Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/30—Nitriles
  • C08F222/32—Alpha-cyano-acrylic acid; Esters thereof
  • C08F222/322—Alpha-cyano-acrylic acid ethyl ester, e.g. ethyl-2-cyanoacrylate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/14—Monomers containing five or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/30—Nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J135/04—Homopolymers or copolymers of nitriles
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
  • B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
  • B32B2037/1261—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive moisture curable

Definitions

• the present invention relates to a resin composition, a cured product, a laminate, and a method for producing a laminate, including a 1,1-dicyanoethylene and a specific polymerizable monomer.
• Monomers such as 2-cyanoacrylic acid alkyl ester, 2-cyanopentadienoic acid alkyl ester, and methylidene malonic acid dialkyl ester are used in resin compositions of fast-curing adhesives because they have excellent reactivity. Although resin compositions containing these monomers have fast curing properties, they have a problem of low adhesion to objects made of polyolefin materials.
• Patent Document 1 proposes a method of performing pretreatment such as primer treatment before applying a resin composition to an adherend.
• Patent Document 2 proposes a method of improving fast curing properties and adhesive strength by copolymerizing the above-mentioned monomers with other monomers.
• Patent Document 1 there is a problem that the production efficiency decreases because it is necessary to pre-process the adherend, and furthermore, the adhesiveness is not sufficiently improved. Furthermore, the method described in Patent Document 2 also has insufficient adhesion, and improvements have been desired.
• R 1 is one or more 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, an ester group represented by -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms) , an acid anhydride group, an acyl group represented by -COR 4 (R 4 is an
• 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 a cyano group, a carboxy group, an ester group represented by -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 an acid anhydride group.
• R 8 is a carboxyl group, an ester group represented by -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 linking group having a valence of 2 or more), and an acid anhydride.
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a linking group having a valence of 2 or more
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a linking group having a valence of 2 or more
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a linking group having a valence of 2 or more
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or
• 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, as described in [1] above.
• resin composition [3]
• 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.
• the polymerizable monomer (C) is one or more selected from 2-cyanoacrylic acid alkyl ester, 2-cyanopentadienoic acid alkyl ester, and methylidene malonic acid dialkyl ester.
• the resin composition according to any one of ⁇ [3].
• 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
• the content of the polymerizable monomer (C) is 19% by mass or more and 98% by mass or less.
• the present invention it is possible to provide a resin composition that exhibits excellent adhesive strength when used as an adhesive, and a cured product using the same. Furthermore, a laminate using the cured product and a method for manufacturing the laminate can be provided.
• the resin composition of the present invention comprises 1,1-dicyanoethylene (A), a polymerizable monomer (B) represented by the following general formula (I), and a polymerizable monomer represented by the following general formula (II). It is characterized by containing monomer (C).
• R 1 is one or more 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, an ester group represented by -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms) , an acid anhydride group, an acyl group represented by -COR 4 (R 4 is an alkyl group having 1 to 12 carbon atoms), -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms).
• 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 a cyano group, a carboxy group, an ester group represented by -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 an acid anhydride group.
• R 8 is a carboxyl group, an ester group represented by -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 linking group having a valence of 2 or more), and an acid anhydride.
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a linking group having a valence of 2 or more
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a linking group having a valence of 2 or more
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a linking group having a valence of 2 or more
• R 10 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or
• 1,1-dicyanoethylene (A) The resin composition of the present invention uses 1,1-dicyanoethylene (A). Since 1,1-dicyanoethylene (A) easily forms a charge transfer complex with the polymerizable monomer (B) described below, 1,1-dicyanoethylene (A), the polymerizable monomer (B) and It becomes easier to obtain a copolymer composed of the polymerizable monomer (C). 1,1-dicyanoethylene can be obtained by the production method described in J.Am.Chem.Soc., 1989, 111, 9078-9081 and US2476270.
• R 1 is one or more selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a halogen atom.
• the alkyl group for R 1 is preferably an alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, and the like.
• the cycloalkyl group for R 1 is preferably a cycloalkyl group having 3 to 12 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• the aryl group for R 1 is preferably an aryl group having 6 to 20 carbon atoms, such as phenyl group, tolyl group, xylyl group, and naphthyl group.
• the alkoxy group for R 1 is preferably an alkoxy group having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group. group, and tert-butoxy group.
• halogen atom for R 1 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• a hydrogen atom and a methyl group are more preferable.
• 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). ), an ester group, an acid anhydride group, an acyl group represented by -COR 4 (R 4 is an alkyl group having 1 to 12 carbon atoms), -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms); 12) is one or more selected from acyloxy groups, halogen atoms, and haloalkyl groups.
• the alkyl group for R 2 is preferably an alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, and the like.
• the alkenyl group represented by R 2 is preferably an alkenyl group having 2 to 12 carbon atoms, such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, prenyl group. , hexenyl group (such as cis-3-hexenyl group), and cyclohexenyl group.
• the cycloalkyl group for R 2 is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• the aryl group for R 2 is preferably an aryl group having 6 to 20 carbon atoms, such as phenyl group, tolyl group, xylyl group, and naphthyl group.
• the alkoxy group for R 2 is preferably an alkoxy group having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group. group, and tert-butoxy group.
• R 2 may be an ester group represented by -COOR 3
• R 3 represents an alkyl group having 1 to 12 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, heptyl group, octyl group, decyl group, and dodecyl group.
• Examples of the acid anhydride group for R2 include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, and anhydride.
• Examples include acid anhydride groups derived from glutaric acid, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like.
• R 2 may be an acyl group represented by -COR 4 , and R 4 represents an alkyl group having 1 to 12 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group.
• R 4 represents an alkyl group having 1 to 12 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group.
• R 2 may be an acyloxy group represented by -OCOR 5
• R 5 is an alkyl group having 1 to 12 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n- Examples include butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and n-hexyl group.
• halogen atom for R 2 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the haloalkyl group for R 2 is preferably a haloalkyl group having 1 to 12 carbon atoms, 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.
• R 2 is selected from a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an ester group represented by -COOR 3 , and an acyloxy group represented by -OCOR 5 from the viewpoint of improving adhesiveness. It is preferably one type of alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an ester group represented by -COOR 3 (R 3 in this case is an alkyl group having 8 to 12 carbon atoms). ), an acyloxy group represented by -OCOR 5 (R 5 in this case is an alkyl group having 1 to 6 carbon atoms) is more preferable.
• the polymerizable monomer (B) includes ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, styrene, methyl methacrylate, and dodecyl methacrylate.
• the object to be adhered which will be described later, is a polyolefin base material
• 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, It is more preferably 4.00 eV or less, and even more preferably 3.90 eV or less.
• 1,1-dicyanoethylene (A) and the polymerizable monomer (B) tend to form a charge transfer complex.
• the electronic energy levels of the bonding orbitals and antibonding orbitals of the vinyl group are important. In many cases, these correspond to the "highest occupied molecular orbital” (HOMO) and “lowest unoccupied molecular orbital” (LUMO), respectively, but in some cases they correspond to "one of the HOMOs". In some cases, the lower level (HOMO-1) is the bonding orbital of the vinyl group. Density Function Theory (hereinafter referred to as DFT) is well established for calculating the electronic energy level of molecular orbitals, and this method allows us to calculate the energy of HOMO-1/HOMO/LUMO. Level can be estimated.
• DFT Density Function Theory
• the HOMO-1/HOMO/LUMO level values of each compound used in the present invention were calculated using the currently widely used quantum chemical 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.
• 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. Scal
• DFT was used as the calculation method and B3LYP was used as the functional.
• the method for producing the polymerizable monomer (B) is not particularly limited, and known methods can be used alone or in combination.
• commercially available products can be used as the polymerizable monomer (B), such as 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.), etc. (manufactured by Kasei Kogyo Co., Ltd.) and styrene (manufactured by Tokyo Kasei Kogyo Co., Ltd.).
• the polymerizable monomer (C) is a monomer represented by the following general formula (II).
• the polymerizable monomer (C) is a monomer represented by the following general formula (II).
• the polymerizable monomer (C) together with the 1,1-dicyanoethylene (A) and the polymerizable monomer (B), excellent adhesion is achieved even to polyolefin substrates, etc. A resin composition exhibiting properties is obtained.
• CHR 6 CR 7 R 8 (II)
• R 6 is one or more selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group.
• the alkyl group for R 6 is preferably an alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, and the like.
• the alkenyl group for R 6 is preferably an alkenyl group having 2 to 12 carbon atoms, such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, prenyl group, Examples include hexenyl group (cis-3-hexenyl group, etc.), cyclohexenyl group, and the like.
• the alkoxy group for R 6 is preferably an alkoxy group having 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group. group, and tert-butoxy group.
• R 6 is preferably a hydrogen atom, an alkyl group, or an alkenyl group, and more preferably a hydrogen atom.
• R 7 is a cyano group, a carboxy group, or an ester group represented by -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 an acid anhydride group.
• R 7 may be an ester group represented by -COOR 9 , in which case R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.
• Examples of the alkyl group having 1 to 10 carbon atoms for R 9 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Examples include pentyl group, isopentyl group, neopentyl group, and n-hexyl group.
• Examples of the aryl group having 6 to 20 carbon atoms for R 9 include phenyl group, tolyl group, xylyl group, and naphthyl group.
• R 7 may be an acid anhydride group, such as phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride
• acid anhydride groups derived from acids, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like.
• R 7 is preferably a cyano group, a carboxy group, or -COOR 9 (R 9 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms); It is more preferable that there be.
• R 8 is a carboxyl group, an ester group represented by -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 linking group having a valence of 2 or more), and an acid anhydride.
• 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 more linking group.
• Examples of the alkyl group having 1 to 10 carbon atoms for R 10 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Examples include pentyl group, isopentyl group, neopentyl group, and n-hexyl group.
• Examples of the aryl group having 6 to 20 carbon atoms for R 10 include phenyl group, tolyl group, xylyl group, and naphthyl group.
• Examples of the divalent or higher-valent linking group for R 10 include linking groups derived from divalent or higher-valent alcohols such as ethylene glycol and glycerin.
• R 10 is a divalent or higher linking group
• a specific compound is a compound obtained by an esterification reaction between ethylene glycol and two 2-cyanoacrylic acids (so-called “bifunctional cyanoacrylate”).
• Examples include compounds obtained by esterification reaction of glycerin and three 2-cyanoacrylic acids (so-called “trifunctional cyanoacrylates”).
• Examples of the compound constituting the linking group include ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, Examples include diols such as 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol, and trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol. It will be done.
• the divalent or higher-valent linking group is preferably a di- to trivalent linking group.
• R 8 may be an acid anhydride group, such as phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride
• acid anhydride groups derived from acids, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like.
• 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 valence linking group). It is preferably an ester group represented by -COOR 10 (R 10 in this case is an alkyl group having 1 to 6 carbon atoms or a divalent to trivalent linking group). It is more preferable.
• the polymerizable monomer (C) includes 2-cyanoacrylic acid alkyl ester, 2-cyanopentadienoic acid alkyl ester, and methylidene malone, from the viewpoint of improving adhesive strength when the resin composition is used as an adhesive. It is preferably one or more selected from acid dialkyl esters, more preferably one or more selected from ethyl 2-cyanoacrylate, butyl 2-cyanoacrylate, and diethyl methylidenemalonate. More preferred is ethyl cyanoacrylate.
• both the LUMO level of the 1,1-dicyanoethylene (A) and the LUMO level of the polymerizable monomer (C) are -1.0 eV or less, - It is more preferably 1.5 eV or less, and even more preferably -2.0 eV or less. If the energy is below the upper limit, 1,1-dicyanoethylene (A) and the polymerizable monomer (C) will easily react.
• the method for producing the polymerizable monomer (C) is not particularly limited, and known methods can be used alone or in combination. Furthermore, the polymerizable monomer (C) may be a commercially available product, such as ethyl 2-cyanoacrylate (manufactured by Aldrich).
• 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
• the content of the polymerizable monomer (C) is 19% by mass or more and 98% by mass or less.
• a resin composition in which the content of each component is within the above range exhibits excellent adhesiveness while maintaining fast curing properties.
• the content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition is preferably from 2 to 60% by mass, more preferably from 5 to 40% by mass, and from 7 to 40% by mass. It is more preferably 30% by mass, and even more preferably from 7 to 18% by mass.
• 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, and 7 to 30% by mass. It is more preferable that the amount is 7 to 18% by mass.
• 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, and 50 to 85% by mass. The content is more preferably 62 to 88% by mass, even more preferably 62 to 88% by mass.
• the resin composition of the present invention further contains a Bronsted acidic compound.
• the resin composition of the present invention contains a Br ⁇ nsted acidic compound, the storage stability of the resin composition is improved and a desired curing speed can be obtained. More specifically, since 1,1-dicyanoethylene (A) hardens with a small amount of moisture, it is preferable to completely remove moisture during the manufacturing process, but it is not realistic to completely remove moisture. Since this is difficult, it is preferable to suppress curing (suppress the initiation of polymerization) by protonating water using a Br ⁇ nsted acid.
• Br ⁇ nsted acidic compound examples include inorganic acids, carboxylic acids, and organic sulfonic acids from the viewpoint of storage stability and ease of availability.
• sulfuric acid, hydrochloric acid, nitric acid It is preferably one or more selected from acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid, and it is a compound that reacts with water and exhibits Bronsted acidity, such as sulfur dioxide and diphosphorus pentoxide. It may also be a compound that is generated.
• the content thereof is preferably 0.001 to 1.0% by mass, and 0.01 to 0.8% by mass in the total amount of the resin composition. It is more preferable that When the content of the Br ⁇ nsted acidic compound is within the above range, storage stability will be good.
• 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, and 30% by mass. % or less, and even more preferably 10% by mass or less.
• the resin composition of the present invention may further contain other components such as a solvent, a filler, a thickener, an anti-aging agent, a plasticizer, a flame retardant, a stabilizer, and an antioxidant.
• the content thereof is preferably 0.001% by mass or more, and preferably 10% by mass or less, and 3% by mass in the total amount of the resin composition. % or less is more preferable.
• ⁇ Method for manufacturing resin composition> There are no particular limitations on the method for producing the resin composition of the present invention, and examples include 1,1-dicyanoethylene (A), the polymerizable monomer (B), the polymerizable monomer (C), and optionally Although it can be produced by a production method including a mixing step of mixing other components, it is preferable to produce it in a dry atmosphere because the polymerization reaction progresses due to moisture. Note that there is no particular restriction on the method of mixing each component, and any known method can be used.
• the cured product of the present invention is obtained by curing the resin composition of the present invention described above with a Lewis basic compound. More specifically, the cured product is obtained by curing each component in the resin composition using a Lewis basic compound as a catalyst. It is a copolymer.
• the Lewis basic compound used in the present invention is not particularly limited as long as it can be used as a polymerization catalyst.
• one or more selected from water, alcohol, and alkylamine can be used, and the alcohol is methanol. , ethanol, propanol, and the like.
• the alkylamine include tertiary amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, and N,N-dimethylisopropylamine.
• Method for producing cured product There is no particular restriction on the method for producing the cured product, and it can be obtained by mixing the resin composition of the present invention and a Lewis basic compound at room temperature (23°C), but generally the resin composition of the present invention A cured product can be obtained by reacting the material with moisture in the air (Lewis basic compound).
• the amount of the Lewis basic compound is not particularly limited, but it is preferably 0.001 to 1.0 parts by weight, and 0.01 to 0.5 parts by weight based on 100 parts by weight of the resin composition. is even more preferable. When the content of the Lewis basic compound is within the above range, the resin composition reacts quickly.
• the laminate of the present invention is a laminate having a layer containing the cured product, and although there is no particular restriction on the laminated structure, it is preferable to have the cured product between two adherends. By having the cured product between two objects to be adhered, it is possible to firmly adhere the objects to be adhered to each other.
• Examples of synthetic resins include polyethylene, polypropylene, copolymers of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms (for example, propylene, 1-butene, 1-pentene, 1-hexene, etc.), and ethylene-propylene.
• Examples include polyolefin resins such as -diene copolymer (EPDM), ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer, polyurethane resin, polyamide resin, polyester resin, and polycarbonate resin.
• Examples of the metal include steel plates such as stainless steel plates, cold-rolled steel plates, and alloyed galvanized steel plates.
• the thickness of the adherend that constitutes the laminate there is no particular limit to the thickness of the adherend that constitutes the laminate.
• 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, from the viewpoint of firmly adhering the objects to be adhered.
• the thickness is preferably 0.02 to 1.2 mm, and more preferably 0.02 to 1.2 mm.
• the method for producing a laminate of the present invention includes an adhesion step of bonding a first adherend and a second adherend with the resin composition. It is preferable. There is no particular restriction on the method of bonding the first adhered object and the second adhered object with the resin composition, but for example, one adherend object is coated with the resin composition, and the other adhered object is coated with the resin composition. Bonding can be achieved by overlapping and curing the objects to be bonded.
• the amount of the resin composition applied to the object to be adhered is preferably 0.01 to 3.0 ⁇ L/mm 2 , more preferably 0.05 to 2.5 ⁇ L/mm 2 . , more preferably 0.1 to 2.0 ⁇ L/mm 2 .
• the application amount is equal to or greater than the lower limit value, objects to be adhered can be firmly adhered to each other.
• the coating amount is below the upper limit value, both can be bonded together with an appropriate amount.
• 1-hexene was expressed as (B1)
• the other polymerizable monomer (B) was expressed as (B2).
• the energy levels of 1,1-dicyanoethylene (A), polymerizable monomer (B), and polymerizable monomer (C) were determined using the quantum chemical calculation program Gaussiann 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.
• Gaussiann 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
• DFT was used as the calculation method and B3LYP was used as the functional.
• the structure is optimized using 6-31+G(d,p) as the basis function, and one-point energy calculation is performed using 6-311++G(3d,2p) for the structure with the minimum generation energy, and HOMO-1 , HOMO and LUMO energy levels were calculated.
• HOMO-LUMO energy level difference The HOMO-LUMO energy level difference was calculated using the following general formula (X).
• LUMO represents the "lowest unoccupied orbital energy level" of 1,1-dicyanoethylene (A) having an electron-withdrawing substituent.
• the above HOMO is the "energy level of the highest occupied molecular orbital" of the polymerizable monomer (B) or "if the highest occupied molecular orbital is a lone pair, the highest occupied molecular orbital represents the energy level of the next occupied molecular orbital.
• Example 1 Under dry nitrogen, 0.5 g of 1,1-dicyanoethylene (A), 9.0 g of ethyl 2-cyanoacrylate (polymerizable monomer (C)) and dehydrated 1-hexene (polymerizable monomer (C)) were added. A resin composition was prepared by mixing 0.5 g of polymer (B)). This resin composition was evaluated according to JIS K6861:1995. Specifically, 100 ⁇ L of the obtained resin composition was applied to an area of 12.5 mm x 25 mm on an HDPE board, and another HDPE board was placed on this coated surface.
• the two HDPE plates are bonded and laminated by leaving the resin composition at room temperature (23°C) and 50% RH environment to cure the resin composition in the base material and/or moisture in the atmosphere for one day. I got a body.
• the tensile shear adhesive strength of the obtained laminate was measured using a universal material testing machine model 5969 (manufactured by Instron) at a tensile rate of 20 mm/min. The results are shown in Table 1.
• Examples 2 to 13 Comparative Examples 1 to 12> A laminate was prepared in the same manner as in Example 1, except that the resin composition was prepared according to the formulations listed in Tables 1 to 3, and the adherends listed in Tables 1 to 3 were used. We measured the The results are shown in Tables 1 to 3.
• Examples 14 to 17> A resin composition prepared according to the formulation shown in Table 4 is stored by standing in a test environment at a temperature of 50°C and a humidity of 50% for 3 hours to mix in moisture from the atmosphere, and checking for the presence or absence of precipitates. Stability was evaluated. The results are shown in Table 4.

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• 2023
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