JP4636867B2 - Moisture curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition that is cured by moisture, and more particularly to a curable resin composition containing a crosslinkable reactive silyl group.

  A vinyl polymer obtained by (co) polymerizing acrylic acid-based monomers, methacrylic acid-based monomers, vinyl monomers, and the like is very useful. In particular, a curable resin having a reactive silyl group introduced in its molecule is an adhesive, Widely used as materials for sealing materials, paints, coating materials, etc. However, such a reactive silyl group-containing curable resin has insufficient adhesion, and there is a problem that when an adhesive resin is added to improve the adhesion, the viscosity becomes high and the workability is inferior. It was. In addition, assuming that the viscosity is increased, in order to reduce the viscosity of the reactive silyl group-containing curable resin itself, when the resin is produced using a compound having a mercapto group as a chain transfer agent, it is obtained. When the obtained resin is cured, the cured product becomes brittle, and there is a problem that sufficient physical properties cannot be obtained and adhesiveness is lowered. Further, there is a problem that the curing becomes slow.

Therefore, as a method for improving the adhesion performance of such a vinyl polymer, for example, as described in Japanese Patent No. 3313360, a compound having a polymerizable vinyl group, a polar group and a reactive silyl group in the molecule is used. A method of obtaining a curable resin by copolymerization has also been attempted, but although the adhesion of the resulting resin is improved, the effect is not sufficient.
In addition, as described in Japanese Patent Nos. 3415091 and 3437560, it has been found that a curable resin composition using a silylated urethane resin and a vinyl polymer in combination is useful as a contact adhesive. Yes. However, in this method, it is possible to prepare a curable resin composition having contact properties and good adhesion to various adherends. For example, depending on individual applications such as an adhesive, the curable resin composition may be further improved. Improvement in performance was desired.

Japanese Patent No. 3313360 Japanese Patent No. 3415091 Japanese Patent No. 34337560

  The present invention has been made in order to solve the above-mentioned problems in conventional curable resin compositions, and even when an adhesive resin is added, there is no significant increase in viscosity, good adhesion, and low viscosity. An object is to provide a curable resin composition. Furthermore, an object of the present invention is to provide a curable resin composition having a low viscosity and exhibiting a fast curing property.

  In order to achieve the above object, the present inventors have conducted extensive research, and as a result, the adhesive resin is not directly added to the reactive silyl group-containing curable resin, but in the presence of the adhesive resin, By polymerizing the curable resin monomer to obtain a curable resin polymer, the adhesiveness does not decrease even when the introduction ratio of the reactive silyl group to the polymer of the curable resin monomer is increased, and the viscosity is low. It has been found that a curable resin composition can be provided, and the present invention has been completed.

That is, the present invention is a polymerization product obtained by polymerizing a polymerizable compound (A) having at least one reactive silyl group in the molecule in a liquid containing the tackifier compound (B) and not containing water. The tackifying compound (B) is a moisture curable resin composition that is an aromatic compound .

The present invention further includes a tackifying compound (B) and a curable resin (C) having at least one reactive silyl group in the molecule, and at least one in the molecule in a liquid not containing water. A polymerization product obtained by polymerizing a polymerizable compound (A) having a reactive silyl group is a component, and the tackifying compound (B) is a moisture curable resin composition which is an aromatic compound. .

Further, the present invention relates to a polymerization product obtained by polymerizing a polymerizable compound (A) having at least one reactive silyl group in the molecule in a liquid containing the tackifier compound (B) and not containing water. And a curable resin (C) having at least one reactive silyl group in the molecule, and the tackifying compound (B) is a moisture curable resin composition which is an aromatic compound. .

Further, moisture-curable resin composition of the present invention, the curable resin (C), characterized in that a compound having at least a urethane bond in the molecule.

Furthermore, the present invention is summarized as moisture-curable resin composition according to Lewis acids and / or curing catalyst (D) a component consisting of the complexes.

The moisture curable resin composition of the present invention is characterized in that the Lewis acid is boron trifluoride.

  The curable resin composition according to the present invention exhibits moisture curability with low viscosity and very good adhesion. Moreover, the curable resin composition according to the present invention has an effect of having good conformability to various materials.

  The polymerizable compound (A) having at least one reactive silyl group in the molecule used in the present invention generally has at least one reactive silyl group in the molecule and can be polymerized by radical polymerization. It refers to all monomers having a typical carbon-carbon double bond. The reactive silyl group is a silyl group having a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, and a mercapto group. Group, oxime group and alkenyloxy group, as well as hydrogen atom and halogen atom, among which hydrogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group An oxime group and an alkenyloxy group are preferable, and an alkoxy group is particularly preferable. Therefore, as the reactive silyl group, an alkoxysilyl group represented by the formula -Si (R1) 3-m (OR2) m is particularly suitable. In the above formula, R1 is an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, particularly preferably 1 or 2 carbon atoms, and R2 is 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, particularly preferably. Is an alkyl group having 1 or 2 carbon atoms, and m is an integer of 1 to 3.

  The polymerizable compound (A) suitably used in the present invention reacts with a monomer having a general carbon-carbon double bond polymerizable by radical polymerization and a polymerizable compound having a reactive silyl group in the molecule. Can be manufactured.

  Examples of monomers having a general carbon-carbon double bond that can be polymerized by radical polymerization include, for example, acrylic acid, methacrylic acid (hereinafter referred to as (meth) acrylic (l) combining acrylic acid compound and methacrylic acid compound). ..., methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (Meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxypolyethyleneglycol (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, Bornyl (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth) acrylate, isobutoxymethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyl Octyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nt-octyl (meth) acrylamide, N-isopropyl Lopyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- [3- (dimethylamino) Propyl] methacrylamide, (meth) acryloylmorpholine, acrylonitrile, α-methylacrylonitrile, 2,4-dicyanobutene, 2- (meth) acryloyloxyethyl succinate, maleic acid, dimethyl maleate, diethyl maleate, dibutyl maleate, Di-2-ethylhexyl maleate, dioctyl maleate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, Alkyl vinyl ethers such as nyl glycidyl ether, allyl glycidyl ether, vinyl pyrrolidone, vinyl carbazole, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, p-methoxy styrene, divinyl benzene, methyl vinyl ether Cinnamyl compounds such as methyl cinnamate, ethyl cinnamate, cinnamic acid, cinnamic aldehyde, cinnamyl alcohol, cinnamic acid amide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxy group-containing (meth) acrylates such as 2-acryloyloxypropyl (meth) acrylate and N-methylolacrylamide, allyl alcohol, allylphenol, allyla , Allyl mercaptan, eugenol, hydroxystyrene, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, propargyl alcohol 2-methyl-3-butyn-2-ol, undecylenic acid, 2-butenoic acid, furfuryl alcohol, furfurylmethyl mercaptan, 9-decenol-1, 5-hexen-1-ol, 2-hydroxyethyl Vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monobutyl ether, mesityl oxide, vinyl chloride, vinyl acetate, vinyl propionate, butadiene, isoprene, chloroprene, ethylene, other olefins, unsaturated esters, And halogenated olefins

  As these commercial products, Kyoeisha Chemical Co., Ltd. trade names: Light Ester Series, Light Acrylate Series, Epoxy Esters M-600A, HOA-MPL, HOA-MPE, HOA-HH, etc. Acetone acrylic amide, etc., trade name made by Showa Denko Co., Ltd .: Karenz MOI-BM, etc., trade name made by Mitsubishi Chemical Corporation, 4-hydroxybutyl acrylate, etc., trade names made by Shell Chemical Co., Ltd .: Veova 9, Veova 10, etc., Shin Nakamura Chemical Co., Ltd. Product names: NK Ester Series, Topolene M, NK Oligo Series, etc., Product Name: New Frontier Series, etc., Daicel Chemical Industries, Ltd. Product Name: Celoxide 2000, MVE, Plaxel Series, CYCLOMER M100, CYCLOMER A200, HEMAC, M-GMA, etc. Daiso brand name: Neoallyl G, Toagosei Co., Ltd. brand name: Aronix M series, etc., Nagase Kasei Kogyo brand name: Denacol acrylate DA-141, etc., Nippon Oil & Fats brand name: Blemmer series, etc., Mitsubishi Product numbers manufactured by Gas Chemical Co., Ltd .: GE series, MMA, EMA, EHMA, DPMA, SMA, AMA, CHMA, DAA, etc. Product names manufactured by Mitsubishi Rayon Co., Ltd .: Acryester series, etc. Product names manufactured by Nippon Kayaku Co., Ltd .: Kayahard series Etc., trade names manufactured by Osaka Organic Chemical Co., Ltd .: Biscoat 3700, etc., trade names manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, KBM-5103, KBM-1403, KBM-1003, etc., but are not limited thereto. Absent. Of these, α, β-unsaturated carbonyl compounds such as acrylic ester compounds and methacrylic ester compounds are most preferred.

  Examples of the polymerizable compound having a reactive silyl group in the molecule that reacts with a monomer having a general carbon-carbon double bond that can be polymerized by radical polymerization include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyl. Triethoxysilane, γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane, Japanese Patent No. 3313360, Special Table No. 02-102812 And polymerizable silane compounds proposed in Japanese Patent Publication No.

  The reaction between the monomer having a carbon-carbon double bond and the polymerizable compound having a reactive silyl group in the molecule is a radical polymerization, anion polymerization, cation ordinarily performed when a normal polymerizable vinyl monomer is copolymerized. Any known method such as polymerization can be employed. In particular, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), a commercial product containing these compounds, manufactured by Wako Pure Chemical Industries, Ltd. Product names: VA-066B, VA-037, VA-061, VA-085, VA-086, VA-096, V-65, VAm-110 and other azo compounds, benzoyl peroxide, t-alkyl peroxyesters A radical polymerization method carried out in the presence of a peroxide polymerization initiator such as acetyl peroxide or diisopropyl peroxycarbonate is preferred. In this case, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, thio-β-naphthol, thiophenol, n-butyl mercaptan, ethylthioglycolate, isopropyl mercaptan, t-butyl mercaptan, γ Polymerization can be carried out in the presence of a chain transfer agent such as trimethoxysilylpropyl disulfide. The reaction is preferably carried out at a temperature of 20 to 200 ° C., particularly 50 to 150 ° C. for 1 hour to several tens of hours. The reaction between the monomer having a carbon-carbon double bond and the polymerizable compound having a reactive silyl group in the molecule is preferably performed in a liquid containing the tackifier compound (B).

Specific examples of the tackifying compound (B) preferably used in the present invention include phenol resins, modified phenol resins (for example, cashew oil modified phenol resin, tall oil modified phenol resin, etc.), terpenes, terpene phenol resins, xylenes. -Phenol resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C ₅ hydrocarbon resins, _{C 9} hydrocarbon _resins, C 5 · _{C 9} hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene resins, DCPD resins and the like. These may be used alone or in combination of two or more. Among the above tackifying compounds, terpene phenol resin, xylene resin, styrene copolymer resin, rosin resin, rosin ester resin, terpene resin are preferable, and terpene phenol resin, xylene resin, styrene copolymer resin, etc. Those which are aromatic compounds are most preferred.

  The tackifier compound (B) is commercially available and can be used in the present invention. Examples of commercially available products include FTR8000 series (Mitsui Chemicals), FTR7000 series (Mitsui Chemicals), FTR6000 series (Mitsui Chemicals), SX100 (Yashara Chemicals), YS Polystar series (Yashara Chemicals), Examples include, but are not limited to, D-limonene (manufactured by Yasuhara Chemical Co., Ltd.), terpineol (manufactured by Yasuhara Chemical Co., Ltd.), YS resin series (manufactured by Yasuhara Chemical Co., Ltd.), and the like.

  The curable resin (C) which is a component of the curable resin composition of the present invention has at least one reactive silyl group in the molecule. The reactive silyl group is a hydrolyzable group-containing silyl group and a hydroxyl group-containing silyl group. Examples of hydrolyzable groups include alkoxy, acyloxy, ketoximate, amino, amide, acid amide, aminooxy, mercapto, oxime and alkenyloxy groups, as well as hydrogen and halogen atoms. Among them, preferred are a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an oxime group, and an alkenyloxy group, particularly high reactivity and low odor. From this point, an alkoxy group is preferable. As an alkoxy group, a C1-C12 thing is preferable and a methoxy group and a methoxy group are especially preferable. Accordingly, the reactive silyl group may be the same as the reactive silyl group in the polymerizable compound (A).

  The curable resin (C) in the present invention is not particularly limited as long as it is a curable compound having at least one reactive silyl group. Specifically, organopolysiloxane, modified silicone (for example, trade names manufactured by Kaneka Corporation: S series, SAT series, MA series, MAX series, EST series, ESX series, SAX series, etc.), trade names manufactured by Asahi Glass Urethane Co., Ltd .: Reactive silyl groups described in JP-B-4-69659, JP-B-7-108928, Japanese Patent No. 2512468, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent No. 2539445, etc. Containing saturated hydrocarbon polymer, trade name manufactured by Kaneka: Epion series, reactive silyl group-containing vinyl polymer (for example, trade name manufactured by Kaneka: SA100S, OR100S, SA300S, SA110S, etc.), silicone alkoxy oligomer (for example, Product name manufactured by Shin-Etsu Chemical Co., Ltd .: KC-89S, K Series, X-40 series, X-41 series, etc.), silicone alkoxy oligomers which are silicone resins having molecular end alkoxysilyl groups, silane coupling agents, and the like, but are not limited thereto. .

  In addition, the curable resin (C) used in the present invention includes JP-A Nos. 11-100197, 2000-143757, 2000-169544, 2002-212415, 2004-123900, No. 2004-123901, Japanese Patent No. 3030020, Japanese Patent No. 3295663, Japanese Patent No. 3313360, Japanese Patent No. 3317353, Japanese Patent No. 3350011, etc., Japanese Patent Application No. 2004-208672 Curable resins described in the document, and curable resins obtained by carbonating an epoxy resin and then silylated with an aminosilane compound, JP-A-63-83131 and JP-A-63-83160, Terminal epoxy groups such as those proposed in Kaihei No. 238045 Aromatic dithiol compound and / or an aromatic diimino compounds curable resin obtained by adding epoxy silane compound was terminated thiolated by the action of such are also included in mer.

  Of the curable resins suitably used in the present invention, oxyalkylene polymers having a main chain skeleton include those described in JP-B Nos. 45-36319, 46-12154, 49-32673, and JP-A-50-156599. No. 51-73561 No. 54-6096 No. 55-82123 No. 55-123620 No. 55-125121 No. 55-130122 No. 55-135135 No. 55-137129 No. Resins generally referred to as modified silicones, which are proposed in publications and the like, are included.

  As a method for producing the oxyalkylene polymer, a method in which a hydrogenated silicon compound having the silicon-containing characteristic group in the molecule is added to the alkenyl group of the polyoxyalkylene having an alkenyl group, or A method of radical addition reaction of an alkenyl group of oxyalkylene with a mercapto group of a mercaptosilane compound having a mercapto group and a silicon-containing characteristic group in the molecule is well known.

  Further, examples of the curable resin suitably used in the present invention include reactive silyl group-containing vinyl polymers such as JP-A-9-272715, JP-A-9-272714, JP-A-11-080249, and JP-A-11-080250. 11-005815, 11-116617, 11-116606, 11-080571, 11-080570, 11-130931, 11-100433, 11-116763, special Reactions described in JP-A 2003-82192, 2003-119339, 2003-171416, 2003-246661, 2003-327852, 2003-327620, 2004-002835, etc. Functional silyl group-containing vinyl polymer, trade name: XPR-15, XPR- 2 or the like of the reactive plasticizer XPR series manufactured by Soken Chemical Engineering Co., Ltd. trade name: ACTFLOW series like, Kaneka Corporation, trade name: SA100S, OR100S, SA300S, SA110S and the like.

  The curable resin (C) suitably used in the present invention includes one or more silicon-containing characteristic groups selected from the group consisting of hydrolyzable silyl groups and silanol groups, and urethane in the molecule. One selected from the group consisting of a bond, a thiourethane bond, a urea bond, a thiourea bond, a substituted urea bond, a substituted thiourea bond, an amide bond, a sulfide bond, a hydroxyl group, a secondary amino group, and a tertiary amino group A curable resin having the above bond and / or group (polar element portion) is included. Among these, the use of a compound having a urethane bond is desirable because the synthesis conditions are simple and the industrial utility value is high.

  Of the polar element part (urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary amino group) The introduction method is not particularly limited. The linking group generated when linking a plurality of raw materials by a chemical reaction may be the polar element part, or the compound containing the polar element part may be linked by a chemical reaction from the beginning. Further, any number of the polar element portions may be included in the curable resin (C). The curable resin (C) preferably has a number average molecular weight of 500 to 30,000, particularly 2,000 to 20,000.

  Examples of the curable resin (C) having a urethane bond preferably used include a resin having a urethane bond and a group represented by the following general formula (1) in the molecule. In addition, resin which has group represented by following General formula (1) and following General formula (2) is also contained in curable resin (C) which has a urethane bond.

However, ^{R 3} is 1-20 substituted or unsubstituted organic group, ^{R 4} is following general formula (3), the following general formula (4), the following general formula (5) or the following general formula (6) A group represented by the formula, a phenyl group, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, n represents 0, 1 or 2, and R ³ represents a plurality. When present, their R ³ may be the same or different, and when there are a plurality of X, their X may be the same or different. In particular, the general formula (1) is particularly preferably an alkoxysilyl group represented by the formula -Si (R1) 3-m (OR2) m. In this formula, R1, R2 and m are as defined above.

However, ^{R 5} is a hydrogen atom or -COOR ^13, the ^{R 6} is a hydrogen atom or a methyl group, an ^{R 7} is -COOR ¹⁴ or a nitrile group, ^{R 8} is a substituted or unsubstituted 1 to 20 carbon atoms 2 R ⁹ is an organic group which may contain a silicon atom having a molecular weight of 500 or less, R ¹⁰ and R ¹¹ are the above general formula (3) or the following general formula (7) (where R ⁹ is R ¹² represents a phenyl group, a cyclohexyl group, or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, and R ¹⁰ and R ¹¹ are the same. But it may be different. R ¹³ and R ¹⁴ each represents an organic group having a molecular weight of 500 or less.

  Examples of the hydrolyzable group of X in the general formula (2) include an alkoxy group, an acetoxy group, and an oxime group, and an alkoxy group is particularly preferable. The curable resin (C) having a urethane bond reacts with a compound having at least one hydroxyl group in the molecule (compound (a)) and a polyisocyanate compound (compound (b)) to produce a urethane prepolymer, Further, a method of reacting a urethane prepolymer and a compound represented by the following general formula (8) (compound (c)), an isocyanate group and a reactive silyl in the molecule such as γ-isocyanatopropyltrimethoxysilane to the compound (a) A method of reacting a compound having a group, after reacting a compound (a) with a compound having an isocyanate group and a vinyl group in the molecule such as allyl isocyanate, m-isopropenyl-α, α-methylbenzyl isocyanate, -A compound having a mercapto group and a reactive silyl group in the molecule such as mercaptopropyltrimethoxysilane It can be produced by a method such as to cull addition reaction.

  The polyoxyalkylene polymer used as a raw material for the compound (a) is preferably a hydroxyl-terminated polymer produced by reacting a monoepoxide or the like with an initiator in the presence of a catalyst. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used.

  As the monoepoxide, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran and the like can be used. The curable resin having a urethane bond in the present invention (C) is preferably a polyoxyalkylene polymer having a main chain containing at least polyoxypolyoxyethylene, and therefore, as a monoepoxide, ethylene oxide is an essential component, It is preferable to use propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran or the like in combination.

  Examples of the catalyst include alkali metal catalysts such as potassium compounds and cesium compounds, composite metal cyanide complex catalysts, and metal porphyrin catalysts. The complex metal cyanide complex catalyst is preferably a complex mainly composed of zinc hexacyanocobaltate, an ether and / or alcohol complex. The composition of the ether and / or alcohol complex essentially described in JP-B-46-27250 can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. As the alcohol, for example, those described in JP-A-4-145123 can be used, and tert-butanol is particularly preferable.

  The raw material polyoxyalkylene polymer preferably has 2 or more functional groups, and specific examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene and the like. In particular, polyoxyethylene, or polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene, or the like containing 1% by mass or more of polyoxyethylene is preferable. A preferred raw material polyoxyalkylene polymer is a divalent to hexavalent polyoxyethylene polyol, or a mixture of polyoxyethylene polyol and polyoxypropylene polyol. In particular, the polyoxyethylene polyol is polyoxyethylene diol, and the polyoxypropylene polyol is polyoxypropylene diol and polyoxypropylene triol.

  Compound (a) is commercially available, and they can be used in the present invention. Examples of commercially available products include Asahi Denka Kogyo Co., Ltd., trade names: P-2000, P-3000, Asahi Glass Co., Ltd., trade names: PML-3005, PML-3010, PML-3012, PML-4002, PML-4010. , PML-5005, manufactured by Sumitomo Bayer Urethane Co., Ltd., trade names: Sumiphen 3700, SBU-Polyol 0319, and the like. In addition, polyoxypropylene having a primary amino group at the terminal (for example, product name: Jeffamine D-230, D-400, D-2000, manufactured by Sun Techno Japan Co., Ltd.) or poly having a secondary amino group at the terminal One or two selected from oxypropylene (for example, trade name: Jeffamine D-230, D-400, D-2000, manufactured by Sun Techno Japan Co., Ltd.), α, β-unsaturated carbonyl compound, maleic acid diester and acrylonitrile Those obtained by reacting more than one species can also be used.

  Examples of the compound (b) include diisocyanate compounds, polyisocyanate compounds excluding diisocyanate compounds, and the like. Examples of the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic diisocyanate compounds. Specific examples thereof will be given below.

Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2 , 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, and the like.
Alicyclic diisocyanate compounds: 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like.
Aroaliphatic diisocyanate compounds: 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate) -1-methylethyl) benzene or a mixture thereof.
Aromatic diisocyanate compounds: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like.

  Examples of the polyisocyanate compound excluding the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds. Specific examples thereof will be given below.

Aliphatic polyisocyanate compounds: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-tri Isocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, and the like.
Alicyclic polyisocyanate compound: 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 3-isocyanate-3,3,5-trimethylcyclohexylisocyanate, 2- (3-isocyanatepropyl)- 2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 5 -(2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3 -Isocyanatopropyl) -bicyclo [2,2,1] heptane, -(2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2- (3-isocyanatopropyl)- Bicyclo [2,2,1] heptane and the like.
Aro-aliphatic polyisocyanate compound: 1,3,5-triisocyanate methylbenzene and the like.
Aromatic polyisocyanate compounds: triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatotoluene, 4,4′-diphenylmethane-2, 2 ', 5,5'-tetraisocyanate and the like.
Other polyisocyanate compounds: diisocyanates containing a sulfur atom such as phenyl diisothiocyanate.

  The compound (c) is a compound represented by the following general formula (8).

Where R ³ , R ⁴ , X and n are as defined above, Y is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, the following general formula (9) or the following general formula Equation (10) is shown respectively.

However, R ⁵ , R ⁶ , R ⁷ and R ⁹ are as defined above, and R ¹⁵ and R ¹⁶ represent a substituted or unsubstituted divalent organic group having 1 to 10 carbon atoms.

  Specific examples of the compound (c) include N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N- (n-butyl) -γ-aminopropyltrimethoxysilane, N- (n-butyl) -γ-aminopropylmethyldimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) Examples thereof include amines, but they can also be produced by the following method.

(1) Compound in which R ⁴ is represented by the above general formula (3) and Y is a divalent organic group Primary amino group and hydrolyzable group-containing silicon group or hydroxyl group-containing silicon group (preferably hydrolyzable A compound (compound (d)) each having one group-containing silicon group) and a chemical equivalent of an α, β-unsaturated carbonyl compound (compound (e)), a maleic acid diester (compound (f)) and acrylonitrile. Method of reacting one or two or more selected (2) A compound in which R ⁴ is represented by the general formula (3) and Y is represented by the general formula (9) Primary amino group, secondary A compound (compound (g)) having an amino group and a hydrolyzable group-containing silicon group or a hydroxyl group-containing silicon group (preferably a hydrolyzable group-containing silicon group), a primary amino group in the compound (g) and Compounds with secondary amino groups and chemical equivalents e), a method of reacting the compound (f) and one or more selected from acrylonitrile (3) R ⁴ is represented by the formula (3), Y is represented by the general formula (10) Compound After reacting compound (g) with a chemical equivalent of compound (e), compound (f) and acrylonitrile in a chemical equivalent to the primary amino group in compound (g), compound the method (g) secondary amino group and a chemical equivalent of the formula R ⁹ NCO in ^{(R 9} is the above as defined above) is reacted monoisocyanate compound represented by (compound (h)) and (4) ^{R 4} is A compound represented by the above general formula (4), wherein Y is a divalent organic group. A method of reacting a primary amino group in compound (g) with a chemical equivalent of compound (h). (5) ^{R 4} is represented by the general formula (5), and having the general formula ( R ¹⁰ and R ¹¹ in) is represented by the formula (3), Y compound compound is a divalent organic radical and (g), primary amino groups and 2 chemical equivalents of the compound (g) (6) A method of reacting one or more selected from compound (e), compound (g) and acrylonitrile (6) wherein R ⁴ is represented by the above general formula (5) and in general formula (5) Compound (g) in which R ¹⁰ is represented by the above general formula (3), R ¹¹ is represented by the above general formula (7), and Y is a divalent organic group, and the primary in the compound (g) After reacting an amino group with a chemical equivalent of compound (e), compound (f) and one or more selected from acrylonitrile, a secondary amino group produced by this reaction and a chemical equivalent of compound (h ) a method of reacting (7) ^{R 4} is represented by the general formula (6), Y is a divalent organic How compound compound is a group and (d), to the compound (d) primary amino groups and the chemical equivalent of the maleimide compound in the (i) reacting.

  Examples of the compound (d) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and the like.

  Examples of the compound (e) include (meth) acrylic compounds, vinyl ketone compounds, vinyl aldehyde compounds, and other compounds. As (meth) acrylic compounds, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , Pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl ( (Meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate Stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol ( (Meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadienyl (meta ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) Acrylate), tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth) acrylate, isobutoxymethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, N -Vinylformaldehyde, N, N-dimethylacrylamide, t-octylacrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N- In addition to dimethyl (meth) acrylamide, N, N′-dimethylaminopropyl (meth) acrylamide, acryloylmorpholine, etc., trade names manufactured by Toagosei Co., Ltd .: Aronix M-102, M-111, M 114, M-117, manufactured by Nippon Kayaku Co., Ltd. under the trade name: KAYAHARD TC110S, R629, R644, Osaka Organic Chemical Co., Ltd. under the trade name: BISCOAT 3700, and the like.

  Further, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxy Ethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate , A polyfunctional compound such as epoxy (meth) acrylate obtained by adding (meth) acrylate to glycidyl ether of bisphenol A, and a commercial name of the product made by Mitsubishi Chemical Co., Ltd .: Iupimer UV, SA1002, SA2007, Osaka Organic Chemical Co., Ltd. trade name: Biscote 700, Nippon Kayaku Co., Ltd. trade name: Kayahard R604, DPCA-20, DPCA-30, DPCA-60, DPCA-120, HX-620, D-310, D-330, trade names manufactured by Toagosei Co., Ltd .: Aronix M-210, M-215, M-315, M-325, etc.

  In addition to the above compounds, γ-methacryloxypropyltrimethoxysilane having an alkoxysilyl group, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxy Examples thereof include propyltrimethoxysilane and γ-acryloxymethyldimethoxysilane.

  Examples of vinyl ketone compounds include vinyl acetone, vinyl ethyl ketone, and vinyl butyl ketone, examples of vinyl aldehyde compounds include acrolein, methacrolein, and crotonaldehyde, and examples of other compounds include maleic anhydride, itaconic anhydride, and itaconic acid. , Crotonic acid, N-methylolacrylamide, diacetone acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, Nt-octylacrylamide, N- Examples include isopropylacrylamide.

  In addition to the above compounds, compounds containing a fluorine atom, a sulfur atom or a phosphorus atom are also included. Examples of the compound containing a fluorine atom include perfluorooctylethyl (meth) acrylate and trifluoroethyl (meth) acrylate, and examples of the compound containing a phosphorus atom include (meth) acryloxyethyl phenyl acid phosphate.

  Among the compounds (e), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, from the viewpoint of easy reaction, wide commercial availability, and availability. Lauryl acrylate and the like are preferable. Of these, methyl acrylate and ethyl acrylate are particularly preferable for imparting fast curability, and 2-ethylhexyl acrylate and lauryl acrylate are particularly desirable for imparting flexibility. Moreover, 1 type (s) or 2 or more types can be used for a compound (e).

  Examples of the compound (f) (maleic acid diester) include dimethyl maleate, diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, dioctyl maleate and the like, and these can be used alone or in combination. Among these, dimethyl maleate, diethyl maleate, dibutyl maleate, and di-2-ethylhexyl maleate are preferred from the viewpoint of easy reaction and wide commercial availability. Moreover, 1 type (s) or 2 or more types can be used for a compound (f).

  Examples of the compound (g) include N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-amino. Propylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, and other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM6063, X-12-896, KBM576, X-12-565, X-12-58 0, X-12-5263, KBM6123, X-12-575, X-12-562, X-12-5202, X-12-5204, KBE9703 and the like.

  Among the above compounds (g), N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-, from the viewpoint of easy reaction, wide commercial availability, and availability. γ-aminopropyltriethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane are preferred.

  Examples of the compound (h) include ethyl isocyanate, n-hexyl isocyanate, n-dodecyl isocyanate, p-toluenesulfonyl isocyanate, n-hexyl isocyanate, benzyl isocyanate, 2-methoxyphenyl isocyanate, and the like. Brand name: Shin-Etsu Chemical Co., Ltd. brand name: Isocyanate silane such as KBM9007 (γ-isocyanatopropyltrimethoxysilane).

  Examples of the compound (i) include N-phenylmaleimide, N-cyclohexylmaleimide, hydroxyphenylmaleimide, N-laurelmaleimide, diethylphenylmaleimide, N- (2-chlorophenyl) maleimide and the like.

  The method of reacting the compound (a) with the compound (b) to form a urethane prepolymer may be carried out in accordance with a normal method for producing a urethane prepolymer by reacting a polyol compound and a polyisocyanate compound. . Moreover, what is necessary is just to perform the method of making the said compound (c) and a urethane prepolymer react and making it a polymeric compound (A) at 50-100 degreeC for 30 minutes-3 hours.

  Polymerization of the polymerizable compound (A) is performed in a liquid containing the tackifier compound (B) or in a liquid containing the tackifier compound (B) and the curable resin (C). When the tackifying compound (B) is a liquid, the liquid containing the tackifying compound (B) is the liquid (I) or a solution containing the liquid (A), and the tackifying compound (B) is a solid. In this case, the liquid (b) in which the tackifier compound (B) is melted, the solution containing the liquid (b), the solution (c) in which the tackifier compound (B) is dissolved in an appropriate solvent, or the solution (c) ). In addition, the liquid containing the tackifying compound (B) and the curable resin (C) means that when the tackifying compound (B) and the curable resin (C) are both liquids, When the tackifying compound (B) and the curable resin (C) are both solid, the solution containing the mixed liquid (d) is a mixed liquid (e) in which the tackifying compound (B) is melted, and the mixed liquid. A solution containing (e), a tackifier compound (B) and a mixed solution (f) in which the curable resin (C) is dissolved in an appropriate solvent or a solution containing the mixed solution (f) are added to the tackifier compound ( When one of B) and the curable resin (C) is solid, a mixed solution (g) dissolved in the other liquid, a solution containing the mixed solution (g), a melt obtained by melting one solid and the other liquid A mixed solution (x), a solution containing the mixed solution (x), the solid and the liquid into an appropriate solvent It refers dissolved mixed solution (i) or a mixture solution containing the (re) respectively. In the above, a solution containing liquid (b), a solution containing liquid (b), a solution containing solution (c), a solution containing liquid mixture (d), a solution containing liquid mixture (e), a mixed solution (f) In addition to the tackifier compound (B) and / or the curable resin (C), the solution containing the mixed solution (g), the solution containing the mixed solution (h), and the solution containing the mixed solution (ri) Can be included.

  In the present invention, when the polymerizable compound (A) is polymerized in the liquid containing the tackifier compound (B), the liquid containing the tackifier compound (B) and the polymerizable compound (A) are mixed, and the mixture A method of polymerizing the polymerizable compound (A) in a liquid and a method of polymerizing the polymerizable compound (A) by gradually adding the polymerizable compound (A) to a liquid containing the tackifier compound (B) can be employed. When polymerizing the polymerizable compound (A) in a liquid containing the tackifying compound (B) and the curable resin (C), the tackifying compound (B) and the curable resin (C) are mixed, and the mixture A method of polymerizing the polymerizable compound (A) in the liquid, gradually adding a mixed liquid of the liquid containing the tackifier compound (B) and the polymerizable compound (A) to the liquid containing the curable resin (C) Then, a method of polymerizing the polymerizable compound (A), a liquid mixture containing the curable resin (C), a mixed liquid of the tackifier compound (B) and the polymerizable compound (A) is added to the polymerizable compound (A ) Can be employed. In the above, when the polymerizable compound (A) is a liquid, the tackifier compound (B), or the tackifier compound (B) and the curable resin (C) are dissolved in the liquid of the polymerizable compound (A). And may be reacted as a solution thereof, and the liquid containing the tackifier compound (B) in the liquid of the polymerizable compound (A), or the tackifier compound (B) and the curable resin (C) are included. It may be mixed with a liquid and reacted as a mixture thereof. Examples of the solvent that can be used above include xylene, toluene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, n-hexane, cyclohexane, methylcyclohexane, isopropanol, methanol, dimethyl carbonate, and the like.

  The (co) polymerization of the polymerizable compound (A) is a known method such as radical polymerization, anionic polymerization, or cationic polymerization that is usually performed when (co) polymerizing a normal polymerizable vinyl monomer such as a (meth) acrylate compound. Any of these can be employed. In particular, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), a commercial product containing the above compound, manufactured by Wako Pure Chemical Industries, Ltd. Product names: VA-066B, VA-037, VA-061, VA-085, VA-086, VA-096, V-65, VAm-110 and other azo compounds, benzoyl peroxide, t-alkyl peroxyesters A radical polymerization method carried out in the presence of a peroxide polymerization initiator such as acetyl peroxide or diisopropyl peroxycarbonate is preferred. In this case, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, thio-β-naphthol, thiophenol, n-butyl mercaptan, ethylthioglycolate, isopropyl mercaptan, t-butyl mercaptan, γ Polymerization can be carried out in the presence of a chain transfer agent such as trimethoxysilylpropyl disulfide. The polymerization reaction is preferably performed at a temperature of 20 to 200 ° C., particularly 50 to 150 ° C. for 1 hour to several tens of hours.

  The use ratio of the tackifier compound (B) and the polymerizable compound (A) is such that the tackifier compound (B) is 1 to 200 parts by weight, preferably 5 to 50 parts per 100 parts by weight of the polymerizable compound (A). Part by mass. The curable resin (C) is used in an amount of 10 to 1,000 parts by mass, preferably 50 to 400 parts by mass, per 100 parts by mass of the polymerizable compound (A).

  The composition of the present invention comprises a curing catalyst (D) comprising a Lewis acid and / or a complex thereof as a component. Included in the curing catalyst comprising a Lewis acid and / or its complex are metal halides such as titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, zinc bromide, copper chloride, and antimony chloride. And boron halide compounds such as boron trifluoride and boron trichloride, tomethylsilyl trifluoromethanesulfonate, and the like. Examples of the Lewis acid complex include, but are not limited to, an amine complex, an alcohol complex, and an ether complex. Amine compounds used for the amine complex include ammonia, monoethylamine, triethylamine, DBU, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, silane compounds having an amino group, etc. However, it is not limited to these. Examples of alcohols used in the alcohol complex include primary alcohols such as methanol, ethanol, propanol and n-butanol, and secondary alcohols such as isopropanol and 2-butanol, but are not limited thereto. Examples of ethers used in the ether complex include, but are not limited to, dimethyl ether, diethyl ether, and di-n-butyl ether.

  Among the above Lewis acids, titanium chloride (IV), tin chloride (IV), zirconium chloride (IV), aluminum chloride (III), and boron trifluoride are preferable. From the viewpoint of stability, zirconium chloride (IV), three Boron fluoride is more preferred, and boron trifluoride is particularly preferred from the viewpoint of catalytic activity.

  As the Lewis acid complex, a boron trifluoride complex is particularly preferable because it is easy to handle. Of the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferred.

  Such boron trifluoride amine complexes are commercially available and can be used in the present invention. Commercially available products of boron trifluoride amine complexes include trade names of Air Products Japan, Inc .: Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222, and BAK 1171.

  A curing catalyst (D) may be used independently and may be used together 2 or more types. The blending ratio of the curing catalyst (D) is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and particularly preferably 0.8 to 100 parts by weight of the curable resin (C). 02 to 3 parts by weight.

  Although the composition of this invention consists of said each component, it can contain curing catalysts other than a curing catalyst (D), a filler, various additives, etc. other than those components as needed.

  Examples of the curing catalyst other than the curing catalyst (D) include organic tin compounds, organic metal compounds other than organic tin compounds, bases such as amines, acids such as carboxylic acids and organic phosphoric acid compounds, and the like.

  Examples of organic tin compounds include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dimaleate, dioctyltin dimaleate, dibutyltin phthalate, dioctyltin phthalate, stannous octoate, dibutyltin methoxide, dibutyltin dimethoxide, dioctyltin dimethoxide, dibutyltin Examples include diacetyl acetate, dioctyltin diacetylacetate, dibutyltin diversate, dioctyltin diversate, reaction products of dibutyltin oxide and phthalic acid diester, and tin compounds such as tin stearate. Absent.

  The organotin compound is commercially available and can be used in the present invention. Examples of commercially available products include Nitto Kasei Co., Ltd., trade names: T-100, U Sees, etc., Sansha Co., Ltd., trade names: SCAT series, No. 918, STANN BL, STANN SNT-1F, etc., trade names manufactured by Sumika Bayer Urethane Co., Ltd .; Desmorapide PA, Desmolrapid SO, and the like are exemplified, but are not limited thereto.

  Examples of organometallic compounds other than the above organotin compounds include bismuth compounds in which tin of the above organotin compounds is replaced with bismuth, titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, lead octylate, and naphthenic acid. Carboxylic acid metal salts such as lead, nickel naphthenate, lithium naphthenate, cobalt naphthenate, metal acetylacetonate complexes such as aluminum acetylacetonate complex, vanadium acetylacetonate complex, product name manufactured by Nitto Kasei Corporation; U-600, Examples thereof include, but are not limited to, bismuth compounds such as U-660.

  Examples of the amines include fats such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, trimethylamine, triethylamine, tributylamine, and oleylamine. Group amines; mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, Bis (4-amino-methylcyclohexyl) methane, polycyclohexylpolyamine, 1,8-diazabicyclo [5,4,0] undec Cycloaliphatic amines such as -7 (DBU); aromatic amines such as metaphenylenediamine and 4,4'-diaminodiphenylsulfone; m-xylylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol Aliphatic aromatic amines such as 2,4,6-tris (dimethylaminomethyl) phenol; 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] Amines having an ether bond such as undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine; hydroxyl group-containing amines such as diethanolamine and triethanolamine; Diethylenetriamine or diethylenetetramine Polyamides obtained by reacting polyamines of the above, polyamide polyamide amines using polycarboxylic acids other than dimer acids; imidazoles such as 2-ethyl-4-methylimidazole; dicyandiamide, polyoxypropylene diamine, polyoxypropylene Polyoxypropylene-based amines such as triamines; epoxy-modified amines obtained by reacting the above amines with epoxy compounds, Mannich-modified amines obtained by reacting the above amines with formalin and phenols, Michael addition-modified amines, Modified amines such as ketimines; compounds such as amine salts such as 2-ethylhexanoate of 2,4,6-tris (dimethylaminomethyl) phenol, quaternary ammonia such as tetramethylammonium chloride and benzalkonium chloride Nium salt, DABCO (registered trademark) series, DABCO BL series, Sankyo Aero Products Co., Ltd., 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] − 5-nonene, 1,4-diazabicyclo [2.2.2] linear or cyclic tertiary amine salt containing a plurality of nitrogen atoms such as octane, the above compound (c), a product manufactured by Sumika Bayer Urethane Co., Ltd. Names include, but are not limited to, desmorrapid DB, desmorrapid PP, desmorrapid PV, desmorrapid 10/9, desmorrapid LA, and the like.

  Examples of the organic phosphate compound include monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, monoethyl phosphate, diethyl phosphate, triethyl phosphate, di-n-butyl phosphate, mono-n-butyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, and the like. Although it is mentioned, it is not limited to these.

  Curing catalysts other than the curing catalyst (D) may be used alone or in combination of two or more.

  Examples of the filler that can be included as necessary include fumed silica, calcium carbonate, clay, talc, silica, organic polymer powders such as acrylic resin, various balloons, and the like.

  Examples of various additives include plasticizers, additives, solvents, and dehydrating agents. Examples of the plasticizer include phthalates such as dioctyl phthalate and dibutyl phthalate, and fatty acid carboxylic acid esters such as dioctyl adipate and dibutyl sebacate.

  Examples of the additive include an antioxidant, a thixotropic agent, an ultraviolet absorber, a pigment, various tackifiers, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and an epoxy such as bisphenol A type or bisphenol F type. Examples thereof include resins. As the silane coupling agent, aminosilane is particularly preferable.

  Any of the above solvents may be used as long as it is compatible with the composition of the present invention and has a moisture content of 500 ppm or less. It is preferred to use.

  Examples of the dehydrating agent include slaked lime, orthosilicate ester, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkyl alkoxysilanes, various vinyl alkoxysilanes, and the like.

  Hereinafter, the present invention will be described in detail with reference to examples. In the following examples, parts and% are based on mass.

(Synthesis Example 1) (Synthesis of Curable Resin (C))
In a reaction vessel, 179.3 g of γ-aminopropyltrimethoxysilane (trade name: KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged, and 240.4 g of lauryl acrylate was stirred for 1 hour at 80 ° C. in a nitrogen atmosphere. The resultant was added dropwise and further reacted at 80 ° C. for 10 hours, and then reacted at 50 ° C. for 7 days to obtain a reaction product (SE-1) having a trimethoxysil group and a secondary amino group in the molecule.
In another reaction vessel, 700 g of PML4010 (trade name, manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000), PR5007 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene polyol) ) And 58.8 g of isophorone diisocyanate are added and reacted at 90 ° C. for 8 hours with stirring at 80 ° C. in a nitrogen atmosphere, so that a polyoxyalkylene resin (PB-1) having an isocyanate group in the molecule is obtained. Obtained. Thereafter, 148.1 g of SE-1 was added to this PB-1, and the mixture was allowed to react at 90 ° C. for 2 hours with stirring and mixing in a nitrogen atmosphere. A curable resin (SB-1) having a methoxysil group was obtained. The viscosity of SB-1 at 23 ° C. was 50,000 mPa · s (using a BH viscometer, rotor No. 7, 10 revolutions, the same shall apply hereinafter).

(Synthesis Example 2) (Synthesis of Curable Resin (C))
In a reaction vessel, 1000 g of PMLS4012 (trade name, manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000) and 80 g of m-isopropenyl-α, α-dimethylbenzyl diisocyanate were placed under a nitrogen atmosphere. The polyoxyalkylene resin (PB-2) which has a vinyl group in a molecule | numerator was obtained by making it react at 90 degreeC for 8 hours, stirring and mixing. Thereafter, 40 g of γ-mercaptopropylmethyldimethoxysilane and V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 15 g of methyl ethyl ketone were used as polymerization initiators. The mixed solution was added and reacted for 2 hours at 90 ° C. with stirring and mixing in a nitrogen atmosphere, and further, a mixed solution of 1 part of V-65 and 5 parts of methyl ethyl ketone was added and stirred and mixed in a nitrogen atmosphere. The reaction was carried out for 4 hours at 90 ° C. Under reduced pressure, unreacted substances and methyl ethyl ketone were distilled off, the main chain was polyoxyalkylene, and a curable resin having a methyldimethoxysyl group in the molecule (SB-2). The viscosity of this SB-2 at 23 ° C. was 20,000 mPa · s.

(Examples 1-5)
SB-1, SB-2 or S203 (trade name, manufactured by Kaneka Corporation, polyoxyalkylene having a methyldimethoxysyl group), which is a curable resin, is placed in a reaction vessel, and D-, which is a tackifying compound, is added thereto. Limonene (trade name, manufactured by Yasuhara Chemical Co., room temperature liquid), SX100 (trade name, manufactured by Yasuhara Chemical Co., room temperature solid) or FTR6100 (trade name, manufactured by Mitsui Chemicals, room temperature solid), a mixture of polymerizable compounds shown in Table 1, A mixed solution in which the chain transfer agent shown in Table 1 and the polymerization initiator shown in Table 1 were mixed at the ratio shown in Table 1 was added dropwise over 1 hour, and further reacted at 80 ° C. for 10 hours. Further, a mixed solution of 1 part of V-65 and 5 parts of methyl ethyl ketone was added and reacted at 80 ° C. for 1 hour, and then the unreacted product and methyl ethyl ketone were distilled off under reduced pressure to obtain the curable resin composition of the present invention. Was synthesized. The viscosity of the obtained curable resin composition was measured, and the results are shown in Table 2.

(Comparative Examples 1-4)
In a reaction vessel, 20 g of toluene is charged with SB-1 or S203, which is a curable resin, and a mixed solution obtained by mixing a polymerization monomer mixture shown in Table 1 and a polymerization initiator shown in Table 1 at a ratio shown in Table 1 is 1 The solution was added dropwise over a period of time, and further reacted at 80 ° C. for 10 hours. Further, a mixed solution of 1 part of V-65 and 5 parts of methyl ethyl ketone was added and reacted at 80 ° C. for 1 hour. Furthermore, D-limonene, SX100 or FTR6100, which is a tackifier compound, was added at a ratio shown in Table 1 and stirred at 100 ° C. for 1 hour. Unreacted substances and methyl ethyl ketone were distilled off under reduced pressure to synthesize a curable resin composition. The viscosity of the obtained curable resin composition was measured, and the results are shown in Table 2. Moreover, although the adhesiveness of the curable resin composition obtained in Examples 1-5 and Comparative Examples 1-4 was measured, all showed the adhesiveness which has no problem practically.

表２に記載した結果から明らかなように、粘着性付与樹脂を硬化性樹脂及び重合性化合物の重合体に単に混合した組成物よりも、粘着性付与樹脂を重合性化合物の重合時に添加して用いて得られるものの方が粘度が相当に低いことが判る。その理由は判らないが、粘着性付与樹脂を重合性化合物に溶解させて重合性化合物を重合した場合、ラジカル重合における連鎖移動等の影響により、粘着性付与樹脂が重合鎖中に取り込まれるか、別の化合物に変化することにより分子的な相溶性が向上して粘度が低下するのではないかと推察される。
一般的には、ＳＸ１００やＦＴＲ６１００のような室温で固体の物質を添加した場合、均一系では粘度が上がるのが通常であるが、同じく均一系である本発明において、固体の物質を添加しても粘度が下がるという事実は実に驚くべきことである。又、Ｄ−リモネンのような室温で液体の物質を後で添加して混合する場合、その添加混合を１００℃以上で行うと該液体の物質が気化損失してしまうが、該液体の物質を重合性化合物の重合時に添加するという本発明においては、たとえ１００℃の減圧下でも気化損失することがないという効果を発揮する。これも上記のように液体の粘着性付与樹脂が重合鎖中に取り込まれるか、別の化合物に変化しているからではないかと考えられる。
そして、上記のように実施例１〜５得られた硬化性樹脂組成物と実施例１〜５に対応する比較例１〜４で得られた硬化性樹脂組成物との間には密着性に殆ど差がなく、いずれも実用上問題がないという効果を示す。

As is apparent from the results described in Table 2, the tackifying resin was added at the time of polymerization of the polymerizable compound rather than the composition obtained by simply mixing the tackifying resin with the polymer of the curable resin and the polymerizable compound. It can be seen that the viscosities obtained by use are considerably lower. The reason is not known, but when the polymerizable compound is polymerized by dissolving the tackifier resin in the polymerizable compound, the tackifier resin is incorporated into the polymer chain due to the influence of chain transfer in radical polymerization, It is presumed that the molecular compatibility is improved and the viscosity is lowered by changing to another compound.
In general, when a solid substance such as SX100 or FTR6100 is added at room temperature, the viscosity is usually increased in a homogeneous system. However, in the present invention, which is also a homogeneous system, a solid substance is added. However, the fact that the viscosity decreases is truly surprising. In addition, when a liquid substance such as D-limonene is added later at room temperature and mixed, if the addition and mixing is performed at 100 ° C. or higher, the liquid substance is vaporized and lost. In the present invention, which is added at the time of polymerization of the polymerizable compound, there is an effect that no vaporization loss occurs even under a reduced pressure of 100 ° C. This is also because the liquid tackifying resin is taken into the polymer chain as described above or is changed to another compound.
And between the curable resin composition obtained in Examples 1-5 as mentioned above and the curable resin composition obtained in Comparative Examples 1-4 corresponding to Examples 1-5, it is in adhesiveness. There is almost no difference, and all show the effect that there is no problem in practical use.

(Example 6)
1,000 g of toluene was put in a reaction vessel, and the temperature was raised to 80 ° C. while stirring in a nitrogen atmosphere. Separately, 1,000 g of butyl acrylate, 300 g of KBM502 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-methacryloxypropylmethyldimethoxysilane), 100 g of FTR6100, and 15 g of V-65 as a polymerization initiator were mixed to obtain a monomer solution. Was prepared. Toluene was stirred at 80 ° C., and this monomer solution was added dropwise over 1 hour in a nitrogen atmosphere, and the mixture was further reacted at 80 ° C. for 1 hour. A polymerization initiator solution in which 5 g of V-65 was dissolved in 20 g of toluene was added dropwise over 10 minutes, and the mixture was further reacted at 80 ° C. for 4 hours. Thereafter, unreacted substances and toluene were distilled off under reduced pressure to synthesize the curable resin composition of the present invention. As a result of measuring the viscosity of the obtained curable resin composition, the viscosity at 23 ° C. was 250,000 mPa · s.

(Comparative Example 5)
1,000 g of toluene was placed in the reaction vessel. Separately, 1,000 g of butyl acrylate, 300 g of KBM502, and 15 g of V-65 as a polymerization initiator were mixed to prepare a monomer solution. Toluene was stirred at 80 ° C., and the monomer solution was added dropwise over 1 hour in a nitrogen atmosphere, and the reaction was further continued for 1 hour. Thereafter, a polymerization initiator solution in which 5 g of V-65 was dissolved in 20 g of toluene was dropped over 10 minutes, and the reaction was further performed at 80 ° C. for 4 hours. Thereafter, 100 g of FTR6100 was added and stirred at 100 ° C. for 2 hours. Unreacted substances and toluene were distilled off under reduced pressure to synthesize a curable resin composition. As a result of measuring the viscosity of the obtained curable resin composition, the viscosity at 23 ° C. was 360,000 mPa · s.

  From the results of Example 6 and Comparative Example 5, the composition obtained by polymerizing the polymerizable compound (A) in a solution containing FTR6100 as the tackifier compound (B) is to add FTR6100 later. It can be seen that the viscosity is lower than that of the composition obtained.

(Example 7)
In a reaction vessel, 1,000 g of toluene and 200 g of FTR6100 were put, and the temperature was raised to 80 ° C. while stirring in a nitrogen atmosphere. Separately, 1,000 g of butyl acrylate, 75 g of KBM502, and 15 g of V-65 as a polymerization initiator were mixed to prepare a monomer solution. Toluene was stirred at 80 ° C., and this monomer solution was added dropwise over 1 hour in a nitrogen atmosphere, and the mixture was further reacted at 80 ° C. for 1 hour. A polymerization initiator solution in which 5 g of V-65 was dissolved in 20 g of toluene was added dropwise over 10 minutes, and the mixture was further reacted at 80 ° C. for 4 hours. Thereafter, unreacted substances and toluene were distilled off under reduced pressure to synthesize the curable resin composition of the present invention. As a result of measuring the viscosity of the obtained curable resin composition, the viscosity at 23 ° C. was 280,000 mPa · s.

(Synthesis Example 3) (Synthesis of Curable Resin (C))
In a reaction vessel, PML S 3011 (trade name, manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, molecular weight 10,000) is 1,000 g, PML S 1004 (trade name, manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, molecular weight 4) 1,000), 144 g of KBE9007 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-isocyanatopropyltriethoxysilane), and 1.5 g of a 10% methyl ethyl ketone solution of dioctyltin diversate as a reaction catalyst, under a nitrogen atmosphere By reacting at 80 ° C. for 3 hours, a reaction product (SE-3) having a trimethoxysyl group in the molecule was obtained. As a result of measuring the viscosity of the obtained SE-3, the viscosity at 23 ° C. was 1,700 mPa · s.

(Example 8)
800 g of the curable resin composition obtained in Example 7 and 200 g of SE-3 were placed in a planetary mixer, kneaded while dehydrating at 100 ° C. for 1 hour under reduced pressure, and cooled to room temperature. Thereafter, 10 g of KBM903 and 10 g of dioctyltin dilaurate were added and kneaded while dehydrating at 100 ° C. for 30 minutes under reduced pressure to synthesize the curable resin composition of the present invention. As a result of measuring the viscosity of the obtained curable resin composition, the viscosity at 23 ° C. was 71,000 mPa · s.

(Comparative Example 6)
A curable resin composition was synthesized in the same manner as in Example 8, except that the curable resin composition obtained in Example 7 in Example 8 was changed to the curable resin composition obtained in Comparative Example 5. did. As a result of measuring the viscosity of the obtained curable resin composition, the viscosity at 23 ° C. was 79,000 mPa · s.

  For the curable resin compositions obtained in Example 8 and Comparative Example 6, the peel adhesion strength was measured in the following manner, and the results are shown in Table 3.

Peel adhesion strength test 1 g of the curable resin composition is uniformly applied to the entire surface of an ABS plate (thickness 3 mm, width 25 mm, length 100 mm), and immediately bonded with a canvas (width 25 mm, length 200 mm). Were bonded so that the width was 25 mm and the length was 80 mm. Each bonded specimen was cured for 7 days at a temperature of 23 ° C. and a relative humidity of 50 ± 5%, and the 180 ° peel strength (N / 25 mm) was measured according to JIS K 6854.

表３の結果から、実施例８及び比較例６で得られた硬化性樹脂組成物からの試験体は、接着強さに大きな差が出ているが、これは比較例６で得られた硬化性樹脂組成物に比べて実施例８で得られた硬化性樹脂組成物の方が密着性が良いことが要因になっているのではないかと考えられる。

From the results of Table 3, the specimens from the curable resin compositions obtained in Example 8 and Comparative Example 6 have a large difference in adhesive strength, which is the cured obtained in Comparative Example 6. It is considered that the adhesiveness of the curable resin composition obtained in Example 8 is better than that of the curable resin composition.

Example 9
1,000 g of SB-1, which is a curable resin, was placed in a reaction vessel, and the temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere. Separately, the tackifier compound (B) shown in Table 4, the polymerizable compound (A) shown in Table 4, the chain transfer agent shown in Table 4, and the polymerization initiator shown in Table 4 were mixed in the proportions shown in Table 4. A solution was prepared. To the place where SB-1 which is a curable resin was stirred at 80 ° C., the mixed solution was added dropwise over 1 hour, and further reacted at 80 ° C. for 10 hours. Thereafter, a polymerization initiator consisting of 1 part of V-65 and 20 parts of methyl ethyl ketone was added dropwise over 10 minutes, and further reacted at 80 ° C. for 4 hours. Then, unreacted substances and methyl ethyl ketone were distilled off under reduced pressure. Then, the curable resin composition of the present invention was synthesized. As a result of measuring the viscosity of the obtained curable resin composition, the viscosity at 23 ° C. was 170,000 mPa · s.

(Comparative Example 7)
1,000 g of SB-1, which is a curable resin, was placed in a reaction vessel, and the temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere. Separately, a mixed solution in which the polymerizable compound (A) shown in Table 4, the polymerization initiator shown in Table 4, and the chain transfer agent shown in Table 4 were mixed at the ratio shown in Table 4 was prepared. To the place where SB-1 which is a curable resin was stirred at 80 ° C., the mixed solution was added dropwise over 1 hour, and further reacted at 80 ° C. for 10 hours. Thereafter, 1 part of V-65 and 20 parts of methyl ethyl ketone were added dropwise over 10 minutes with a polymerization initiator, and the mixture was further reacted at 80 ° C. for 4 hours. Thereafter, 200 g of FTR6100 was added and stirred at 100 ° C. for 2 hours. Unreacted substances and methyl ethyl ketone were distilled off under reduced pressure to synthesize a curable resin composition. As a result of measuring the viscosity of the obtained curable resin composition, the viscosity at 23 ° C. was 165,000 mPa · s.

（実施例１０）
実施例９又は比較例７で得られた硬化性樹脂組成物５００ｇ及びサイロホービック２００（商品名、富士シリシア化学社製、疎水処理されたシリカ微粉末）２０ｇをプラネタリーミキサーに投入し、減圧下にて１時間加熱脱水しながら混練し、室温まで冷却した。その後、ＫＢＭ９０３を２０ｇ、ウンデカンを５０ｇ及び三フッ化ホウ素モノエチルアミン錯体を１．０ｇ投入し、減圧下にて３０分間混練し、硬化性樹脂組成物を得た。得られた硬化性樹脂組成物を２３℃で２週間静置し、粘度、皮張時間及び剥離接着強さを測定した。それらの結果を表５に示した。

(Example 10)
500 g of the curable resin composition obtained in Example 9 or Comparative Example 7 and 20 g of silo hovic 200 (trade name, manufactured by Fuji Silysia Chemical Co., Ltd., hydrophobized silica fine powder) were put into a planetary mixer, and the pressure was reduced. The mixture was kneaded under heat dehydration for 1 hour and cooled to room temperature. Thereafter, 20 g of KBM903, 50 g of undecane and 1.0 g of boron trifluoride monoethylamine complex were added and kneaded for 30 minutes under reduced pressure to obtain a curable resin composition. The obtained curable resin composition was allowed to stand at 23 ° C. for 2 weeks, and the viscosity, skinning time and peel adhesion strength were measured. The results are shown in Table 5.

(Comparative Example 8)
The curable resin composition was the same as Example 10 except that 10 g of Neostan U-303 (trade name, manufactured by Nitto Kasei Co., Ltd., silver-based curing catalyst) was used instead of 1.0 g of boron trifluoride monoethylamine complex. I got a thing. The obtained curable resin composition was allowed to stand at 23 ° C. for 2 weeks, and the viscosity, skinning time and peel adhesion strength were measured. The results are shown in Table 5. In addition, the skinning time and peeling adhesive strength of the curable resin composition obtained in Example 10 and Comparative Example 8 were measured in the following manner.

The skin hardening time- curable resin composition was allowed to stand in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50 ± 5%, and was determined as the time until the cured film stretched on the surface by finger touching was not transferred to the finger.
For the peelable adhesive strength curable resin composition, a mild steel plate (thickness 3 mm, width 25 mm, length 100 mm) and canvas (width 25 mm, length 200 mm) were applied in an amount of 1 g, and the bonded portion was 25 mm wide and 80 mm long. I stuck together. The bonded specimen was cured for 7 days at a temperature of 23 ° C. and a relative humidity of 50 ± 5%, peeled in the direction of 180 °, and the adhesive strength at that time was measured according to JIS K 6854.

実施例９及び比較例７並びに実施例１０及び比較例８の結果から、一般的な連鎖移動剤を多量に用いることで低粘度に調製した比較例８で得られた硬化性樹脂組成物は、硬化が遅く、又硬化後の物性が脆いため、剥離接着強さにおいて十分な強度が発現しないことが判った。一方、実施例１０で得られた硬化性樹脂組成物は、硬化後の物性を損なうことなく低粘度で、速硬化性を示すことが判った。

From the results of Example 9 and Comparative Example 7 and Example 10 and Comparative Example 8, the curable resin composition obtained in Comparative Example 8 prepared to have a low viscosity by using a large amount of a general chain transfer agent, It was found that since the curing was slow and the physical properties after curing were brittle, sufficient strength was not exhibited in the peel adhesion strength. On the other hand, it was found that the curable resin composition obtained in Example 10 had a low viscosity and a fast curability without impairing the physical properties after curing.

Claims (6)

A component obtained by polymerizing the polymerizable compound (A) having at least one reactive silyl group in the molecule in a liquid containing the tackifier compound (B) and not containing water , The tackifying compound (B) is a moisture curable resin composition which is an aromatic compound . It includes a tackifying compound (B) and a curable resin (C) having at least one reactive silyl group in the molecule, and has at least one reactive silyl group in the molecule in a liquid not containing water. A moisture curable resin composition comprising a polymerization product obtained by polymerizing the polymerizable compound (A) as a component, and the tackifier compound (B) being an aromatic compound . A polymerization product obtained by polymerizing a polymerizable compound (A) having at least one reactive silyl group in the molecule in a liquid containing the tackifier compound (B) and not containing water, and at least one in the molecule A moisture curable resin composition comprising a curable resin (C) having one reactive silyl group as a component, and the tackifying compound (B) being an aromatic compound . The moisture curable resin composition according to any one of claims 2 to 3, wherein the curable resin (C) is a compound having at least a urethane bond in the molecule. Furthermore, the moisture curable resin composition of any one of Claims 1-4 which uses the curing catalyst (D) which consists of a Lewis acid and / or its complex as a component. The moisture curable resin composition according to claim 5, wherein the Lewis acid is boron trifluoride.