Curable composition, reaction product, and polyfunctional lactone compound

Abstract

To provide a curable composition having excellent reactivity under light irradiation.SOLUTION: A curable composition includes a polyfunctional lactone compound, at least one of a polyfunctional thiol compound and a polyfunctional alcohol compound, and a photo base generator. A pKa in acetonitrile of conjugate acid of a base generated by irradiating the photo base generator with light is 12 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a reaction product, and a polyfunctional lactone compound. [Background technology]

[0002] Photopolymerizable materials, which are polymerized by irradiation with light, are widely used in practical applications because the polymerization reaction can be precisely controlled with relatively simple operations, and they occupy an important position in, for example, the fields of electronic materials and printing materials. As photopolymerizable materials, for example, radical polymerization type resin compositions containing a photoinitiator that generates radical species upon exposure and a radically polymerizable monomer or oligomer, and acid catalyst type resin compositions containing a photoacid generator that generates acid upon exposure and a monomer or oligomer that polymerizes by the action of acid, have been actively studied.

[0003] On the other hand, photopolymerizable materials also include base-catalyzed materials containing a photobase generator that generates a base upon exposure and a monomer or oligomer that polymerizes under the action of a base. Known photobase generators include, for example, ionic photobase generators that correspond to salts of carboxylic acids with strong bases such as guanidine (see, for example, Non-Patent Document 1). In such ionic photobase generators, a decarboxylation reaction occurs at the carboxy group upon exposure, liberating the strong base that formed a salt with the carboxy group, thereby generating a base.

[0004] In response to this, non-ionic photobase generators have also been investigated. Known examples of non-ionic photobase generators include carbamates having a nitrobenzyl skeleton, which undergo a decarboxylation reaction upon exposure to light, liberating a primary amine or a secondary amine to generate a base (see, for example, Non-Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Non-Patent Document 1] K.Arimitsu,R.Endo,Chem.Mater.2013,25,4461-4463. [Non-patent document 2] JFCameron,JMJFrechet,J.Am.Chem.Soc.1991,113,4303. Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have investigated a resin composition containing a photobase generator and a polyfunctional lactone compound that undergoes ring-opening polymerization via a nucleophilic reaction with a base or an anion species as a photopolymerizable material. Such a resin composition has the advantage of being highly degradable and biocompatible due to its ester main chain. However, it has the disadvantage of low reactivity upon light irradiation.

[0007] An object of the present invention is to provide a curable composition that exhibits excellent reactivity upon irradiation with light, a reaction product obtained by reacting this photoreactive composition, and a novel polyfunctional lactone compound that can be used to prepare the curable composition. [Means for solving the problem]

[0008] Specific means for solving the above problems are as follows. <1> a polyfunctional lactone compound; At least one compound selected from the group consisting of a polyfunctional thiol compound and a polyfunctional alcohol compound; a photobase generator; The curable composition, wherein the pKa in acetonitrile of a conjugate acid of a base generated by irradiating the photobase generator with light is 12 or more. <2> The polyfunctional lactone compound contains a plurality of δ-valerolactone skeletons. <1> The curable composition according to claim 1. <3> The polyfunctional lactone compound includes a compound represented by the following general formula (1): <1> or <2> The curable composition according to claim 1.

[0009] [ka]

[0010] In the general formula (1), R is an n-valent organic group, and n is an integer of 2 to 6. <4> The polyfunctional thiol compound includes a compound having 2 to 6 primary thiol groups. <1> ~ <3> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more. <5> The polyfunctional thiol compound includes a compound represented by the following general formula (2): <1> ~ <4> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more.

[0011] [ka]

[0012] In the general formula (2), R is an n-valent organic group, and n is an integer of 2 to 6. <6> The polyfunctional thiol compound includes at least one compound selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrapropanethiol, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, dipentaerythritol hexakis(3-mercaptopropionate), and tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate. <1> ~ <4> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more. <7> The photobase generator is at least one selected from the group consisting of carbamates having a nitrobenzyl skeleton, compounds having a coumaric acid amide skeleton, and ionic base generators which are salts of a base and a carboxylic acid. <1> ~ <6> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more. <8> The photobase generator includes a structure represented by general formula (1)-12, (1)-13, or (1-14). <1> ~ <7> 10. The curable composition according to claim 9, wherein the curable composition is a curable composition having a molecular weight of 100 or more.

[0013] [ka]

[0014] In general formula (1)-12 to general formula (1)-14, R 22 , R 23 , R 24 , R 32 , R 33 , R 41 , R 42 , R 43 and R 44 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R 21 and R 31 R each independently represents a hydrocarbon group which may have a substituent, and * represents the bonding position at which it bonds to * in general formula (a) to form a single bond. 21 ~R 24 At least two of may be bonded to each other to form a ring structure, R 31 ~R 33 At least two of may be bonded to each other to form a ring structure, R 41 ~R 44 At least two of these may be bonded to each other to form a ring structure. <9> <1> ~ <8> 10. A reaction product obtained by reacting the curable composition according to any one of the above items. <10> A polyfunctional lactone compound represented by the following general formula (1):

[0015] [ka]

[0016] In the general formula (1), R is an n-valent organic group, and n is an integer of 2 to 6. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a curable composition that has excellent reactivity when irradiated with light, a reaction product obtained by reacting this photoreactive composition, and a novel polyfunctional lactone compound that can be used for preparing the curable composition. [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a graph showing lactone conversion rates in a coating film after light irradiation and in a coating film that has not been irradiated with light. [Figure 2] 1 is a graph showing the tensile shear adhesive strength of a sample after light irradiation and a sample that has not been irradiated with light. DETAILED DESCRIPTION OF THE INVENTION

[0019] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in stages in the present disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range. The upper or lower limit of a numerical range described in the present disclosure may be replaced by a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.

[0020] [Photobase generator] The curable composition of the present disclosure comprises a polyfunctional lactone compound, at least one compound selected from the group consisting of a polyfunctional thiol compound and a polyfunctional alcohol compound, and a photobase generator, wherein the photobase generator is irradiated with light to generate a base, the conjugate acid of which has a pKa in acetonitrile of 12 or more.

[0021] When the curable composition containing the photobase generator is irradiated with light, a base is generated from the photobase generator, and the generated base acts to abstract a proton from the thiol group in the multifunctional thiol compound, thereby generating a sulfur anion (-S - ) is generated. The reaction of polyfunctional lactone compounds with sulfur anions produces reaction products.

[0022] When radical polymerization by light irradiation proceeds, problems such as reaction inhibition in the presence of oxygen, volumetric shrinkage, and poor adhesion to the adherend are likely to occur. Furthermore, when cationic polymerization by light irradiation proceeds, problems such as corrosion of the metal substrate are likely to occur. On the other hand, anionic polymerization by light irradiation has the advantages of suppressing the reaction in the presence of oxygen, reducing volumetric shrinkage, improving adhesion to the adherend, and reducing corrosion of the metal substrate.

[0023] Furthermore, in a curable composition using a photobase generator, the conjugate acid of the generated base has a pKa in acetonitrile of 12 or more, and therefore the curable composition has good reactivity when irradiated with light.

[0024] The curable composition can be used, for example, as a photosensitive material, a semiconductor encapsulation material, an adhesive, etc. Since the reaction product obtained by reacting the curable composition contains an ester group, the reaction product can be decomposed by hydrolysis or the like. For example, when the curable composition is used as an adhesive, the adhesion between adherends may be released by hydrolyzing the reaction product.

[0025] (Polyfunctional lactone compounds) The curable compositions of the present disclosure include a polyfunctional lactone compound. The polyfunctional lactone compound is not particularly limited as long as it is a compound having two or more lactone skeletons that are cyclic esters.

[0026] Examples of the lactone skeleton contained in the polyfunctional lactone compound include an α-acetolactone skeleton, a β-propylolactone skeleton, a γ-butyrolactone skeleton, a δ-valerolactone skeleton, etc. Among these, a δ-valerolactone skeleton is preferred. The lactone skeleton contained in the polyfunctional lactone compound may be one type or two or more types.

[0027] The number of lactone skeletons contained in the polyfunctional lactone compound is not particularly limited as long as it is two or more, and may be, for example, two to six or two to four.

[0028] The polyfunctional lactone compound may contain a structure in which a sulfide bond (-S-) is bonded to a cyclic ester such as an α-acetolactone skeleton, a β-propylolactone skeleton, a γ-butyrolactone skeleton, or a δ-valerolactone skeleton (hereinafter referred to as a specific structure), and may contain two or more, two to six, or two to four of the specific structures.

[0029] The polyfunctional lactone compound preferably includes a compound represented by the following general formula (1).

[0030] [ka]

[0031] In the general formula (1), R is an n-valent organic group, and n is an integer of 2 to 6. n is preferably an integer of 2 to 4.

[0032] R is an n-valent organic group, and examples thereof include an organic group containing an ether bond (—O—), an organic group containing an isocyanuric ring, and an organic group containing a glycoluril ring.

[0033] The organic group containing an ether bond (—O—) preferably contains two or more ether bonds, more preferably contains two to six ether bonds, and even more preferably contains two to four ether bonds.

[0034] Examples of the organic group containing an ether bond (-O-) include groups represented by the following general formula (X1) or (X2). In general formula (1), when n=2, R may be a group represented by general formula (X1). In general formula (1), when n=4, R may be a group represented by general formula (X2).

[0035] [ka]

[0036] [ka]

[0037] In general formula (X1), R1, R2, and R3 each independently represent an organic group having 1 to 10 carbon atoms, x represents an integer of 0 to 10, and * represents the bonding position with the sulfur atom in general formula (1). In general formula (X2), R4, R5, R6 and R7 each independently represent an organic group having 1 to 10 carbon atoms. * indicates the bonding position with the sulfur atom in general formula (1).

[0038] R1, R 2、 R3, R4, R5, R6, and R7 are each independently preferably an organic group having 1 to 5 carbon atoms, more preferably an organic group having 2 to 4 carbon atoms, and even more preferably an organic group having 2 or 3 carbon atoms. x is preferably an integer of 1 to 5, more preferably an integer of 2 to 4, and even more preferably an integer of 2 or 3.

[0039] R1, R 2、The organic group in R3, R4, R5, R6, and R7 may be an alkylene group which may have a substituent. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethyltrimethylene group, a 2,2-dimethyltrimethylene group, a 1,2-dimethyltrimethylene group, a propylethylene group, an ethylmethylethylene group, a 1-methylpentylene group, a 2-methylpentylene group, a 3-methylpentylene group, a 1-ethyl Examples thereof include a tetramethylene group, a 2-ethyltetramethylene group, a 1-propyltrimethylene group, a 2-propyltrimethylene group, a butylethylene group, a 1,1-dimethyltetramethylene group, a 2,2-dimethyltetramethylene group, a 1,2-dimethyltetramethylene group, a 1,3-dimethyltetramethylene group, a 1,4-dimethyltetramethylene group, a 1,2,3-trimethyltrimethylene group, a 1,1,2-trimethyltrimethylene group, a 1,1,3-trimethyltrimethylene group, a 1,2,2-trimethyltrimethylene group, a 1-ethyl-1-methyltrimethylene group, a 2-ethyl-2-methyltrimethylene group, a 1-ethyl-2-methyltrimethylene group, a 2-ethyl-1-methyltrimethylene group, and a 2,2-ethylmethyltrimethylene group. Examples of the substituent in the alkylene group include a carbonyl group, an ester group, an amide group, a halogen atom, a hydroxyl group, an amino group, and a nitro group. The carbonyl group, ester group, or amide group may be contained in the main chain or in a side chain.

[0040] R1, R2 and R3 are preferably ethylene or trimethylene groups.

[0041] R4, R5, R6, and R7 are preferably a trimethylene group or a carbonylethylene group (for example, *1-C(=O)CH2CH2-*2, where *1 is the bonding position to the oxygen atom in general formula (X2), and *2 is the bonding position to the sulfur atom in general formula (1)).

[0042] Examples of the organic group containing an isocyanuric ring include a group represented by the following general formula (X3): In general formula (1), when n=3, R may be a group represented by general formula (X3).

[0043] [ka]

[0044] In the general formula (X3), R8, R9 and R 10 are each independently an organic group having 1 to 20 carbon atoms. * indicates the bonding position with the sulfur atom in general formula (1).

[0045] R8, R9 and R 10 may each independently be a group represented by the following general formula (Y1):

[0046] [ka]

[0047] In general formula (Y1), R 11 and R 12 are each independently an organic group having 1 to 10 carbon atoms. A means the bonding position to the nitrogen atom in general formula (X3), and * B means the bonding position to the sulfur atom in general formula (1).

[0048] R 11 and R 12 Specific examples of the organic group in 2、 The specific examples of the organic groups in R3, R4, R5, R6 and R7 are the same as those in R 11 and R 12is preferably an ethylene group or a trimethylene group.

[0049] Examples of organic groups containing a glycoluril ring include groups represented by the following general formula (X4): In general formula (1), when n=4, R may be a group represented by general formula (X4).

[0050] [ka]

[0051] In general formula (Y1), R 13 , R 14 , R 15 and R 16 are each independently an organic group having 1 to 10 carbon atoms. * indicates the bonding position to the sulfur atom in general formula (1).

[0052] R 13 , R 14 , R 15 and R 16 Specific examples of the organic group in 2、 The specific examples of the organic groups in R3, R4, R5, R6 and R7 are the same as those in R 13 , R 14 , R 15 and R 16 is preferably an ethylene group or a trimethylene group.

[0053] The content of the polyfunctional lactone compound may be 30% by mass to 80% by mass, 40% by mass to 70% by mass, or 50% by mass to 65% by mass, based on the total of the polyfunctional lactone compound, the polyfunctional thiol compound, the polyfunctional alcohol compound, and the photobase generator.

[0054] The compound represented by general formula (1) can be synthesized, for example, by an enethiol reaction between a polyfunctional thiol compound described below and a lactone compound having an ethylenically unsaturated double bond (e.g., 5,6-dihydro-2H-pyran-2-one). In the enethiol reaction, a known catalyst such as an amine catalyst may be used.

[0055] The curable composition of the present disclosure includes at least one compound selected from the group consisting of a polyfunctional thiol compound and a polyfunctional alcohol compound. The curable composition of the present disclosure may include only the polyfunctional thiol compound, may include only the polyfunctional alcohol compound, or may include both the polyfunctional thiol compound and the polyfunctional alcohol compound.

[0056] (Multifunctional thiol compounds) The polyfunctional thiol compound is not particularly limited as long as it is a compound having two or more thiol groups (—SH).

[0057] The polyfunctional thiol compound may be a compound having two or more primary thiol groups, a compound having two or more secondary thiol groups, or a compound having two or more tertiary thiol groups.

[0058] The number of thiol groups contained in the polyfunctional thiol compound may be 2 to 6, 2 to 4, or 3 or 4.

[0059] The polyfunctional thiol compound preferably includes a compound having 2 to 6 primary thiol groups.

[0060] Polyfunctional thiol compounds are (HS) n1 It is preferable to contain a compound represented by —R′ (general formula (1A)). In general formula (1A), R′ is an n-valent organic group, and n1 is an integer of 2 to 6. It is preferable that n1 is an integer of 2 to 4.

[0061] R' is an n-valent organic group, and examples thereof include an organic group containing an ether bond (-O-), an organic group containing an isocyanuric ring, and an organic group containing a glycoluril ring.

[0062] Examples of the polyfunctional thiol compound containing an organic group containing an ether bond include polyfunctional thiol compounds represented by the following general formula (X1') and polyfunctional thiol compounds represented by the following general formula (X2').

[0063] [ka]

[0064] [ka]

[0065] R1, R2, R3 and x in the general formula (X1') are the same as R1, R2, R3 and x in the general formula (X1). R4, R5, R6 and R7 in general formula (X2') are the same as R4, R5, R6 and R7 in general formula (X2).

[0066] Examples of the polyfunctional thiol compound containing an organic group containing an isocyanuric ring include polyfunctional thiol compounds represented by the following general formula (X3').

[0067] [ka]

[0068] R8, R9 and R in general formula (X3') 10 represents R8, R9 and R in general formula (X3). 10 is the same as:

[0069] Examples of polyfunctional thiol compounds containing an organic group containing a glycoluril ring include polyfunctional thiol compounds represented by the following general formula (X4').

[0070] [ka]

[0071] R in general formula (X4') 13 , R 14 , R 15 and R 16 is R in general formula (X4) 13 , R14 , R 15 and R 16 is the same as:

[0072] The polyfunctional thiol compound preferably contains a compound represented by the following general formula (2).

[0073] [ka]

[0074] In the general formula (2), R is an n-valent organic group, and n is an integer of 2 to 6.

[0075] The polyfunctional thiol compound preferably contains at least one compound selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrapropanethiol, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, dipentaerythritol hexakis(3-mercaptopropionate), and tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate.

[0076] The content of the polyfunctional thiol compound may be 15% by mass to 40% by mass, 20% by mass to 35% by mass, or 25% by mass to 30% by mass relative to the total of the polyfunctional lactone compound, the polyfunctional thiol compound, the polyfunctional alcohol compound, and the photobase generator.

[0077] (Polyfunctional alcohol compound) The polyfunctional alcohol compound is not particularly limited as long as it is a compound having two or more hydroxy groups (—OH).

[0078] The polyfunctional alcohol compound may be a compound having two or more primary hydroxy groups, a compound having two or more secondary hydroxy groups, or a compound having two or more tertiary hydroxy groups.

[0079] Examples of polyfunctional alcohol compounds include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, methylpropanediol, cyclohexanedimethanol, 3,3-diethyl-1,5-pentanediol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0080] The content of the polyfunctional alcohol compound may be 15% by mass to 40% by mass, 20% by mass to 35% by mass, or 25% by mass to 30% by mass relative to the total of the polyfunctional lactone compound, the polyfunctional thiol compound, the polyfunctional alcohol compound, and the photobase generator.

[0081] (Photobase Generator) The curable composition of the present disclosure contains a photobase generator. The photobase generator is a compound that generates a base upon irradiation with light, and the conjugate acid of the base has a pKa in acetonitrile of 12 or greater.

[0082] From the viewpoint of reactivity upon irradiation with light, the photobase generator preferably has a pKa of 14 or more, more preferably 16 or more, in acetonitrile of the conjugate acid of the base generated.

[0083] The photobase generator is preferably at least one selected from the group consisting of carbamates having a nitrobenzyl skeleton, compounds having a coumaric acid amide skeleton, and ionic base generators which are salts of a base and a carboxylic acid.

[0084] Examples of carbamates having a nitrobenzyl skeleton include compounds having a structure represented by the following general formula (3): Carbamates having a nitrobenzyl skeleton are compounds that undergo a decarboxylation reaction upon irradiation with light, generating a base.

[0085] [ka]

[0086] In general formula (3), R a , R b , R c and R d are each independently a hydrogen atom or a monovalent substituent, and R e is a monovalent substituent containing a nitrogen atom attached to the carbonyl carbon.

[0087] R a , R b , R c and R d Examples of the monovalent substituent in the above formula include an alkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylthio group, an arylthio group, a cyano group (-CN), a halogen atom, a nitro group, a haloalkyl group (halogenated alkyl group), a hydroxyl group (-OH), a mercapto group (-SH), an amino group, an aromatic hydrocarbon group, and an aromatic heterocyclic group.

[0088] R a and R d is preferably a hydrogen atom, and R b and R c is preferably an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or an n-butoxy group.

[0089] The photobase generator may contain a structure represented by general formula (1)-12, (1)-13, or (1)-14. For example, in the structure represented by general formula (3) in a carbamate having a nitrobenzyl skeleton, R e may be a structure represented by general formula (1)-12, (1)-13 or (1)-14.

[0090] [ka]

[0091] In general formula (1)-12 to general formula (1)-14, R 22 , R 23 , R 24 , R 32 , R 33 , R 41 , R 42 , R 43 and R 44 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R 21 and R 31 R each independently represents a hydrocarbon group which may have a substituent, and * represents the bonding position at which it bonds to * in general formula (a) to form a single bond. 21 ~R 24 At least two of may be bonded to each other to form a ring structure, R 31 ~R 33 At least two of may be bonded to each other to form a ring structure, R 41 ~R 44 At least two of these may be bonded to each other to form a ring structure.

[0092] R 21 ~R 24 , R 31 ~R 33 , and R 41 ~R 44The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group (aryl group), may be an aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with an aromatic hydrocarbon group, or may be a polycyclic hydrocarbon group in which a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group are condensed.

[0093] The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group.

[0094] The linear or branched alkyl group preferably has 1 to 20 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1-methylbutyl group, an n-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, an n-heptyl group, Examples of such alkyl groups include 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups.

[0095] The cyclic alkyl group preferably has 3 to 20 carbon atoms, and examples of the alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, and tricyclodecyl groups. Examples of the cyclic alkyl group include those in which one or more hydrogen atoms are substituted with a linear, branched, or cyclic alkyl group. Examples of the linear, branched, and cyclic alkyl group that substitutes a hydrogen atom include those exemplified above for the alkyl group.

[0096] The unsaturated aliphatic hydrocarbon group may be linear, branched, or cyclic, and if cyclic, may be monocyclic or polycyclic. The unsaturated aliphatic hydrocarbon group preferably has 2 to 20 carbon atoms. Examples of the unsaturated aliphatic hydrocarbon group include groups in which one or more single bonds (CC) between carbon atoms in the alkyl group are replaced with unsaturated double bonds (C=C) or triple bonds (C≡C). The unsaturated aliphatic hydrocarbon group may have one or more unsaturated bonds. When the number of unsaturated bonds is two or more, the unsaturated bonds may be double bonds only, triple bonds only, or a mixture of double and triple bonds. In the unsaturated aliphatic hydrocarbon group, the position of the unsaturated bond is not particularly limited.

[0097] Preferred examples of the unsaturated aliphatic hydrocarbon group include linear or branched alkenyl and alkynyl groups, which correspond to groups having one unsaturated bond, and cyclic cycloalkenyl and cycloalkynyl groups. Examples of the alkenyl group include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), and a cyclohexenyl group.

[0098] The aryl group may be either monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms. Examples of such aryl groups include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, and xylyl (dimethylphenyl) groups, and also include aryl groups in which one or more hydrogen atoms are further substituted with such aryl groups, the alkyl groups, or the like. The aryl groups having such substituents preferably have 6 to 20 carbon atoms, including the carbon atoms of the substituents.

[0099] In general formula (1)-12, R 21 , R 22 , R 23 and R 24 When two or more of the hydrocarbon groups are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring together with the nitrogen atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom (the same carbon atom to which all three nitrogen atoms are bonded). Here, "two or more hydrocarbon groups are bonded to each other" means, for example, 21 ~R 24 In the case where only two, three or all (four) of the above are hydrocarbon groups, and only two or three of the hydrocarbon groups are bonded to each other, or in the case where R 21 ~R 24 All of the above (four types) are hydrocarbon groups, and there are cases where all of these hydrocarbon groups are bonded to each other.

[0100] When two or more hydrocarbon groups are bonded to each other, the position of the carbon atom to which they are bonded (bonding position) is not particularly limited. For example, when the hydrocarbon groups to be bonded are linear or branched, the bonding position may be a terminal carbon atom of the hydrocarbon group, or a so-called root carbon atom directly bonded to the nitrogen atom shown in general formula (1)-12 of the hydrocarbon group, or a carbon atom intermediate between the terminal and root. On the other hand, when the hydrocarbon groups to be bonded are cyclic or have both a chain structure and a cyclic structure, the bonding position may be a root carbon atom or any other carbon atom.

[0101] R 21 , R 22 , R 23 and R 24 When two of the hydrocarbon groups are bonded to each other, the ring formed thereby may be either monocyclic or polycyclic.

[0102] In general formula (1)-13, R 31 , R 32 and R 33 When two or more of the hydrocarbon groups are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring together with the nitrogen atom or carbon atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom or the nitrogen atom bonded to the carbon atom. Here, "two or more hydrocarbon groups are bonded to each other" means that, as described above, R 21 ~R 24 This means that the hydrocarbon groups of either R 31 ~R 33 In the case where only two or all (three) of the above are hydrocarbon groups, and only two of the hydrocarbon groups are bonded to each other, or in the case where R 31 ~R 33 All three of these are hydrocarbon groups, and all of these hydrocarbon groups may bond to each other. The way in which the hydrocarbon groups bond to each other also varies depending on the R 21 ~R 24 The same is true for the case.

[0103] In general formula (1)-14, R 41 , R 42 , R 43 and R 44 When two or more of the hydrocarbon groups are hydrocarbon groups, these hydrocarbon groups may be bonded to each other to form a ring together with the nitrogen atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom (the same carbon atom to which all three nitrogen atoms are bonded). Here, "two or more hydrocarbon groups are bonded to each other" means that, as described above, 21 ~R 24 This means that the hydrocarbon groups of either R 41~R 44 In the case where only two, three or all (four) of the above are hydrocarbon groups, and only two or three of the hydrocarbon groups are bonded to each other, or in the case where R 41 ~R 44 All of these (four types) are hydrocarbon groups, and all of these hydrocarbon groups may bond to each other. The way in which the hydrocarbon groups bond to each other also varies depending on the R 21 ~R 24 This is the same as in the case of

[0104] Among the structures represented by the general formula (1-13), R 32 is a hydrocarbon group, and R 31 and R 33 are preferably hydrocarbon groups bonded to each other, and R 32 is a methyl group, and R 31 and R 33 More preferably, they are bonded to each other to form an ethylene group.

[0105] Among the structures represented by the general formula (1-14), R 41 ~R 44 are preferably all hydrocarbon groups, and R 41 ~R 44 are more preferably all methyl groups.

[0106] The compound having a coumaric acid amide skeleton includes a compound having a structure represented by the following general formula (4): The compound having a coumaric acid amide skeleton can be irradiated with light to form a compound having a structure represented by the general formula (4) below.

[0107] [ka]

[0108] In general formula (3), R f , R g , R h and R i are each independently a hydrogen atom or a monovalent substituent, and R j is a monovalent substituent containing a nitrogen atom attached to the carbonyl carbon.

[0109] The compound having a coumaric acid amide skeleton is preferably a compound that generates, upon irradiation with light, a base in which a hydrogen atom is bonded to a nitrogen atom bonded to a carbonyl carbon, and coumarin or a coumarin derivative.

[0110] In general formula (4), R f , R g , R h and R i R each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylthio group, an arylthio group, a cyano group (-CN), a halogen atom, a nitro group, a haloalkyl group (halogenated alkyl group), a hydroxyl group (-OH), a mercapto group (-SH), an amino group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. f ~R i At least two of these may be bonded to each other to form a ring structure.

[0111] R j may be a structure represented by general formula (1)-12, (1)-13 or (1)-14.

[0112] Examples of ionic base generators that are salts of a base and a carboxylic acid include conventionally known ionic base generators, such as the ionic base generator corresponding to a salt of a strong base such as guanidine with an aromatic component-containing carboxylic acid described in "K. Arimitsu, R. Endo, Chem. Mater. 2013, 25, 4461-4463," ionic base generators such as carboxylates formed from carboxylic acids and bases described in JP-A-2011-80032, and ionic photobase generators such as salts of aromatic component-containing carboxylic acids with tertiary amines described in JP-A-2017 / 122744.

[0113] The photobase generator contained in the curable composition of the present disclosure may be one type only, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0114] In the curable composition of the present disclosure, the content of the photobase generator is preferably 4% by mass to 39% by mass, more preferably 6% by mass to 36% by mass, and even more preferably 8% by mass to 33% by mass, relative to the total content of the polyfunctional lactone compound, polyfunctional thiol compound, and polyfunctional alcohol compound. When the content of the photobase generator is 4% by mass or more, the reaction of the aforementioned components proceeds more easily. Furthermore, when the content of the photobase generator is 39% by mass or less, excessive use of the photobase generator is suppressed.

[0115] (Other ingredients) The curable composition of the present disclosure may further contain other components in addition to the polyfunctional lactone compound, the polyfunctional thiol compound, the polyfunctional alcohol compound, and the photobase generator. The other components are not particularly limited as long as they do not impair the effects of the present invention, and can be selected arbitrarily depending on the purpose. The curable composition may contain only one type of other component, or two or more types. When two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0116] Examples of the other components include reactive compounds other than polyfunctional lactone compounds, polyfunctional thiol compounds, and polyfunctional alcohol compounds (other reactive compounds), sensitizers, fillers, pigments, solvents, and the like.

[0117] <Other reactive compounds> The curable compositions of the present disclosure may contain other reactive compounds. Other reactive compounds include compounds having a functional group that is converted into a reactive group by the action of a base (sometimes referred to as "base-reactive compound (9-2a)" in the present disclosure), and compounds having a group that reacts by the action of a base (sometimes referred to as "base-reactive compound (9-2b)" in the present disclosure). The base-reactive compound (9-2b) differs from the base-reactive compound (9-2a) in that the reactive group is not a functional group that is converted into a reactive group by the action of a base.

[0118] Examples of reactions that proceed in the base-reactive compound include addition polymerization and condensation polymerization (polycondensation polymerization).

[0119] The base-reactive compound may be, for example, any of a monomer, an oligomer, and a polymer, and may be any of a low molecular weight compound and a high molecular weight compound.

[0120] As the base-reactive compound, known compounds can be used, for example, the base-reactive compounds described in JP-A-2011-80032, although this is just one example.

[0121] Examples of the base-reactive compound (9-2a) include compounds that are decomposed by the action of a base and have a functional group converted into a reactive group. Examples of such base-reactive compounds (9-2a) include compounds having a carbonate skeleton (-OC(=O)-O-), photosensitive polyimides, etc.

[0122] Examples of the base-reactive compound (9-2b) include epoxy resins, silicone resins, alkoxysilane compounds, and (meth)acrylate compounds. In the present disclosure, the term "(meth)acrylate" is a concept that encompasses both "acrylate" and "methacrylate."

[0123] The other reactive compounds may be used alone or in combination of two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be set arbitrarily.

[0124] <Sensitizer> The curable compositions of the present disclosure may contain a sensitizer. The sensitizer is not particularly limited, and examples thereof include benzophenone, naphthoquinone, anthraquinone, xanthene, thioxanthene, xanthone, thioxanthone, anthracene, phenanthrene, phenanthroline, pyrene, pentacene, and derivatives thereof. The sensitizer may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be set arbitrarily. The content of the sensitizer in the curable composition is not particularly limited and may be adjusted appropriately.

[0125] <Filling material> The curable composition of the present disclosure may contain a filler. By including a filler, it is possible to adjust properties such as the viscosity of the curable composition itself and the strength of the curable composition after reaction (the reaction product described below). The filler may be any known filler without any particular limitation. For example, the filler may be fibrous, plate-like, or granular, and the shape, size, and material thereof may all be appropriately selected depending on the purpose. The curable composition may contain only one type of filler, or two or more types. When two or more types are contained, the combination and ratio of the fillers can be set arbitrarily. The content of the filler in the curable composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0126] <Pigments> The curable composition of the present disclosure may contain a pigment. By including a pigment, for example, light transmittance and the like can be adjusted. The pigment contained in the curable composition may be any known pigment, such as white, blue, red, yellow, or green pigment, and is not particularly limited. The curable composition may contain one kind of pigment or two or more kinds of pigments, and when two or more kinds of pigments are contained, the combination and ratio thereof can be set arbitrarily. The content of the pigment in the curable composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0127] <Solvent> The curable composition of the present disclosure may contain a solvent. By containing a solvent, handling properties are improved. The solvent is not particularly limited and may be appropriately selected in consideration of the solubility, stability, etc. of the curable composition and the photobase generator. The solvent is not particularly limited, and examples thereof include halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; aliphatic hydrocarbons such as hexane, heptane, and octane; carboxylic acid esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), and 1,2-dimethoxyethane (dimethylcellosolve); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and cyclopentanone; nitriles such as acetonitrile; and amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide.

[0128] The curable composition may contain one or more solvents, and when two or more solvents are contained, the combination and ratio thereof can be set arbitrarily.

[0129] In the curable composition, the content of the solvent is preferably 3 to 20 times by mass, more preferably 4 to 15 times by mass, and even more preferably 5 to 10 times by mass, relative to the total content of the polyfunctional lactone compound, polyfunctional thiol compound, and polyfunctional alcohol compound. When the content of the solvent is within this range, the handleability of the curable composition is further improved.

[0130] The curable composition can be obtained by blending a polyfunctional lactone compound, at least one compound selected from a polyfunctional thiol compound and a polyfunctional alcohol compound, a photobase generator, and, if necessary, other components. After blending the components, the resulting composition may be used as the curable composition as is, or may be used as the curable composition after, if necessary, performing a known purification procedure or the like.

[0131] When blending the components, all the components may be added and then mixed, or some of the components may be added sequentially while mixing, or all the components may be added sequentially while mixing. The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, or a method of mixing by adding ultrasound.

[0132] The temperature during blending is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 3°C to 30°C. The blending time is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 30 seconds to 1 hour. However, these compounding conditions are merely examples.

[0133] <Reaction products> The reaction product of the present disclosure is obtained by reacting the above-described curable composition. A method for producing the reaction product of the present disclosure will be described later in the method for producing the reaction product of the present disclosure. The shape of the reaction product of the present disclosure can be selected arbitrarily depending on the purpose, for example, in the form of a film or a line.

[0134] (Method for producing reaction product) The method for producing a reaction product of the present disclosure includes a step of irradiating the curable composition with light to generate the base from the photobase generator. By irradiating the curable composition containing the photobase generator with light, a base is generated from the photobase generator, and the generated base acts to abstract a proton from the thiol group in the polyfunctional thiol compound, thereby generating a sulfur anion (-S -) is generated. The reaction of polyfunctional lactone compounds with sulfur anions produces reaction products.

[0135] The curable composition may be applied to an object by a known method, and then optionally pre-baked (dried) to form a photoreactive composition layer, and the curable composition layer may be irradiated with light. For example, when a film-like reaction product is produced, the curable composition may be applied to a target object using a coating means such as a spin coater, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Mayer bar coater, or a kiss coater, or an applicator, or the like, or the target object may be immersed in the curable composition, thereby adhering the curable composition to the target object. For example, when producing a film-like or linear reaction product, the curable composition may be attached to a target object by using a printing method such as screen printing, flexographic printing, offset printing, inkjet printing, dispenser printing, jet dispenser printing, gravure printing, gravure offset printing, or pad printing.

[0136] The pre-baking may be carried out under conditions of, for example, 30° C. to 120° C. and 30 seconds to 10 minutes, and is not particularly limited.

[0137] The wavelength of the light irradiated onto the curable composition is not particularly limited and may be, for example, a wavelength in the ultraviolet to visible light range. The wavelength of the light irradiated onto the curable composition may be 10 nm or more, 200 nm or more, or 300 nm or more. Furthermore, the wavelength of the light irradiated onto the curable composition may be 600 nm or less, 500 nm or less, or 400 nm or less.

[0138] The illuminance of the light irradiated onto the curable composition is, for example, 1 mW / cm 2 ~100mW / cm 2 and preferably 5 mW / cm2 ~80mW / cm 2 More preferably, it is 10 mW / cm 2 ~60mW / cm 2 It is more preferable that: The light irradiation dose applied to the curable composition is, for example, 100 mJ / cm 2 ~20,000mJ / cm 2 and preferably 200 mJ / cm 2 ~15000mJ / cm 2 More preferably, it is 300 mJ / cm 2 ~12000mJ / cm 2 It is more preferable that: However, the light irradiation conditions given here are merely examples and are not limited to these.

[0139] The reaction product obtained by irradiating the curable composition with light may be further subjected to post-baking (heat treatment after light irradiation). The post-baking may be carried out under conditions of, for example, 50° C. to 180° C. and 20 minutes to 2 hours, and is not particularly limited.

[0140] The thickness of the reaction product may be appropriately set depending on the purpose and is not particularly limited. The thickness of the reaction product is, for example, preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm. To form a reaction product of such a thickness, for example, the thickness of the curable composition layer may be set to be equal to or greater than the thickness of the desired reaction product. [Example]

[0141] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0142] <Production of Polyfunctional Lactone Compound 1> First, as shown below, 5,6-dihydro-2H-pyran-2-one (DHP) was reacted with a polyfunctional thiol compound (DODT, 3,6-dioxa-1,8-octanedithiol) to produce a polyfunctional lactone compound 1 (Bis-DODT-VL). Specifically, a mixture of excess DHP (1.5 g, 15 mmol), triethylamine (0.10 g, 1.0 mmol), DODT (0.91 g, 5.0 mmol), and 20 mL of dry acetonitrile was stirred at room temperature for 6 hours to carry out the reaction. After completion of the reaction, the solvent was distilled off. Next, the reaction solution from which the solvent was distilled off was washed, and the washed reaction solution was purified by silica gel column chromatography using a mixed solvent of acetone / chloroform (1 / 4, volume ratio) as the mobile phase. The fractions containing the target product were collected and concentrated, yielding the target product, polyfunctional lactone compound 1, as a colorless, transparent, viscous liquid (yield: 1.5 g, 79%). The obtained polyfunctional lactone compound 1 1 The results of analysis by H-NMR and ESI-MS are shown in Table 1.

[0143] [ka]

[0144] [Table 1] JPEG2025175875000021.jpg13164

[0145] <Production of Polyfunctional Lactone Compound 2> First, as shown below, 5,6-dihydro-2H-pyran-2-one (DHP) was reacted with a polyfunctional thiol compound (TS-G, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril) to produce a polyfunctional lactone compound 2 (Tetrakis-TSG-VL). Specifically, a mixture of excess DHP (2.9 g, 30 mmol), triethylamine (0.20 g, 2.0 mmol), TS-G (1.91 g, 5.0 mmol), and 60 mL of dry acetonitrile was stirred at room temperature overnight to carry out the reaction. After completion of the reaction, the solvent was distilled off. Next, the reaction solution from which the solvent was distilled off was washed, and the washed reaction solution was purified by silica gel column chromatography using a mixed solvent of acetone / chloroform (2 / 1, volume ratio) as the mobile phase. Fractions containing the target product were collected and concentrated, yielding the target product, polyfunctional lactone compound 2, as a colorless, transparent, viscous liquid (yield: 3.0 g, 77%). The obtained polyfunctional lactone compound 2 1 The results of analysis by H-NMR and ESI-MS are shown in Table 2.

[0146] [ka]

[0147] JPEG2025175875000023.jpg2780 [Table 2]

[0148] <Production of Polyfunctional Lactone Compound 3> First, as shown below, 5,6-dihydro-2H-pyran-2-one (DHP) was reacted with a polyfunctional thiol compound (C3TS-G, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril) to produce polyfunctional lactone compound 3 (Tetrakis-C3TSG-VL). Specifically, a mixture of excess DHP (2.9 g, 30 mmol), triethylamine (0.20 g, 2.0 mmol), C3TS-G (2.2 g, 5.0 mmol), and 40 mL of dry acetonitrile was stirred at room temperature overnight to carry out the reaction. After completion of the reaction, the solvent was distilled off. Next, the reaction solution from which the solvent was distilled off was washed, and the washed reaction solution was purified by silica gel column chromatography using a mixed solvent of acetone / chloroform (2 / 1, volume ratio) as the mobile phase. Fractions containing the target product were collected and concentrated, yielding the target product, polyfunctional lactone compound 3, as a colorless, transparent, viscous liquid (yield: 0.3 g, 7%). The obtained polyfunctional lactone compound 3 1 The results of analysis by H-NMR and ESI-MS are shown in Table 3.

[0149] [ka]

[0150] [Table 3] JPEG2025175875000027.jpg13164

[0151] <Production of Polyfunctional Lactone Compound 4> First, as shown below, 5,6-dihydro-2H-pyran-2-one (DHP) was reacted with a polyfunctional thiol compound (PEMP, pentaerythritol tetra(3-mercaptopropionate)) to produce polyfunctional lactone compound 4 (Tetrakis-PEMP-VL). Specifically, a mixture of DHP (2.9 g, 30 mmol), triethylamine (0.20 g, 2.0 mmol), PEMP (2.4 g, 5.0 mmol), and 40 mL of dry acetonitrile was stirred at room temperature overnight to carry out the reaction. After completion of the reaction, the solvent was distilled off. Next, the reaction solution from which the solvent was distilled off was washed, and the washed reaction solution was purified by silica gel column chromatography using a mixed solvent of acetone / chloroform (1 / 1, volume ratio) as the mobile phase. Fractions containing the target product were collected and concentrated to obtain the target product, polyfunctional lactone compound 4, as a colorless, transparent, viscous liquid (yield: 1.3 g, 30%). The obtained polyfunctional lactone compound 41 The results of analysis by H-NMR and ESI-MS are shown in Table 4.

[0152] [ka]

[0153] JPEG2025175875000029.jpg2777 [Table 4]

[0154] <Production of Polyfunctional Lactone Compound 5> First, as shown below, 5,6-dihydro-2H-pyran-2-one (DHP) was reacted with a polyfunctional thiol compound (Y-4, pentaerythritol tetrapropanethiol) to produce a polyfunctional lactone compound 5 (Tetrakis-Y4-VL). That is, a mixture of DHP (8.8 g, 90 mmol), triethylamine (0.61 g, 6.0 mmol), Y-4 (6.5 g, 15 mmol), and 90 mL of dry acetonitrile was stirred at room temperature overnight to carry out the reaction. After completion of the reaction, the solvent was distilled off. Next, the reaction solution from which the solvent was distilled off was washed, and the washed reaction solution was purified by silica gel column chromatography using a mixed solvent of acetone / chloroform (1 / 5, volume ratio) as the mobile phase. Fractions containing the target product were collected and concentrated, yielding the target product, polyfunctional lactone compound 5, as a colorless, transparent, viscous liquid (yield: 8.1 g, 68%). The obtained polyfunctional lactone compound 5 1 The results of analysis by H-NMR and ESI-MS are shown in Table 5.

[0155] [ka]

[0156] [Table 5]

[0157] <Base Consideration> A mixture of polyfunctional lactone compound 5 (Tetrakis-Y4-VL, 0.082 g, 0.10 mmol), polyfunctional thiol compound (Y-4, 0.043 g, 100 mol % based on polyfunctional lactone compound 5), any one of the bases shown below (20 mol % based on polyfunctional lactone compound 5), dry dichloromethane (0.20 mL), and dry acetonitrile (0.10 mL) was prepared in a glass bottle by stirring. The mixed solution was dried under reduced pressure for 30 minutes, and then stored in a dark place at 25°C, and the number of days until gelation was confirmed. The number of days until gelation and the pKa of the conjugate acid of each base in acrylonitrile are shown in Table 6. In Table 6, "-" means that no data is available. (Bases investigated) TMG 1,1,3,3-tetramethylguanidine DBU Diazabicycloundecene TBD Triazabicyclodecene DBN 1,5-diazabicyclo[4.3.0]-5-nonene Im imidazole 2M2I 2-methylimidazole DMAP 4-dimethylaminopyridine

[0158] [Table 6]

[0159] Considering the fact that the photobase generator can be synthesized, that it takes a short time for gelation in the presence of a base, and that it has excellent reactivity, it was decided to use a photobase generator that generates TMG in the preparation of the curable composition.

[0160] <Study on multifunctional thiol compounds> A mixture was prepared in a glass bottle by adding polyfunctional lactone compound 5 (Tetrakis-Y4-VL, 0.082 g, 0.10 mmol), one of the following polyfunctional thiol compounds (100 mol % based on polyfunctional lactone compound 5), 1,1,3,3-tetramethylguanidine (TMG) (0.0024 g, 20 mol % based on polyfunctional lactone compound 5), dry dichloromethane (0.20 mL), and dry acetonitrile (0.10 mL). The mixed solution was dried under reduced pressure for 30 minutes, and then stored in a dark place at 25°C, and the number of days until gelation was confirmed. The results are shown in Table 7. (Polyfunctional thiol compounds investigated) Y-4 Pentaerythritol tetrapropanethiol C3TS-G 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril DPMP Dipentaerythritol hexakis(3-mercaptopropionate) PEMP Pentaerythritol tetra(3-mercaptopropionate) TEPMIC Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate

[0161] [Table 7]

[0162] Considering the fact that it takes a short time for gelation in the presence of a base and has excellent reactivity, it was decided to use pentaerythritol tetrapropanethiol as the polyfunctional thiol compound in preparing the curable composition.

[0163] <Preparation of Curable Composition> A curable composition was prepared by adding polyfunctional lactone compound 5 (Tetrakis-Y4-VL, 0.82 g, 1.0 mmol), polyfunctional thiol compound (Y-4, 0.43 g, 100 mol % based on polyfunctional lactone compound 5), a photobase generator (NV-TMG) shown below (0.14 g, 40 mol % based on polyfunctional lactone compound 5), and dry dichloromethane (0.60 mL) to a glass bottle and stirring.

[0164] [ka]

[0165] (Production of reaction products) The curable composition obtained above was dissolved in methanol and the resulting mixture was applied to a calcium fluoride plate. This coating (photoreactive composition layer) was then heated (prebaked) at 40°C for 5 minutes. The calcium fluoride plate formed on the photoreactive composition layer was then laminated using a silica spacer (10µm) and fixed with polytetrafluoroethylene tape to produce Laminate 1. Next, an LED lamp was used to set the illuminance at 50mW / cm. 2 , light irradiation dose 5.0 J / cm 2 The coating film was irradiated with light at a wavelength of 365 nm. Two types of coating film were prepared after light irradiation, and one was left standing at room temperature for 24 hours, while the other was left standing at 60°C for 24 hours to attempt to produce a reaction product. The peak intensity of the coating film after standing was measured using a Fourier transform infrared spectrophotometer (FT-IR). For comparison, two types of unirradiated samples of the aforementioned laminate 1 were prepared, one was left standing at room temperature for 24 hours, and the other was left standing at 60°C for 24 hours, and the peak intensity of the coating film after standing was measured using a Fourier transform infrared spectrophotometer (FT-IR). The results are shown in Figure 1.

[0166] As shown in Figure 1, light irradiation increased the lactone conversion rate, and for the coating film after light irradiation, the lactone conversion rate was 33% after standing at room temperature for 24 hours and 36% after standing at 60°C for 24 hours. On the other hand, for the coating film not irradiated with light, the lactone conversion rate was 10% or less after standing at room temperature or 60°C for 24 hours, indicating that the progress of the reaction was inhibited. Therefore, it was confirmed that the reaction can be inhibited in the dark in the curable composition and can be controlled by light irradiation.

[0167] (Evaluation of Adhesion of Curable Composition by Light Irradiation) A curable composition was prepared in the same manner as in the above <Preparation of curable composition>. The curable composition obtained above was applied onto a glass plate. The size of the coating film was 26 mm long x 10 mm wide. Next, this coating film (photoreactive composition layer) was heated (prebaked) at 40°C for 5 minutes, and then a glass plate of the same size as above was placed over the 26 mm long x 10 mm wide area at the edge of the coating film and laminated to form a laminate 2. Thereafter, an LED lamp was used to illuminate the glass plate at an illuminance of 50 mW / cm. 2 , light irradiation dose 5.0 J / cm 2 The coating film was irradiated with light of 365 nm wavelength. Two types of coating film were prepared after light irradiation, and one was left standing at room temperature for 8 days, while the other was left standing at 60°C for 4 days to prepare samples for measuring tensile shear bond strength. The tensile shear bond strength (MPa) of the samples was measured using a tensile shear load parallel to the adhesive surface in accordance with JIS K 6850 1999 "Test method for tensile shear bond strength of rigid adherends." For comparison, two types of samples of the aforementioned laminate 2 that were not irradiated with light were prepared, and the tensile shear bond strength (MPa) of these samples was measured in the same manner as above. The results are shown in Figure 2. In Figure 2,

[0168] As shown in Figure 2, it was confirmed that light irradiation improves the tensile shear bond strength. Furthermore, it was confirmed that heating can shorten the curing time, further improving the tensile shear bond strength.

Claims

1. a polyfunctional lactone compound; At least one compound selected from the group consisting of a polyfunctional thiol compound and a polyfunctional alcohol compound; a photobase generator; The curable composition, wherein a conjugate acid of a base generated by irradiating the photobase generator with light has a pKa in acetonitrile of 12 or more.

2. The curable composition according to claim 1, wherein the polyfunctional lactone compound contains a plurality of δ-valerolactone skeletons.

3. The curable composition according to claim 1 , wherein the polyfunctional lactone compound comprises a compound represented by the following general formula (1): 【Chemistry 1】 In the general formula (1), R is an n-valent organic group, and n is an integer of 2 to 6.

4. The curable composition according to claim 1, wherein the polyfunctional thiol compound includes a compound having 2 to 6 primary thiol groups.

5. The curable composition according to claim 1 , wherein the polyfunctional thiol compound includes a compound represented by the following general formula (2): 【Chemistry 2】 In the general formula (2), R is an n-valent organic group, and n is an integer of 2 to 6.

6. The curable composition according to claim 1, wherein the polyfunctional thiol compound comprises at least one compound selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrapropanethiol, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, dipentaerythritol hexakis(3-mercaptopropionate), and tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate.

7. 2. The curable composition according to claim 1, wherein the photobase generator is at least one selected from the group consisting of carbamates having a nitrobenzyl skeleton, compounds having a coumaric acid amide skeleton, and ionic base generators which are salts of a base and a carboxylic acid.

8. The curable composition according to claim 1, wherein the photobase generator comprises a structure represented by general formula (1)-12, (1)-13, or (1)-14. 【Transformation 3】 (In general formula (1)-12 to general formula (1)-14, R ２２ , R ２３ , R ２４ , R ３２ , R ３３ , R ４１ , R ４２ , R ４３ and R ４４ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R ２１ and R ３１ R each independently represents a hydrocarbon group which may have a substituent, and * represents the bonding position at which it bonds to * in general formula (a) to form a single bond. ２１ ~R ２４ At least two of may be bonded to each other to form a ring structure, and R ３１ ~R ３３ At least two of may be bonded to each other to form a ring structure, and R ４１ ~R ４４ At least two of may be bonded to each other to form a ring structure.)

9. A reaction product obtained by reacting the curable composition according to any one of claims 1 to 8.

10. A polyfunctional lactone compound which is a compound represented by the following general formula (1): 【Chemistry 4】 In the general formula (1), R is an n-valent organic group, and n is an integer of 2 to 6.

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