Composition containing 1,1-dicyanovinyl, cured product, laminate, and method for producing composition containing 1,1-dicyanovinyl

Abstract

A composition containing 1,1-dicyanethylene, containing 1,1-dicyanethylene, water, and an acidic compound (A), wherein the content of the above-mentioned acidic compound (A) and the content of the above-mentioned water in the composition satisfy a specific relationship formula (Ia): -4.00 ≤ α ≤ 0 (α is represented by pKa + Log(C H2O / C a ), pKa is the logarithmic acid dissociation constant of the above-mentioned acidic compound (A), C H2O is the molar concentration of the above-mentioned water in the above-mentioned composition, and C a is the molar concentration of the above-mentioned acidic compound (A) in the above-mentioned composition).

Description

Technical Field

[0001] This invention relates to compositions containing 1,1-dicyanoethylene, cured products, laminates, and methods for manufacturing compositions containing 1,1-dicyanoethylene. Background Technology

[0002] 1,1-Dicyanoethylene has excellent reactivity and is therefore sometimes used in curing adhesives.

[0003] However, it is highly reactive, therefore, acid stabilizers must be used to improve its storage stability in order to use 1,1-dicyanoethylene. Patent documents 1 and 2 propose the use of benzenesulfonic acid, chlorobenzenesulfonic acid, p-toluenesulfonic acid, etc., as acid stabilizers.

[0004] Methylenemalonic acid is a compound that is as highly reactive as 1,1-dicyanoethylene. Patent Document 3 proposes improving storage stability by coexisting an antioxidant and an acid in methylenemalonic acid. Specifically, in Patent Document 3, acetic acid is used as the acid in the examples.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: US Patent No. 2,665,298

[0008] Patent Document 2: US Patent No. 2,535,861

[0009] Patent Document 3: Japanese Patent Application Publication No. 2008-174494 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] However, the inventors' research revealed that in the methods described in Patent Documents 1, 2, and 3, stability degradation, such as the formation of solids, occurs due to excessively high acid concentrations. Furthermore, the inventors' research also found that even when using acetic acid as described in Patent Document 3, the polymerization of 1,1-dicyanoethylene is sometimes insufficiently suppressed.

[0012] Therefore, for compositions containing 1,1-dicyanoethylene, there remains a demand for methods of manufacturing compositions containing 1,1-dicyanoethylene that improve their storage stability and provide excellent storage stability. Furthermore, if compositions containing 1,1-dicyanoethylene with excellent storage stability can be provided, it is expected that cured products and laminates will not impair the desired physical properties.

[0013] The objective of this invention is to provide a composition containing 1,1-dicyanoethylene with excellent storage stability and a method for manufacturing the same. Furthermore, the objective is to provide a cured product using the same components as the 1,1-dicyanoethylene-containing composition, and a laminate containing the cured product.

[0014] Methods for solving problems

[0015] The inventors conducted an in-depth study on why the polymerization of 1,1-dicyanoethylene could not be sufficiently suppressed simply by adding an optional acidic compound. The results showed that the amount of water and acid in the composition containing 1,1-dicyanoethylene had an effect. Furthermore, the inventors discovered that by combining water and acid in a manner that satisfies a specific relationship between the molar concentrations of water and acid, a composition containing 1,1-dicyanoethylene with excellent storage stability could be obtained, thus completing this invention.

[0016] That is, the present invention provides the following [1] to

[11] .

[0017] [1] A composition containing 1,1-dicyanoethylene, comprising 1,1-dicyanoethylene, water and an acidic compound (A), wherein the content of the acidic compound (A) in the composition and the content of the water satisfy the following relationship (Ia).

[0018] -4.00≤α≤0 …(Ia)

[0019] (In the above relation (Ia), α is represented by the following expression (Ib).

[0020] α=pKa+Log(C H2O / C a …(Ib)

[0021] In the above formula (Ib), pKa is the logarithmic acid dissociation constant of the acidic compound (A) mentioned above.

[0022] C H2O The molar concentration of water in the above composition.

[0023] C a This refers to the molar concentration of the acidic compound (A) in the above composition.

[0024] [2] The composition containing 1,1-dicyanoethylene according to [1], wherein the acidic compound (A) is selected from acidic compounds whose logarithmic acid dissociation constant pKa is less than -1.7.

[0025] [3] The composition containing 1,1-dicyanoethylene according to [1] or [2], wherein the acidic compound (A) is selected from at least one of methanesulfonic acid, sulfuric acid, p-toluenesulfonic acid and hydrochloric acid.

[0026] [4] The composition containing 1,1-dicyanoethylene according to any one of [1] to [3] further contains a polymerizable monomer (B).

[0027] [5] The composition containing 1,1-dicyanoethylene according to [4], wherein the polymerizable monomer (B) is selected from one or more of the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate, alkyl 2-cyanoprene acid, and dialkyl methylene malonate.

[0028] [6] The composition containing 1,1-dicyanoethylene according to [5], wherein the polymerizable monomer (B) comprises alkyl 2-cyanoacrylate.

[0029] [7] The composition containing 1,1-dicyanoethylene according to [6], wherein the alkyl 2-cyanoacrylate is ethyl 2-cyanoacrylate.

[0030] [8] The composition containing 1,1-dicyanoethylene according to any one of [1] to [7], wherein the molar concentration of the acidic compound (A) in the composition is 1000 mmol / L or less.

[0031] [9] A cured product obtained by reacting a composition containing 1,1-dicyanoethylene as described in any one of [1] to [8].

[0032]

[10] A laminate comprising a cured product obtained by reacting a composition containing 1,1-dicyanoethylene as described in any one of [1] to [8] and an adherend bonded to the cured product.

[0033]

[11] A method for manufacturing a composition containing 1,1-dicyanoethylene, comprising a step of mixing an acidic compound (A) such that the content of the acidic compound (A) in the composition and the content of water in the composition satisfy the following relationship (Ia).

[0034] -4.00≤α≤0 …(Ia)

[0035] (In the above relation (Ia), α is represented by the following equation (Ib): α = pKa + Log(C H2O / C a …(Ib) In the above formula (Ib), pKa is the logarithmic acid dissociation constant of the acidic compound (A) mentioned above.

[0036] C H2O The molar concentration of water in the above composition.

[0037] C a This refers to the molar concentration of the acidic compound (A) in the above composition.

[0038] Invention Effects

[0039] According to the present invention, a composition containing 1,1-dicyanoethylene with excellent storage stability and a method for manufacturing the same thereof can be provided. Furthermore, according to the present invention, a cured product using the same components as the composition containing 1,1-dicyanoethylene and a laminate containing the cured product can be provided. Detailed Implementation

[0040] The following description is based on an example of a method for implementing the present invention (hereinafter sometimes referred to as "this embodiment"). However, the embodiments shown below are illustrative examples for embodying the technical concept of the present invention, and the present invention is not limited to the following description.

[0041] Furthermore, while preferred embodiments are shown in this specification, combinations of two or more preferred embodiments are also preferred. Regarding the matters shown in the numerical ranges, when there are several numerical ranges, the lower and upper limits can be selectively combined to form a preferred embodiment.

[0042] In this specification, when a numerical range such as "XX~YY" is mentioned, it means "above XX and below YY".

[0043] [Compositions containing 1,1-dicyanoethylene]

[0044] The 1,1-dicyanoethylene composition of the present invention is a 1,1-dicyanoethylene composition containing 1,1-dicyanoethylene, water and acidic compound (A), wherein the content of the acidic compound (A) in the composition and the content of water satisfy the following specific relationship (Ia).

[0045] -4.00≤α≤0 …(Ia)

[0046] (In the above relation (Ia), α is represented by the following expression (Ib).

[0047] α=pKa+Log(C H2O / C a …(Ib)

[0048] In the above formula (Ib), pKa is the logarithmic acid dissociation constant of the acidic compound (A) mentioned above.

[0049] C H2O The molar concentration of water in the above composition.

[0050] C a This refers to the molar concentration of the acidic compound (A) in the above composition.

[0051] For compositions containing 1,1-dicyanoethylene, by ensuring that the content of water and acidic compound (A) satisfies a specific relationship (Ia), compositions containing 1,1-dicyanoethylene with excellent storage stability can be provided. It should be noted that acidic compound (A) can be one type or two or more types.

[0052] (1,1-Dicyanoethylene)

[0053] 1,1-Dicyanoethylene may be manufactured according to the manufacturing method described in J. Am. Chem. Soc., 1989, 111, 9078-9081 or the manufacturing method described in U.S. Patent No. 2,476,270. 1,1-Dicyanoethylene is preferably manufactured by the manufacturing method described in Manufacturing Example 1 described later. The manufactured 1,1-Dicyanoethylene is preferably stored frozen or in the presence of an acidic compound (A) just before use.

[0054] In addition, the manufactured 1,1-dicyanoethylene can be stored in a state of coexistence with aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane and heptane; cycloalkane solvents such as cyclohexane; ester solvents such as ethyl acetate; and ether solvents such as tetrahydrofuran and diethyl ether before use.

[0055] (purity)

[0056] In the embodiments of the present invention, the purity of the 1,1-dicyanoethylene used in the composition containing 1,1-dicyanoethylene is preferably 95% or more, more preferably 97% or more, further preferably 98% or more, and even more preferably 99% or more. The purity of 1,1-dicyanoethylene can be determined, for example, by gas chromatography.

[0057] (Water content of 1,1-dicyanoethylene)

[0058] Depending on its manufacturing or purification method, 1,1-dicyanoethylene may contain trace amounts of water. Undoubtedly, the trace water content is preferably low, relative to the total amount of 1,1-dicyanoethylene, for example, less than 10,000 mmol / L, preferably less than 1,000 mmol / L, more preferably less than 100 mmol / L, further preferably less than 50 mmol / L, and even more preferably less than 25 mmol / L. The water content of 1,1-dicyanoethylene can be quantified as the water content of the composition in the presence of an acidic compound (A).

[0059] (water)

[0060] The composition containing 1,1-dicyanoethylene in this embodiment contains water. The amount of water is the sum of the water content of 1,1-dicyanoethylene, the water content of the acidic compound (A), and the amount of water added. It should be noted that water may be added, for example, as illustrated in the examples or comparative examples described later. Additionally, if an excess of the acidic compound (A) is added, water may also be added in a manner that satisfies the above-described relationship. The amount of water (total) in the composition containing 1,1-dicyanoethylene can be quantified by the method described in the example section below (specifically, Karl Fischer titration).

[0061] (Acidic compound (A))

[0062] In this embodiment, the acidic compound (A) is not limited as long as it satisfies the specific relationship (Ia) described above. Preferably, the acidic compound (A) is selected in a manner that satisfies this relationship (Ia), and the amount of the selected acidic compound is determined.

[0063] From the viewpoint of satisfying relation (Ia), the acidic compound (A) is preferably selected from acidic compounds with a logarithmic acid dissociation constant pKa of -1.7 or less. The logarithmic acid dissociation constant pKa of the acidic compound (A) is typically the logarithmic acid dissociation constant in an aqueous system at room temperature. As the logarithmic acid dissociation constant, reference can be made to Non-Patent Literature 1 (based on the pKa table of DH Ripin and DA Evans; this can be obtained from https: / / depts.washington.edu / eooptic / linkfiles / evans_pKa_table.pdf). In the case where the acidic compound (A) undergoes multi-stage dissociation, the first-stage logarithmic acid dissociation constant pKa is typically used as the logarithmic acid dissociation constant. The logarithmic acid dissociation constant of the acidic compound (A) not described in Non-Patent Literature 1 can be determined by methods known to those skilled in the art (e.g., neutralization titration). Although not disclosed in the aforementioned Non-Patent Literature 1, the pKa of p-toluenesulfonic acid monohydrate is -1.7.

[0064] By reducing the logarithmic acid dissociation constant pKa of the acidic compound (A) to below -1.7, water (H₂O) in a composition containing 1,1-dicyanoethylene can be efficiently protonated to form oxygen. Ions (H3O) + From this perspective, the logarithmic acid dissociation constant pKa of the acidic compound (A) is more preferably -1.8 or less, even more preferably -1.9 or less, more preferably -2.0 or less, and even more preferably -2.1 or less.

[0065] Specific examples of the acidic compound (A) include methanesulfonic acid (pKa: -2.6), sulfuric acid (pKa: -3.0), hydrochloric acid (pKa: -8.0), nitric acid (pKa: -1.3), sulfurous acid (pKa: 1.9), and trifluoroacetic acid (pKa: -0.25). In one embodiment of this invention, the acidic compound (A) is at least one selected from methanesulfonic acid, sulfuric acid, trifluoroacetic acid, hydrochloric acid, and nitric acid, preferably at least one selected from methanesulfonic acid, sulfuric acid, and hydrochloric acid. In another embodiment of this invention, the acidic compound (A) is at least one selected from methanesulfonic acid, sulfuric acid, p-toluenesulfonic acid, and hydrochloric acid.

[0066] (Specific relation)

[0067] In this embodiment, the above relationship is shown again, as follows.

[0068] -4.00≤α≤0 …(Ia)

[0069] (In the above relation (Ia), α is represented by the following expression (Ib).

[0070] α=pK a +Log(C H2O / C a …(Ib)

[0071] In the above formula (Ib), pKa is the logarithmic acid dissociation constant of the acidic compound (A) mentioned above.

[0072] C H2O The molar concentration of water in the above composition.

[0073] C a This refers to the molar concentration of the acidic compound (A) in the above composition.

[0074] From the viewpoint of reliably achieving the desired effect of the present invention, α in the above relation (Ia) is preferably -3.90 or more, more preferably -3.80 or more, even more preferably -3.70 or more, and even more preferably -3.60 or more.

[0075] However, when there are two acidic compounds (A), the above relationship (Ib) is preferably understood as the following formula (Ib-2).

[0076] 10 α ={C a1 ×K a1 / (K a1 +10 α )}+{C a2 ×K a2 / (K a2 +10 α )} …(Ib-2)

[0077] In the above formula (Ib-2), C a1 This represents the molar concentration of the first acidic compound.

[0078] K a1 is the acid dissociation constant of the first acidic compound.

[0079] C a2 This represents the molar concentration of the second acidic compound.

[0080] K a2 is the acid dissociation constant of the second acidic compound.

[0081] It should be noted that when there are three or more acidic compounds (A), similar to the above formula (Ib-2), the sum on the right side can be calculated by considering the molar concentration and acid dissociation constant of each acidic compound.

[0082] In this embodiment, the reason why a composition containing 1,1-dicyanoethylene with excellent storage stability is obtained by satisfying a specific relationship (Ia) between the content of the acidic compound (A) and the content of water is not yet certain, but the inventors speculate as follows.

[0083] It is believed that the water contained in the composition containing 1,1-dicyanoethylene forms oxygen. The ions thereby stabilize 1,1-dicyanoethylene in the composition. This inhibits the polymerization of 1,1-dicyanoethylene, suppresses the increase in viscosity or the formation of precipitates (these phenomena are illustratively confirmed in the Examples section). Here, the acidic compound (A) in the composition containing 1,1-dicyanoethylene has oxygen... Ion-forming ability. Therefore, there is a close relationship between the water content and the acidic compound (A). This is first clarified through the examples in the "Examples" section described later. Moreover, the higher the water content, the greater the content of the acidic compound (A); or, alternatively, oxygen... Acidic compounds with excellent ion-forming ability, such as those with lower pKa values, are used as acidic compounds (A); or, by satisfying both of these conditions, they can efficiently convert water into oxygen. Ions. On the other hand, if the content of acidic compound (A) is too high, there is a tendency for colored precipitates derived from 1,1-dicyanoethylene to be produced in compositions containing 1,1-dicyanoethylene. This is believed to be due to a side reaction in which acidic compound (A) reacts with cyano groups. It is thought that the pKa value of strong acidic compounds such as sulfuric acid is lower (the absolute value of the pKa value is higher) due to the decrease in water content in the composition. Therefore, the water content is lower relative to the acid, resulting in increased reactivity with cyano groups, and the aforementioned side reaction is promoted. Based on the above, it can be said that acidic compound (A) needs to have a relatively low pKa value, and in an amount corresponding to the water content, that is, sufficient to convert water into oxygen. The amount of ions needs to be moderate, and from the viewpoint of suppressing coloration, it should not be excessive. However, as long as 1,1-dicyanoethylene can be stabilized, the amount of precipitates can be limited to a minimum, so the problem of suppressing coloration can be considered a secondary issue. Such research results are expressed in this embodiment using the pKa and molar concentration of the acidic compound (A) through the above-described relationship.

[0084] (Content of acidic compound (A))

[0085] The content of acidic compound (A) is not limited as long as the above relationship is satisfied. The mass ratio of acidic compound (A) to water content is, for example, in the range of 1:0.001 to 0.0001:1, preferably in the range of 1:0.01 to 0.01:1, more preferably in the range of 1:0.1 to 0.1:1, and even more preferably in the range of 1:0.1 to 0.1:0.6. This achieves the goal of converting as much water as possible into oxygen while satisfying the above relationship. From the perspective of ions, it is preferable that the content of acidic compound (A) is equal to or greater than that of water (i.e., the content of (C) in equation (Ib) is equal to or greater than that of water). H2O / C a (The value of ) is less than 1).

[0086] The molar concentration of the acidic compound (A) in the composition containing 1,1-dicyanoethylene is not limited as long as the above-described relationship is satisfied. From the viewpoint of suppressing coloration in the composition containing 1,1-dicyanoethylene, the molar concentration of the acidic compound (A) in the composition containing 1,1-dicyanoethylene is preferably 1000 mmol / L or less, more preferably 500 mmol / L or less, even more preferably 150 mmol / L or less, and even more preferably 20 mmol / L or less. On the other hand, from the viewpoint of the storage stability of the composition containing 1,1-dicyanoethylene, the molar concentration of the acidic compound (A) in the composition containing 1,1-dicyanoethylene is preferably 0.001 mmol / L or more.

[0087] (Water content of acidic compound (A))

[0088] The acidic compound (A) may contain trace amounts of water, depending on its manufacturing or purification method. The trace amounts of water can be quantified as the water content of the composition in the presence of 1,1-dicyanoethylene.

[0089] ((B) Component: Polymerizing monomer)

[0090] The composition containing 1,1-dicyanoethylene in this embodiment may further contain a polymerizable monomer (B). 1,1-dicyanoethylene is excluded from the polymerizable monomer (B). The polymerizable monomer (B) preferably reacts with 1,1-dicyanoethylene. The polymerizable monomer (B) may be one or more. The polymerizable monomer (B) may be a free radical polymerizable monomer or an anionic polymerizable monomer.

[0091] Examples of polymerizable monomers (B) include ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, butyl acrylate and other alkyl acrylates, methyl methacrylate, dodecyl methacrylate and other alkyl methacrylates, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate, alkyl 2-cyanoprene acid, and dialkyl methylene malonate. From the viewpoint of excellent reactivity with 1,1-dicyanoethylene, alkyl 2-cyanoacrylate is preferred for polymerizable monomer (B), and ethyl 2-cyanoacrylate is more preferred.

[0092] There are no particular restrictions on the manufacturing method of polymerizable monomer (B), which can be manufactured by using known methods alone or in combination. Polymerizable monomer (B) may also be a commercially available product.

[0093] (Other ingredients)

[0094] The composition containing 1,1-dicyanoethylene in this embodiment may contain one or more other components.

[0095] Examples of other components include thickeners, dehydrating agents, free radical polymerization inhibitors, plasticizers, pigments, organic solvents, rubber, organic fillers, and inorganic fillers. These other components can be used in amounts that do not impair the desired effects of the invention. Rubber can also function as an organic filler. Inorganic fillers can also function as thickeners.

[0096] It should be noted that, from the viewpoint of heat resistance and moisture resistance, the composition containing 1,1-dicyanoethylene in this embodiment preferably does not contain ethyl 2-cyanoacrylate, butyl 2-cyanoacrylate and diethyl methylene malonate.

[0097] (Content of each component)

[0098] When the composition containing 1,1-dicyanoethylene in the embodiment is set to 100% by mass, from the viewpoint of having desired physical properties, the total amount of monomer (1,1-dicyanoethylene and polymerizable monomer (B) used as needed) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. When using polymerizable monomer (B), the mass ratio of 1,1-dicyanoethylene to polymerizable monomer (B) is not particularly limited, and can be 99:1 to 1:99, 80:20 to 20:80, or 70:30 to 30:70.

[0099] [Method for manufacturing compositions containing 1,1-dicyanoethylene]

[0100] The method for manufacturing a composition containing 1,1-dicyanoethylene according to an embodiment of the present invention includes a step (combining step) of combining an acidic compound (A) such that the content of the acidic compound (A) in the composition and the content of water in the composition satisfy the following relationship (Ia).

[0101] -4.00≤α≤0 …(Ia)

[0102] (In the above relation (Ia), α is represented by the following expression (Ib).

[0103] α=pKa+Log(C H2O / C a …(Ib)

[0104] In the above formula (Ib), pKa is the logarithmic acid dissociation constant of the acidic compound (A) mentioned above.

[0105] C H2OThe molar concentration of water in the above composition.

[0106] C a This refers to the molar concentration of the acidic compound (A) in the above composition.

[0107] By employing the above manufacturing method, the composition containing 1,1-dicyanoethylene of the above embodiment can be manufactured, that is, a composition containing 1,1-dicyanoethylene with excellent storage stability. In the above compounding step, stirring may or may not be performed. Furthermore, in the above compounding step, when the water content is determined, the type and amount of the acidic compound (A) are preferably determined in a manner that satisfies the above-described relationship. If the amount of acidic compound (A) is excessive from the viewpoint of the above-described relationship (or if it is unavoidable to be excessive), water is compounded in a manner that satisfies the above-described relationship. That is, the above compounding step can be a step in which water and acidic compound (A) are compounded in such a manner that the content of the acidic compound (A) in the composition satisfies the above-described relationship (Ia) with the content of the water.

[0108] (use)

[0109] The composition containing 1,1-dicyanoethylene of this embodiment can be used as a (instant) adhesive. Examples of uses for this adhesive include general household adhesives, medical applications, hemostatic adhesives, lamination, binding, shoe assembly, automotive parts, air conditioning units, materials for electrical or electronic devices or other durable consumer goods, assembly and encapsulation of materials used in the construction industry (e.g., for insulation, thermal, and / or acoustic applications), chip bonding, wound closure, surgical sutures, medical device applications, and all kinds of labels, eyelash extension adhesives, cosmetic adhesives, etc.

[0110] It should be noted that instant adhesives containing ethyl 2-cyanoacrylate as the main raw material are widely known, but ethyl 2-cyanoacrylate has drawbacks such as poor heat and moisture resistance, resulting in poor heat and moisture resistance in such instant adhesives. On the other hand, 1,1-dicyanoethylene has excellent heat and moisture resistance, and adhesives using the compositions containing 1,1-dicyanoethylene according to embodiments of this application exhibit excellent heat and moisture resistance.

[0111] The composition containing 1,1-dicyanoethylene in this embodiment can also be used as a coating material. Examples of applications for this coating material include thin-film capacitors, insulating layers for EL elements, electrostatic induction conversion elements, sensors (e.g., touch sensors, vibration sensors, biosensors, tire sensors (especially sensors disposed on the inner surface of tires)), actuators, touch panels, tactile devices, vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, microphones, vibration damping sheets, hollow fiber membranes for water purification, and corrosion-resistant membranes. One example of a tactile device is a device that provides tactile feedback to the user.

[0112] [cured material]

[0113] The cured product of the embodiments of the present invention is a cured product obtained by reacting the above-described composition containing 1,1-dicyanoethylene. Specifically, the cured product of the embodiments of the present invention is a cured product obtained by reacting a composition containing 1,1-dicyanoethylene, water, and an acidic compound (A); or a composition containing 1,1-dicyanoethylene, water, an acidic compound (A), and a polymerizable monomer (B), wherein the content of the acidic compound in the composition and the content of water satisfy the following relationship (Ia).

[0114] -4.00≤α≤0 …(Ia)

[0115] (In the above relation (Ia), α is represented by the following expression (Ib).

[0116] α=pK1+Log(C H2O / C a …(Ib)

[0117] In the above formula (Ib), pK1 is the logarithmic acid dissociation constant of the acidic compound (A) mentioned above.

[0118] C H2O The molar concentration of water in the above composition.

[0119] C a This refers to the molar concentration of the acidic compound (A) in the above composition.

[0120] (Molecular mixture)

[0121] 1,1-Dicyanoethylene may or may not be used to form a monomer mixture with the polymerizable monomer (B). In the case of a monomer mixture, the 1,1-dicyanoethylene and polymerizable monomer (B) are the same as those contained in the composition containing 1,1-dicyanoethylene described in this embodiment. The monomer mixture may contain one or more other components. These other components are also the same as those contained in the composition containing 1,1-dicyanoethylene described above.

[0122] (Lewis basic compounds)

[0123] In addition to water, Lewis basic compounds other than water can be used, or Lewis basic compounds other than water can be used without water. Lewis basic compounds typically function as polymerization catalysts for 1,1-dicyanoethylene or mixtures of the aforementioned monomers. Examples of Lewis basic compounds include alcohols and alkylamines.

[0124] Examples of alcohols include methanol, ethanol, and propanol.

[0125] Examples of alkylamines include tertiary amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, and N,N-dimethylisopropylamine.

[0126] (Other additives)

[0127] The cured product of this embodiment may contain at least one additive selected from the group consisting of thickeners (e.g., organic thickeners, inorganic thickeners such as silica), dehydrating agents (e.g., carboxylic anhydrides such as acetic anhydride, cyclic sulfonates such as propanesulfonate lactone, phosphoric anhydrides such as phosphorus pentoxide), free radical polymerization inhibitors (e.g., phenolic compounds, quinone compounds, free radical stabilizing compounds, metal salts), plasticizers (e.g., ester compounds such as phthalates and adipates), rubbers (e.g., natural rubber, styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, acrylic rubber, nitrile rubber, hydrogenated nitrile rubber, etc.), pigments, and fillers (e.g., inorganic fillers, organic fillers). Specific examples of organic thickeners include polymers such as ethylene-vinyl acetate copolymer, methyl methacrylate resin, polystyrene resin, (modified) cellulose resin, and acrylonitrile resin. Specific examples of phenolic compounds include BHT (butylated hydroxytoluene). Specific examples of quinone compounds include hydroquinone. Specific examples of stabilizing free radical compounds include DPPH (2,2-diphenyl-1-picrylhydrazine) and TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy). Inorganic thickeners can also function as inorganic fillers. The aforementioned phenolic compounds are excluded from the list of free radical polymerization inhibitors. Rubber can also function as an organic filler. Furthermore, to improve bonding speed, curing accelerators such as polyethylene glycol derivatives, crown ethers, and calixarenes can be added. Moreover, depending on the purpose, fillers, elastomers, thixotropic agents, adhesion promoters, crosslinking agents, and fragrances can also be added.

[0128] (Method for manufacturing solidified products)

[0129] There are no particular limitations on the method for manufacturing the cured product. For example, the cured product can be obtained by mixing the above-mentioned monomer mixture with a Lewis basic compound at room temperature (23°C).

[0130] The amount of Lewis basic compound is not particularly limited, but is preferably 0.001 to 1.0 parts by mass relative to 100 parts by mass of the monomer mixture described above, and more preferably 0.01 to 0.5 parts by mass. When the content of Lewis basic compound is within the above range, the monomer mixture reacts rapidly.

[0131] (use)

[0132] The cured product in this embodiment can be a cured product of (instant) adhesive. The application of the adhesive is as described above.

[0133] The cured product in this embodiment can be a coating material. The uses of the coating material are as described above.

[0134] [Layered Body]

[0135] The laminate of embodiments of the present invention comprises a cured product obtained by reacting the above-described composition containing 1,1-dicyanoethylene and an adherend bonded to the cured product. The laminate of embodiments of the present invention may be a laminate comprising the cured product of the above-described embodiments and an adherend bonded to the cured product. The laminate structure is not particularly limited; the cured product may be formed on one adherend or may be present between two adherends. By presenting the cured product between two adherends, the adherends can be firmly bonded to each other.

[0136] The substrate used in the laminate of the present invention is not particularly limited, and examples include synthetic resins, metals, ceramics, and fabrics.

[0137] Examples of synthetic resins include polyethylene, polypropylene, copolymers of ethylene with one or more α-olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, etc.), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and other polyolefin resins, polyurethane resins, polyamide resins, polyester resins, as well as polycarbonate resins, vinyl chloride resins, acrylonitrile-butadiene-styrene rubber, natural rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, etc.

[0138] As metals, examples include stainless steel plates, cold-rolled steel plates, alloyed galvanized steel plates, copper, aluminum, magnesium alloys, etc.

[0139] There is no particular limitation on the thickness of the adherends constituting the laminate. On the other hand, from the viewpoint of firmly bonding the adherends to each other, the thickness of the layer containing the cured material 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.

[0140] There are no particular limitations on the manufacturing method of the laminate, but it is preferred to manufacture it by the manufacturing method of the present invention, which includes an bonding step of bonding the first substrate and the second substrate via the above-mentioned cured material.

[0141] There are no particular limitations on the method of bonding the first and second adherends with the composition containing 1,1-dicyanoethylene described above. For example, they can be bonded by applying the composition containing 1,1-dicyanoethylene described above to one adherend and then overlapping the other adherend on it and allowing it to cure.

[0142] There are no particular limitations on the method of coating the above-mentioned composition containing 1,1-dicyanoethylene onto the substrate, and examples include spin coating, spray coating, bar coating, knife coating, roller coating, roller-blade coating, blade coating, mold coating, and gravure coating.

[0143] The above-mentioned composition containing 1,1-dicyanoethylene does not have particular limitations on the coating amount of the substrate, but is preferably 0.01 to 3.0 μL / mm. 2 More preferably, it is 0.05–2.5 μL / mm 2 More preferably, it is 0.1–2.0 μL / mm 2 When the coating amount is above the lower limit mentioned above, the adhered objects can be firmly bonded to each other. On the other hand, when the coating amount is below the upper limit mentioned above, the two objects can be bonded with an appropriate amount.

[0144] Example

[0145] The present invention will be described in detail below by way of examples, but the present invention is not limited to these examples.

[0146] [Compositions containing 1,1-dicyanoethylene]

[0147] [Element]

[0148] The ingredients used in the examples and comparative examples are described below.

[0149] <1,1-Dicyanoethylene>

[0150] 1,1-Dicyanoethylene: 1,1-Dicyanoethylene (99% purity) manufactured according to the following manufacturing example 1.

[0151] (Example 1: Manufacturing of 1,1-dicyanoethylene)

[0152] 1,1-Dicyanoethylene is manufactured as described below.

[0153] 1,1,3,3-Tetracyanopropane was synthesized from malononitrile in 73% yield using the method described in J. Am. Chem. Soc., 1989, 111, 9078-9081. The resulting crystalline 1,1,3,3-tetracyanopropane was mixed with phosphorus pentoxide and then heated at 180°C to decompose it, thereby yielding crude 1,1-dicyanoethylene (60% yield).

[0154] The crude product was purified by vacuum distillation (480 Pa) to obtain 1,1-dicyanoethylene with a purity of 99%.

[0155] <Water>

[0156] Water: Ion-exchanged water

[0157] <Acidic Compound (A)>

[0158] • (A1): Mesylate (manufactured by Tokyo Chemical Industry Co., Ltd. (purity >99.0%)) (pKa = -2.6)

[0159] • (A2): Sulfuric acid (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd. (purity: 96-98%)) (pKa=-3.0)

[0160] • (A3): Acetic acid (manufactured by Kanto Chemical Co., Ltd. (purity >99.0%)) (pKa=4.8)

[0161] • (A4): Trifluoroacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd. (purity >99.0%)) (pKa = -0.25)

[0162] • (A5): p-Toluenesulfonic acid (p-Toluenesulfonic acid monohydrate) (manufactured by Tokyo Chemical Industry Co., Ltd. (purity >98.0%)) (pKa = -2.8)

[0163] <polymerizable monomers>

[0164] • Ethyl (B1)-2-cyanoacrylate (manufactured by Sigma-Aldrich (purity >99.9%))

[0165] • (B2) Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd. (purity >99.8%))

[0166] • (B3) Styrene (manufactured by Tokyo Chemical Industry Co., Ltd. (purity >99.0%))

[0167] • (B4) Vinyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd. (purity >99.0%))

[0168] [Evaluation Method]

[0169] The liquid compositions containing 1,1-dicyanoethylene obtained in the Examples and Comparative Examples were evaluated as samples as described below.

[0170] <Maintaining Stability>

[0171] (Preservation test)

[0172] Place 1 mL of sample into a 10 mL high-density polyethylene container and seal it tightly. Mark the corresponding position of the sample liquid level on the side of the container. Prepare three containers in this manner. Visually observe the state of the sample in each container before the preservation test begins. Then, in an environment with 50% humidity, incubate the three containers at 70°C for 6 hours, 24 hours, and 48 hours respectively. This completes the preservation test.

[0173] (observe)

[0174] Then, invert each container and visually observe the state of the sample inside the container 5 seconds after the inversion is completed.

[0175] The observation results are divided into the following three levels of scoring.

[0176] Rating "1": More than 90% of the sample volume in the container exceeds the mark when viewed from the side. This means that the sample maintained adequate fluidity as it did just before the preservation test began (0 minutes).

[0177] Rating "2": More than 10% by volume of the sample in the container exceeds the mark when viewed from the side, but more than 90% by volume does not exceed the mark when viewed from the side. This means that the flowability of the sample has decreased (thickening) compared to when the preservation test was about to begin (0 minutes).

[0178] Rating "3": The sample volume exceeding the mark when viewed from the side is less than 10% of the sample in the container. This means that the polymerization of 1,1-dicyanoethylene has occurred and the sample has been cured.

[0179] (evaluate)

[0180] Next, based on three observations after the 70°C preservation test of samples in three containers, the following criteria were used for evaluation.

[0181] "A": The total score is 3.

[0182] "B": The total score is 4 to 7.

[0183] "C": The total score is 8 to 9.

[0184] <Coloring properties>

[0185] (observe)

[0186] Visually observe the color of the samples in the containers used in the preservation test at 70°C for 48 hours. The observed sample colors are categorized into four levels: "transparent," "pale yellow," "yellow," and "yellowish-brown." It should be noted that "yellow" refers to a color more intense than "pale yellow" and lighter than "yellowish-brown."

[0187] (evaluate)

[0188] Next, based on the observations, an evaluation was conducted according to the following criteria.

[0189] “A”: means “transparent”.

[0190] "B": means "pale yellow".

[0191] “C”: means “yellow”.

[0192] “D”: means “yellowish-brown”.

[0193] <Comprehensive Evaluation of Preservation Stability and Colorfastness>

[0194] Based on the above evaluation results for <preservation stability> and <colorability>, a comprehensive evaluation is conducted according to the following criteria.

[0195] "A": The evaluation result for preservation stability is "A" or "B", and the evaluation result for colorimetry is "A".

[0196] "B": The evaluation result for preservation stability is "A" or "B", and the evaluation result for colorimetry is "B" or "C".

[0197] "C": The evaluation result for preservation stability is "C", or the evaluation result for colorimetry is "D".

[0198] (Molar concentration C of acidic compound (A) in the composition) a (quantitative)

[0199] For the acidic compound (A) used in the examples and comparative examples, the molar concentration was quantified by ion chromatography (IC) according to the following method. It should be noted that, regarding this method, even if two acidic compounds (A) are present, quantification can be performed using the same method.

[0200] First, 0.1 g of the composition containing 1,1-dicyanoethylene was added to 99.9 g of ion chromatography eluent (a mixed aqueous solution of 0.6 mmol / L sodium carbonate and 12 mmol / L sodium bicarbonate) to obtain a solution.

[0201] The resulting solution was stirred for one day. Then, it was filtered through a 0.22 μm PTFE filter. This yielded the test sample solution.

[0202] For the determination of the sample solution, the following ion chromatography apparatus was used, and the determination was performed under the following conditions.

[0203] The molar concentration of acidic compound (A) in a composition containing 1,1-dicyanoethylene was quantified using a standard curve prepared using acidic compound (A).

[0204] (Ion chromatography apparatus and determination conditions)

[0205] Equipment Name: Shimadzu Corporation Liquid Chromatograph / 10A Series

[0206] Column: Shim-pack IC-SA2 (inner diameter 4.0mm, length 250mm)

[0207] Measurement temperature: 40℃

[0208] Rinse solution: The above-mentioned rinse solution

[0209] <Example 1>

[0210] Under nitrogen atmosphere, 0.00010 parts by mass of sulfuric acid ((A2) component) was mixed with 100g of 1,1-dicyanoethylene (which is equivalent to 100 parts by mass) manufactured in Manufacturing Example 1 to prepare a composition X1 containing 1,1-dicyanoethylene.

[0211] The water content of the prepared composition X1 containing 1,1-dicyanoethylene was determined to be 0.055 mmol / L by the water determination method according to JIS K0068:2001, specifically by the coulometric titration of Karl Fischer titration.

[0212] The molar concentration of component (A2) in the composition containing 1,1-dicyanoethylene was quantified by the above method (IC method), and the result was 0.010 mmol / L.

[0213] The prepared composition containing 1,1-dicyanoethylene was sealed in a high-density polyethylene container and stored in an environment with a moisture concentration of 0.3 ppm.

[0214] The above-mentioned storage stability and colorability, as well as the overall evaluation, were performed using the stored composition X1 containing 1,1-dicyanoethylene. The results are shown in Table 1.

[0215] <Example 2>

[0216] Under nitrogen atmosphere, 0.10 parts by mass of methanesulfonic acid ((A1) component) was mixed with 100g of 1,1-dicyanoethylene (which is equivalent to 100 parts by mass) manufactured in Manufacturing Example 1 to prepare a first composition containing 1,1-dicyanoethylene. For the first composition containing 1,1-dicyanoethylene, the water content and the molar concentration of the (A1) component were determined by the same method as in Example 1.

[0217] Next, deionized water was mixed into the first composition containing 1,1-dicyanoethylene to obtain a second composition 2 containing 1,1-dicyanoethylene. As a result, the water content (parts by mass and molar concentration) and the molar concentration of the (Al) component of the second composition containing 1,1-dicyanoethylene are shown in Table 1.

[0218] The prepared second composition X2 containing 1,1-dicyanoethylene was sealed in a high-density polyethylene container and stored in an environment with a moisture concentration of 0.3 ppm.

[0219] The storage stability and colorability of the second composition X2 containing 1,1-dicyanoethylene were evaluated in the same manner as in Example 1, as well as the overall evaluation. The results are shown in Table 1.

[0220] <Examples 3, Examples 5-11, Examples 14-15, Comparative Examples 1-6>

[0221] The second compositions containing 1,1-dicyanoethylene, X3, X5-X11, X14, X15 and Y1-Y6, were prepared in the same proportions as shown in Tables 1 and 2, as in Example 2. The prepared second compositions containing 1,1-dicyanoethylene, X3, X5-X11, X14-X15 and Y1-Y6, were stored in the same manner as in Example 2.

[0222] Using the second compositions containing 1,1-dicyanoethylene, X3, X5-X11, X14-X15 and Y1-Y6, the storage stability and colorability were evaluated, as well as the overall evaluation, in the same manner as in Example 2. The results are shown in Tables 1 and 2.

[0223] <Examples 4, 12, 13>

[0224] Compositions X4, X12, and X13 containing 1,1-dicyanoethylene were prepared in the same proportions as shown in Tables 1 and 2, as in Example 1. The prepared compositions containing 1,1-dicyanoethylene were stored in the same manner as in Example 1.

[0225] Compositions X4, X12, and X13 containing 1,1-dicyanoethylene were used in storage, and their storage stability, colorability, and overall performance were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[0226] <Example 16>

[0227] Under nitrogen atmosphere, p-toluenesulfonic acid monohydrate was mixed with 100g of 1,1-dicyanoethylene (which is equivalent to 100 parts by mass) manufactured in Manufacturing Example 1 in such a way that the p-toluenesulfonic acid component (A4) was 0.001 parts by mass, thereby preparing a first composition containing 1,1-dicyanoethylene. For the first composition containing 1,1-dicyanoethylene, the water content and the molar concentration of the (A4) component were determined by the same method as in Example 1.

[0228] Next, deionized water was mixed into the first composition containing 1,1-dicyanoethylene to obtain a second composition X16 containing 1,1-dicyanoethylene. As a result, the water content (parts by mass and molar concentration) and the molar concentration of component (A4) of the second composition containing 1,1-dicyanoethylene are shown in Table 2.

[0229] The prepared second composition X16 containing 1,1-dicyanoethylene was sealed in a high-density polyethylene container and stored in an environment with a moisture concentration of 0.3 ppm.

[0230] The storage stability and colorability of the second composition X16 containing 1,1-dicyanoethylene were evaluated, as well as the overall evaluation, in the same manner as in Example 1. The results are shown in Table 2.

[0231] <Example 17, Comparative Example 7>

[0232] Compositions X17 and Y7 containing 1,1-dicyanoethylene were prepared in the same proportions as shown in Table 2, as in Example 12. The prepared compositions X17 and Y7 containing 1,1-dicyanoethylene were stored in the same manner as in Example 1.

[0233] Using stored compositions X17 and Y7 containing 1,1-dicyanoethylene, the storage stability and colorability, as well as the overall evaluation, were performed in the same manner as in Example 1. The results are shown in Table 2.

[0234] <Examples 18-35, Comparative Examples 8-19>

[0235] The second compositions X18-35 and Y8-19 containing 1,1-dicyanoethylene were prepared in the same proportions as shown in Tables 3 and 4, as in Example 2. The prepared second compositions X18-35 and Y8-19 containing 1,1-dicyanoethylene were stored in the same manner as in Example 2.

[0236] Using the second compositions containing 1,1-dicyanoethylene, X18–35 and Y8–19, the storage stability and colorability, as well as the overall evaluation, were performed in the same manner as in Example 2. The results are shown in Tables 3 and 4.

[0237] <Refer to Examples 1-4>

[0238] The second compositions Z1 to Z4 containing ethyl 2-cyanoacrylate were prepared in the same manner as in Example 2, with the proportions shown in Table 5. The prepared second ethyl 2-cyanoacrylate compositions Z1 to Z4 were stored in the same manner as in Example 2.

[0239] The storage stability and colorability of the second compositions Z1 to Z4 containing ethyl 2-cyanoacrylate were evaluated, as well as the overall evaluation, in the same manner as in Example 2. The results are shown in Table 5.

[0240]

[0241] As shown in Tables 1 and 2, the compositions containing 1,1-dicyanoethylene in Examples 1 to 17 exhibit superior storage stability compared to the compositions containing 1,1-dicyanoethylene in Comparative Examples 1 to 7. Furthermore, as shown in Comparative Examples 3, 4, 5, and 6, it is difficult to obtain compositions containing 1,1-dicyanoethylene with excellent storage stability when α exceeds 0. Additionally, it is observed that when the molar concentration of the acidic compound relative to the molar concentration of water is high, as in Examples 10, 13, and 14, the evaluation of colorability tends to be slightly worse compared to Examples 1 to 9.

[0242] As shown in Tables 3 and 4, compared with the compositions containing 1,1-dicyanoethylene in Comparative Examples 8-19, the compositions containing 1,1-dicyanoethylene in Examples 18-35 also exhibited excellent storage stability and colorability even when containing the polymerizable monomer (B). Furthermore, compared with compositions containing 1,1-dicyanoethylene such as Comparative Examples 1-3 and Example 10, the compositions not containing 1,1-dicyanoethylene, as shown in Reference Examples 1-4 (Table 5), exhibited superior storage stability and colorability, indicating that this is a characteristic property of compositions containing 1,1-dicyanoethylene.

[0243] [Layered Body]

[0244] [Object to be glued]

[0245] • Steel plate (manufactured by Standard Test Piece Co., Ltd., 25mm in length, 100mm in width, 1.6mm in thickness)

[0246] • Aluminum sheet (manufactured by Standard Test Piece Co., Ltd., 25mm in length, 100mm in width, 1.6mm in thickness)

[0247] • Polyvinyl chloride (PVC) sheet (manufactured by Nippon Testpanel Co., Ltd., 25mm long, 100mm wide, 2.0mm thick)

[0248] [Determination Method]

[0249] Using the laminates obtained in the examples and comparative examples as samples, the tensile shear bond strength was determined as follows.

[0250] <Evaluation of Tensile Shear Bond Strength>

[0251] The tensile shear bond strength of the laminate was determined at 25°C and 25%RH using a Model 5969 universal testing machine (manufactured by Instron) at a tensile speed of 20 mm / min.

[0252] <Examples 36-44, Comparative Examples 20-22>

[0253] Within a 12.5 mm × 25 mm area of ​​the substrate (1) shown in Table 6, 100 μL of the composition containing 1,1-dicyanoethylene shown in Table 6 is applied, and the substrate (2) shown in Table 6 is overlapped on this coated surface. Then, the substrate (1) and (2) are left to stand for one day at room temperature of 23°C and humidity of 50% to cure the composition containing 1,1-dicyanoethylene, thereby bonding the substrates (1) and (2) together to obtain a laminate.

[0254] The tensile shear bond strength of the resulting laminate was determined. The results are shown in Table 6.

[0255]

[0256] As shown in Table 6, the tensile shear bond strength of the laminates obtained by curing the compositions containing 1,1-dicyanoethylene in Comparative Examples 20-22 is superior compared to that obtained by curing the compositions containing 1,1-dicyanoethylene in Examples 36-44.

[0257] Furthermore, it is understood that, according to this embodiment, a composition containing 1,1-dicyanoethylene with excellent storage stability and a method for manufacturing the same can be provided. Therefore, for the cured products and laminates thereof, it is also expected that the reduction in physical properties caused by the impaired storage stability of the composition containing 1,1-dicyanoethylene can be suppressed.

Claims

1. A composition containing 1,1-dicyanoethylene, comprising 1,1-dicyanoethylene, water, and an acidic compound (A), wherein, The content of the acidic compound (A) in the composition and the content of the water satisfy the following relationship (Ia). -4.00≤α≤0 …(Ia) In the relation (Ia), α is represented by the following equation (Ib), α=pKa+Log(C H2O / C a ) …(Ib) In the aforementioned formula (Ib), pKa is the logarithmic acid dissociation constant of the acidic compound (A). C H2O The molar concentration of water in the composition. C a The molar concentration of the acidic compound (A) in the composition.

2. The composition containing 1,1-dicyanoethylene according to claim 1, wherein, The acidic compound (A) is selected from acidic compounds with a logarithmic acid dissociation constant pKa of -1.7 or less.

3. The composition containing 1,1-dicyanoethylene according to claim 1, wherein, The acidic compound (A) is selected from at least one of methanesulfonic acid, sulfuric acid, p-toluenesulfonic acid and hydrochloric acid.

4. The composition containing 1,1-dicyanoethylene according to claim 1, further comprising a polymerizable monomer (B).

5. The composition containing 1,1-dicyanoethylene according to claim 4, wherein, The polymerizable monomer (B) is selected from one or more of the group consisting of ethylene, propylene, butadiene, isobutylene, isoprene, 1-hexene, 1-octene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylidene fluoride, alkyl 2-cyanoacrylate, alkyl 2-cyanoprene acid, and dialkyl methylene malonate.

6. The composition containing 1,1-dicyanoethylene according to claim 5, wherein, The polymerizable monomer (B) comprises an alkyl 2-cyanoacrylate.

7. The composition containing 1,1-dicyanoethylene according to claim 6, wherein, The alkyl 2-cyanoacrylate is ethyl 2-cyanoacrylate.

8. The composition containing 1,1-dicyanoethylene according to claim 1, wherein, The molar concentration of the acidic compound (A) in the composition is less than 1000 mmol / L.

9. A cured product obtained by reacting the composition containing 1,1-dicyanoethylene as described in claims 1 to 8.

10. A laminate comprising a cured product obtained by reacting the composition containing 1,1-dicyanoethylene as described in any one of claims 1 to 8, and an adherend bonded to the cured product.

11. A method for manufacturing a composition containing 1,1-dicyanoethylene, wherein, The process includes a step of combining an acidic compound (A) in such a way that the content of said acidic compound (A) in the composition satisfies the following relationship (Ia) with the content of water in the composition. -4.00≤α≤0 …(Ia) In the relation (Ia), α is represented by the following equation (Ib), α=pKa+Log(C H2O / C a ) …(Ib) In the aforementioned formula (Ib), pKa is the logarithmic acid dissociation constant of the acidic compound (A). C H2O The molar concentration of water in the composition. C a The molar concentration of the acidic compound (A) in the composition.

Images