JP5582333B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition, and more particularly to a curable composition containing a vinyl resin having a reactive alkoxysilyl group.

  Organic polymers having curable alkoxysilyl groups and curable compositions have already been industrially produced and sold, and are widely used in applications such as adhesives, sealants, and paints. Conventionally, as a method for synthesizing an organic polymer having an alkoxysilyl group, a method of polymerizing a compound having a polymerizable unsaturated bond and an alkoxysilyl group with a vinyl monomer is known. As the compound having an alkoxysilyl group, (meth) acryloxypropyl polyalkoxysilane such as methacryloxypropyltrimethoxysilane is used (Patent Document 1).

  Usually, these curable compositions are cured using various metal catalysts, and are used for various applications depending on the type and amount of addition. However, these conventional curable compositions are difficult to achieve both curability and toughness. Furthermore, although the metal catalyst generally used for these uses is an organotin compound, it may contain a highly toxic tributyltin derivative and is treated as a material of concern.

  On the other hand, as described in Patent Document 2, there is an alkoxysilane-terminated polymer having such a high reactivity that the content of the tin-containing catalyst can be significantly reduced. As the report content, a report that a catalyst containing tin and other heavy metals can be deleted is cited. However, although the alkoxysilane-terminated polymer described in Patent Document 2 has excellent curability, it has a problem in storage stability and has a problem in producing an industrialized product.

Japanese Unexamined Patent Publication No. Sho 63-112642 JP 2005-501146 A

  An object of the present invention is to provide a curable composition that realizes both curability and toughness, further exhibits fast curability and excellent storage stability, and does not require a tin catalyst.

The present inventors have intensively investigated high reactivity and excellent storage stability in a curable composition containing an alkoxysilyl group-containing organic polymer, and completed the present invention. The curable composition of the present invention comprises (A) a vinyl resin obtained by reacting a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and (B) a curing catalyst. see containing the (B) curing catalyst is an amine compound, characterized in that it is used in the adhesive. As the amine compound, it is particularly preferable to use aminosilanes.

In (Formula (1), ^{R 1} is an alkyl group, an alkenyl group having 1 to 18 carbon atoms, an aryl group, or a phenyl group, ^{R 2} is an alkyl group having 1 to 4 carbon atoms, an alkenyl group, an aryl group Or a phenyl group, R ³ is hydrogen or a methyl group, and m is an integer of 1 to ^3. )

(In the formula (2), R ⁴ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom, an alkali metal atom, or a hydrocarbon-containing group having 1 to 24 carbon atoms. .)

The (B) curing catalyst is preferably an amine compound. The curable composition of the present invention preferably has a tin content of 100 ppm or less.
In the curable composition of the present invention, it is preferable to blend 0.000001 to 10 parts by mass of the (B) curing catalyst with respect to 100 parts by mass of the (A) vinyl resin.

  The (A) vinyl-based resin preferably includes a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4).

In (Formula (3), ^{R 1} represents an alkyl group, an alkenyl group having 1 to 18 carbon atoms, an aryl group, or a phenyl group, ^{R 2} is an alkyl group having 1 to 4 carbon atoms, an alkenyl group, an aryl group Or a phenyl group, R ³ is hydrogen or a methyl group, and m is an integer of 1 to ^3. )

(In the formula (4), R ⁴ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom, an alkali metal atom, or a hydrocarbon-containing group having 1 to 24 carbon atoms. .)

  The reaction of the compound represented by the general formula (1) and the compound represented by the general formula (2) is preferably a radical polymerization reaction. The radical polymerization is preferably free radical polymerization or living radical polymerization.

  The curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, or the like, and particularly preferably used as an adhesive.

  The curable composition of the present invention achieves both a curability and a toughness, and further has a tremendous effect that it does not require a tin catalyst and is excellent in fast curability and storage stability.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The curable composition of the present invention comprises (A) a vinyl resin obtained by reacting a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and (B) a curing catalyst. The (A) vinyl resin includes a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4).

In the formulas (1) and (3), R ¹ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aryl group, or a phenyl group, and R ² is an alkyl group having 1 to 4 carbon atoms or an alkenyl group. , An aryl group or a phenyl group, R ³ is hydrogen or a methyl group, and m is an integer of 1 to 3.
In the formulas (2) and (4), R ⁴ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom, an alkali metal atom, or a carbon atom having 1 to 24 carbon atoms. It is a hydrogen-containing group.

In the compound represented by the formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aryl group, or a phenyl group, an alkyl group having 1 to 18 carbon atoms, or a carbon number having 6 to 20 carbon atoms. An aryl group or an aralkyl group having 7 to 20 carbon atoms is preferred, and a methyl group is most preferred. When a plurality of R ¹ are present, they may be the same or different. R ² is an alkyl group having 1 to 4 carbon atoms, an alkenyl group, an aryl group, or a phenyl group, and a methyl group is preferable. When a plurality of R ² are present, they may be the same or different. R ³ is hydrogen or a methyl group. m is 1, 2 or 3, and 3 is more preferable from the viewpoint of fast curability.

  Specific examples of the compound represented by the formula (1) include acryloxymethyltrimethoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethyldimethylmethoxysilane, acryloxymethyltriethoxysilane, and acryloxymethylmethyldisilane. Ethoxysilane, Acryloxymethyldimethylethoxysilane, Acryloxymethyltripropoxysilane, Acryloxymethylmethyldipropoxysilane, Acryloxymethyldimethylpropoxysilane, Acryloxymethylphenyldimethoxysilane, Acryloxymethyldiphenylmethoxysilane, Acryloxymethylphenyl Diethoxysilane, acryloxymethyldiphenylethoxysilane, acryloxymethylphenyldipropoxy silane, acryloxymethyldi Phenylpropoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethyldimethylmethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldiethoxysilane, methacryloxymethyldimethylethoxysilane, methacryloxymethyl Tripropoxysilane, methacryloxymethylmethyldipropoxysilane, methacryloxymethyldimethylpropoxysilane, methacryloxymethylphenyldimethoxysilane, methacryloxymethyldiphenylmethoxysilane, methacryloxymethylphenyldiethoxysilane, methacryloxymethyldiphenylethoxysilane, methacryloxy Methylphenyl dipropoxy silane, methacryloxyme In particular, acryloxymethyltrimethoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethyldimethylmethoxysilane, acryloxymethyltriethoxysilane, acryloxymethylmethyldiethoxysilane, acryloxymethyl Dimethylethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethyldimethylmethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldiethoxysilane, methacryloxymethyl Dimethylethoxysilane is preferred. These may be used alone or in combination of two or more.

In the compound represented by the formula (2), R ⁴ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. R ⁵ is a hydrogen atom, an alkali metal atom, or a hydrocarbon-containing group having 1 to 24 carbon atoms, and the hydrocarbon-containing group may be linear or have a side chain, At least a part of the hydrogen atoms in the hydrocarbon-containing group or the group forming the side chain of the hydrocarbon-containing group are a chlorine atom, a fluorine atom, a primary amino group, a secondary amino group, a tertiary amino group At least one selected from the group consisting of quaternary amine salt groups, amide groups, isocyanate groups, alkylene oxide groups, hydroxysilyl groups, methoxysilyl groups, ethoxysilyl groups, propoxysilyl groups, chlorosilyl groups, bromosilyl groups, and glycidyl groups. It may be substituted with a kind of polar group or a reactive functional group, and the hydrocarbon-containing group may have a double bond, and the hydrocarbon-containing group is cyclic You may have a structure. Examples of R ⁵ include alkyl groups having 1 to 24 carbon atoms, cycloalkyl groups, aryl groups, alkenyl groups, cycloalkenyl groups, alkoxy groups, and alkyl ether groups. At least a part of the hydrogen atoms constituting the group R ⁵ may be substituted with a halogen atom, a sulfonic acid group, a glycidyl group, or the like.

Examples of the compound represented by the formula (2) include salts such as acrylic acid and alkali metal acrylate salts; salts such as methacrylic acid and alkali metal methacrylate salts; methyl acrylate, ethyl acrylate, propyl acrylate, Acrylic acid alkyl esters such as butyl acrylate, pentyl acrylate, hexyl acrylate, -2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate; phenyl acrylate, benzyl acrylate Acrylic acid aryl esters; methoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, alkoxyalkyl acrylates such as ethoxypropyl acrylate; , Alkyl methacrylates such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate Methacrylate aryl esters such as phenyl methacrylate and benzyl methacrylate; alkoxyalkyl methacrylates such as methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, ethoxypropyl methacrylate; ethylene glycol Diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene (Poly) alkylene glycol diacrylates such as ethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate; ethylene glycol dimethacrylate, Like diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate Dimethacrylic acid ester of (poly) alkylene glycol; trimethylolpropane triacrylic acid ester Polyvalent acrylates such as trimethylolpropane trimethacrylates; vinyl halide compounds such as 2-chloroethyl acrylate and 2-chloroethyl methacrylate; cyclohexyl acrylate Acrylic esters of alicyclic alcohols; Methacrylic esters of alicyclic alcohols such as cyclohexyl methacrylate; Oxazoline group-containing polymerizable compounds; Acrylic acid-2-aziridinylethyl, Methacrylic acid-2-aziridin Aziridine group-containing polymerizable compounds such as ruethyl; epoxy group-containing vinyl monomers such as glycidyl acrylate, glycidyl methacrylate, acrylate-2-ethyl glycidyl ether, and -2-ethyl glycidyl methacrylate 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, monoesters of acrylic acid or methacrylic acid and polypropylene glycol or polyethylene glycol, lactones and (meth) acrylic Hydroxyl group-containing vinyl compounds such as adducts with 2-hydroxyethyl acid; fluorine-containing vinyl monomers such as fluorine-substituted methacrylic acid alkyl esters and fluorine-substituted acrylic acid alkyl esters; Saturated carboxylic acids, salts thereof and (partial) ester compounds and acid anhydrides thereof; reactive halogen-containing vinyl monomers; N, N′-dimethylaminoethyl acrylate ; amide group-containing vinyl monomers. These may be used alone or in combination of two or more.

  In the present invention, a method of reacting the compound represented by the general formula (1) with the compound represented by the general formula (2) may be a known polymerization method (for example, JP-A-63-112642, JP-A-2007- 230947, JP-A-2001-40037, JP-A-2003-313397, etc.) can be used, and a radical polymerization method using a radical polymerization reaction is preferred. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned, and the controlled radical polymerization method is preferred. Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and an addition-fragmentation chain transfer (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. A reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound (Japanese Patent Laid-Open No. 2001-40037) are also suitable.

<Free radical polymerization method>
When using a free radical polymerization method, it is preferable to make it react at 0 to 200 degreeC using a chain transfer agent and an initiator. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the free radical polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 1 to 144 hours, preferably It is preferable to set within a range of 2 to 8 hours.

  As the chain transfer agent, known chain transfer agents can be widely used, and there is no particular limitation. However, a thiol compound is preferable, and a thiol compound having a reactive silyl group is more preferable. For example, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethyltripropoxysilane, mercaptomethylmethyldisilane Propoxysilane, mercaptomethyldimethylpropoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysilane, 3-mercaptopropyl -Dimethylmonomethoxysilane, 3-mercaptopropyl-monomethyldiethoxysilane, 4- Rukaputobuchiru - trimethoxysilane and 3-mercaptopropyl butyl - trimethoxysilane. These may be used alone or in combination of two or more.

  The chain transfer agent can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a usual amount, specifically, 100 mol parts of a polymerizable unsaturated compound to be polymerized. The amount is usually 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

  The initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, an ionic initiator, and a redox initiator. These may be used alone or in combination of two or more.

  Examples of the azo initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis. (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobisisobutyronitrile (V-60, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylbutyronitrile) (V-59, manufactured by Wako Pure Chemical Industries, Ltd.), 1,1′-azobis (cyclohexane-1-carbonitrile) (V-40, Wako Pure) Yakuhin Kogyo Co., Ltd.), 1-[(1-cyano-1-methylethyl) azo] formamide (V-30, Wako Pure Chemical Industries, Ltd.), 2-phenylazo-4-methoxy-2,4 -Dimethyl-valeronitrile (V-19, manufactured by Wako Pure Chemical Industries, Ltd.) Nitrile compound, 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide] (VA-080, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide] (VA-082, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [ 2-methyl-N- [2- (1-hydroxybutyl)]-propionamide] (VA-085, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- (2 -Hydroxyethyl) -propionamide] (VA-086, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropionamide) dihydrate (VA-088, manufactured by Wako Pure Chemical Industries, Ltd.) ), 2, 2'- Zobis [N- (2-propenyl) -2-methylpropionamide] (VF-096, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (N-butyl-2-methylpropionamide) (VAm -110, manufactured by Wako Pure Chemical Industries, Ltd.), azoamide compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) (VAm-111, manufactured by Wako Pure Chemical Industries, Ltd.), 2 2,2′-azobis (2,4,4-trimethylpentane) (VR-110, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropane) (VR-160, Wako Pure Chemical) And alkylazo compounds such as those manufactured by Kogyo Co., Ltd.

  Examples of the peroxide initiator include methyl ethyl ketone peroxide (Permec H, manufactured by NOF Corporation), cyclohexanone peroxide species (Perhexa H, manufactured by NOF Corporation), methylcyclohexanone peroxide (Perhexa Q). , Manufactured by NOF Corporation), methylacetoacetate peroxide (Percure SA, manufactured by NOF Corporation), ketone peroxides such as acetylacetone peroxide (Percure A, manufactured by NOF Corporation), 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation), 1,1-bis (t-hexylperoxy) cyclohexane (Perhexa HC, NOF Corporation ), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 3M, manufactured by NOF Corporation, 1,1-bis (t-butylperoxy) cyclohexane (Perhexa C, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclododecane (Perhexa CD-R, manufactured by NOF Corporation), 2,2′-bis (t-butylperoxy) butane (Perhexa 22, manufactured by NOF Corporation), n-butyl 4,4-bis (t -Butylperoxy) valerate) Perhexa V, manufactured by NOF Corporation), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (Pertetra A, manufactured by NOF Corporation), etc. Peroxyketals, t-butyl hydroperoxide (Perbutyl H-69, manufactured by NOF Corporation), p-menthane hydroperoxide (Permenta H, manufactured by NOF Corporation), diisopropylbenzene hydroperoxide ( Pa Cumyl P, manufactured by NOF Corporation, 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H, manufactured by NOF Corporation), cumene hydroperoxide (Perk Mill H-80, NOF Corporation) Co., Ltd.), hydroperoxides such as t-hexyl hydroperoxide (Perhexyl H, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (Perhexin 25B, manufactured by NOF Corporation), di-t-butyl peroxide (Perbutyl DR, manufactured by NOF Corporation), t-butyl cumyl peroxy species (Perbutyl C, manufactured by NOF Corporation) ), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by NOF Corporation), Dicumyl Peroxy species (Park Mill DR, manufactured by NOF Corporation), α, α'-bis (t-bu Dialkyl peroxides such as luperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation), octanoyl peroxy species (Perroyl O, manufactured by NOF Corporation), lauroyl peroxy species (Perroyl L, NOF Corporation) Co., Ltd.), stearoyl peroxy species (Perroyl S, manufactured by NOF Corporation), succinic acid peroxy species (Perloyl SA, manufactured by NOF Corporation), benzoyl peroxide (Nyper BW, NOF Corporation) )), Isobutyryl peroxide (Perroyl IB, manufactured by NOF Corporation), 2,4-dichlorobenzoyl peroxy species (Nyper CS, manufactured by NOF Corporation), 3,5,5-trimethylhexanoyl Diacyl peroxides such as peroxy species (Perroyl 355, manufactured by NOF Corporation), di-n-propyl peroxydicarbonate (Perroyl) NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (Perroyl IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, NOF Corporation) ), Di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by NOF Corporation), di-2-ethoxyhexyl peroxydicarbonate (Perloyl OPP, manufactured by NOF Corporation), Di-2-methoxybutyl peroxydicarbonate (Perroyl MBP, manufactured by NOF Corporation), di (3-methyl-3-methoxybutyl) peroxydicarbonate (Perloyl SOP, manufactured by NOF Corporation), etc. Peroxydicarbonates, α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Nyper ND-R, JP Fatty Co., Ltd.), cumyl peroxyneodecanoate (Park Mill ND-R, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (Perocta ND-R) , Manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxyneodecanoate (percyclo ND-R, manufactured by NOF Corporation), t-hexylperoxyneodecanoate (perhexyl ND-) R, manufactured by NOF Corporation), t-butyl peroxyneodecanoate (perbutyl ND-R, manufactured by NOF Corporation), t-hexyl peroxypivalate (perhexyl PV, manufactured by NOF Corporation) ), T-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, NOF Corporation) Made) 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (Perhexa 250, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by NOF Corporation), t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexanoate (perbutyl) O, manufactured by NOF Corporation), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, manufactured by NOF Corporation), t-butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF Corporation), t-butylperoxy 3,5,5-trimethylhexanoate (Perbuthi 355, manufactured by NOF Corporation), t-butyl peroxylaurate (Perbutyl L, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane ( Perhexa 25MT, manufactured by NOF Corporation, t-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexyl monocarbonate (Perbutyl E, NOF Corporation) )), T-hexyl peroxybenzoate (Perhexyl Z, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (Perhexa 25Z, manufactured by NOF Corporation) T-butyl peroxyacetate (Perbutyl A, manufactured by NOF Corporation), t-butyl peroxy-m-toluoyl benzoate (Perbutyl ZT, manufactured by NOF Corporation) Peroxyesters such as t-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF Corporation), bis (t-butylperoxy) isophthalate (Perbutyl IF, manufactured by NOF Corporation), t-butyl Peroxyallyl monocarbonate (Peromer AC, manufactured by NOF Corporation), t-butyltrimethylsilyl peroxide (Perbutyl SM, manufactured by NOF Corporation), 3,3′-4,4′-tetra (t-butyl) Peroxycarbonyl) benzophenone (BTTB-50, manufactured by NOF Corporation), 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC, manufactured by NOF Corporation) and the like.

  Examples of the ionic initiator include 2,2′-azobis [2- (phenylamidino) propane] dihydrochloride (VA-545, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2 -[N- (4-chlorophenyl) amidino] propane} dihydrochloride (VA-546, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyphenyl) amidino] Propane} dihydrochloride (VA-548, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, Wako Pure Chemical Industries, Ltd.) 2,2′-azobis [2- (N-allylamidino) propane] dihydrochloride (VA-553, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-amidinop) Pan) dihydrochloride (VA-50, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyethyl) amidino] propane} dihydrochloride (VA-558, Wako Pure) Yakuhin Kogyo Co., Ltd.), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, manufactured by Wako Pure Chemical Industries, Ltd.), 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (4,5, 6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (VA-054, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (3,4) , 5,6-Tetrahydropyrimidine 2-yl) propane] dihydrochloride (VA-058, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-2- Yl) propane] dihydrochloride (VA-059, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} Dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, manufactured by Wako Pure Chemical Industries, Ltd.) And anionic initiators such as potassium persulfate (KPS, manufactured by Wako Pure Chemical Industries, Ltd.) and ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries, Ltd.).

  Such redox initiators include, for example, systems based on organic peroxides and tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as cumene hydroperoxide. And systems based on cobalt naphthate.

  The initiator can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a normal amount, specifically, in 100 mol parts of the polymerizable unsaturated compound to be polymerized. On the other hand, it is usually used in an amount of 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

<Addition-cleavage transfer reaction polymerization method>
When the addition-cleavage transfer reaction polymerization method is used, it is preferable to react at 0 ° C. to 200 ° C. using a chain transfer agent and an initiator. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the addition-cleavage transfer reaction polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 30 minutes to 144. It is preferable to set the time, preferably within the range of 1 to 24 hours.

  Examples of the chain transfer agent include benzoyl-1-pyrrolecarbodithioate, benzoyldithiobenzoate, cyanoisopropyldithiobenzoate, cumyldithiobenzoate, methoxycarbonylphenylmethyldithiobenzoate, cyanobenzyldithiobenzoate, 1-phenylethyldithioate. Benzoate, t-butyldithiobenzoate S- (thiobenzyl) thioglycolic acid, 1-phenylethylphenyldithiobenzoate, 3-benzylsulfanylthiocarbonylsulfanyl-propionic acid, 2- (benzylsulfanylthiocarbonylsulfanyl) ethanol, 3-benzylsulfanyl Thiocarbonylsulfanylpropionic acid, S- (1-ethoxycarbonylethyl) O-ethylxanthate, ethyl -2- (2-trifluoroethoxythiocarbonylsulfanyl) propionate, ethyl-2- (1-diethoxyphosphonyl-2,2,2-trifluoroethoxythiocarbonylsulfanyl) propionate, bisthiobenzoyl disulfide, bis (2 , 6-Dimethylthiobenzoyl) disulfide, bis (2,4-dimethylthiobenzoyl) disulfide, bis (4-methoxythiobenzoyl) disulfide, bis (2,4dimethoxythiobenzoyl) disulfide, bis (4-fluorothiobenzoyl) Disulfide, bis (2,4-difluorothiobenzoyl) disulfide, bis (4-cyanothiobenzoyl) disulfide, bis (3,5-dicyanothiobenzoyl) disulfide, bis (3,5-bis (trifluoromethyl) ) Dithiobenzoate) disulfide, bis (2,3,4,5,6-pentafluorothiobenzoyl) disulfide, bis (4-phenylthiobenzoyl) disulfide, bis (2-naphthylthionyl) disulfide, bis (1-naphthylthionyl) ) Disulfide, triphenylmethyldithioisonicotinate, 2-cyanoisopropyl (2,6-dimethyl) dithiobenzoate, 2-cyanoisopropyl (2,4-dimethyl) dithiobenzoate, 2-cyanoisopropyl (4-methoxy) dithiobenzoate 2-cyanoisopropyl (2,4-dimethoxy) dithiobenzoate, 2-cyanoisopropyl (4-fluoro) dithiobenzoate, 2-cyanoisopropyl (2,4-difluoro) dithiobenzoate, 2-cyanoisopro Pyrdithioisonicotinate, 2-cyanoisopropyl 4-cyanodithiobenzoate, 2-cyanoisopropyl 3,5-dicyanodithiobenzoate, 2-cyanoisopropyl 3,5-bis (trifluoromethyl) dithiobenzoate, 2-cyano Isopropyl 2,3,4,5,6-pentafluorodithiobenzoate, 2-cyanoisopropyl 4-pyridinium dithiocarboxyate 4-toluenesulfonate salt, 2-cyanoisopropyl (4-phenyl) dithiobenzoate, 2-cyanoisopropyl 2-naphthyl dithiolate, 2-cyanoisopropyl-1-naphthyl dithiolate, 2-cyano-4-methylpent-2-yldithiobenzoate, 2-cyano-4-methylpent-2-yl-4-cyanodithiobenzoate, - cyano-4-methylpent-2-yl 3,5-bis-trifluoromethyl dithiobenzoate, 2-cyano-4-methylpent-2-yl-4-methoxy sulfonyl dithio benzoate. These may be used alone or in combination of two or more.

  The chain transfer agent can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a usual amount, specifically, 100 mol parts of a polymerizable unsaturated compound to be polymerized. The amount is usually 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

  The initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, and an ionic initiator. These may be used alone or in combination of two or more.

  Examples of the azo initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis. (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobisisobutyronitrile (V-60, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylbutyronitrile) (V-59, manufactured by Wako Pure Chemical Industries, Ltd.), 1,1′-azobis (cyclohexane-1-carbonitrile) (V-40, Wako Pure) Yakuhin Kogyo Co., Ltd.), 1-[(1-cyano-1-methylethyl) azo] formamide (V-30, Wako Pure Chemical Industries, Ltd.), 2-phenylazo-4-methoxy-2,4 -Dimethyl-valeronitrile (V-19, manufactured by Wako Pure Chemical Industries, Ltd.) Nitrile compound, 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide] (VA-080, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide] (VA-082, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [ 2-methyl-N- [2- (1-hydroxybutyl)]-propionamide] (VA-085, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- (2 -Hydroxyethyl) -propionamide] (VA-086, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropionamide) dihydrate (VA-088, manufactured by Wako Pure Chemical Industries, Ltd.) ), 2, 2'- Zobis [N- (2-propenyl) -2-methylpropionamide] (VF-096, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (N-butyl-2-methylpropionamide) (VAm -110, manufactured by Wako Pure Chemical Industries, Ltd.), azoamide compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) (VAm-111, manufactured by Wako Pure Chemical Industries, Ltd.), 2 2,2′-azobis (2,4,4-trimethylpentane) (VR-110, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropane) (VR-160, Wako Pure Chemical) And alkylazo compounds such as those manufactured by Kogyo Co., Ltd.

  Examples of the peroxide initiator include methyl ethyl ketone peroxide (Permec H, manufactured by NOF Corporation), cyclohexanone peroxide species (Perhexa H, manufactured by NOF Corporation), methylcyclohexanone peroxide (Perhexa Q). , Manufactured by NOF Corporation), methylacetoacetate peroxide (Percure SA, manufactured by NOF Corporation), ketone peroxides such as acetylacetone peroxide (Percure A, manufactured by NOF Corporation), 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation), 1,1-bis (t-hexylperoxy) cyclohexane (Perhexa HC, NOF Corporation ), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 3M, manufactured by NOF Corporation, 1,1-bis (t-butylperoxy) cyclohexane (Perhexa C, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclododecane (Perhexa CD-R, manufactured by NOF Corporation), 2,2′-bis (t-butylperoxy) butane (Perhexa 22, manufactured by NOF Corporation), n-butyl 4,4-bis (t -Butylperoxy) valerate) Perhexa V, manufactured by NOF Corporation), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (Pertetra A, manufactured by NOF Corporation), etc. Peroxyketals, t-butyl hydroperoxide (Perbutyl H-69, manufactured by NOF Corporation), p-menthane hydroperoxide (Permenta H, manufactured by NOF Corporation), diisopropylbenzene hydroperoxide ( Pa Cumyl P, manufactured by NOF Corporation, 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H, manufactured by NOF Corporation), cumene hydroperoxide (Perk Mill H-80, NOF Corporation) Co., Ltd.), hydroperoxides such as t-hexyl hydroperoxide (Perhexyl H, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (Perhexin 25B, manufactured by NOF Corporation), di-t-butyl peroxide (Perbutyl DR, manufactured by NOF Corporation), t-butyl cumyl peroxy species (Perbutyl C, manufactured by NOF Corporation) ), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by NOF Corporation), Dicumyl Peroxy species (Park Mill DR, manufactured by NOF Corporation), α, α'-bis (t-bu Dialkyl peroxides such as luperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation), octanoyl peroxy species (Perroyl O, manufactured by NOF Corporation), lauroyl peroxy species (Perroyl L, NOF Corporation) Co., Ltd.), stearoyl peroxy species (Perroyl S, manufactured by NOF Corporation), succinic acid peroxy species (Perloyl SA, manufactured by NOF Corporation), benzoyl peroxide (Nyper BW, NOF Corporation) )), Isobutyryl peroxide (Perroyl IB, manufactured by NOF Corporation), 2,4-dichlorobenzoyl peroxy species (Nyper CS, manufactured by NOF Corporation), 3,5,5-trimethylhexanoyl Diacyl peroxides such as peroxy species (Perroyl 355, manufactured by NOF Corporation), di-n-propyl peroxydicarbonate (Perroyl) NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (Perroyl IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, NOF Corporation) ), Di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by NOF Corporation), di-2-ethoxyhexyl peroxydicarbonate (Perloyl OPP, manufactured by NOF Corporation), Di-2-methoxybutyl peroxydicarbonate (Perroyl MBP, manufactured by NOF Corporation), di (3-methyl-3-methoxybutyl) peroxydicarbonate (Perloyl SOP, manufactured by NOF Corporation), etc. Peroxydicarbonates, α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Nyper ND-R, JP Fatty Co., Ltd.), cumyl peroxyneodecanoate (Park Mill ND-R, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (Perocta ND-R) , Manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxyneodecanoate (percyclo ND-R, manufactured by NOF Corporation), t-hexylperoxyneodecanoate (perhexyl ND-) R, manufactured by NOF Corporation), t-butyl peroxyneodecanoate (perbutyl ND-R, manufactured by NOF Corporation), t-hexyl peroxypivalate (perhexyl PV, manufactured by NOF Corporation) ), T-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, NOF Corporation) Made) 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (Perhexa 250, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo O, manufactured by NOF Corporation), t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexanoate (perbutyl) O, manufactured by NOF Corporation), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, manufactured by NOF Corporation), t-butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF Corporation), t-butylperoxy 3,5,5-trimethylhexanoate (Perbuthi 355, manufactured by NOF Corporation), t-butyl peroxylaurate (Perbutyl L, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane ( Perhexa 25MT, manufactured by NOF Corporation, t-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexyl monocarbonate (Perbutyl E, NOF Corporation) )), T-hexyl peroxybenzoate (Perhexyl Z, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (Perhexa 25Z, manufactured by NOF Corporation) T-butyl peroxyacetate (Perbutyl A, manufactured by NOF Corporation), t-butyl peroxy-m-toluoyl benzoate (Perbutyl ZT, manufactured by NOF Corporation) Peroxyesters such as t-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF Corporation), bis (t-butylperoxy) isophthalate (Perbutyl IF, manufactured by NOF Corporation), t-butyl Peroxyallyl monocarbonate (Peromer AC, manufactured by NOF Corporation), t-butyltrimethylsilyl peroxide (Perbutyl SM, manufactured by NOF Corporation), 3,3′-4,4′-tetra (t-butyl) Peroxycarbonyl) benzophenone (BTTB-50, manufactured by NOF Corporation), 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC, manufactured by NOF Corporation) and the like.

  Examples of the ionic initiator include 2,2′-azobis [2- (phenylamidino) propane] dihydrochloride (VA-545, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2 -[N- (4-chlorophenyl) amidino] propane} dihydrochloride (VA-546, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyphenyl) amidino] Propane} dihydrochloride (VA-548, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, Wako Pure Chemical Industries, Ltd.) 2,2′-azobis [2- (N-allylamidino) propane] dihydrochloride (VA-553, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-amidinop) Pan) dihydrochloride (VA-50, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyethyl) amidino] propane} dihydrochloride (VA-558, Wako Pure) Yakuhin Kogyo Co., Ltd.), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, manufactured by Wako Pure Chemical Industries, Ltd.), 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (4,5, 6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (VA-054, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (3,4) , 5,6-Tetrahydropyrimidine 2-yl) propane] dihydrochloride (VA-058, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-2- Yl) propane] dihydrochloride (VA-059, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} Dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, manufactured by Wako Pure Chemical Industries, Ltd.) And anionic initiators such as potassium persulfate (KPS, manufactured by Wako Pure Chemical Industries, Ltd.) and ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries, Ltd.).

  The initiator can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a normal amount, specifically, in 100 mol parts of the polymerizable unsaturated compound to be polymerized. On the other hand, it is usually used in an amount of 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

<Polymerization method using a thiol compound having a reactive silyl group and a metallocene compound>
It is preferable to use a metallocene compound as a metal catalyst and to react at 0 ° C. to 150 ° C. using a thiol compound having at least one reactive silyl group in the molecule. More preferably, it is particularly preferably set within the range of 25 ° C to 120 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 1 to 12 hours, preferably 2 It is preferable to set within a range of ˜8 hours.

  The metallocene compound is not particularly limited, and examples thereof include dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,4,5,6-pentafluoropheny. -1-yl, dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Ti-bis-2,5,6-trifluorophen-1-yl Dicyclopentadiene-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadiene-Ti-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2 , 3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3 5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro-3 Titanocene compounds such as-(pyr-1-yl) -phen-1-yl; dicyclopentadienyl-Zr-dichloride, dicyclopentadiene-Zr-bisphenyl, dicyclopentadiene-Zr-bis-2,3 , 4,5,6-pentafluorophen-1-yl, dicyclopentadiene-Zr-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Zr-bis-2,5 , 6-trifluorophen-1-yl, dicyclopentadiene-Zr-bis-2,6-difluorophen-1-yl, dicyclopentadiene -Zr-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl- Zr-bis-2,3,5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis Zirconocene compounds such as 2,6-difluoro-3- (pyr-1-yl) -phen-1-yl); dicyclopentadienyl-V-chloride, bismethylcyclopentadienyl-V-chloride, Bispentamethylcyclopentadienyl-V-chloride, dicyclopentadienyl-Ru-chloride, dicyclopentadienyl-Cr-chloro Can be mentioned. These may be used alone or in combination of two or more.

  The metallocene compound can be used in a usual catalytic amount. Specifically, it is usually 0.1 to 0.00001 mol part, preferably 100 to 100 mol part of the polymerizable unsaturated compound to be polymerized, preferably Used in an amount of 0.0001-0.00005 mol parts.

  The thiol compound having a reactive silyl group is not particularly limited. For example, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldiethoxysilane, mercapto Methyldimethylethoxysilane, mercaptomethyltripropoxysilane, mercaptomethylmethyldipropoxysilane, mercaptomethyldimethylpropoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxy Silane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysila , 3-mercaptopropyl - dimethyl mono silane, 3-mercaptopropyl - monomethyl diethoxy silane, 4-mercaptomethyl-butyl - trimethoxysilane and 3-mercaptopropyl butyl - and tri methoxy silane. These may be used alone or in combination of two or more.

  The amount of the thiol compound having a reactive silyl group can be appropriately set in consideration of the molecular weight of the polymer to be obtained, the polymerization rate, etc., but the reaction proceeds smoothly and does not cause the reaction to run away. The metallocene compound and the thiol compound having a reactive silyl group are usually used in a molar ratio within the range of 100: 1 to 1: 50000, preferably 10: 1 to 1: 10000.

<Radical polymerization using transition metal complex>
When using the radical polymerization method using a transition metal complex, it is preferable to make it react at 0 to 200 degreeC using a transition metal complex, an organic halide, and / or a ligand. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the addition-cleavage transfer reaction polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 30 minutes to 144. It is preferable to set the time, preferably within the range of 1 to 24 hours.

It does not specifically limit as said transition metal complex, For example, what is described in WO97 / 18247 can be utilized. Among these, a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel is preferable. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When using cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, if necessary, zero-valent copper, cuprous chloride Dicopper, cupric bromide, and cupric iodide can also be used.
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  When using a copper compound as a catalyst, the ligand described in WO97 / 18247 can be used as the ligand. Although not particularly limited, amine-based ligands are preferable, and bipyridyl compounds such as 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, hexamethyltriethylenetetraamine, bispicolylamine , Ligands such as aliphatic amines such as trialkylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine. In the present invention, among these, polyamine compounds, particularly aliphatic polyamines such as pentamethyldiethylenetriamine and hexamethyl (2-aminoethyl) amine are preferred. Moreover, when using a polyamine compound, a pyridine-type compound, or an aliphatic amine compound as a ligand in the case of using a copper compound as a catalyst, these ligands must have three or more amino groups. Is preferred. The amino group in the present invention represents a group having a nitrogen atom-carbon atom bond, and among these, a group in which a nitrogen atom is bonded only to a carbon atom and / or a hydrogen atom is preferable. The metallocene compounds listed above can also be used.

  The amount of the ligand as described above is determined from the number of coordination sites of the transition metal and the number of groups coordinated by the ligand under the conditions of normal atom transfer radical polymerization, so that they are almost equal. Is set to For example, the amount of 2,2'-bipyridyl and its derivatives added to CuBr is usually twice as much as the molar ratio, and in the case of pentamethyldiethylenetriamine, it is once as high as the molar ratio. In the present invention, when a ligand is added to initiate polymerization, and / or when a catalyst activity is controlled by adding a ligand, there is no particular limitation, but the metal atom is excessive relative to the ligand. Is preferred. The ratio between the coordination position and the coordinating group is preferably 1.2 times or more, more preferably 1.4 times or more, particularly preferably 1.6 times or more, and particularly preferably 2 times or more. It is.

As an initiator, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position) or a sulfonyl halide is used. Used.
If Specific _{examples, C 6 H 5 -CH 2 X} , C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2, XCH 2 - _{C 6 H 5 -CH 2 X,} XC (H) (CH 3) -C 6 H5-C (H) (CH 3) X ( where in the above _formula, C 6 _{H 5} is a phenyl group, X is chlorine , bromine or ^{_{iodine), R 6 -C, (H}} ) (X) -CO 2 R 7, R 6 -C (CH 3) (X) -CO 2 R 7, R 6 -C (H) (X) _{^{-C (O) R 7, R}} 6 -C (CH 3) (X) -C (O) R 7, ( ^wherein, R 6, ^{R 7} is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, aryl Group, or aralkyl group, X is chlorine, bromine, or iodine), R ⁶ -C ₆ H ₄ -SO ₂ X (in the above formulas, R ⁶ is a hydrogen atom or a carbon number of 1 to 20 alkyl groups, aryl groups, or aralkyl groups, X is chlorine, bromine, or iodine).

  In radical polymerization methods using transition metal complexes, aluminum trial chelates such as triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-t-butoxyaluminum, trisec-butoxyaluminum and dioctyltin And divalent tin compounds such as diethylhexyltin and dibutyltin, and organic substances such as glucose and ascorbic acid can be used as additives for activating the polymerization.

  In the synthesis of the vinyl resin (A), the polymerization can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene, xylene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketone solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, etc., nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ethyl acetate, butyl acetate, etc. Polyoxyalkylene polymers such as ester solvents, carbonate solvents such as ethylene carbonate and propylene carbonate, and the like can be mentioned, and these can be used alone or in admixture of two or more. Further, by using a reactive silyl group-containing polymer as a solvent, a subsequent degassing step or the like can be made unnecessary.

The molecular weight of the (A) vinyl resin is not limited, but the number average molecular weight is preferably 1,000 or more and 100,000 or less, and more preferably 1,500 or more and 50,000 or less.
The (A) vinyl-based resin includes a structural unit represented by the general formula (3) and a structural unit represented by the general formula (4), and the structural unit represented by the general formula (3); The structural unit represented by the general formula (4) is preferably 0.001: 1 to 5: 1 as a structural unit ratio, and more preferably 0.005: 1 to 0.5: 1.
The number of structural units represented by the general formula (3) contained in the vinyl resin (A) is not particularly limited, but is preferably 0.2 to 5 on average per molecule. More preferably, 5 to 3.0 are included. The average number of structural units represented by the general formula (4) is preferably 10 to 2000, and more preferably 15 to 1000 in one molecule.

  Although it does not specifically limit as said (B) curing catalyst, For example, an amine compound, an organometallic compound, etc. are mentioned, An amine compound and a silanol condensation catalyst are preferable, and an amine compound is more preferable.

As the amine compound, known amine compounds can be widely selected and are not particularly limited. For example, a compound having one or both of a primary amino group and a secondary amino group in the molecule is preferable. Used for.
Specifically, a primary amine is suitable as the compound having a primary amino group. Examples of the primary amino include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, 2-butylamine, 1,2-dimethylpropylamine, hexylamine, heptylamine, 2-ethylhexylamine, and nonylamine. , Decylamine, amylamine, octylamine, 3-pentylamine, isoamylamine, 2-octylamine, 3-methoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, laurylamine, penta Decylamine, rosinamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine, trimethylcyclohexylamine, benzylamine, aniline 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, aminomethyltrimethoxysilane, aminomethylaminomethyltriethoxysilane, amino Monoamines such as methylmethyldimethoxysilane, aminomethylmethyldiethoxysilane, aminomethyldimethylmethoxysilane, aminomethyldimethylethoxysilane; ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, Hexamethylenediamine, 1,7-diaminoheptane, trimethylhexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-di Minoundedecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18 -Diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 1,2-diaminohenticosane, 1,2-diaminodocosane, 1,23-diaminotricosane, 1,24-diamino Tetracosane, isophoronediamine, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, phenylenediamine, diaminodiphenylmethane , Diaminodiethylphenylmethane, polio Examples thereof include diamines such as xylethylenediamine and polyoxypropylenediamine; and polyamines such as tri (methylamino) hexane.

  Examples of the compound having a plurality of primary amino groups include N-methyl-3,3′-iminobis (propylamine), diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,4-diaminobutane, 1,2- Diaminopropane, ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane), CTU guanamine, dodecanoic acid dihydrazide, hexamethylenediamine, m-xyl Range amine, dianisidine, 4,4′-diamino-3,3′-diethyldiphenylmethane, diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, tolidine base, m-toluylenediamine, o-phenylene Diamine, m-phenylenediamine, p- Enirenjiamin, melamine, and the like.

  Examples of the compound having one or more primary amino group and secondary amino group in the molecule include, for example, methylaminopropylamine, ethylaminopropylamine, ethylaminoethylamine, laurylaminopropylamine, 2-hydroxyethylamino Propylamine, 1- (2-aminoethyl) piperazine, N-aminopropylpiperazine, N-laurylpropylenediamine, N-stearylpropylenediamine, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-β ( Aminoethyl) -γ-aminomethyltrimeth Sisilane, N-β (aminoethyl) -γ-aminomethyltriethoxysilane, N-β (aminoethyl) -γ-aminomethylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminomethylmethyldiethoxysilane N-β (aminoethyl) -γ-aminomethyldimethylmethoxysilane, N-β (aminoethyl) -γ-aminomethyldimethylethoxysilane, and the like.

  Examples of the compound having only one or more secondary amino groups in the molecule include, for example, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine , Monoamines such as didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine, methyllaurylamine, N, N'-dilaurylpropylamine, N, N'-distearylbutylamine Diamine piperazines such as N-butyl-N′-laurylethylamine, N-butyl-N′-laurylpropylamine, N-lauryl-N′-stearylbutylamine, cis-2,6-dimethylpipera Cis-2,5-dimethylpiperazine, 2-methylpiperazine, N, N′-di-t-butylethylenediamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) ) -Propane, 4-aminopropylaniline, 3-aminopyrrolidine, homopiperazine and the like.

  Examples of other amines include monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethylamine, diethylaminoethylamine, 3-hydroxypropylamine, diethylenetriamine, triethylenetetramine, benzylamine, 3-lauryloxypropylamine, and 3-dimethylamino. Propylamine, 3-diethylaminopropylamine, N-methyl-1,3-propanediamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) Phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,4,0) Decene-7, 1,5-diazabicyclo (4,3,0) nonene -5 (DBN), 3- (1-piperazinyl) propylamine, 3-morpholinopropyl amine.

  As the amine compound, it is particularly preferable to use aminosilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, and aminopropyltrimethoxysilane.

  Examples of the silanol condensation catalyst include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dimethyltin oxide, dioctyltin oxide, dibutyl Tin-based catalysts such as tin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, tin octylate and tin naphthenate, and other tin compounds such as reaction products of dibutyltin oxide and phthalate; tetrabutyl titanate , Titanates such as tetrapropyl titanate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminium Organoaluminum compounds such as ethyl acetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Leads of organic acids such as lead octylate and lead naphthenate; Bismuth octylate, bismuth neodecanoate and rosin acid Examples include bismuth organic acids such as bismuth; other known acidic catalysts and basic catalysts as silanol condensation catalysts.

  The blending ratio of the (B) curing catalyst is not particularly limited, but is preferably 0.000001 to 10 parts by mass, more preferably 0.00001 to 5 parts by mass with respect to 100 parts by mass of the (A) vinyl resin. . These curing catalysts may be used alone or in combination of two or more.

  The (A) vinyl-based resin is excellent in rapid curability, is cured without using a tin-based catalyst, and the curing speed is remarkably faster than a curable composition that requires a conventional tin-based catalyst. There is an effect. The curable composition of the present invention preferably contains no tin-based catalyst from the viewpoint of toxicity. Specifically, the tin content in the curable composition of the present invention is preferably 100 wtppm or less, more preferably 50 wtppm or less, and even more preferably 0 wtppm.

  In addition to the above-described components, the curable composition of the present invention, if necessary, a silane coupling agent, a physical property modifier, a filler, a plasticizer, a reactive diluent, a thixotropic agent, a dehydrating agent (storage stability) Property improvers), tackifiers, sagging inhibitors, ultraviolet absorbers, antioxidants, flame retardants, colorants, radical polymerization initiators, and various solvents such as toluene and alcohol. Other compatible polymers may be blended.

  As the silane coupling agent, conventionally known silane coupling agents can be widely used and are not particularly limited. For example, aminosilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethylmethoxysilane, and the like. , Epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane And isocyanate silanes. The silane coupling agent may be used alone or in combination of two or more.

  The physical property modifier is added for the purpose of improving the tensile physical properties. Examples of the physical property modifier include a silicon compound having one silanol group in one molecule, and examples thereof include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol, and the like. Various silane coupling agents such as silicon compounds that can be decomposed to produce a compound having one silanol group in one molecule, such as triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, diphenylalkylmethoxy Silane, triphenylethoxysilane, trialkylethoxysilane, etc. are mentioned. The said physical property modifier may be used independently and may be used together 2 or more types.

  The filler is added for the purpose of reinforcing the cured product. Examples of the filler include calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, and zeolite. Of these, calcium carbonate is preferable, and fatty acid-treated calcium carbonate is more preferable. In addition, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, etc. can be used. Among them, an acrylic balloon is more preferable from the viewpoint that the decrease in elongation after curing of the composition is small. The fillers may be used alone or in combination of two or more.

  The plasticizer is added for the purpose of enhancing the elongation physical properties after curing or enabling low modulus. The type of the plasticizer is not particularly limited. For example, phthalates such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diisoundecyl phthalate; dioctyl adipate, isodecyl succinate, sebacine Aliphatic dibasic acid esters such as dioctyl acid and dibutyl adipate; Glycol esters such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate and pentaerythritol ester; Aliphatics such as butyl oleate and methyl acetylricinoleate Esters; Phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributyl phosphate, tricresyl phosphate; Epoxy plasticizers such as modified soybean oil, epoxidized linseed oil, and epoxy benzyl stearate; Polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol; Polyethers such as polypropylene glycol and polyethylene glycol derivatives Polystyrenes such as poly-α-methylstyrene and polystyrene; Hydrocarbon oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and process oil Chlorinated paraffins; MS polymer 203H (manufactured by Kaneka Corporation), silylyl SAT200 (manufactured by Kaneka Corporation), ES-GX2443ST (manufactured by Asahi Glass Co., Ltd.), ES-GX3440ST (manufactured by Asahi Glass Co., Ltd.) Hydrolyzable silyl group-containing polymers such as UP-1080 (manufactured by Toagosei Co., Ltd.) and acrylic plasticizers such as UP-1061 (manufactured by Toagosei Co., Ltd.); UP-2000 (Toagosei Co., Ltd.) ) And UHE-2012 (manufactured by Toagosei Co., Ltd.); hydroxyl group-containing acrylic plasticizers such as UC-3510 (manufactured by Toagosei Co., Ltd.); carboxyl group-containing acrylic polymers such as UG-4000; Epoxy group-containing acrylic polymers such as (manufactured by Toagosei Co., Ltd.); Silyl group-containing acrylic polymers such as US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.) Etc. are exemplified. These plasticizers may be used alone or in combination of two or more.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate. The thixotropic agent may be used alone or in combination of two or more.

  The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimetholdimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.

  The antioxidant is used to prevent oxidation of the cured sealant and improve weather resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine antioxidant include N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioic acid) 1 (octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenol antioxidants include pentane. Erythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-ter t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5 5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calci Mudiethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine Product of 2,4,4-trimethylpentene with 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 Triazin-2-ylamino) phenol and the like, but not limited thereto. The antioxidants may be used alone or in combination of two or more.

  The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the cured sealant, for example, an ultraviolet absorber such as benzotriazole, triazine, benzophenone, or benzoate. Etc. Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4 -Benzotriazole ultraviolet absorbers such as methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(he Sil) oxy] -phenol and the like triazine ultraviolet absorbers, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Examples include, but are not limited to, benzoate ultraviolet absorbers. The said ultraviolet absorber may be used independently or may use 2 or more types together.

  The curable composition of the present invention can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type. The curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like. The curable composition of the present invention is excellent in adhesiveness, physical properties of rubber, storage stability, deep curability, and fast curability. Therefore, the curable composition is particularly preferably used for an adhesive, but for various other buildings and automobiles. It can be used for civil engineering, civil engineering, and electric / electronic fields.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

Analysis and measurement in Synthesis Examples, Examples and Comparative Examples were performed according to the following methods.
1) Measurement of number average molecular weight It measured on the following conditions by the gel permeation chromatography (GPC). In the present invention, the maximum frequency molecular weight measured by GPC under the measurement conditions and converted with standard polyethylene glycol is referred to as the number average molecular weight.
THF solvent measuring device / analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millenium data processing device (manufactured by Waters)
Column: Plgel GUARD + 5 μmMixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by Polymer Lab)
・ Flow rate: 1 mL / min ・ Converted polymer: Polyethylene glycol ・ Measurement temperature: 40 ° C.

2) Storage stability test The curable composition in the flask was allowed to stand at room temperature for 3 weeks, the flask was tilted, and the viscosity was visually confirmed.

3) Curability test The touch drying time (TFT) was measured according to JIS A 1439 4.19 to evaluate curability. It was evaluated as ○ (good) when the film was formed within 60 seconds, Δ (slightly good) when it was within 60 to 600 seconds, and x (bad) when it was over 600 seconds.

4) Adhesive Test 4-1) Adhesiveness 0.2 g of the curable composition was uniformly applied on the adherend and immediately bonded to an area of 25 mm × 25 mm. After pasting, measurement was performed according to the tensile shear bond strength test method of a rigid adherend immediately after pressing with a small eyeball clip for 7 days in an atmosphere of 23 ° C. and 50% relative humidity. Polycarbonate and Al were used as the adherend.

4-2) Rising Adhesiveness 0.2 g of the curable composition was uniformly applied onto a lauan plywood (thickness 5 mm, width 25 mm, length 100 mm), and immediately pasted in an area of 25 mm × 25 mm. After pasting, measurement was performed according to the tensile shear adhesion test method of a rigid adherend immediately after pressing with a small eyeball clip for a predetermined time in an atmosphere of 23 ° C. and 50% relative humidity.

Example 1
As shown in Table 1, 50.0 parts by mass of n-butyl acrylate, acryloxymethyltrimethoxysilane 2.06 were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. Part by mass, and further 3.37 parts by mass of mercaptomethyltrimethoxysilane were added and heated to 80 ° C. 2.48 parts by mass of AIBN dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin A1. The number average molecular weight of the obtained vinyl resin A1 was 5000, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0256: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 50 parts by mass of the obtained vinyl resin A1 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 2)
As shown in Table 1, 100.0 parts by mass of n-butyl acrylate, methacryloxymethyltrimethoxysilane 2.20 were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. Part by mass, and further 3.93 parts by mass of mercaptopropyltrimethoxysilane were added and heated to 80 ° C. 2.42 parts by mass of BPO dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl-based resin A2. The obtained vinyl resin A2 had a number average molecular weight of 10,000 and Mw / Mn = 1.8. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0128: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 50 parts by mass of the obtained vinyl resin A2 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 3)
As shown in Table 1, 40 parts by mass of n-butyl acrylate, 7.81 parts by mass of methyl methacrylate, acryloxymethyl were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. 2.06 parts by mass of trimethoxysilane and 3.93 parts by mass of mercaptopropyltrimethoxysilane were added and heated to 80 ° C. 2.42 parts by mass of BPO dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin A3. The number average molecular weight of the obtained vinyl resin A3 was 5000, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0256: 1.

  Into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A3 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

Example 4
As shown in Table 1, 25 parts by mass of n-butyl acrylate, 65.92 parts by mass of stearyl methacrylate, acryloxymethyl were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. 2.06 parts by mass of trimethoxysilane and 3.37 parts by mass of mercaptomethyltrimethoxysilane were added and heated to 80 ° C. 2.48 parts by mass of AIBN dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin A4. The number average molecular weight of the obtained vinyl resin A4 was 5000, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0256: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A4 was added, and after degassing under reduced pressure, the nitrogen gas was replaced, and under a nitrogen stream 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 5)
As shown in Table 1, 25 parts by mass of n-butyl acrylate, 38.62 parts by mass of 2-ethylhexyl methacrylate, acrylic acid were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. 2.06 parts by mass of roxymethyltrimethoxysilane and 3.37 parts by mass of mercaptopropyltrimethoxysilane were added and heated to 80 ° C. 2.48 parts by mass of AIBN dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin A5. The number average molecular weight of the obtained vinyl resin A5 was 5000, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0256: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A5 was added, and after degassing under reduced pressure, nitrogen gas substitution was carried out under a nitrogen stream. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4, and the adhesion test results are shown in Table 7.

(Example 6)
As shown in Table 1, 50.0 parts by mass of n-butyl acrylate, acryloxymethyltrimethoxysilane 2.06 were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. Part by mass was added and heated to 80 ° C. 10 parts by weight of ADVN dissolved in 20 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin A6. The number average molecular weight of the obtained vinyl resin A6 was 5000, and Mw / Mn = 3.0. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0256: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 50 parts by mass of the obtained vinyl resin A6 was added, and after degassing under reduced pressure, the gas was replaced with nitrogen gas. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 7)
As shown in Table 2, 43 parts by mass of xylene, 20 parts by mass of methyl methacrylate, 80 parts by mass of 2-ethylhexyl methacrylate, acryloxymethyltrimethyl were added to a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. 20 parts by mass of methoxysilane and 0.1 parts by mass of zirconocene dichloride as a metal catalyst were charged, and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. Then, 20 parts by mass of mercaptomethyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 20 parts by mass of mercaptomethyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. Further, 20 parts by mass of mercaptomethyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After additional addition of 20 parts by mass of mercaptomethyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product was returned to room temperature, and 20 parts by mass of a benzoquinone solution (95% THF solution) was added to the reaction product to terminate the polymerization, thereby obtaining a vinyl resin A7. The number average molecular weight of the obtained vinyl resin A7 was 5000, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.1607: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A7 was added, and after degassing under reduced pressure, the nitrogen gas was replaced, and under a nitrogen stream 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 8)
As shown in Table 2, 43 parts by mass of xylene, 20 parts by mass of methyl methacrylate, 80 parts by mass of stearyl methacrylate, methacryloxymethyltrimethoxysilane were added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. 20 parts by mass and 0.1 parts by mass of ruthenocene dichloride as a metal catalyst were charged, and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. Then, 20 parts by mass of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 20 parts by mass of 3-mercaptopropyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. Furthermore, 20 parts by mass of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After additional addition of 20 parts by mass of 3-mercaptopropyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. . After the reaction for 8 hours and 5 minutes in total, the temperature of the reaction product was returned to room temperature, and 20 parts by mass of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, thereby obtaining a vinyl resin A8. The number average molecular weight of the obtained vinyl resin A8 was 5000, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.2082: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A8 was added, and after degassing under reduced pressure, the nitrogen gas was replaced, 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4, and the adhesion test results are shown in Table 7.

Example 9
As shown in Table 2, 100 parts by mass of n-butyl acrylate and 5.95 parts by mass of acryloxymethyltrimethoxysilane were synthesized in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. -4 parts by mass of phenylethyldithiobenzoate and 1.27 parts by mass of AIBN were charged, and the contents of the flask were heated to 80 ° C while introducing nitrogen gas into the flask. Heating and cooling were performed for 8 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. After the reaction, the temperature of the reaction product was returned to room temperature to obtain vinyl resin A9. The obtained vinyl-based resin A9 had a number average molecular weight of 7000 and Mw / Mn = 1.1. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0369: 1.

  Into a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A9 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 10)
As shown in Table 2, 43 parts by mass of toluene, 100 parts by mass of 2-ethylhexyl methacrylate, 5.95 parts by weight of methacryloxymethyltrimethoxysilane were added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. Parts, 4 parts by mass of methyl 2-bromopropionate and 1 part by mass of zirconocene dichloride as a metal catalyst and 1 part by mass of triisopropoxyaluminum, and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. . After the reaction for 8 hours, the temperature of the reaction product was returned to room temperature, and 20 parts by mass of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, thereby obtaining a vinyl resin A10. The number average molecular weight of the obtained vinyl resin A10 was 6400, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.0535: 1.

  Into a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A10 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 11)
As shown in Table 2, 10 parts by mass of propylene carbonate, 100 parts by mass of n-butyl acrylate, 6 parts by mass of acryloxymethyltrimethoxysilane were added to a flask equipped with a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. Parts, methyl 2-bromopropionate 5.21 parts by mass, transition metal catalyst CuBr 4.46 parts by mass, ligand N, N, N ′, N ″, N ″ -pentamethylenediethylenetriamine 2.76 The contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the mass flask. After the reaction for 12 hours, the temperature of the reaction product was returned to room temperature, and 20 parts by mass of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, and dehydrated methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) The reaction product was purified by precipitation to obtain vinyl resin A11. The number average molecular weight of the obtained vinyl resin A11 was 6500, and Mw / Mn = 1.1. The structural unit ratio of the structural unit represented by the general formula (3) to the structural unit represented by the general formula (4) was 0.0372: 1.

  Into a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A11 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4, and the adhesion test results are shown in Table 7.

(Example 12)
As shown in Table 3, 72.0 parts by mass of 2-ethylhexyl methacrylate, 32.1 acryloxymethyltrimethoxysilane were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. Part by mass, and further 10.1 parts by mass of mercaptopropyltrimethoxysilane were added and heated to 80 ° C. 5.0 parts by mass of AIBN dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin A12. The number average molecular weight of the obtained vinyl resin A12 was 2200, and Mw / Mn = 1.8. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.4286: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 50 parts by mass of the obtained vinyl resin A12 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 0.5 part by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4, and the adhesion test results are shown in Table 7.

(Example 13)
As shown in Table 3, 100 parts by mass of ethyl acetate was added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, and heated to 80 ° C. In another container, 20.0 parts by weight of methyl methacrylate, 203.2 parts by weight of lauryl methacrylate, 22.0 parts by weight of methacryloxymethyltrimethoxysilane, 9.82 parts by weight of mercaptopropylmethyldixysilane, 5.0 parts by weight of AIBN Was added dropwise over 3 hours with a dropping funnel, and the mixture was further reacted at 80 ° C. for 6 hours. Ethyl acetate and unreacted components were removed under reduced pressure at 80 ° C. to obtain a vinyl resin A13. The number average molecular weight of the obtained vinyl resin A13 was 5100, and Mw / Mn = 1.6. The structural unit ratio of the structural unit represented by the general formula (3) to the structural unit represented by the general formula (4) was 0.1: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A13 was added, degassed under reduced pressure, and then replaced with nitrogen gas, under a nitrogen stream. 1.5 parts by mass of N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4, and the adhesion test results are shown in Table 7.

(Example 14)
As shown in Table 3, 100 parts by mass of ethyl acetate was added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, and heated to 80 ° C. In a separate container, 10.0 parts by weight of methyl methacrylate, 203.2 parts by weight of lauryl methacrylate, 16.9 parts by weight of stearyl methacrylate, 4.95 parts by weight of N, N-dimethylacrylamide, 26.14 parts by weight of acryloxymethyldimethylmethoxysilane Part, further 10.12 parts by mass of lauryl mercaptan and 4.11 parts by mass of AIBN were added dropwise over 3 hours with a dropping funnel, further reacted at 80 ° C. for 6 hours, and ethyl acetate or unreacted at 80 ° C. under reduced pressure. The component was removed to obtain vinyl resin A14. The number average molecular weight of the obtained vinyl resin A14 was 5100, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.133: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A14 was added, and after degassing under reduced pressure, the nitrogen gas was replaced. 2.5 parts by mass of N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4.

(Example 15)
As shown in Table 3, 100 parts by mass of toluene was added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, and heated to 100 ° C. In a separate container, 203.2 parts by weight of lauryl methacrylate, 33.8 parts by weight of stearyl methacrylate, 4.95 parts by weight of N, N-dimethylacrylamide, 7.16 parts by weight of N, N-dimethylaminoethyl acrylate, acryloxymethylmethyl Add 28.54 parts by mass of dimethoxysilane, 9.82 parts by mass of mercaptopropyltrimethoxysilane, 4.11 parts by mass of AIBN, add dropwise over 3 hours with a dropping funnel, and further react at 100 ° C. for 2 hours to 100 ° C. Then, toluene and unreacted components were removed under reduced pressure to obtain vinyl resin A15. The number average molecular weight of the obtained vinyl resin A15 was 5100, and Mw / Mn = 1.6. The structural unit ratio between the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) was 0.133: 1.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin A15 was added, degassed under reduced pressure, and then replaced with nitrogen gas. 2.5 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition of the present invention. The storage stability and curability (TFT) results of the curable composition are shown in Table 4, and the adhesion test results are shown in Table 7.

(Comparative Example 1)
As shown in Table 5, 50.0 parts by mass of n-butyl acrylate, 2.34 parts of acryloxypropyltrimethoxysilane were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. Part by mass, and further 3.93 parts by mass of mercaptopropyltrimethoxysilane were added and heated to 80 ° C. 2.48 parts by mass of AIBN dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin X1. The number average molecular weight of the obtained vinyl resin X1 was 5000, and Mw / Mn = 1.6.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin X1 was added, and after degassing under reduced pressure, the nitrogen gas was replaced, and under a nitrogen stream 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition. The results of storage stability and curability (TFT) of the curable composition are shown in Table 6, and the results of the adhesion test are shown in Table 7.

(Comparative Example 2)
As shown in Table 5, 50.0 parts by mass of n-butyl acrylate, 2.48 parts of methacryloxypropyltrimethoxysilane were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. Part by mass, and further 3.93 parts by mass of mercaptopropyltrimethoxysilane were added and heated to 80 ° C. 2.48 parts by mass of AIBN dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin X2. The number average molecular weight of the obtained vinyl resin X2 was 5000, and Mw / Mn = 1.6.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin X2 was added, and after degassing under reduced pressure, the nitrogen gas was replaced, and under a nitrogen stream 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition. The storage stability and curability (TFT) results of the curable composition are shown in Table 6.

(Comparative Example 3)
As shown in Table 5, 40 parts by mass of ethyl acetate was placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, and heated to 80 ° C. In a separate container, 62.4 parts by weight of methyl methacrylate, 45.58 parts by weight of stearyl methacrylate, 1.99 parts by weight of methacryloxypropyltrimethoxysilane, 7.60 parts by weight of mercaptopropyltrimethoxysilane, and 2.60 parts by weight of AIBN are mixed. Then, it was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin X3. The number average molecular weight of the obtained vinyl resin X3 was 5000, and Mw / Mn = 1.6.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 50 parts by mass of the obtained vinyl resin X3 was added, degassed under reduced pressure, and then replaced with nitrogen gas, under a nitrogen stream. 0.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain a curable composition. The storage stability and curability (TFT) results of the curable composition are shown in Table 6.

(Comparative Example 4)
As shown in Table 5, 50.0 parts by mass of lauryl methacrylate and 2.48 parts by mass of methacryloxypropyltrimethoxysilane were added to a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. Further, 3.93 parts by mass of mercaptopropyltrimethoxysilane was added and heated to 80 ° C. 2.48 parts by mass of AIBN dissolved in 5 mL of THF was added dropwise over 3 hours, and further reacted at 80 ° C. for 6 hours to obtain a vinyl resin X4. The number average molecular weight of the obtained vinyl resin X4 was 5000, and Mw / Mn = 1.6.

  To a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 50 parts by mass of the obtained vinyl resin X4 was added, degassed under reduced pressure, and then replaced with nitrogen gas. Add 1.50 parts by mass of 3-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.50 parts by mass of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and curable composition I got a thing. The results of storage stability and curability (TFT) of the curable composition are shown in Table 6, and the results of the adhesion test are shown in Table 7.

In Table 1, Table 2, Table 3, and Table 5, the compounding quantity of each compounding substance is shown by g except THF, The detail of each compound is as follows.
n-Butyl acrylate: Tokyo Chemical Industry Co., Ltd. Methyl methacrylate: Trade name “Light Ester M”, Kyoeisha Co., Ltd. Stearyl methacrylate: Trade name “Light Ester S”, Kyoeisha Co., Ltd. 2-ethylhexyl methacrylate: Product Name "Light Ester EH", Kyoeisha Co., Ltd. Lauryl Methacrylate: Trade name "Light Ester L", Kyoeisha Co., Ltd. N, N-dimethylacrylamide, Kojin Co., Ltd. N, N-dimethylaminoethyl acrylate, KOHJIN Co., Ltd. Acryloxymethyltrimethoxysilane: Gelest acryloxymethyldimethylmethoxysilane: Gelest acryloxymethylmethyldimethoxysilane: Gelest methacryloxymethyltrimethoxysilane: Gelest Mercaptomethyl Limethoxysilane: Trade name “LS535”, Shin-Etsu Chemical Co., Ltd. Mercaptopropyltrimethoxysilane: Trade name “KBM803”, Shin-Etsu Chemical Co., Ltd. Mercaptopropylmethyldimethoxysilane: Trade name “KBM802”, Shin-Etsu Chemical Industrial: THF: Tetrahydrofuran, Wako Pure Chemical Industries, Ltd. AIBN: 2,2'-azobisisobutyronitrile (V-60, Wako Pure Chemical Industries, Ltd.)
BPO: Benzoyl peroxide (Niper BW, manufactured by NOF Corporation)
ADVN: 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.)
Acryloxypropyltrimethoxysilane: trade name “KBM5103”, manufactured by Shin-Etsu Chemical Co., Ltd. Methacryloxypropyltrimethoxysilane: trade name “KBM503”, manufactured by Shin-Etsu Chemical Co., Ltd. Lauryl mercaptan: manufactured by Tokyo Chemical Industry Co., Ltd. Ethyl acetate: zirconocene dichloride manufactured by Wako Pure Chemical Industries, Ltd., ruthenocene dichloride manufactured by Tokyo Chemical Industry Co., Ltd., methyl 2-bromopropionate manufactured by Tokyo Chemical Industry Co., Ltd., propylene carbonate manufactured by Tokyo Chemical Industry Co., Ltd. CuBr manufactured by Tokyo Chemical Industry Co., Ltd., N, N, N ′, N ″, N ″ -pentamethylenediethylenetriamine manufactured by Tokyo Chemical Industry Co., Ltd., manufactured by Aldrich

  As shown in Tables 4 and 7, the curable compositions of the present invention exhibited sufficient curability, storage stability, adhesiveness, and rising adhesiveness.

Claims (5)

(A) viewed including the following general formula (1) below and a compound general formula (2) vinyl resin obtained by reacting a compound represented by represented, and (B) a curing catalyst,
(B) The curable composition, wherein the curing catalyst is an amine compound and is used for an adhesive .

In (Formula (1), ^{R 1} is an alkyl group, an alkenyl group having 1 to 18 carbon atoms, an aryl group, or a phenyl group, ^{R 2} is an alkyl group having 1 to 4 carbon atoms, an alkenyl group, an aryl group Or a phenyl group, R ³ is hydrogen or a methyl group, and m is an integer of 1 to ^3. )

(In the formula (2), R ⁴ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom, an alkali metal atom, or a hydrocarbon-containing group having 1 to 24 carbon atoms. .) The curable composition according to claim 1, wherein the amine compound is an aminosilane . The curable composition according to claim 1 or 2, wherein the (A) vinyl-based resin includes a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4). .

In (Formula (3), ^{R 1} represents an alkyl group, an alkenyl group having 1 to 18 carbon atoms, an aryl group, or a phenyl group, ^{R 2} is an alkyl group having 1 to 4 carbon atoms, an alkenyl group, an aryl group Or a phenyl group, R ³ is hydrogen or a methyl group, and m is an integer of 1 to ^3. )

(In the formula (4), R ⁴ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom, an alkali metal atom, or a hydrocarbon-containing group having 1 to 24 carbon atoms. .)   The curable composition according to any one of claims 1 to 3, wherein the reaction is free radical polymerization or living radical polymerization.   The curable composition according to any one of claims 1 to 4, wherein 0.000001 to 10 parts by mass of the (B) curing catalyst is blended with respect to 100 parts by mass of the (A) vinyl resin. object.