WO2009154205A1 - Composition adhésive - Google Patents

Composition adhésive Download PDF

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Publication number
WO2009154205A1
WO2009154205A1 PCT/JP2009/060959 JP2009060959W WO2009154205A1 WO 2009154205 A1 WO2009154205 A1 WO 2009154205A1 JP 2009060959 W JP2009060959 W JP 2009060959W WO 2009154205 A1 WO2009154205 A1 WO 2009154205A1
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WO
WIPO (PCT)
Prior art keywords
mass
parts
polymer
polymerization
crosslinkable silyl
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PCT/JP2009/060959
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English (en)
Japanese (ja)
Inventor
道弘 河合
賢一 中村
Original Assignee
東亞合成株式会社
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Priority to JP2010517928A priority Critical patent/JP5067482B2/ja
Publication of WO2009154205A1 publication Critical patent/WO2009154205A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

  • the present invention relates to an adhesive composition. More specifically, the present invention relates to an adhesive composition having high normal state adhesive strength, excellent durability such as heat resistance, thermal shock resistance, weather resistance, and oil resistance, and good handleability due to low viscosity.
  • Patent Document 1 discloses an adhesive composition containing an organic silicon compound having at least two crosslinkable silyl groups in the molecule. Further, it is disclosed that an adhesive composition containing an oxyalkylene polymer having a crosslinkable silyl group is useful as a speaker assembly (Patent Document 2) or an FRP adhesive (Patent Document 3).
  • an oxyalkylene polymer having a crosslinkable silyl group is insufficient in terms of weather resistance and heat resistance, and a vinyl having a crosslinkable silyl group that exhibits very high performance compared to the oxyalkylene polymer.
  • the use of a polymer is being studied.
  • Patent Document 4 describes an adhesive curable composition containing a vinyl polymer having a crosslinkable silyl group as a main component.
  • a vinyl polymer is produced using a living radical polymerization method, and both ends thereof are produced.
  • the living radical polymerization method is a method in which a polymer chain is grown by successive growth, and is a method capable of controlling the molecular weight, molecular weight distribution, terminal group, and block structure.
  • the adhesive composition as disclosed in Patent Document 1 has a problem that the normal adhesive strength is low and durability such as heat resistance and weather resistance is insufficient.
  • the ATRP (Atom Transfer Polymerization) method disclosed in Patent Document 4 is a method using copper bromide as a catalyst, and it is difficult to remove toxic copper from a vinyl polymer, which requires a great economic burden. .
  • halides, such as a bromine remain and have a bad influence also on durability, such as a weather resistance.
  • An object of the present invention is to provide a moisture-curable adhesive composition having high normal adhesive strength and excellent durability such as heat resistance, weather resistance and oil resistance.
  • the present inventors have produced a vinyl polymer having a carboxyl group at its end using a specific living radical polymerization initiator, and further, the vinyl polymer and a specific glycidyl A composition containing a vinyl polymer having at least one crosslinkable silyl group obtained by reacting a compound has excellent mechanical properties, and thus has high normal adhesive strength, excellent heat resistance, and weather resistance. As a result, the present invention was completed.
  • the adhesive composition according to the present invention is characterized by including a vinyl polymer having at least one crosslinkable silyl group obtained by the following steps.
  • a vinyl polymer having at least one crosslinkable silyl group obtained by the following steps.
  • living radical polymerization of the monomer a vinyl polymer having a carboxyl group at the terminal is produced
  • the vinyl polymer is reacted with a glycidyl compound having a crosslinkable silyl group represented by the general formula (3).
  • R 1 is an alkyl group having 1 to 2 carbon atoms or a hydrogen atom
  • R 2 is an alkyl group having 1 to 2 carbon atoms or a nitrile group
  • R 3 is — (CH 2 ) m—, m Is 0 to 2
  • R 4 and R 5 are alkyl groups having 1 to 4 carbon atoms ⁇
  • R 6 is a hydrogen atom or a methyl group
  • R is an alkyl group having 1 to 3 carbon atoms
  • X is an alkoxy group having 1 to 3 carbon atoms
  • n is an integer of 0 to 2 ⁇
  • R is an alkyl group having 1 to 3 carbon atoms
  • X is an alkoxy group having 1 to 3 carbon atoms
  • n is an integer of 0 to 2 ⁇
  • the step [1] is preferably performed in a solvent.
  • the solvent is preferably methyl orthoformate or methyl orthoacetate.
  • the reaction between the vinyl polymer having a carboxyl group at the terminal and the glycidyl compound having a crosslinkable silyl group represented by the general formula (3) is simultaneously performed. .
  • a crosslinkable silyl group-containing (meth) acrylic monomer represented by the general formula (2) is added and copolymerized in a range of 70% to 99% in the polymerization rate of living radical polymerization.
  • the molar ratio of the vinyl polymer having a carboxyl group at the terminal obtained in the above step [1] and the glycidyl compound having a crosslinkable silyl group represented by the general formula (3) is 1: 0.8 to 2.0. It is preferable that
  • the vinyl polymer having at least one crosslinkable silyl group has a number average molecular weight of 5,000 to 50,000 as measured by gel permeation chromatography, and the ratio of the weight average molecular weight to the number average molecular weight is 1.05. It is preferable that it is ⁇ 3.0 or less.
  • the adhesive composition according to the present invention produces a vinyl polymer having a carboxyl group at the terminal using a specific living radical polymerization initiator, and further, the vinyl polymer and a specific glycidyl A vinyl polymer having at least one crosslinkable silyl group obtained by reacting a compound is included. Therefore, the cured product has excellent mechanical properties (breaking elongation and breaking strength) and exhibits high adhesive strength required for an adhesive. Moreover, it is excellent also in durability, such as heat resistance, thermal shock resistance, weather resistance, and oil resistance. Furthermore, the vinyl polymer having at least one crosslinkable silyl group can be produced inexpensively and easily by the process of the present invention.
  • the living radical polymerization method used in the present invention is a living radical polymerization method using a nitrooxide radical shown in JP-T-2003-500378, which allows various vinyl monomers to be polymerized with good control, and a specific polymerization represented by the general formula (1). If an initiator is used, a vinyl polymer having a carboxyl group at the terminal can be obtained.
  • the living radical polymerization used in the present invention can be polymerized by any process such as a batch process, a semi-batch process, a tubular continuous polymerization process, and a continuous stirred tank process (CSTR). A batch process, a semi-batch process, a tubular continuous polymerization process, and a batch process are more preferable.
  • the polymerization method may be bulk polymerization without using a solvent, or solvent-based solution polymerization.
  • the polymerization temperature is preferably 100 to 150 ° C., preferably 105 to 135 ° C., more preferably 110 to 125 ° C.
  • the polymerization rate is remarkably slowed.
  • the polymerization temperature is higher than 150 ° C., the nitrooxide radical cannot cap the growing radical, and the recombination reaction or disproportionation reaction between the growing radicals, the hydrogen abstraction reaction from the polymer main chain or the back-biting reaction. A ⁇ -decomposition reaction occurs, the living polymerizability is lost, and radical polymerization cannot be controlled.
  • the molecular weight distribution can be controlled and the polymerization rate can be adjusted.
  • the amount to be used is preferably 0.001 to 0.2 times with respect to 1 mol of the living radical polymerization initiator [general formula (1)]. More preferably, it is 0.003 to 0.1 times, and particularly preferably 0.005 to 0.05 times. If the molar ratio is less than 0.001 times, the effect of the nitroxy radical cannot be obtained, and if the amount exceeding 0.2 times is added, the reaction rate is remarkably lowered, so that the production efficiency is deteriorated.
  • nitroxy radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1-pi Peridinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1 , 3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidinyloxy radical
  • 2,2,6,6-tetraethyl-1-pi Peridinyloxy radical 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical
  • 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical 1,1 , 3,3-tetramethyl-2-iso
  • the polymerization solvent used in the present invention is suitably an organic hydrocarbon compound, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, and esters such as ethyl acetate and butyl acetate.
  • organic hydrocarbon compound such as cyclic ethers such as tetrahydrofuran and dioxane
  • aromatic hydrocarbon compounds such as benzene, toluene and xylene
  • esters such as ethyl acetate and butyl acetate.
  • ketones such as acetone, methyl ethyl ketone, and cyclohexanone
  • alcohols such as methyl orthoformate, methyl orthoacetate, methanol, ethanol, and isopropanol, and one or more of these can be used.
  • Particularly preferred solvents are methyl orthoformate and methyl orthoacetate which can dissolve
  • the amount of the solvent used is preferably 0 to 200 parts by mass, more preferably 0 to 100 parts by mass, with respect to 100 parts by mass of the monomer. More preferred is 5 to 35 parts by weight, and particularly preferred is 10 to 20 parts by weight.
  • chain transfer reaction resulting from a solvent will generate
  • polymerization control such as molecular weight control, molecular weight distribution control, and the living property of a terminal, will worsen.
  • the amount of the solvent is too small, the crosslinking reaction of the crosslinkable silyl group may proceed.
  • the vinyl monomer used in the polymerization of the present invention is not particularly limited as long as it has radical polymerizability, and various types can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylic acid-n- Butyl, (butyl) (meth) acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecy
  • the amount of the hydrophilic monomer used is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass based on the total amount of the vinyl monomer. If the amount of the hydrophilic vinyl monomer used is less than 20% by mass, it tends to be difficult to satisfy the oil resistance. On the other hand, if it exceeds 80% by mass, the viscosity becomes high and the handleability deteriorates.
  • the crosslinkable silyl group-containing (meth) acrylic monomer copolymerized by living radical polymerization in the present invention is represented by the general formula (2).
  • Specific examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • the crosslinkable silyl group-containing (meth) acrylic monomer may be added to the polymerization system from the beginning, but is preferably added to the polymerization system when the polymerization rate is 70% to 99%.
  • the polymerization rate is more preferably 85% to 98%, particularly preferably 93% to 97%.
  • the polymerization rate exceeds 99%, the copolymerization rate is lowered and may not be introduced into the polymer chain.
  • the amount of the crosslinkable silyl group-containing (meth) acrylic monomer in the present invention is preferably in the range of 0.5 to 10% by mass with respect to the entire polymerizable monomer. If it is less than 0.5% by mass, the cured product is weak and does not exhibit excellent tensile properties and durability. If it exceeds 10% by mass, the crosslink density of the cured product is too high, the elongation at break is low, and it becomes brittle.
  • the crosslinkable silyl group-containing glycidyl compound represented by the general formula (3) is reacted with a terminal carboxy group obtained by living radical polymerization to introduce a silyl group at the polymer terminal.
  • Specific examples of the crosslinkable silyl group-containing glycidyl compound represented by the general formula (3) include 3-glycoxypropyltrimethoxysilane, 3-glycoxypropyltriethoxysilane, 3-gridoxypropylmethyldimethoxysilane, 3-glyco Examples include xylpropylmethyldiethoxysilane.
  • the amount of the crosslinkable silyl group-containing glycidyl compound used in the reaction is preferably 0.8 to 2.0 mol times when the compound of the general formula (1) is 1 mol. More preferably, it is 1.0 to 1.7, and particularly preferably 1.1 to 1.5.
  • the molar ratio is less than 0.8, the amount of silyl groups introduced at the terminal decreases, and the tensile properties of the cured product deteriorate.
  • it exceeds 2.0 mol an unreacted crosslinkable silyl group-containing glycidyl compound remains in the system, and the crosslinking density is excessively lowered at the time of curing, thereby deteriorating the mechanical properties of the cured product.
  • the reaction temperature is preferably 80 ° C. to 200 ° C. 100 to 170 ° C is more preferable, and 110 to 150 ° C is particularly preferable.
  • the reaction temperature is higher than 200 ° C., the terminal nitrooxide is detached, back-biting reaction and beta-cleavage occur, low molecular weight components increase, and the physical properties of the cured product are adversely affected. If it is lower than 80 ° C., the reaction is slow and the production efficiency is remarkably deteriorated.
  • the catalyst is not particularly limited as long as it accelerates the reaction between the glycidyl group and the carboxyl group and does not affect the crosslinkable silyl group, but a preferred catalyst is tributylammonium bromide. Tributylammonium bromide does not affect the reaction of the silyl group, and can effectively accelerate the reaction between the glycidyl group and the carboxy group.
  • the addition amount of the catalyst is preferably 0.1 to 2% by mass, more preferably 0.2 to 1% by mass, based on the amount of the (meth) acrylic polymer having a carboxyl group at the terminal, It is particularly preferably 3 to 0.5% by mass.
  • the amount of the catalyst is less than 0.1% by mass, the effect is small and the productivity cannot be improved.
  • the amount of the catalyst exceeds 2% by mass, there is an adverse effect such as precipitation in the subsequent product.
  • the reaction time of the reaction is not particularly limited, but it is preferable that the reaction time is short. In view of productivity, it is most preferable to perform the reaction simultaneously with an in-situ reaction with living radical polymerization in order to increase production efficiency.
  • the molecular weight of the vinyl polymer having at least one crosslinkable silyl group produced in the present invention is preferably a number average molecular weight (Mn) of 5,000 to 50,000 in terms of polystyrene by gel permeation chromatography (GPC). . More preferred is 8000 to 25000.
  • Mn number average molecular weight
  • Mn is lower than 5000, the crosslink density of the cured product becomes too high, and the elongation of the cured product becomes extremely small.
  • Mn is higher than 50000, the viscosity becomes very high and workability is remarkably deteriorated.
  • the molecular weight distribution (Mw / Mn) is not particularly limited, but is preferably 1.05 to 3.0. More preferably, it is 1.3 to 2.5, and 1.6 to 2.1 is particularly preferable.
  • the number f (Si) of hydrolyzable silyl groups per polymer chain is preferably 1.0 to 10.0.
  • the number is more preferably 1.4 to 3.0, and particularly preferably 1.6 to 2.3.
  • f (Si) is calculated as follows.
  • f (Si) Concentration of alkoxysilyl group in polymer [mol / kg] / (1000 / number average molecular weight) If f (Si) is less than 1.0, the cured product has a low crosslink density, so that the breaking strength is very weak. On the other hand, when it is higher than 10.0, the crosslink density is too high, and the cured product is brittle and does not stretch.
  • the vinyl polymer having at least one crosslinkable silyl group produced in the present invention may require a step of removing residual volatiles after the reaction.
  • Any demelting process may be used as long as it is a commonly used demelting process such as a falling evaporator, a thin film evaporator or an extruder dryer.
  • the demelting temperature condition is preferably 250 ° C. or lower. More preferably, it is 170 degrees C or less, Most preferably, it is 100 degrees C or less. If it is 250 degrees C or less, a living radical polymerization terminal will not dissociate and the production
  • the vinyl polymer having at least one crosslinkable silyl group of the present invention is used as a main component of the moisture curable adhesive composition.
  • the adhesive composition is mainly composed of a base resin having a crosslinkable silyl group, a plasticizer, a filler, a curing accelerator, an adhesion promoter, a stabilizer, an antioxidant, and an additive (thixotropic agent, etc.). Is done.
  • the base resin is a vinyl polymer having at least one crosslinkable silyl group of the present invention, a mixture of the polymer and an oxyalkylene polymer having a hydrolyzable silyl group, or a crosslink synthesized by general radical polymerization.
  • a vinyl polymer having at least one silyl group may be mixed.
  • the content of the vinyl polymer having at least one crosslinkable silyl group of the present invention in the base resin is preferably 100 to 30% by mass, more preferably 100 to 50% by mass, and still more preferably. It is particularly preferably 100 to 70% by mass.
  • the content of the vinyl polymer having at least one crosslinkable silyl group of the present invention is low, the weather resistance, heat resistance and oil resistance are lowered.
  • plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate; non-aromatic diesters such as dioctyl adipate and dioctyl sebacate.
  • a (meth) acrylate polymer having a Mw of 1000 to 7000 and a Tg of -10 ° C. or lower is particularly preferable for maintaining weather resistance, heat resistance and oil resistance.
  • a plasticizer having a (meth) acrylic polymer trade names “ARUFON UP1000”, “ARUFON UP1010”, “ARUFON UP1020”, “ARUFON UP1060”, “ARUFON UP1080”, “ARUFON UP1110” manufactured by Toagosei Co., Ltd. , “ARUFON UH2000”, “ARUFON UH2130”, etc. (“ARUFON” is a trademark of Toagosei Co., Ltd.)
  • These plasticizers can also be blended at the time of polymer production.
  • the amount of the plasticizer is preferably added in the range of 0 to 400 parts by mass with respect to 100 parts by mass of the base resin, more preferably 0 to 200 parts by mass, and particularly preferably 0 to 100 parts by mass. .
  • Fillers include reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite Fillers such as organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloons; fibrous fillers such as asbestos, glass fibers and filaments can be used.
  • reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black
  • fibrous fillers such as asbestos, glass fibers and filaments can be used.
  • a hardened product with high strength with these fillers it is mainly fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc.
  • a preferable result can be obtained by adding a filler selected from white and the like in the range of 0 to 250 parts by mass with respect to 100 parts by mass of the base resin having a crosslinkable silyl group. A range of 80 to 180 parts by mass is more preferable.
  • a filler selected from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. is used, and a crosslinkable silyl group is used.
  • a preferable result can be obtained by adding in an amount of 0 to 200 parts by mass with respect to 100 parts by mass of the vinyl polymer. A range of 80 to 150 parts by weight is more preferable.
  • These fillers may be used alone or in combination of two or more.
  • Catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetoacetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutyl Malate, dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin Tetravalent tin compounds such as diisooctyl malate, titanates such as t
  • Low molecular weight polyamide resin reaction product of excess polyamine and epoxy compound, silane coupling agent having amino group such as ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) aminopropylmethyldimethoxysilane, etc.
  • silane coupling agent having amino group such as ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) aminopropylmethyldimethoxysilane, etc.
  • known silanol condensation catalysts such as other acidic catalysts and basic catalysts.
  • aminosilane, epoxysilane, vinylsilane, methylsilanes, etc. may be used as the adhesion-imparting agent.
  • Epoxy silanes, vinyl silanes, and methyl silanes are also used as storage stabilizers.
  • An antioxidant and an organic solvent such as a hindered phenol may be added as an antioxidant.
  • the adhesive composition according to the present invention contains the above components, but the production method is not particularly limited. Specifically, it can be produced by mixing using a stirrer, a planetary stirrer, or the like.
  • the adhesive composition of the present invention can also be prepared as a one-component type that cures by pre-blending and storing all the blended components in advance and absorbing moisture in the air after construction.
  • Components such as a curing catalyst, a filler, a plasticizer, and water may be blended, and the blended material and the polymer composition may be adjusted as a two-component type that is mixed before use.
  • a one-component type that is easy to handle and has few errors during construction is more preferable.
  • the adhesive composition according to the present invention is excellent in storage stability even at a relatively high temperature, the composition can be handled with a lower viscosity and is suitable for liquid injection molding at a high temperature.
  • the adhesive composition is preferably fluidized at a temperature of 30 ° C. or higher and lower than 80 ° C., more preferably 40 ° C. or higher and lower than 70 ° C.
  • the adhesive composition of the present invention can also be used as a resin for injection molding [LIM (Liquid Injection Molding) and the like].
  • the molding method when the adhesive composition of the present invention is used as a molded body is not particularly limited, and various commonly used molding methods can be used. Examples thereof include cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, and thermoforming. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.
  • the adhesive composition of the present invention When the adhesive composition of the present invention is cured as a molded product, it can be removed without substantially damaging the molded product.
  • the fact that the molded body is not substantially damaged means that the molded body has a surface good enough to fulfill its role.
  • the adhesive composition of the present invention can be used in various applications such as architectural applications, automobile-related applications, and electrical / electronic material applications.
  • Examples of the building use include an elastic adhesive for construction, an adhesive for multilayer glass, and an adhesive for artificial marble.
  • applications for electrical and electronic materials for example, semiconductor sealing resins, insulating materials for printed wiring boards, insulation coating materials for electric wires and cables, electronic component heat radiation sheets, electronic component heat conduction sheets, electronic component coating agents, electronic Examples include potting agents for parts and electrical sealers. It can also be used for packing, O-rings and the like.
  • waterproof packing insect-proof packing, anti-vibration / sound absorption and air sealing material for cleaner, drip-proof cover for electric water heater, waterproof packing, heater unit packing, electrode unit packing, safety valve diaphragm, solenoid valve, Waterproof packing for steam microwave ovens and jar rice cookers, water tank packing, water absorption valve, water receiving packing, heat insulation heater packing, steam blower seal, etc. oil packing for combustion equipment, O-ring, drain packing, feed / intake packing, Speaker gaskets, speaker edges, etc. for acoustic equipment such as anti-vibration rubber, oil filler packing, oil meter packing, diaphragm valve, and the like.
  • the adhesive composition of the present invention is a gasket method [MIPG (Mold In Place Gasket), FIPG (FIPG) that automatically bonds and seals a liquid adhesive with a robot or the like on an assembly line of electric / electronic parts and automobile parts. It can also be used for “Formed In Place Gasket” and CIPG (Cured In Place Gasket)].
  • MIPG Mold In Place Gasket
  • FIPG FIPG
  • TBAB tetrabutylammonium bromide
  • the properties of the polymer were Mw43200, Mn12700, Mw / Mn3.4, E-type viscosity (25 ° C.) 350,000 mPa ⁇ s.
  • the acid value was 0 mgKOH / g, and the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 100%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.0.
  • a 1 liter pressurized stirring tank reactor equipped with an oil jacket has 450 parts by weight of BA, 40 parts by weight of MMA, 15 parts by weight of a living radical polymerization initiator [Formula (5)], butyl acetate (Hereinafter also referred to as “BAc”)
  • BAc living radical polymerization initiator
  • a mixed solution consisting of 100 parts by mass, 11.1 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the mixture was sufficiently deaerated by nitrogen bubbling. It was done.
  • the jacket temperature was raised to 120 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 120 ° C.
  • the polymerization rate of BA was 88%, and the polymerization rate of MMA was 95%.
  • 10 mass parts of MTMS was added there, and it was made to react for 4 hours with 120 degreeC.
  • the polymerization rate of BA was 95%
  • the polymerization rate of MMA was 99%
  • the polymerization rate of MTMS was 98%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 480 parts by mass of a polymer.
  • the properties of the polymer were Mw 34500, Mn 12300, Mw / Mn 2.8, E-type viscosity (25 ° C.) 280000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 97%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.1.
  • the polymerization rate of BA was 90%, and the polymerization rate of MMA was 98%.
  • MTMS 9.8 mass parts was added there, and it was made to react with it at 120 degreeC for 4 hours.
  • the polymerization rate of BA was 97%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 98%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 490 parts by mass of a polymer.
  • the properties of the polymer were Mw19500, Mn12600, Mw / Mn1.6, E-type viscosity (25 ° C.) 200000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 97%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.1.
  • the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 460 parts by mass of a polymer.
  • the properties of the polymer were Mw28000, Mn17400, Mw / Mn1.6, E-type viscosity (25 ° C.) of 150,000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 95%.
  • the number of alkoxysilyl groups f (Si) per polymer polymer chain was 2.4.
  • the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 470 parts by mass of a polymer.
  • the properties of the polymer were Mw 30000, Mn 19000, Mw / Mn 1.6, E-type viscosity (25 ° C.) 160000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 95%.
  • the number of alkoxysilyl groups f (Si) per polymer polymer chain was 2.7.
  • the polymerization rate of BA was 90%, and the polymerization rate of MMA was 95%.
  • 12.9 parts by mass of MTMS was added and reacted at 120 ° C. for 4 hours.
  • the polymerization rate of BA was 97%
  • the polymerization rate of MMA was 99%
  • the polymerization rate of MTMS was 99%.
  • the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 460 parts by mass of a polymer.
  • the properties of the polymer were Mw32700, Mn21100, Mw / Mn1.6, E-type viscosity (25 ° C.) 250,000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 97%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 3.8.
  • the polymerization rate of BA was 92%, and the polymerization rate of MMA was 96%.
  • the polymerization rate of BA was 97%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 99%.
  • the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 460 parts by mass of a polymer.
  • the properties of the polymer were Mw19800, Mn12600, Mw / Mn1.6, E-type viscosity (25 ° C.) 290000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 97%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.0.
  • MMA 100 parts by mass of MMA and 11.7 parts by mass of MTMS were added and reacted at 120 ° C. for 4 hours.
  • the polymerization rate of BA was 99%
  • the polymerization rate of MMA was 83%
  • the polymerization rate of MTMS was 82%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 450 parts by mass of a polymer.
  • the properties of the polymer were Mw18700, Mn12400, Mw / Mn1.5, E-type viscosity (25 ° C.) 1200000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 97%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.0.
  • the properties of the polymer were Mw22500, Mn14100, Mw / Mn1.6, E-type viscosity (25 ° C.) 600000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 98%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.2.
  • BA butyl acrylate
  • EA ethyl acrylate
  • C-1 2-methoxyethyl acrylate
  • C-1 2-methoxyethyl acrylate
  • C-1 living radical polymerization initiator
  • TBAB tetrabutylammonium bromide
  • the jacket temperature was adjusted so that the reaction liquid temperature was maintained at 115 ° C.
  • the polymerization rate of BA was 87.8%.
  • MTMS 3-methacryloxypropyltrimethoxysilane
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 85 ° C. for 5 hours to obtain about 500 parts by mass of a polymer.
  • the properties of the polymer were Mw29900, Mn11500, Mw / Mn2.6, E-type viscosity (25 ° C.) 250,000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living radical polymerization initiator [Formula (5)] was about 95%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.5.
  • the jacket temperature was raised to 115 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction liquid temperature was maintained at 115 ° C.
  • the polymerization rate of BA was 88.6%.
  • MTMS 3-methacryloxypropyltrimethoxysilane
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 85 ° C. for 5 hours to obtain about 500 parts by mass of a polymer.
  • the properties of the polymer were Mw 30000, Mn 12500, Mw / Mn 2.4, E-type viscosity (25 ° C.) 380000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living radical polymerization initiator [Formula (5)] was about 95%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.7.
  • the jacket temperature was raised to 115 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction liquid temperature was maintained at 115 ° C.
  • the polymerization rate of BA was 89.2%.
  • MTMS 3-methacryloxypropyltrimethoxysilane
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 85 ° C. for 5 hours to obtain about 500 parts by mass of a polymer.
  • the properties of the polymer were Mw27700, Mn13200, Mw / Mn2.1, E-type viscosity (25 ° C.) 510000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living radical polymerization initiator [Formula (5)] was about 97%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.8.
  • the mixture was thoroughly degassed with nitrogen bubbling.
  • the jacket temperature was raised to 115 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction liquid temperature was maintained at 115 ° C.
  • the polymerization rate of BA was 87.8%.
  • 10.4 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter also referred to as “MTMS”) was added thereto, and the mixture was reacted at 115 ° C. for 3 hours.
  • the polymerization rate of BA was 99.6%
  • the polymerization rate of EA was 99.0%
  • the polymerization rate of C-1 was 99.2%
  • the polymerization rate of MTMS was 98.6%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 85 ° C. for 5 hours to obtain about 500 parts by mass of a polymer.
  • the properties of the polymer were Mw26800, Mn14100, Mw / Mn1.9, and E-type viscosity (25 ° C.) of 680000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living radical polymerization initiator [Formula (5)] was about 96%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.0.
  • the mixture was thoroughly degassed with nitrogen bubbling.
  • the jacket temperature was raised to 115 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction liquid temperature was maintained at 115 ° C.
  • the polymerization rate of BA was 88.6%.
  • 10.4 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter also referred to as “MTMS”) was added thereto, and the mixture was reacted at 115 ° C. for 3 hours.
  • the polymerization rate of BA was 99.8%
  • the polymerization rate of EA was 98.9%
  • the polymerization rate of C-1 was 99.1%
  • the polymerization rate of MTMS was 97.8%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 85 ° C. for 5 hours to obtain about 500 parts by mass of a polymer.
  • the properties of the polymer were Mw23600, Mn12400, Mw / Mn1.9, and E-type viscosity (25 ° C.) of 1200000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living radical polymerization initiator [Formula (5)] was about 99%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.0.
  • a 1 liter pressurized stirred tank reactor equipped with an oil jacket has 206 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”).
  • BA butyl acrylate
  • EA ethyl acrylate
  • C-1 2-methoxyethyl acrylate
  • C-1 16 parts by weight of a living radical polymerization initiator [Formula (5)], methyl orthoacetate (hereinafter referred to as “C-1”)
  • a mixed liquid consisting of 56 parts by mass also referred to as “MOA”
  • MOA methoxyethyltrimethoxysilane
  • TBAB tetrabutylammonium bromide
  • the jacket temperature was adjusted so that the reaction liquid temperature was maintained at 115 ° C.
  • the polymerization rate of BA was 89.1%.
  • 10.4 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter also referred to as “MTMS”) was added thereto, and the mixture was reacted at 115 ° C. for 3 hours.
  • the polymerization rate of BA was 99.7%
  • the polymerization rate of EA was 99.9%
  • the polymerization rate of C-1 was 98.2%
  • the polymerization rate of MTMS was 98.0%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 85 ° C. for 5 hours to obtain about 500 parts by mass of a polymer.
  • the properties of the polymer were Mw25800, Mn12900, Mw / Mn2.0, E-type viscosity (25 ° C.) 560000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living radical polymerization initiator [Formula (5)] was about 98%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.0.
  • the mixture was thoroughly degassed with nitrogen bubbling.
  • the jacket temperature was raised to 115 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction liquid temperature was maintained at 115 ° C.
  • the polymerization rate of BA was 88.8%.
  • 10.4 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter also referred to as “MTMS”) was added thereto, and the mixture was reacted at 115 ° C. for 3 hours.
  • the polymerization rate of BA was 99.6%
  • the polymerization rate of EA was 98.9%
  • the polymerization rate of C-1 was 99.0%
  • the polymerization rate of MTMS was 99.0%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 85 ° C. for 5 hours to obtain about 500 parts by mass of a polymer.
  • the properties of the polymer were Mw26200, Mn13100, Mw / Mn2.0, E-type viscosity (25 ° C.) 450,000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living radical polymerization initiator [Formula (5)] was about 98%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.0.
  • the polymerization rate of BA was 95%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 99%.
  • the reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 450 parts by mass of a polymer.
  • the properties of the polymer were Mw19800, Mn12400, Mw / Mn1.6, and the number of alkoxysilyl groups f (Si) per polymer polymer chain was 2.2.
  • a mixed solution comprising 400 parts by mass of BA, 40 parts by mass of MMA, 8.8 parts by mass of MTMS, 5 parts by mass of AIVN, and 150 parts by mass of MOA is continuously supplied to the flask over 4 hours, and the reaction temperature in the reactor can be kept constant at 80 ° C. So that the outside temperature was controlled.
  • 0.5 part by mass of AIVN was added and cooled after aging for 1 hour.
  • the BA reaction rate was 97%
  • the MMA reaction rate was 98%
  • the MTMS reaction rate was 98%.
  • a mixed solution consisting of 400 parts by mass of BA, 40 parts by mass of MMA, 19.5 parts by mass of MTMS, 10 parts by mass of AIVN, and 150 parts by mass of MOA is continuously supplied to the flask over 4 hours, and the reaction temperature in the reactor can be kept constant at 80 ° C. So that the outside temperature was controlled.
  • 0.5 part by mass of AIVN was added and cooled after aging for 1 hour.
  • the reaction rate of BA was 94%
  • the reaction rate of MMA was 94%
  • the reaction rate of MTMS was 95%.
  • a constant feed rate (48 g / min, residence time: 12 minutes) is continuously supplied from the raw material tank to the reactor, and the polymer is discharged from the reactor outlet so that the weight of the mixed liquid in the reactor is constant at 580 parts by mass. Extracted continuously. At that time, the jacket temperature was adjusted around 185 ° C. so that the internal temperature of the reactor was a desired 180 ° C. Furthermore, the volatile component was continuously isolate
  • ⁇ Evaluation method> (1) Normal adhesiveness According to JIS A 5557, a mortar piece of 40 mm ⁇ 40 mm was applied to a thickness of 2 mm and bonded to a tile piece. Then, it was left to stand at 23 ° C. and 50% RH ⁇ 7 days, and the tensile bond strength was measured using a tensile tester (Toyo Seiki Co., Ltd., Tensilon 200).
  • ⁇ in the table indicates no change, ⁇ indicates a minute crack, and ⁇ indicates a crack. Moreover, the workability at the time of application was evaluated as ⁇ : good, ⁇ ⁇ : somewhat difficult, ⁇ : bad, ⁇ : very bad.
  • Heat resistance of cured product A part of the cured product sheet was put in an oven at 150 ° C., taken out after 24 hours, and the surface state was observed. No change was indicated by ⁇ , slight change ⁇ , and change ⁇ .
  • Oil resistance of the cured product A part of the cured product sheet for each formulation was immersed in a commercially available engine oil (trade name “GEOMA”, SJ grade, 5W-30, manufactured by JOMO), and then at 160 ° C. for 10 days.
  • the adhesive composition of the present invention has high normal adhesive strength and excellent heat resistance, weather resistance, oil resistance, etc., it can be widely applied in architectural applications, automotive applications, electrical / electronic applications, etc. it can.

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  • Polymers & Plastics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L’invention concerne une composition adhésive durcissable à l’humidité qui présente une force d’adhésion élevée à l’état normal, tout en présentant une excellente durabilité ainsi que d’excellentes qualités de résistance thermique, résistance aux chocs thermiques, résistance aux intempéries et résistance à l’huile. La composition adhésive contient un polymère de vinyle possédant au moins un groupe silyle réticulable. Le polymère de vinyle possédant au moins un groupe silyle réticulable est obtenu par une procédure au cours de laquelle [1] on produit un polymère de vinyle possédant un groupe carboxyle à une extrémité par polymérisation radicalaire vivante d’un monomère de vinyle contenant de 0,1 à 10 % en masse d’un monomère (méth)acrylique contenant un groupe silyle réticulable spécifique, en utilisant un composé représenté par la formule générale (1) en tant qu’initiateur de polymérisation radicalaire vivante ; et [2] on fait réagir le polymère de vinyle ainsi obtenu avec un composé glycidyle possédant un groupe silyle polymérisable spécifique.
PCT/JP2009/060959 2008-06-20 2009-06-16 Composition adhésive WO2009154205A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016870A (ja) * 2009-07-07 2011-01-27 Toagosei Co Ltd 接着剤組成物
JP2011079994A (ja) * 2009-10-08 2011-04-21 Toagosei Co Ltd 塗料用湿気硬化性組成物
JP2011157409A (ja) * 2010-01-29 2011-08-18 Toagosei Co Ltd 塗料用熱硬化性組成物
JP2012077167A (ja) * 2010-09-30 2012-04-19 Toagosei Co Ltd 硬化性組成物
JP2016066006A (ja) * 2014-09-25 2016-04-28 日立化成株式会社 感光性樹脂組成物
WO2020071553A1 (fr) * 2018-10-05 2020-04-09 東亞合成株式会社 Composition adhésive pour assembler un haut-parleur, procédé d'assemblage de haut-parleur et haut-parleur
JPWO2021014794A1 (fr) * 2019-07-19 2021-01-28
JP7391492B2 (ja) 2016-09-26 2024-01-29 シーカ テクノロジー アクチェンゲゼルシャフト シーリング材用組成物

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5228882B2 (ja) * 2008-12-19 2013-07-03 東亞合成株式会社 シーリング材組成物
JP5499501B2 (ja) * 2009-03-17 2014-05-21 東亞合成株式会社 接着剤組成物
KR101714216B1 (ko) * 2015-09-10 2017-03-08 현대자동차주식회사 고강성 및 고강도 발포형 충전제 조성물
JP6511115B2 (ja) * 2017-10-23 2019-05-15 積水化学工業株式会社 電子部品・ガラス基板加工用粘着剤組成物、電子部品・ガラス基板加工用粘着テープ及び電子部品・ガラス基板の製造方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6363768A (ja) * 1986-09-04 1988-03-22 Semedain Kk 接着剤組成物
JPS6445486A (en) * 1987-08-13 1989-02-17 Cemedine Co Ltd Adhesive composition for speaker assembly
JPH04168187A (ja) * 1990-10-31 1992-06-16 Cemedine Co Ltd Ｆｒｐ成型物の接着方法
JPH11130931A (ja) * 1997-07-28 1999-05-18 Kanegafuchi Chem Ind Co Ltd 接着性硬化性組成物
JP2003500378A (ja) * 1999-05-19 2003-01-07 アトフィナ β‐置換ニトロキシドから得られるポリアルコキシアミン
JP2005534712A (ja) * 2002-08-07 2005-11-17 アルケマ ラジカル重合のβ−リン化されたニトロオキシドから生じているアルコキシアミンとそれらの使用
WO2006066971A1 (fr) * 2004-12-23 2006-06-29 Arkema France Utilisation de copolymeres presentant un gradient de composition en tant que stabilisateurs dans la polymerisation de radicaux libres en emulsion
WO2007017614A2 (fr) * 2005-08-09 2007-02-15 Arkema France Procede de preparation d'un materiau polymerique comprenant un copolymere multibloc obtenu par polymerisation radicalaire controlee
WO2007057620A1 (fr) * 2005-11-21 2007-05-24 Arkema France Procede de preparation d'un polymere vivant comprenant des unites methacryliques et/ou methacrylates
WO2007078819A2 (fr) * 2005-12-16 2007-07-12 Arkema Inc. Procedes de fabrication d’un copolymere sequence a faible energie de surface et applications

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6363768A (ja) * 1986-09-04 1988-03-22 Semedain Kk 接着剤組成物
JPS6445486A (en) * 1987-08-13 1989-02-17 Cemedine Co Ltd Adhesive composition for speaker assembly
JPH04168187A (ja) * 1990-10-31 1992-06-16 Cemedine Co Ltd Ｆｒｐ成型物の接着方法
JPH11130931A (ja) * 1997-07-28 1999-05-18 Kanegafuchi Chem Ind Co Ltd 接着性硬化性組成物
JP2003500378A (ja) * 1999-05-19 2003-01-07 アトフィナ β‐置換ニトロキシドから得られるポリアルコキシアミン
JP2005534712A (ja) * 2002-08-07 2005-11-17 アルケマ ラジカル重合のβ−リン化されたニトロオキシドから生じているアルコキシアミンとそれらの使用
WO2006066971A1 (fr) * 2004-12-23 2006-06-29 Arkema France Utilisation de copolymeres presentant un gradient de composition en tant que stabilisateurs dans la polymerisation de radicaux libres en emulsion
WO2007017614A2 (fr) * 2005-08-09 2007-02-15 Arkema France Procede de preparation d'un materiau polymerique comprenant un copolymere multibloc obtenu par polymerisation radicalaire controlee
WO2007057620A1 (fr) * 2005-11-21 2007-05-24 Arkema France Procede de preparation d'un polymere vivant comprenant des unites methacryliques et/ou methacrylates
WO2007078819A2 (fr) * 2005-12-16 2007-07-12 Arkema Inc. Procedes de fabrication d’un copolymere sequence a faible energie de surface et applications

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016870A (ja) * 2009-07-07 2011-01-27 Toagosei Co Ltd 接着剤組成物
JP2011079994A (ja) * 2009-10-08 2011-04-21 Toagosei Co Ltd 塗料用湿気硬化性組成物
JP2011157409A (ja) * 2010-01-29 2011-08-18 Toagosei Co Ltd 塗料用熱硬化性組成物
JP2012077167A (ja) * 2010-09-30 2012-04-19 Toagosei Co Ltd 硬化性組成物
JP2016066006A (ja) * 2014-09-25 2016-04-28 日立化成株式会社 感光性樹脂組成物
JP7391492B2 (ja) 2016-09-26 2024-01-29 シーカ テクノロジー アクチェンゲゼルシャフト シーリング材用組成物
JPWO2020071553A1 (ja) * 2018-10-05 2021-09-09 東亞合成株式会社 スピーカー組立用接着剤組成物、スピーカー組立方法及びスピーカー
WO2020071553A1 (fr) * 2018-10-05 2020-04-09 東亞合成株式会社 Composition adhésive pour assembler un haut-parleur, procédé d'assemblage de haut-parleur et haut-parleur
JPWO2021014794A1 (fr) * 2019-07-19 2021-01-28
CN114026138A (zh) * 2019-07-19 2022-02-08 日本瑞翁株式会社 保存稳定性优异的丙烯酸橡胶
EP4001326A4 (fr) * 2019-07-19 2023-08-16 Zeon Corporation Caoutchouc acrylique ayant une excellent stabilité au stockage
WO2021014794A1 (fr) * 2019-07-19 2021-01-28 日本ゼオン株式会社 Caoutchouc acrylique ayant une excellent stabilité au stockage
CN114026138B (zh) * 2019-07-19 2024-03-19 日本瑞翁株式会社 保存稳定性优异的丙烯酸橡胶
JP7556353B2 (ja) 2019-07-19 2024-09-26 日本ゼオン株式会社 保存安定性に優れるアクリルゴム

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