Photobase generator, compound, photoreactive composition and reaction product

Abstract

A photobase generator comprises a compound having a first skeleton represented by the following general formula (a) and a second skeleton having a nitrogen atom that is bound to a binding position of the first skeleton and constitutes an amide group, wherein in one molecule, the number of the first skeletons is 2 or more, the number of nitrogen atoms constituting the amide group in the second skeleton is the same as the number of the first skeleton, and at least one of the nitrogen atoms constituting the amide group is converted into a nitrogen atom constituting a secondary amine or a tertiary amine by light irradiation. In the general formula (a), G is a divalent aromatic group, and * represents a binding position with a nitrogen atom. [Chemical Formula 1]

Description

Technical Field

[0001] The present invention relates to a photobase generator, a compound, a photoreactive composition and a reaction product. Background Art

[0002] Photopolymerizable materials that polymerize upon irradiation with light are widely used because the polymerization reaction can be precisely controlled with a relatively simple operation, and they occupy an important position in, for example, the electronic material field and the printing material field.

[0003] As photopolymerizable materials, free radical polymerization resin compositions containing photoinitiators that generate free radical substances upon exposure and free radical polymerizable monomers or oligomers; acid-catalyzed resin compositions containing photoacid generators that generate acids upon exposure and monomers or oligomers that are polymerized by the action of acids, etc. are being actively studied so far.

[0004] On the other hand, as photopolymerizable materials, base-catalyzed substances containing a photobase generator that generates a base by exposure and a monomer or oligomer that polymerizes by the action of a base are also known. Furthermore, as photobase generators, ionic substances such as salts of strong bases such as guanidine and carboxylic acids are known (for example, see Non-Patent Document 1). Such ionic photobase generators undergo a decarboxylation reaction in a carboxyl group by exposure, and a strong base that forms a salt with the carboxyl group is released, thereby generating a base.

[0005] However, such ionic photobase generators have problems such as low stability or low solubility during storage, although they have high reactivity. Furthermore, resin compositions using such ionic photobase generators also have problems such as low stability.

[0006] In this regard, non-ionic photobase generators are also being studied. As non-ionic photobase generators, for example, carbamates having a nitrobenzyl skeleton are known, which undergo a decarboxylation reaction upon exposure and generate a base by releasing a primary amine or a secondary amine (for example, see Non-Patent Document 2). In such non-ionic photobase generators, the problems in the above-mentioned ionic photobase generators are solved.

[0007] Patent Literature

[0008] Non-patent literature 1: K. Arimitsu, R. Endo, Chem. Mater. 2013, 25, 4461-4463.

[0009] Non-patent document 2: JF Cameron, JMJ Frechet, J. Am. Chem. Soc. 1991, 113, 4303. Summary of the invention

[0010] However, since the base generated by the nonionic photobase generator disclosed in Non-Patent Document 2 is relatively weak in basicity, the resin compound using the nonionic photobase generator still has room for improvement in terms of improving the reactivity upon light irradiation.

[0011] The present disclosure aims to provide a photobase generator and a compound capable of preparing a photoreactive composition having excellent reactivity upon light irradiation, a photoreactive composition having excellent reactivity upon light irradiation, and a reaction product obtained by reacting the photoreactive composition.

[0012] The specific methods for solving the above problems are as follows.

[0013] <1> A photobase generator comprising a compound having a first skeleton represented by the following general formula (a) and a second skeleton having nitrogen atoms bonded to the bonding position of the first skeleton and constituting an amide group, wherein in one molecule, the number of the first skeletons is 2 or more, the number of nitrogen atoms constituting the amide group in the second skeleton is the same as the number in the first skeleton, and at least one of the nitrogen atoms constituting the amide group is converted into a nitrogen atom constituting a secondary amine or a tertiary amine by light irradiation.

[0014] [Chemical formula 1]

[0015]

[0016] (In the general formula (a), G is a divalent aromatic group, and * indicates the bonding position to the nitrogen atom.)

[0017] <2> The photobase generator according to <1>, wherein the second skeleton is a structure represented by the following general formula (b).

[0018] [Chemical formula 2]

[0019]

[0020] (In general formula (b), R y Each independently represents a hydrocarbon group which may have a hydrogen atom or a substituent, * represents a bonding position to form a single bond with * in the general formula (a), and ** represents a bonding position to R which is an n-valent linking group. x The binding position of the first skeleton or the binding position of the straight chain or side chain of the polymer compound. n represents an integer greater than 2 and is the same as the number of the first skeleton. y They can also be independently compared with R xOr the straight chain or side chain of the polymer compound is combined with each other to form a ring structure. The n first skeletons combined with * in the general formula (b) may be the same or different. )<3> The photobase generator according to <1>, wherein the number of the first skeletons is 2, and the second skeleton is a structure represented by the following general formula (b-1).

[0021] [Chemical formula 3]

[0022]

[0023] (In the general formula (b-1), R5 and R6 each independently represent a hydrocarbon group which may have a hydrogen atom or a substituent, R7 represents a divalent linking group, and * represents a bonding position which combines with * in the general formula (a) to form a single bond. At least two of R5 to R7 may combine with each other to form a ring structure. The two first skeletons combined with * in the general formula (b-1) may be the same or different.)

[0024] <4> A compound having a first skeleton represented by the following general formula (a) and a second skeleton having nitrogen atoms bonded to the bonding position of the first skeleton and constituting an amide group, wherein in one molecule, the number of the first skeletons is 2 or more, the number of nitrogen atoms constituting the amide group in the second skeleton is the same as the number in the first skeleton, and at least one of the nitrogen atoms constituting the amide group is converted into a nitrogen atom constituting a secondary amine or a tertiary amine by light irradiation.

[0025] [Chemical formula 4]

[0026]

[0027] (In the general formula (a), G is a divalent aromatic group, and * indicates the bonding position to the nitrogen atom.)

[0028] <5> The compound according to <4>, wherein the second skeleton is a structure represented by the following general formula (b).

[0029] [Chemical formula 5]

[0030]

[0031] (In general formula (b), R y Each independently represents a hydrocarbon group which may have a hydrogen atom or a substituent, * represents a bonding position to form a single bond with * in the general formula (a), and ** represents a bonding position to R which is an n-valent linking group. x The binding position of the first skeleton or the binding position of the straight chain or side chain of the polymer compound. n represents an integer greater than 2 and is the same as the number of the first skeleton. y They can also be independently compared with R xOr the straight chains or side chains of the polymer compound are bonded to each other to form a ring structure. The n first skeletons bonded to * in the general formula (b) may be the same or different. )<6> The compound according to <4>, wherein the number of the first skeletons is 2, and the second skeleton is a structure represented by the following general formula (b-1).

[0032] [Chemical formula 6]

[0033]

[0034] (In the general formula (b-1), R5 and R6 each independently represent a hydrocarbon group which may have a hydrogen atom or a substituent, R7 represents a divalent linking group, and * represents a bonding position which combines with * in the general formula (a) to form a single bond. At least two of R5 to R7 may combine with each other to form a ring structure. The two first skeletons combined with * in the general formula (b-1) may be the same or different.)

[0035] <7> A photoreactive composition comprising the photobase generator according to any one of <1> to <3> 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.

[0036] <8> A reaction product obtained by reacting the photoreactive composition according to <7>.

[0037] Effects of the Invention

[0038] According to the present disclosure, a photobase generator and a compound capable of preparing a photoreactive composition having excellent reactivity upon light irradiation, a photoreactive composition having excellent reactivity upon light irradiation, and a reaction product obtained by reacting the photoreactive composition can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 These are data showing the absorbance measurement results of compound (1)-1 in Test Example 1.

[0040] Figure 2 These are data showing the measurement results of the IR spectrum of Compound (1)-1 in Test Example 2.

[0041] Figure 3 This is a graph showing the relationship between the light irradiation dose of compound (1)-1 in Test Example 2 and the peak areas of the aldehyde group and the lactone structure in the IR spectrum.

[0042] Figure 4 This is a graph showing the relationship between the light irradiation amount and the residual film ratio of the coating film in Example 1.

[0043] Figure 5 This is a graph showing the relationship between the light irradiation amount and the residual film rate of the coating film in Example 2 and Comparative Example 1.

[0044] Figure 6 This is a graph showing the relationship between the light irradiation amount and the residual film ratio of the coating film in Example 3.

[0045] Figure 7 These are data showing the measurement results of the IR spectrum of compound (9)-301 in Example 4.

[0046] Figure 8 This is a graph showing the relationship between the heating time and the peak area of ​​the methoxy group under light irradiation conditions and light non-irradiation conditions in Example 4.

[0047] Fig. 9 This is a graph showing the relationship between the heating time under light irradiation conditions in Example 4 and the peak area of ​​the methoxy group.

[0048] Fig.10 This is a graph showing the relationship between the heating temperature in Example 4 and the pencil hardness of the obtained cured product. DETAILED DESCRIPTION

[0049] In the present disclosure, a numerical range expressed using “to” means a range including the numerical values ​​described before and after “to” as a lower limit and an upper limit.

[0050] [Photobase generator]

[0051] The photobase generator disclosed herein comprises a compound having a first skeleton represented by the following general formula (a) and a second skeleton having nitrogen atoms bound to the binding position of the first skeleton and constituting an amide group, wherein in one molecule, the number of the first skeletons is greater than 2, the number of nitrogen atoms constituting the amide group in the second skeleton is the same as the number of the first skeleton, and at least one of the nitrogen atoms constituting the amide group is converted into a nitrogen atom constituting a secondary amine or a tertiary amine by light irradiation.

[0052] [Chemical formula 7]

[0053]

[0054] In the general formula (a), G is a divalent aromatic group, and * indicates a bonding position to a nitrogen atom.

[0055] For example, the photobase generator of the present disclosure is used to modulate a photoreactive composition capable of producing a reaction product by light irradiation. More specifically, by irradiating the photoreactive composition contained in the photobase generator with light, a base is generated from the photobase generator, and by the action of the generated base, the functional group of the base-reactive compound contained in the photoreactive composition is converted to show reactivity, or, by the action of the generated base, the functional group contained in the base-reactive compound reacts. 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.

[0056] The photobase generator disclosed in the present invention comprises a compound (referred to as "compound (1)" in the present invention) having a first skeleton represented by the general formula (a) and a second skeleton having a nitrogen atom that is bound to the binding position of the first skeleton and constitutes an amide group, and generates a base by irradiation with light. In addition, in compound (1), as shown in the following formula (i), by irradiation with light, a cyclization reaction occurs in a manner such that the formyl group and the amide group disappear, thereby generating a compound represented by the following general formula (1') (referred to as "compound (1')" in the present invention). In addition, X in compound (1) is the second skeleton, and n represents the number of the first skeleton, which is an integer greater than 2. The compound (1') is an amide compound in which the nitrogen atom constituting the amide group of X in compound (1) is converted into a nitrogen atom constituting a secondary amine or a tertiary amine by irradiation with light.

[0057] In addition, in the following formula (i), the aldehyde groups in the n first skeletons are converted into a lactone structure by light irradiation, but in the present disclosure, the aldehyde groups in at least one first skeleton are converted into a lactone structure by light irradiation. From the point of view that the reactivity of the base-reactive compound is better when irradiated with light, it is preferred that the aldehyde groups in the n first skeletons are converted into a lactone structure by light irradiation, that is, the n nitrogen atoms that are bound to the binding position of the first skeleton and constitute an amide group are converted into nitrogen atoms that constitute a secondary amine or a tertiary amine by light irradiation.

[0058] The "secondary amine" herein refers to a base having a structure in which the nitrogen atom in X bonded to the carbon atom of the carbonyl group is directly bonded to one hydrogen atom, and the "tertiary amine" refers to a base having a structure in which the nitrogen atom in X bonded to the carbon atom of the carbonyl group is not directly bonded to a hydrogen atom.

[0059] In addition, compound (1) is a non-ionic photobase generator, and unlike conventional ionic photobase generators, it has high stability during storage and high solubility, and a photoreactive composition using it has high stability. Furthermore, a photoreactive composition using a photobase generator containing compound (1) has good reactivity of the base-reactive compound when irradiated with light.

[0060] [Chemical reaction formula 8]

[0061]

[0062] In the general formula (a), G is a divalent aromatic group, and a formyl group (-C(=O)-H) is bonded to -C(=O)-*.

[0063] Then, the bonding positions of the formyl group and -C(=O)-* in G are in an ortho positional relationship. That is, among the atoms constituting the ring skeleton of G, the atom to which the formyl group is bonded and the atom to which -C(=O)-* is bonded are adjacent to each other in the ring skeleton of G and are directly bonded.

[0064] The aromatic group in G may be any of a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group, or may be a divalent group formed by condensing an aromatic hydrocarbon group or an aromatic heterocyclic group (in the present disclosure, such a group is regarded as an aromatic heterocyclic group).

[0065] Furthermore, these aromatic hydrocarbon groups and aromatic heterocyclic groups may have a substituent.

[0066] Here, “the aromatic hydrocarbon group has 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.

[0067] Furthermore, "the 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.

[0068] The aromatic group in G may be either monocyclic or polycyclic. The number of atoms (ring members) constituting the ring skeleton is not particularly limited, but is preferably 3 to 20.

[0069] Among the aromatic groups in G, as aromatic hydrocarbon groups, for example, 1,2-phenylene, 1,2-dinaphthylene, 2,3-dinaphthylene, 2,3-xylene, 3,4-xylene, 3,4-di-o-xylene, 4,5-di-o-xylene, 4,5-di-m-xylene, 2,3-di-p-xylene, 1,2-dianthryl, 2,3-dianthryl, etc. are listed. As aromatic hydrocarbon groups, one or more hydrogen atoms of these aromatic hydrocarbon groups may also be substituted by substituents such as the aromatic hydrocarbon groups and alkyl groups exemplified above. The aromatic hydrocarbon group having the substituent preferably also includes a substituent and has a carbon number of 6 to 20.

[0070] The alkyl group replacing one or more hydrogen atoms of the exemplified aromatic hydrocarbon group (hereinafter referred to as "substituted alkyl group") may be linear, branched or cyclic, and may be monocyclic or polycyclic. The substituted alkyl group preferably has 1 to 10 carbon atoms.

[0071] The linear or branched substituted alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 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, and decyl.

[0072] The carbon number of the cyclic substituted alkyl group is preferably 3 to 10, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl, etc., and substances in which one or more hydrogen atoms of these cyclic alkyl groups are substituted by linear, branched or cyclic alkyl groups are listed. Here, the linear, branched and cyclic alkyl groups that replace the hydrogen atoms are the same as those of the substituted alkyl groups.

[0073] Among the aromatic groups in G, examples of the aromatic heterocyclic group include groups obtained by removing two hydrogen atoms bonded to carbon atoms or heteroatoms constituting the ring skeleton of various aromatic heterocyclic compounds.

[0074] Preferred among the aromatic heterocyclic compounds are 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 hetero atoms selected from sulfur atoms, nitrogen atoms and oxygen atoms as atoms constituting the aromatic heterocyclic skeleton.

[0075] Examples of the sulfur-containing aromatic heterocyclic compound include thiophene and benzothiophene.

[0076] 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.

[0077] Examples of the oxygen-containing aromatic heterocyclic compound include furan, benzofuran (1-benzofuran), and isobenzofuran (2-benzofuran).

[0078] Examples of the compound in which atoms constituting the aromatic heterocyclic skeleton have the above-mentioned two different hetero atoms include oxazole, isoxazole, thiazole, benzoxazole, benzisoxazole, and benzothiazole.

[0079] The atom to which the formyl group is bonded and the atom to which -C(=O)-* is bonded among the atoms constituting the ring skeleton of the aromatic heterocyclic group may be a carbon atom or a heteroatom, respectively, but preferably both are carbon atoms.

[0080] In the aromatic heterocyclic group, the number of heteroatoms constituting the ring skeleton is preferably one to three, more preferably one or two.

[0081] In the aromatic heterocyclic group, when the number of hetero atoms constituting the ring skeleton is two or more, these hetero atoms may be all the same, all different, or only part of them may be the same.

[0082] As the substituent possessed by the aromatic hydrocarbon group or aromatic heterocyclic group in G, for example, the substituted alkyl group, alkoxy group, aryloxy group, dialkylamino group, diarylamino group, alkylarylamino group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl 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, the aromatic heterocyclic group, etc. are listed.

[0083] The number of the substituents possessed by the aromatic hydrocarbon group or aromatic heterocyclic group in G may be only one, may be two or more, or all hydrogen atoms may be substituted by the substituents. The number of the substituents depends on the number of replaceable hydrogen atoms, for example, preferably one to four, more preferably one to three, and further preferably one or two.

[0084] 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 part of them may be the same.

[0085] Examples of the alkoxy group as a substituent include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a cyclopropoxy group. The substituted alkyl group is a monovalent group bonded to an oxygen atom.

[0086] 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, xylyl (dimethylphenyl), and the like, and examples include those in which one or more hydrogen atoms of these aryl groups are further substituted by these aryl groups, the substituted alkyl groups, and the like. The aryl group having these substituents preferably also includes a substituent and has 6 to 10 carbon atoms.

[0087] The dialkylamino group as a substituent includes a monovalent group in which two hydrogen atoms of an amino group (-NH2) such as dimethylamino and methylethylamino are substituted by the substituted alkyl group. In the dialkylamino group, the two alkyl groups bonded to the nitrogen atom may be the same as or different from each other.

[0088] The diarylamino group as a substituent includes a monovalent group in which two hydrogen atoms of an amino group such as diphenylamino and phenyl-1-naphthylamino are substituted with the aryl group. In the diarylamino group, the two aryl groups bonded to the nitrogen atom may be the same or different.

[0089] The arylamino group as a substituent includes, for example, a monovalent group in which one of two hydrogen atoms of an amino group such as a methylphenylamino group is substituted with the substituted alkyl group and one hydrogen atom is substituted with the aryl group.

[0090] Examples of the alkylcarbonyl group as a substituent include a monovalent group in which the substituted alkyl group such as methylcarbonyl (acetyl) is bonded to a carbonyl group (—C(═O)—).

[0091] Examples of the arylcarbonyl group as a substituent include a monovalent group in which the aryl group and a carbonyl group are bonded, such as a phenylcarbonyl group (benzoyl group).

[0092] Examples of the alkoxycarbonyl group as a substituent include a monovalent group in which the alkoxy group and a carbonyl group are bonded, such as a methoxycarbonyl group (methoxycarbonyl).

[0093] Examples of the aryloxycarbonyl group as a substituent include a monovalent group in which the aryloxy group and a carbonyl group are bonded, such as a phenoxycarbonyl group (phenyloxycarbonyl).

[0094] Examples of the alkylcarbonyloxy group as a substituent include a monovalent group in which the substituted alkyl group such as methylcarbonyloxy is bonded to a carbon atom of a carbonyloxy group (—C(═O)—O—).

[0095] Examples of the arylcarbonyloxy group as a substituent include a monovalent group in which the aryl group such as phenylcarbonyloxy group is bonded to a carbon atom of a carbonyloxy group.

[0096] Examples of the alkylthio group as a substituent include a monovalent group in which the substituted alkyl group such as methylthio, ethylthio, n-propylthio, isopropylthio, cyclopropylthio and the like is bonded to a sulfur atom.

[0097] Examples of the arylthio group as a substituent include a monovalent group in which the aryl group such as phenylthio, 1-naphthylthio, 2-naphthylthio and the like is bonded to a sulfur atom.

[0098] 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).

[0099] Examples of the halogenated alkyl group as a substituent include groups in which one or more hydrogen atoms of the substituted alkyl group are substituted with halogen atoms.

[0100] Examples of the halogen atom in the haloalkyl group include those exemplified above as the halogen atom of the substituent.

[0101] The number of halogen atoms in the haloalkyl group is not particularly limited, and may be one or more than two. When the number of halogen atoms in the haloalkyl group is more than two, these multiple halogen atoms may be all the same, all different, or only part of them may be the same. The haloalkyl group may also be a perhaloalkyl group in which all hydrogen atoms in the alkyl group are replaced by halogen atoms.

[0102] The haloalkyl group is not particularly limited, and examples thereof include chloromethyl, dichloromethyl, trichloromethyl, and trifluoromethyl.

[0103] When the substituent possessed by 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 arylamino group, an alkylthio group or an arylthio group, the wavelength of light required for compound (1) to generate a base by light irradiation becomes longer (longer wavelength). That is, the substituent of these electron-donating groups is advantageous in that the wavelength of light required to generate a base in compound (1) can be lengthened.

[0104] The substitution position of the substituent in the aromatic hydrocarbon group or aromatic heterocyclic group is not particularly limited.

[0105] G is preferably an aromatic hydrocarbon group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a total of one or two or more substances selected from the group consisting of alkoxy, aryloxy, dialkylamino, diarylamino, alkylarylamino, alkylthio and arylthio as the substituent. As such G, for example, a group represented by the following general formula (a)-1 is listed.

[0106] [Chemical formula 9]

[0107]

[0108] In the general formula (a)-1, m1 is an integer from 0 to 2; n1 is an integer from 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 greater than 2, a plurality of Z 1 They may be the same as or different from each other; one of the bonds marked with the symbol ** is formed with respect to the carbon atom of the formyl group which is one of the bonding targets of G, and the other is formed with respect to the carbon atom of the carbonyl group which is another bonding target of G.

[0109] In the general formula (a)-1, m1 is an integer of 0 to 2 (0, 1 or 2), which specifies the number of ring skeletons constituting the aromatic hydrocarbon group. That is, when m1 is 0, the aromatic hydrocarbon group is 1,2-phenylene, when m1 is 1, the aromatic hydrocarbon group is 2,3-dinaphthylene, and when m1 is 2, the aromatic hydrocarbon group is 2,3-dianthryl.

[0110] In the general formula (a)-1, n1 is an integer from 0 to 2m1+4, indicating that Z 1 The number of aromatic hydrocarbon groups bonded to the

[0111] 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.

[0112] 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.

[0113] 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.

[0114] In the general formula (a)-1, 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 is the same as the substituents that the aromatic hydrocarbon group or the aromatic heterocyclic group in G described above may have.

[0115] n1 is an integer greater than 2, Z 1 When there are multiple Z 1 In the case of 1 can be the same or different from each other. That is, in this case, Z 1They may all be the same, all be different, or only partly be the same.

[0116] When n1 is an integer other than 0, Z 1 The position at which the aromatic hydrocarbon group is bonded is not particularly limited.

[0117] In the general formula (a)-1, one of the bonds marked with the symbol ** is formed with respect to the carbon atom in the carbonyl group to which the hydrogen atom in the general formula (a) is bonded, which is one of the bonding targets of G. Furthermore, the other of the bonds marked with the symbol ** is formed with respect to the carbon atom in the carbonyl group adjacent to the bonding position * in the general formula (a), which is another bonding target of G.

[0118] The first skeleton is preferably a group represented by, for example, the following general formula (a)-2.

[0119] [Chemical formula 10]

[0120]

[0121] In the general formula (a)-2, R1 to R4 each independently represents a hydrogen atom, the substituted alkyl, alkoxy, aryloxy, dialkylamino, diarylamino, alkylarylamino, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkylthio, arylthio, cyano (-CN), halogen atom, nitro, halogenated alkyl (halogenated alkyl), hydroxyl (-OH), mercapto (-SH), amino, the aromatic hydrocarbon group, or the aromatic heterocyclic group, * represents the binding position to the nitrogen atom. At least two of R1 to R4 may also be combined with each other to form a ring structure.

[0122] The two or more first skeletons contained in the compound (1) may be the same skeleton or different skeletons.

[0123] The second skeleton is preferably a structure represented by the following general formula (b).

[0124] [Chemical formula 11]

[0125]

[0126] In the general formula (b), R y Each independently represents a hydrocarbon group which may have a hydrogen atom or a substituent, * represents a bonding position to form a single bond with * in the general formula (a), and ** represents a bonding position to R which is an n-valent linking group. x The binding position of the first skeleton or the binding position of the straight chain or side chain of the polymer compound. n represents an integer greater than 2 and is the same as the number of the first skeleton. y They can also be independently compared with Rx Alternatively, the straight chains or side chains of the polymer compound are bonded to each other to form a ring structure. The n first skeletons bonded to * in the general formula (b) may be the same or different.

[0127] Examples of the n-valent linking group include an n-valent hydrocarbon group, and more specifically, an n-valent aliphatic hydrocarbon group, an n-valent aromatic hydrocarbon group, etc. The aliphatic hydrocarbon group may be any of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.

[0128] ** is an n-valent linking group R x When ** is a bonding position to a polymer compound, n is preferably 2 or 3, and more preferably 2. When ** is a bonding position to a linear chain or a side chain of a polymer compound, there is no particular limitation as long as n is 2 or more.

[0129] In the compound (1), the number of the first skeleton is 2, and the second skeleton is more preferably a structure represented by the following general formula (b-1).

[0130] [Chemical formula 12]

[0131]

[0132] In the general formula (b-1), R5 and R6 each independently represent a hydrocarbon group which may have a hydrogen atom or a substituent, R7 represents a divalent linking group, and * represents a bonding position which combines with * in the general formula (a) to form a single bond. At least two of R5 to R7 may also combine with each other to form a ring structure. The two first skeletons combined with * in the general formula (b-1) may be the same or different.

[0133] Examples of the divalent linking group include divalent hydrocarbon groups, more specifically, divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, etc. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

[0134] In the compound (1), the number of the first skeleton is 2, and the second skeleton is preferably a structure represented by the following general formula (b-2).

[0135] [Chemical formula 13]

[0136]

[0137] In the general formula (b-2), R8 represents a divalent linking group, and * represents a bonding position that bonds to * in the general formula (a) to form a single bond. The two first skeletons that bond to * in the general formula (b-2) may be the same or different.

[0138] Examples of the divalent linking group include divalent hydrocarbon groups, more specifically, divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, etc. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

[0139] The divalent hydrocarbon group is preferably a divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms, and more specifically includes methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0140] <Method for producing compound (1)>

[0141] Compound (1) can be produced, for example, by a method of forming an amide group.

[0142] As a method for producing such a compound (1), the following production method is listed, which has, for example, a step (hereinafter simply recorded as "compound (1a)") of reacting a compound represented by the following general formula (1a) (hereinafter simply recorded as "compound (1a)") with a compound represented by the following general formula (1b) (hereinafter simply recorded as "compound (1b)") to obtain compound (1) (hereinafter simply recorded as "compound (1) production step").

[0143] [Chemical reaction formula 14]

[0144]

[0145] In the general formula (1a), G is the same as G in the general formula (a), and L is a halogen atom. In the general formula (1b), X is the same as X in the compound (1). n is an integer of 2 or more.

[0146] In the general formula (1a), L is a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

[0147] In the step of producing compound (1), compound (1a) and compound (1b) are reacted.

[0148] During the reaction, the amount of compound (1b) used relative to the amount of compound (1a) used can be appropriately adjusted by the value of n. For example, when n is 2, the amount of compound (1b) used is preferably 0.5 to 2.5 times the molar amount of compound (1a), and more preferably 0.5 to 1.8 times the molar amount.

[0149] The reaction of compound (1a) and compound (1b) is preferably carried out using a solvent.

[0150] The solvent is not particularly limited and can be appropriately selected according to the types of compound (1a) and compound (1b). Preferred solvents include ketones such as acetone; ethers such as tetrahydrofuran (THF); halogenated hydrocarbons such as dichloromethane; and amides such as N,N-dimethylformamide and N,N-dimethylacetamide.

[0151] The solvent may be mixed with any component other than the solvent of compound (1a) and compound (1b) to dissolve or disperse the component in advance before use, or may be mixed with the components without dissolving or dispersing the component in advance.

[0152] The solvent may be used alone or in combination of two or more. When two or more solvents are used in combination, the combination and ratio thereof may be arbitrarily selected.

[0153] The amount of the solvent used in the reaction is not particularly limited, and is, for example, preferably 1 to 100 times by mass, more preferably 1.5 to 60 times by mass, based on the total amount of Compound (1a) and Compound (1b).

[0154] The temperature during the reaction of Compound (1a) and Compound (1b) is not particularly limited and may be appropriately adjusted in consideration of other reaction conditions, but is preferably -5°C to 10°C, more preferably -2°C to 5°C.

[0155] The reaction time of the compound (1a) and the compound (1b) is not particularly limited and may be appropriately adjusted in consideration of other reaction conditions, but is preferably 0.5 to 48 hours, more preferably 1 to 36 hours.

[0156] The reaction of compound (1a) with compound (1b) is preferably carried out with a reduced amount of water in the reaction system. For example, the reaction is preferably carried out using a dry solvent or in an inert gas atmosphere such as nitrogen, argon or helium.

[0157] Furthermore, as the compound (1a), a commercial product or a product produced by a known method may be used.

[0158] The compound (1a) in which L is a chlorine atom is obtained by, for example, reacting L in the general formula (1a) with a hydroxyl group (-OH) (i.e., a compound represented by the general formula "G(-CHO)-C(=O)-OH (wherein G is the same as above)") with any chlorinating agent such as thionyl chloride (SOCl2), sulfuryl chloride (SO2Cl2), phosphorus oxychloride (POCl3), oxalyl chloride ((COCl)2), phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5), etc.

[0159] In the process of producing compound (1), after the reaction is completed, the compound (1) can be taken out by performing subsequent treatment as required by a known method. That is, as appropriate, any one or a combination of two or more post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, concentration, etc. can be performed, and the compound (1) can be taken out by concentration, crystallization, reprecipitation, column chromatography, etc. In addition, the taken out compound (1) can be further refined by performing one or more operations such as crystallization, reprecipitation, column chromatography, extraction, crystal stirring and washing with a solvent, etc., as appropriate, as required.

[0160] In the step of producing compound (1), after completion of the reaction, compound (1) may be used for the intended purpose without being taken out.

[0161] When a commercial product is not used as compound (1a) but a product produced as described above is used, after compound (1a) is generated in the reaction, it may be subjected to post-treatment as necessary, similarly to the case of compound (1) above, and the compound (1a) thus taken out may be used in the next step. Alternatively, after compound (1a) is generated in the reaction, it may be subjected to post-treatment as necessary, and the reaction solution containing compound (1a) may be used in the next step without taking out compound (1a).

[0162] Here, the case of reacting compound (1b) with compound (1a) is described. However, for example, for a substance having a group represented by the formula "-NH-" in compound (1b) which easily undergoes a reaction other than the intended one when reacting with compound (1a), a protecting group may be introduced into such a group before reacting with compound (1a), and deprotection may be performed after the reaction to obtain compound (1). In this way, compound (1) can be easily produced by partially adding or changing the steps in the above-mentioned production method.

[0163] Here, the case where compound (1b) and compound (1a) are reacted is described. However, depending on the type of the target product, a compound represented by the following general formula (1c) (hereinafter referred to as "compound (1c)") may be reacted instead of compound (1a). In this case, compound (1) can be produced by the same method as the above-mentioned production method except that compound (1c) is used instead of compound (1a).

[0164] [Chemical reaction formula 15]

[0165]

[0166] In the general formula (1b) and the general formula (1c), G, X, L and n are the same as described above.

[0167] In addition, here, as a method for producing compound (1), a method having the above-mentioned steps for producing compound (1) is described, but compound (1) can also be produced by using a combination of raw material compounds other than compound (1a) and compound (1b) to form a different bond without using a method for forming an amide group.

[0168] The structure of compound (1) can be confirmed by a known method such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), etc.

[0169] [Photoreactive composition]

[0170] The photoreactive composition of the present disclosure comprises the 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 exhibiting 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 exhibiting reactivity by the action of a base may be a compound having only one of the functional groups, a compound having two or more of the 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 of the groups that react by the action of a base, a compound having two or more of the groups that react by the action of a base, or a mixture thereof.

[0171] For example, by irradiating the photoreactive composition of the present disclosure with light, a base is generated from the photobase generator, and the functional groups contained in the base-reactive compound in the photoreactive composition are converted and become reactive by the action of the generated base, or the functional groups contained in the base-reactive compound react by 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.

[0172] The photoreactive composition may be a photocurable composition that is cured by reacting a base-reactive compound by light irradiation, and the photocurable composition may be used to produce a cured product by light irradiation.

[0173] 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).

[0174] The photoreactive composition of the present disclosure may contain only one type of photobase generator or two or more types of photobase generator. When the photobase generator contains two or more types of photobase generator, the combination and ratio of the photobase generators may be arbitrarily set.

[0175] In the photoreactive composition of the present disclosure, the content of the photobase generator is preferably 4% to 39% by mass, more preferably 6% to 36% by mass, and further preferably 8% to 33% by mass relative to the content of the base-reactive compound. The content of the photobase generator is 4% by mass or more, so that the reaction of the base-reactive compound proceeds more easily. In addition, the content of the photobase generator is 39% by mass or less, so as to suppress excessive use of the photobase generator.

[0176] (Base-reactive compound)

[0177] 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 showing reactivity by the action of a base (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 (referred to as "base-reactive compound (9-2b)" in the present disclosure. The base-reactive compound (9-2b) is different from the base-reactive compound (9-2a) in that the group that reacts is not a functional group that is converted into a group showing reactivity by the action of a base.

[0178] Examples of the reaction that occurs in the base-reactive compound include addition polymerization and condensation polymerization (polycondensation).

[0179] 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 compound and a high-molecular compound.

[0180] As the base-reactive compound, a known substance can be used, and for example, a base-reactive compound described in “Japanese Patent Application Laid-Open No. 2011-80032” can be used. However, this is only an example.

[0181] Examples of the base-reactive compound (9-2a) include compounds that convert a functional group into a reactive group by decomposition by a base. Examples of such base-reactive compounds (9-2a) include compounds having a carbonate skeleton (-OC(=O)-O-), photosensitive polyimides, and the like.

[0182] Examples of the base-reactive compound (9-2b) include epoxy resins, (meth)acrylate resins, silicone resins, and alkoxysilane compounds.

[0183] In addition, in this disclosure, "(meth)acrylate" is a concept including both "acrylate" and "methacrylate".

[0184] The base-reactive compound contained in the photoreactive composition of the present disclosure may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of the base-reactive compounds can be arbitrarily set.

[0185] (Other ingredients)

[0186] The photoreactive composition of the present disclosure may contain other components in addition to the base-reactive compound and the photobase generator.

[0187] The other components are not particularly limited as long as the effects of the present invention are not impaired, and can be arbitrarily selected according to the purpose.

[0188] The photoreactive composition may contain only one type of other component or two or more types of other components. When the photoreactive composition contains two or more types of other components, the combination and ratio of these components can be arbitrarily set.

[0189] Examples of the other components include sensitizers, fillers, pigments, and solvents.

[0190] <Sensitizer>

[0191] The photoreactive composition of the present disclosure may contain a sensitizer.

[0192] The sensitizer is not particularly limited, and examples thereof include benzophenone, naphthoquinone, anthraquinone, xanthene, thioxanthene, xanthone, thioxanthone, anthracene, phenanthrol, phenanthroline, pyrene, pentacene, and derivatives thereof. Among them, the photobase generator has excellent photoresponsivity in the long-wavelength ultraviolet region of, for example, 300 nm or more, and more specifically, has excellent photoresponsivity to i-line (365 nm) or active energy rays having a longer wavelength than that. From the perspective of wider applicability, anthraquinone, thioxanthrone, anthracene, and derivatives thereof are preferred, and thioxanthrone, anthracene, and derivatives thereof are more preferred.

[0193] The sensitizer may be used alone or in combination of two or more. When used in combination of two or more, the combination and ratio thereof can be arbitrarily set.

[0194] The sensitizer is preferably at least one selected from the group consisting of a compound represented by the following general formula (A), a compound represented by the following general formula (B), and a compound represented by the following general formula (C).

[0195] [Chemical formula 16]

[0196]

[0197] In the general formulas (A) to (C), R 1 , R 2 and R 3Each is independently an alkyl group, an alkoxy group, an amino group, an alkylthio group, a cyano group, a halogen atom, a nitro group, a haloalkyl group, a hydroxyl group or a mercapto group; p and q are each independently an integer of 0 to 4; and r is an integer of 0 to 2.

[0198] In the general formula (A), R 1 and R 2 Each independently is preferably a halogen atom or an alkyl group, more preferably a halogen atom, and further preferably a chlorine atom.

[0199] In the general formula (A), p and q are preferably an integer of 0 to 2, more preferably 1 or 2, each independently.

[0200] In the general formula (B), R 1 , R 2 and R 3 Each independently is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, further preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 3 to 5 carbon atoms, and most preferably a branched alkyl group having 3 to 5 carbon atoms such as tert-butyl group.

[0201] In the general formula (B), p and q are each independently preferably an integer of 0 to 2, more preferably 0 or 1. r is preferably 0 or 1, more preferably 0.

[0202] In the general formula (C), R 1 and R 2 Each independently is preferably a halogen atom or an alkyl group.

[0203] In the general formula (C), p and q are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.

[0204] In the photoreactive composition of the present invention, the content of the sensitizer is preferably 30 mol% to 200 mol%, more preferably 50 mol% to 150 mol% relative to the photobase generator. The content of the sensitizer is 30 mol% or more, so that the photobase generator can easily generate a base. In addition, the content of the specific polycyclic aromatic compound is 200 mol% or less, so as to suppress the excessive use of the sensitizer.

[0205] <Packing>

[0206] The photoreactive composition of the present disclosure may contain a filler (filler). By containing a filler, for example, the viscosity of the photoreactive composition itself, the strength of the photoreactive composition after the reaction (reaction product described below), and other properties can be adjusted.

[0207] The filler may be any known filler without particular limitation. For example, the filler may be in the form of fibers, plates or particles, and its shape, size and material may be appropriately selected according to the purpose.

[0208] The filler contained in the photoreactive composition may be one type or two or more types. In the case of two or more types, the combination and ratio of the fillers can be arbitrarily set.

[0209] The content of the filler in the photoreactive composition is not particularly limited and may be appropriately adjusted depending on the purpose.

[0210] <Pigment>

[0211] The photoreactive composition of the present disclosure may contain a pigment. By containing a pigment, for example, light transmittance and the like can be adjusted.

[0212] The pigment contained in the photoreactive composition may be a known pigment, and may be any pigment such as white, cyan, red, yellow, green, etc., without particular limitation.

[0213] The photoreactive composition may contain only one type of pigment or two or more types of pigment. When the photoreactive composition contains two or more types of pigment, the combination and ratio of the pigments can be arbitrarily set.

[0214] The content of the pigment in the photoreactive composition is not particularly limited and may be appropriately adjusted depending on the purpose.

[0215] <Solvent>

[0216] The photoreactive composition of the present disclosure may contain a solvent. By containing a solvent, handling properties are improved.

[0217] The solvent is not particularly limited and may be appropriately selected in consideration of the solubility and stability of the base-reactive compound and the photobase generator.

[0218] 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 (dimethylcellulose solution); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and cyclopentanone; nitriles such as acetonitrile; amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide, and the like.

[0219] The photoreactive composition may contain only one type of solvent or two or more types of solvent. In the case of two or more types of solvent, the combination and ratio of the solvents may be arbitrarily set.

[0220] 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 further 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.

[0221] The photoreactive composition can be obtained by mixing a base-reactive compound, a photobase generator, a specific polycyclic aromatic compound, and other components as needed. After mixing the components, the obtained product can be used directly as a photoreactive composition, or the obtained product can be used as a reactive composition by further performing a known purification operation as needed.

[0222] When the components are blended, all the components may be added and then mixed, some of the components may be added sequentially and then mixed, or all the components may be added sequentially and then mixed.

[0223] 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 a stirring blade, a method of mixing using a mixer, and a method of mixing by adding ultrasonic waves.

[0224] The temperature during the mixing is not particularly limited as long as the respective components are not degraded, and can be, for example, 3°C to 30°C.

[0225] The blending time is not particularly limited as long as the blending components are not degraded, and can be, for example, 30 seconds to 1 hour.

[0226] However, these matching conditions are just examples.

[0227] <Reaction products>

[0228] The reaction product of the present disclosure is obtained by reacting the photoreactive composition. The method for producing the reaction product of the present disclosure will be described in the method for producing the reaction product of the present disclosure described later.

[0229] The shape of the reaction product of the present disclosure is, for example, a film shape, a line shape, etc., and can be arbitrarily selected according to the purpose.

[0230] (Method for producing reaction product)

[0231] The method for producing the reaction product disclosed in the present invention 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 converts the polarity of the functional group contained in the base-reactive compound through the action of the generated base, thereby showing reactivity, or the functional group contained in the base-reactive compound reacts through 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.

[0232] After the photoreactive composition is attached to a target object by a known method, it may be pre-baked (dried) as necessary to form a photoreactive composition layer, and the photoreactive composition layer may be irradiated with light.

[0233] For example, when producing a film-like reaction product, the photoreactive composition may be applied to a target object by using a coating device 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, or an applicator, or by immersing the target object in the photoreactive composition, thereby attaching the photoreactive composition to the target object.

[0234] For example, when producing a film-like or linear reaction product, the photoreactive composition may be attached to the target object by a printing method such as screen printing, flexographic printing, offset printing, inkjet printing, dispensing printing, jet dispensing printing, gravure printing, gravure offset printing, pad printing, or the like.

[0235] The pre-baking can be performed at, for example, 40° C. to 120° C. for 30 seconds to 10 minutes, without particular limitation.

[0236] The wavelength of the light irradiated to the photoreactive composition is not particularly limited, and may be, for example, a wavelength in the ultraviolet region to the visible light region. 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.

[0237] The illuminance of the light irradiated to the photoreactive composition is preferably, for example, 1 mW / cm 2 ~10mW / cm 2 , more preferably 1mW / cm 2 ~5mW / cm 2 , more preferably 1 mW / cm 2 ~3mW / cm2 .

[0238] The light irradiation dose to the photoreactive composition is preferably 100 mJ / cm 2 ~10000mJ / cm 2 , more preferably 200mJ / cm 2 ~5000mJ / cm 2 , more preferably 300mJ / cm 2 ~3000mJ / cm 2 .

[0239] However, the light irradiation conditions listed here are just examples and are not limited thereto.

[0240] The reaction product obtained by irradiating the photoreactive composition with light may be further subjected to post-baking (heat treatment after light irradiation).

[0241] The post-baking can be performed, for example, at 80° C. to 180° C. for 20 minutes to 2 hours, without particular limitation.

[0242] The thickness of the reaction product can be appropriately set according to the purpose and is not particularly limited. The thickness of the reaction product is preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm. In order to form a reaction product of such thickness, for example, the thickness of the photoreactive composition layer can be set to be greater than the target thickness of the reaction product.

[0243] For example, the ratio of the thickness of the reaction product (the thickness of the photoreactive composition layer after light irradiation) to the thickness of the photoreactive composition layer (the thickness of the photoreactive composition layer before light irradiation) ("the thickness of the photoreactive composition layer after light irradiation" / "the thickness of the photoreactive composition layer before light irradiation") can be set to, for example, 0.2 to 1.0, and can be set 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 by further adjusting the reaction conditions.

[0244] Example

[0245] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples.

[0246] <Production of Compound (1)-1>

[0247] As shown below, 3-bromophthalide and 4,4'-trimethylenedipiperidine are reacted to produce compound (1)-1.

[0248] That is, a mixed solution of 4,4'-trimethylenedipiperidine (1.1 g, 0.011 mol) and dry dichloromethane (40 mL) was added to a mixed solution of 3-bromophthalide (2.1 g, 0.010 mol), dry dichloromethane (40 mL) and triethyleneamine (2.4 g, 0.022 mol), and the mixture was stirred at 0° C. for 14 hours to react. After the reaction was completed, unreacted 4,4'-trimethylenedipiperidine was distilled off under reduced pressure from the reaction solution.

[0249] Next, dichloromethane was added to the obtained reaction solution, and hydrochloric acid having a concentration of 5% by mass was further added, and the reaction solution was shaken in a separatory funnel to wash the reaction solution. The washing with the hydrochloric acid was further performed once, and the washing was performed twice in total.

[0250] Next, a saturated sodium bicarbonate aqueous solution was added to the reaction solution after washing with the hydrochloric acid, and the reaction solution was shaken in a separatory funnel to wash the reaction solution. The saturated sodium bicarbonate aqueous solution was further used for washing once, and the washing was performed twice in total.

[0251] Next, a saturated sodium chloride aqueous solution was added to the reaction solution washed with the saturated sodium bicarbonate aqueous solution, and the reaction solution was shaken in a separatory funnel to wash the reaction solution. The saturated sodium chloride aqueous solution was further used to wash the reaction solution once, and the washing was performed twice in total.

[0252] Next, the reaction solution washed with the saturated sodium chloride aqueous solution was purified by silica gel column chromatography using ethyl acetate as the mobile phase to obtain the target compound (1)-1 as a white solid (yield 53%).

[0253] Table 1 shows the obtained compound (1)-1. 1 H-NMR analysis results.

[0254] [Chemical reaction formula 17]

[0255]

[0256] [Table 1]

[0257]

[0258] <Production of Compound (2)-1>

[0259] As shown below, the reaction product of o-formylbenzoic acid and thionyl chloride is reacted with piperidine to produce compound (2)-1.

[0260] That is, o-formylbenzoic acid (8.04 g, 53.6 mmol) was added to thionyl chloride (32.0 g, 269 mmol), and dry DMF (4 mL) was further added thereto, and stirred at room temperature for 3 hours to carry out reaction. After the reaction was completed, unreacted thionyl chloride was distilled off under reduced pressure from the reaction solution.

[0261] Furthermore, dry THF (20 mL) was added to piperidine (13.0 g, 152 mmol), and the reaction solution obtained by distilling thionyl chloride under reduced pressure was further added thereto, and the mixture was stirred at 0° C. for 4 hours to react. After the reaction was completed, the solvent was distilled off.

[0262] Next, dichloromethane was added to the obtained reaction solution, and hydrochloric acid having a concentration of 5% by mass was further added, and the reaction solution was shaken in a separatory funnel to wash the reaction solution. The washing with the hydrochloric acid was further performed once, and the washing was performed twice in total.

[0263] Next, a saturated sodium bicarbonate aqueous solution was added to the reaction solution after washing with the hydrochloric acid, and the reaction solution was shaken in a separatory funnel to wash the reaction solution. The saturated sodium bicarbonate aqueous solution was further used for washing once, and the washing was performed twice in total.

[0264] Next, a saturated sodium chloride aqueous solution was added to the reaction solution washed with the saturated sodium bicarbonate aqueous solution, and the reaction solution was shaken in a separatory funnel to wash the reaction solution. The saturated sodium chloride aqueous solution was further used to wash the reaction solution once, and the washing was performed twice in total.

[0265] Next, the reaction solution after washing with the above-mentioned saturated sodium chloride aqueous solution was purified by silica gel column chromatography using a mixed solvent of ethyl acetate / n-hexane (1 / 1, volume ratio) as the mobile phase, and the groups containing the target product were collected and concentrated to obtain the target compound (2)-1 as a yellow viscous liquid (yield 11.4 g, yield 98%).

[0266] Table 2 shows the obtained compound (2)-1. 1 H-NMR, 13 Analytical results of C-NMR and ESI-MS.

[0267] [Chemical reaction formula 18]

[0268]

[0269] [Table 2]

[0270]

[0271] Furthermore, the obtained compound (2)-1 was subjected to simultaneous differential thermal analysis / thermogravimetric (TG-DTA) measurement at a temperature increase rate of 5°C / min and a measurement temperature range of 20°C to 500°C, and it was confirmed that the compound decomposed at 240.2°C.

[0272] [Test Example 1]

[0273] (Confirmation of the behavior of compound (1)-1 under light irradiation in a solvent)

[0274] Compound (1)-1 obtained above was added to a concentration of 2.0×10 -5 Then, a low-pressure mercury lamp was used with an illumination of 1.2 mW / cm 2 , the light irradiation was set to 0, 60, 240, 600, and 960 mJ / cm 2 The acetonitrile solution obtained by these five methods was irradiated with ultraviolet light of wavelength 254nm. Then, the absorbance of compound (1)-1 was measured. The results were Figure 1 Shown in.

[0275] In Experimental Example 1, the molar absorption coefficient is ε 254 =1.6×10 4 L / (mol·cm). Figure 1 It is clear that the light exposure is 0mJ / cm 2 That is, compared with the spectrum in the case of no light irradiation, the spectra in the cases of other irradiation doses have both increased peaks and decreased peaks. This measurement result supports that compound (1)-1 generates a base by light irradiation.

[0276] [Test Example 2]

[0277] (Confirmation of the behavior of compound (1)-1 in a polymer solid when irradiated with light)

[0278] Polytetramethylene glycol (0.20 g), compound (1)-1 (0.017 g, 8.5% by mass relative to polytetramethylene glycol), and chloroform (1.2 g) were mixed and stirred at 25° C. for 1 minute to obtain a test resin composition.

[0279] Next, the test resin composition obtained above was applied on a calcium fluoride plate by spin coating at 3000 rpm for 30 seconds, and the obtained coating film was heated at 60° C. for 3 minutes, and then a low-pressure mercury lamp was used to set the illumination to 1.8 mW / cm 2 , irradiate the coating with light of 254nm wavelength. Figure 2 The specific light exposure (mJ / cm 2), the peak intensity (1700 cm-1) of the stretching vibration of C=O from the aldehyde group was measured by Fourier transform infrared spectrophotometer (FT-IR). -1 ) and the peak intensity of the stretching vibration of C=O from the lactone structure (1760 cm -1 ). The result is Figure 2 In addition, Figure 3 Graphs showing the relationship between the light irradiation dose of compound (1)-1 and the peak areas of the aldehyde group and lactone structure in the IR spectrum are shown in FIG.

[0280] from Figure 2 as well as Figure 3 It is clear that as the light irradiation amount increases, the peak intensity of the stretching vibration of C=O from the aldehyde group decreases, while the peak intensity of the stretching vibration of C=O from the lactone structure increases. This is because compound (1')-1, which is a base, is generated from compound (1)-1 by light irradiation as shown in the following chemical reaction formula.

[0281] [Chemical reaction formula 19]

[0282]

[0283] Furthermore, from the above results, when compound (2)-1 is irradiated with light, it is estimated that compound (2′)-1, which is a base, is generated from compound (2)-1 as shown in the following chemical reaction formula.

[0284] [Chemical reaction formula 20]

[0285]

[0286] <Production of base-reactive compound (9)-201>

[0287] Base-reactive compound (9)-201 was produced as shown below.

[0288] That is, dry THF (45 mL) was added to glycidyl methacrylate (6.13 g, 43.1 mmol), and the obtained solution was bubbled with nitrogen for 30 minutes.

[0289] Next, the solution after bubbling was heated to 70° C., 2,2′-azobis(isobutyronitrile) (AIBN) (0.074 g, 0.45 mmol) was added, and the solution was heated under reflux for 8 hours.

[0290] Next, the obtained reaction solution was cooled to room temperature, THF was added, and then ethanol was added as a poor solvent to precipitate the target product, which was filtered and the obtained solid matter was washed with THF to obtain the target product.

[0291] Then, the obtained target product was dissolved in THF, ethanol was added to precipitate the product, the product was collected by filtration, and reprecipitation including washing with THF was repeated twice.

[0292] The target base-reactive compound (9)-201 was obtained as a white solid (yield 4.37 g, yield 71%).

[0293] Table 3 shows the obtained base-reactive compound (9)-201. 1 H-NMR analysis results.

[0294] The weight average molecular weight (Mw) of the base-reactive compound (9)-201 in terms of standard polystyrene determined by gel permeation chromatography (GPC) was 27454, and the molecular weight distribution coefficient (Mw / Mn) was 1.52.

[0295] [Chemical reaction formula 21]

[0296]

[0297] In chemical formula (9)-201, p is an integer of 2 or more.

[0298] [Table 3]

[0299]

[0300] [Example 1]

[0301] (Production of Photoreactive Composition)

[0302] A base-reactive compound (9)-201 (0.14 g), a compound (1)-1 (0.034 g, 5 mol % relative to glycidyl methacrylate as a raw material of the base-reactive compound) and acetonitrile (0.68 g, about 5.0 times the mass of the base-reactive compound) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0303] (Production of Reaction Product)

[0304] The photoreactive composition obtained above was applied to a silicon wafer by spin coating at 2000 rpm for 30 seconds, and the thickness of the obtained coating film (the thickness of the coating film before light irradiation) was measured. Then, the coating film (photoreactive composition layer) was heated (prebaked) at 60° C. for 3 minutes, and then a low-pressure mercury lamp was used with an illumination of 1.2 mW / cm 2 The coating film was irradiated with light of 254 nm wavelength. The light irradiation amount was set as follows at 100°C for heating (post-baking). Figure 4 0~480mJ / cm 2The above results show that, except for the case where the light irradiation amount was set to 0 mJ / cm 2 In addition, an attempt was made to finally form a coating film as a reaction product obtained by polymerizing the base-reactive compound (9)-201.

[0305] Next, the post-baked coatings were washed with chloroform, and the thickness of the eight types of coatings after washing (coating thickness after post-baking) was measured, and the residual film ratio of the eight types of coatings was calculated by the following formula (ii). Figure 4 Shown in.

[0306] [Residual film ratio] = [Coating film thickness after post-baking] / [Coating film thickness before light irradiation] (ii)

[0307] [Example 2]

[0308] In the preparation of the photoreactive composition, the same treatment as in Example 1 was carried out except that compound (1)-1 (0.017 g, 2.5 mol % relative to glycidyl methacrylate as a raw material of the base-reactive compound) and acetonitrile (0.70 g, 5.0 times by mass of the base-reactive compound) were added to obtain a photoreactive composition.

[0309] Next, the residual film rate of the coating film was calculated under the same conditions as in Example 1. Figure 5 Shown in.

[0310] [Comparative Example 1]

[0311] A photoreactive composition was obtained in the same manner as in Example 1 except that compound (2)-1 (5 mol % based on glycidyl methacrylate as a raw material of the base-reactive compound) was used instead of compound (1)-1.

[0312] Next, in addition to setting the illumination to 1.2 mW / cm 2 , set the light exposure to Figure 5 0~1000mJ / cm 2 The remaining film rate of the coating film was calculated under the same conditions as in Example 1 except for the above conditions. Figure 5 Shown in.

[0313] In addition, if Figure 5 As shown, in Example 2, the residual film rate at the same light irradiation amount is higher than that in Comparative Example 1. This is because in Example 2, compound (1')-1, which is a base generated from compound (1)-1, functions more appropriately as a catalyst than compound (2')-1, which is a base generated from compound (2)-1 in Comparative Example 1, and therefore the base-reactive compound (9)-201 has high reactivity and high efficiency in generating the reaction product.

[0314] Moreover, from Figure 5 As can be seen from the figure, in Example 2, the light irradiation dose at a residual film rate of 0.5 (50%) is about 44 mJ / cm 2 In Comparative Example 1, the light irradiation dose at a residual film rate of 0.5 (50%) is about 790 mJ / cm 2 This shows that, in Example 2, the reaction product can be appropriately produced with a small amount of light irradiation.

[0315] [Example 3]

[0316] (Production of Photoreactive Composition)

[0317] A base-reactive compound (9)-201 (0.14 g), a compound (1)-1 (0.017 g, 2.5 mol % relative to glycidyl methacrylate as a raw material of the base-reactive compound), t-butylanthracene (0.090 g, 100 mol % relative to the compound (1)-1) as a sensitizer, and cyclopentanone (0.70 g, 5.0 times the mass of the base-reactive compound) were mixed and stirred at 25°C for 1 minute to obtain a photoreactive composition.

[0318] (Production of Reaction Product)

[0319] The photoreactive composition obtained above was applied to a silicon wafer by spin coating at 1500 rpm for 20 seconds, and the thickness of the obtained coating (coating thickness before light irradiation) was measured. Then, the coating (photoreactive composition layer) was heated (pre-baked) at 60° C. for 1 minute, and then an LED lamp was used with an illumination of 1.2 mW / cm 2 The coating film is irradiated with light of 365 nm wavelength. The light irradiation amount is set as follows Figure 6 0~1000mJ / cm 2 The eight coating films were heated (post-baked) at 100°C for 90 minutes. 2 In addition, an attempt was made to finally form a coating film as a reaction product obtained by polymerizing the base-reactive compound (9)-201.

[0320] The residual film rate of the coating film was calculated under the same conditions as in Example 1. Figure 6 Shown in.

[0321] like Figure 6 As shown, it is known that the reaction product can be suitably produced at 365 nm, which is a long-wavelength ultraviolet region of 300 nm or more, by using a sensitizer.

[0322] [Example 4]

[0323] (Production of Photoreactive Composition)

[0324] The following base-reactive compound (9)-301 (0.24 g), compound (1)-1 (0.041 g, 10 mol% based on the methoxy group in the base-reactive compound) and cyclopentanone (1.1 g) were mixed and stirred at 25° C. for 1 minute to obtain a photoreactive composition.

[0325] [Chemical formula 22]

[0326]

[0327] (Production of Reaction Product)

[0328] The photoreactive composition obtained above was applied to a silicon wafer by spin coating at 1500 rpm for 20 seconds, and the thickness of the obtained coating film (coating film thickness before light irradiation) was measured. Then, the coating film (photoreactive composition layer) was heated (pre-baked) at 60° C. for 1 minute, and then a low-pressure mercury lamp was used with an illumination of 1.2 mW / cm 2 The coating film was irradiated with light of 254 nm wavelength. Three types of light irradiation were prepared with a light irradiation dose of 1000 mJ / cm 2 The coating film was heated (post-baked) at 60° C., 80° C. or 100° C. for 60 minutes. Through the above, it was attempted to finally use the three coating films as reaction products of polymerizing the base-reactive compound (9)-301.

[0329] In Example 4, the peak intensity (2830 cm-1) of the CH stretching vibration derived from the methoxy group was measured using a Fourier transform infrared spectrophotometer (FT-IR) for the coating film before light irradiation, the coating film after light irradiation, the coating film further heated for 20 minutes after light irradiation, and the coating film further heated for 60 minutes after light irradiation. -1 ). The result is Figure 7 Shown in.

[0330] Moreover, in Figure 8 The figure shows the case where the coating film before light irradiation is heated at 100°C for 0 to 60 minutes, and the case where the coating film before light irradiation is heated at an illuminance of 1.2 mW / cm 2 、Light irradiation 1000mJ / cm 2 The relationship between the peak area of ​​methoxyl groups and the heating relationship when the sample was irradiated with light at a wavelength of 254 nm and then heated at 100°C for 0 to 60 minutes. Fig. 9 The coating before irradiation is shown in Figure 1. 2 、Light irradiation 1000mJ / cm 2And the relationship between the peak area of ​​the methoxy group when irradiating with light at a wavelength of 254 nm and then heating at 60° C., 80° C. or 100° C. for 0 to 60 minutes.

[0331] In addition, the pencil hardness of the cured product obtained by heating the coating film before light irradiation at 60°C, 80°C or 100°C for 60 minutes and the cured product obtained by irradiating the coating film before light irradiation under the above conditions and then heating at 60°C, 80°C or 100°C for 60 minutes were determined. Fig.10 Shown in.

[0332] from Figure 7 It was confirmed that the methoxyl groups in the coating film were reduced by irradiating the coating film with light and heating it. Figure 8 as well as Fig. 9 It was confirmed that the reduction rate of the methoxy group differed depending on whether the coating film was irradiated with light or not and the degree of heating of the coating film.

[0333] from Fig.10 It was confirmed that a cured product having excellent pencil hardness was obtained as a reaction product by irradiating the coating film with light and heating it.

[0334] The disclosure of Japanese Patent Application No. 2019-164869 filed on September 10, 2019 is incorporated herein by reference in its entirety.

[0335] All documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually stated to be incorporated by reference.

Claims

1. A photobase generator comprising a compound, The compound has: a first skeleton represented by the following general formula (a); and A second skeleton having a nitrogen atom that is bonded to the bonding position of the first skeleton and constitutes an amide group, wherein the second skeleton is represented by the following general formula (b-2): In one molecule, the number of the first skeleton is 2, the number of nitrogen atoms constituting the amide group in the second skeleton is the same as the number of the first skeleton, and at least one of the nitrogen atoms constituting the amide group is converted into a nitrogen atom constituting a secondary amine or a tertiary amine by light irradiation, [Chemical formula 1] [Chemical formula 2] In the general formula (a), G is a divalent aromatic group, * indicates the bonding position to the nitrogen atom, In the general formula (b-2), R8 represents a divalent linking group, and * represents a bonding position that bonds to * in the general formula (a) to form a single bond.

2. A compound having: a first skeleton represented by the following general formula (a); and A second skeleton having a nitrogen atom that is bonded to the bonding position of the first skeleton and constitutes an amide group, wherein the second skeleton is represented by the following general formula (b-2): In one molecule, the number of the first skeleton is 2, the number of nitrogen atoms constituting the amide group in the second skeleton is the same as the number of the first skeleton, and at least one of the nitrogen atoms constituting the amide group is converted into a nitrogen atom constituting a secondary amine or a tertiary amine by light irradiation, [Chemical formula 3] [Chemical formula 4] In the general formula (a), G is a divalent aromatic group, * indicates the bonding position to the nitrogen atom, In the general formula (b-2), R8 represents a divalent linking group, and * represents a bonding position that bonds to * in the general formula (a) to form a single bond.

3. A photoreactive composition comprising: The photobase generator according to claim 1; and Base-reactive compounds, The base-reactive compound is a compound having a functional group that is converted into a group showing reactivity by the action of a base, or a compound having a group that reacts by the action of a base.

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