CURABLE COMPOSITION, TWO-PART CURABLE COMPOSITION SET, AND METHOD FOR PRODUCING BONDED ARTICLE

Abstract

A curable composition which contains a methylene malonate compound, a Lewis acidic compound and a photobase generator. A compound represented by formula (1) or formula (2) is preferable as the methylene malonate compound. In formula (1) and formula (2), each of X1 to X4 independently represents O, NR or C(R)2; each R independently represents a hydrogen atom, an alkyl group or an aryl group; each of R1 and R2 independently represents an alkyl group or an aryl group; and R3 represents an alkylene group, an arylene group or a group wherein two or more of these groups are combined.

Description

[Technical field]

[0001] The present invention relates to a curable composition, a two-component curable composition set, and a method for producing an adhesive article. [Background technology]

[0002] Curable compositions are widely used as adhesives, coating agents, sealants, excipients, etc. Polymerization reactions using curable compositions are classified into three types, radical polymerization, cationic polymerization, and anionic polymerization, depending on the active species generated during polymerization.

[0003] Known anionically polymerizable monomers include cyanoacrylate compounds such as 2-ethyl cyanoacrylate, and methylene malonate compounds such as diethyl methylene malonate.

[0004] Cyanoacrylate compounds are known to polymerize rapidly in weak bases such as water. On the other hand, Non-Patent Document 1 predicts that dialkyl methylene malonate compounds, unlike cyanoacrylate compounds, do not exhibit anionic polymerizability in a weak base such as water, and the inventors' investigations also showed that methylene malonate compounds do not exhibit anionic polymerizability in a weak base such as water.

[0005] Non-Patent Document 2 shows the results of thermogravimetric analysis of 2-ethyl cyanoacrylate homopolymer and diethyl methylene malonate homopolymer. It has been reported that 2-ethyl cyanoacrylate homopolymer loses weight due to decomposition at temperatures below 200°C, whereas diethyl methylene malonate homopolymer hardly loses weight even at 250°C, and has excellent heat resistance. Therefore, if the curing property of methylene malonate compounds can be improved, they are expected to be applicable to various uses as materials with excellent heat resistance. Patent Document 1 discloses a method for curing 1,1-dialkoxycarbonylethylenes (methylene malonates), and a curing method using a specific basic compound as an activator for the compound is investigated.

[0006] Furthermore, the application of anionically polymerizable monomers to photocurable compositions has also been investigated. In the above-mentioned Patent Document 1, ultraviolet curing of a composition containing a methylene malonate compound and a photopolymerization initiator using an acylphosphine oxide and a metallocene in combination is considered. However, it is described that the methylene malonate compound alone does not cure with ultraviolet light, but cures with ultraviolet light when used in combination with a cyanoacrylate compound. Patent Document 2 describes an ion-pair type photobase generator consisting of a compound having a substituent with a cationized amidine skeleton and an anion, and examines the photocuring of a methylene malonate compound. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] J.Am.Chem.Soc.,vol.117,pp3605-3610,1995 [Non-Patent Document 2] Polymer,vol.39,No.1,pp173-181,1998. [Patent documents]

[0008] [Patent Document 1] Special Publication No. 2015-512460 [Patent Document 2] JP 2017-036361 A Summary of the Invention [Problem to be solved by the invention]

[0009] Meanwhile, in the technical fields of adhesives, sealants, and the like, a so-called dual curing type composition has been studied in which, after a substrate is laminated with a curing type composition, the light-transmitting portion is cured by light such as ultraviolet light, and the light-non-transmitting portion (dark portion) is cured by a different curing mechanism. When a methylene malonate compound, which is an anionically polymerizable monomer, is applied to a dual curing type composition, as described above, its use as a photocurable composition is known, but the dialkyl methylene malonate compound is difficult to cure due to a weak base, and the activator described in Patent Document 1 may also have insufficient curing properties, resulting in insufficient dark curing properties.

[0010] An object of the present invention is to provide a curable composition which is light-curable and dark-curable, or a method for producing an adhesive article using the curable composition. Another problem to be solved by the present invention is to provide a two-component curable composition set that is light curable and dark curable, or a method for producing an adhesive article using the two-component curable composition set. [Means for solving the problem]

[0011] Means for solving the above problems include the following aspects. <1> A curable composition comprising a methylene malonate compound, a Lewis acidic compound, and a photobase generator. <2> The methylene malonate compound is a compound represented by the following formula (1) or (2): <1> The curable composition according to claim 1.

[0012] [ka]

[0013] In formula (1) and formula (2), X 1 ~X 4 each independently represents O, NR, or C(R), each R independently represents a hydrogen atom, an alkyl group, or an aryl group, R 1 and R 2each independently represents an alkyl group or an aryl group; R 3 represents an alkylene group, an arylene group, or a combination of two or more of these.

[0014] <3> The Lewis acidic compound includes a Lewis acidic compound having a metal cation. <1> or <2> The curable composition according to claim 1. <4> The Lewis acid compound is Fe 2+ , Cu 2+ , Zn 2+ , Ag + , Yb 3+ , and Ti 4+ A Lewis acidic compound having at least one metal cation selected from the group consisting of: <1> ~ <3> 13. The curable composition according to claim 12, <5> the Lewis acidic compound includes a Lewis acidic compound having at least one counter anion selected from the group consisting of a trifluoromethanesulfonate anion, a tert-butoxide anion, an acetylacetonate anion, a chloride ion, and a bromide ion; <1> ~ <4> 13. The curable composition according to claim 12, <6> The content of the Lewis acid compound is 0.001 parts by mass to 1.0 parts by mass with respect to 100 parts by mass of the methylene malonate compound. <1> ~ <5> 13. The curable composition according to claim 12, <7> X 1 ~X 4 are each independently O or NR; <1> ~ <6> 13. The curable composition according to claim 12, <8> X 1 ~X 4 is O, <1> ~ <7> 13. The curable composition according to claim 12, <9> R 1 and R 2 are each independently an alkyl group; <1> ~ <8> 13. The curable composition according to claim 12, <10> R 3 is an alkylene group; <1> ~ <9> 13. The curable composition according to claim 12, <11> Contains a compound represented by formula (1), <1> ~ <10> 13. The curable composition according to claim 12, <12> The photobase generator includes a compound that generates an amine compound by exposure to light. <1> ~ <11> 13. The curable composition according to claim 12, <13> <1> ~ <12> a step of applying the curable composition described in any one of the above to a surface of a first adherend, a step of bonding the surface of the first adherend to which the curable composition has been applied and a second adherend, and a step of irradiating light to the curable composition between the first adherend and the second adherend from the side of the adherend having optical transparency, wherein at least one of the first adherend and the second adherend is an optically transparent adherend. <14> A two-part curable composition set comprising: composition A containing a methylene malonate compound and a photobase generator; and composition B containing a Lewis acid compound.

[0015] <15> The methylene malonate compound is a compound represented by the following formula (1) or (2): <14> The two-component curable composition set according to claim 1.

[0016] [ka]

[0017] In formula (1) and formula (2), X 1 ~X 4 each independently represents O, NR, or C(R), each R independently represents a hydrogen atom, an alkyl group, or an aryl group, R 1 and R 2 each independently represents an alkyl group or an aryl group; R 3 represents an alkylene group, an arylene group, or a combination of two or more of these.

[0018] <16> A method for producing an adherend, comprising the steps of: applying composition B containing a Lewis acid compound to a surface of a first adherend; applying composition A containing a methylene malonate compound and a photobase generator to a surface of the first adherend or a surface of a second adherend; bonding the surface of the first adherend to which composition B has been applied and the surface of the second adherend to which composition A has been applied, or bonding the surface of the first adherend to which composition A and composition B have been applied and the surface of the second adherend; and irradiating light to the curable composition between the first adherend and the second adherend, wherein at least one of the first adherend and the second adherend is a light-transmitting adherend. <17> The methylene malonate compound is a compound represented by the following formula (1) or (2): <16> A method for producing the adhesive article according to claim 1.

[0019] [ka]

[0020] In formula (1) and formula (2), X 1 ~X 4 each independently represents O, NR, or C(R), each R independently represents a hydrogen atom, an alkyl group, or an aryl group, R 1 and R 2 each independently represents an alkyl group or an aryl group; R 3 represents an alkylene group, an arylene group, or a combination of two or more of these. Effect of the Invention

[0021] According to the present invention, it is possible to provide a curable composition which is photocurable and dark curable, or a method for producing an adhesive article using the curable composition. Furthermore, according to the present invention, it is possible to provide a two-component curable composition set which is light-curable and dark-curable, and a method for producing an adhesive article using the two-component curable composition set. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In the numerical ranges described in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in another stepwise manner. In addition, in the numerical ranges described in this specification, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present invention, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the present invention, the term "step" includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In the present invention, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Also, in the present invention, a combination of two or more preferred embodiments is a more preferred embodiment. In addition, in this specification, "(meth)acryloyl" refers to both or either of acryloyl and methacryloyl, and "(meth)acryloxy" refers to both or either of acryloxy and methacryloxy. Furthermore, in some of the compounds in this specification, the hydrocarbon chain may be represented by a simplified structural formula in which the symbols for carbon (C) and hydrogen (H) are omitted. In the present invention, "application" means performing an operation so that at least a portion of the curable composition comes into contact with the surface of the adherend, or performing an operation so that at least a portion of composition A and / or composition B comes into contact with the surface of the adherend. Specifically, the surface of the adherend may be partially or entirely covered with the curable composition, or with composition A and / or composition B, using coating, filling or other means. The present invention will be described in detail below.

[0023] (Curable composition) The curable composition of the present invention contains a methylene malonate compound, a Lewis acidic compound, and a photobase generator.

[0024] For example, conventional curable compositions containing a methylene malonate compound have only been cured using a polymerization initiator or, as in the invention described in Patent Document 1, by mixing a basic compound with the composition immediately before curing. As a result of intensive research, the present inventors have found that a curable composition containing a methylene malonate compound, a Lewis acid compound, and a photobase generator can be cured by light and can also be cured by moisture in the air even in a dark area. Although the detailed reaction mechanism is unknown, it is presumed that the inclusion of a photobase generator enables photocuring by the base generated by light irradiation, and that the Lewis acid compound coordinates to the oxygen atoms of one or two carbonyl groups in the methylene malonate compound, thereby improving the anionic polymerization activity of the methylene malonate compound and making it possible to undergo anionic polymerization even with moisture in the air. In particular, it has not been known that a methylene malonate compound can be anionically polymerized by moisture in the air, and a curable composition that allows a methylene malonate compound to be photocurable and dark-curable has been discovered for the first time.

[0025] Furthermore, the curable composition of the present invention, having the above-mentioned constitution, can be cured both by light and in the dark, and therefore has excellent internal curability and thick-film curability.

[0026] The present invention will be described in detail below.

[0027] <Methylene malonate compounds> The curable composition of the present invention contains a methylene malonate compound. The methylene malonate compound is a compound having a -CO-C(=CH2)-CO- structure, as shown in the following formula (1) or formula (2). Among them, as the methylene malonate compound, from the viewpoints of reaction rate and storage stability, a compound represented by the following formula (1) or formula (2) is preferable, and a methylene malonate compound represented by the following formula (1) is more preferable.

[0028] [ka]

[0029] In formula (1) and formula (2), X 1 ~X 4 each independently represents O, NR, or C(R), each R independently represents a hydrogen atom, an alkyl group, or an aryl group, R 1 and R 2 each independently represents an alkyl group or an aryl group; R 3 represents an alkylene group, an arylene group, or a combination of two or more of these.

[0030] X in formula (1) and formula (2) 1 ~X 4 are each independently preferably O or NR, more preferably O or NH, and particularly preferably O, from the viewpoints of heat resistance, reaction rate, and storage stability. X in formula (1) 1 and X 2 are preferably the same group from the viewpoints of heat resistance, reaction rate, and storage stability. In addition, X in formula (2) 3 and X 4 are preferably the same group from the viewpoints of heat resistance, reaction rate, and storage stability. R in formula (1) and formula (2) is preferably each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (also referred to as "number of carbon atoms"), or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, further preferably a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. That is, NR is particularly preferably NH, and C(R)2 is particularly preferably CH2. R in formula (1) 1 and R 2 are each independently, from the viewpoints of heat resistance, reaction rate, and storage stability, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group or an ethyl group. Also, R in formula (1) 1 and R 2 is preferably an alkyl group from the viewpoints of heat resistance, reaction rate, and storage stability. Furthermore, R in formula (1) 1 and R 2 are preferably the same group from the viewpoints of heat resistance, reaction rate, and storage stability. R in Equation (2) 3 From the viewpoint of reaction rate, is preferably an alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, or a group having 7 to 20 carbon atoms in combination of one or more alkylene groups and one or more arylene groups, more preferably an alkylene group having 1 to 20 carbon atoms, still more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably a methylene group, an ethylene group, or a dimethylmethylene group. Also, R in formula (2) 3 From the viewpoint of reaction rate, is preferably an alkylene group.

[0031] The alkyl group or alkylene group of each group in formula (1) and formula (2) may be linear, branched, or have a ring structure, and may have a substituent. Examples of the substituent that the alkyl group or alkylene group may have include an aryl group, an alkoxy group, an alkoxycarbonyl group, and an acyl group. The aryl group or arylene group in each of the groups in formula (1) and formula (2) may have a substituent. Examples of the substituent that the aryl group or arylene group may have include an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, and an acyl group.

[0032] Preferred specific examples of the methylenemalonate compound represented by the formula (1) include dialkyl 2-methylenemalonates such as dimethyl 2-methylenemalonate, diethyl 2-methylenemalonate, dibutyl 2-methylenemalonate, 1-methyl-3-hexyl 2-methylenemalonate, and dicyclohexyl 2-methylenemalonate. Of these, diethyl 2-methylenemalonate is particularly preferred.

[0033] Preferred specific examples of the methylene malonate compound represented by the formula (2) include 5-methylene-1,3-dioxane-4,6-dione compounds such as 5-methylene-1,3-dioxane-4,6-dione and 2,2-dimethyl-5-methylene-1,3-dioxane-4,6-dione.

[0034] The curable composition of the present invention may contain one type of methylene malonate compound alone, or may contain two or more types. The content of the methylene malonate compound in the curable composition of the present invention is preferably 10 mass% to 99.9 mass%, more preferably 30 mass% to 99.5 mass%, further preferably 50 mass% to 99.5 mass%, and particularly preferably 90 mass% to 99 mass%, based on the total solid content of the curable composition. In this specification, the term "total solid content" refers to the total mass of the components excluding the solvent from the entire composition of the composition. As described above, the term "solid content" refers to the components excluding the solvent, and may be, for example, solid or liquid at 25°C.

[0035] <Lewis acid compounds> The curable composition of the present invention contains a Lewis acidic compound. The Lewis acid compound used in the present invention is preferably a Lewis acid compound capable of acting, for example, as a coordinate with a methylene malonate compound. From the viewpoints of curing speed and storage stability, the Lewis acid compound preferably contains a Lewis acid compound having a metal cation, more preferably contains a Lewis acid compound having a monovalent to tetravalent metal cation, and particularly preferably contains a Lewis acid compound having a monovalent to trivalent metal cation. As the metal cation, from the viewpoints of curing speed and storage stability, metal cations of Groups 3 to 12 are preferred, and Fe 2+ , Cu 2+ , Zn 2+ , Ag + , Yb 3+ , Ti 4+ , Zr 4+ , Hf 4+ , In 3+ , Au + , Sn 4+ ,Cd 2+ , Ni 2+ , Mn 2+ , Co 2+ , Cr 2+ , Ga 2+ More preferably, the metal cation is at least one selected from the group consisting of Fe 2+ , Cu 2+ , Zn 2+ , Ag + , Yb 3+ , and Ti 4+ It is particularly preferred that the metal cation is at least one selected from the group consisting of Cu 2+ , Zn 2+ , and Ag +It is most preferable that the metal cation is at least one selected from the group consisting of:

[0036] From the viewpoints of curing speed and storage stability, the Lewis acid compound is preferably a salt of a metal cation and a counter anion. From the viewpoints of curing speed and storage stability, the Lewis acidic compound preferably contains a Lewis acidic compound having at least one counter anion selected from the group consisting of a sulfonate ion, a hypochlorite ion, a 1,3-diketonate anion, an alkoxide anion, and a halide ion, more preferably contains a Lewis acidic compound having at least one counter anion selected from the group consisting of a trifluoromethanesulfonate anion, a methanesulfonate anion, a tosylate anion, a benzenesulfonate anion, a hypochlorite anion, a tert-butoxide anion, an acetylacetonate anion, a chloride ion, and a bromide ion, further preferably contains a Lewis acidic compound having at least one counter anion selected from the group consisting of a trifluoromethanesulfonate anion, a methanesulfonate anion, a tert-butoxide anion, an acetylacetonate anion, a chloride ion, and a bromide ion, and particularly preferably contains a Lewis acidic compound having a trifluoromethanesulfonate anion.

[0037] Specific preferred examples of the Lewis acid compound include copper(II) trifluoromethanesulfonate, zinc(II) trifluoromethanesulfonate, silver(I) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, titanium(IV) butoxide, titanium(IV) tert-butoxide, copper(II) chloride, copper(II) bromide, zinc(II) chloride, and zinc(II) bromide. Among these, from the viewpoints of curing speed and storage stability, copper(II) trifluoromethanesulfonate, zinc(II) trifluoromethanesulfonate, silver(I) trifluoromethanesulfonate, or ytterbium(III) trifluoromethanesulfonate are more preferred, and copper(II) trifluoromethanesulfonate, zinc(II) trifluoromethanesulfonate, or silver(I) trifluoromethanesulfonate are particularly preferred.

[0038] The curable composition of the present invention may contain one type of Lewis acid compound alone, or may contain two or more types of Lewis acid compounds. The content of the Lewis acid compound in the curable composition of the present invention is preferably 0.001 to 1.0 part by mass, more preferably 0.001 to 0.5 parts by mass, and particularly preferably 0.001 to 0.1 parts by mass, relative to 100 parts by mass of the methylene malonate compound.

[0039] <Photobase Generator> The curable composition of the present invention contains a photobase generator. The photobase generator used in the present invention is not particularly limited, but is preferably a photobase generator that generates a Brønsted base when exposed to light, more preferably a photobase generator that generates an organic base when exposed to light, and particularly preferably a photobase generator that generates an amine compound when exposed to light. In the present invention, the term "light" refers to electromagnetic waves or radiation that can impart energy to generate an anionic polymerization initiating species (base) from a photobase generator in a curable composition by irradiation, and includes α-rays, γ-rays, X-rays, ultraviolet rays, visible light, infrared rays, and the like.

[0040] Examples of photobase generators include compounds that generate a base when exposed to light, such as compounds having a carbamate group (urethane bond), compounds having an acyloxyimino group, anion-cation complexes, and compounds having a carbamoyloxyimino group. Further, examples of the photobase generator include those described in JP2015-087612A, JP2008-247747A, WO2010 / 064631A, WO2009 / 122664A, JP2015-28540A, JP2013-80206A, JP2008-208342A, and the like.

[0041] In addition, commercially available photobase generators are not particularly limited, but Fujifilm Wako Pure Chemical Industries' WPBG series "WPBG-082", "WPBG-167", "WPBG-168", "WPBG-018", "WPBG-027", "WPBG-140", etc. can also be used.

[0042] As described above, the photobase generator is preferably a photobase generator that generates an amine compound by light. Among them, from the viewpoints of photocurability, photocuring speed, and thick film curability, it is preferable to include a compound represented by the following formula (Pb1): When the compound represented by the following formula (Pb1) is irradiated with light, the aldehyde group and the carbonyl group of the amide group form a lactone ring, and the structure containing the nitrogen atom of the amide group becomes an amino group, producing an amine compound (base).

[0043] [ka]

[0044] In formula (Pb1), ring X represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent; R b1 and R b2 each independently represents a hydrogen atom or an alkyl group, and R b1 and R b2 may be bonded to each other to form a ring.

[0045] The ring X in the formula (Pb1) is preferably an aromatic ring which may have a substituent. The aromatic ring in ring X may be a single ring or an aromatic ring in which two or more rings are condensed. Specific examples include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Among these, a benzene ring is preferable. The heteroaromatic ring in ring X may be a single ring or a heteroaromatic ring having two or more condensed rings containing at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, specifically, for example, a thiophene ring, a furan ring, a pyrrole ring, a pyridine ring, a pyrazine ring, etc. The aromatic ring or the heteroaromatic ring in the ring X may have a substituent. Examples of the substituent include an alkyl group (e.g., an alkyl group having 1 to 6 carbon atoms). The aromatic ring or the heteroaromatic ring may be substituted with 1 to 3 groups selected from the group consisting of these substituents.

[0046] R in formula (Pb1) b1 and R b2 are each independently an alkyl group, or R b1 and R b2 and preferably bond to each other to form a ring. Also, R b1 and R b2 are the same group, or R b1 and R b2 and preferably bond to each other to form a ring. The alkyl group may be a linear or branched alkyl group, preferably an alkyl group having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Of these, alkyl groups having 1 to 10 carbon atoms are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, alkyl groups having 1 to 3 carbon atoms are even more preferred, and a methyl group or an ethyl group is particularly preferred. In addition, R in formula (Pb1) b1 and R b2R may be bonded to each other to form a ring. b1 and R b2 The ring formed by these rings may be a single ring or a ring in which two or more rings are condensed. Examples of the ring include an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring, a morpholine ring, an imidazole ring, a pyrazole ring, and a 1,2,3,4-tetrahydroisoquinoline ring. Among these, a piperidine ring is preferable. Furthermore, R b1 and R b2 The ring formed by these groups may have a substituent. Examples of the substituent include an alkyl group (e.g., an alkyl group having 1 to 6 carbon atoms). The ring may be substituted with 1 to 6 groups selected from the group consisting of these substituents.

[0047] A preferred specific example of the compound represented by the formula (Pb1) is a compound in which the ring X is a benzene ring and R b1 and R b2 are each independently an alkyl group having 1 to 6 carbon atoms (more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group or an ethyl group), or b1 and R b2 and are bonded to each other to form a piperidine ring or a pyrrolidine ring.

[0048] The compound represented by formula (Pb1) may be a commercially available product, or may be produced by a known method, for example, according to or in accordance with the description in J. Chem. Soc., Perkin Trans. I, p. 344-348.

[0049] In addition to the compound represented by formula (Pb1), examples of the compound that generates an amine compound when exposed to light include carbamate compounds. Specific examples of carbamate compounds include 9-anthrylmethyl N,N-diethylcarbamate.

[0050] The curable composition of the present invention may contain one type of photobase generator alone, or may contain two or more types. The content of the photobase generator in the curable composition of the present invention is preferably 0.01 mass % to 30 mass %, more preferably 0.1 mass % to 15 mass %, even more preferably 0.2 mass % to 10 mass %, and particularly preferably 0.5 mass % to 5 mass %, relative to the total solid content of the curable composition.

[0051] <Polymerization inhibitor> From the viewpoint of storage stability, the curable composition of the present invention preferably contains a polymerization inhibitor, and more preferably contains a radical polymerization inhibitor. From the viewpoint of storage stability, the polymerization inhibitor preferably contains a phenol radical polymerization inhibitor.The phenol radical polymerization inhibitor is preferably at least one selected from the group consisting of hydroquinone, mequinol, butyl hydroxyanisole, di-tert-butyl hydroxytoluene, methyl hydroquinone, methoxy hydroquinone, 2,6-dimethyl hydroquinone, 2,6-di-tert-butyl hydroquinone, 4-tert-butyl catechol, tert-butyl hydroquinone, 6-tert-butyl-4-xylenol, 2,6-di-tert-butylphenol and 1,2,4-trihydroxybenzene, and is particularly preferably at least one selected from the group consisting of hydroquinone, methyl hydroquinone, methoxy hydroquinone, 2,6-dimethyl hydroquinone and 2,6-di-tert-butyl hydroquinone, which are radical polymerization inhibitors having a hydroquinone structure.

[0052] Preferred examples of the polymerization inhibitor include anionic polymerization inhibitors such as diphosphorus pentoxide, SO2, p-toluenesulfonic acid, methanesulfonic acid, propane sultone, and BF3 complexes. From the viewpoint of storage stability, it is also preferable to use, as the polymerization inhibitor, a radical polymerization inhibitor having a hydroquinone structure and an anionic polymerization inhibitor in combination.

[0053] From the viewpoint of storage stability, the polymerization inhibitor preferably contains a polymerization inhibitor having a phenolic hydroxy group, more preferably a compound represented by the following formula (In1), and particularly preferably a compound represented by the following formula (In2). From the viewpoint of storage stability, it is particularly preferable to use, as the polymerization inhibitor, a radical polymerization inhibitor having a hydroquinone structure, an anionic polymerization inhibitor, and a polymerization inhibitor having a phenolic hydroxy group in combination.

[0054] [ka]

[0055] In formula (In1) and formula (In2), R1 to R5 each independently represent a hydrogen atom or a substituent other than a hydroxy group (excluding a phenolic hydroxy group) which may be bonded to each other to form a ring, R6 represents a hydrogen atom or an alkyl group, R7 to R 10 each independently represents an alkyl group, a cycloalkyl group, or an alkenyl group; R 11 represents a hydrogen atom or a (meth)acryloyl group.

[0056] In formula (In1), from the viewpoint of storage stability, it is preferable that at least one of R1 to R5 is the above-mentioned substituent, it is more preferable that at least R1 and R5 are the above-mentioned substituent, and it is particularly preferable that at least R1, R3 and R5 are the above-mentioned substituent. In formula (In1), from the viewpoint of storage stability, it is preferable that R1 and R5 are each independently a linear or branched alkyl group, a cycloalkyl group, an alkyl group having a structure having a phenolic hydroxy group, or an alkyl group having a (meth)acryloxyphenyl structure, it is more preferable that R1 is a linear or branched alkyl group and R5 is an alkyl group having a structure having a phenolic hydroxy group or an alkyl group having a (meth)acryloxyphenyl structure, and it is particularly preferable that R1 is a linear or branched alkyl group and R5 is an alkyl group having a (meth)acryloxyphenyl structure. From the viewpoint of storage stability, R3 in formula (In1) is preferably a hydrogen atom, an alkyl group, or an alkoxy group, more preferably a linear or branched alkyl group, a cycloalkyl group, or an alkoxy group, and further preferably a linear or branched alkyl group, or an alkoxy group. The alkyl group in R1, R3, and R5 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 1 to 6 carbon atoms, a t-butyl group, or a 2-methyl-2-butyl group, and particularly preferably a methyl group, a t-butyl group, or a 2-methyl-2-butyl group. The alkyl group may be linear, branched, or have a ring structure, and may have a substituent. The substituent may be any group that does not lose its polymerization-inhibiting ability, and examples of the substituent include a halogen atom, an alkoxy group, an aryl group, etc. The above-mentioned substituent may be further substituted with at least one group selected from the group consisting of the above-mentioned substituents and alkyl groups. In formula (In1), R2 and R4 each independently preferably represent a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0057] From the viewpoint of storage stability, R6 in formula (In2) is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group. R7 and R in formula (In2) 10 From the viewpoint of storage stability, is preferably a tertiary alkyl group, more preferably a tertiary alkyl group having 4 to 8 carbon atoms, and particularly preferably a t-butyl group or a 2-methyl-2-butyl group. From the viewpoint of storage stability, R8 and R9 in formula (In2) are preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group, a t-butyl group, a 2-methyl-2-butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. R in formula (In2) 11 From the viewpoint of storage stability, is preferably a hydrogen atom or a (meth)acryloyl group.

[0058] Among these, from the viewpoint of storage stability, the polymerization inhibitor having a phenolic hydroxy group is preferably at least one compound selected from the group consisting of 2,2'-methylenebis(6-tert-butyl-p-cresol), 2,2'-methylenebis(4-ethyl-6-tert-butyl-phenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) monoacrylate, 2,2'-ethylenebis(4,6-di-tert-amylphenol) monoacrylate, and 2,2'-methylenebis(6-(1-methylcyclohexyl)-p-cresol).

[0059] The curable composition of the present invention may contain one type of polymerization inhibitor alone, or may contain two or more types of polymerization inhibitors. From the viewpoint of storage stability, the content of the polymerization inhibitor in the curable composition of the present invention is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass, relative to 100 parts by mass of the methylene malonate compound.

[0060] <Other ingredients> The curable composition of the present invention may further contain other components depending on its application. For example, it may contain an anion-polymerizable compound other than the methylene malonate compound, a radical-polymerizable compound, a photopolymerization initiator other than the photobase generator, a solvent, an anion-polymerization accelerator, a plasticizer, a thickener, a sensitizer, an adhesion imparting agent (such as a silane coupling agent), and the like. Further, other additives include, for example, fillers, pigments, dyes, leveling agents, defoamers, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, antisagging agents, hardening accelerators, viscoelasticity adjusters, antibacterial agents, fluorescent brighteners, antioxidants, etc. Among these, one or more of them may be used in combination.

[0061] The other anionically polymerizable compounds are not particularly limited as long as they can exhibit the effects of the present invention. Examples include cyanoacrylates such as 2-ethyl cyanoacrylate, polymerizable epoxy compounds (e.g., compounds having two or more glycidyl groups such as bisphenol A diglycidyl ether, etc.), etc. The radical polymerizable compound is not particularly limited as long as it can exhibit the effects of the present invention. Examples thereof include (meth)acrylate compounds and (meth)acrylamide compounds.

[0062] The curable composition of the present invention may contain a polymerization initiator in order to assist or accelerate curing. When the curable composition contains a radical polymerizable compound, it is preferable that the curable composition further contains a radical polymerization initiator, and it is more preferable that the curable composition further contains a photoradical generator. As the photoradical generator, a known photoradical generator used for photopolymerizing a radically polymerizable compound can be used. Examples of photoradical generators include acylgermane compounds, acylphosphine oxide compounds, acetophenone compounds having no hydroxyl group, nitrogen atom, or thioether bond, and benzoin compounds having no hydroxyl group, nitrogen atom, or thioether bond. Among these, as the photoradical generator, acylgermane compounds are preferred from the viewpoints of photocurability, adhesion speed, and storage stability. Preferred examples of the acylgermane compound include monoacylgermane compounds and bisacylgermane compounds, and more preferred examples include bisacylgermane compounds. A preferred example of the acylgermane compound is Ivocerin (manufactured by Ivoclar Vivadent). Preferred examples of the acylphosphine oxide compound include monoacylphosphine oxide compounds and bisacylphosphine oxide compounds, and more preferred examples include bisacylphosphine oxide compounds.

[0063] The curable composition of the present invention may contain one type of photoradical generator alone, or may contain two or more types. The content of the polymerization initiator in the curable composition of the present invention is, from the viewpoints of photocurability and storage stability, preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 2% by mass, and particularly preferably 0.05% by mass to 1% by mass, based on the total solid content of the curable composition.

[0064] The solvent is not particularly limited as long as it can exhibit the effects of the present invention. For example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc.; saturated hydrocarbon solvents such as hexane, cyclohexane, heptane, etc.; ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, etc.; halogenated hydrocarbon solvents such as chloroform, etc. can be used alone or in combination of two or more of these. When the curable composition contains a solvent, the content of the solvent is preferably 1 part by mass to 1,000 parts by mass, more preferably 1 part by mass to 500 parts by mass, and particularly preferably 1 part by mass to 300 parts by mass, per 100 parts by mass of the methylene malonate compound.

[0065] Examples of the anionic polymerization accelerator include polyalkylene oxides, crown ethers, silacrown ethers, calixarenes, cyclodextrins, and pyrogallol-based cyclic compounds. The polyalkylene oxides are polyalkylene oxides and their derivatives, such as those disclosed in JP-B-60-37836, JP-B-1-43790, JP-A-63-128088, JP-A-3-167279, U.S. Pat. No. 4,386,193, and U.S. Pat. No. 4,424,327. Specific examples of the polyalkylene oxide include (1) diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and the like, and (2) derivatives of polyalkylene oxide such as polyethylene glycol monoalkyl ester, polyethylene glycol dialkyl ester, polypropylene glycol dialkyl ester, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, dipropylene glycol dialkyl ether, and the like. Examples of the crown ethers include those disclosed in JP-B-55-2236 and JP-A-3-167279. Specific examples thereof include 12-crown-4, 15-crown-5, 18-crown-6, benzo-12-crown-4, benzo-15-crown-5, benzo-18-crown-6, dibenzo-18-crown-6, dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphthyl-16-crown-5, 1,2-methylbenzo-18-crown-6, 1,2-tert-butyl-18-crown-6, and 1,2-vinylbenzo-15-crown-5. Examples of silacrown ethers include those disclosed in JP-A-60-168775.Specific examples include dimethylsila-11-crown-4, dimethylsila-14-crown-5, dimethylsila-17-crown-6, etc. Examples of calixarenes include those disclosed in JP-A-60-179482, JP-A-62-235379, JP-A-63-88152, etc. Specifically, 5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41,42-hexahydroxycalix[6]arene, 37,38,39,40,41,42-hexahydroxycalix[6]arene, 37,38,39,40,41,42-hexa-(2-oxo-2-ethoxy)-ethoxycalix[6]arene, 25,26,27,28-tetra-(2-oxo-2-ethoxy)-ethoxycalix[4]arene, tetrakis(4-t-butyl-2-methylenephenoxy)ethyl acetate, etc. Examples of cyclodextrins include those disclosed in JP-A-5-505835 and the like. Specifically, α-, β-, or γ-cyclodextrin may be mentioned. Examples of pyrogallol-based cyclic compounds include those disclosed in JP-A-2000-191600. Specifically, 3,4,5,10,11,12,17,18,19,24,25,26-dodecaethoxycarbomethoxy-C-1,C-8,C-15,C-22-tetramethyl

[14] metacyclophane may be mentioned. These anionic polymerization accelerators may be used alone or in combination of two or more.

[0066] A plasticizer can be contained within a range that does not impair the effects of the present invention. Examples of the plasticizer include triethyl acetyl citrate, tributyl acetyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, diisotridecyl phthalate, dipentadecyl phthalate, dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis(2-ethylhexyl) camphorate, 2-ethylhexyl cyclohexyl carboxylate, diisobutyl fumarate, diisobutyl maleate, triglyceride caproate, 2-ethylhexyl benzoate, and dipropylene glycol dibenzoate. Among these, acetyl tributyl citrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate, and dipropylene glycol dibenzoate are preferred because they have good compatibility with 2-cyanoacrylic acid esters and high plasticizing efficiency. These plasticizers may be used alone or in combination of two or more. The content of the plasticizer is not particularly limited, but is preferably 3 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 20 to 40 parts by mass, when the content of the methylene malonate compound is 100 parts by mass. If the content of the plasticizer is 3 to 50 parts by mass, the retention rate of the adhesive strength after a thermal cycle test can be improved.

[0067] Further examples of the thickener include polymethyl methacrylate, copolymers of methyl methacrylate and acrylic esters, copolymers of methyl methacrylate and other methacrylic esters, acrylic rubber, polyvinyl chloride, polystyrene, cellulose esters, polyalkyl-2-cyanoacrylates, and ethylene-vinyl acetate copolymers, etc. These thickeners may be used alone or in combination of two or more.

[0068] The curable composition of the present invention may also contain fumed silica as a filler or the like. This fumed silica is anhydrous silica of ultrafine powder (preferably with a primary particle diameter of 500nm or less, particularly preferably 1nm-200nm), and this anhydrous silica is, for example, made of silicon tetrachloride as a raw material, and is anhydrous silica of ultrafine powder (preferably with a primary particle diameter of 500nm or less, particularly preferably 1nm-200nm) that is generated due to oxidation in a gas phase state in a high-temperature flame, and there are hydrophilic silica with high hydrophilicity and hydrophobic silica with high hydrophobicity.As this fumed silica, either one can be used, but hydrophobic silica is preferred from the viewpoint of good dispersibility in methylene malonate compound.

[0069] As the hydrophilic silica, various commercially available products can be used, such as Aerosil 50, 130, 200, 300 and 380 (all of which are trade names, manufactured by Nippon Aerosil Co., Ltd.). The specific surface area of ​​these hydrophilic silicas is 50±15 m. 2 / g, 130±25m 2 / g, 200±25m 2 / g, 300±30m 2 / g, 380±30m 2 / g. Commercially available hydrophilic silica includes Reolosil QS-10, QS-20, QS-30 and QS-40 (all of which are trade names and manufactured by Tokuyama Corporation). The specific surface area of ​​these hydrophilic silicas is 140±20 m 2 / g, 220±20m 2 / g, 300±30m 2 / g, 380±30m 2 / g. Alternatively, commercially available hydrophilic silica such as that manufactured by CABOT may be used.

[0070] Furthermore, as the hydrophobic silica, a product can be used which is produced by contacting a compound capable of reacting with a hydroxy group present on the surface of hydrophilic silica to form a hydrophobic group, or a compound capable of being adsorbed on the surface of hydrophilic silica to form a hydrophobic layer on the surface, with hydrophilic silica in the presence or absence of a solvent, and preferably heating the resulting product to treat the surface of the hydrophilic silica.

[0071] Compounds used for surface-treating hydrophilic silica to make it hydrophobic include various silane coupling agents of alkyl, aryl, and aralkyl series having hydrophobic groups such as n-octyltrialkoxysilane, silylating agents such as methyltrichlorosilane, dimethyldichlorosilane, and hexamethyldisilazane, silicone oils such as polydimethylsiloxane, higher alcohols such as stearyl alcohol, and higher fatty acids such as stearic acid, etc. As the hydrophobic silica, products that have been hydrophobized using any compound may be used.

[0072] Examples of commercially available hydrophobic silica include Aerosil RY200 and R202 which are surface-treated with silicone oil and hydrophobized, Aerosil R974, R972, and R976 which are surface-treated with a dimethylsilylating agent and hydrophobized, Aerosil R805 which is surface-treated with n-octyltrimethoxysilane and hydrophobized, Aerosil R811 and R812 which are surface-treated with a trimethylsilylating agent and hydrophobized (all of these are trade names, manufactured by Nippon Aerosil Co., Ltd.), and Reolosil MT-10 which is surface-treated with methyltrichlorosilane and hydrophobized (trade name, manufactured by Tokuyama Corporation). The specific surface area of ​​these hydrophobic silicas is 100±20 m. 2 / g, 100±20m 2 / g, 170±20m 2 / g, 110±20m 2 / g, 250±25m 2 / g, 150±20m 2 / g, 150±20m 2 / g, 260±20m 2 / g, 120±10m 2 / g.

[0073] The preferred content of fumed silica in the curable composition of the present invention is 1 to 30 parts by mass when the content of the methylene malonate compound is 100 parts by mass. The preferred content of this fumed silica, depending on the type of methylene malonate compound and the type of fumed silica, is 1 to 25 parts by mass, and a particularly preferred content is 2 to 20 parts by mass. When the content is within the above range, an adhesive composition with good workability can be obtained.

[0074] <Method of producing curable composition> The method for producing the curable composition of the present invention is not particularly limited, and the composition may be produced by mixing the above-mentioned components. However, it is preferable to mix the components in an atmosphere free of moisture and oxygen or with little moisture and oxygen (e.g., 0.01 vol % or less), and it is more preferable to mix the components in an inert gas atmosphere. The inert gas includes nitrogen, argon, and the like. The method for producing the curable composition of the present invention is preferably carried out under light-shielded conditions. The mixing method is not particularly limited, and any known mixing method can be used.

[0075] <Storage method of the curable composition> The curable composition of the present invention may be stored by any known method. For example, it is preferable to store the composition in an atmosphere free of moisture and oxygen or with little moisture and oxygen (for example, 0.01% by volume or less) or in a sealed container, and it is more preferable to store the composition in an inert gas atmosphere or in a sealed container. The inert gas includes nitrogen, argon, and the like. In addition, the curable composition of the present invention is preferably stored in a light-shielded state.

[0076] <Curing method of curable composition> The curing method of the curable composition of the present invention is not particularly limited as long as it is possible to polymerize and cure the composition using a methylene malonate compound. The composition may be cured by moisture such as humidity or by light, but it is preferable to cure the composition by moisture such as humidity. When the curable composition of the present invention is cured by light, it can be cured by irradiating it with ultraviolet light or visible light using a high-pressure mercury lamp, a halogen lamp, a xenon lamp, an LED (light-emitting diode) lamp, sunlight, or the like.

[0077] <Application> The curable composition of the present invention can be used for applications in which known curable compositions are used. For example, it can be suitably used as a so-called instant adhesive. The curable composition of the present invention has photocurability and dark curability, and also has excellent storage stability, and therefore can be used in a wide range of fields such as general, industrial and medical applications. Examples of the adhesive include, but are not limited to, adhesives, coating agents (protective coating agents, etc.), printing inks (inkjet inks, etc.), photoresists, and sealants. Specifically, the material can be suitably used for adhesion or fixation between similar or different articles or coating, for example, sealing of electronic components, attachment of reel seats or threading guides on fishing rods, fastening of wire such as coils, fastening of magnetic heads to bases, filling agents used in dental treatment, adhesion or decoration of artificial nails, etc.

[0078] <Method of manufacturing an adhesive using a curable composition> The curable composition of the present invention can be preferably used in a first embodiment of the method for producing an adhesive article of the present invention described below. A first embodiment of the method for producing an adhesive of the present invention includes a step of applying the curable composition of the present invention to the surface of a first adherend (hereinafter also referred to as a "curable composition application step"); a step of bonding the surface of the first adherend to which the curable composition has been applied and a second adherend (hereinafter also referred to as a "first bonding step"); and a step of irradiating light to the curable composition between the first adherend and the second adherend, where at least one of the first adherend and the second adherend is an adherend having optical transparency, from the side of the adherend having optical transparency (hereinafter also referred to as a "first light irradiation step"). Furthermore, the curable composition of the present invention can be cured in the dark without irradiation with light, and the method for producing the bonded article of the present invention may be a method that does not involve irradiation with light.

[0079] In the first embodiment of the method for producing an adherend of the present invention, the curable composition of the present invention may be applied only to the surface of the first adherend, or the curable composition of the present invention may be applied to both the surface of the first adherend and the surface of the second adherend. Furthermore, the first and second adherends may be different adherends or may be the same adherend, i.e., an adhesive may be applied to one surface of the first adherend and then pasted and adhered to another surface of the same first adherend. The shapes of the surfaces of the first and second adherends to be bonded together are not particularly limited, and may be any shape, such as a flat surface, an uneven surface, or an irregular surface.

[0080] Examples of materials for the adherend include plastics, rubber, wood, metals, inorganic materials, and paper. Specific examples of plastics include polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, cyclic polyolefin resins having cyclic olefins as monomers such as norbornene, polyvinyl chloride, epoxy resins, and polyurethane resins. Specific examples of rubber include natural rubber and styrene-butadiene rubber (SBR). Specific examples of wood include natural wood and synthetic wood. Specific examples of metals include metals such as steel plate, aluminum, and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). Specific examples of inorganic materials include glass, mortar, concrete, and stone. Specific examples of the paper include fine paper, coated paper, art paper, construction paper, thin paper, thick paper, and various synthetic papers. In the first embodiment of the method for producing an adherend of the present invention, at least one of the first adherend and the second adherend has optical transparency.

[0081] In the curable composition applying step, the method for applying the curable composition to the surface of the first adherend is not particularly limited. Examples of application methods include methods using application tools such as a brush, spatula, cotton swab, roller, and spray, and methods using a coating machine such as a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, lip coater, spray coater, gravure coater, microgravure coater, and dispenser.

[0082] Thereafter, the coated surface of the first adherend is laminated to the second adherend. At least one of the first adherend and the second adherend is irradiated with light from the side of the adherend having optical transparency, thereby curing the curable composition.

[0083] In the photocuring, a base is generated from the photobase generator by light, and the methylene malonate compound is anionically polymerized and cured, thereby bonding the surface of the first adherend and the surface of the second adherend. The light to be irradiated in the photocuring step is preferably ultraviolet light. Examples of the light source for ultraviolet irradiation include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. Other examples include an ultraviolet device using a light emitting diode as a light source (UV-LED), a laser beam in the ultraviolet region, etc.

[0084] In dark curing, the Lewis acid compound acts on the methylene malonate compound, and the methylene malonate compound is cured by moisture in the air, etc., thereby bonding the surface of the first adherend and the surface of the second adherend. When the surface of the first adherend and the surface of the second adherend are brought together, the surface of the first adherend and / or the surface of the second adherend may be moved, if necessary.

[0085] In the first embodiment, the composition can be cured at room temperature (for example, 10° C. to 35° C.), but the surface of the first adherend, the surface of the second adherend, and / or the adherends may be heated in order to promote the curing. For the purpose of promoting the dark reaction, it is preferable to heat the composition after the light irradiation step. The heating temperature may be within a range that does not affect the adherend, for example, about 35°C to 100°C, for curing. Furthermore, in the first embodiment, if necessary, pressure may be applied in the direction in which the surfaces of the first and second adherends overlap until adhesion by curing is completed.

[0086] (Two-component curing composition set) The two-part curable composition set of the present invention includes a composition A containing a methylene malonate compound and a photobase generator, and a composition B containing a Lewis acid compound. For example, the composition A and the composition B are applied to the surfaces of the adherends, preferably, the composition A and the composition B are applied to the surface of one of the adherends to be bonded, or the composition A is applied to the surface of one of the adherends to be bonded and the composition B is applied to the surface of the other adherend, and if necessary, the solvent is removed, and the surfaces of the two adherends are overlapped and cured to bond them.

[0087] In the two-component curable composition set of the present invention, preferred aspects of the methylene malonate compound and the photobase generator in composition A, as well as preferred aspects of the Lewis acid compound in composition B, are similar to the preferred aspects of the methylene malonate compound, the preferred aspects of the photobase generator, and the preferred aspects of the Lewis acid compound in the curable composition of the present invention described above, except as described below. Furthermore, the composition A and the composition B in the two-part curable composition set of the present invention may each independently contain the polymerization inhibitor and / or the other component. Preferred aspects of the polymerization inhibitor and the other components in the two-component curable composition set of the present invention are the same as the preferred aspects of the polymerization inhibitor and the other components in the curable composition of the present invention described above. Moreover, the composition B may further contain a photobase generator.

[0088] The content of the methylene malonate compound in the composition A is preferably 10% by mass to 99.9% by mass, more preferably 30% by mass to 99.5% by mass, even more preferably 50% by mass to 99.5% by mass, and particularly preferably 90% by mass to 99% by mass, based on the total solid content of the composition A. The content of the photobase generator in the composition A is preferably 0.01 mass % to 30 mass %, more preferably 0.1 mass % to 15 mass %, further preferably 0.2 mass % to 10 mass %, and particularly preferably 0.5 mass % to 5 mass %, based on the total solid content of the composition A.

[0089] The content of the Lewis acid compound in composition B is preferably 1% by mass to 100% by mass, more preferably 10% by mass to 100% by mass, and particularly preferably 50% by mass to 100% by mass, based on the total solid content of composition B. The composition B preferably contains a solvent. Suitable examples of the solvent include those described above in relation to the curable composition of the present invention. The content of the solvent in the composition B is preferably 10% by mass to 99.99% by mass, more preferably 50% by mass to 99.9% by mass, and particularly preferably 80% by mass to 99% by mass, based on the total mass of the composition B.

[0090] Furthermore, the two-component curable composition set of the present invention may contain compositions or articles other than the composition A and the composition B. The composition other than the composition A and the composition B is not particularly limited, and examples thereof include a cleaning liquid for the surface of the adherend to which the composition A and / or the composition B is applied, a removal liquid for the cured product of the composition A and the composition B, and the like. The article is not particularly limited, and examples thereof include application tools such as a brush, spatula, cotton swab, roller, spray, etc. for applying the composition A or the composition B, and removal tools such as paper, cloth, etc. for removing excess of the composition A and the composition B.

[0091] (Method of manufacturing an adhesive using a two-liquid curing composition set) A second embodiment of the method for producing an adhesive product of the present invention, which is a method for producing an adhesive product using the two-component curing composition set of the present invention, includes a step of applying composition B containing a Lewis acid compound to the surface of a first adherend, a step of applying composition A containing a methylene malonate compound and a photobase generator to the surface of the first adherend or the surface of a second adherend, a step of bonding the surface of the first adherend to which composition B has been applied and the surface of the second adherend to which composition A has been applied, or a step of bonding the surface of the first adherend to which composition A and composition B have been applied and the surface of the second adherend, and a step of irradiating light to the curable composition between the first adherend and the second adherend, in which at least one of the first adherend or the second adherend is an adherend having optical transparency, from the side of the adherend having optical transparency.

[0092] The preferred aspects of the composition A and the composition B in the second embodiment of the method for producing an adhesive article of the present invention are the same as the preferred aspects of the composition A and the composition B in the two-component curable composition set of the present invention described above.

[0093] <Composition B Application Step and Composition A Application Step> A second embodiment of the method for producing an adherend of the present invention includes a step of applying composition B containing a Lewis acidic compound to the surface of a first adherend (also referred to as a "composition B application step"), and a step of applying composition A containing a methylene malonate compound and a photobase generator to the surface of the first adherend or the surface of a second adherend (also referred to as a "composition A application step"). The composition B application step and the composition A application step may be performed in either order, or may be performed simultaneously. In a second embodiment of the method for producing an adhesive of the present invention, both composition A and composition B may be applied to the surface of one of the adherends (the surface of the first adherend), and composition A and composition B may be applied to the surface of the other adherend (the surface of the second adherend), or composition A and / or composition B may be applied, or composition A may be applied to the surface of one of the adherends (the surface of the first adherend), and composition B may be applied to the surface of the other adherend (the surface of the second adherend). Furthermore, the surface of the first adherend and the surface of the second adherend may be partial surfaces of different adherends, or may be two adherendable surfaces of a single adherend. The shapes of the surfaces of the first and second adherends are not particularly limited, and may be any shape, such as a flat surface, an uneven surface, or an irregular surface.

[0094] The amount of the composition A applied in the composition A application step is not particularly limited as long as it is an amount that allows adhesion, and can be appropriately selected as desired. After applying the composition A, the solvent may be removed by air drying, heat drying, or the like, if necessary.

[0095] The amount of composition B applied in the composition B application step is not particularly limited as long as it is an amount that allows adhesion, but the amount of the Lewis acid compound contained in composition B applied is preferably 0.001 part by mass to 1.0 part by mass, more preferably 0.001 part by mass to 0.5 part by mass, and particularly preferably 0.001 part by mass to 0.1 part by mass, relative to 100 parts by mass of the methylene malonate compound applied by composition A in the composition A application step. After applying the composition B, the solvent may be removed by air drying, heat drying, or the like, if necessary.

[0096] The application method used in the composition B application step and the composition A application step is not particularly limited, and the composition B or the composition A can be applied to the surface of the first adherend or the surface of the second adherend by a known method.

[0097] <Second lamination process> A second embodiment of the method for producing an adhesive of the present invention includes a step of laminating a surface of the first adherend to which composition B has been applied and a surface of the second adherend to which composition A has been applied, or a step of laminating a surface of the first adherend to which composition A and composition B have been applied and a surface of the second adherend (hereinafter also referred to as a "second lamination step"). In the second bonding step, the surface of the first adherend and the surface of the second adherend may be overlapped and bonded together.

[0098] In the second photocuring step, the methylene malonate compound may be photocured, dark cured, or both photocured and dark cured.

[0099] <Second light irradiation step> A second embodiment of the method for producing an adhesive of the present invention includes a step of irradiating light onto the curable composition between the first adherend and the second adherend from the side of the adherend having optical transparency, the curable composition being between the first adherend and the second adherend (also referred to as a "second light irradiation step").

[0100] In the photocuring, a base is generated from the photobase generator by light, and the methylene malonate compound is anionically polymerized and cured, thereby bonding the surface of the first adherend and the surface of the second adherend. In addition, with regard to the first adherend and the second adherend, only one of the first adherend and the second adherend has optical transparency, or both of the first adherend and the second adherend have optical transparency. The light to be irradiated in the photocuring step is preferably ultraviolet light, etc. Examples of the light source for irradiating ultraviolet light include the same as those mentioned above.

[0101] In dark curing, the Lewis acid compound contained in composition B acts on the methylene malonate compound contained in composition A, and the methylene malonate compound hardens due to moisture in the air, etc., bonding the surface of the first adherend and the surface of the second adherend. When the surface of the first adherend and the surface of the second adherend are brought together, if necessary, the surface of the first adherend and / or the surface of the second adherend may be moved to promote mixing of Composition A and Composition B.

[0102] In the second embodiment, the composition can be cured at room temperature (for example, 10° C. to 35° C.), but the surface of the first adherend, the surface of the second adherend, and / or the adherends may be heated in order to promote the curing. For the purpose of promoting the dark reaction, it is preferable to heat the composition after the light irradiation step. The heating temperature may be within a range that does not affect the adherend, for example, about 35°C to 100°C, for curing. Furthermore, in the second embodiment, if necessary, pressure may be applied in the direction in which the surfaces of the first and second adherends overlap until adhesion by curing is completed.

[0103] The object to be bonded by the curable composition of the present invention, the two-component curable composition set of the present invention, or the method for producing an adhesive product of the present invention is not particularly limited, and may be an inorganic compound, an organic compound, or an inorganic-organic composite, and may be made of the same material or different materials. The curable composition of the present invention, the two-component curable composition set of the present invention, or the method for producing an adhesive product of the present invention can bond solid objects of any shape. Examples of the adherend include the same materials as those mentioned above. EXAMPLES

[0104] The present invention will be specifically described below based on examples. Note that the present invention is not limited to these examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0105] <Preparation of diethyl methylenemalonate> Diethyl methylenemalonate (hereinafter also referred to as "DEMM") prepared according to the following document was used. Purity: 99% by mass or more ( 1 (From H-NMR). Journal of the Chemical Society of Japan, 1972, No. 3, pp. 596-598

[0106] Comparative Example 1 <Light curing> 200 μL of DEMM was poured into a cylindrical hole of φ8 mm and depth 5 mm made in a 10 mm thick polypropylene sheet, and exposed to an ultraviolet irradiation device (SUV-16: AS ONE Corporation) with an integrated light dose of 3 J / cm. 2 Ultraviolet light was irradiated from above using a Heraeus UV meter (UV Power Puck, UV-C). After irradiation, 2 μL of methanesulfonic acid and deuterated chloroform were added to terminate the polymerization. Regarding the obtained cured product, 1 The reaction rate of DEMM was measured by H-NMR (manufactured by Bruker), and the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC, Tosoh Corporation HPLC8021, free liquid: chloroform).

[0107] <Dark area hardening> Two drops (approximately 5 mg) of DEMM were placed on a copper test piece (a square pillar with a base of 12.7 mm x 12.7 mm) and another test piece was bonded to it. After bonding, the time it took for the bonded test piece to be able to lift a weight of 2.586 kg was recorded as the set time, up to a maximum of 30 minutes.

[0108] Comparative Example 2 0.02 g of zinc trifluoromethanesulfonate (hereinafter also referred to as "Zn(OTf)2"), which is a Lewis acid, was added to 2 mL of acetone and completely dissolved to obtain a Lewis acid catalyst solution. 500 μL of the Lewis acid catalyst solution was mixed with 5 g of DEMM obtained in Synthesis Example 1, and then the mixture was vacuum dried to remove acetone derived from the Lewis acid catalyst solution, thereby obtaining a composition of Comparative Example 2. The obtained composition was used and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0109] Comparative Example 3 1.2 g of DEMM obtained in Synthesis Example 1 was mixed with 0.0214 g of 9-anthrylmethyl N,N-diethylcarbamate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., product name WPBG-018, hereinafter also referred to as "WPBG") as a photobase generator, and the mixture was stirred until completely dissolved, thereby obtaining a composition of Comparative Example 3 (curable composition). The obtained composition was used and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0110] Example 1 0.0214 g of WPBG-018, a photobase generator, was mixed with 1.2 g of the composition obtained in Comparative Example 2 and stirred until completely dissolved, thereby obtaining the composition of Example 1 (curable composition). The obtained composition was used and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0111] Example 2 The composition used was that of Example 1. The composition of Example 1 was used, and the accumulated light dose was 6 J / cm 2 Other than that, the same operations as in Comparative Example 1 were carried out and evaluations were performed in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0112] Example 3 The composition used was that of Example 1. The composition of Example 1 was used, and the accumulated light dose was 9 J / cm 2 Other than that, the same operations as in Comparative Example 1 were carried out and evaluations were performed in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0113] [Table 1]

[0114] The numerical values ​​of each component of the composition in Table 1 represent the mass ratio in the composition. As shown in Table 1, the curable compositions of Examples 1 to 3 can be both photocured and dark cured. On the other hand, the curable composition of Comparative Example 1, which did not contain either a Lewis acid compound or a photobase generator, and the curable composition of Comparative Example 3, which did not contain a Lewis acid compound but only a photobase generator, did not photocure and the dark curing was also unsatisfactory, as shown in Table 1. Moreover, the curable composition of Comparative Example 2, which did not contain a photobase generator but only a Lewis acid compound, cured in the dark but did not photocure.

[0115] The disclosure of Japanese Patent Application No. 2019-164835, filed on September 10, 2019, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A methylene malonate compound; Lewis acidic compound; and a photobase generator, The content of the methylene malonate compound is 90% by mass to 99% by mass based on the total solid content of the curable composition, the content of the Lewis acid compound is 0.001 parts by mass to 0.1 parts by mass relative to 100 parts by mass of the methylene malonate compound, The content of the photobase generator is 0.5% by mass to 5% by mass based on the total solid content of the curable composition. Curable composition.

2. The curable composition according to claim 1 , wherein the methylene malonate compound is a compound represented by the following formula (1) or formula (2): 【Chemistry 1】 In formula (1) and formula (2), X １ ~X ４ Each independently represents O, NR, or C(R) ２ Each R independently represents a hydrogen atom, an alkyl group, or an aryl group; R １ and R ２ each independently represents an alkyl group or an aryl group; R ３ is an alkylene group , an arylene group, or a group formed by combining two or more of these.

3. The X １ ~X ４ The curable composition according to claim 2 , wherein each is independently O or NR.

4. The X １ ~X ４ The curable composition according to claim 2 or claim 3, wherein is O.

5. The R １ and R ２ The curable composition according to any one of claims 2 to 4, wherein each of the groups independently represents an alkyl group.

6. The R ３ The curable composition according to any one of claims 2 to 5, wherein is an alkylene group.

7. The curable composition according to any one of claims 2 to 6, comprising a compound represented by formula (1).

8. The curable composition according to any one of claims 1 to 7, wherein the Lewis acidic compound comprises a Lewis acidic compound having a metal cation.

9. The Lewis acid compound is Fe ２＋ , Cu ２＋ , Zn ２＋ , Ag ＋ , Yb ３＋ , and Ti ４＋ The curable composition according to any one of claims 1 to 8, comprising a Lewis acidic compound having at least one metal cation selected from the group consisting of:

10. The curable composition according to any one of claims 1 to 9, wherein the Lewis acidic compound includes a Lewis acidic compound having at least one counter anion selected from the group consisting of a trifluoromethanesulfonate anion, a tert-butoxide anion, an acetylacetonate anion, a chloride ion, and a bromide ion.

11. The curable composition according to any one of claims 1 to 10, wherein the photobase generator comprises a compound that generates an amine compound by exposure to light.

12. A step of applying the curable composition according to any one of claims 1 to 11 to a surface of a first adherend; a step of bonding the surface of the first adherend to which the curable composition has been applied and a second adherend; and At least one of the first adherend and the second adherend is an adherend having optical transparency, and the method includes a step of irradiating the curable composition between the first adherend and the second adherend with light from the side of the adherend having optical transparency. A method for producing an adhesive.

13. A composition A containing a methylene malonate compound and a photobase generator; and composition B comprising a Lewis acidic compound; The content of the methylene malonate compound is 90% by mass to 99% by mass based on the total solid content of the composition A, The content of the photobase generator is 0.5% by mass to 5% by mass based on the total solid content of the composition A, The content of the Lewis acid compound is 50% by mass to 100% by mass based on the total solid content of the composition B, The content of the Lewis acid compound is 0.001 parts by mass to 0.1 parts by mass relative to 100 parts by mass of the methylene malonate compound. A two-part curable composition set.

14. The two-part curing composition set according to claim 13, wherein the methylene malonate compound is a compound represented by the following formula (1) or formula (2): 【Chemistry 2】 In formula (1) and formula (2), X １ ~X ４ Each independently represents O, NR, or C(R) ２ Each R independently represents a hydrogen atom, an alkyl group, or an aryl group; R １ and R ２ each independently represents an alkyl group or an aryl group; R ３ represents an alkylene group, an arylene group, or a combination of two or more thereof.

15. applying a composition B containing a Lewis acidic compound to a surface of a first adherend; A step of applying a composition A containing a methylene malonate compound and a photobase generator to a surface of the first adherend or a surface of a second adherend; a step of laminating a surface of the first adherend to which the composition B has been applied and a surface of the second adherend to which the composition A has been applied, or a step of laminating a surface of the first adherend to which the composition A and the composition B have been applied and a surface of the second adherend; and At least one of the first adherend and the second adherend is an adherend having optical transparency, and the method includes a step of irradiating light onto the composition A and the composition B between the first adherend and the second adherend from the side of the adherend having optical transparency, The content of the methylene malonate compound is 90% by mass to 99% by mass based on the total solid content of the composition A, The content of the photobase generator is 0.5% by mass to 5% by mass based on the total solid content of the composition A, The content of the Lewis acid compound is 50% by mass to 100% by mass based on the total solid content of the composition B. The amount of the Lewis acid compound added is 0.001 parts by mass to 0.1 parts by mass relative to 100 parts by mass of the methylene malonate compound added. A method for producing an adhesive.

16. The method for producing a bonded article according to claim 15, wherein the methylene malonate compound is a compound represented by the following formula (1) or formula (2): 【Chemistry 3】 In formula (1) and formula (2), X １ ~X ４ Each independently represents O, NR, or C(R) ２ Each R independently represents a hydrogen atom, an alkyl group, or an aryl group; R １ and R ２ each independently represents an alkyl group or an aryl group; R ３ represents an alkylene group, an arylene group, or a combination of two or more thereof.

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