Resin composition, cured product, laminate, and method for producing laminate

Abstract

Provided are: a resin composition which exhibits excellent adhesive strength when used as an adhesive; and a cured product obtained using the resin composition. Also provided are a laminate using the cured product, and a method for producing the laminate. A resin composition characterized by containing (A) 1, 1-dicyanoethylene, (B) a polymerizable monomer represented by general formula (I), and (C) a polymerizable monomer represented by general formula (II). CH2-CR1R2 (I) CHR6-CR7R8 (II)

Description

Technical Field

[0001] The present invention relates to a resin composition containing 1,1-dicyanoethylene and a specific polymerizable monomer, a cured product, a laminate, and a method for producing the laminate. Background Art

[0002] Monomers such as alkyl 2-cyanoacrylate, alkyl 2-cyanopentadienoate and dialkyl methylenemalonate have excellent reactivity and can therefore be used in resin compositions of fast-curing adhesives. Resin compositions containing these monomers have fast curing properties, but on the other hand, have the problem of low adhesion to adherends made of polyolefin materials. As a method for improving this problem, for example, a method of pre-treating the adherend by applying the resin composition to the adherend, such as a primer treatment, is proposed in Patent Document 1. In addition, a method of improving fast curing properties and adhesion by copolymerizing the above-mentioned monomers with other monomers is proposed in Patent Document 2.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2003-041200

[0006] Patent Document 2: Japanese Patent Application Laid-Open No. 01-103614 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The method described in Patent Document 1 requires pretreatment of the adherend, which reduces production efficiency and does not improve adhesion sufficiently. In addition, the method described in Patent Document 2 also has insufficient adhesion and needs improvement.

[0009] The present invention aims to provide a resin composition that exhibits excellent adhesive strength when used as an adhesive and a cured product using the resin composition. Another object of the present invention is to provide a laminate using the cured product and a method for producing the laminate.

[0010] Methods used to solve problems

[0011] The inventors of the present invention have conducted research and found that the above-mentioned highly reactive monomers preferentially generate homopolymers due to their reactivity and are generally difficult to copolymerize with other monomers. Therefore, they have conducted research on copolymerizable monomers and found that when 1,1-dicyanoethylene, which has a low LUMO energy level and easily forms a charge transfer complex with the above-mentioned monomers, is used, copolymerization based on anionic polymerization is easy to proceed. Therefore, further repeated research has been conducted and found that by combining 1,1-dicyanoethylene with a specific monomer, a resin composition that exhibits excellent adhesion to a polyolefin substrate that lacks adhesion using a conventional adhesive can be obtained, thereby completing the present invention.

[0012] That is, the present invention provides the following [1] to [9].

[0013] [1] A resin composition comprising 1,1-dicyanoethylene (A), a polymerizable monomer (B) represented by the following general formula (I), and a polymerizable monomer (C) represented by the following general formula (II).

[0014] CH 2 =CR 1 R 2 (I)

[0015] CHR 6 =CR 7 R 8 (II)

[0016] (In the general formula (I), R 1 is one or more selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom,

[0017] R 2 is selected from hydrogen, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, carboxyl, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms), an ester group, an acid anhydride group, a -COR 4 (R 4 is an alkyl group having 1 to 12 carbon atoms), an acyl group represented by -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms), one or more of an acyloxy group, a halogen atom and a halogenated alkyl group.

[0018] Furthermore, in the general formula (II), R 6 is one or more selected from a hydrogen atom, an alkyl group, an alkenyl group and an alkoxy group,

[0019] R 7 is selected from cyano, carboxyl, -COOR 9 (R 9is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms), and one or more of an ester group and an acid anhydride group,

[0020] R 8 is selected from carboxyl, -COOR 10 (R 10 It is one or more of an ester group and an acid anhydride group represented by an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group.

[0021] [2] The resin composition according to [1] above, wherein the energy difference between the LUMO level of the 1,1-dicyanoethylene (A) and the HOMO level of the polymerizable monomer (B) is less than 4.40 eV.

[0022] [3] The resin composition according to [1] or [2] above, wherein the polymerizable monomer (B) is one or more selected from ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, styrene, methyl methacrylate and dodecyl methacrylate.

[0023] [4] The resin composition according to any one of [1] to [3] above, wherein the polymerizable monomer (C) is at least one selected from the group consisting of alkyl 2-cyanoacrylates, alkyl 2-cyanopentadienoates, and dialkyl methylenemalonates.

[0024] [5] The resin composition according to any one of [1] to [4] above, wherein the content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition is 1% by mass or more and 80% by mass or less, the content of the polymerizable monomer (B) is 1% by mass or more and 80% by mass or less, and the content of the polymerizable monomer (C) is 19% by mass or more and 98% by mass or less.

[0025] [6] The resin composition according to any one of [1] to [5] above, further comprising a Bronsted acidic compound.

[0026] [7] A cured product obtained by curing the resin composition according to any one of [1] to [6] above with a Lewis basic compound.

[0027] [8] A laminate having a layer comprising the cured product according to [7] above.

[0028] [9] A method for producing a laminate, comprising a bonding step of bonding a first adherend and a second adherend using the resin composition according to any one of [1] to [6] above.

[0029] Effects of the Invention

[0030] According to the present invention, a resin composition that exhibits excellent adhesive strength when used as an adhesive and a cured product using the resin composition can be provided. In addition, a laminate using the cured product and a method for producing the laminate can be provided. DETAILED DESCRIPTION

[0031] [Resin composition]

[0032] The resin composition of the present invention is characterized by containing 1,1-dicyanoethylene (A), a polymerizable monomer (B) represented by the following general formula (I), and a polymerizable monomer (C) represented by the following general formula (II).

[0033] CH 2 =CR 1 R 2 (I)

[0034] CHR 6 =CR 7 R 8 (II)

[0035] (In the general formula (I), R 1 is one or more selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom,

[0036] R 2 is selected from hydrogen, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, carboxyl, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms), an ester group, an acid anhydride group, a -COR 4 (R 4 is an alkyl group having 1 to 12 carbon atoms), an acyl group represented by -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms), one or more of an acyloxy group, a halogen atom and a halogenated alkyl group.

[0037] Furthermore, in the general formula (II), R 6 is one or more selected from a hydrogen atom, an alkyl group, an alkenyl group and an alkoxy group,

[0038] R 7 is selected from cyano, carboxyl, -COOR 9 (R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms), and one or more of an ester group and an acid anhydride group,

[0039] R 8 is selected from carboxyl, -COOR 10 (R10 It is one or more of an ester group and an acid anhydride group represented by an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group.

[0040] <1,1-Dicyanoethylene(A)>

[0041] The resin composition of the present invention uses 1,1-dicyanoethylene (A). 1,1-dicyanoethylene (A) easily forms a charge transfer complex with the polymerizable monomer (B) described below, so a copolymer composed of 1,1-dicyanoethylene (A), the polymerizable monomer (B) and the polymerizable monomer (C) is easily obtained.

[0042] 1,1-Dicyanoethylene can be obtained by the production method described in J. Am. Chem. Soc., 1989, 111, 9078-9081 and US Pat. No. 2,476,270.

[0043] <Polymerizable monomer (B)>

[0044] The polymerizable monomer (B) is a monomer represented by the following general formula (I).

[0045] CH 2 =CR 1 R 2 (I)

[0046] In the general formula (I), R 1 is at least one selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom.

[0047] As R 1 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl.

[0048] As R 1 The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0049] As R 1 The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl, tolyl, xylyl and naphthyl.

[0050] As R 1 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

[0051] As R 1The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0052] Among these, R 1 A hydrogen atom and an alkyl group having 1 to 6 carbon atoms are preferred, a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are more preferred, and a hydrogen atom and a methyl group are further preferred.

[0053] In the general formula (I), R 2 is selected from hydrogen, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, carboxyl, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms), an ester group, an acid anhydride group, a -COR 4 (R 4 is an alkyl group having 1 to 12 carbon atoms), an acyl group represented by -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms), one or more of an acyloxy group, a halogen atom and a halogenated alkyl group.

[0054] As R 2 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl.

[0055] As R 2 The alkenyl group represented is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl (such as cis-3-hexenyl) and cyclohexenyl.

[0056] As R 2 The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0057] As R 2 The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl, tolyl, xylyl and naphthyl.

[0058] As R 2 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

[0059] R 2 Can be made by -COOR 3 The ester group represented by R 3Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, heptyl, octyl, decyl and dodecyl.

[0060] As R 2 Examples of the acid anhydride group include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0061] R 2 Can be made by -COR 4 The acyl group represented by R 4 Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl.

[0062] R 2 Can be by-OCOR 5 The acyloxy group represented by R 5 Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl.

[0063] As R 2 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0064] In addition, as R 2 The haloalkyl group is preferably a haloalkyl group having 1 to 12 carbon atoms, and more preferably a haloalkyl group having 1 to 6 carbon atoms. Examples of the halogen atom constituting the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0065] Among these, R 2 It is preferably selected from a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a -COOR 3 The ester group represented by -OCOR 5 One of the acyloxy groups represented by -COOR 3 The ester group represented by 3 is an alkyl group with 8 to 12 carbon atoms), represented by -OCOR 5 The acyloxy group represented by 5 is an alkyl group having 1 to 6 carbon atoms).

[0066] More specifically, from the viewpoint of improving adhesion, the polymerizable monomer (B) is preferably one or more selected from ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, styrene, methyl methacrylate and dodecyl methacrylate. In particular, when the adherend described later is a polyolefin substrate, 1-hexene and 1-octene are preferably used as the polymerizable monomer (B). By using these monomers, a stronger adhesion can be achieved.

[0067] In the present invention, the energy difference between the LUMO energy level of the 1,1-dicyanoethylene (A) and the HOMO energy level of the polymerizable monomer (B) is preferably less than 4.40 eV, more preferably 4.00 eV or less, and further preferably 3.90 eV or less. When the energy difference is below the upper limit, 1,1-dicyanoethylene (A) and the polymerizable monomer (B) easily form a charge transfer complex.

[0068] In the present invention, when two or more polymerizable monomers (B) are used, at least one of them may satisfy the above energy level difference, but it is more preferable that all polymerizable monomers (B) satisfy the above energy level difference.

[0069] In the formation of charge transfer complexes, the electronic energy levels of the bonding orbital and antibonding orbital of the vinyl group are important in the vacuum energy level of the electronic energy level. In most cases, they correspond to the "highest occupied molecular orbital" (HOMO) and the "lowest unoccupied molecular orbital" (LUMO), respectively, but some "the next energy level of HOMO (HOMO-1)" is the bonding orbital of the vinyl group. Density functional theory (hereinafter referred to as DFT (Density Function Theory)) is a well-established theory for calculating the electronic energy levels of molecular orbitals, and the energy levels of HOMO-1 / HOMO / LUMO can be estimated by this method.

[0070] The HOMO-1 / HOMO / LUMO conformation of the HOMO-1 / HOMO / LUMO spectrum is based on the Gaussian flow rate 16W(Gaussian 16, Revision A.03, MJ Frisch, GWTrucks, HB Schlegel, GE Scuseria, MA Robb, JR Cheeseman, G.Scalmani, V. Barone, Petersson GA, H. Nakatsuji, X. Li, M. Caricato, AVMarenich, J. Bloino, Janesko BG, Gomperts R, Mennucci, 16W(Gaussian 16, Revision A.03; HPHratchian, JV Ortiz, AF Izmaylov, JL Sonnenberg, D. Williams-Young, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, VG Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M.S. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, JAMontgomery, Jr., JE Peralta, F. Ogliaro, MJ Bearpark, JJ Heyd, ENBrothers, KN ​​Kudin, VN Staroverov, Keith TA , Kobayashi R , Normand J , Raghavachari K , Rendell AP , Burant JC , Iyengar SS , Thomas J , Cossi M , Millam JM , Klene M , Adamo C , Cammi R , Martin RL , K .Morokuma, O. Farkas, JB Foresman, and DJFox, Gaussian, Inc., Wallingford CT, 2016.)

[0071] DFT was used as the calculation method, and B3LYP was used as the functional. Structural optimization was performed using 6-31+G(d,p) as the basis function, and single-point energy calculation was performed using 6-311++G(3d,2p) as the basis function for the structure with the minimum generation energy, and the energy levels of HOMO-1, HOMO, and LUMO were calculated.

[0072] The manufacturing method of the above-mentioned polymerizable monomer (B) is not particularly limited, and it can be manufactured by using it alone or in combination with known methods. In addition, the above-mentioned polymerizable monomer (B) can also use commercially available products, for example, 1-hexene (manufactured by Tokyo Chemical Industry Co., Ltd.), dodecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) can be listed.

[0073] <Polymerizable monomer (C)>

[0074] The polymerizable monomer (C) is a monomer represented by the following general formula (II). In the present invention, by using the polymerizable monomer (C) together with the above-mentioned 1,1-dicyanoethylene (A) and the above-mentioned polymerizable monomer (B), a resin composition having excellent adhesion to polyolefin substrates and the like can be obtained.

[0075] CHR 6 =CR 7 R 8 (II)

[0076] In the general formula (II), R 6 It is one or more selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group and an alkoxy group.

[0077] As R 6 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl.

[0078] As R 6 The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl (such as cis-3-hexenyl) and cyclohexenyl.

[0079] As R 6The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

[0080] Among these, R 6 Preferred are a hydrogen atom, an alkyl group and an alkenyl group, and more preferred is a hydrogen atom.

[0081] In the general formula (II), R 7 is selected from cyano, carboxyl, -COOR 9 (R 9 It is one or more of an ester group and an acid anhydride group represented by an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0082] R 7 Can be made by -COOR 9 In this case, R 9 It is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0083] As R 9 Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl.

[0084] As R 9 The aryl group having 6 to 20 carbon atoms includes, for example, phenyl, tolyl, xylyl and naphthyl.

[0085] R 7 The acid anhydride group may be an acid anhydride group, for example, an acid anhydride group derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like.

[0086] Among these, R 7 Preferred are cyano, carboxyl and -COOR 9 (R 9 It is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms), and is more preferably a cyano group.

[0087] R 8 is selected from carboxyl, -COOR 10 (R 10 It is one or more of an ester group and an acid anhydride group represented by an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group.

[0088] In R8 -COOR 10 In the case of R 10 It is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group.

[0089] As R 10 Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl.

[0090] As R 10 The aryl group having 6 to 20 carbon atoms includes, for example, phenyl, tolyl, xylyl and naphthyl.

[0091] As R 10 Examples of divalent or higher-valent linking groups include linking groups derived from divalent or higher-valent alcohols such as ethylene glycol and glycerol. 10 Specific compounds in the case of a divalent or higher linking group include compounds obtained by esterification reaction of ethylene glycol with two 2-cyanoacrylic acids (so-called "difunctional cyanoacrylates") and compounds obtained by esterification reaction of glycerol with three 2-cyanoacrylic acids (so-called "trifunctional cyanoacrylates").

[0092] Examples of the compound constituting the linking group include diols such as ethylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol; and trivalent or higher polyols such as glycerol, pentaerythritol, trimethylolpropane and sorbitol.

[0093] In the present invention, the divalent or higher valent linking group is preferably a di- to trivalent linking group from the viewpoint of availability.

[0094] R 8 The acid anhydride group may be an acid anhydride group, for example, an acid anhydride group derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like.

[0095] From the perspective of improving adhesion, R 8 Preferably, the carboxyl group, -COOR 10 (R 10is an ester group represented by an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group, and more preferably -COOR 10 (At this time, R 10 An ester group represented by an alkyl group having 1 to 6 carbon atoms or a di- to tri-valent linking group).

[0096] From the viewpoint of improving the adhesive force when the resin composition is used as an adhesive, the polymerizable monomer (C) is preferably one or more selected from alkyl 2-cyanoacrylates, alkyl 2-cyanopentadienoates and dialkyl methylenemalonates, more preferably one or more selected from ethyl 2-cyanoacrylate, butyl 2-cyanoacrylate and diethyl methylenemalonate, and even more preferably ethyl 2-cyanoacrylate.

[0097] In the present invention, the LUMO energy level of the 1,1-dicyanoethylene (A) and the LUMO energy level of the polymerizable monomer (C) are preferably -1.0 eV or less, more preferably -1.5 eV or less, and further preferably -2.0 eV or less. When the energy is below the upper limit, 1,1-dicyanoethylene (A) and the polymerizable monomer (C) react easily.

[0098] The method for producing the polymerizable monomer (C) is not particularly limited, and the polymerizable monomer (C) may be produced by using a single method or a combination of known methods. In addition, commercially available products may be used as the polymerizable monomer (C), for example, ethyl 2-cyanoacrylate (manufactured by Aldrich Co., Ltd.) may be mentioned.

[0099] <Content of each ingredient>

[0100] The content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition of the present invention is 1% by mass or more and 80% by mass or less, the content of the polymerizable monomer (B) is 1% by mass or more and 80% by mass or less, and the content of the polymerizable monomer (C) is preferably 19% by mass or more and 98% by mass or less. The resin composition having the contents of the above components within the above ranges exhibits excellent adhesion while maintaining rapid curing properties.

[0101] From the above viewpoints, the content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition is preferably 2 to 60% by mass, more preferably 5 to 40% by mass, further preferably 7 to 30% by mass, and further preferably 7 to 18% by mass.

[0102] The content of the polymerizable monomer (B) in the total amount of the resin composition is preferably 2 to 60% by mass, more preferably 5 to 40% by mass, further preferably 7 to 30% by mass, and further preferably 7 to 18% by mass.

[0103] The content of the polymerizable monomer (C) in the total amount of the resin composition is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, further preferably 50 to 85% by mass, and further preferably 62 to 88% by mass.

[0104] <Brønsted acid compounds>

[0105] The resin composition of the present invention preferably further contains a Bronsted acidic compound. When the resin composition of the present invention contains a Bronsted acidic compound, the storage stability of the resin composition is improved, and the desired curing speed can be obtained. More specifically, 1,1-dicyanoethylene (A) cures in a trace amount of water, so it is preferred to completely remove the water during the manufacturing process, but since it is difficult to completely remove the water in reality, it is preferred to suppress the curing (inhibit polymerization initiation) by protonating water using a Bronsted acid.

[0106] As the Bronsted acidic compound that can be used in the present invention, from the viewpoint of storage stability and easy availability, inorganic acids, carboxylic acids and organic sulfonic acids can be listed, among which one or more selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid are preferred. It may also be a compound that reacts with water to generate a compound showing Bronsted acidity, such as sulfur dioxide and phosphorus pentoxide.

[0107] When the resin composition of the present invention contains a Bronsted acidic compound, the content thereof is preferably 0.001 to 1.0 mass %, more preferably 0.01 to 0.8 mass %, based on the total amount of the resin composition. When the content of the Bronsted acidic compound is within the above range, storage stability is improved.

[0108] From the viewpoint of storage stability, the content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition is preferably 80% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, and further preferably 10% by mass or less.

[0109] <Other ingredients>

[0110] The resin composition of the present invention may contain, in addition to the above-mentioned components, a solvent, a filler, a tackifier, an antioxidant, a plasticizer, a flame retardant, a stabilizer, an antioxidant and the like as other components.

[0111] When the resin composition of the present invention contains other components, the content thereof is preferably 0.001% by mass or more and preferably 10% by mass or less, and more preferably 3% by mass or less in the total amount of the resin composition.

[0112] <Method for producing resin composition>

[0113] The method for producing the resin composition of the present invention is not particularly limited, and for example, the resin composition can be produced by a production method including a mixing step of mixing 1,1-dicyanoethylene (A), the polymerizable monomer (B), the polymerizable monomer (C) and other components as required, but the polymerization reaction proceeds due to moisture, so it is preferably produced under a dry atmosphere. It should be noted that the method for mixing the components is not particularly limited, and the components can be mixed by a known method.

[0114] [cured material]

[0115] The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention described above with a Lewis basic compound, and more specifically, is a copolymer obtained by copolymerizing the components in the resin composition described above with a Lewis basic compound as a catalyst.

[0116] <Lewis basic compounds>

[0117] The Lewis basic compound used in the present invention is not particularly limited as long as it can be used as a polymerization catalyst. For example, one or more selected from water, alcohols and alkylamines can be used. Examples of alcohols include methanol, ethanol and propanol.

[0118] Examples of the alkylamine include tertiary amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, and N,N-dimethylisopropylamine.

[0119] <Method for producing cured product>

[0120] The method for producing the cured product is not particularly limited, and the cured product can be obtained by mixing the resin composition of the present invention with a Lewis basic compound at room temperature (23° C.), but can usually be obtained by reacting the resin composition of the present invention with moisture (Lewis basic compound) in the air.

[0121] The amount of the Lewis basic compound is not particularly limited, but is preferably 0.001 to 1.0 parts by mass, more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the resin composition. When the content of the Lewis basic compound is within the above range, the resin composition reacts rapidly.

[0122] [Laminate and method for producing the same]

[0123] The laminate of the present invention is a laminate having a layer containing the above-mentioned cured product. The laminate structure is not particularly limited, but preferably the above-mentioned cured product is present between two adherends. By having the above-mentioned cured product between the two adherends, the adherends can be firmly bonded to each other.

[0124] The adherend used in the laminate of the present invention is not particularly limited, and examples thereof include synthetic resins, metals, ceramics, and fabrics.

[0125] Examples of synthetic resins include polyethylene, polypropylene, copolymers of ethylene and one or more α-olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, etc.), ethylene-propylene-diene copolymers (EPDM), ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and other polyolefin resins, polyurethane resins, polyamide resins, polyester resins and polycarbonate resins.

[0126] Examples of the metal include steel sheets such as stainless steel sheets, cold-rolled steel sheets, and alloyed galvanized steel sheets.

[0127] The thickness of the adherend constituting the laminate is not particularly limited. On the other hand, from the viewpoint of firmly bonding the adherends to each other, the thickness of the layer containing the cured product is preferably 0.01 to 2.0 mm, more preferably 0.015 to 1.5 mm, and even more preferably 0.02 to 1.2 mm.

[0128] The method for producing the laminate is not particularly limited, but the laminate is preferably produced by the method for producing the laminate of the present invention including a bonding step of bonding a first adherend and a second adherend with the resin composition.

[0129] The method for bonding the first adherend and the second adherend using the resin composition is not particularly limited. For example, the resin composition may be applied to one adherend, and the other adherend may be stacked thereon and cured to achieve bonding.

[0130] The method for coating the above-mentioned resin composition on the adherend is not particularly limited, and examples thereof include spin coating, spray coating, rod coating, knife coating, roll coating, roll knife coating, blade coating, die coating and gravure coating.

[0131] The coating amount of the resin composition on the adherend is not particularly limited, but is preferably 0.01 to 3.0 μL / mm 2 , more preferably 0.05 to 2.5 μL / mm 2 , more preferably 0.1 to 2.0 μL / mm 2 When the coating amount is not less than the above lower limit, the adherends can be firmly bonded to each other. On the other hand, when the coating amount is not more than the above upper limit, the two can be bonded with an appropriate amount.

[0132] Example

[0133] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

[0134] The compounds used in Examples and Comparative Examples are as follows.

[0135] <1,1-Dicyanoethylene(A)>

[0136] 1,1-Dicyanoethylene

[0137] <Polymerizable monomer (B)>

[0138] 1-Hexene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0139] · Dodecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0140] ·Vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0141] ·Styrene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0142] In addition, in Table 2, 1-hexene is described as (B1), and other polymerizable monomers (B) are described as (B2).

[0143] <Polymerizable monomer (C)>

[0144] Ethyl 2-cyanoacrylate (manufactured by Aldrich)

[0145] 2-Butyl cyanoacrylate (manufactured by United States Biological Co., Ltd.)

[0146] Diethyl methylenemalonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0147] <Material of laminate>

[0148] ·HDPE sheet (produced by Standard Test Piece Co., Ltd., 25 mm in length, 100 mm in width, 2.0 mm in thickness)

[0149] ·Steel plate (produced by Standard Test Piece Co., Ltd., 25 mm in length, 100 mm in width, 1.6 mm in thickness)

[0150] <Energy level measurement method>

[0151] 1,1-Inorganic Catalysts (A) and Polymers (B) and Solvents (C) Developed by the Gaussiann 16W(Gaussian). 16, Revision A.03, Frisch MJ, GW Trucks HB Schlegel, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li, M Caricato, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci, B Mennucci, HP Hratchian, 16; JVOrtiz , AF Izmaylov , JL Sonnenberg , D Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery, Jr., Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, EN Brothers, KNKudin, VN Staroverov, TA Keith, R. Kobayashi , Normand J , Raghavachari K , Rendell AP , Burant JC , Iyengar SS , Tomasi J , Cossi M , Millam JM , Klene M , Adamo C , Cammi R , Ochterski JW , RLMartin , K .Morokuma, O. Farkas, JB Foresman, and DJ Fox, Gaussian, Inc., Wallingford CT, 2016.)

[0152] DFT was used as the calculation method, and B3LYP was used as the functional. 6-31+G(d,p) was used as the basis function to optimize the structure, and 6-311++G(3d,2p) was used to calculate the single-point energy of the structure with the minimum generation energy, and the energy levels of HOMO-1, HOMO, and LUMO were calculated.

[0153] [HOMO-LUMO energy level difference]

[0154] The HOMO-LUMO energy level difference was calculated by the following general formula (X).

[0155] General formula (X): LUMO (acceptor) - HOMO (donor)

[0156] The above-mentioned LUMO (acceptor) represents the “lowest unoccupied molecular orbital energy level” of 1,1-dicyanoethylene (A) having an electron-withdrawing substituent.

[0157] The above HOMO (donor) represents the "energy level of the highest occupied molecular orbital" of the polymerizable monomer (B) or the "energy level of the next highest occupied molecular orbital when the highest occupied molecular orbital is an unshared electron pair".

[0158] <Evaluation method of storage stability>

[0159] The resin compositions prepared according to the formulations described in Examples and Comparative Examples were left to stand for 3 hours in a test environment at a temperature of 50° C. and a humidity of 50% to confirm the presence or absence of precipitates, thereby evaluating storage stability.

[0160] <Example 1>

[0161] Under dry nitrogen, 0.5 g of 1,1-dicyanoethylene (A), 9.0 g of ethyl 2-cyanoacrylate (polymerizable monomer (C)) and 0.5 g of dehydrated 1-hexene (polymerizable monomer (B)) were mixed to prepare a resin composition. The resin composition was evaluated according to JIS K6861:1995. Specifically, 100 μL of the obtained resin composition was applied to a 12.5 mm × 25 mm area of ​​a HDPE plate, and other HDPE plates were overlapped on the coated surface. Then, the resin composition was allowed to stand at room temperature (23°C) and humidity of 50% RH for 1 day, and the resin composition was cured using moisture in the substrate and / or the atmosphere, thereby bonding the two HDPE plates to obtain a laminate. Next, for the obtained laminate, the tensile shear bonding strength was measured using a universal material testing machine 5969 (manufactured by Instron) at a tensile speed of 20 mm / min. The results are shown in Table 1.

[0162] <Examples 2 to 13, Comparative Examples 1 to 12>

[0163] A laminate was prepared in the same manner as in Example 1 except that the resin composition was prepared according to the formulation described in Tables 1 to 3 and the adherends described in Tables 1 to 3 were used, and the tensile shear adhesive strength was measured. The results are shown in Tables 1 to 3.

[0164] <Examples 14 to 17>

[0165] The resin composition prepared according to the formulation described in Table 4 was left to stand for 3 hours in a test environment of a temperature of 50° C. and a humidity of 50% to allow moisture in the air to mix in, and the presence or absence of precipitates was confirmed to evaluate the storage stability. The results are shown in Table 4.

[0166] [Table 1]

[0167]

[0168] [Table 2]

[0169]

[0170] [Table 3]

[0171]

[0172] [Table 4]

[0173]

[0174] The results in Tables 1 to 3 show that the resin composition of the present invention is excellent in adhesive strength. In addition, the results in Table 4 show that the resin composition of the present invention is also excellent in storage stability.

Claims

1. A resin composition, characterized in that Containing 1,1-dicyanoethylene (A), a polymerizable monomer (B) represented by the following general formula (I) and a polymerizable monomer (C) represented by the following general formula (II), CH2=CR 1 R 2 (I) CHR 6 =CR 7 R 8 (II) In the general formula (I), R 1 is one or more selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom, R 2 is selected from hydrogen, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, carboxyl, -COOR 3 Ester groups, anhydride groups, -COR 4 Acyl represented by -OCOR 5 One or more of an acyloxy group, a halogen atom and a halogenated alkyl group, wherein R 3 is an alkyl group having 1 to 12 carbon atoms, R 4 is an alkyl group having 1 to 12 carbon atoms, R 5 is an alkyl group having 1 to 12 carbon atoms, Furthermore, in the general formula (II), R 6 is one or more selected from a hydrogen atom, an alkyl group, an alkenyl group and an alkoxy group, R 7 is selected from cyano, carboxyl, -COOR 9 One or more of an ester group and an anhydride group represented by 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 8 is selected from carboxyl, -COOR 10 One or more of an ester group and an anhydride group represented by 10 It is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group.

2. The resin composition according to claim 1, wherein The energy difference between the LUMO energy level of the 1,1-dicyanoethylene (A) and the HOMO energy level of the polymerizable monomer (B) is less than 4.40 eV.

3. The resin composition according to claim 1 or 2, wherein The polymerizable monomer (B) is at least one selected from ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, styrene, methyl methacrylate and dodecyl methacrylate.

4. The resin composition according to any one of claims 1 to 3, wherein The polymerizable monomer (C) is at least one selected from the group consisting of alkyl 2-cyanoacrylate, alkyl 2-cyanopentadienoate, and dialkyl methylenemalonate.

5. The resin composition according to any one of claims 1 to 4, wherein The content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition is 1% by mass or more and 80% by mass or less, the content of the polymerizable monomer (B) is 1% by mass or more and 80% by mass or less, and the content of the polymerizable monomer (C) is 19% by mass or more and 98% by mass or less.

6. The resin composition according to any one of claims 1 to 5, wherein It also contains Bronsted acid compounds. 7 . A cured product obtained by curing the resin composition according to claim 1 with a Lewis basic compound. 8 . A laminate comprising a layer comprising the cured product according to claim 7 . 9 . A method for producing a laminate, comprising a bonding step of bonding a first adherend and a second adherend using the resin composition according to claim 1 .

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