Photobase generator, compound, photoreactive composition, and reaction product

Abstract

To provide a photobase generator excellent in stability during storage.SOLUTION: A photobase generator comprising a compound comprising a carboxylate anion and a quaternary ammonium cation, wherein the carboxylate anion has a structure in which two aromatic rings are bonded to a carbon atom of a carbonyl group and releases carbon dioxide by a decarboxylation reaction caused by light irradiation, and the compound generates a base by releasing carbon dioxide from the carboxylate anion by a decarboxylation reaction caused by light irradiation.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to photobase generators, compounds, photoreactive compositions and reaction products. [Background technology]

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

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

[0004] [Non-Patent Document 1] K.Arimitsu,R.Endo,Chem.Mater.2013,25,4461-4463. Summary of the Invention [Problem to be solved by the invention]

[0005] However, such ionic photobase generators have the problem that they have active hydrogen on the nitrogen atom, and therefore tend to generate very small amounts of free base due to acid-base equilibrium.Furthermore, resin compositions using such ionic photobase generators also have the problem that they have low storage stability due to the influence of the free base, and monomers and the like in the resin composition are prone to reaction due to the action of the base generated by decomposition of the ionic photobase generator.

[0006] An object of the present disclosure is to provide a photobase generator having excellent storage stability, a compound having excellent storage stability, a photoreactive composition containing the photobase generator, and a reaction product obtained by reacting the photoreactive composition. [Means for solving the problem]

[0007] Specific means for solving the above problems are as follows. <1> A carboxylate anion that contains a structure in which two aromatic rings are bonded to the carbon atom of a carbonyl group and that releases carbon dioxide through a decarboxylation reaction upon irradiation with light; a quaternary ammonium cation; A photobase generator comprising a compound that generates a base by desorbing carbon dioxide from the carboxylate anion through a decarboxylation reaction upon irradiation with light. <2> The carboxylate anion includes a structure represented by the following general formula (a): <1> The photobase generator according to claim 1.

[0008] [ka]

[0009] In general formula (a), R1 is a divalent linking group, R2 and R3 each independently represent 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 is an integer of 0 to 4, q is an integer of 0 to 3, two * each independently represent a hydrogen atom or an organic group, and the two * may be bonded to each other to form a divalent linking group, and when p is 2 or greater, some or all of the multiple R2 may be the same, or the multiple R2 may be different, and when q is 2 or greater, some or all of the multiple R3 may be the same, or the multiple R3 may be different. <3> The two * are both hydrogen atoms, or the two * are bonded to each other to form an ether bond, a sulfide bond, or a carbonyl group. <2> The photobase generator according to claim 1. <4> The quaternary ammonium cation includes a structure represented by the following general formula (b): <1> ~ <3> 10. The photobase generator according to claim 9, wherein the base is a hydroxybenzoate.

[0010] [ka]

[0011] In the general formula (b), R4 to R7 each independently represent a hydrocarbon group which may have a substituent. <5> A carboxylate anion that contains a structure in which two aromatic rings are bonded to the carbon atom of a carbonyl group and that releases carbon dioxide through a decarboxylation reaction upon irradiation with light; a quaternary ammonium cation; A compound that generates a base by desorbing carbon dioxide from the carboxylate anion through a decarboxylation reaction caused by irradiation with light. <6> The carboxylate anion includes a structure represented by the following general formula (a): <5> The compound described in

[0012] [ka] In general formula (a), R1 is a divalent linking group, R2 and R3 each independently represent 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 is an integer of 0 to 4, q is an integer of 0 to 3, two * each independently represent a hydrogen atom or an organic group, and the two * may be bonded to each other to form a divalent linking group, and when p is 2 or greater, some or all of the multiple R2 may be the same, or the multiple R2 may be different, and when q is 2 or greater, some or all of the multiple R3 may be the same, or the multiple R3 may be different. <7> The two * are both hydrogen atoms, or the two * are bonded to each other to form an ether bond, a sulfide bond, or a carbonyl group. <6> The compound described in <8> The quaternary ammonium cation includes a structure represented by the following general formula (b): <5> ~ <7> 1. The compound according to any one of claims 1 to 9.

[0013] [ka]

[0014] In the general formula (b), R4 to R7 each independently represent a hydrocarbon group which may have a substituent. <9> <4> and a base-reactive compound, wherein the base-reactive compound is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base. <10> <9> A reaction product obtained by reacting the photoreactive composition described in 1. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a photobase generator having excellent storage stability, a compound having excellent storage stability, a photoreactive composition containing the photobase generator, and a reaction product obtained by reacting the photoreactive composition. [Brief explanation of the drawings]

[0016] [Figure 1] 1 shows data showing the results of measuring the absorbance of an acetonitrile solution containing Compound (1)-1 in Test Example 1. [Figure 2] 1 shows data showing the results of measuring the absorbance of an acetonitrile solution containing Compound (1)-2 in Test Example 2. [Figure 3] 1 shows data showing the results of measuring the absorbance of an acetonitrile solution containing Compound (1)-3 in Test Example 3. [Figure 4] 1 shows data showing the results of measuring the absorbance of an acetonitrile solution containing Compound (1)-1 and phenol red in Test Example 4. [Figure 5] 1 shows data showing the results of measuring the absorbance of an acetonitrile solution containing Compound (1)-2 and phenol red in Test Example 4. [Figure 6] 10 is a graph showing the change in peak area ratio of the peak intensity derived from epoxy groups when post-baking was performed without light irradiation in Test Example 8. [Figure 7] 10 is a graph showing the change in peak area ratio of the peak intensity derived from epoxy groups when post-baking is performed after light irradiation in Test Example 8. [Figure 8] 10 is a graph showing the change in the peak area ratio of the peak intensity derived from epoxy groups to the peak intensity derived from thiol groups when post-baking was performed without light irradiation in Test Example 9. [Figure 9] 10 is a graph showing the change in the peak area ratio of the peak intensity derived from epoxy groups to the peak intensity derived from thiol groups when post-baking was performed after light irradiation in Test Example 9. DETAILED DESCRIPTION OF THE INVENTION

[0017] 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 present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component contained in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in this disclosure, 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. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples.

[0018] In this disclosure, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylic" means acrylic or methacrylic.

[0019] In the present disclosure, examples of the substituent include hydrocarbon groups and alkylene groups substituted with an alkoxy group, amino group, alkylthio group, cyano group, halogen atom, nitro group, haloalkyl group, hydroxyl group, mercapto group, etc. In the present disclosure, the term "light" is a concept that encompasses active energy rays such as ultraviolet light and visible light.

[0020] [Photobase generator] The photobase generator of the present disclosure includes a compound that includes a structure in which two aromatic rings are bonded to the carbon atom of a carbonyl group, and that includes a carboxylate anion that releases carbon dioxide through a decarboxylation reaction upon light irradiation, and a quaternary ammonium cation, and that generates a base when carbon dioxide is released from the carboxylate anion through a decarboxylation reaction upon light irradiation.

[0021] For example, the photobase generator of the present disclosure is used to prepare a photoreactive composition that can produce a reaction product by light irradiation. More specifically, by irradiating a photoreactive composition containing a photobase generator with light, a base is generated from the photobase generator, and the functional group contained in the base-reactive compound in the photoreactive composition is converted and becomes reactive by the action of the generated base, or the functional group contained in the base-reactive compound reacts by the action of the generated base. Therefore, by irradiating the above-mentioned photoreactive composition with light to generate a base, the base-reactive compound contained in the photoreactive composition reacts to obtain a reaction product.

[0022] The photobase generator of the present disclosure is an ionic photobase generator. Generally, ionic photobase generators have the problem that they tend to generate a very small amount of free base due to acid-base equilibrium due to the presence of active hydrogen on the nitrogen atom of the base. However, the photobase generator of the present disclosure contains a compound containing the above-mentioned combination of a cation and an anion (particularly a quaternary ammonium cation), thereby suppressing base generation due to decomposition during storage and providing excellent storage stability.

[0023] Hereinafter, preferred forms of the compounds contained in the photobase generator of the present disclosure will be described.

[0024] The compound included in the photobase generator of the present disclosure (hereinafter also referred to as "specific compound") has a structure in which two aromatic rings are bonded to the carbon atom of a carbonyl group, and includes a carboxylate anion that releases carbon dioxide by a decarboxylation reaction upon irradiation with light, and a quaternary ammonium cation. The specific compound is a compound that generates a base by releasing carbon dioxide from the carboxylate anion by a decarboxylation reaction upon irradiation with light.

[0025] The carboxylate anion preferably contains a structure represented by the following general formula (a):

[0026] [ka]

[0027] In general formula (a), R1 is a divalent linking group, R2 and R3 each independently represent 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 is an integer of 0 to 4, and q is an integer of 0 to 3. Two * are each independently a hydrogen atom or an organic group, and the two * may be bonded to each other to form a divalent linking group. When p is 2 or greater, some or all of the multiple R2s may be the same, or the multiple R2s may be different. When q is 2 or greater, some or all of the multiple R3s may be the same, or the multiple R3s may be different.

[0028] In general formula (a), R1 is not limited as long as it is a divalent linking group, and is preferably, for example, a hydrocarbon group which may have a substituent, and more preferably an alkylene group which may have a substituent. The number of carbon atoms in the alkylene group which may have a substituent may be, for example, 1 to 10 or 2 to 6.

[0029] Examples of the alkylene group for R1 include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; and branched alkylene groups such as methylmethylene, ethylmethylene, dimethylmethylene, methylethylene, 1,1-dimethylethylene, ethylethylene, 2-ethyltrimethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, and 3-methylpentamethylene.

[0030] In general formula (a), R2 and R3 may each independently be an alkyl group or a halogen atom, and p and q may each independently be an integer of 0 to 2, or may be 0 or 1, or may be 0.

[0031] The alkyl group for R2 and R3 includes an alkyl group having 1 to 10 carbon atoms, such as 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.

[0032] Examples of the halogen atom in R2 and R3 include a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).

[0033] In general formula (a), two * are each independently a hydrogen atom or an organic group, and the two * may be bonded to each other to form a divalent linking group. It is preferred that the two * are hydrogen atoms or that the two * are bonded to each other to form a divalent linking group.

[0034] When two * are bonded to each other to form a divalent linking group, the two * are preferably bonded to each other to form an ether bond, a sulfide bond, or a carbonyl group, and more preferably to form an ether bond, since this has excellent photoresponsiveness to long-wavelength active energy rays and is applicable to a wider range of applications.

[0035] The carboxylate anion containing a structure represented by general formula (a) is preferably a carboxylate anion containing a structure represented by general formula (a-1) or a carboxylate anion containing a structure represented by general formula (a-2).

[0036] [ka]

[0037] [ka]

[0038] The quaternary ammonium cation preferably contains a structure represented by the following general formula (b).

[0039] [ka]

[0040] In the general formula (b), R4 to R7 each independently represent a hydrocarbon group which may have a substituent.

[0041] Examples of the hydrocarbon group for R4 to R7 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination of two or more thereof. Among these, an aliphatic hydrocarbon group and a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group are preferred.

[0042] Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Examples of the alicyclic hydrocarbon group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a norbornyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a biphenyl group. Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group include aralkyl groups, such as benzyl, phenylethyl, phenylpropyl, and 4-phenylbutyl groups.

[0043] Two to four of R4 to R7 may be the same group (for example, the same aliphatic hydrocarbon group), and three or four of R4 to R7 may be the same group (for example, the same aliphatic hydrocarbon group). Three of R4 to R7 may be the same aliphatic hydrocarbon group, and the remaining one of R4 to R7 may be a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0044] The photobase generator of the present disclosure may consist solely of the specific compound described above, or may be a mixture of the specific compound described above with one or more other compounds. When the photobase generator of the present disclosure is the above-described mixture, the content of the specific compound may be 50% by mass or more and less than 100% by mass, 70% by mass or more and less than 100% by mass, or 90% by mass or more and less than 100% by mass, relative to the total amount of the photobase generator.

[0045] [Photoreactive composition] The photoreactive composition of the present disclosure comprises a photobase generator of the present disclosure and a base-reactive compound, wherein the base-reactive compound is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base. The compound having a functional group that is converted into a group that exhibits reactivity by the action of a base may be a compound having only one of the above-mentioned functional groups, or a compound having two or more of the above-mentioned functional groups, or a mixture thereof. The compound having a group that reacts by the action of a base may be a compound having only one group that reacts by the action of a base, or a compound having two or more groups that react by the action of a base, or a mixture thereof.

[0046] 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 give a reaction product.

[0047] The photoreactive composition may be a photocurable composition that is cured by reaction of a base-reactive compound upon irradiation with light, and the photocurable composition may be used to produce a cured product upon irradiation with light. The photoreactive composition may be a photoreactive material (positive type) that is solubilized by light irradiation, or a photoreactive material (negative type) that is cured by light irradiation.

[0048] The photoreactive composition of the present disclosure may contain only one type of photobase generator, or two or more types, and when two or more types are used, the combination and ratio thereof can be set arbitrarily.

[0049] 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 30% by mass, and even more preferably 3% by mass to 20% 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. Furthermore, when the content of the photobase generator is 40% by mass or less, excessive use of the photobase generator is suppressed.

[0050] (Base-reactive compounds) The photoreactive composition of the present disclosure includes a base-reactive compound. The base-reactive compound is a compound having a functional group that is converted into a reactive group by the action of a base (sometimes referred to as "base-reactive compound (9-2a)" in the present disclosure), or a compound having a group that reacts by the action of a base (sometimes referred to as "base-reactive compound (9-2b)" in the present disclosure). The base-reactive compound (9-2b) differs from the base-reactive compound (9-2a) in that the reactive group is not a functional group that is converted into a reactive group by the action of a base.

[0051] Examples of reactions that proceed in the base-reactive compound include addition polymerization and condensation polymerization (polycondensation polymerization).

[0052] 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.

[0053] As the base-reactive compound, known compounds can be used, for example, the base-reactive compounds described in JP-A-2011-80032, although this is just one example.

[0054] Examples of the base-reactive compound (9-2a) include compounds that are decomposed by the action of a base and have a functional group converted into a reactive group. Examples of such base-reactive compounds (9-2a) include compounds having a carbonate skeleton (-OC(=O)-O-), photosensitive polyimides, etc.

[0055] Examples of the base-reactive compound (9-2b) include epoxy compounds, silicone resins, alkoxysilane compounds, (meth)acrylate compounds, and thiol compounds. For example, the base-reactive compound (9-2b) may be a combination of an epoxy compound and a thiol compound, whereby a base generated by light irradiation reacts with the thiol compound to generate a thiolate anion, which then reacts with the epoxy compound to facilitate the polymerization reaction.

[0056] The photoreactive composition of the present disclosure may contain only one type of base-reactive compound, or two or more types. When two or more types are used, the combination and ratio thereof can be set arbitrarily.

[0057] 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 nonvolatile components of the photoreactive composition.

[0058] (Other ingredients) The photoreactive composition of the present disclosure may further contain other components in addition to the base-reactive compound and the photobase generator. The other components are not particularly limited as long as they do not impair the effects of the present invention, and can be selected arbitrarily depending on the purpose. The photoreactive composition may contain only one type of other component, or two or more types. When two or more types are contained, the combination and ratio thereof can be set arbitrarily.

[0059] Examples of the other components include a sensitizer, a filler, a pigment, and a solvent.

[0060] <Sensitizer> The photoreactive compositions of the present disclosure may also include a sensitizer. The sensitizer is not particularly limited, and examples thereof include benzophenone, naphthoquinone, anthraquinone, xanthene, thioxanthene, xanthone, thioxanthone, anthracene, phenanthrene, phenanthroline, pyrene, pentacene, derivatives thereof, etc. Among these, anthraquinone, thioxanthone, anthracene, and derivatives thereof are preferred, and thioxanthone, anthracene, and derivatives thereof are more preferred, in that they exhibit excellent photoresponsiveness as a photobase generator in the long-wavelength ultraviolet region of, for example, 300 nm or more, more specifically, excellent photoresponsiveness to i-line (365 nm) or longer wavelength active energy rays, and are applicable to a wider range. 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.

[0061] The sensitizer is preferably at least one selected from the group consisting of compounds represented by the following general formula (A), compounds represented by the general formula (B), and compounds represented by the general formula (C).

[0062] [ka]

[0063] In general formula (A) to general formula (C), R 1 , R 2 and R 3 are each independently an alkyl group, an alkoxy group, an amino group, an alkylthio group, a cyano group, a halogen atom, a nitro group, a halo group, It is an alkyl 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.

[0064] In general formula (A), R 1 and R 2 are each independently preferably a halogen atom or an alkyl group, more preferably a halogen atom, and even more preferably a chlorine atom. In general formula (A), p and q each independently represent an integer of 0 to 2, and more preferably 1 or 2.

[0065] In general formula (B), R 1 , R 2 and R 3 are each independently preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 3 to 5 carbon atoms, and extremely preferably a branched alkyl group having 3 to 5 carbon atoms such as a t-butyl group. In formula (B), p and q each independently represent preferably an integer of 0 to 2, more preferably 0 or 1. r is preferably 0 or 1, more preferably 0.

[0066] In general formula (C), R 1 and R 2 are preferably each independently a halogen atom or an alkyl group. In general formula (C), p and q each independently represent an integer of 0 to 2, and 0 or 1 is more preferable.

[0067] In the photoreactive composition of the present disclosure, the content of the sensitizer relative to the photobase generator is preferably 30 mol% to 200 mol%, more preferably 50 mol% to 150 mol%. When the content of the sensitizer is 30 mol% or more, a base is more likely to be generated from the photobase generator. Furthermore, when the content of the specific polycyclic aromatic compound is 200 mol% or less, excessive use of the sensitizer is suppressed.

[0068] <Filling material> The photoreactive composition of the present disclosure may contain a filler, which can adjust properties such as the viscosity of the photoreactive composition itself and the strength of the photoreactive composition after reaction (the reaction product described below). The filler may be any known filler without any particular limitation. For example, the filler may be fibrous, plate-like, or granular, and the shape, size, and material thereof may all be appropriately selected depending on the purpose. The photoreactive composition may contain only one type of filler, or two or more types. When two or more types are contained, the combination and ratio thereof can be set arbitrarily. The content of the filler in the photoreactive composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0069] <Pigments> The photoreactive composition of the present disclosure may contain a pigment, which can adjust, for example, light transmittance. The pigment contained in the photoreactive composition may be any known pigment, such as white, blue, red, yellow, or green, and is not particularly limited. The photoreactive composition may contain one kind of pigment or two or more kinds of pigments, and when two or more kinds of pigments are contained, the combination and ratio thereof can be set arbitrarily. The content of the pigment in the photoreactive composition is not particularly limited and may be adjusted appropriately depending on the purpose.

[0070] <Solvent> The photoreactive composition of the present disclosure may contain a solvent, which improves handling properties. The solvent is not particularly limited and may be appropriately selected in consideration of the solubility, stability, etc. of the base-reactive compound and the photobase generator. The solvent is not particularly limited, and examples thereof include halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; aliphatic hydrocarbons such as hexane, heptane, and octane; carboxylic acid esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran (THF), and 1,2-dimethoxyethane (dimethylcellosolve); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and cyclopentanone; nitriles such as acetonitrile; and amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide.

[0071] The photoreactive composition may contain only one type of solvent, or two or more types of solvents. When two or more types of solvents are used, the combination and ratio thereof can be set arbitrarily.

[0072] In the photoreactive composition, the content of the solvent is preferably 3 to 20 times by mass, more preferably 4 to 15 times by mass, and even more preferably 5 to 10 times by mass, relative to the content of the base-reactive compound. When the content of the solvent is within this range, the handleability of the photoreactive composition is further improved.

[0073] The photoreactive composition can be obtained by blending a base-reactive compound, a photobase generator, a specific polycyclic aromatic compound, and other components as needed. After blending the components, the resulting composition may be used as a photoreactive composition as is, or may be used as a photoreactive composition after further performing a known purification procedure as needed.

[0074] When blending the components, all the components may be added and then mixed, or some of the components may be added sequentially while being mixed, or all the components may be added sequentially while being mixed. The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, or a method of mixing by adding ultrasound.

[0075] The temperature during blending is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 3°C to 30°C. The blending time is not particularly limited as long as the blended components do not deteriorate, and can be, for example, 30 seconds to 1 hour. However, these compounding conditions are merely examples.

[0076] <Reaction products> The reaction product of the present disclosure is obtained by reacting the above-described photoreactive composition. A method for producing the reaction product of the present disclosure will be described later in the method for producing the reaction product of the present disclosure. The shape of the reaction product of the present disclosure can be selected arbitrarily depending on the purpose, for example, in the form of a film or a line.

[0077] (Method for producing reaction product) The method for producing a reaction product of the present disclosure includes a step of irradiating the photoreactive composition with light to generate the base from the photobase generator. By irradiating the photoreactive composition containing the photobase generator with light, a base is generated from the photobase generator, and the functional group contained in the base-reactive compound in the photoreactive composition is converted by the action of the generated base, becoming reactive, or the functional group contained in the base-reactive compound reacts 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.

[0078] The photoreactive composition may be attached to an object by a known method, and then optionally pre-baked (dried) to form a photoreactive composition layer, which may then be irradiated with light. For example, when producing a film-like reaction product, the photoreactive composition may be applied to a target object using a coating means such as a spin coater, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Mayer bar coater, or kiss coater, or an applicator, or the like, or the target object may be immersed in the photoreactive composition, thereby adhering the photoreactive composition to the target object. For example, when producing a film-like or linear reaction product, the photoreactive composition may be attached to the target object by using a printing method such as screen printing, flexographic printing, offset printing, inkjet printing, dispenser printing, jet dispenser printing, gravure printing, gravure offset printing, or pad printing.

[0079] The pre-baking may be carried out under conditions of, for example, 40° C. to 120° C. and 30 seconds to 10 minutes, and is not particularly limited.

[0080] The wavelength of the light irradiated onto the photoreactive composition is not particularly limited and may be, for example, a wavelength in the ultraviolet to visible light range. The wavelength of the light irradiated onto the photoreactive composition may be 10 nm or more, 200 nm or more, or 300 nm or more. Furthermore, the wavelength of the light irradiated onto the photoreactive composition may be 600 nm or less, 500 nm or less, or 400 nm or less.

[0081] The illuminance of the light irradiated onto the photoreactive composition is, for example, 1 mW / cm 2 ~100mW / cm 2 and preferably 1 mW / cm 2 ~50mW / cm 2 More preferably, it is 2 mW / cm 2 ~50mW / cm 2 It is more preferable that: The light irradiation dose applied to the photoreactive composition is, for example, 100 mJ / cm 2 ~10,000mJ / cm2 and preferably 200 mJ / cm 2 ~5000mJ / cm 2 More preferably, 300 mJ / cm 2 ~3000mJ / cm 2 It is more preferable that: However, the light irradiation conditions given here are merely examples and are not limited to these.

[0082] 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, at 40° C. to 150° C. for 20 minutes to 2 hours, or at 40° C. to 100° C. for 20 minutes to 1 hour.

[0083] The thickness of the reaction product may be appropriately set depending on the purpose and is not particularly limited. The thickness of the reaction product is, for example, preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm. To form a reaction product of such a thickness, for example, the thickness of the photoreactive composition layer may be set to be equal to or greater than the thickness of the desired reaction product.

[0084] 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]) The ratio (thickness of the photoreactive composition layer before irradiation) / (thickness of the photoreactive composition layer before 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. [Example]

[0085] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0086] <Production of Compound (1)-1> As shown below, compound (a)-1 was reacted with compound (b)-1 to produce compound (1)-1. Compound (a)-1 (0.34 g, 1.3 mmol), a xanthone derivative, and compound (b)-1 (25% in methanol) (0.50 g, 1.2 mmol), a tetraethylammonium hydroxide, were added to dry methanol (5.0 mL) and stirred at room temperature for 5 minutes. The solvent was then removed by distillation under reduced pressure. The residue was then dried under reduced pressure and reprecipitated in 500 mL of diethyl ether, followed by stirring for 1 hour. The target compound (1)-1 was obtained as a brown solid by suction filtration (yield: 53%). The obtained compound (1)-1 1 The results of the H-NMR analysis are shown in Table 1.

[0087] [ka]

[0088] [Table 1]

[0089] <Production of Compound (1)-2> As shown below, compound (a)-1 was reacted with compound (b)-2 to produce compound (1)-2. Compound (a)-1 (0.34 g, 1.3 mmol), a xanthone derivative, and compound (b)-2 (37% in methanol) (0.88 g, 1.3 mmol), a tetrabutylammonium hydroxide, were added to dry methanol (5.0 mL) and stirred at room temperature for 5 minutes, after which the solvent was distilled off under reduced pressure. After further drying under reduced pressure, the residue was reprecipitated by adding it to 500 mL of diethyl ether and stirring for 1 hour. The target compound (1)-2 was obtained as a brown solid by suction filtration (yield 35%). The obtained compound (1)-2 1 The results of the H-NMR analysis are shown in Table 2.

[0090] [ka]

[0091] [Table 2]

[0092] <Production of Compound (1)-3> As shown below, compound (a)-2 was reacted with compound (b)-3 to produce compound (1)-3. Compound (a)-2 (1.3 g, 5.0 mmol), which is ketoprofen, and compound (b)-3 (40% in methanol) (2.1 g, 5.0 mmol), which is benzyltrimethylammonium hydroxide, were added to dry methanol (5.0 mL) and stirred at room temperature for 5 minutes, and the solvent was distilled off under reduced pressure. After further drying under reduced pressure, the residue was poured into 500 mL of a 1:1 (V / V) ethyl acetate:toluene solution for reprecipitation and stirred for 1 hour. The target compound (1)-3 was obtained as a white solid by suction filtration (yield 46%). The obtained compound (1)-3 1 The results of the H-NMR analysis are shown in Table 3.

[0093] [ka]

[0094] [Table 3]

[0095] <Production of Compound (1)-4> As shown below, compound (a)-2 was reacted with compound (b)-4 to produce compound (1)-4. Compound (a)-2 (2.3 g, 9.2 mmol), which is ketoprofen, and compound (b)-4 (10% in methanol) (5.55 g, 6.1 mmol), which is tetramethylammonium hydroxide, were added to dry methanol (20 mL) and stirred at room temperature for 5 minutes. The solvent was then distilled off under reduced pressure. After further drying under reduced pressure, the residue was reprecipitated by adding it to 500 mL of a 1:1 (V / V) solution of ethyl acetate and toluene, and filtered by suction to obtain the target compound (1)-4 as a white solid (yield 46%). The obtained compound (1)-4 1 The results of the H-NMR analysis are shown in Table 4.

[0096] [ka]

[0097] [Table 4]

[0098] [Test Example 1] (Confirmation of the behavior of compound (1)-1 in a solvent when irradiated with light at a wavelength of 365 nm) The compound (1)-1 obtained above was added to a solution of 2.4×10 -5 The compound was dissolved in acetonitrile to a concentration of 100 mol / L. An LED lamp was used to illuminate the compound at an intensity of 50 mW / cm. 2 The light irradiation dose was set to 0, 100, 200 and 300 mJ / cm 2 The resulting acetonitrile solution was irradiated with light at a wavelength of 365 nm. The absorbance of the acetonitrile solution was then measured. The results are shown in Figure 1.

[0099] [Test Example 2] (Confirmation of the behavior of compound (1)-2 in a solvent when irradiated with light at a wavelength of 365 nm) The compound (1)-2 obtained above was added to a solution of 1.0×10 -4 The compound was dissolved in acetonitrile to a concentration of 100 mol / L. An LED lamp was used to illuminate the compound at an intensity of 50 mW / cm. 2The light irradiation dose was set to 0, 100, 200, 300 and 400 mJ / cm 2 The resulting acetonitrile solutions were irradiated with light at a wavelength of 365 nm. The absorbance of the acetonitrile solutions was then measured. The results are shown in Figure 2.

[0100] As is clear from Figures 1 and 2, the light irradiation dose was 0 mJ / cm 2 In other words, compared to the spectrum without light irradiation, the spectra with other irradiation doses contained both increasing and decreasing peaks, and this measurement result confirmed that compound (1)-1 and compound (1)-2 were decomposed by light irradiation.

[0101] It is presumed that when compound (1)-1 is irradiated with light, the reaction shown in the following reaction formula (X) occurs, generating compound (c)-1, which is a base. It is presumed that when compound (1)-2 is irradiated with light, the reaction shown in the following reaction formula (Y) occurs, generating compound (c)-1, which is a base.

[0102] [ka]

[0103] [ka]

[0104] [Test Example 3] (Confirmation of the behavior of compound (1)-3 in a solvent when irradiated with light at a wavelength of 254 nm) The compound (1)-3 obtained above was added to a solution of 2.0×10 -4 The compound was dissolved in acetonitrile to a concentration of 1.0 mol / L. Then, a low-pressure mercury lamp was used to illuminate the compound at an intensity of 2.0 mW / cm. 2 The light irradiation dose was set to 0, 100, 500, 1000, 5000 and 10000 mJ / cm 2 The resulting acetonitrile solutions were irradiated with light at a wavelength of 254 nm in six different ways. The absorbance of the acetonitrile solutions was then measured. The results are shown in Figure 3.

[0105] As is clear from Figure 3, the light irradiation dose was 0 mJ / cm 2 In other words, compared to the spectrum without light irradiation, the spectra with other irradiation doses had increased peaks, and this measurement result confirmed that compound (1)-3 was decomposed by light irradiation.

[0106] It is presumed that when compound (1)-3 is irradiated with light, the reaction shown in the following reaction formula (Z) occurs, generating compound (c)-2, which is a base.

[0107] [ka]

[0108] [Test Example 4] (Confirmation of basicity of compound (1)-1 upon photoirradiation) The compound (1)-1 obtained above was diluted to a concentration of 3.2 × 10 -4 mol / L in acetonitrile, and then phenol red was added to a concentration of 2.0 × 10 -4 The compound was dissolved in acetonitrile at a concentration of 100 mol / L. An LED lamp was used to illuminate the compound at an intensity of 20 mW / cm. 2 The light irradiation dose was set to 0, 100, 200 and 400 mJ / cm 2 The acetonitrile solution containing the obtained compound (1)-1 and phenol red was irradiated with light having a wavelength of 365 nm. The absorbance of the acetonitrile solution was then measured. The results are shown in Figure 4.

[0109] [Test Example 5] (Confirmation of basicity of compound (1)-2 upon photoirradiation) The compound (1)-2 obtained above was diluted to a concentration of 3.2 × 10 -4 mol / L in acetonitrile, and then phenol red was added to a concentration of 2.0 × 10 -4 The compound was dissolved in acetonitrile at a concentration of 100 mol / L. An LED lamp was used to illuminate the compound at an intensity of 20 mW / cm.2 The light irradiation dose was set to 0, 20, 40 and 100 mJ / cm 2 The acetonitrile solution containing the obtained compound (1)-2 and phenol red was irradiated with light having a wavelength of 365 nm. The absorbance of the acetonitrile solution was then measured. The results are shown in Figure 5.

[0110] As is clear from FIGS. 4 and 5, the light irradiation dose was 0 mJ / cm 2 In other words, compared to the spectrum without light irradiation, both increasing and decreasing peaks were observed in the spectra with other irradiation doses. This measurement result confirmed that the structure of phenol red changed when the acetonitrile solution became basic upon light irradiation. The reason why the acetonitrile solution became basic is presumably because compound (1)-1 and compound (1)-2 decomposed, generating compound (c)-1, which is a base, as shown in the above-mentioned reaction formulas (X) and (Y).

[0111] [Test Example 6] (Production of Photoreactive Composition 1) Pentaerythritol tetrakis(3-mercaptopropionate) (0.61 g, 1.2 mmol, PEMP), bisphenol A epoxy compound (0.93 g, 2.5 mmol, jER828), compound (1)-1 (92 mg, 10% by mass relative to jER828), and dry N,N-dimethylformamide (DMF) shown below were mixed and stirred at 25°C for 1 minute, thereby obtaining photoreactive composition 1.

[0112] [ka]

[0113] (Production of reaction products) The photoreactive composition 1 obtained above was applied onto a silicon wafer by a bar coating method. Then, this coating film (photoreactive composition layer) was dried under reduced pressure for 30 minutes, and then, using an LED lamp, the illuminance was set to 50 mW / cm. 2 The light irradiation dose was 5000 mJ / cm2 The coating film was irradiated with light at a wavelength of 365 nm. After light irradiation, the coating film was left at room temperature for 30 minutes. This process was used to attempt to convert the coating film into a polymerized reaction product of PEMP and jER828. During light irradiation and heating, the peak intensities derived from the thiol groups of PEMP and the epoxy groups of jER828 were measured using a Fourier transform infrared spectrophotometer (FT-IR). Furthermore, the changes in the peak area ratios of the peak intensities derived from thiol groups and the peak intensities derived from epoxy groups, relative to the values ​​before light irradiation, were confirmed. For comparison, the coating film was left in the dark for 1,000 seconds without light irradiation, and then heated at 60°C for 30 minutes (post-baking). The changes in the peak area ratios of the peak intensities derived from thiol groups and the peak area ratios of the peak intensities derived from epoxy groups, relative to the values ​​before exposure, were confirmed. The results are shown in Table 5.

[0114] [Test Example 7] (Production of Photoreactive Composition 2) Photoreactive composition 2 was obtained in the same manner as in Test Example 6, except that compound (1)-1 (92 mg, 10% by mass relative to jER828) was changed to compound (1)-2 (92 mg, 10% by mass relative to jER828).

[0115] (Production of reaction products) An attempt was made to produce a reaction product in the same manner as in Test Example 6, except that Photoreactive Composition 1 was changed to Photoreactive Composition 2 and the coating film after light irradiation was left at room temperature for 30 minutes or heated at 60°C for 30 minutes (post-baked). The results are shown in Table 5.

[0116] [Test Example 8] (Production of Photoreactive Composition 3) Polyglycidyl methacrylate (30 mg, PGMA), compound (1)-3 (6.0 mg, 20% by mass relative to PGMA), and dry N,N-dimethylformamide (DMF) shown below were mixed and stirred at 25°C for 1 minute to obtain photoreactive composition 3.

[0117] [ka]

[0118] (Production of reaction products) The photoreactive composition 3 obtained above was applied onto a silicon wafer by a bar coating method. Then, this coating film (photoreactive composition layer) was dried under reduced pressure for 30 minutes, and then exposed to a low-pressure mercury lamp at an illuminance of 2.0 mW / cm. 2 The light irradiation dose was 2000 mJ / cm 2 The coating film was irradiated with light at a wavelength of 254 nm. After light irradiation, the coating film was heated at 60°C for 30 minutes (post-baked). This process attempted to convert the coating film into a reaction product in which PGMA was polymerized. During light irradiation and heating, the peak intensity derived from the epoxy groups of PGMA was measured using a Fourier transform infrared spectrophotometer (FT-IR). Furthermore, the change in the peak area ratio of the peak intensity derived from the epoxy groups relative to the value before light irradiation was confirmed. For comparison, the coating film was left in the dark for 1,000 seconds without light irradiation, and then heated at 60°C for 30 minutes (post-baked). The change in the peak area ratio of the peak intensity derived from the epoxy groups relative to the value before leaving was confirmed. The results are shown in Figures 6 and 7 and Table 5.

[0119] [Test Example 9] (Production of Photoreactive Composition 4) Photoreactive composition 4 was obtained in the same manner as in Test Example 6, except that compound (1)-1 (92 mg, 10% by mass relative to jER828) was changed to compound (1)-3 (92 mg, 10% by mass relative to jER828).

[0120] (Production of reaction products) The photoreactive composition 4 obtained above was applied onto a silicon wafer by bar coating. Then, this coating film (photoreactive composition layer) was dried under reduced pressure for 30 minutes, and then exposed to a low-pressure mercury lamp at an illuminance of 2.0 mW / cm. 2 The light irradiation dose was 2000 mJ / cm 2The coating film was irradiated with light at a wavelength of 254 nm. After light irradiation, the coating film was left at room temperature for 30 minutes or heated (post-baked) at 60°C for 30 minutes. This attempted to convert the coating film into a polymerized reaction product of PEMP and jER828. During light irradiation and heating, the peak intensities derived from the thiol groups of PEMP and the peak intensities derived from the epoxy groups of jER828 were measured using a Fourier transform infrared spectrophotometer (FT-IR). Furthermore, the changes in the peak area ratios of the peak intensities derived from the thiol groups and the epoxy groups, relative to the values ​​before light irradiation, were confirmed. For comparison, the coating film was left in the dark for 1,000 seconds without light irradiation and then post-baked at 60°C for 30 minutes. The changes in the peak area ratios of the peak intensities derived from the thiol groups and the epoxy groups, relative to the values ​​before exposure, were confirmed. The results are shown in Figures 8 and 9 and Table 5.

[0121] [Test Example 10] (Production of Photoreactive Composition 5) Photoreactive composition 5 was obtained in the same manner as in Test Example 9, except that compound (1)-3 (92 mg, 10% by mass relative to jER828) was changed to compound (1)-4 (92 mg, 10% by mass relative to jER828).

[0122] (Production of reaction products) An attempt was made to produce a reaction product in the same manner as in Test Example 9, except that Photoreactive Composition 4 was changed to Photoreactive Composition 5. The results are shown in Table 5.

[0123] (Pencil hardness in each test example) In each test example, the pencil hardness of the reaction product obtained without light irradiation and the pencil hardness of the reaction product obtained after light irradiation and then standing or heating were measured. The results are shown in Table 5.

[0124] [Table 5]

[0125] As shown in Test Examples 6 to 10, the increase in the conversion rate of thiol groups and epoxy groups was suppressed especially at room temperature without light irradiation, and the photoreactive composition was in a liquid state, confirming excellent storage stability.

Claims

1. a carboxylate anion that includes a structure in which two aromatic rings are bonded to the carbon atom of a carbonyl group and that releases carbon dioxide by a decarboxylation reaction upon irradiation with light; a quaternary ammonium cation; A photobase generator comprising a compound that generates a base by desorbing carbon dioxide from the carboxylate anion through a decarboxylation reaction upon irradiation with light.

2. The photobase generator according to claim 1 , wherein the carboxylate anion has a structure represented by the following general formula (a): 【Chemistry 1】 In general formula (a), R １ is a divalent linking group, and R ２ and R ３ are each 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 is an integer of 0 to 4; q is an integer of 0 to 3; two * are each independently a hydrogen atom or an organic group; two * may be bonded to each other to form a divalent linking group; when p is 2 or more, a plurality of R ２ may be partly or entirely the same, and multiple R ２ may be different, and when q is 2 or more, a plurality of R ３ may be partly or entirely the same, and multiple R ３ may be different.

3. The photobase generator according to claim 2, wherein the two *'s are both hydrogen atoms, or the two *'s are bonded to each other to form an ether bond, a sulfide bond, or a carbonyl group.

4. The photobase generator according to any one of claims 1 to 3, wherein the quaternary ammonium cation comprises a structure represented by the following general formula (b): 【Chemistry 2】 In general formula (b), R ４ ~R ７ are each independently a hydrocarbon group which may have a substituent.

5. a carboxylate anion that includes a structure in which two aromatic rings are bonded to the carbon atom of a carbonyl group and that releases carbon dioxide by a decarboxylation reaction upon irradiation with light; a quaternary ammonium cation; A compound that generates a base by desorbing carbon dioxide from the carboxylate anion through a decarboxylation reaction caused by irradiation with light.

6. The compound according to claim 5 , wherein the carboxylate anion comprises a structure represented by the following general formula (a): 【Transformation 3】 In general formula (a), R １ is a divalent linking group, and R ２ and R ３ are each 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 is an integer of 0 to 4; q is an integer of 0 to 3; two * are each independently a hydrogen atom or an organic group; two * may be bonded to each other to form a divalent linking group; when p is 2 or more, a plurality of R ２ may be partly or entirely the same, and multiple R ２ may be different, and when q is 2 or more, a plurality of R ３ may be partly or entirely the same, and multiple R ３ may be different.

7. The compound according to claim 6, wherein the two *'s are both hydrogen atoms, or the two *'s are bonded to each other to form an ether bond, a sulfide bond, or a carbonyl group.

8. The compound according to any one of claims 5 to 7, wherein the quaternary ammonium cation comprises a structure represented by the following general formula (b): 【Chemistry 4】 In general formula (b), R ４ ~R ７ are each independently a hydrocarbon group which may have a substituent.

9. 5. A photoreactive composition comprising the photobase generator according to claim 4 and a base-reactive compound, wherein the base-reactive compound is a compound having a functional group that is converted into a group that exhibits reactivity by the action of a base, or a compound having a group that reacts by the action of a base.

10. A reaction product obtained by reacting the photoreactive composition according to claim 9.

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