Photobase generators, compounds, photoreactive compositions and reaction products

Abstract

A photobase generator that comprises a compound including a first skeleton, which is represented by general formula (a), and a second skeleton, which includes a nitrogen atom that has been bonded to the combining site of the first skeleton to constitute an amide group, wherein the compound, upon irradiation with light, generates a base comprising the second skeleton and a hydrogen atom bonded to the nitrogen atom thereof, the conjugate acid of the base having a pKa in water of 12 or greater. In general formula (a), G is a divalent aromatic group and * indicates the site of combining with the nitrogen atom.

Description

[Technical Field]

[0001] The present invention relates to photobase generators, compounds, photoreactive compositions and reaction products. [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] However, although such ionic photobase generators have high reactivity, they have problems such as low storage stability and low solubility, and further, resin compositions using such ionic photobase generators also have problems such as low stability.

[0005] 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). Such non-ionic photobase generators solve the problems associated with ionic photobase generators. [Prior art documents] [Patent documents]

[0006] [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]

[0007] However, the non-ionic photobase generator disclosed in Non-Patent Document 2 generates a base with weak basicity, and therefore resin compositions using such a base still have room for improvement in terms of improving reactivity upon light irradiation. Furthermore, the non-ionic photobase generator disclosed in Non-Patent Document 2 has the problem that a decarboxylation reaction occurs along with the generation of a base upon exposure to light.

[0008] The present invention aims to provide a photobase generator and compound with which a photoreactive composition that exhibits excellent reactivity upon light irradiation and does not undergo a decarboxylation reaction upon light irradiation can be prepared, a photoreactive composition that exhibits excellent reactivity upon light irradiation and does not undergo a decarboxylation reaction upon light irradiation, and a reaction product obtained by reacting this photoreactive composition. [Means for solving the problem]

[0009] Specific means for solving the above problems are as follows. <1> A photobase generator comprising a compound having a first skeleton represented by the following general formula (a) and a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, wherein the compound generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton upon irradiation with light, and the pKa of the conjugate acid of the base in water is 12 or more:

[0010] [ka]

[0011] (In general formula (a), G is a divalent aromatic group, and * represents the bonding position to the nitrogen atom.) <2> The second skeleton is a structure represented by the following general formula (1)-12, (1)-13, or (1)-14: <1> The photobase generator according to claim 1.

[0012] [ka]

[0013] (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 33At least two of may be bonded to each other to form a ring structure, R 41 ~R 44 At least two of may be bonded to each other to form a ring structure. <3> A photobase generator comprising a compound having a first skeleton represented by the following general formula (a) and a second skeleton represented by the above general formula (1)-12, (1)-13 or (1)-14, which has a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, wherein the compound generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton upon irradiation with light.

[0014] [ka]

[0015] [ka]

[0016] (In general formula (a), G is a divalent aromatic group, and * represents the bonding position with the nitrogen atom. In general formulas (1)-12 to (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 44At least two of the groups may be bonded to each other to form a ring structure. 31 and R 33 When a ring structure is formed by bonding to each other, the ring structure does not exhibit aromaticity. <4> A compound having a first skeleton represented by the following general formula (a) and a second skeleton having a nitrogen atom bonding to a bonding position of the first skeleton to form an amide group, wherein upon irradiation with light, a base is generated in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton, and the pKa of the conjugate acid of the base in water is 12 or more:

[0017] [ka]

[0018] (In general formula (a), G is a divalent aromatic group, and * represents the bonding position to the nitrogen atom.)

[0019] <5> The second skeleton is a structure represented by the following general formula (1)-12, (1)-13, or (1)-14: <4> The compound described in

[0020] [ka]

[0021] (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 ~R24 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 may be bonded to each other to form a ring structure. <6> A compound having a first skeleton represented by the following general formula (a) and a second skeleton represented by the above general formula (1)-12, (1)-13 or (1)-14, which has a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and which generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton upon irradiation with light:

[0022] [ka]

[0023] [ka]

[0024] (In general formula (a), G is a divalent aromatic group, and * represents the bonding position with the nitrogen atom. In general formulas (1)-12 to (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, R41 ~R 44 At least two of the groups may be bonded to each other to form a ring structure. 31 and R 33 When a ring structure is formed by bonding to each other, the ring structure does not exhibit aromaticity. <7> <1> ~ <3> and a base-reactive compound, wherein the base-reactive compound is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base. <8> <7> A reaction product obtained by reacting the photoreactive composition described in 1. [Effects of the Invention]

[0025] According to the present invention, it is possible to provide a photobase generator and compound with which a photoreactive composition that has excellent reactivity when irradiated with light and does not undergo a decarboxylation reaction when irradiated with light can be prepared, a photoreactive composition that has excellent reactivity when irradiated with light and does not undergo a decarboxylation reaction when irradiated with light, and a reaction product obtained by reacting this photoreactive composition. [Brief explanation of the drawings]

[0026] [Figure 1] 1 shows data showing the results of measuring the absorbance of Compound (1)-1 in Test Example 1. [Figure 2] 1 shows data showing the results of measuring the absorbance of Compound (1)-1 in Test Example 2. [Figure 3] 1 shows data showing the results of measuring the IR spectrum of a base-reactive compound (9)-301 in Comparative Example 1. [Figure 4] 1 is a graph showing the relationship between the heating time under light irradiation conditions and the peak area derived from methoxy groups in Comparative Example 1. [Figure 5] 1 is a graph showing the relationship between the heating time under light irradiation conditions and the peak area derived from methoxy groups in Example 1 and Comparative Example 1. [Figure 6]1 is a graph showing the relationship between heating temperature and pencil hardness of the cured products obtained in Example 1 and Comparative Example 1. [Figure 7] 1 is a graph showing the relationship between the amount of light irradiated onto the photoreactive composition and the peak area derived from the acryloyl group in the IR spectrum in Example 2. [Figure 8] 1 is a graph showing the relationship between the heating time under light irradiation conditions and the peak area derived from acryloyl groups in Examples 2 and 3. [Figure 9] 1 is a graph showing the relationship between the heating time under light irradiation conditions and the peak area derived from mercapto groups in Examples 2 and 3. [Figure 10] Graph (a) is a graph showing the relationship between the amount of light irradiated onto the photoreactive composition and the heating time of the photoreactive composition, and the peak areas derived from epoxy groups and mercapto groups in Example 4, and graph (b) is a diagram comparing the peak areas derived from hydroxyl groups under each condition by enlarging the part corresponding to the peak areas derived from hydroxyl groups in graph (a). [Figure 11] 10 is a graph showing the relationship between the heating time under light irradiation conditions and non-light irradiation conditions and the peak area derived from the epoxy group in Example 4. [Figure 12] 10 is a graph showing the relationship between the heating time under light irradiation conditions and non-light irradiation conditions and the peak area derived from mercapto groups in Example 4. [Figure 13] 1 is a graph showing the relationship between the amount of light irradiation of Compound (1)-3 and the peak areas of the amide group and lactone structure in the IR spectrum in Test Example 9. [Figure 14] 1 is a graph showing the relationship between the amount of light irradiation of Compound (1)-3 and the peak areas of the amide group and lactone structure in the IR spectrum in Test Example 10. [Figure 15] 1 is a graph showing the relationship between the heating time under light irradiation conditions and the peak area derived from acryloyl groups in Examples 5 and 6. [Figure 16] 1 is a graph showing the relationship between the heating time under light irradiation conditions and the peak area derived from mercapto groups in Examples 5 and 6. [Figure 17] 1 shows the results of measuring the UV-Vis spectrum of a methanol solution containing 2-methyl-2-imidazoline (2MI), cyclohexylamine (CyA) or diazabicycloundecene (DBU), and phenol red in Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0027] 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.

[0028] [Photobase generator] The photobase generator of the present disclosure includes a compound having a first skeleton represented by the following general formula (a) and a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, wherein the compound generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton upon irradiation with light, and the pKa of the conjugate acid of the base in water is 12 or higher.

[0029] [ka]

[0030] In the general formula (a), G is a divalent aromatic group, and * represents the bonding position to the nitrogen atom.

[0031] For example, the photobase generator of the present disclosure is used to prepare a photoreactive composition that can produce a reaction product by light irradiation. More specifically, by irradiating a photoreactive composition containing a photobase generator with light, a base is generated from the photobase generator, and the functional group contained in the base-reactive compound in the photoreactive composition is converted and becomes reactive by the action of the generated base, or the functional group contained in the base-reactive compound reacts by the action of the generated base. Therefore, by irradiating the above-mentioned photoreactive composition with light to generate a base, the base-reactive compound contained in the photoreactive composition reacts to obtain a reaction product.

[0032] The photobase generator of the present disclosure includes a compound (sometimes referred to as "compound (1)" in the present disclosure) that generates a base upon irradiation with light, having a first skeleton represented by the general formula (a) and a second skeleton (X in the following formula (i)) that has a nitrogen atom bonded to the bonding position of the first skeleton to form an amide group. Furthermore, as shown in the following formula (i), compound (1) becomes a cis-isomer upon irradiation with light. Thereafter, the oxygen atom of the hydroxyl group in general formula (a) bonds with the carbonyl carbon in general formula (a), and the nitrogen atom in the second skeleton that was bonded to the carbonyl carbon dissociates and bonds with a hydrogen atom. This generates a compound represented by the following general formula (1') and an amine compound represented by HX. The generated amine compound is a base, and the conjugate acid of this base has a pKa of 12 or higher in water.

[0033] In addition, compound (1) is a non-ionic photobase generator, and unlike conventional ionic photobase generators, it has high storage stability and high solubility, and photoreactive compositions using it are highly stable. Furthermore, in photoreactive compositions using a photobase generator containing compound (1), the conjugate acid of the generated base has a pKa in water of 12 or more, and therefore the reactivity of the base-reactive compound when irradiated with light is good.

[0034] [ka]

[0035] In terms of reactivity upon irradiation with light, the pKa of the conjugate acid of the base generated from compound (1) in water is preferably 14 or higher, more preferably 16 or higher.

[0036] Further, as a conventionally known non-ionic photobase generator, for example, a carbamate having a nitrobenzyl skeleton shown below is known. When such a carbamate having a nitrobenzyl skeleton is irradiated with light, a decarboxylation reaction proceeds as shown in the following formula (ii), generating a base (a primary amine in the following reaction formula).

[0037] [ka]

[0038] On the other hand, the compound (1) contained in the photobase generator of the present disclosure does not undergo decarboxylation upon irradiation with light, as shown in the above formula (i), which can suppress the generation of bubbles due to carbon dioxide and the reduction in strength of the cured reaction product.

[0039] In the general formula (a), G is a divalent aromatic group in which a hydroxyl group and —CH═CH—C(═O)—* are bonded. The bonding positions of the hydroxyl group and -CH=CH-C(=O)-* in G are in an ortho position relative to each other. That is, among the atoms constituting the ring skeleton of G, the atom to which the hydroxyl group is bonded and the atom to which -CH=CH-C(=O)-* is bonded are adjacent to each other (directly bonded) in the ring skeleton of G.

[0040] The aromatic group in G may be either a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, or may be a divalent group formed by condensing an aromatic hydrocarbon group and an aromatic heterocyclic group (in the present disclosure, such a group is treated as an aromatic heterocyclic group).

[0041] These aromatic hydrocarbon groups and aromatic heterocyclic groups may also have a substituent. Here, "the aromatic hydrocarbon group has a substituent" means that one or more hydrogen atoms constituting the aromatic hydrocarbon group have been substituted with a group (substituent) other than a hydrogen atom. The phrase "an aromatic heterocyclic group has a substituent" means that one or more hydrogen atoms constituting the aromatic heterocyclic group are substituted with a group (substituent) other than a hydrogen atom.

[0042] The aromatic group in G may be either monocyclic or polycyclic, and the number of atoms constituting the ring skeleton (number of ring members) is not particularly limited, but is preferably 3 to 20.

[0043] Among the aromatic groups represented by G, examples of the aromatic hydrocarbon group include a 1,2-phenylene group, a naphthalene-1,2-diyl group, a naphthalene-2,3-diyl group, a toluene-2,3-diyl group, a toluene-3,4-diyl group, an o-xylene-3,4-diyl group, an o-xylene-4,5-diyl group, a m-xylene-4,5-diyl group, a p-xylene-2,3-diyl group, an anthracene-1,2-diyl group, and an anthracene-2,3-diyl group. The aromatic hydrocarbon group may have one or more hydrogen atoms substituted with a substituent such as the aforementioned aromatic hydrocarbon group or alkyl group. The aromatic hydrocarbon group having the aforementioned substituent preferably has 6 to 20 carbon atoms, including the carbon atoms of the substituent.

[0044] The alkyl group substituting one or more hydrogen atoms of the above-mentioned exemplified aromatic hydrocarbon groups (hereinafter sometimes referred to as "substituted alkyl group") may be linear, branched, or cyclic, and if cyclic, may be monocyclic or polycyclic. The substituted alkyl group preferably has 1 to 10 carbon atoms.

[0045] The linear or branched substituted alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, 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, a 2-methylhexyl group, a 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3,3-dimethylpentyl group, a 3-ethylpentyl group, a 2,2,3-trimethylbutyl group, an n-octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group.

[0046] The cyclic substituted alkyl group preferably has 3 to 10 carbon atoms, and examples thereof 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 have been substituted with a linear, branched, or cyclic alkyl group. Examples of the linear, branched, and cyclic alkyl group substituting the hydrogen atom are the same as those for the substituted alkyl group.

[0047] Among the aromatic groups for G, examples of the aromatic heterocyclic group include groups formed by removing two hydrogen atoms bonded to carbon atoms or heteroatoms constituting the ring skeleton of various aromatic heterocyclic compounds. Preferred examples of the aromatic heterocyclic compound include compounds having one or more sulfur atoms as atoms constituting the aromatic heterocyclic skeleton (sulfur-containing aromatic heterocyclic compounds), compounds having one or more nitrogen atoms as atoms constituting the aromatic heterocyclic skeleton (nitrogen-containing aromatic heterocyclic compounds), compounds having one or more oxygen atoms as atoms constituting the aromatic heterocyclic skeleton (oxygen-containing aromatic heterocyclic compounds), and compounds having two different heteroatoms selected from a sulfur atom, a nitrogen atom, and an oxygen atom as atoms constituting the aromatic heterocyclic skeleton.

[0048] Examples of the sulfur-containing aromatic heterocyclic compound include thiophene and benzothiophene.

[0049] Examples of the nitrogen-containing aromatic heterocyclic compound include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, isoindole, benzimidazole, purine, indazole, quinoline, isoquinoline, quinoxaline, quinazoline, and cinnoline.

[0050] Examples of the oxygen-containing aromatic heterocyclic compound include furan, benzofuran (1-benzofuran), and isobenzofuran (2-benzofuran).

[0051] Examples of compounds having the above-mentioned two different heteroatoms as atoms constituting an aromatic heterocyclic skeleton include oxazole, isoxazole, thiazole, benzoxazole, benzisoxazole, and benzothiazole.

[0052] Of the atoms constituting the ring skeleton of the aromatic heterocyclic group, the atom to which the hydroxyl group is bonded and the atom to which -CH=CH-C(=O)-* is bonded may each be a carbon atom or a hetero atom, but it is preferable that both are carbon atoms.

[0053] In the aromatic heterocyclic group, the number of heteroatoms constituting the ring skeleton is preferably 1 to 3, and more preferably 1 or 2. In the aromatic heterocyclic group, when the number of heteroatoms constituting the ring skeleton is two or more, these heteroatoms may all be the same, all be different, or only some may be the same.

[0054] Examples of the substituent possessed by the aromatic hydrocarbon group or aromatic heterocyclic group in G include the substituted alkyl group, alkoxy group, aryloxy group, dialkylamino group, diarylamino group, alkylarylamino group, alkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, arylthio group, cyano group (—CN), halogen atom, nitro group, haloalkyl group (halogenated alkyl group), hydroxyl group (—OH), mercapto group (—SH), amino group, the aromatic hydrocarbon group, and the aromatic heterocyclic group.

[0055] The number of the substituents possessed by the aromatic hydrocarbon group or aromatic heterocyclic group in G may be one or more, and all hydrogen atoms may be substituted with the substituents. The number of the substituents depends on the number of substitutable hydrogen atoms, but is, for example, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. When the aromatic hydrocarbon group or aromatic heterocyclic group has two or more substituents, these substituents may all be the same, all be different, or only some may be the same.

[0056] Examples of the alkoxy group as a substituent include a monovalent group in which the substituted alkyl group is bonded to an oxygen atom, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or a cyclopropoxy group.

[0057] In the aryloxy group as a substituent, the aryl group bonded to the oxygen atom may be either monocyclic or polycyclic, and preferably has 6 to 10 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 of these aryl groups are further substituted with these aryl groups, the above-mentioned substituted alkyl groups, etc. The aryl group having these substituents preferably has 6 to 10 carbon atoms, including the carbon atoms of the substituent.

[0058] Examples of the dialkylamino group as a substituent include a monovalent group in which two hydrogen atoms of an amino group (-NH2) are substituted with the substituted alkyl group, such as a dimethylamino group or a methylethylamino group. In the dialkylamino group, the two alkyl groups bonded to the nitrogen atom may be the same or different. Examples of the diarylamino group as a substituent include a monovalent group in which two hydrogen atoms of an amino group are substituted with the aryl group, such as a diphenylamino group or a phenyl-1-naphthylamino group. In the diarylamino group, the two aryl groups bonded to the nitrogen atom may be the same or different. Examples of the alkylarylamino group as a substituent include monovalent groups such as a methylphenylamino group in which one of two hydrogen atoms of an amino group is substituted with the substituted alkyl group and one hydrogen atom is substituted with the aryl group.

[0059] Examples of the alkylcarbonyl group as a substituent include a monovalent group formed by bonding the substituted alkyl group to a carbonyl group (-C(=O)-), such as a methylcarbonyl group (acetyl group). Examples of the arylcarbonyl group as a substituent include a monovalent group formed by bonding the aryl group to a carbonyl group, such as a phenylcarbonyl group (benzoyl group).

[0060] Examples of the alkyloxycarbonyl group as a substituent include a monovalent group formed by bonding the alkoxy group to a carbonyl group, such as a methyloxycarbonyl group (methoxycarbonyl group). Examples of the aryloxycarbonyl group as a substituent include a monovalent group formed by bonding the aryloxy group to a carbonyl group, such as a phenyloxycarbonyl group (phenoxycarbonyl group).

[0061] Examples of the alkylcarbonyloxy group as a substituent include a monovalent group formed by bonding the substituted alkyl group to the carbon atom of a carbonyloxy group (—C(═O)—O—), such as a methylcarbonyloxy group. Examples of the arylcarbonyloxy group as a substituent include a monovalent group formed by bonding the aryl group to a carbonyloxy group carbon atom, such as a phenylcarbonyloxy group.

[0062] Examples of the alkylthio group as a substituent include a monovalent group in which the substituted alkyl group is bonded to a sulfur atom, such as a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, and a cyclopropylthio group. Examples of the arylthio group as a substituent include a monovalent group in which the aryl group is bonded to a sulfur atom, such as a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

[0063] Examples of the halogen atom as a substituent include a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).

[0064] Examples of the haloalkyl group as a substituent include groups in which one or more hydrogen atoms of the substituted alkyl group are substituted with halogen atoms. Examples of the halogen atom in the haloalkyl group include those exemplified above as the halogen atom that is a substituent. The number of halogen atoms in the haloalkyl group is not particularly limited and may be one or two or more. When the number of halogen atoms in the haloalkyl group is two or more, these multiple halogen atoms may all be the same, all be different, or only some may be the same. The haloalkyl group may be a perhaloalkyl group in which all hydrogen atoms in the alkyl group are substituted with halogen atoms. The haloalkyl group is not particularly limited, and examples thereof include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a trifluoromethyl group.

[0065] When the substituent on the aromatic hydrocarbon group or aromatic heterocyclic group in G is an electron-donating group such as an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylthio group, or an arylthio group, the wavelength of the light required to generate a base from compound (1) upon irradiation with light becomes longer (the wavelength becomes longer). That is, these electron-donating group substituents are advantageous in that they can lengthen the wavelength of the light required to generate a base from compound (1).

[0066] The substitution position of the substituent on the aromatic hydrocarbon group or aromatic heterocyclic group is not particularly limited.

[0067] G is preferably an aromatic hydrocarbon group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have as a substituent one or more in total selected from the group consisting of an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylthio group, and an arylthio group. Examples of such G include a group represented by the following general formula (a)-1:

[0068] [ka]

[0069] In the general formula (a)-1, m1 is an integer of 0 to 2; n1 is an integer of 0 to 2m1+4; Z 1 is an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylthio group, or an arylthio group, and when n1 is an integer of 2 or more, a plurality of Z 1 may be the same or different; one of the bonds marked with a symbol ** is formed with a hydroxyl group to which one of Gs is bonded, and the other is formed with a carbon atom having a double bond to which the other of Gs is bonded.

[0070] In general formula (a)-1, m1 is an integer of 0 to 2 (0, 1, or 2) and defines the number of ring skeletons constituting the aromatic hydrocarbon group. That is, when m1 is 0, the aromatic hydrocarbon group is a 1,2-phenylene group, when m1 is 1, the aromatic hydrocarbon group is a naphthalene-2,3-diyl group, and when m1 is 2, the aromatic hydrocarbon group is an anthracene-2,3-diyl group.

[0071] In the general formula (a)-1, n1 is an integer of 0 to 2m1+4, and Z 1 represents the number of bonds to the aromatic hydrocarbon group. That is, when m1 is 0, n1 is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0 or 1. When m1 is 1, n1 is an integer of 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 3, even more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When m1 is 2, n1 is an integer of 0 to 8, preferably an integer of 0 to 4, more preferably an integer of 0 to 3, even more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

[0072] In general formula (a)-1, Z 1represents an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylthio group, or an arylthio group, and is the same as the substituents possessed by the aromatic hydrocarbon group or aromatic heterocyclic group in G described above.

[0073] n1 is an integer equal to or greater than 2, and Z 1 When compound (1) has a plurality of Z 1 (if the Z 1 may be the same or different from each other. 1 may all be the same, may all be different, or may only be partially the same. If n1 is a non-zero integer, then Z 1 The bonding position of to the aromatic hydrocarbon group is not particularly limited.

[0074] In general formula (a)-1, one of the bonds marked with the symbol ** is formed with a hydroxyl group in general formula (a) to which one of Gs is bonded, and the other of the bonds marked with the symbol ** is formed with a carbon atom having a double bond in general formula (a) to which the other of Gs is bonded.

[0075] The first skeleton is preferably, for example, a group represented by the following general formula (a)-2: The compound having the first skeleton and the second skeleton preferably generates, upon light irradiation, a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton, and coumarin or a coumarin derivative.

[0076] [ka]

[0077] In general formula (a)-2, R1 to R4 each independently represent a hydrogen atom, the substituted 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, the aromatic hydrocarbon group, or the aromatic heterocyclic group, where * indicates the bonding position to the nitrogen atom. At least two of R1 to R4 may be bonded to each other to form a ring structure.

[0078] The second skeleton is preferably a structure represented by the following general formula (1)-12, (1)-13 or (1)-14, and more preferably a structure represented by the following general formula (1)-13 or (1)-14.

[0079] [ka]

[0080] 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 33At 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.

[0081] R 21 ~R 24 , R 31 ~R 33 , and R 41 ~R 44 The 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.

[0082] The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group.

[0083] 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.

[0084] 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, or cyclic alkyl group that substitutes a hydrogen atom include those exemplified above for the alkyl group.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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 of these (three 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 The same is true for the case.

[0092] 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

[0093] 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 (preferably saturated hydrocarbon groups) and are bonded to each other, and R 32 is a hydrocarbon group, and R 31 and R 33 are more preferably bonded to each other to form an ethylene group, 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.

[0094] 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.

[0095] [Variations] A modified example of the photobase generator of the present disclosure includes a compound having a first skeleton represented by the above general formula (a) and a second skeleton represented by the above general formula (1)-12, (1)-13, or (1)-14, which has a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and the compound is a photobase generator that generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton upon irradiation with light. Regarding the modified photobase generator, a description of the configuration common to the above-described photobase generator of the present disclosure will be omitted, and the following will describe the differences between the above-described photobase generator of the present disclosure and the modified photobase generator. In a variant, the structure represented by general formula (1)-13 is R 31 and R 33 When R 31 and R 33 are more preferably bonded to each other to form a saturated hydrocarbon group, and R 31 and R 33 More preferably, they are bonded to each other to form an ethylene group.

[0096] [Photoreactive composition] The photoreactive composition of the present disclosure comprises a photobase generator of the present disclosure and a base-reactive compound, wherein the base-reactive compound is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base. The compound having a functional group that is converted into a group that exhibits reactivity by the action of a base may be a compound having only one of the above-mentioned functional groups, or a compound having two or more of the above-mentioned functional groups, or a mixture thereof. The compound having a group that reacts by the action of a base may be a compound having only one group that reacts by the action of a base, or a compound having two or more groups that react by the action of a base, or a mixture thereof.

[0097] For example, by irradiating the photoreactive composition of the present disclosure with light, a base is generated from the photobase generator, and the functional group contained in the base-reactive compound in the photoreactive composition is converted by the action of the generated base to become reactive, or the functional group contained in the base-reactive compound is reacted by the action of the generated base. Therefore, by irradiating the above-mentioned photoreactive composition with light to generate a base, the base-reactive compound contained in the photoreactive composition reacts to give a reaction product.

[0098] The photoreactive composition may be a photocurable composition that is cured by reaction of a base-reactive compound upon irradiation with light, and the photocurable composition may be used to produce a cured product upon irradiation with light. The photoreactive composition may be a photoreactive material (positive type) that is solubilized by light irradiation, or a photoreactive material (negative type) that is cured by light irradiation.

[0099] The photoreactive composition of the present disclosure may contain only one type of photobase generator, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0100] In the photoreactive 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 content of the base-reactive compound. When the content of the photobase generator is 4% by mass or more, the reaction of the base-reactive compound 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.

[0101] (Base-reactive compounds) The photoreactive composition of the present disclosure contains a base-reactive compound. The base-reactive compound is a compound 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), or a compound 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.

[0102] Examples of reactions that proceed in the base-reactive compound include addition polymerization and condensation polymerization (polycondensation polymerization).

[0103] 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.

[0104] 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.

[0105] 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.

[0106] Examples of the base-reactive compound (9-2b) include epoxy resins, silicone resins, alkoxysilane compounds, (meth)acrylate compounds, and thiol compounds. In the present disclosure, the term "(meth)acrylate" is a concept that encompasses both "acrylate" and "methacrylate."

[0107] The photoreactive composition of the present disclosure may contain only one type of base-reactive compound, or two or more types, and when two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0108] (Other ingredients) The photoreactive composition of the present disclosure may further contain other components in addition to the base-reactive 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 photoreactive composition may contain only one type of other component, or two or more types. When there are two or more types, the combination and ratio thereof can be set arbitrarily.

[0109] The other components include a sensitizer, a filler, a pigment, a solvent, and the like.

[0110] <Sensitizer> The photoreactive 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 photoreactive composition is not particularly limited and may be adjusted appropriately.

[0111] <Filling material> The photoreactive 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 photoreactive composition itself and the strength of the photoreactive 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 photoreactive 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 photoreactive composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0112] <Pigments> The photoreactive 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 photoreactive composition may be any known pigment, such as white, blue, red, yellow, or green, and is not particularly limited. The photoreactive composition may contain only one type of pigment, or two or more types. When two or more types are contained, the combination and ratio of the pigments can be set arbitrarily. The content of the pigment in the photoreactive composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0113] <Solvent> The photoreactive composition of the present disclosure may contain a solvent, which improves handling properties. The solvent is not particularly limited and may be appropriately selected in consideration of the solubility, stability, etc. of the base-reactive compound 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.

[0114] The photoreactive composition may contain only one type of solvent, or two or more types of solvents. When two or more types of solvents are contained, the combination and ratio thereof can be set arbitrarily.

[0115] In the photoreactive 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 content of the base-reactive compound. When the content of the solvent is within this range, the handleability of the photoreactive composition is further improved.

[0116] The photoreactive composition can be obtained by blending a base-reactive compound, a photobase generator, a specific polycyclic aromatic compound, and other components as needed. After blending the components, the resulting composition may be used as a photoreactive composition as is, or may be used as a photoreactive composition after further performing a known purification procedure as needed.

[0117] When blending the components, all the components may be added and then mixed, or some of the components may be added sequentially while being mixed, or all the components may be added sequentially while being mixed. 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.

[0118] 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.

[0119] <Reaction products> The reaction product of the present disclosure is obtained by reacting the above-described photoreactive 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.

[0120] (Method for producing reaction product) The method for producing a reaction product of the present disclosure includes a step of irradiating the photoreactive composition with light to generate the base from the photobase generator. The base-reactive compound contained in the photoreactive composition becomes reactive by converting a functional group contained in the base-reactive compound under the action of the generated base, or the functional group contained in the base-reactive compound reacts under the action of the generated base. Therefore, by irradiating the photoreactive composition with light to generate a base, the base-reactive compound contained in the photoreactive composition reacts to obtain a reaction product.

[0121] The photoreactive composition may be attached to an object by a known method, and then optionally pre-baked (dried) to form a photoreactive composition layer, which may then be irradiated with light. For example, when producing a film-like reaction product, the photoreactive composition may be applied to a target object using a coating means such as a spin coater, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Mayer bar coater, or kiss coater, or an applicator, or the like, or the target object may be immersed in the photoreactive composition, thereby adhering the photoreactive composition to the target object. For example, when producing a film-like or linear reaction product, the photoreactive composition may be attached to the 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.

[0122] The pre-baking may be carried out under conditions of, for example, 40° C. to 120° C. and 30 seconds to 10 minutes, and is not particularly limited.

[0123] The wavelength of the light irradiated onto the photoreactive 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 photoreactive 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 photoreactive composition may be 600 nm or less, 500 nm or less, or 400 nm or less.

[0124] The illuminance of the light irradiated onto the photoreactive composition is, for example, 1 mW / cm 2 ~100mW / cm 2 and preferably 5 mW / cm 2 ~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 photoreactive 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.

[0125] The reaction product obtained by irradiating the photoreactive 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.

[0126] 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 photoreactive composition layer may be set to be equal to or greater than the thickness of the desired reaction product.

[0127] For example, the ratio of the thickness of the reaction product (thickness of the photoreactive composition layer after light irradiation) to the thickness of the photoreactive composition layer (thickness of the photoreactive composition layer before light irradiation) ([thickness of the photoreactive composition layer after light irradiation] / [thickness of the photoreactive composition layer before light irradiation]) can be, for example, 0.2 to 1.0, and by further adjusting the reaction conditions, it is also possible to set the ratio to any of 0.3 to 1.0, 0.4 to 1.0, 0.5 to 1.0, 0.6 to 1.0, 0.7 to 1.0, 0.8 to 1.0, and 0.9 to 1.0. [Example]

[0128] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0129] <Production of Compound (1)-1> First, as shown below, compound (X) was reacted with thionyl chloride and 1,1,3,3-tetramethylguanidine in that order to prepare compound (Y). That is, a mixture of compound (X) (2.1 g, 0.020 mol) and thionyl chloride (SOCl, 10 mL) was stirred at room temperature for 7 hours, and then dry dichloromethane (20 mL) and a mixture of 1,1,3,3-tetramethylguanidine (2.3 g, 0.022 mol) and dry dichloromethane (15 mL) were added to this mixture, and the mixture was stirred at 0°C for 2 hours to carry out the reaction. Next, saturated aqueous sodium chloride solution was added to the reaction mixture, and the mixture was shaken in a separatory funnel to wash the reaction mixture, which was then washed once more with saturated aqueous sodium chloride solution, for a total of two times. This gave compound (Y) as a viscous yellow liquid (yield 94%). The obtained compound (Y) 1 H-NMR, 13 The results of analysis by C-NMR and ESI-MS are shown in Table 1.

[0130] [ka]

[0131] [Table 1]

[0132] Next, compound (Y) was hydrolyzed by the reaction shown below to produce compound (1)-1. That is, a mixture of water (10 mL) and potassium carbonate (0.19 g, 1.5 mmol) was added to a mixture of compound (Y) (0.31 g, 1.2 mmol) and methanol (20 mL), and the mixture was stirred for 3 hours under heating to carry out the reaction. After completion of the reaction, the reaction mixture was quenched with saturated ammonium chloride solution. Next, dichloromethane was added to the resulting reaction solution, and the mixture was shaken in a separatory funnel to wash the reaction solution. Washing with dichloromethane was carried out two more times, for a total of three times. As a result, the target compound (1)-1 was obtained as a yellow solid (yield 82%). The obtained compound (1)-1 1 H-NMR, 13 The results of the C-NMR analysis are shown in Table 2. The pKa in water of the conjugate acid of 1,1,3,3-tetramethylguanidine generated by light irradiation is 15.2.

[0133] [ka]

[0134] [Table 2]

[0135] <Production of Compound (2)-1> As shown below, compound (2)-101 was reacted with 1,1,3,3-tetramethylguanidine to produce compound (2)-1, an ionic photobase generator. That is, a mixture of 1,1,3,3-tetramethylguanidine (2.3 g, 0.022 mol) and dry tetrahydrofuran (10 mL) was added to a mixture of compound (2)-1 (0.58 g, 0.024 mol) and dry tetrahydrofuran (20 mL), and the mixture was stirred at 0°C for 2 hours to carry out the reaction. Next, dichloromethane was added to the resulting reaction solution, and the mixture was shaken in a separatory funnel to wash the reaction solution. Washing with dichloromethane was carried out two more times, for a total of three times. As a result, the target compound (2)-1 was obtained as a yellow solid (yield 90%, acid:base=1.2:1.0). The obtained compound (2)-1 1 The results of the H-NMR analysis are shown in Table 3.

[0136] [ka]

[0137] [Table 3]

[0138] <Preparation of Compound (3)-1> The following compound (3)-1, which is an ionic photobase generator, was prepared.

[0139] [ka]

[0140] <Preparation of Compound (4)-1> The following compound (4)-1, which is a non-ionic photobase generator, was prepared. The pKa in water of the conjugate acid of piperidine generated by irradiation with light is 11.2.

[0141] [ka]

[0142] [Test Example 1] (Confirmation of the behavior of compound (1)-1 in a solvent when irradiated with light at a wavelength of 365 nm) The compound (1)-1 obtained above was added to a solution of 2.5×10 -5 The compound was dissolved in methanol at a concentration of 100 mol / L. An LED lamp was used to measure the intensity of the light, with an illumination intensity of 50 mW / cm. 2 The light irradiation dose was set to 0, 50, 150 and 300 mJ / cm 2 The resulting methanol solution was irradiated with light having a wavelength of 365 nm in four ways. The absorbance of Compound (1)-1 was then measured. The results are shown in Figure 1.

[0143] [Test Example 2] (Confirmation of the behavior of compound (1)-1 in a solvent when irradiated with light at a wavelength of 313 nm) The compound (1)-1 obtained above was added to a solution of 2.5×10 -5 The compound was dissolved in methanol at a concentration of 100 mol / L, and then illuminated with a mercury xenon lamp at an illumination intensity of 50 mW / cm. 2 The light irradiation doses were 0, 50, 100 and 280 mJ / cm 2 The resulting methanol solution was irradiated with light having a wavelength of 313 nm in four ways. The absorbance of Compound (1)-1 was then measured. The results are shown in Figure 2.

[0144] In Test Example 1, the molar absorption coefficient is ε 365 =3.1×10 3 L / (mol cm), and in Test Example 2, the molar absorption coefficient is ε 313 =1.6×10 4L / (mol cm). As is clear from Figures 1 and 2, the light irradiation dose was 0 mJ / cm 2 In other words, compared to the spectrum without light irradiation, the spectra with other irradiation doses showed both increasing and decreasing peaks, and this measurement result confirmed that light irradiation generates a base from compound (1)-1 through the following reaction. Furthermore, it was confirmed that there is no significant difference in the exposure dose required to decompose compound (1)-1 between 365 nm and 313 nm light irradiation.

[0145] [ka]

[0146] [Test Example 3] (Storage stability of compound (1)-1) A mixed solution was prepared by adding the following base-reactive compound (9)-301 (0.10 g), compound (1)-1 (0.012 g, 8 mol % relative to the methoxy groups in the base-reactive compound), and methanol (0.51 g) to a glass bottle. The mixture was stored for 6 days in a dark place at 25° C. After 6 days of storage, the glass bottle was shaken and turned upside down to confirm that the mixture in the glass bottle was a liquid.

[0147] [ka]

[0148] [Test Example 4] (Storage stability of compound (2)-1) A mixed solution was prepared by adding the following base-reactive compound (9)-301 (0.10 g), compound (2)-1 (0.013 g, 8 mol % relative to the methoxy groups in the base-reactive compound), and methanol (0.50 g) to a glass bottle. The mixture was stored in a dark place at 25° C. for 4 days. After storage for 4 days, the glass bottle was shaken and turned upside down, and it was confirmed that the mixture in the glass bottle had gelled.

[0149] From the results of Test Examples 3 and 4, it was inferred that the crosslinking reaction of the base-reactive compound (9)-301 was suppressed in the mixed solution containing the compound (1)-1, whereas the crosslinking reaction of the base-reactive compound (9)-301 proceeded in the mixed solution containing the compound (2)-1. From the above, it was demonstrated that the composition containing compound (1)-1 and base-reactive compound (9)-301 has better storage stability in the dark than the composition containing compound (2)-1 and base-reactive compound (9)-301.

[0150] [Test Example 5] (Outgassing confirmation test of compound (1)-1) Triglycidyl isocyanurate (0.041 g), compound (1)-1 (0.020 g), and methanol (0.097 g) were mixed and stirred at 25° C. for 1 minute to obtain a test resin composition. Next, the test resin composition obtained above was coated on a calcium fluoride plate, and the calcium fluoride plate was placed on the obtained coating film, and the coating film was sandwiched between the two calcium fluoride plates to prepare a laminate. An LED lamp was used to set the illuminance at 50 mW / cm. 2 The coating film of the laminate was irradiated with light having a wavelength of 365 nm. 2 ) at 10,000mJ / cm 2 It was decided. After the light irradiation, the appearance of the laminate was checked to see if outgassing had occurred.

[0151] In Test Example 5, a transparent film was obtained between the calcium fluoride plates by light irradiation, and no outgassing was observed, as shown in the following reaction formula.

[0152] [ka]

[0153] [Test Example 6] (Outgassing confirmation test of compound (3)-1) Triglycidyl isocyanurate (0.055 g), compound (3)-1 (0.032 g), and chloroform (0.080 g) were mixed and stirred at 25° C. for 1 minute to obtain a test resin composition. Next, a laminate was produced and irradiated with light in the same manner as in Test Example 5. After the light irradiation, the appearance of the laminate was checked to see if outgassing had occurred.

[0154] In Test Example 6, the film between the calcium fluoride plates yellowed due to light irradiation, and bubbles were observed. Therefore, it is presumed that carbon dioxide was generated as an outgas in Test Example 6, as shown in the following reaction formula. It is also presumed that the yellowing of the film in Test Example 6 was due to the generation of nitroso groups derived from nitro groups.

[0155] [ka]

[0156] [Example 1] (Production of Photoreactive Composition) The above-mentioned base-reactive compound (9)-301 (0.24 g), compound (1)-1 (7 mol % relative to the methoxy groups in the base-reactive compound), and methanol (1.2 g) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0157] (Production of reaction products) The photoreactive composition obtained above was applied onto a silicon wafer by spin coating at 1000 rpm for 10 seconds. Then, this coating film (photoreactive composition layer) was pre-baked at 60°C for 1 minute, and then heated at an illuminance of 50 mW / cm using a mercury xenon lamp. 2 The coating was irradiated with light of 313 nm wavelength at a light irradiation dose of 1000 mJ / cm 2Three types of coating films were prepared and heated (post-baked) at 60°C, 80°C, or 100°C for 30 minutes, respectively. In this way, we attempted to convert the three types of coating films into reaction products by polymerizing the base-reactive compound (9)-301.

[0158] [Comparative Example 1] (Production of Photoreactive Composition) The above-mentioned base-reactive compound (9)-301 (0.24 g), compound (4)-1 (0.016 g, 7 mol % relative to the methoxy groups in the base-reactive compound), and methanol (1.2 g) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0159] (Production of reaction products) The same procedure as in Example 1 was carried out to finally convert the three types of coating films into reaction products by polymerizing the base-reactive compound (9)-301.

[0160] In Comparative Example 1, the peak intensity (2830 cm) derived from the CH stretching vibration of the methoxy group was measured for the coating film before light irradiation, the coating film after light irradiation, the coating film heated for an additional 10 minutes after light irradiation, and the coating film heated for an additional 30 minutes after light irradiation. -1 ) was measured using a Fourier transform infrared spectrophotometer (FT-IR). The results are shown in Figure 3.

[0161] Furthermore, in Comparative Example 1, the coating film before light irradiation was exposed to light at an illuminance of 50 mW / cm 2 , light irradiation amount 1000mJ / cm 2 The relationship between the heating time and the peak area of ​​the methoxy group when the sample was irradiated with light at a wavelength of 313 nm and then heated at 100° C. for 0 to 30 minutes is shown in FIG. In Example 1 and Comparative Example 1, the coating film before light irradiation was exposed to light at an illuminance of 50 mW / cm 2 , light irradiation amount 1000mJ / cm 2 The relationship between the heating time and the peak area of ​​the methoxy group when the sample was irradiated with light at a wavelength of 313 nm and then heated at 100° C. for 0 to 30 minutes is shown in FIG.

[0162] Furthermore, the pencil hardness of the reaction products obtained by heating the coating films after light irradiation at 60° C., 80° C., or 100° C. for 30 minutes in Example 1 and Comparative Example 1 was measured. The results are shown in FIG.

[0163] 3 and 4, it was confirmed that the methoxy groups in the coating film were slightly reduced by light irradiation and heating in Comparative Example 1. Furthermore, it was confirmed from Fig. 5 that the reduction rate of the methoxy groups in Example 1 was greater than that in Comparative Example 1 by light irradiation and heating of the coating film, i.e., the reactivity of the base-reactive compound (9)-301 was superior. Furthermore, it was confirmed from Fig. 5 that the reduction rate of the methoxy groups differed depending on whether the coating film was irradiated with light and the degree of heating of the coating film.

[0164] As shown in FIG. 6, in Comparative Example 1, the coating film was liquid after heating, and the pencil hardness of the reaction product could not be measured, or the pencil hardness of the reaction product after heating was less than 6B. On the other hand, in Example 1, the pencil hardness of the reaction product after heating was B or higher, confirming that a cured product with excellent pencil hardness was obtained as the reaction product.

[0165] [Example 2] (Production of Photoreactive Composition) Trimethylolpropane triacrylate (0.14 g), the following compound (9)-401 (0.28 g, the ratio of mercapto groups to acryloyl groups in trimethylolpropane triacrylate is 100 mol %), compound (1)-1 (0.013 g, 10 mol % relative to trimethylolpropane triacrylate), and methanol (0.43 g) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0166] [ka]

[0167] (Production of reaction products) The photoreactive composition obtained above was applied to a calcium fluoride plate by spin coating at 1000 rpm for 10 seconds. Then, this coating film (photoreactive composition layer) was pre-baked at 60°C for 1 minute, and then heated at an illuminance of 50 mW / cm using an LED lamp. 2 The coating was irradiated with light of 365 nm wavelength at a light irradiation dose of 1000 mJ / cm 2 Based on the above, we attempted to generate a reaction product by crosslinking the generated thiolate anion from compound (9)-401 with trimethylolpropane triacrylate through the action of a base generated from compound (1)-1 upon light irradiation.

[0168] In Example 2, the coating film before light irradiation, the light irradiation doses were 0, 100, 600 and 1000 mJ / cm 2 For the coating film, the peak intensity (1405 cm) derived from the C=C stretching vibration of the acryloyl group -1 ) was measured using a Fourier transform infrared spectrophotometer (FT-IR). The results are shown in Figure 7. From Figure 7, it can be seen that the -1 It was shown that the peak area of ​​α-acryloyl group decreased, and the consumption of acryloyl groups was confirmed by irradiation with 365 nm light.

[0169] [Example 3] A photoreactive composition was produced in the same manner as in Example 2, except that in Example 3, the coating film was irradiated with 313 nm light using a mercury-xenon lamp instead of irradiating the coating film with 365 nm light using an LED lamp, and an attempt was made to produce a reaction product.

[0170] In Example 3, measurement was performed with a Fourier transform infrared spectrophotometer (FT-IR) to evaluate the change in the peak area of ​​the acryloyl group and the change in the peak area of ​​the mercapto group due to light irradiation, as in Example 2. The results are shown in Figures 8 and 9.

[0171] As shown in Figures 8 and 9, it was found that the crosslinking reaction progressed as a result of the consumption of acryloyl groups and mercapto groups by irradiating the coating film with light. Furthermore, it was found that the crosslinking reaction progressed more in Example 2, in which the coating film was irradiated with light at 365 nm, than in Example 3, in which the coating film was irradiated with light at 313 nm. This is presumably because the irradiation of the coating film with light at a longer wavelength shifts the chemical equilibrium to the cis isomer of compound (1)-1 in the coating film, making it easier for the cyclization reaction that generates a base to proceed.

[0172] [Example 4] (Production of Photoreactive Composition) A bisphenol A type epoxy compound (JER-828, Mitsubishi Chemical Corporation, 0.19 g) shown in the structure below, the following compound (9)-501 (0.19 g, the ratio of mercapto groups to epoxy groups in the bisphenol A type epoxy compound is 50 mol %), compound (1)-1 (0.013 g, the ratio of epoxy groups in the bisphenol A type epoxy compound is 3 mol %), and cyclopentanone (0.052 g) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0173] [ka]

[0174] (Production of reaction products) The photoreactive composition obtained above was applied onto a calcium fluoride plate by spin coating at 1000 rpm for 10 seconds. Then, an LED lamp was used to apply the photoreactive composition to the plate at an illumination intensity of 50 mW / cm. 2 The coating was irradiated with light of 365 nm wavelength at a light irradiation dose of 1000 mJ / cm 2 The coating was then heated at 60°C for 30 seconds. As a result, we attempted to generate a thiolate anion from compound (9)-501 through the action of the base generated from compound (1)-1 upon light irradiation, and then to generate a reaction product through a crosslinking reaction between the generated thiolate anion and a bisphenol A-type epoxy compound.

[0175] In Example 4, the peak intensity (920 cm) derived from the CO stretching vibration of the epoxy group was measured for the coating film before light irradiation, the coating film after light irradiation, the coating film heated for 5 seconds after light irradiation, and the coating film heated for 30 seconds after light irradiation. -1 ), and the peak intensity due to the SH stretching vibration of the mercapto group (2550 cm -1 ) and the peak intensity due to the OH stretching vibration of the hydroxyl group (3600 cm -1 The chromatograms (near the wavelength of the crosslinked polymer) were measured using a Fourier transform infrared spectrophotometer (FT-IR). The results are shown in Figure 10. Figure 10 confirms that the consumption of epoxy groups and mercapto groups and the increase of hydroxyl groups were confirmed by 365 nm light irradiation, confirming that a crosslinking reaction was occurring.

[0176] In Example 4, the coating film was heated for 0 to 30 seconds without light irradiation, and the peak intensity of each functional group was measured with a Fourier transform infrared spectrophotometer (FT-IR) in the same manner as described above, and the changes in the peak area of ​​the epoxy group and the peak area of ​​the mercapto group due to light irradiation were evaluated. The results are shown in Figures 11 and 12.

[0177] As shown in Figures 11 and 12, when the coating film was irradiated with light, it was found that the epoxy groups and mercapto groups were consumed more and the crosslinking reaction progressed more than when the coating film was not irradiated with light.

[0178] <Production of Compound (1)-2> First, as shown below, o-coumaric acid was reacted with compound (Z) to produce compound (1)-2. First, a mixture of o-coumaric acid (1.8 g, 0.010 mol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (2.1 g, 0.012 mol, EDAC·HCl), and dry dichloromethane (20 mL) was added, and the mixture was stirred at 0°C for 1 hour. Next, compound (Z) (1.0 g, 0.012 mol) was added to the stirred mixture, and the mixture was stirred for 70 hours to carry out the reaction. Finally, the mixture was washed with chloroform. This gave compound (1)-2 as a pale yellow solid (yield 44%). The obtained compound (1)-2 1 H-NMR, 13 The results of analysis by C-NMR and ESI-MS are shown in Table 4.

[0179] Next, 2-methyl-2-imidazoline (2MI), generated by light irradiation of compound (1)-2, was confirmed to be a stronger base than the aliphatic amine cyclohexylamine (CyA) by a phenol red coloration experiment. First, 2MI, CyA, and diazabicycloundecene (DBU) were prepared as bases, and 2.0 × 10 HCl was added to 1.5 mL of a methanol solution containing each base. -5 1.5 mL of a methanol solution of phenol red adjusted to 1.0 mol / L was added. The UV-Vis spectrum of the solution was measured to evaluate the basicity of each base. The evaluation results are shown in Figure 17.

[0180] As shown in Figure 17, DBU and 2MI showed peaks indicating basicity around 570 nm, whereas CyA did not show any peak indicating basicity around 570 nm. Because the peak intensity around 570 nm depends on the strength of the base, 2MI was found to be weaker in basicity than DBU, but stronger in basicity than CyA.

[0181] [ka]

[0182] [Table 4]

[0183] The aqueous solution of the compound (1)-2 was irradiated with light of 365 nm wavelength and tested using pH test paper to see if it exhibited basicity. As a result, the pH test paper changed color to the basic side.

[0184] <Production of compound (4)-3> As shown below, compound (4)-1 was reacted with compound (4)-2 to produce compound (4)-3. First, a mixture of compound (4)-1 (2.4 g, 0.010 mol) and dry tetrahydrofuran (20 mL) was added to a mixture of potassium tert-butoxide (1.4 g, 0.012 mol), compound (4)-2 (5.7 g, 0.012 mol), and dry tetrahydrofuran (20 mL), and the mixture was stirred for 1 hour to cause a reaction. The reaction mixture was then purified to give compound (4)-3 as a white solid (yield 88%). The obtained compound (4)-3 1 H-NMR, 13 The analytical results by C-NMR and ESI-MS are shown in Table 5.

[0185] [ka]

[0186] [Table 5]

[0187] <Production of compound (4)-4> Compound (4)-4 was prepared by reacting compound (4)-3 as shown below. First, a mixture of compound (4)-3 (2.6 g, 0.080 mol), methanol (20 mL), and 2N sodium hydroxide (20 mL) was stirred for 5 hours to react. After completion of the reaction, the reaction mixture was quenched with 5% by mass hydrochloric acid. Next, dichloromethane was added to the resulting reaction solution, and the mixture was shaken in a separatory funnel to wash the reaction solution. Washing with dichloromethane was carried out three more times, for a total of four times. As a result, the target compound (4)-4 was obtained as a white solid (yield 84%). The obtained compound (4)-4 1 H-NMR, 13The results of the C-NMR and ESI-MS analyses are shown in Table 6.

[0188] [ka]

[0189] [Table 6]

[0190] <Production of Compound (1)-3> As shown below, compound (4)-4 was reacted with compound (Z) to produce compound (1)-3. First, a mixture of compound (4)-4 (1.8 g, 0.0067 mol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1.9 g, 0.010 mol, EDAC·HCl), and dry dichloromethane (20 mL) was added and stirred at 0°C for 1 hour. Then, the compound (Z) (0.84 g, 0.010 mol) was added to the stirred mixture, and the mixture was stirred for 12 hours to carry out the reaction, followed by washing with water and acetone. This gave compound (1)-3 as a pale yellow solid (yield 31%). The obtained compound (1)-3 1 H-NMR, 13 The analytical results by C-NMR and ESI-MS are shown in Table 7.

[0191] [ka]

[0192] [Table 7]

[0193] A solubility test was carried out on Compound (1)-2 and Compound (1)-3, and it was found that Compound (1)-3, into which a tert-butyl group was introduced, had improved solubility in chloroform, dimethyl sulfoxide, etc. compared to Compound (1)-2.

[0194] [Test Example 7] (Confirmation of the behavior of compound (1)-3 in a solvent when irradiated with light at a wavelength of 365 nm) The compound (1)-1 obtained above was added to a solution of 1.5×10 -5 The compound was dissolved in methanol at a concentration of 100 mol / L. An LED lamp was used to measure the intensity of the light, with an illumination intensity of 50 mW / cm. 2 The light irradiation doses were 0, 50, 100, 200 and 350 mJ / cm 2 The obtained methanol solution was irradiated with light having a wavelength of 365 nm. Then, the absorbance of Compound (1)-3 was measured. In Test Example 7, the molar absorption coefficient was ε 365 =1.2×10 4 L / (mol·cm). In Test Example 7, the light irradiation amount was 0 mJ / cm 2 In other words, compared to the spectrum without light irradiation, the spectra with other irradiation doses showed both increasing and decreasing peaks. This measurement result confirmed that a base was generated from compound (1)-3 by the following reaction upon light irradiation:

[0195] [Test Example 8] (Confirmation of the behavior of compound (1)-3 in a solvent when irradiated with light at a wavelength of 313 nm) The compound (1)-1 obtained above was added to a solution of 1.5×10 -5 The compound was dissolved in methanol at a concentration of 10 mol / L, and then illuminated with a mercury xenon lamp at an illumination intensity of 10 mW / cm. 2 The light irradiation doses were 0, 50, 100, 200 and 350 mJ / cm 2 The obtained methanol solution was irradiated with light having a wavelength of 313 nm. Then, the absorbance of Compound (1)-3 was measured. In Test Example 8, the molar absorption coefficient was ε 313 =2.8×10 4L / (mol·cm). In Test Example 8, the light irradiation amount was 0 mJ / cm 2 In other words, compared to the spectrum without light irradiation, the spectra with other irradiation doses showed both increasing and decreasing peaks. This measurement result confirmed that a base was generated from compound (1)-3 by the following reaction upon light irradiation:

[0196] [ka]

[0197] [Test Example 9] (Confirmation of the behavior of compound (1)-3 in a polymer solid upon light irradiation) Polytetramethylene glycol (0.058 g), compound (1)-3 (0.0081 g, 14% by mass based on polytetramethylene glycol), and chloroform (0.42 g) were mixed and stirred at 25°C for 1 minute to obtain a test resin composition. Next, the test resin composition obtained above was applied to a calcium fluoride plate by spin coating at 1500 rpm for 20 seconds, and the resulting coating film was heated at 60°C for 3 minutes. After that, it was heated with a mercury xenon lamp at an illuminance of 12 mW / cm. 2 The coating was irradiated with light of 313 nm wavelength. 2 ~24000mJ / cm 2 The peak intensities derived from the amide group and the lactone structure were measured using a Fourier transform infrared spectrophotometer (FT-IR) at the irradiation dose of Compound (1)-3. Figure 13 shows a graph showing the relationship between the irradiation dose of Compound (1)-3 and the peak areas of the amide group and the lactone structure in the IR spectrum.

[0198] [Test Example 10] (Confirmation of the behavior of compound (1)-3 in a polymer solid upon light irradiation) In Test Example 9, an LED lamp was used instead of a mercury xenon lamp, and the illuminance was set to 50 mW / cm 2An experiment similar to that of Test Example 9 was carried out, except that the coating film was irradiated with light having a wavelength of 365 nm. A graph showing the relationship between the amount of light irradiation of Compound (1)-3 and the peak areas of the amide group and lactone structure in the IR spectrum is shown in Figure 14.

[0199] 13 and 14, as the amount of light irradiation increased, the peak intensity derived from the amide group decreased and the peak intensity derived from the lactone structure increased. This is because the same reactions as those in Test Examples 7 and 8 occurred upon light irradiation.

[0200] [Example 5] (Production of Photoreactive Composition) Trimethylolpropane triacrylate (0.14 g), the above-mentioned compound (9)-401 (0.28 g, the ratio of mercapto groups to acryloyl groups in trimethylolpropane triacrylate was 100 mol %), compound (1)-3 (0.013 g, 10 mol % relative to trimethylolpropane triacrylate), and chloroform (0.43 g) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0201] (Production of reaction products) The photoreactive composition obtained above was applied to a calcium fluoride plate by spin coating at 1000 rpm for 10 seconds. Then, this coating film (photoreactive composition layer) was pre-baked at 60°C for 1 minute, and then heated at an illuminance of 50 mW / cm using an LED lamp. 2 The coating was irradiated with light of 365 nm wavelength at a light irradiation dose of 1000 mJ / cm 2 Based on the above, we attempted to generate a reaction product by generating a thiolate anion from compound (9)-401 through the action of a base generated from compound (1)-3 upon light irradiation, and then crosslinking the generated thiolate anion with trimethylolpropane triacrylate.

[0202] [Example 6] In Example 5, a mercury xenon lamp was used instead of the LED lamp, and the illuminance was 10 mW / cm2 An attempt was made to produce a reaction product in the same manner as in Example 5, except that the coating film was irradiated with light having a wavelength of 313 nm.

[0203] In Examples 5 and 6, measurements were performed using a Fourier transform infrared spectrophotometer (FT-IR) to evaluate the changes in the peak area of ​​the acryloyl group and the peak area of ​​the mercapto group due to light irradiation. As a result, it was confirmed that the acryloyl group and mercapto group were consumed by light irradiation of the coating film, and the crosslinking reaction proceeded. The results are shown in Figures 15 and 16.

[0204] As shown in Figures 15 and 16, it was found that the crosslinking reaction progressed as a result of the consumption of acryloyl groups and mercapto groups by irradiating the coating film with light. Furthermore, it was found that the crosslinking reaction progressed more in Example 6, in which the coating film was irradiated with 313 nm light, than in Example 5, in which the coating film was irradiated with 365 nm light. The reason for the different results from Examples 2 and 3 is thought to be that in Compound (1)-3, the absorption spectrum is shifted to a longer wavelength due to the introduction of a tert-butyl group, and therefore, the crosslinking reaction progressed more when the coating film was irradiated with 313 nm light, unlike when Compound (1)-1 was used.

[0205] The disclosure of Japanese Patent Application No. 2019-164946, 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 first skeleton represented by the following general formula (a)-2, a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, The compound is a photobase generator that generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton when irradiated with light, and the pKa of a conjugate acid of the base in water is 12 or more. 【Chemistry 1】 (In general formula (a)-2, R 1 to R 4 each independently represent a hydrogen atom, a substituted alkyl group, a cyano group, or a nitro group, and * represents the bonding position with the nitrogen atom.)

2. The photobase generator according to claim 1, wherein the second skeleton is a structure represented by the following general formula (1)-12, (1)-13 or (1)-14: 【Chemistry 2】 (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)-2 to form a single bond. ２１ ~R ２４ may be bonded to each other to form a ring structure, and R ３１ ~R ３３ 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.)

3. A first skeleton represented by the following general formula (a)-2, a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and represented by the following general formula (1)-12, (1)-13 or (1)-14, The compound is a photobase generator that generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton when irradiated with light. 【Chemistry 3】 【Chemistry 4】 (In general formula (a)-2, R 1 to R 4 each independently represent a hydrogen atom, a substituted alkyl group, a cyano group, or a nitro group, and * represents the bonding position with the nitrogen atom. In general formulas (1)-12 to (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)-2 to form a single bond. ２１ ~R ２４ may be bonded to each other to form a ring structure, and R ３１ ~R ３３ 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. ３１ and R ３３ are bonded to each other to form a ring structure, the ring structure does not exhibit aromaticity.

4. A first skeleton represented by the following general formula (a)-2, a second skeleton having a nitrogen atom that is bonded to a bonding position of the first skeleton to form an amide group; a base is generated by light irradiation in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton, and a conjugate acid of the base has a pKa in water of 12 or more; The second skeleton is a compound having a structure represented by the following general formula (1)-12 or (1)-13. 【Chemistry 5】 【Chemistry 6】 (In general formula (a)-2, R 1 to R 4 each independently represent a hydrogen atom, a substituted alkyl group, a cyano group, or a nitro group, and * represents the bonding position with the nitrogen atom. In general formula (1)-12 and general formula (1)-13, R ２２ , R ２３ , R ２４ , R ３２ and R ３３ 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)-2 to form a single bond. ２１ ~R ２４ 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.)

5. A first skeleton represented by the following general formula (a)-2, A second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and represented by the following general formula (1)-12 or (1)-13: A compound that generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton when irradiated with light. 【Chemistry 7】 【Chemistry 8】 (In general formula (a)-2, R 1 to R 4 each independently represent a hydrogen atom, a substituted alkyl group, a cyano group, or a nitro group, and * represents the bonding position with the nitrogen atom. In general formula (1)-12 and general formula (1)-13, R ２２ , R ２３ , R ２４ , R ３２ and R ３３ 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)-2 to form a single bond. ２１ ~R ２４ 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. ３１ and R ３３ are bonded to each other to form a ring structure, the ring structure does not exhibit aromaticity.

6. A photobase generator according to any one of claims 1 to 3, A base-reactive compound; Including, The base-reactive compound is a photoreactive composition which is a compound having a functional group that is converted into a group exhibiting reactivity by the action of a base, or a compound having a group that reacts by the action of a base.

7. A reaction product obtained by reacting the photoreactive composition according to claim 6.

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