimensionally crosslinked and hardened). Further, in the component (C) (curing agent) of the present invention, one silethylene structure ( ⁇ Si-CH 2 CH 2 -Si ⁇ ) is contained in the molecule as shown in the following general formula (2) or (3).
  • R 2 and R 3 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, respectively.
  • B and c are independently integers of 0 to 2 respectively. It is an integer such that the sum of b and c is 3 or less.
  • N indicates an integer of 0 to 50.
  • the hydrolyzable organic silicon compound (that is, the hydrolyzable organosilane compound or the organosiloxane compound) represented by the above general formula (2) or (3) of the component (C) is one at each end of the molecular chain. It has a hydrolyzable silyl group bonded to a silicon atom adjacent to one or both sides of a carbon atom forming a silethylene structure (that is, two in the molecule), and two are present in the molecule. For the whole (total) of each hydrolyzable silyl group, 3 or more hydrolyzable groups in the molecule (usually 3 to 6 in the molecule, preferably 2 or 2 per each hydrolyzable silyl group).
  • the partially hydrolyzed condensate of the hydrolyzable organic silicon compound (hydrolyzable organosilane compound or organosiloxane compound) represented by the above formula (2) or (3) as the component (C) is hydrolyzed.
  • It is an organosiloxane oligomer having three or more residual hydrolyzable groups in the molecule, which is produced by partially hydrolyzing and condensing the terminal hydrolyzable silyl group of the sex organosilane compound or the organosiloxane compound.
  • an organosiloxane oligomer having two residual hydrolyzable groups in the molecule may be used in combination.
  • the hydrolyzable group of the hydrolyzable organosilane compound or organosiloxane compound of the component (C) and its partially hydrolyzed condensate is an isopropenoxy group.
  • a sealing material having excellent LLC resistance and curability can be provided.
  • the organic group other than the above hydrolyzable group that is, the organic group bonded to the site where the hydrolyzable group of the silicon atom present in the hydrolyzable organic silicon compound or its partially hydrolyzed condensate does not bond, is unsubstituted or substituted.
  • a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms is used.
  • alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group.
  • alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group and decyl group.
  • examples thereof include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and an aryl group such as a phenyl group, a tolyl group and a x
  • halogen atoms such as fluorine, bromine and chlorine or cyano groups.
  • alkyl halide groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group can be mentioned.
  • organic group a methyl group, an ethyl group, a propyl group and a phenyl group are preferable.
  • organosilicon compound as the component (C) examples include compounds having the following structures.
  • the number average molecular weight of the hydrolyzable organosilane compound of the component (C) or the partially hydrolyzed condensate of the organosiloxane compound, that is, the siloxane oligomer is not particularly limited, but is usually 500 to 20,000 and 700 to 700. 10,000 is preferable. Further, it is preferable that the above-mentioned hydrolyzable organosilicon compound is an oligomer obtained by polymerizing 2 to 100 pieces, preferably 2 to 20 pieces.
  • the siloxane may be a mixture of a plurality of types of oligomers having different degrees of polymerization.
  • the component (C) may be used alone or in combination of two or more. Further, the composition of the present invention is a general-purpose composition used for a general moisture-curable room temperature-curable silicone composition (organopolysiloxane composition) other than the component (C) as long as the effect of the present invention is not impaired. Hardener (crosslinking agent) may be used in combination.
  • crosslinking agents examples include methyltrimethoxysilane, ethyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and vinyltri.
  • Ekoxysilanes such as ethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane; methyltris (dimethylketooxime) silane, methyltris (methylethylketooxime) silane, ethyltris (methylethylketooxime) silane, methyltris (methylisobutylketooxime) silane , Vinyltris (methylethylketooxime) silane and other ketooxime silanes; methyltri (methoxymethoxy) silane, ethyltri (methoxymethoxy) silane, vinyltri (methoxymethoxy) silane, phenyltri (methoxymethoxy) silane, methyltri (ethoxymethoxy) silane, ethyltri Alkoxyalkoxysilanes such as (ethoxymethoxy) silane,
  • the blending amount of the component (C) is 0.1 to 40 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount of the component (C) is less than 0.1 part by mass of the above lower limit value, the curability and storage stability may be deteriorated. Further, if it exceeds 40 parts by mass of the above upper limit value, not only is it disadvantageous in terms of price, but also there is a risk that the elongation of the cured product may decrease or the durability may deteriorate. In particular, it is preferable that the number of hydrolyzable groups in the component (C) exceeds the number of hydroxyl groups in the component (A).
  • the component (D) is a silane coupling agent represented by the following general formula (4) (that is, a hydrolyzable organosilane compound having a functional group-containing monovalent hydrocarbon group or a carbon functional silane) and /.
  • a silane coupling agent represented by the following general formula (4) (that is, a hydrolyzable organosilane compound having a functional group-containing monovalent hydrocarbon group or a carbon functional silane) and /.
  • it is a partially hydrolyzed condensate thereof, and is an essential component for exhibiting good adhesiveness to the cured product of the room temperature curable organopolysiloxane composition for LLC of the present invention.
  • R 4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms having at least one atom of any one or more selected from a nitrogen atom, a sulfur atom and an oxygen atom, and R 5 Is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is a hydrolyzable group, and d is 0, 1 or 2.
  • R 4 is a functional group other than a guanidyl group containing an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom (for example, an unsubstituted or substituted amino group, an unsubstituted or substituted imino group, an amide). It is a monovalent hydrocarbon group having at least one group (group, ureido group, mercapto group, epoxy group, (meth) acryloxy group, etc.) and having 1 to 20 carbon atoms. Specifically, ⁇ - (2,3-epoxy).
  • Cyclohexyl) ethyl group ⁇ - (3,4-epoxycyclohexyl) ethyl group, ⁇ -glycidoxypropyl group, ⁇ - (meth) acryloxypropyl group, ⁇ -acryloxypropyl group, N- ⁇ (aminoethyl)
  • Nitrogen atoms such as - ⁇ -aminopropyl group, ⁇ -aminopropyl group, N-phenyl- ⁇ -aminopropyl group, ⁇ -ureidopropyl group, ⁇ -mercaptopropyl group, ⁇ -isocyanoxide propyl group, sulfur atom and oxygen atom
  • a monovalent hydrocarbon group having 3 to 20 carbon atoms, more preferably 8 to 14 carbon atoms, which contains at least one of the atoms selected from the above can be mentioned.
  • R 5 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group and an isopropyl group are preferable.
  • examples of the hydrolyzable group X include a ketooxime group, an alkoxy group, an alkoxyalkoxy group, an asyloxy group, an alkenyloxy group and the like.
  • examples thereof include an asyloxy group having 2 to 4 carbon atoms such as a group and a propionoxy group, a vinyloxy group, an allyloxy group, a propenoxy group, an alkenyloxy group having 2 to 4 carbon atoms such as an isopropenoxy group and the like.
  • silane coupling agent of the component (D) examples include aminosilanes such as ⁇ -aminopropyltriethoxysilane and 3-2- (aminoethylamino) propyltrimethoxysilane, and ⁇ -glycidoxypropyltri.
  • Epoxysilanes such as methoxysilane and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (meth) such as ⁇ - (meth) acryloxipropyltrimethoxysilane and ⁇ - (meth) acryloxipropyltriethoxysilane.
  • Acrylic silanes such as ⁇ -mercaptopropyltrimethoxysilane, isocyanatesilanes such as ⁇ -isocyanuspropyltrimethoxysilane, and the like can be mentioned.
  • the silane coupling agent of the component (D) and / or its partially hydrolyzed condensate may be used alone or in combination of two or more.
  • the blending amount of the component (D) is 0.01 to 10 parts by mass, preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 0.01 parts by mass, the cured product does not exhibit sufficient adhesive performance, and if it is blended in excess of 10 parts by mass, the rubber strength after curing is lowered or the curability is lowered.
  • the component (E) is a curing catalyst.
  • a condensation catalyst generally used conventionally as a curing accelerator for the composition can be used.
  • organic tin compounds such as dibutyltin methoxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dioctate, dimethyltin dimethoxide, dimethyltin diacetate; tetrapropyl titanate, tetrabutyl titanate.
  • Tetra-2-ethylhexyl titanate organic titanium compounds such as dimethoxytitanium diacetylacetonate; amine compounds such as hexylamine and tetramethylguanidylpropyltrimethoxysilane and salts thereof, and one of them alone. Or two or more types can be used in combination.
  • the blending amount of the component (E) is 0.01 to 20 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the component (A). It is a department. If the blending amount of the component (E) is less than 0.01 parts by mass of the above lower limit value, the catalytic effect cannot be obtained. Further, if the blending amount of the component (E) exceeds 20 parts by mass of the above upper limit value, the adhesiveness of the room temperature curable organopolysiloxane composition may be lowered, or the storage stability may be deteriorated.
  • additives other than the components (A) to (E) may be used as long as the object of the present invention is not impaired.
  • the additive include polyether as a thixophilic improver, silicone oil as a plasticizer, isoparaffin and the like, and if necessary, pigments, dyes, colorants such as fluorescent whitening agents, antifungal agents and antibacterial agents.
  • Physiologically active additives such as marine organism repellents can be added.
  • phenylsilicone oil as bleed oil fluorosilicone oil
  • surface modifiers such as organic liquids incompatible with silicone
  • solvents such as toluene, xylene, solvent volatile oil, cyclohexane, methylcyclohexane, and low boiling point isoparaffin
  • silicone resin and a solution thereof which are generally used for improving LLC resistance performance.
  • the organopolysiloxane composition of the present invention is a room temperature curable composition, and the curing conditions thereof are not limited as long as the effects of the present invention can be obtained.
  • the room temperature curable organopolysiloxane composition of the present invention is poured into a mold having a depth of 2 mm and cured at 23 ° C. and 50% RH for 5 days to obtain a room temperature curable organopolysiloxane having a thickness of 2 mm.
  • a cured product (silicone rubber sheet) of the composition can be obtained.
  • room temperature curable organopolysiloxane composition of the present invention is suitably used as an automobile LLC sealing material, and in particular, it is excellent in LLC resistance and heat resistance, and also provides good adhesiveness and curability.
  • the residual amount of VOC in the composition is preferably 5,000 ppm or less, more preferably 1,000 ppm or less, and below the detection limit (substantially). 0 ppm) is particularly preferable.
  • the residual amount of VOC in the composition is the amount of a specific organic chemical substance such as toluene, which is measured as a volatile component by gas chromatography when the room temperature curable organopolysiloxane composition is heated at 100 ° C. for 20 minutes. Is.
  • the room temperature curable organopolysiloxane composition of the present invention is cured, it is immersed in an automobile long life coolant at 120 ° C.
  • the room temperature curable organopolysiloxane composition of the present invention is particularly suitable for automobile long life coolant seals.
  • the room temperature curable organopolysiloxane composition of the present invention described above may be produced, for example, by the following procedure. That is, first, 100 parts by mass of the component (A) and 1 to 500 parts by mass of the component (B) are mixed, and then 0.1 to 40 parts by mass of the component (C) is added to the mixture of (A) and (B). E) Add 0.01 to 20 parts by mass of the component (add at this time when a general-purpose curing agent or other additive is added), and mix under reduced pressure. Then, 0.01 to 10 parts by mass of the component (D) is further added and mixed under reduced pressure to obtain the room temperature curable organopolysiloxane composition of the present invention.
  • a room temperature curable organopolysiloxane composition was prepared using the above compounds (curing agents 1 to 4).
  • Examples and comparative examples are shown below.
  • a planetary mixer manufactured by Inoue Seisakusho Co., Ltd.
  • the mixing was carried out at a temperature condition of 25 ° C. for a required time until the components were homogeneously mixed.
  • the physical property values such as viscosity showed the values at 23 ° C. Viscosity is a value measured by a rotational viscometer.
  • Example 1 (A) 100 parts by mass of dimethylpolysiloxane (number average degree of polymerization: about 620) in which both ends of the molecular chain having a viscosity at 23 ° C. of 20,000 mPa ⁇ s are sealed with silanol groups (hydroxyl groups bonded to silicon atoms). (B-1) 100 parts by mass of heavy calcium carbonate (trade name; MC coat P-20, manufactured by Maruo Calcium Co., Ltd.) whose surface is treated with fatty acid, and (B-2) powdered carbon black (denca). After adding 10 parts by mass of black Li-100 and Denka Co., Ltd.
  • Example 2 (A) 100 parts by mass of dimethylpolysiloxane (number average degree of polymerization: about 620) in which both ends of the molecular chain having a viscosity of 20,000 mPa ⁇ s at 23 ° C. are sealed with silanol groups, and (B-1) the surface is fatty acid.
  • Example 3 (A) 100 parts by mass of dimethylpolysiloxane (number average degree of polymerization: about 620) in which both ends of the molecular chain having a viscosity of 20,000 mPa ⁇ s at 23 ° C. are sealed with silanol groups, and (B-1) the surface is fatty acid.
  • Example 4 (A) 100 parts by mass of dimethylpolysiloxane (number average degree of polymerization: about 620) in which both ends of the molecular chain having a viscosity at 23 ° C. of 20,000 mPa ⁇ s are sealed with silanol groups, and (B-1) the surface is fatty acid.
  • Example 5 (A) 100 parts by mass of dimethylpolysiloxane (number average degree of polymerization: about 620) in which both ends of the molecular chain having a viscosity of 20,000 mPa ⁇ s at 23 ° C. are sealed with a silane group, and (B-1) the surface is a fatty acid.
  • SiO 4/2 units and Me 3 It consists SiO 1/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.71, a molecular weight of about 5,400, and silanol group content 0.096 mol /
  • a silane group SiO 4/2 units and Me 3 It consists SiO 1/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.71, a molecular weight of about 5,400, and silanol group content 0.096 mol /
  • composition 8 After adding 100 parts by mass of P-20 (manufactured by Maruo Calcium Co., Ltd.) and 10 parts by mass of (B-2) powdered carbon black (Denka Black Li-100, manufactured by Denka Co., Ltd.) and mixing, (general purpose) Hardener) 6 parts by mass of vinyltriisopropenoxysilane and 0.5 part by mass of (E) tetramethylguanidylpropyltrimethoxysilane were added and mixed under reduced pressure. Finally, 1 part by mass of (D) ⁇ -aminopropyltrimethoxysilane was added and mixed until the whole became uniform to obtain composition 8.
  • compositions 1 to 8 room temperature curable organopolysiloxane composition prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were poured into a mold having a depth of 2 mm, respectively, at 23 ° C. and 50% RH.
  • a rubber sheet having a thickness of 2 mm (a cured product containing a room temperature curable organopolysiloxane composition) was obtained by curing for 7 days.
  • the tack free time (drying time to the touch) was measured according to the method specified in JIS A 5758, and the rubber physical characteristics (hardness, elongation at cutting, tensile strength) of a 2 mm thick sheet were measured according to JIS K 6249. ..
  • the curing rate test was carried out by filling a glass petri dish having an inner diameter of 10 mm with compositions 1 to 8, respectively, and measuring the thickness of the cured portion from the portion exposed to air after standing at 23 ° C. and 50% RH for 1 day. ..
  • a pressure resistance test was performed using a pressure vessel similar to the flange pressure vessel for pressure resistance test specified in JIS K 6820 as a test device.
  • the pressure vessel is composed of an upper vessel having an upper flange having an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange having the same dimensions as the upper flange, and the inner side of the sealing surface of the lower flange.
  • An annular notch having a width of 3 mm and a depth of 3 mm is provided on the edge portion along the circumference.
  • the sealing surface of the lower flange was washed with toluene.
  • the above composition was applied in a bead shape to the central portion of the lower sealing surface with an application amount sufficient to sufficiently fill the sealing surface.
  • the upper container is placed on the lower container so that the sealing surfaces of the upper flange and the lower flange come into contact with each other, and the distance between the sealing surfaces of the upper and lower flanges is specified (thickness direction of the flange).
  • An iron spacer with a height of 20.50 mm was installed and four tightening bolts were assembled. The spacer creates a gap of 0.5 mm between the sealing surfaces, because this is a so-called accelerated test that makes the pressure resistance test on the sealing material more severe.
  • a gas was inserted from the upper pressure port, and the gas pressure that the sealing material, which was a cured product of the above composition, could withstand was measured.
  • test piece aluminum having a width of 25 mm and a length of 100 mm is used as a test piece, and test pieces of the same material are used with each other using compositions 1 to 8, and the adhesion area of each test piece is 2.5 mm 2 .
  • a shear bond test piece bonded with a bond thickness of 1 mm was prepared and cured at 23 ° C. and 50% RH for 7 days. Using these test pieces, the shear adhesive force to aluminum and the cohesive fracture rate were measured according to the method specified in JIS K 6249, and the cohesive fracture rates were compared.
  • the obtained cured silicone rubber sheet of the compositions 1 to 8 and the shear adhesive test piece were mixed with a 50% by mass solution of tap water of long life coolant [trade name: Toyota Super Long Life Coolant]. ]
  • a pressure-resistant container allow 240 hours to elapse at 120 ° C. to deteriorate the cured product in the sheet and the test piece, and then perform the same test as in the initial stage of production to obtain rubber physical properties (hardness, hardness, Elongation during cutting, tensile strength), shear adhesive strength and cohesive failure rate were measured, and a confirmation test of LLC resistance performance was conducted.
  • the cured silicone rubber sheet and the shear adhesive test piece of the obtained compositions 1 to 8 are heated at 120 ° C. for 1,000 hours to obtain a cured product of the sheet and the test piece.
  • the rubber physical properties hardness, elongation at cutting, tensile strength
  • shear adhesive force and cohesive fracture rate were measured by conducting the same test as in the initial stage of production, and a confirmation test of heat resistance performance was performed.
  • the toluene content of the obtained compositions 1 to 8 was measured as the VOC residual amount.
  • the toluene content is determined by a headspace gas chromatograph device (Agilent 7697A manufactured by Agilent Technologies), a column; HP-5MS (length: 30 m, inner diameter: 0.25 mm, film thickness: 0.25 ⁇ m), carrier gas. He (1.0 mL / min), column temperature; 50 ° C.-10 ° C./min-280 ° C., heating conditions; 100 ° C. x 20 minutes.
  • a headspace gas chromatograph device Align 7697A manufactured by Agilent Technologies
  • HP-5MS length: 30 m, inner diameter: 0.25 mm, film thickness: 0.25 ⁇ m
  • He 1.0 mL / min
  • column temperature 50 ° C.-10 ° C./min-280 ° C., heating conditions; 100 ° C. x 20 minutes.
  • the room temperature curable organopolysiloxane composition according to the present invention exhibits good LLC resistance, heat resistance, adhesiveness, and quick curing (initial sealing property), and is effective for automobile LLC sealing applications. all right.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
PCT/JP2020/026628 2019-07-19 2020-07-08 室温硬化性オルガノポリシロキサン組成物及び自動車ロングライフクーラントシール材 WO2021014968A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025079344A1 (ja) * 2023-10-11 2025-04-17 信越化学工業株式会社 光硬化性シリコーン組成物

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472888A (en) * 1964-10-12 1969-10-14 Rhone Poulenc Sa Preparation of vinyloxy containing organosilicon compounds
JPS5677230A (en) * 1979-11-29 1981-06-25 Shin Etsu Chem Co Ltd Production of organosilicon compound containing silaklylene bond and alkenyloxy group
JPS6363684A (ja) * 1986-09-04 1988-03-22 Shin Etsu Chem Co Ltd 有機ケイ素化合物
JPS63192791A (ja) * 1987-02-05 1988-08-10 Shin Etsu Chem Co Ltd 有機けい素化合物
JPH01165663A (ja) * 1987-12-21 1989-06-29 Shin Etsu Chem Co Ltd 室温硬化性組成物
JPH02206654A (ja) * 1989-02-03 1990-08-16 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
JPH02218755A (ja) * 1989-02-20 1990-08-31 Toray Dow Corning Silicone Co Ltd 硬化性オルガノポリシロキサン組成物
JP2010530023A (ja) * 2007-06-11 2010-09-02 ヘンケル コーポレイション 低比ｒｔｖ組成物およびこの製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472888A (en) * 1964-10-12 1969-10-14 Rhone Poulenc Sa Preparation of vinyloxy containing organosilicon compounds
JPS5677230A (en) * 1979-11-29 1981-06-25 Shin Etsu Chem Co Ltd Production of organosilicon compound containing silaklylene bond and alkenyloxy group
JPS6363684A (ja) * 1986-09-04 1988-03-22 Shin Etsu Chem Co Ltd 有機ケイ素化合物
JPS63192791A (ja) * 1987-02-05 1988-08-10 Shin Etsu Chem Co Ltd 有機けい素化合物
JPH01165663A (ja) * 1987-12-21 1989-06-29 Shin Etsu Chem Co Ltd 室温硬化性組成物
JPH02206654A (ja) * 1989-02-03 1990-08-16 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
JPH02218755A (ja) * 1989-02-20 1990-08-31 Toray Dow Corning Silicone Co Ltd 硬化性オルガノポリシロキサン組成物
JP2010530023A (ja) * 2007-06-11 2010-09-02 ヘンケル コーポレイション 低比ｒｔｖ組成物およびこの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025079344A1 (ja) * 2023-10-11 2025-04-17 信越化学工業株式会社 光硬化性シリコーン組成物

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