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

Abstract

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

Description

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

[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.

[0002] Monomers such as 2-cyanoacrylic acid alkyl ester, 2-cyanopentadienoic acid alkyl ester, and methylidenemalonic acid dialkyl ester have excellent reactivity and are therefore used in resin compositions for fast-curing adhesives. While resin compositions containing these monomers have fast-curing properties, they suffer from the problem of poor adhesion to adherends made of polyolefin materials. To address this issue, for example, Patent Document 1 proposes a method of performing a pretreatment such as a primer treatment before applying the resin composition to the adherend. Patent Document 2 also proposes a method of improving fast-curing properties and adhesive strength by copolymerizing the aforementioned monomers with other monomers.

[0003] JP 2003-041200 JP 01-103614

[0004] The method described in Patent Document 1 has the problem of reducing production efficiency due to the need to pretreat the adherend, and furthermore, the improvement in adhesiveness is insufficient. Similarly, the method described in Patent Document 2 also has insufficient adhesiveness, and improvement is desired.

[0005] The present invention aims to provide a resin composition that exhibits excellent adhesive strength when used as an adhesive, a cured product using the same, a laminate using the cured product, and a method for producing the laminate.

[0006] The inventors conducted studies and found that the highly reactive monomers described above preferentially produce homopolymers due to their reactivity, and that copolymerization with other monomers is generally difficult. Therefore, the inventors further investigated copolymerizable monomers and found that copolymerization by anionic polymerization is facilitated when 1,1-dicyanoethylene, which has a low LUMO energy level and is likely to form a charge-transfer complex with the monomer, is used. Further studies revealed that by combining 1,1-dicyanoethylene with a specific monomer, a resin composition can be obtained that exhibits excellent adhesion even to polyolefin substrates, which have previously shown poor adhesion with conventional adhesives, and thus the present invention was completed.

[0007] That is, the present invention provides the following items [1] to [9]: [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): CH2=CR 1 R 2 (I) CHR 6 =CR 7 R 8 (II) (In general formula (I), R 1 is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom; 2 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4 is an alkyl group having 1 to 12 carbon atoms; 5 (R 5 is an alkyl group having 1 to 12 carbon atoms. In general formula (II), R is one or more selected from an acyloxy group represented by the formula (II), a halogen atom, and a haloalkyl group. 6 is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group; R 7is a cyano group, a carboxy group, -COOR 9 (R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; 8 is a carboxy group, -COOR 10 (R 10 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. ) is at least one selected from an ester group and an acid anhydride group represented by the following formula:

[0008] [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. [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. [4] The resin composition according to any one of [1] to [3] above, wherein the polymerizable monomer (C) is one or more selected from 2-cyanoacrylic acid alkyl esters, 2-cyanopentadienoic acid alkyl esters, and methylidenemalonic acid dialkyl esters. [5] The resin composition according to any one of [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.

[0009] [6] The resin composition according to any one of [1] to [5] above, further comprising a Bronsted acidic compound. [7] A cured product obtained by curing the resin composition according to any one of [1] to [6] above with a Lewis basic compound. [8] A laminate having a layer comprising the cured product according to [7] above. [9] A method for producing a laminate, comprising a bonding step of bonding a first adherend and a second adherend with the resin composition according to any one of [1] to [6] above.

[0010] According to the present invention, it is possible to provide a resin composition that exhibits excellent adhesive strength when used as an adhesive, a cured product using the same, a laminate using the cured product, and a method for producing the laminate.

[0011] [Resin Composition] 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): CH2=CR 1 R 2 (I) CHR 6 =CR 7 R 8 (II) (In general formula (I), R 1 is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom; 2 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4 is an alkyl group having 1 to 12 carbon atoms; 5 (R 5 is an alkyl group having 1 to 12 carbon atoms. In general formula (II), R is one or more selected from an acyloxy group represented by the formula (II), a halogen atom, and a haloalkyl group. 6 is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group; R 7 is a cyano group, a carboxy group, -COOR 9 (R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; 8 is a carboxy group, -COOR 10 (R 10is 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. ) is at least one selected from an ester group and an acid anhydride group represented by the following formula:

[0012] <1,1-dicyanoethylene (A)> 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), which will be described later, making it easier to obtain a copolymer composed of 1,1-dicyanoethylene (A), the polymerizable monomer (B), and the polymerizable monomer (C). 1,1-dicyanoethylene can be obtained by the production methods described in J. Am. Chem. Soc., 1989, 111, 9078-9081 and U.S. Pat. No. 2,476,270.

[0013] <Polymerizable Monomer (B)> The polymerizable monomer (B) is a monomer represented by the following general formula (I): CH═CR 1 R 2 (I)

[0014] In general formula (I), R 1 R is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom. 1 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0015] R 1 The cycloalkyl group of R is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. 1 The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0016] R 1The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0017] R 1 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0018] R 1 Among these, from the viewpoint of improving adhesiveness, is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a methyl group.

[0019] In general formula (I), R 2 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4 is an alkyl group having 1 to 12 carbon atoms; 5 (R 5 is an alkyl group having 1 to 12 carbon atoms.

[0020] R 2 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0021] R 2The alkenyl group represented by is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a prenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group.

[0022] R 2 The cycloalkyl group of R is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. 2 The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0023] R 2 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0024] R 2 Ha-COOR 3 and R 3 represents an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a heptyl group, an octyl group, a decyl group, and a dodecyl group.

[0025] 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, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0026] R 2 Ha-COR 4 and R 4 represents an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0027] R 2 Ha-OCOR 5 and R 5 is an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0028] R 2 Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 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 halogen atoms constituting the haloalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0029] R 2 Among these, from the viewpoint of improving adhesiveness, a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, -COOR 3 and an ester group represented by —OCOR 5 and an acyloxy group represented by the formula: 3 An ester group represented by the formula (in this case, R 3 is an alkyl group having 8 to 12 carbon atoms, 5 An acyloxy group represented by the formula (in this case, R 5 is an alkyl group having 1 to 6 carbon atoms.

[0030] More specifically, from the viewpoint of improving adhesiveness, 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 below is a polyolefin substrate, it is preferable to use 1-hexene or 1-octene as the polymerizable monomer (B). Use of these monomers enables stronger adhesion.

[0031] In the present invention, the energy difference between the LUMO level of the 1,1-dicyanoethylene (A) and the HOMO level of the polymerizable monomer (B) is preferably less than 4.40 eV, more preferably 4.00 eV or less, and even more preferably 3.90 eV or less. When the energy difference is equal to or less than the upper limit, the 1,1-dicyanoethylene (A) and the polymerizable monomer (B) are likely to form a charge-transfer complex. In the present invention, when two or more polymerizable monomers (B) are used, it is sufficient that at least one of them satisfies the energy level difference, but it is more preferable that all of the polymerizable monomers (B) satisfy the energy level difference.

[0032] Among the vacuum levels of electronic energy levels, the electronic energy levels of the bonding orbital and antibonding orbital of the vinyl group are important for the formation of charge-transfer complexes. In many cases, these correspond to the "highest occupied molecular orbital" (HOMO) and "lowest unoccupied molecular orbital" (LUMO), respectively. However, in some cases, the "level one level below the HOMO (HOMO-1)" is the bonding orbital of the vinyl group. Density functional theory (hereinafter referred to as DFT) is well established for calculating the electronic energy levels of molecular orbitals, and this method can be used to estimate the energy levels of HOMO-1 / HOMO / LUMO.

[0033] The values of the HOMO-1 / HOMO / LUMO levels of each compound used in the present invention were calculated using the widely used quantum chemistry calculation program Gaussian 16W (Gaussian 16, Revision A.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W.Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2016.) The calculation method was DFT, and the functional used was B3LYP. The structure was optimized using the 6-31+G(d,p) basis set, and for the structure with the lowest energy of formation, a single-point energy calculation was performed using the 6-311++G(3d,2p) basis set to calculate the energy levels of HOMO-1, HOMO, and LUMO.

[0034] The method for producing the polymerizable monomer (B) is not particularly limited, and known methods can be used alone or in combination to produce the polymerizable monomer (B). In addition, commercially available products can be used as the polymerizable monomer (B), and examples thereof include 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.).

[0035] <Polymerizable Monomer (C)> 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 1,1-dicyanoethylene (A) and the polymerizable monomer (B), a resin composition exhibiting excellent adhesion even to polyolefin substrates and the like can be obtained. CHR 6 =CR 7 R 8 (II)

[0036] In general formula (II), R 6 is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group.

[0037] R 6 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0038] R 6 The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a prenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group.

[0039] R 6 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0040] R 6 Among these, is preferably a hydrogen atom, an alkyl group, or an alkenyl group, and more preferably a hydrogen atom.

[0041] In general formula (II), R 7 is a cyano group, a carboxy group, -COOR 9 (R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. R is at least one selected from ester groups and acid anhydride groups represented by the following formula: 7 Ha-COOR 9 In this case, R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. 9 Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. 9 Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0042] R 7may be an acid anhydride group, and examples thereof include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0043] R 7 Among these, a cyano group, a carboxy group, and —COOR 9 (R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.) is preferably a cyano group, and more preferably a cyano group.

[0044] R 8 is a carboxy group, -COOR 10 (R 10 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. R is at least one selected from ester groups and acid anhydride groups represented by the following formula: 8 Ga-COOR 10 If R 10 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. 10 Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. 10 Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0045] R 10 Examples of the divalent or higher valent linking group include linking groups derived from divalent or higher valent alcohols such as ethylene glycol and glycerin. 10Specific examples of compounds in which is a divalent or higher linking group include a compound obtained by esterifying ethylene glycol with two 2-cyanoacrylic acids (so-called "bifunctional cyanoacrylate") and a compound obtained by esterifying glycerin with three 2-cyanoacrylic acids (so-called "trifunctional cyanoacrylate"). Examples of compounds constituting the linking group include diols such as ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol, and trivalent or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol. In the present invention, from the viewpoint of availability, the divalent or higher linking group is preferably a divalent or trivalent linking group.

[0046] R 8 may be an acid anhydride group, and examples thereof include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0047] R 8 is a carboxy group, -COOR from the viewpoint of improving adhesiveness. 10 (R 10 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. 10 (In this case, R 10 is an alkyl group having 1 to 6 carbon atoms or a divalent or trivalent linking group.

[0048] From the viewpoint of improving adhesive strength when the resin composition is used as an adhesive, the polymerizable monomer (C) is preferably at least one selected from 2-cyanoacrylic acid alkyl ester, 2-cyanopentadienoic acid alkyl ester, and methylidenemalonic acid dialkyl ester, more preferably at least one selected from 2-cyanoacrylate ethyl, 2-cyanoacrylate butyl, and methylidenemalonate diethyl, and even more preferably 2-cyanoacrylate ethyl.

[0049] In the present invention, the LUMO level of the 1,1-dicyanoethylene (A) and the LUMO level of the polymerizable monomer (C) are both preferably −1.0 eV or less, more preferably −1.5 eV or less, and even more preferably −2.0 eV or less. When the energies are equal to or less than the upper limit, the 1,1-dicyanoethylene (A) and the polymerizable monomer (C) are likely to react with each other.

[0050] The method for producing the polymerizable monomer (C) is not particularly limited, and known methods can be used alone or in combination. Alternatively, commercially available products can be used as the polymerizable monomer (C), such as ethyl 2-cyanoacrylate (manufactured by Aldrich).

[0051] <Content of Each Component> The content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition of the present invention is preferably 1% by mass or more and 80% by mass or less, the content of the polymerizable monomer (B) is preferably 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. A resin composition in which the contents of the components are within the above ranges exhibits excellent adhesive properties while maintaining rapid curing properties. From this viewpoint, 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, even more preferably 7 to 30% by mass, and even more preferably 7 to 18% by mass. Furthermore, 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, even more preferably 7 to 30% by mass, and even more preferably 7 to 18% by mass. Furthermore, the content of the polymerizable monomer (C) in the total amount of the resin composition is preferably 30 to 95 mass%, more preferably 40 to 90 mass%, even more preferably 50 to 85 mass%, and even more preferably 62 to 88 mass%.

[0052] <Bronsted Acidic Compound> 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 a desired curing rate can be obtained. More specifically, since 1,1-dicyanoethylene (A) cures with even a small amount of moisture, it is preferable to completely remove moisture during the production process. However, since completely removing moisture is practically difficult, it is preferable to suppress curing (suppress the initiation of polymerization) by protonating water using a Bronsted acid.

[0053] From the viewpoints of storage stability and availability, examples of the Bronsted acidic compound that can be used in the present invention include inorganic acids, carboxylic acids, and organic sulfonic acids. Among these, one or more acids selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid are preferred. Compounds that react with water to produce a compound that exhibits Bronsted acidity, such as sulfur dioxide and diphosphorus pentoxide, may also be used.

[0054] When the resin composition of the present invention contains a Brønsted acidic compound, the content thereof is preferably 0.001 to 1.0 mass %, more preferably 0.01 to 0.8 mass %, of the total amount of the resin composition. When the content of the Brønsted acidic compound is within this range, storage stability is improved.

[0055] 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, even more preferably 30% by mass or less, and even more preferably 10% by mass or less.

[0056] <Other Components> In addition to the above-described components, the resin composition of the present invention may further contain other components such as a solvent, a filler, a thickener, an antioxidant, a plasticizer, a flame retardant, a stabilizer, and an antioxidant. 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, of the total amount of the resin composition.

[0057] <Method for producing resin composition> There are no particular limitations on the method for producing the resin composition of the present invention, and the resin composition can be produced, for example, 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 necessary, but since the polymerization reaction proceeds in the presence of moisture, it is preferable to produce the resin composition in a dry atmosphere. The method for mixing the components is also no particular limitation, and they can be mixed by any known method.

[0058] [Cured Product] The cured product of the present invention is obtained by curing the above-described resin composition of the present invention with a Lewis basic compound, and more specifically, is a copolymer obtained by copolymerizing each component in the resin composition using a Lewis basic compound as a catalyst.

[0059] <Lewis Basic Compound> The Lewis basic compound used in the present invention is not particularly limited as long as it can be used as a polymerization catalyst, and for example, one or more compounds selected from water, alcohols, and alkylamines can be used, and examples of the alcohols include methanol, ethanol, propanol, etc. Examples of the alkylamines include tertiary amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, and N,N-dimethylisopropylamine.

[0060] <Method for Producing Cured Product> There are no particular limitations on the method for producing the cured product, 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). However, the cured product can generally be obtained by reacting the resin composition of the present invention with moisture in the air (Lewis basic compound). The amount of the Lewis basic compound is not particularly limited, but is preferably 0.001 to 1.0 part by mass, and more preferably 0.01 to 0.5 part by mass, per 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 quickly.

[0061] [Laminate and manufacturing method thereof] The laminate of the present invention is a laminate having a layer containing the cured product, and although there are no particular limitations on the lamination configuration, it is preferable that the cured product is placed between two adherends. By placing the cured product between the two adherends, the adherends can be firmly bonded to each other.

[0062] The adherend used in the laminate of the present invention is not particularly limited, and examples thereof include synthetic resins, metals, ceramics, fabrics, etc. Examples of synthetic resins include polyolefin resins such as 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, and ethylene-acrylic acid copolymers, polyurethane resins, polyamide resins, polyester resins, and polycarbonate resins. Examples of metals include steel sheets such as stainless steel sheets, cold-rolled steel sheets, and galvannealed steel sheets.

[0063] There is no particular limitation on the thickness of the adherends that constitute the laminate. On the other hand, 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, from the viewpoint of firmly bonding the adherends together.

[0064] Although there are no particular limitations on the method for producing the laminate, it is preferable to produce the laminate by the method for producing a laminate of the present invention, which includes a bonding step of bonding a first adherend and a second adherend with the resin composition. There are no particular limitations on the method for bonding a first adherend and a second adherend with the resin composition, but for example, the first adherend and the second adherend can be bonded by applying the resin composition to one adherend, placing the other adherend on top of it, and curing the mixture.

[0065] The method for applying the resin composition to the adherend is not particularly limited, but examples thereof include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, and gravure coating.

[0066] There is no particular limitation on the amount of the resin composition applied to the adherend, but it is preferably 0.01 to 3.0 μL / mm 2 It is preferable that the concentration is 0.05 to 2.5 μL / mm 2 More preferably, it is 0.1 to 2.0 μL / mm 2When the coating amount is equal to or greater than the lower limit, the objects to be bonded can be firmly bonded together, whereas when the coating amount is equal to or less than the upper limit, the objects to be bonded can be bonded together with an appropriate amount.

[0067] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The compounds used in the examples and comparative examples are as follows.

[0068] <1,1-dicyanoethylene (A)> 1,1-dicyanoethylene

[0069] <Polymerizable monomer (B)> 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.) Styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) In Table 2, 1-hexene is represented as (B1), and other polymerizable monomers (B) are represented as (B2).

[0070] <Polymerizable Monomer (C)> Ethyl 2-cyanoacrylate (manufactured by Aldrich) Butyl 2-cyanoacrylate (manufactured by United States Biologicals) Diethyl methylidenemalonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0071] <Laminate Materials> HDPE plate (manufactured by Standard Test Piece Co., Ltd., length 25 mm, width 100 mm, thickness 2.0 mm) Steel plate (manufactured by Standard Test Piece Co., Ltd., length 25 mm, width 100 mm, thickness 1.6 mm)

[0072] <Method for Measuring Energy Levels> The energy levels of 1,1-dicyanoethylene (A), polymerizable monomer (B), and polymerizable monomer (C) are calculated using the quantum chemistry calculation program Gaussian 16W (Gaussian 16, Revision A.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F.Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R.Calculations were performed using the Gaussian (Gaussian, Inc., Wallingford, CT, 2016) algorithm (J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox). DFT was used as the calculation method, and the B3LYP functional was used. The structure was optimized using the 6-31+G(d,p) basis set, and a single-point energy calculation was performed using the 6-311++G(3d,2p) basis set for the structure with the lowest formation energy, to calculate the energy levels of HOMO-1, HOMO, and LUMO.

[0073] [HOMO-LUMO Energy Level Difference] The HOMO-LUMO energy level difference was calculated according to the following general formula (X): General formula (X): LUMO (Acceptor) - HOMO (Donor)

[0074] The LUMO (Acceptor) represents the "energy level of the lowest unoccupied molecular orbital" of 1,1-dicyanoethylene (A) having an electron-withdrawing substituent.

[0075] The HOMO (Doner) represents the "energy level of the highest occupied molecular orbital" of the polymerizable monomer (B) or "when the highest occupied molecular orbital is an unshared electron pair, the energy level of the occupied molecular orbital immediately below the highest occupied molecular orbital."

[0076] <Method for evaluating storage stability> Resin compositions prepared according to the formulations described in the Examples and Comparative Examples were left to stand for 3 hours in a test environment of a temperature of 50°C and a humidity of 50%, and the storage stability was evaluated by checking whether or not precipitates were generated.

[0077] Example 1 A resin composition was prepared by mixing 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)) under dry nitrogen. This resin composition was evaluated in accordance with JIS K6861:1995. Specifically, 100 μL of the resulting resin composition was applied to a 12.5 mm × 25 mm area of ​​an HDPE plate, and another HDPE plate was placed on top of the applied surface. The two HDPE plates were then left to stand at room temperature (23°C) and 50% RH to cure with moisture from the substrate and / or air for one day, thereby bonding the two HDPE plates together to obtain a laminate. The tensile shear adhesive strength of the resulting laminate was then measured at a tensile speed of 20 mm / min using a universal testing machine, Model 5969 (manufactured by Instron). The results are shown in Table 1.

[0078] Examples 2 to 13, Comparative Examples 1 to 12 Laminates were produced and the tensile shear adhesive strength was measured in the same manner as in Example 1, except that resin compositions were prepared according to the formulations shown in Tables 1 to 3 and adherends shown in Tables 1 to 3 were used. The results are shown in Tables 1 to 3.

[0079] Examples 14 to 17 Resin compositions prepared according to the formulations shown in Table 4 were left to stand for 3 hours in a test environment at a temperature of 50°C and a humidity of 50% to allow moisture from the air to be mixed in, and the presence or absence of precipitates was checked to evaluate storage stability. The results are shown in Table 4.

[0080]

[0081]

[0082]

[0083]

[0084] As is clear from the results in Tables 1 to 3, the resin composition of the present invention has excellent adhesive strength. Furthermore, the results in Table 4 show that the resin composition of the present invention also has excellent storage stability.

Claims

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): CH 2 =CR 1 R 2 (I) CHR 6 =CR 7 R 8 (II) (In general formula (I), R 1 is at least one selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom, R 2 is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, a carboxy group, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4 is an alkyl group having 1 to 12 carbon atoms; 5 (R 5 is an alkyl group having 1 to 12 carbon atoms. In addition, in the general formula (II), R 6 is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group, R 7 is a cyano group, a carboxy group, -COOR 9 (R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; R 8 is a carboxy group, -COOR 10 (R 10 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; and is at least one selected from an ester group and an acid anhydride group represented by the following formula:

2. The resin composition according to claim 1, 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.

3. 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. The resin composition according to claim 1 or 2.

4. The resin composition according to claim 1 or 2, wherein the polymerizable monomer (C) is at least one selected from the group consisting of 2-cyanoacrylic acid alkyl esters, 2-cyanopentadienoic acid alkyl esters, and methylidenemalonic acid dialkyl esters.

5. 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 resin composition according to claim 1 or 2, wherein 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 claim 1 or 2, further comprising a Bronsted acidic compound.

7. A cured product obtained by curing the resin composition according to claim 1 or 2 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 with the resin composition according to claim 1 or 2.