JP5067482B2 - Adhesive composition - Google Patents

Description

  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.

  An oxyalkylene polymer having a crosslinkable silyl group in the molecule has the feature of reacting with moisture in the air at room temperature to cure in a rubbery form, and is used as a sealing material, adhesive, etc. for architectural applications, automotive applications It is widely used for electrical and electronic materials. For example, 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). However, 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 mainly composed of a vinyl polymer having a crosslinkable silyl group. A vinyl polymer is produced using a living radical polymerization method, and both ends thereof are produced. Discloses a method for modifying a silyl group into a crosslinkable silyl group. Unlike a general radical polymerization method, 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.
JP-A 63-63768 JP-A-64-45486 JP-A-4-168187 JP-A-11-130931

  However, the adhesive composition as disclosed in Patent Document 1 has a problem that normal adhesive strength is low and durability such as heat resistance and weather resistance is insufficient. In addition, 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. . Moreover, there exists a problem that 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-curing adhesive composition having high normal adhesive strength and excellent durability such as heat resistance, weather resistance and oil resistance.

  As a result of intensive studies in view of the above problems, 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.

That is, 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.
[1] A vinyl compound containing 0.1 to 10% by mass of a crosslinkable silyl group-containing (meth) acrylic monomer represented by the general formula (2) using the compound represented by the general formula (1) as a living radical polymerization initiator. By living radical polymerization of the monomer, a vinyl polymer having a carboxyl group at the terminal is produced,
[2] The vinyl polymer is reacted with a glycidyl compound having a crosslinkable silyl group represented by the general formula (3).

｛式中、Ｒ¹は炭素数１〜２のアルキル基または水素原子であり、Ｒ²は炭素数１〜２のアルキル基またはニトリル基であり、Ｒ³は−（ＣＨ₂）ｍ−、ｍは０〜２であり、Ｒ⁴、Ｒ⁵は炭素数１〜４のアルキル基である｝

{In the formula, 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, and R ³ is — (CH ₂ ) m —, m Are 0 to 2, and R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms}

｛式中、Ｒ⁶は水素原子またはメチル基であり、Ｒは炭素数１〜３のアルキル基であり、Ｘは炭素数１〜３のアルコキシ基であり、ｎは０〜２の整数である｝

{Wherein 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, and n is an integer of 0 to 2. }

｛式中、Ｒは炭素数１〜３のアルキル基であり、Ｘは炭素数１〜３のアルコキシ基であり、ｎは０〜２の整数である｝

{In the formula, R is an alkyl group having 1 to 3 carbon atoms, X is an alkoxy group having 1 to 3 carbon atoms, and 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.

  During the living radical polymerization in the above step [1], it is preferable that 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. .

  The crosslinkable silyl group-containing (meth) acrylic monomer represented by the general formula (2) is preferably added and copolymerized in a range of 70% to 99% polymerization rate of living radical polymerization.

  The molar ratio of the vinyl polymer having a carboxyl group at the terminal obtained in the 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

  Furthermore, the number average molecular weight measured by gel permeation chromatography of the vinyl polymer having at least one crosslinkable silyl group is 5,000 to 50,000, 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.

  As described above, 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.

  An embodiment of the present invention will be described as follows, but the present invention is not limited to this.

  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 can polymerize various vinyl monomers with good control, and is 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 from 100 to 150 ° C, preferably from 105 to 135 ° C, more preferably from 110 to 125 ° C. When the polymerization temperature is less than 100 ° C., the polymerization rate is remarkably slowed. On the other hand, when 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 β-decomposition reaction occurs, the living polymerizability is lost, and radical polymerization cannot be controlled.

  By adding a nitroxy radical during the polymerization, the molecular weight distribution can be controlled and the polymerization rate can be adjusted. The amount 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.

  Specific 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. Moreover, you may use the nitroxy radical of General formula (4). A stable free radical such as a galvinoxyl free radical may be used in place of the nitroxy radical.

  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. Examples thereof include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and 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 vinyl polymer well and remove water. This is because, since a polymer containing a moisture-curable silyl group is produced, if the water in the polymerization system is not reduced as much as possible, a crosslinking reaction occurs during the polymerization, resulting in a polymer having a wide molecular weight distribution. When methyl orthoformate or methyl orthoacetate is used, stable polymerization can be performed without causing a crosslinking reaction of the silyl group.

  0-200 mass parts is preferable with respect to 100 mass parts of monomers, and, as for the usage-amount of a solvent, it is more preferable to set it as 0-100 mass parts. More preferably, it is 5-35 weight part, Most preferably, it is 10-20 weight part. When there is too much solvent, chain transfer reaction resulting from a solvent will generate | occur | produce and superposition | polymerization control, such as molecular weight control, molecular weight distribution control, and the living property of a terminal, will worsen. On the other hand, if 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. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxypropyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) 2-aminoethyl acrylate, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid-2-perfluoro Ethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethyl (meth) acrylate Methyl, (meth) acrylic acid 2-perfluoromethyl-2-perful (Meth) acrylic acid monomers such as roethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate; styrene, Styrenic monomers such as vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; maleic anhydride, maleic acid, maleic acid Monoalkyl and dialkyl esters of fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octyl Maleimide monomers such as maleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, propion Vinyl esters such as vinyl acid vinyl, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. Can be mentioned. These may be used alone or a plurality of these may be copolymerized. In the above expression format, for example, (meth) acrylic acid represents acrylic acid or methacrylic acid.

  In addition, for applications where oil resistance is required, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, (meth It is preferable to copolymerize a hydrophilic vinyl monomer such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate. 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 with respect to 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%. When added at a polymerization rate of 70% or less, it becomes close to an α-terminal silyl group, and excellent tensile properties cannot be obtained. On the other hand, if 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 relative 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.

  In the present invention, 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-glycoxypropylmethyldimethoxysilane, and 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 amount of the compound of the general formula (1) is 1 mol. More preferably, it is 1.0-1.7, Most preferably, it is 1.1-1.5. When 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. On the other hand, when 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.

  Moreover, it is preferable that reaction temperature is 80 to 200 degreeC. 100-170 degreeC is more preferable, and it is especially preferable that it is 110-150 degreeC. When 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 production efficiency is remarkably deteriorated.

  In the reaction, a catalyst is preferably used in order to increase production efficiency. 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 with respect to the amount of the (meth) acrylic polymer having a carboxyl group at the terminal, It is particularly preferably 3 to 0.5% by mass. When the amount of the catalyst is less than 0.1% by mass, the effect is small and the productivity cannot be improved. On the other hand, when 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 5000 to 50000 in terms of polystyrene by gel permeation chromatography (GPC). . More preferred is 8000 to 25000. When 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. When Mn is higher than 50000, the viscosity becomes very high and workability is remarkably deteriorated. Although there is no restriction | limiting in particular in molecular weight distribution (Mw / Mn), 1.05-3.0 are preferable. More preferably, it is 1.3-2.5, and 1.6-2.1 is especially preferable.

The number f (Si) of hydrolyzable silyl groups per polymer chain is preferably 1.0 to 10.0. More preferably, the number is 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 | generation of the low molecular weight substance by decomposition | disassembly of a polymer will not occur. On the other hand, when it exceeds 250 ° C., the living polymerization terminal is dissociated, and the polymer chain is partially decomposed to produce a low molecular weight product. Moreover, since coloring will also generate | occur | produce, it is not preferable.

  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 especially preferable that it is 100-70 mass%. When 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.

  Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, and butyl benzyl phthalate; non-aromatic diester such as dioctyl adipate and dioctyl sebacate Basic acid esters; Esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Polyerylene glycol, polypropylene glycol or hydroxyl groups thereof are converted Polyethers; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; Tg-10 ° C. or less with a weight average molecular weight (Mw) of 1000 to 7000 Poly (meth) acrylate. These can be used alone or in admixture of two or more, but are not necessarily required.

  Among the plasticizers, a (meth) acrylate-based 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. As 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. When you want to obtain 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 a range of 0 to 250 parts by mass with respect to 100 parts by mass of the base resin having a crosslinkable silyl group. The range of 80-180 mass parts is more preferable. When it is desired to obtain a cured product having low strength and large elongation, 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 will be obtained if it adds in the range of 0-200 mass parts with respect to 100 mass parts of vinyl-type polymers to have. 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 (curing accelerators) 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 tetrabutyl titanate and tetrapropyl titanate, aluminum trisacetylacetonate, aluminum tris Organoaluminum compounds such as tylacetoacetate and diisopropoxyaluminum ethylacetoacetate, chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octylate, butylamine, octylamine, laurylamine, dibutylamine, Monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylamino) Methyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) and other amine compounds, salts of these amine compounds with carboxylic acids, etc., low polyamines obtained from excess polyamines and polybasic acids Silanols such as silane coupling agents having amino groups such as molecular weight polyamide resin, reaction product of excess polyamine and epoxy compound, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane Examples of the condensation catalyst include other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

  If the amount of these catalysts used is in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the base resin having a crosslinkable silyl group, preferable results are obtained. The range of 0.1-1 mass part is more preferable. These catalysts may be used alone or in combination of two or more.

  As the adhesion-imparting agent, aminosilane, epoxysilane, vinylsilane, methylsilane, or the like may be used. Epoxy silanes, vinyl silanes, and methyl silanes are also used as storage stabilizers. Methyl orthoformate and methyl orthoacetate as dehydrating agents, hindered amine compounds as light stabilizers, benzophenone compounds, benzotriazole compounds and oxalic acid anilide compounds as ultraviolet absorbers, amide waxes and silica as thixotropic agents An antioxidant and an organic solvent such as a hindered phenol may be added as an antioxidant. Moreover, you may mix | blend aliphatic carboxylic acid in order to prevent hardening delay.

  Although the adhesive composition which concerns on this invention contains the above components, the manufacturing method is not specifically 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.

  Since 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. In the present invention, 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. Moreover, in this invention, while making an adhesive composition flow at the temperature of 30 degreeC or more and less than 80 degreeC, hardening reaction can be performed, further making it flow at 30 degreeC or more. That is, 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.

  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 for 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. In addition, as 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. Specifically, 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 packing, electrode 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. In addition, as automobile-related applications, for example, as body parts, it can be used for adhesive seal materials for airtight maintenance, glass vibration prevention materials, vibration isolation materials for car body parts, especially wind seal gaskets, and door glass gaskets. it can. As an engine part, it can be used as an adhesive seal material for engine oil. Furthermore, the adhesive composition of the present invention is a gasket method [MIPG (Mold In Place Gasket), FIPG (FIPG), which automatically applies a liquid adhesive on an assembly line of electric / electronic parts and automobile parts by a robot or the like. It can also be used for Formed In Place Gasket (CIPG) and Cured In Place Gasket (CIPG).

<Synthesis of vinyl polymer>
Examples of the present invention will be described below together with synthesis examples and comparative examples, but it goes without saying that the scope of the present invention is not limited to these examples. In the following, “part” is based on mass unless otherwise specified.
(Method for Producing Polymer A) In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 450 parts by mass of butyl acrylate (hereinafter also referred to as “BA”) and methyl methacrylate (hereinafter referred to as “MMA”). 40 parts by mass, 15 parts by mass of a living radical polymerization initiator [Formula (5)], 11.1 parts by mass of 3-glycidoxypropyltrimethoxysilane, tetrabutylammonium bromide (hereinafter also referred to as “TBAB”). A mixed liquid consisting of 1.0 part by mass was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 90%, and the polymerization rate of MMA was 97%. 9.8 mass parts of 3-methacryloxypropyl trimethoxysilane (henceforth "MTMS") was added there, and it was made to react with it at 120 degreeC for 4 hours. At this time, the polymerization rate of BA was 98%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 99%. After cooling, 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 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.

(Manufacturing method of polymer B) In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 450 parts by mass of BA, 40 parts by mass of MMA, 15 parts by mass of a living radical polymerization initiator [Formula (5)], butyl acetate (Hereinafter also referred to as “BAc”) 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. After 6 hours, 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. At this time, the polymerization rate of BA was 95%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 98%. After cooling, 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.

(Manufacturing method of the polymer C) BA1 mass part, MMA 40 mass part, living radical polymerization initiator [Formula (5)] 15 mass parts, orthoacetic acid in a 1 liter pressurized stirred tank reactor equipped with an oil jacket A mixed liquid consisting of 150 parts by weight of methyl (hereinafter also referred to as “MOA”), 11.1 parts by weight of 3-glycidoxypropyltrimethoxysilane, and 1.0 part by weight of TBAB was prepared, and the liquid mixture was sufficiently desorbed by nitrogen bubbling. I was worried. 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. After 6 hours, 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. At this time, the polymerization rate of BA was 97%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 98%. After cooling, 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.

(Manufacturing method of the polymer D) BA1 mass part, living radical polymerization initiator [Formula (6)] 15 mass parts, MOA 150 mass parts, 3-liter pressurized stirring tank type reactor equipped with an oil jacket and having a capacity of 1 liter A liquid mixture consisting of 11.1 parts by mass of glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the liquid mixture was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 89%. 5.9 mass parts of MTMS was added there, and it was made to react with it at 120 degreeC for 4 hours. At this time, the polymerization rate of BA was 97%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 98%. After cooling, 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 Mw18400, Mn11500, Mw / Mn1.6, E-type viscosity (25 ° C.) 110000 mPa · s. The reaction rate of the carboxyl group of the living polymerization initiator [Formula (6)] was 96%. The number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.5.

(Manufacturing method of the polymer E) BA1 mass part, living radical polymerization initiator [Formula (5)] 5 mass parts, MOA 150 mass parts, 3-part pressure-stirred tank reactor equipped with an oil jacket and having a capacity of 1 liter A mixed liquid consisting of 7.4 parts by mass of glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 90%. Thereto was added 2.6 parts by mass of MTMS and reacted at 120 ° C. for 4 hours. At this time, the polymerization rate of BA was 96%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 99%. After cooling, 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 Mw65100, Mn33400, Mw / Mn2.0, E-type viscosity (25 ° C.) 400000 mPa · s. The reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 93%. The number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.7.

(Manufacturing method of polymer F) BA1 mass part, living radical polymerization initiator [Formula (5)] 10.0 mass parts, MOA 150 mass parts in a 1 liter pressurized stirring tank reactor equipped with an oil jacket, A liquid mixture consisting of 7.4 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the liquid mixture was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 91%. 9.8 mass parts of MTMS was added there, and it was made to react with it at 120 degreeC for 4 hours. At this time, the polymerization rate of BA was 98%, the polymerization rate of MMA was 98%, and the polymerization rate of MTMS was 98%. After cooling, 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.

(Manufacturing method of the polymer G) BA1 mass part, living radical polymerization initiator [Formula (5)] 9.0 mass part, MOA 150 mass part in a 1 liter capacity | capacitance type stirring tank reactor equipped with the oil jacket, A mixed liquid consisting of 6.7 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 90%. Thereto was added 10.5 parts by mass of MTMS, and the mixture was reacted at 120 ° C. for 4 hours. At this time, the polymerization rate of BA was 96%, the polymerization rate of MMA was 97%, and the polymerization rate of MTMS was 97%. After cooling, 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.

(Manufacturing method of the polymer H) BA1 mass part, living radical polymerization initiator [Formula (5)] 9.0 mass part, MOA 50 mass part in a 1 liter capacity | capacitance type stirring tank reactor equipped with the oil jacket, A liquid mixture consisting of 7.2 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the liquid mixture was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 91%. 5.9 mass parts of MTMS was added there, and it was made to react with it at 120 degreeC for 4 hours. At this time, the polymerization rate of BA was 97%, the polymerization rate of MMA was 98%, and the polymerization rate of MTMS was 99%. After cooling, 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 53600, Mn 19000, Mw / Mn 2.8, E-type viscosity (25 ° C.) 330000 mPa · s. The reaction rate of the carboxyl group of the living polymerization initiator [Formula (5)] was 99%. The number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.1.

(Production Method of Polymer I) In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 450 parts by mass of BA, 40 parts by mass of MMA, 15.0 parts by mass of a living radical polymerization initiator [Formula (5)], A mixed liquid consisting of 150 parts by mass of MOA, 11.1 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 2 hours, the polymerization rate of BA was 50%, and the polymerization rate of MMA was 60%. 9.8 mass parts of MTMS was added there, and it was made to react with it at 120 degreeC for 7 hours. At this time, the polymerization rate of BA was 96%, the polymerization rate of MMA was 98%, and the polymerization rate of MTMS was 98%. After cooling, 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 Mw20300, Mn12500, Mw / Mn1.6, E-type viscosity (25 ° C.) 190000 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.

(Manufacturing method of the polymer J) BA1 mass part, MMA40 mass part, living radical polymerization initiator [Formula (5)] 9.0 mass part in a 1 liter capacity | capacitance type stirring tank type reactor provided with the oil jacket, A mixed liquid consisting of 150 parts by mass of MOA, 11.1 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 90%, and the polymerization rate of MMA was 95%. Thereto, 12.9 parts by mass of MTMS was added and reacted at 120 ° C. for 4 hours. At this time, the polymerization rate of BA was 97%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 99%. After cooling, 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.

(Manufacturing method of the polymer K) BA1370 mass part, MMA120 mass part, living radical polymerization initiator [Formula (5)] 15.0 mass parts in a 1 liter pressurized stirring tank reactor equipped with an oil jacket, A mixed liquid consisting of 150 parts by mass of MOA, 11.1 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 92%, and the polymerization rate of MMA was 96%. 9.8 mass parts of MTMS was added there, and it was made to react with it at 120 degreeC for 4 hours. At this time, the polymerization rate of BA was 97%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 99%. After cooling, 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.

(Production Method of Polymer L) In a pressurized stirring tank reactor having a capacity of 1 liter equipped with an oil jacket, 271 parts by mass of BA, 200 parts by mass of MMA, 45.0 parts by mass of a living radical polymerization initiator [Formula (5)], A mixed liquid consisting of 150 parts by mass of MOA, 33.4 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 1.0 part by mass of TBAB was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 94%, and the polymerization rate of MMA was 98%. Thereto, 29.3 parts by mass of MTMS was added, and reacted at 120 ° C. for 4 hours. At this time, the polymerization rate of BA was 99%, the polymerization rate of MMA was 99%, and the polymerization rate of MTMS was 99%. After cooling, 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 Mw 6000, Mn 4400, Mw / Mn 1.35, and E-type viscosity (25 ° C.) 550000 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 2.0.

(Manufacturing method of the polymer M) BA388 mass part, living radical polymerization initiator [Formula (5)] 15.0 mass part, MOA 150 mass part in a 1 liter capacity | capacitance type stirring tank reactor equipped with the oil jacket, A liquid mixture consisting of 11.1 parts by mass of 3-glycidoxypropyltrimethoxysilane and 1.0 part by mass of TBAB was charged, and the liquid mixture was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 90%. MMA100 mass part and MTMS11.7 mass part were added there, and it was made to react with it at 120 degreeC for 4 hours. At this time, the polymerization rate of BA was 99%, the polymerization rate of MMA was 83%, and the polymerization rate of MTMS was 82%. After cooling, 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.

(Manufacturing method of the polymer N) BA1 mass part, living radical polymerization initiator [Formula (5)] 15.0 mass parts, MOA 150 mass parts in a 1 liter pressurized stirred tank reactor equipped with an oil jacket, A mixed liquid consisting of 9.4 parts by mass of 3-glycidoxypropylmethyldimethoxysilane and 1.0 part by mass of TBAB was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. 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. After 6 hours, the polymerization rate of BA was 88%. 80 mass parts of MA and 10.6 mass parts of 3-methacryloxypropylmethyldimethoxysilane (hereinafter also referred to as “MDMS”) were added thereto, and the mixture was reacted at 120 ° C. for 4 hours. At this time, the polymerization rate of BA was 99%, the polymerization rate of MA was 96%, and the polymerization rate of MDMS was 96%. After cooling, 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 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.

(Production Method of Polymer O) 172 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”) in a 1 liter pressurized stirred tank reactor equipped with an oil jacket 86 parts by mass), 86 parts by mass of 2-methoxyethyl acrylate (hereinafter also referred to as “C-1”), 10.9 parts by mass of a living radical polymerization initiator [formula (5)], methyl orthoacetate ( Hereinafter, a mixed liquid comprising 229 parts by mass of “MOA”, 8.1 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 2.2 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”) The charged and mixed liquid was sufficiently deaerated by 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. After 4 hours, the polymerization rate of BA was 87.8%. Thereto was added 7.1 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter also referred to as “MTMS”), and the mixture was reacted at 115 ° C. for 3 hours. At this time, the polymerization rate of BA was 99.0%, the polymerization rate of EA was 99.2%, the polymerization rate of C-1 was 98.5%, and the polymerization rate of MTMS was 98.2%. After cooling, 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. Moreover, 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.

(Production Method of Polymer P) 199 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”) in a 1 liter pressurized stirred tank reactor equipped with an oil jacket 99 parts by weight, 99 parts by weight of 2-methoxyethyl acrylate (hereinafter also referred to as “C-1”), 12.6 parts by weight of a living radical polymerization initiator [Formula (5)], methyl orthoacetate ( Hereinafter, a mixed liquid consisting of 170 parts by mass (also referred to as “MOA”), 9.4 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 2.6 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”) The charged and mixed liquid was sufficiently deaerated by 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. After 4 hours, the polymerization rate of BA was 88.6%. Thereto was added 8.2 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter also referred to as “MTMS”), and the mixture was reacted at 115 ° C. for 3 hours. At this time, the polymerization rate of BA was 99.2%, the polymerization rate of EA was 99.4%, the polymerization rate of C-1 was 99.3%, and the polymerization rate of MTMS was 99.0%. After cooling, 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. Moreover, 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.

(Production Method of Polymer Q) In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 225 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”). 113 parts by weight, 113 parts by weight of 2-methoxyethyl acrylate (hereinafter also referred to as “C-1”), 14.3 parts by weight of a living radical polymerization initiator [formula (5)], methyl orthoacetate ( (Hereinafter also referred to as “MOA”) 113 parts by mass, 3-glycidoxypropyltrimethoxysilane 10.6 parts by mass, tetrabutylammonium bromide (hereinafter also referred to as “TBAB”) 2.9 parts by mass The charged and mixed liquid was sufficiently deaerated by 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. After 4 hours, the polymerization rate of BA was 89.2%. 9.3 mass parts of 3-methacryloxypropyl trimethoxysilane (henceforth "MTMS") was added there, and it was made to react with 115 degreeC for 3 hours. At this time, the polymerization rate of BA was 99.5%, the polymerization rate of EA was 99.6%, the polymerization rate of C-1 was 99.4%, and the polymerization rate of MTMS was 98.4%. After cooling, 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. Moreover, 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.

(Production Method of Polymer R) 251 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”) in a 1 liter pressurized stirred tank reactor equipped with an oil jacket 126 parts by mass), 126 parts by mass of 2-methoxyethyl acrylate (hereinafter also referred to as “C-1”), 16 parts by mass of a living radical polymerization initiator [Formula (5)], methyl orthoacetate (hereinafter, A mixed liquid consisting of 56 parts by mass (also referred to as “MOA”), 11.9 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 3.2 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”); 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. After 4 hours, the polymerization rate of BA was 87.8%. 10.4 mass parts of 3-methacryloxypropyl trimethoxysilane (henceforth "MTMS") was added there, and it was made to react with 115 degreeC for 3 hours. At this time, 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%, and the polymerization rate of MTMS was 98.6%. After cooling, 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. Moreover, 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.

(Production Method of Polymer S) In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 69 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”). 138 parts by mass, acrylic acid-2-methoxyethyl (hereinafter also referred to as “C-1”) 138 parts by mass, living radical polymerization initiator [Formula (5)] 16 parts by mass, methyl orthoacetate (hereinafter, A mixed liquid consisting of 56 parts by mass (also referred to as “MOA”), 11.9 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 3.2 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”); 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. After 4 hours, the polymerization rate of BA was 88.6%. 10.4 mass parts of 3-methacryloxypropyl trimethoxysilane (henceforth "MTMS") was added there, and it was made to react with 115 degreeC for 3 hours. At this time, 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%, and the polymerization rate of MTMS was 97.8%. After cooling, 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. Moreover, 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.

(Production Method of Polymer T) In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 206 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”). 69 parts by mass, 69 parts by mass of 2-methoxyethyl acrylate (hereinafter also referred to as “C-1”), 16 parts by mass of a living radical polymerization initiator [Formula (5)], methyl orthoacetate (hereinafter, A mixed liquid consisting of 56 parts by mass (also referred to as “MOA”), 11.9 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 3.2 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”); 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. After 4 hours, the polymerization rate of BA was 89.1%. 10.4 mass parts of 3-methacryloxypropyl trimethoxysilane (henceforth "MTMS") was added there, and it was made to react with 115 degreeC for 3 hours. At this time, 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%, and the polymerization rate of MTMS was 98.0%. After cooling, 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. Moreover, 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.

(Production Method of Polymer U) 275 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), ethyl acrylate (hereinafter referred to as “EA”) in a 1 liter pressurized stirred tank reactor equipped with an oil jacket 34 parts by mass, 34 parts by mass of 2-methoxyethyl acrylate (hereinafter also referred to as “C-1”), 16 parts by mass of a living radical polymerization initiator [Formula (5)], methyl orthoacetate (hereinafter, A mixed liquid consisting of 56 parts by mass (also referred to as “MOA”), 11.9 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 3.2 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”); 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. After 4 hours, the polymerization rate of BA was 88.8%. 10.4 mass parts of 3-methacryloxypropyl trimethoxysilane (henceforth "MTMS") was added there, and it was made to react with 115 degreeC for 3 hours. At this time, 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%, and the polymerization rate of MTMS was 99.0%. After cooling, 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. Moreover, 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.

(Comparative Synthesis Example 1) In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 450 parts by mass of BA, 40 parts by mass of MMA, 15 parts by mass of a living radical polymerization initiator [Formula (5)], 150 parts by mass of MOA, A mixed solution consisting of 19.5 parts by mass of MTMS was charged, and the mixed solution was sufficiently degassed by nitrogen bubbling. 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. After 8 hours, the reaction solution was cooled and extracted. 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.

(Comparative Synthesis Example 2) A 1-liter four-necked flask equipped with a stirrer, thermometer, liquid feed pump, nitrogen inlet tube and condenser was set in a water bath capable of temperature control, MOA 100 parts by mass, BA 50 parts by mass, MTMS 1.0 part by mass was added and kept at 80 ° C. under a nitrogen atmosphere. Next, 0.5 part by mass of azobisisovaleronitrile (hereinafter also referred to as “AIVN”) was added as a polymerization initiator to initiate polymerization. Subsequently, 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. After completion of liquid feeding at the same temperature, 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%, and the MTMS reaction rate was 98%. Thereafter, in order to remove volatile components such as the solvent and residual monomers, vacuum desorption was performed under conditions of a vacuum degree of 0.3 kPa, 90 ° C., and 5 hours. About 460 parts by mass of a polymer was obtained. The properties of the polymer were Mw101000, Mn25000, Mw / Mn4.0, E-type viscosity (25 ° C.) 660000 mPa · s. The number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 2.2.

(Comparative Synthesis Example 3) A 1-liter four-necked flask equipped with a stirrer, thermometer, liquid feed pump, nitrogen inlet tube and condenser was set in a water bath capable of temperature control, MOA 100 parts by mass, BA 50 parts by mass, MTMS 2 parts And kept at 80 ° C. under a nitrogen atmosphere. Next, 0.65 parts by mass of AIVN was added as a polymerization initiator to initiate polymerization. Subsequently, 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. After completion of liquid feeding at the same temperature, 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%, and the reaction rate of MTMS was 95%. Thereafter, in order to remove volatile components such as the solvent and residual monomers, vacuum desorption was performed under conditions of a vacuum degree of 0.3 kPa, 90 ° C., and 5 hours. About 450 parts by mass of a polymer was obtained. The properties of the polymer were Mw 61000, Mn 13500, Mw / Mn 4.5, E-type viscosity (25 ° C.) 420,000 mPa · s. The number f (Si) of alkoxysilyl groups per polymer chain of the polymer was 2.3.

(Comparative Synthesis Example 4) The oil jacket temperature of a 1 liter pressurized stirred tank reactor equipped with an oil jacket was kept at 200 ° C. Subsequently, ditertiary butyl peroxide (hereinafter referred to as “polymerization initiator”) was added to a monomer mixed solution composed of 87 parts by mass of BA, 10 parts by mass of MMA, 3.0 parts by mass of MTMS, and 10 parts by mass of isopropanol (hereinafter also referred to as “IPA”). Also referred to as “DTBP”.) 0.2 parts by mass were mixed and charged into a raw material tank. 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 | separated with the thin film evaporator which maintained the pressure reduction degree of 20 kPa, and the temperature of 250 degreeC for the extracted reaction material, The copolymer which hardly contains a volatile component was collect | recovered. After starting the supply of the monomer mixture, it was determined that 36 minutes after the temperature inside the reactor was stabilized, the equilibrium state was reached, and the resin recovery start point after evaporation of the thin film was used. Then, about 180 minutes, As a result of continuing the supply of the raw material, about 7000 parts by mass of the polymer was recovered.
Mw of polymer A was 13,200, Mn was 4,000, Mw / Mn was 3.2, and E-type viscosity (25 ° C.) was 76000 mPa · s. The number of alkoxysilyl groups f (Si) per polymer polymer chain was 0.5.

Examples 1 to 23, Comparative Examples 1 to 6
It mix | blended according to the mixture ratio of Table 2, according to JISA5557, it apply | coated to the mortar piece 40mm x 40mm by thickness 2mm, and it bonded together with the tile piece. Then, it was left to stand at 23 ° C. and 50% RH × 7 days, and the adhesive strength was measured (normal adhesiveness).
Moreover, after apply | coating to the mortar piece 40mm x 40mm by thickness 2mm, the metalling weather meter test was done. Every 300 hours, it was visually observed up to 2700 hours (weather resistance). These results are shown in Table 3.
The quantities in Table 2 mean parts by mass. The materials used are as follows.
[Base resin]
Acrylic silicon base material: see Table 1 (polymers A to U, synthesis examples 1 to 4)
・ Modified Silicone: Asahi Glass Co., Ltd., trade name “Exstar ESS2420”
[Plasticizer]
-Acrylic plasticizer: manufactured by Toagosei Co., Ltd., trade name "ARUFON UP-1000" (Mw2900, Mn1600)
[Filler]
Calcium carbonate: 50 wt / 50 wt mixture of light coal (product name “Shiraka Hana CCR” manufactured by Shiroishi Calcium Co., Ltd.) and heavy coal (product name “Super SS” manufactured by Maruo Calcium Co., Ltd.) [additive]
-Epoxy resin: manufactured by Japan Epoxy Resin Co., Ltd., trade name “Epicoat 828”
Anti-aging agent: Product name “Chinubin B75” manufactured by Ciba Specialty
・ Vinylsilane: Nippon Unicar Co., Ltd., trade name “A171”
Ketimine silane: manufactured by Chisso Corporation, trade name “S340”
-Ketimine: Product name "Epicure H30" manufactured by Japan Epoxy Resin Co., Ltd.
・ Curing catalyst: Dibutyltin diacetylacetonate

<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 adhesive strength was measured using a tensile tester (manufactured by Toyo Seiki Co., Ltd., Tensilon 200).
Measurement environment: 23 ° C, 50% RH
Tensile speed: 3 mm / min Criteria for determining the fracture state:
○: Cohesive failure or base material failure, Δ: Cohesive failure and interfacial failure are mixed, ×: Interfacial failure (2) Weather resistance test and workability For each compound, a mortar piece is applied in a thickness of 2 mm to 40 mm × 40 mm The cured sheet was prepared by curing for 1 week under the conditions of 23 ° C. and 50% RH. An accelerated weather resistance test was conducted with a metering weather meter (DAIPLA METAL WEATHER KU-R5NCI-A, manufactured by Daipura Wintes), and cracks were visually observed every 300 hours.
○ in the table indicates no change, Δ indicates a minute crack, and × indicates a crack.
Moreover, the workability at the time of application was evaluated as ○: good, ○ Δ: somewhat difficult, Δ: bad, ×: very bad.
(3) 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 Δ, and change ×.
(4) Oil resistance of cured product A part of the cured product sheet is immersed in a commercially available engine oil (trade name “GEOMA”, SJ grade, 5W-30, manufactured by JOMO) for each formulation, and is subjected to 160 ° C. for 10 days. After heating, the surface state was observed. Furthermore, the weight change rate before and after the test was measured. A cured product having a smaller weight change rate is a cured product having excellent oil resistance.
(5) Bleed Each part of the cured product sheet was allowed to stand at 23 ° C. and 50% RH for 30 days, and then the tentacles were used to confirm whether the liquid content was bleeding. No bleed was marked with ◯, and bleed was marked with x.
These results are shown in Tables 3 and 4.

  Since 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.

Claims (7)

A vinyl polymer having at least one crosslinkable silyl group is subjected to the following steps:
[1] A vinyl compound containing 0.1 to 10% by mass of a crosslinkable silyl group-containing (meth) acrylic monomer represented by the general formula (2) using the compound represented by the general formula (1) as a living radical polymerization initiator. By living radical polymerization of the monomer, a vinyl polymer having a carboxyl group at the terminal is produced,
[2] The vinyl polymer is reacted with a glycidyl compound having a crosslinkable silyl group represented by the general formula (3).
An adhesive composition comprising a vinyl polymer having at least one crosslinkable silyl group obtained by:

{In the formula, 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, and R ³ is — (CH ₂ ) m —, m Are 0 to 2, and R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms}

{Wherein 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, and n is an integer of 0 to 2. }

{In the formula, R is an alkyl group having 1 to 3 carbon atoms, X is an alkoxy group having 1 to 3 carbon atoms, and n is an integer of 0 to 2}   The adhesive composition according to claim 1, wherein the step [1] is performed in a solvent.   The adhesive composition according to claim 2, wherein the solvent is methyl orthoformate or methyl orthoacetate.   During the living radical polymerization in the above step [1], 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 performed simultaneously. The adhesive composition according to any one of claims 1 to 3.   The crosslinkable silyl group-containing (meth) acrylic monomer represented by the general formula (2) is added and copolymerized in a range of 70% to 99% polymerization rate of living radical polymerization. The adhesive composition according to any one of the above.   The molar ratio of the vinyl polymer having a carboxyl group at the terminal obtained in the step [1] and the glycidyl compound having a crosslinkable silyl group represented by the general formula (3) is 1: 0.8 to 2.0. The adhesive composition according to claim 1, wherein the adhesive composition is any one of the following.   The number average molecular weight measured by gel permeation chromatography of the vinyl polymer having at least one crosslinkable silyl group is 5000 to 50000, and the ratio of the weight average molecular weight to the number average molecular weight is 1.05 to 3 The adhesive composition according to any one of claims 1 to 6, wherein the adhesive composition is 0.0 or less.