Photobase generators, compounds, photoreactive compositions and reaction products

Abstract

Provided is a photobase generator comprising a compound which has: a first skeleton represented by general formula (a); and a second skeleton which has a nitrogen atom bonded to a binding position of the first skeleton to constitute an amide group, and has a pyridine skeleton together with the nitrogen atom, and which, by being irradiated with light, generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton. In general formula (a), G is a divalent aromatic group, and * represents a binding position to a 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 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, as a photopolymerizable material, a base catalyst system containing a photobase generator that generates a base upon exposure and a monomer or oligomer that polymerizes by the action of a base is also known. As the photobase generator, for example, an ionic type equivalent to a salt of a strong base such as guanidine and a carboxylic acid is known (see, for example, Non-Patent Document 1). In such an ionic type photobase generator, a decarboxylation reaction proceeds in the carboxy group upon exposure, and the strong base that formed a salt with the carboxy group is liberated, thereby generating a base.

[0004] However, although such an ionic photobase generator has high reactivity, it has problems such as low stability during storage and low solubility. Furthermore, a resin composition using such an ionic photobase generator also has a problem of low stability.

[0005] In response to this, non-ionic photobase generators have also been studied. For example, a carbamate having a nitrobenzyl skeleton is known as a non-ionic photobase generator, which undergoes a decarboxylation reaction upon exposure to light and liberates 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 as described above. [Non-patent document 1] K. Arimitsu, R. Endo, Chem. Mater. 2013, 25, 4461-4463. [Non-patent document 2] JFCameron, JMJFrechet, J.Am.Chem.Soc.1991,113,4303. Summary of the Invention [Problem to be solved by the invention]

[0006] The non-ionic photobase generator disclosed in Non-Patent Document 2 has a problem in that a decarboxylation reaction occurs in addition to the generation of a base upon exposure to light.

[0007] Furthermore, there is a demand for a photobase generator that can prepare a photoreactive composition that exhibits excellent reactivity of a base-reactive compound (for example, an epoxy compound) upon irradiation with light and heating.

[0008] The present disclosure aims to provide a photobase generator and compound capable of preparing a photoreactive composition which exhibits excellent reactivity of a base-reactive compound when irradiated with light and heated, and which does not undergo a decarboxylation reaction when irradiated with light; a photoreactive composition which exhibits excellent reactivity of a base-reactive compound when irradiated with light and heated, and which does not undergo a decarboxylation reaction when irradiated with light; 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), a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and having a pyridine skeleton together with the nitrogen atom, the photobase generator generating a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton upon irradiation with light:

[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 has an aminopyridine skeleton. <1> The photobase generator according to claim 1,

[0012] <3> A compound having a first skeleton represented by the following general formula (a), a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and having a pyridine skeleton together with the nitrogen atom, which generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton when irradiated with light:

[0013] [ka]

[0014] (In general formula (a), G is a divalent aromatic group, and * represents the bonding position to the nitrogen atom.)

[0015] <4> The second skeleton has an aminopyridine skeleton. <3> The compound according to claim 1,

[0016] <5> <1> or <2> and a base-reactive compound, wherein the base-reactive compound 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. <6> <5> 2. A reaction product obtained by reacting the photoreactive composition according to claim 1. Effect of the Invention

[0017] According to one embodiment of the present invention, it is possible to provide a photobase generator and compound capable of preparing a photoreactive composition which exhibits excellent reactivity of a base-reactive compound when irradiated with light and heated, and which does not undergo a decarboxylation reaction when irradiated with light; a photoreactive composition which exhibits excellent reactivity of a base-reactive compound when irradiated with light and heated, and which does not undergo a decarboxylation reaction when irradiated with light; and a reaction product obtained by reacting this photoreactive composition. [Brief description of the drawings]

[0018] [Figure 1] 1 shows data showing the results of measuring the absorbance of Compound (1)-1 in Test Example 1. [Diagram 2] 1 shows data indicating the results of measuring the absorbance of Compound (1)-1 in Test Example 2. [Diagram 3] 1 is a graph showing the relationship between the amount of light irradiation of compound (1)-1 and the peak areas of the amide group and lactone structure in the IR spectrum in Test Example 3. [Figure 4] 1 is a graph showing the relationship between the amount of light irradiation of compound (1)-1 and the peak areas of the amide group and lactone structure in the IR spectrum in Test Example 4. [Diagram 5] 1 is a graph showing the relationship between the amount of light irradiation and the pencil hardness of the reaction product after the coating film after light irradiation was heated at 80° C. for 60 minutes in Test Example 5. [Figure 6] 1 is a graph showing the relationship between the amount of light irradiation and the pencil hardness of the reaction product after the coating film after light irradiation was heated at 100° C. for 60 minutes in Test Example 5. [Figure 7] 1 is a graph showing the relationship between the amount of light irradiation and the pencil hardness of the reaction product after the coating film after light irradiation was heated at 120° C. for 60 minutes in Test Example 5. [Figure 8] In Test Example 5, the absorption spectrum was measured with a Fourier transform infrared spectrophotometer (FT-IR) under the condition that the coating film was heated at 120° C. after light irradiation to obtain a reaction product. [Figure 9]1 is a graph showing the relationship between the heating time under light irradiation and non-light irradiation conditions and the peak area derived from the epoxy group in Test Example 6. [Figure 10] 13 is a graph showing the relationship between heating time and film remaining rate when 4-aminopyridine (4APy) or 4-methylaminopyridine (4MAPy) was used in Test Example 7. [Figure 11] 1 shows data showing the results of measuring the absorbance of Compound (1)-2 in Test Example 8. [Figure 12] 1 shows data showing the results of measuring the absorbance of Compound (1)-2 in Test Example 9. [Figure 13] 13 is a graph showing the relationship between the amount of light irradiation and the film remaining rate in Test Example 11. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0020] [Photobase generator] The photobase generator of the present disclosure includes a compound that has a first skeleton represented by the following general formula (a), a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group and having a pyridine skeleton together with the nitrogen atom, and that generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton upon irradiation with light.

[0021] [ka]

[0022] In general formula (a), G is a divalent aromatic group, and * represents the bonding position to the nitrogen atom.

[0023] For example, the photobase generator of the present disclosure is used to prepare a photoreactive composition capable of producing a reaction product by reacting a base-reactive compound by light irradiation and heating. More specifically, by irradiating a photoreactive composition containing a photobase generator and a base-reactive compound 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.

[0024] The photobase generator of the present disclosure includes a compound (sometimes referred to as "compound (1)" in the present disclosure) that has a first skeleton represented by the general formula (a) and a second skeleton having a nitrogen atom that is bonded to the bonding position of the first skeleton to form an amide group and a pyridine skeleton together with the nitrogen atom, and generates a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton by irradiation with light. In addition, as shown in the following formula (i), compound (1) becomes a cis isomer by irradiation with light, and then the oxygen atom of the hydroxyl group in general formula (a) is bonded to the carbonyl carbon in general formula (a), and the nitrogen atom in the second skeleton that was bonded to the carbonyl carbon is dissociated and bonded to 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 in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton.

[0025] 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 a photoreactive composition using this is highly stable. Furthermore, a photoreactive composition using a photobase generator containing compound (1) is a base in which a hydrogen atom is bonded to a nitrogen atom of a second skeleton having a pyridine skeleton, so that, for example, when the base-reactive compound is an epoxy compound, the reactivity of the base-reactive compound when irradiated with light and heated is good.

[0026] [ka]

[0027] 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), and a base (a primary amine in the following reaction formula) is generated.

[0028] [ka]

[0029] On the other hand, in the compound (1) contained in the photobase generator of the present disclosure, as shown in the above formula (i), decarboxylation reaction does not occur by light irradiation, which makes it possible to suppress the generation of bubbles due to carbon dioxide generation and the decrease in strength of the cured product of the reaction product.

[0030] In general formula (a), G is a divalent aromatic group having a hydroxyl group and -CH=CH-C(=O)-* bonded thereto. The bond positions of the hydroxyl group and -CH=CH-C(=O)-* in G are in an ortho positional relationship with each other. In other words, 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.

[0031] 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 (such a group is treated as an aromatic heterocyclic group in the present disclosure).

[0032] In addition, these aromatic hydrocarbon groups and aromatic heterocyclic groups may have a substituent. Here, the phrase "an aromatic hydrocarbon group having a substituent" means that one or more hydrogen atoms constituting the aromatic hydrocarbon group are substituted with a group (substituent) other than a hydrogen atom. And, "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.

[0033] The aromatic group for 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.

[0034] Among the aromatic groups in 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, an 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. As the aromatic hydrocarbon group, one or more hydrogen atoms of these aromatic hydrocarbon groups may be substituted with a substituent such as the aromatic hydrocarbon group or an alkyl group exemplified above. The aromatic hydrocarbon group having the above-mentioned substituent preferably has a carbon number of 6 to 20, including the substituent.

[0035] The alkyl group substituting one or more hydrogen atoms of the above-mentioned 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 above-mentioned substituted alkyl group preferably has 1 to 10 carbon atoms.

[0036] 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.

[0037] 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, and further includes those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with linear, branched, or cyclic alkyl groups. Here, examples of the linear, branched, and cyclic alkyl groups substituting the hydrogen atoms are the same as those of the substituted alkyl groups.

[0038] 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 a compound having one or more sulfur atoms as atoms constituting the aromatic heterocyclic skeleton (sulfur-containing aromatic heterocyclic compound), a compound having one or more nitrogen atoms as atoms constituting the aromatic heterocyclic skeleton (nitrogen-containing aromatic heterocyclic compound), a compound having one or more oxygen atoms as atoms constituting the aromatic heterocyclic skeleton (oxygen-containing aromatic heterocyclic compound), and a compound having two different heteroatoms selected from a sulfur atom, a nitrogen atom, and an oxygen atom as atoms constituting the aromatic heterocyclic skeleton.

[0039] Examples of the sulfur-containing aromatic heterocyclic compound include thiophene and benzothiophene.

[0040] 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.

[0041] Examples of the oxygen-containing aromatic heterocyclic compound include furan, benzofuran (1-benzofuran), and isobenzofuran (2-benzofuran).

[0042] Examples of the compound having the above-mentioned two different heteroatoms as atoms constituting an aromatic heterocyclic skeleton include oxazole, isoxazole, thiazole, benzoxazole, benzisoxazole, and benzothiazole.

[0043] Among 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 heteroatom, but it is preferable that both are carbon atoms.

[0044] 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 be all the same, all different, or only some of them may be the same.

[0045] 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.

[0046] The number of the substituents possessed by the aromatic hydrocarbon group or aromatic heterocyclic group in G may be only 1 or may be 2 or more, and all hydrogen atoms may be substituted with the substituents. The number of the substituents depends on the number of hydrogen atoms that can be substituted, and is, for example, preferably 1 to 4, more preferably 1 to 3, and further preferably 1 or 2. When the number of the substituents in the aromatic hydrocarbon group or aromatic heterocyclic group is two or more, these substituents may be all the same, all different, or only some of them may be the same.

[0047] Examples of the alkoxy group which is 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.

[0048] 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 substituted alkyl groups, and the like. The aryl groups having these substituents preferably have 6 to 10 carbon atoms including the substituent.

[0049] 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, a methylethylamino group, etc. 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, a phenyl-1-naphthylamino group, etc. In the diarylamino group, the two aryl groups bonded to the nitrogen atom may be the same or different. Examples of the alkylarylamino group which is a substituent include a monovalent group, 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.

[0050] Examples of the alkylcarbonyl group as a substituent include a monovalent group in which the substituted alkyl group is bonded to a carbonyl group (-C(=O)-), such as a methylcarbonyl group (acetyl group). Examples of the arylcarbonyl group which is a substituent include a monovalent group in which the aryl group is bonded to a carbonyl group, such as a phenylcarbonyl group (benzoyl group).

[0051] 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 which is a substituent include a monovalent group in which the aryloxy group is bonded to a carbonyl group, such as a phenyloxycarbonyl group (phenoxycarbonyl group).

[0052] Examples of the alkylcarbonyloxy group as a substituent include a monovalent group formed by bonding the substituted alkyl group to a carbonyloxy group (-C(=O)-O-), such as a methylcarbonyloxy group. Examples of the arylcarbonyloxy group which is a substituent include a monovalent group in which the aryl group is bonded to a carbonyloxy group, such as a phenylcarbonyloxy group.

[0053] 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.

[0054] 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).

[0055] The haloalkyl group as a substituent includes groups in which one or more hydrogen atoms of the above-mentioned 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 which is a substituent. The number of halogen atoms in the haloalkyl group is not particularly limited, and may be 1 or 2 or more. When the number of halogen atoms in the haloalkyl group is 2 or more, these multiple halogen atoms may be all the same, all different, or only some of them may be the same. The haloalkyl group may be a perhaloalkyl group in which all hydrogen atoms in the alkyl group are replaced 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.

[0056] When the substituent of 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 in compound (1) becomes longer (the wavelength becomes longer) upon irradiation with light. That is, the substituent of these electron-donating groups is advantageous in that the wavelength of the light required to generate a base in compound (1) can be made longer.

[0057] The substitution position of the substituent on the aromatic hydrocarbon group or aromatic heterocyclic group is not particularly limited.

[0058] 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.

[0059] [ka]

[0060] 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; 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 the 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.

[0061] 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.

[0062] In the general formula (a)-1, n1 is an integer of 0 to 2m1+4, 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, further 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, further preferably an integer of 0 to 2, and particularly preferably 0 or 1.

[0063] 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 substituent possessed by the aromatic hydrocarbon group or aromatic heterocyclic group in G described above.

[0064] 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. That is, in this case, Z 1 may all be the same, may all be different, or may be only partially the same. If n1 is a nonzero integer, Z 1 The bonding position of to the aromatic hydrocarbon group is not particularly limited.

[0065] 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.

[0066] 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 a base in which a hydrogen atom is bonded to the nitrogen atom of the second skeleton, and coumarin or a coumarin derivative, upon irradiation with light.

[0067] [ka]

[0068] In the 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, and * represents a bonding position with a nitrogen atom. At least two of R1 to R4 may be bonded to each other to form a ring structure.

[0069] The second skeleton may have a nitrogen atom that is bonded to the bonding position of the first skeleton to form an amide group, and may have a pyridine skeleton together with the nitrogen atom. In addition, when the base-reactive compound is an epoxy compound, the second skeleton preferably has an aminopyridine skeleton from the viewpoint of excellent reactivity of the epoxy compound when irradiated with light and heated, and more preferably has a 4-aminopyridine skeleton from the viewpoint of further improving the reactivity of the epoxy compound by the terminal portion containing a nitrogen atom derived from the amino group of the aminopyridine skeleton functioning as a base when the base generated by irradiation with light reacts with the epoxy compound.

[0070] The second skeleton is preferably a group represented by the following general formula (C).

[0071] [ka]

[0072] In general formula (C), R 11 represents a hydrogen atom or the above-mentioned substituted alkyl group, R 12 ~R 15each independently represents 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 (a halogenated alkyl group), a hydroxyl group (-OH), a mercapto group (-SH), an amino group, the aromatic hydrocarbon group, or the aromatic heterocyclic group, and * represents the bonding position with * in general formula (a). 11 ~R 15 At least two of these may be bonded to each other to form a ring structure.

[0073] In general formula (C), R 11 R is preferably a hydrogen atom or a methyl group, and more preferably a methyl group from the viewpoint of excellent storage stability when formed into a photoreactive composition. 12 ~R 15 is preferably a hydrogen atom or the above-mentioned substituted alkyl group, and more preferably a hydrogen atom.

[0074] (Production method of compound (1)) An example of a method for producing compound (1) will be described below. As an example of the method for producing compound (1), a method for producing a compound in which the first skeleton is a group represented by general formula (a)-2 and the second skeleton is a group represented by general formula (C) (a compound represented by general formula (X-4)) will be described.

[0075] First, a compound (compound represented by general formula (X-1)) in which the hydroxyl group in the group represented by general formula (a)-2 is acetylated and a hydroxyl group is bonded to the bonding position is prepared.

[0076] Next, the OH of the carboxy group in the compound represented by the general formula (X-1) is replaced with a halogen atom to obtain a compound represented by the general formula (X-2) (Y is a halogen atom such as a chlorine atom or a bromine atom). For example, the compound represented by the general formula (X-2) can be obtained by reacting the compound (X-1) with thionyl chloride, phosphorus pentachloride, or the like.

[0077] Furthermore, the compound represented by the general formula (X-2) is reacted with a compound having a group represented by the general formula (C) and a hydrogen atom bonded to the bonding position, whereby the halogen atom in the compound represented by the general formula (X-2) is substituted with the group represented by the general formula (C), thereby obtaining a compound represented by the general formula (X-3).

[0078] By hydrolyzing the compound represented by the general formula (X-3) under basic conditions, the acetyl group is replaced with a hydroxyl group to obtain a compound represented by the general formula (X-4).

[0079] The reaction for obtaining a compound represented by general formula (X-4) from a compound represented by general formula (X-1) is as follows.

[0080] [ka]

[0081] In the general formulas (X-1) to (X-4), R1 to R4 are the same as R1 to R4 in the general formula (a)-2. 11 ~R 15 R in general formula (C) 11 ~R 15 and Y represents a halogen atom.

[0082] [Photoreactivity composition ] Photoreactivity of the present disclosure compositionThe present invention includes a photobase generator and a base-reactive compound, and 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 may be a compound having two or more of the above-mentioned functional groups, or may be 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 may be a compound having two or more groups that react by the action of a base, or may be a mixture thereof.

[0083] 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 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.

[0084] 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 that is solubilized by light irradiation (positive type), or a photoreactive material that is cured by light irradiation (negative type).

[0085] The photoreactive composition of the present disclosure may contain only one type of photobase generator, or two or more types. When there are two or more types, the combination and ratio thereof can be set arbitrarily.

[0086] In the photoreactive composition of the present disclosure, the content of the photobase generator is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 35% by mass, and even more preferably 3% by mass to 10% by mass, relative to the content of the base-reactive compound. When the content of the photobase generator is 1% by mass or more, the reaction of the base-reactive compound proceeds more easily. In addition, when the content of the photobase generator is 40% by mass or less, excessive use of the photobase generator is suppressed.

[0087] (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 group exhibiting reactivity by the action of a base (sometimes referred to as "base-reactive compound (9-2a)" in this 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 this 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 group exhibiting reactivity by the action of a base.

[0088] Examples of the reaction that proceeds in the base-reactive compound include addition polymerization and condensation polymerization (polycondensation polymerization).

[0089] 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.

[0090] As the base-reactive compound, known compounds can be used, for example, the base-reactive compounds described in JP 2011-80032 A can be used, however, this is only one example.

[0091] Examples of the base-reactive compound (9-2a) include compounds that are decomposed by the action of a base and have a functional group that is 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.

[0092] Examples of the base-reactive compound (9-2b) include epoxy compounds, 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".

[0093] The photoreactive composition of the present disclosure may contain only one type of base-reactive compound, or two or more types. When there are two or more types, the combination and ratio thereof can be set arbitrarily.

[0094] The content of the base-reactive compound in the photoreactive composition of the present disclosure is preferably 40% by mass to 90% by mass, and more preferably 45% by mass to 80% by mass, based on the total amount of non-volatile components in the photoreactive composition.

[0095] <Epoxy compounds> The photoreactive composition of the present disclosure preferably contains an epoxy compound as a base-reactive compound. The epoxy compound may contain an epoxy compound having one or more epoxy groups in one molecule, and preferably contains an epoxy compound having two or more epoxy groups. The epoxy compound can be arbitrarily selected according to the purpose. The epoxy 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.

[0096] Since the photoreactive composition of the present disclosure contains an epoxy compound, when the photoreactive composition is irradiated with light and heated, the reactivity of the epoxy compound is good at a relatively low heating temperature (for example, 120° C. or lower).

[0097] The epoxy compound is not particularly limited, and examples thereof include diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid monoglycidyl ether, spiroglycol diglycidyl ether, glycidylpropoxytrimethoxysilane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, etc. These epoxy compounds may be halogenated or hydrogenated.

[0098] (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 arbitrarily selected 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 of these components can be set arbitrarily.

[0099] The other components include a sensitizer, a filler, a pigment, a solvent, and the like.

[0100] <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 appropriately adjusted.

[0101] <Filling material> The photoreactive composition of the present disclosure may contain a filler. By including a filler, for example, the viscosity of the photoreactive composition itself, the strength of the photoreactive composition after reaction (the reaction product described later), and other properties can be adjusted. The filler may be a known one and is not particularly limited. For example, the filler may be any of fibrous, plate-like, and granular, and the shape, size, and material may be appropriately selected according to 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 thereof can be set arbitrarily. The content of the filler in the photoreactive composition is not particularly limited and may be appropriately adjusted depending on the purpose.

[0102] <Pigments> The photoreactive composition of the present disclosure may contain a pigment. By including a pigment, for example, the light transmittance and the like can be adjusted. The pigment contained in the photoreactive composition may be a known pigment, and may be, for example, any of white, blue, red, yellow, green, etc., without any particular limitation. 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 appropriately adjusted depending on the purpose.

[0103] <Solvent> The photoreactive composition of the present disclosure may contain a solvent. By containing a solvent, the handling property is improved. 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.

[0104] The photoreactive composition may contain only one type of solvent, or two or more types. When two or more types are contained, the combination and ratio of the solvents can be set arbitrarily.

[0105] 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 such a range, the handleability of the photoreactive composition is further improved.

[0106] The photoreactive composition includes a base-reactive compound, a photobase generator, Agents and After the components are mixed, the resultant composition may be used as it is as a photoreactive composition, or may be used as a photoreactive composition after a known purification procedure or the like is carried out as necessary.

[0107] 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 blade, a method of mixing using a mixer, or a method of mixing by applying ultrasonic waves.

[0108] 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 each blended component does not deteriorate, and can be, for example, 30 seconds to 1 hour. However, these compounding conditions are merely examples.

[0109] <Reaction products> The reaction product of the present disclosure is obtained by reacting the above-mentioned photoreactive composition. The 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.

[0110] (Method of 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 exhibits reactivity 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, the base-reactive compound contained in the photoreactive composition reacts by irradiating the photoreactive composition with light to generate a base, thereby obtaining a reaction product.

[0111] The photoreactive composition may be applied to an object by a known method, and then optionally pre-baked (e.g., dried) to form a photoreactive composition layer, and the photoreactive composition layer may be irradiated with light. For example, when producing a film-like reaction product, the photoreactive composition may be applied to an 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, kiss coater, etc., or an applicator, or the like, or the object may be immersed in the photoreactive composition, thereby adhering the photoreactive composition to the 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.

[0112] The pre-baking may be performed under conditions of, for example, 40° C. to 120° C. and 30 seconds to 10 minutes, and is not particularly limited.

[0113] The wavelength of the light irradiated to 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 to the photoreactive composition may be 10 nm or more, 200 nm or more, or 300 nm or more. In addition, the wavelength of the light irradiated to the photoreactive composition may be 600 nm or less, 500 nm or less, or 400 nm or less.

[0114] The illuminance of the light irradiated to 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 / cm2 It is even more preferable that: The amount of light irradiated to the photoreactive composition is, for example, 100 mJ / cm 2 ~20000mJ / cm 2 and preferably 200 mJ / cm 2 ~15000mJ / cm 2 More preferably, 300 mJ / cm 2 ~12000mJ / cm 2 It is even more preferable that: However, the light irradiation conditions given here are merely examples and are not limited to these.

[0115] 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, for example, under conditions of 50°C to 180°C and 20 minutes to 2 hours. When an epoxy compound is used as the base-reactive compound, the post-baking may be carried out preferably under conditions of 70°C to 140°C and 20 minutes to 2 hours, more preferably under conditions of 90°C to 120°C and 20 minutes to 2 hours, and even more preferably under conditions of 90°C to 100°C and 20 minutes to 2 hours.

[0116] The thickness of the reaction product may be appropriately set according to 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. In order to form a reaction product having 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 intended reaction product.

[0117] 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 it to any one 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. EXAMPLES

[0118] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0119] <Production of compound (1)-1> First, as shown below, compound (X) was reacted with thionyl chloride and 4-aminopyridine in that order to produce compound (Y). That is, a mixture of compound (X) (1.2 g, 0.0055 mol) and thionyl chloride (SOCl2, 10 mL) was stirred at room temperature for 10 hours, and then dry tetrahydrofuran (20 mL) and 4 -a A mixture of minopyridine (1.3 g, 0.012 mol) and dry tetrahydrofuran (50 mL) was added thereto, and the mixture was stirred at 0° C. for 12 hours to carry out the reaction. Next, a saturated aqueous solution of sodium chloride was added to the reaction solution, and the reaction solution was washed by shaking in a separatory funnel. This washing with the saturated aqueous solution of sodium chloride was carried out once more, for a total of two times. This gave compound (Y).

[0120] [ka]

[0121] Next, compound (Y) was hydrolyzed by the reaction shown below to produce compound (1)-1. That is, a mixture of the compound (Y) obtained as described above and methanol (30 mL) was added to a mixture of saturated potassium carbonate aqueous solution (20 mL), and the mixture was stirred for 20 hours while heating to carry out a reaction. After the reaction was completed, 35% by mass hydrochloric acid was added to the reaction solution. The resulting reaction solution was then filtered to obtain the target compound (1)-1 as a yellow solid (yield 66%). The obtained compound (1)-1 1 H-NMR, 13 The analytical results by C-NMR and ESI-MS are shown in Table 1.

[0122] [ka]

[0123] [Table 1] JPEG0007626459000013.jpg28156 JPEG0007626459000014.jpg37154

[0124] The solubility of compound (1)-1 in the solvent was also confirmed. Specifically, the amount of solvent required to dissolve 10 mg of compound (1)-1 was confirmed for each solvent. The amount of solvent required was 1 mL to 5 mL when tetrahydrofuran or acetone was used, and 1 mL or less when cyclopentanone, methanol or dimethyl sulfoxide was used.

[0125] <Production of compound (1)-2> First, as shown below, compound (X) was reacted with thionyl chloride and 4-methylaminopyridine in that order to produce compound (Z). That is, a mixture of compound (X) (2.1 g, 0.010 mol) and thionyl chloride (SOCl, 10 mL) was stirred at room temperature for 10 hours, and then dry tetrahydrofuran (30 mL) and a mixture of 4-methylaminopyridine (2.3 g, 0.022 mol) and dry tetrahydrofuran (40 mL) were added to this mixture, and the mixture was stirred at 0° C. for 12 hours to carry out the reaction. Next, a saturated aqueous solution of sodium chloride was added to the reaction solution, and the reaction solution was washed by shaking in a separatory funnel. This washing with the saturated aqueous solution of sodium chloride was carried out once more, for a total of two times. This gave compound (Z).

[0126] [ka]

[0127] Next, compound (Z) was hydrolyzed by the reaction shown below to produce compound (1)-2. That is, a mixture of the compound (Z) obtained as described above and methanol (30 mL) was added to a mixture of saturated potassium carbonate aqueous solution (20 mL), and the mixture was stirred for 20 hours while heating to carry out a reaction. After the reaction was completed, 35% by mass hydrochloric acid was added to the reaction solution. Next, the obtained reaction solution was purified by silica gel column chromatography using a mixed solvent of chloroform / methanol (14 / 1, volume ratio) as the mobile phase, and the fractions containing the target product were collected and concentrated to obtain the target compound (1)-2 as a pale yellow solid (yield 7.1%). The obtained compound (1)-2 1 H-NMR, 13 The analytical results by C-NMR and ESI-MS are shown in Table 2.

[0128] [ka]

[0129] [Table 2]

[0130] [Test Example 1] (Confirmation of the behavior of compound (1)-1 in a solvent when irradiated with light having a wavelength of 313 nm) The compound (1)-1 obtained above was diluted with water at a concentration of 2.0 × 10 -5 The compound was dissolved in methanol at a concentration of mol / L. The illuminance was set to 5 mW / cm using a mercury xenon lamp. 2 The light irradiation dose was set to 0, 10, 30, 60 and 100 mJ / cm 2 The resulting methanol solution was irradiated with light having a wavelength of 313 nm. The absorbance of compound (1)-1 was then measured. The results are shown in FIG.

[0131] [Test Example 2] (Confirmation of the behavior of compound (1)-1 in a solvent when irradiated with light having a wavelength of 365 nm) The compound (1)-1 obtained above was diluted with water at a concentration of 2.0 × 10 -5 The compound was dissolved in methanol at a concentration of 1.2 mol / L. Then, an LED lamp was used to set the illumination intensity to 10 mW / cm 2 The light irradiation dose was set to 0, 10, 30, 60 and 100 mJ / cm 2 The resulting methanol solution was irradiated with light having a wavelength of 365 nm. The absorbance of compound (1)-1 was then measured. The results are shown in FIG. 2.

[0132] In Test Example 1, the molar absorption coefficient is ε 313 =2.3×10 4 L / (mol cm), and in Test Example 2, the molar absorption coefficient is ε 365 =6.9×10 3 L / (mol cm). As is clear from FIG. 1 and FIG. 2, the light irradiation amount was 0 mJ / cm 2In other words, compared with the spectrum without light exposure, the spectra with other irradiation doses had both increasing and decreasing peaks. This measurement result confirmed that a base was generated from compound (1)-1 by the reaction shown below upon light exposure.

[0133] [ka]

[0134] [Test Example 3] (Confirmation of the behavior of compound (1)-1 in a polymer solid upon irradiation with light) Polytetramethylene glycol (0.13 g), compound (1)-1 (0.035 g, 26% by mass based on polytetramethylene glycol), and tetrahydrofuran (0.54 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 onto a calcium fluoride plate by spin coating at 500 rpm for 10 seconds, and the resulting coating film was heated at 60°C for 3 minutes, and then heated under an illumination intensity of 12 mW / cm using a mercury xenon lamp. 2 The coating was irradiated with light of 313 nm wavelength. 2 ~30000mJ / cm 2 The peak intensity derived from the amide group and the peak intensity derived from the lactone structure were measured using a Fourier transform infrared spectrophotometer (FT-IR) at the light irradiation dose of Compound (1)-1. A graph showing the relationship between the light irradiation dose of Compound (1)-1 and the peak areas of the amide group and the lactone structure in the IR spectrum is shown in Figure 3.

[0135] [Test Example 4] (Confirmation of the behavior of compound (1)-1 in a polymer solid upon irradiation with light) An experiment similar to that of Test Example 3 was conducted, except that an LED lamp was used instead of the mercury xenon lamp, the illuminance was set to 50 mW / cm2, and light with a wavelength of 365 nm was irradiated onto the coating film. Compound (1)-1FIG. 4 is a graph showing the relationship between the amount of light irradiation and the peak areas of the amide group and lactone structure in the IR spectrum.

[0136] As is clear from Figures 3 and 4, as the amount of light irradiation increased, the peak intensity derived from the amide group tended to decrease and the peak intensity derived from the lactone structure tended to increase. This demonstrated that a base was generated from compound (1)-1 by the following reaction upon irradiation with light.

[0137] [ka]

[0138] [Test Example 5] (UV curing of liquid epoxy compounds using compound (1)-1) First, a glycidylamine type epoxy compound (0.21 g, hereinafter also referred to as "NN"), which is a liquid epoxy compound having the structure shown below, compound (1)-1 (0.0030 g, 0.0062 g, 0.012 g, respectively 2.5 mol %, 5 mol %, and 10 mol % relative to NN), and cyclopentanone (0.67 g, 0.72 g, and 0.69 g, respectively, relative to 0.030 g, 0.0062 g, and 0.012 g of compound (1)-1) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0139] [ka]

[0140] The photoreactive composition obtained above was applied onto a silicon wafer by spin coating at 1500 rpm for 10 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 3 minutes, 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. The light irradiation dose was 0 mJ / cm 2 (unirradiated), 1000mJ / cm 2 , 5000mJ / cm 2and 10,000 mJ / cm 2 Three types of coating films were prepared, and after light irradiation, they were heated (post-baked) at 80°C, 100°C, or 120°C for 60 minutes. In this way, we attempted to turn each coating film into a reaction product by polymerizing the epoxy compound NN.

[0141] In addition, the light irradiation dose was 0 mJ / cm 2 (unirradiated), 1000mJ / cm 2 (1J / cm 2 ), 5000mJ / cm 2 (5J / cm 2 ) and 10,000 mJ / cm 2 (10J / cm 2 ) was heated at 80°C, 100°C or 120°C for 60 minutes, and the pencil hardness of the reaction product obtained was measured. The results are shown in Figures 5 to 7 (in the figures, PBG means compound (1)-1), respectively. As shown in Figures 5 to 7, it was possible to cure the liquid epoxy compound by UV irradiation at a low temperature of 120°C or less without using a curing accelerator such as an imidazole compound.

[0142] Next, a photoreactive composition containing 5 mol % of compound (1)-1 relative to NN was formed into a coating film, and the film was heated at 120°C after light irradiation to obtain a reaction product (conditions for obtaining a reaction product with a pencil hardness of F). The absorption spectrum was measured using a Fourier transform infrared spectrophotometer (FT-IR). The results are shown in Figure 8. In Figure 8, the light irradiation dose was 0 mJ / cm 2 (unirradiated) or 10,000 mJ / cm 2 The absorption spectrum of the coating film before and after heating was measured and the light irradiation dose was 10,000 mJ / cm 2 FIG. 8 shows the results of measuring the absorption spectrum of the coating film which was then heated at 120° C. for 20 or 60 minutes. It was confirmed from FIG. 8 that the number of hydroxyl groups was reduced by the reaction of compound (1)-1, the number of ether bonds was increased by the reaction of NN, and the number of epoxy groups was reduced by the reaction of NN, by the irradiation of light or by heating.

[0143] In addition, a photoreactive composition containing 5 mol % of compound (1)-1 relative to NN was used as a coating film, and the light exposure dose was 0 mJ / cm 2 (unirradiated) or light irradiation dose of 10,000 mJ / cm 2 The relationship between the heating time and the peak area of ​​the epoxy group is shown in Figure 9. As shown in Figure 9, it was confirmed that there was a difference in the conversion rate of the epoxy group between the case where light was irradiated and the case where light was not irradiated.

[0144] [Test Example 6] (Storage stability of photoreactive composition containing compound (1)-1 or compound (1)-2) The following polyfunctional aliphatic epoxy compound (EX-622), 4-aminopyridine, 4-methylaminopyridine, the following 4-aminopyridine derivative (Urea-4APy), compound (1)-1 or compound (1)-2, and methanol were added to a glass test tube to prepare mixed solutions 1 to 5, which are photoreactive compositions. The compositions of mixed solutions 1 to 5 are as follows. Mixture 1: 0.40 g of EX-622, 0.0046 g of 4-aminopyridine (5 mol % relative to EX-622), 0.40 g of methanol Mixture 2: 0.20 g of EX-622, 0.0027 g of 4-methylaminopyridine (5 mol % relative to EX-622), and 0.20 g of methanol Mixture 3: 0.40 g of EX-622, 0.011 g of 4-aminopyridine derivative (5 mol % relative to EX-622), 0.41 g of methanol Mixture 4: 0.40 g of EX-622, 0.012 g of compound (1)-1 (5 mol % relative to EX-622), and 0.42 g of methanol Mixture 5: 0.10 g of EX-622, 0.0034 g of compound (1)-2 (5 mol % relative to EX-622), and 0.34 g of methanol

[0145] [ka]

[0146] Mixtures 1 to 4 were stored in a dark place at 25°C, and after storage for 2 days, the glass test tube was shaken or inverted. It was confirmed that the viscosity of mixtures 1 to 4 increased significantly. On the other hand, when mixture 5 was stored in a dark place at 25°C, and after storage for 2 days, the glass test tube was shaken or inverted, the viscosity of mixture 5 hardly increased and it was liquid. When mixture 5 was stored in a dark place at 25°C, and after storage for 10 days, the glass test tube was shaken or inverted, the viscosity of mixture 5 hardly increased and it was liquid.

[0147] Mixtures 1-3 and 4 were stored in a dark place at 9°C. After 24 days of storage, the glass test tubes were shaken or inverted. Mixtures 1-3 and 4 showed almost no increase in viscosity and remained liquid. Mixture 5 was stored in a dark place at 9°C. After 10 days of storage, the glass test tubes were shaken or inverted. Mixture 5 showed almost no increase in viscosity and remained liquid.

[0148] Therefore, it was confirmed that mixed solution 4 containing compound (1)-1 has excellent storage stability in a dark place under refrigerated conditions (9°C), and mixed solution 5 containing compound (1)-2 has excellent storage stability in a dark place under room temperature conditions (25°C) and refrigerated conditions (9°C).

[0149] [Test Example 7] (Evaluation of the reactivity of PGMA in the presence of 4-aminopyridine or 4-methylaminopyridine) Polyglycidyl methyl acrylate (PGMA, 0.14 g) having the structure shown below, 4-aminopyridine (0.0018 g, 2 mol % relative to PGMA) or 4-methylaminopyridine (0.0021 g, 2 mol % relative to PGMA), and cyclopentanone (0.71 g) were mixed and stirred at 25° C. for 1 minute to obtain photoreactive compositions.

[0150] [ka]

[0151] The photoreactive compositions obtained above were coated on silicon wafers by spin coating at 1500 rpm for 10 seconds. Next, the coatings (photoreactive composition layers) were pre-baked at 60°C for 1 minute, and then post-baked at 60°C or 100°C for 2 minutes. In this way, each coating was converted into a reaction product obtained by polymerizing the epoxy compound PGMA, and the coatings were developed for 30 seconds using cyclohexanone, after which the ratio of the thickness of the reaction product after development to the coating before heating (residual film ratio) was measured. The results are shown in FIG. 10.

[0152] [Test Example 8] (Confirmation of the behavior of compound (1)-2 in a solvent when irradiated with light having a wavelength of 313 nm) The compound (1)-2 obtained above was diluted with water at a concentration of 2.0 × 10 -5 The compound was dissolved in methanol at a concentration of 1.2 mol / L. The illuminance was set to 10 mW / cm using a mercury xenon lamp. 2 The light irradiation dose was set to 0, 30, 100, 200 and 300 mJ / cm 2 The resulting methanol solution was irradiated with light having a wavelength of 313 nm. The absorbance of compound (1)-2 was then measured. The results are shown in FIG.

[0153] [Test Example 9] (Confirmation of the behavior of compound (1)-2 in a solvent when irradiated with light having a wavelength of 365 nm) The compound (1)-2 obtained above was diluted with water at a concentration of 2.0 × 10 -5 The compound was dissolved in methanol at a concentration of 1.2 mol / L. Then, an LED lamp was used to set the illumination intensity to 10 mW / cm 2 The light irradiation dose was set to 0, 30, 100, 200 and 300 mJ / cm 2 The resulting methanol solution was irradiated with light having a wavelength of 365 nm. The absorbance of compound (1)-2 was then measured. The results are shown in FIG.

[0154] In Test Example 8, the molar absorption coefficient is ε 313 =1.3×10 4 L / (mol cm), and in Test Example 9, the molar absorption coefficient is ε365 =3.2×10 3 L / (mol cm). As is clear from FIG. 11 and FIG. 12, the light irradiation amount was 0 mJ / cm 2 In other words, compared to the spectrum without light exposure, the spectra with other irradiation doses had both increasing and decreasing peaks. This measurement result confirmed that a base was generated from compound (1)-2 by the reaction shown below upon light exposure.

[0155] [ka]

[0156] [Test Example 10] (Negative Patterning Using Photoreactive Composition Containing Compound (1)-2) Polyglycidyl methyl acrylate (PGMA, 0.14 g) having the structure shown above, compound (1)-2 (0.0060 g, 2 mol % relative to PGMA), and cyclopentanone (0.63 g) were mixed and stirred at 25° C. for 1 minute to obtain a photoreactive composition.

[0157] The photoreactive composition obtained above was applied onto a silicon wafer by spin coating at 1500 rpm for 10 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 1 minute, and then heated at an illuminance of 50 mW / cm using an LED lamp. 2 The light irradiation dose was 1000 mJ / cm 2 The coating film was irradiated with light having a wavelength of 365 nm, so that the irradiated and non-irradiated areas were alternately exposed to light. After the light irradiation, the coating film was heated (post-baked) at 80°C for 270 seconds. The heated coating film was developed using cyclohexanone for 30 seconds, and the ratio of the thickness of the coating film after development to the thickness of the coating film before light irradiation was measured. As a result, the thickness of the coating film after development was 1.6 μm, and the ratio of the thickness of the coating film after development to the thickness of the coating film before light irradiation (residual film ratio) was 0.96.

[0158] [Test Example 11] (Production of reaction product using photoreactive composition containing compound (1)-2) Polyglycidyl methyl acrylate (PGMA, 0.14 g) having the structure shown above, compound (1)-2 (0.0060 g, 2 mol % relative to PGMA), and cyclopentanone (0.63 g) were mixed and stirred at 25° C. for 1 minute to obtain a photoreactive composition.

[0159] The photoreactive composition obtained above was applied onto a silicon wafer by spin coating at 1500 rpm for 10 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 60°C for 3 minutes, and then heated at an illuminance of 50 mW / cm using an LED lamp. 2 The light irradiation dose was set to 0 to 1000 mJ / cm 2 The coating film was irradiated with light having a wavelength of 365 nm. After the light irradiation, the coating film was heated (post-baked) at 80°C for 5 minutes. After the heating, the coating film was developed using cyclohexanone for 30 seconds, and the ratio of the thickness of the coating film after development to the thickness of the coating film before light irradiation (residual film ratio) was measured. The results are shown in Figure 13.

[0160] As shown in FIG. 13, the light irradiation dose at the gel point (e.g., the point where a residual film occurs) was 200 mJ / cm 2 The light irradiation dose at which the residual film ratio is approximately 0.55 is 293 mJ / cm 2 and the light irradiation dose is 1000 mJ / cm 2 The residual film ratio was 0.98.

[0161] <Production of compound (2)> First, as shown below, trans-o-coumaric acid was reacted with cyclohexylamine to produce compound (2). Specifically, trans-o-coumaric acid (4.00 g) and cyclohexylamine (3.63 g) were added to a mixture of 60 mL of N,N-dimethylformamide (DMF) and 9.35 g of N-ethyl-N'-dimethylaminopropylcarbodiimide (EDAC), and the mixture was stirred at room temperature for 24 hours to produce compound (2). The produced compound (2) was washed to obtain the target compound (2) as a white solid (yield 24%). The obtained compound (2) 1 H-NMR, 13 The results of the C-NMR analysis are shown in Table 3.

[0162] [ka]

[0163] [Table 3]

[0164] [Test Example 12] (Production of reaction product using photoreactive composition containing compound (2)) Polyglycidyl methyl acrylate (PGMA, 0.1 g, molecular weight: 22000) having the structure described above, compound (2) (0.005 g) and tetrahydrofuran (1 g) were mixed and stirred at 25° C. for 1 minute to obtain a photoreactive composition.

[0165] The photoreactive composition obtained above was applied onto a silicon wafer by spin coating at 1500 rpm for 30 seconds. Then, this coating film (photoreactive composition layer) was heated (pre-baked) at 100°C for 1 minute, and then irradiated with light from a Hg-Xe lamp with a wavelength of 365 nm and an illuminance of 50 mW / cm. 2 The light irradiation dose was 0 to 10,000 mJ / cm 2 After the light irradiation, the coating film was heated (post-baked) at 160°C for 20 minutes. After the heating, the coating film was developed using tetrahydrofuran for 30 seconds, and the ratio of the thickness of the coating film after development to that before light irradiation (remaining film ratio) was measured. The light irradiation dose was 100 mJ / cm 2 , 1000mJ / cm 2 and 10,000 mJ / cm 2 However, the residual film rate was 0% in all cases, and an insolubilized reaction product could not be produced from the photoreactive composition containing compound (2).

[0166] The disclosure of Japanese Patent Application No. 2019-237416, filed on December 26, 2019, is incorporated herein by reference in its entirety. All publications, patent applications, and standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A first skeleton represented by the following general formula (a), a second skeleton having a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and having a pyridine skeleton together with the nitrogen atom; A photobase generator comprising 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 1】 (In general formula (a), G is a divalent aromatic group, and * represents the bonding position with the nitrogen atom.)

2. The photobase generator according to claim 1 , wherein the second skeleton has an aminopyridine skeleton.

3. A first skeleton represented by the following general formula (a), a second skeleton which has a nitrogen atom bonded to a bonding position of the first skeleton to form an amide group, and which has a pyridine skeleton together with the nitrogen atom, and which is a group represented by the following general formula (C): 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 2】 【Chemistry 3】 (In general formula (a), G is a divalent aromatic group, and * represents the bonding position with a nitrogen atom. In general formula (C), R １１ represents a hydrogen atom or an alkyl group; R １２ ~R １５ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, an alkylarylamino group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylthio group, an arylthio group, a cyano group (-CN), a halogen atom, a nitro group, a haloalkyl group (a halogenated alkyl group), a hydroxyl group (-OH), a mercapto group (-SH), an amino group, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and * represents the bonding position with * in general formula (a).

4. The compound according to claim 3 , wherein the second skeleton has an aminopyridine skeleton.

5. The photobase generator according to claim 1 or 2, 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.

6. A reaction product obtained by reacting the photoreactive composition according to claim 5.

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