JP2011116869A - Photo base-generating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo base-generating agent capable of efficiently generating a base having high catalytic activity by being exposed to a light having a wave length of 200-500 nm. <P>SOLUTION: The photo base-generating agent is a specific diamine derivative such as N-(N'-((1-(4,5-dimethoxy-2-nitrophenyl)ethoxy)carbonyl)aminopropyl)-N-methylacetamide and N-(N'-(4,5-dimethoxy-2-nitrobenzyloxycarbonyl)aminopropyl)-6-heptanolactam, and generates amidine by light irradiation. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photobase generator that generates a base by light irradiation. More specifically, a material formed by patterning using a material that is cured using a base generated by light irradiation (for example, a coding agent or paint), or a difference in solubility in a developer in an exposed area or an unexposed area, or The present invention relates to a photobase generator suitably used for producing a member (for example, electronic component, optical product, optical component forming material, layer forming material, or adhesive).

  [(4,5-Dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine is known as a photobase generator that generates an amine upon exposure (Patent Document 1).

JP 2006-189591 A

Conventional photobase generators have the problem that the basicity of the generated amine is low (pKa <11) and the activity as a catalyst for polymerization reaction or crosslinking reaction is insufficient.
An object of the present invention is to provide a photobase generator that can sensitize light having a wavelength of 200 to 500 nm and efficiently generate amine (amidine) having high catalytic activity.

  The feature of the photobase generator of the present invention is summarized in the point represented by the general formula (1) or (2).

R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n is 2 Is an integer of -3, m is an integer of 3-5, and A is a group represented by Formula (3) or Formula (4).

R ³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, or a carbon number Phenyl having at least one substituent selected from the group consisting of 7-18 aroyl groups, nitro groups, cyano groups, C1-C18 alkoxy groups, C1-C18 alkylthio groups, hydroxyl groups and halogen atoms Group {hereinafter abbreviated as a phenyl group having a substituent. An alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, an aroyl group, a nitro group, a cyano group, an alkoxy group, an alkylthio group, a hydroxyl group, and a halogen atom may be either singular or plural. Represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 8 carbon atoms, R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms. Group, aryl group having 6 to 12 carbon atoms, acyl group having 1 to 18 carbon atoms, aroyl group having 7 to 18 carbon atoms, nitro group, cyano group, alkoxy group having 1 to 18 carbon atoms or alkylthio group, hydroxyl group or halogen Represents an atom, q is an integer of 1 to 4, and when q is 2 to 4, R ⁴ may be the same or different.

  The gist of the feature of the curable resin composition of the present invention is that it contains the photobase generator and a curable resin.

    The characteristic of the manufacturing method of the curable resin (cured body) of the present invention is that the curable resin composition containing the photobase generator and the curable resin is irradiated with light having a wavelength of 200 to 500 nm. After generating the carbamoyl group-containing primary amine from the generator, the carbamoyl group-containing primary amine is intramolecularly cyclized to amidine by heating to 50 to 250 ° C., and the curable resin is cured. The gist is that it includes a step of obtaining a cured resin.

The photobase generator of the present invention can efficiently generate primary amines by exposing light having a wavelength of 200 to 500 nm, and can generate amidine having high catalytic activity by heating.
Moreover, since the photobase generator of the present invention does not contain a halogen ion or the like as a counter anion, there is no concern about metal corrosion.
Further, since the photobase generator of the present invention is not basic before exposure, even if it is contained in the reaction composition, the storage stability of the reactive composition is not reduced.
Moreover, the photobase generator of the present invention is stable against heat, and it is difficult to generate a base even when heated unless it is irradiated with light.

  Since the curable resin composition of the present invention contains the above-mentioned photobase generator, it does not have basicity before exposure, so that the storage stability of the curable resin composition is not lowered.

  According to the method for producing a cured resin (cured product) of the present invention, the above photobase generator is used, and light having a wavelength of 200 to 500 nm is irradiated and heated at 80 to 250 ° C., so that the catalytic activity is efficiently high. An amine (amidine) can be generated, and a cured resin (cured product) can be produced efficiently.

  The photobase generator is a compound that decomposes its chemical structure upon irradiation with light and generates a base (amine). The generated base can act as a catalyst for curing reaction of epoxy resin, urethanization reaction of isocyanate and polyol, crosslinking reaction of acrylate, and the like.

<General formula (1)>
Among R ¹ and R ² , the alkyl group having 1 to 18 carbon atoms (preferably 1 to 12, more preferably 1 to 8) is a linear alkyl group (methyl, ethyl, n-propyl, n -Butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc., branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl) , Neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl) and bridged cyclic alkyl groups (norbornyl, Adamantyl and pinanyl, etc.). R ¹ and R ² may be the same or different. As the alkyl group, in addition to the above, a part of hydrogen atoms of the alkyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an aryl group having 6 to 14 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and / or A substituted alkyl group substituted with an alkylthio group having 1 to 18 carbon atoms is also included. Substituted alkyl groups include arylalkyl groups (such as benzyl).

Among R ¹ and R ² , an alkenyl group having 2 to 18 carbon atoms (preferably 2 to 12 and more preferably 2 to 8) is a linear or branched alkenyl group (vinyl, allyl, 1- Propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl And cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As the alkenyl group, in addition to the above, a part of hydrogen atoms of the alkenyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, and / or an alkylthio group having 1 to 18 carbon atoms. Substituted substituted alkenyl groups are also included. Substituted alkenyl groups include arylalkenyl groups (such as styryl and cinnamyl).

Among R ¹ and R ² , the alkynyl group having 2 to 18 carbon atoms (preferably 2 to 12 and more preferably 2 to 8) is a linear or branched alkynyl group (ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl 1-methyl-2-butynyl, 3-methyl-1-butynyl, 1-decynyl, 2-decynyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl and 10-dodecynyl). As the alkynyl group, in addition to the above, a part of the hydrogen atoms of the alkynyl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms and / or an alkylthio group having 1 to 18 carbon atoms. Substituted substituted alkynyl groups are also included. Substituted alkynyl groups include arylalkynyl groups (such as phenylethynyl).

Among R ¹ and R ² , the aryl group having 6 to 14 carbon atoms includes a monocyclic aryl group (such as a phenyl group), a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinonyl, fluorenyl, and naphthoquinolyl). Etc.) and aromatic heterocyclic hydrocarbon groups (ethynyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (derived from pyridine) Group), 9-oxoxanthenyl (group derived from xanthone), 9-oxothioxanthenyl (group derived from thioxanthone) and the like. As the aryl group, in addition to the above, some of the hydrogen atoms of the aryl group may be a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, or 1 carbon atom. Also included are substituted aryl groups substituted with an -18 alkyl group, an alkenyl group having 2 to 18 carbon atoms, and / or an alkynyl group having 2 to 18 carbon atoms.

Among R ¹ and R ² , from the viewpoint of ease of cyclization reaction from primary amine to amidine (steric hindrance) and basicity of the generated base, a hydrogen atom and an alkyl group having 1 to 18 carbon atoms are More preferably, it is a linear alkyl group having 1 to 8 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-octyl), particularly preferably methyl and ethyl.

  n is an integer of 2 to 3, and 3 is preferable from the viewpoint of ease of cyclization reaction from primary amine to amidine.

  Preferred examples of the photobase generator represented by the general formula (1) include those represented by any one of the formulas (1-1) to (1-4).

<(Formula 2)>
n is an integer of 2 to 3, and 3 is preferable from the viewpoint of easiness of cyclization reaction from primary amine to amidine.

  m is an integer of 3 to 5, and is preferably 3 or 5 from the viewpoint of the basic strength of the bicyclic amidine produced by cyclization.

  Preferred examples of the photobase generator represented by the general formula (2) include those represented by the formula (2-1) or the formula (2-2).

<A>
A is a substituent that absorbs light, and by absorbing light, the A—O—CO—NH— (CH ₂ ) n- moiety is represented by Formula (3 ′) or Formula (4 ′). The compound is decomposed into carbon dioxide and NH ₂ — (CH ₂ ) n—.

Among R ³ , regarding the phenyl group having a substituent, the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the alkynyl group having 2 to 18 carbon atoms, and the aryl group having 6 to 12 carbon atoms are as described above. The same thing is included.
Examples of the acyl group having 1 to 18 carbon atoms include formyl, acetyl, octadecyloyl and the like.
Examples of the aroyl group having 7 to 18 carbon atoms include benzoyl and naphthanoyl.
Examples of the alkoxy group having 1 to 18 carbon atoms and the alkylthio group having 1 to 18 carbon atoms include methoxy, ethoxy, decyloxy, octadecyloxy, isooctadecyl, methylthio, ethylthio and octylthio.
Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

  Examples of the phenyl group having a substituent include nitrophenyl, methoxyphenyl, ethoxyphenyl, octylphenyl, dimethoxyphenol, diethoxyphenyl, methoxyethoxyphenyl, methylphenyl, ethylphenyl, vinylphenyl, allylphenyl, ethynylphenyl, biphenyl, Examples include methylthiophenyl, acetylphenyl, benzoylphenyl, hydroxyphenyl and chlorophenyl.

Among R ³ , the alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) includes an alkyl group having 1 to 8 carbon atoms among the above alkyl groups.

Of R ³ , a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group, a phenyl group, and a phenyl group having a substituent are preferable, and methyl, ethyl, n-propyl, n-butyl, isopropyl are more preferable. , Isobutyl, sec-butyl, tert-butyl, nitrophenyl and dinitrophenyl groups, particularly preferably methyl, isopropyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl and 2,6-dinitrophenyl It is.

Among R ⁴ , an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, The same thing as the above is contained in a C1-C18 alkoxythio group, a C1-C18 acyl group, and a C7-C18 aroyl group.

When the substituent (R ⁴ ) is bonded to the benzene ring, the absorption wavelength of the benzene ring can be shifted to the long wavelength side. Depending on the wavelength of light to be used, the substituent (R ⁴ ) necessary for photolysis is appropriately selected to have absorption, thereby improving the efficiency of photodegradability.

The degree to which the absorption wavelength shifts (shift value) varies depending on the type of the substituent (R ⁴ ). For the shift value, refer to the table described in “Organic Chemistry Spectral Identification Method 5th Edition (RMSilverstein, 281, published by Tokyo Kagaku Dojin)” (Original “Spectrometric Identification of Organic Compounds 5th ed” (RMSilverstein, published by John Wiley & Sons in 1991) ").

From the viewpoint of the above shift values and the like, the substituent (R ⁴ ) includes a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and an aroyl group having 7 to 13 carbon atoms (particularly a benzoyl group). Nitro group, cyano group, and aryl group having 6 to 12 carbon atoms are preferable.

Of R ⁴ , an alkoxy group and a nitro group are preferable, and methoxy and nitro are more preferable.

q is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
When q is 2 or more, all R ^{4 s} may be the same, all different, or partly different.

  Preferred examples of the group represented by the formula (3) include those represented by the formula (3-1) to the formula (3-3).

  Preferred examples of the group represented by formula (4) include those represented by formula (14) to formula (16).

The photobase generator of the present invention can be obtained, for example, by connecting A—OH {A is a group represented by formula (3) or formula (4)} and a primary amine by a carbamate bond.
Carbamate bonds can be formed by reacting with alcohol (A-OH), primary amine, and carbamate bond forming agents (phosgene, diphosgene, triphosgene, N, N′-carbonyldiimidazole, etc.). (Reaction conditions and the like may be known).
Among the carbamate bond forming agents, N, N′-carbonyldiimidazole is preferable from the viewpoint of safety and the like.

Alcohol (A-OH) can be easily obtained by a known method. For example, 2-nitro-α-alkylbenzyl alcohol is obtained by reacting 2-nitrobenzaldehyde and an alkyl Grignard reagent (1); Benzene and alkanoyl halide (or allyloyl halide) are reacted with each other in the presence of aluminum halide, etc. to form a phenyl alkyl ketone, and then a nitro group is introduced into the benzene ring using a nitrating agent (such as nitric acid), Reduction with a reducing agent (such as sodium tetrahydroborate) to obtain 2-nitro-α-alkylbenzyl alcohol (2); 2-nitrobenzaldehyde is reduced with a reducing agent (such as sodium tetrahydroborate) to give 2-nitro Method for obtaining benzyl alcohol (3); 2-nitrobenzaldehyde and pheny Method of obtaining 2-nitro-α-phenylbenzyl alcohol by reacting with alkali metal (phenyllithium etc.) (4); reacting benzene with alkyl halide in the presence of catalyst (eg aluminum halide) to obtain alkylbenzene Then, a nitro group is introduced into the benzene ring using a nitrating agent (such as nitric acid) and reacted with paraformaldehyde in the presence of a base (such as t-butoxypotassium) to give 2- (2-nitrophenyl) -2- Method (5) for obtaining alkyl ethyl alcohol: benzene and benzyl halide are reacted in the presence of a catalyst (such as aluminum halide) to form diphenylmethane (C ₆ H ₅ —CH ₂ —C ₆ H ₅ ), and then nitration Introducing a nitro group into the benzene ring using an agent (such as nitric acid), and in the presence of a base (such as potassium t-butoxy) It is produced by a method (6) for obtaining 2,2-bis (2-nitrophenyl) ethyl alcohol by reacting with laformaldehyde. Among these methods, the method (2) and the method (4) are preferable from the viewpoint of convenience and the like.

In the methods (1) to (6), 2-nitrobenzaldehyde and benzene are substituents corresponding to the formula (3) or the formula (4) (R ⁴ ; alkyl group, alkenyl group, alkynyl group, aryl group, nitro group , A cyano group, an alkoxy group, an alkylthio group, an acyl group, an aroyl group, a hydroxyl group, or a halogen atom). Nitrobenzaldehyde and benzene having such a substituent (R ⁴ ) can be obtained by a known method.

For example, nitrobenzaldehyde having a nitro group as R ⁴ can be obtained by reacting benzaldehyde with fuming nitric acid. Also, benzene having a nitro group as R ⁴ can be obtained by reacting benzene and nitric acid.

Further, nitrobenzene having an alkoxy group as R ⁴ is obtained by converting phenol into a phenolate using a base (such as sodium hydroxide), then reacting with an alkyl halide to form alkoxybenzene, and then reacting with nitric acid.
Nitrobenzaldehyde and benzene having other substituents (R ⁴ ) may be obtained by a known organic chemical reaction (such as Friedel-Craft reaction) or may be obtained from the market (Wako Pure Chemical Industries, Ltd.). .

The primary amine has a primary amino group (NH ₂ —) and a carbamoyl group (R ² NCO—) in one molecule, and includes those represented by the following formula. N, m, R ¹ and R ² are the same as those in the general formulas (1) and (2).

  The primary amine used to synthesize the photobase generator represented by the general formula (1) is, for example, one amino group obtained by reacting 0.5 equivalent of an ester with 1 equivalent of alkylenediamine. A method for obtaining a carbamoyl group-containing primary amine by protecting the amino group of the carbamoyl group-containing primary amine (acetone, etc.) and then reacting with an alkylating agent (dialkyl sulfate, etc.). It can be obtained by, for example, a method in which the amino group is removed and an N-alkylcarbamoyl group-containing primary amine is obtained.

The primary amine used for synthesizing the photobase generator represented by the general formula (2) is obtained by reacting lactam and alkenenitrile, and then hydrogenating.
The above reaction conditions are the same as the known ranges.

Examples of the ester include an ester represented by R ² COOR ⁵ .
R ² is the same as in general formulas (1) and (2). R ⁵ includes an alkyl having 1 to 8 carbon atoms.
Of the esters, methyl acetic acid, methyl propionic acid, ethyl acetic acid and ethyl propionic acid are preferable, and methyl acetic acid and methyl propionic acid are more preferable.

The lactam includes a lactam represented by the following formula.

  Among the lactams, 4-pentane lactam, 5-hexane lactam and 6-heptane lactam are preferable, and 4-pentane lactam and 6-heptane lactam are more preferable.

Examples of the alkene nitrile include vinyl nitrile and 2-propylene nitrile.
Of the alkenenitriles, 2-propylenenitrile is preferred.

  Primary amines can also be obtained by hydrolyzing amidine. Examples of the amidine include 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, Sun Apro Co., Ltd., “DBU” is a registered trademark of the company), 1,5-diazabicyclo “4. 3.0 "Non-5-ene (DBN, Sun Apro).

  The photobase generator represented by the general formula (2) is preferably obtained by hydrolyzing amidine, from the viewpoint of ease of synthesis and the like.

  When the photobase generator of the present invention is exposed, a primary amine is produced. Furthermore, amidine can be generated by heating the primary amine.

The exposure wavelength (nm) is preferably 200 to 500, more preferably 300 to 450, and particularly preferably 300 to 425, from the absorption wavelength of the photobase generator.
The exposure amount (mJ / cm ² ) is preferably from 100 to 100,000, more preferably from 500 to 50,000, particularly preferably from 1,000 to 30,000, from the viewpoint of the amount of generated base and energy cost.

  Heating may be performed with exposure, may be performed after exposure, or may be performed on both. The heating temperature (° C.) is preferably 50 to 250, more preferably 80 to 150, and particularly preferably 90 to 140 from the viewpoint of the progress of the cyclization reaction and the like.

  The heating time (minutes) is preferably 1 to 300, more preferably 3 to 120, from the viewpoint of the progress of the cyclization reaction, energy cost, and the like.

  The atmosphere in exposure and heating may be any of reduced pressure, increased pressure, and atmospheric pressure, but atmospheric pressure is preferable from the viewpoint of process simplicity. Further, an inert gas atmosphere may be used.

The photobase generator of the present invention can be applied to a latent base catalyst (a catalyst that does not have a catalytic action before being irradiated with light, but develops an action of a basic catalyst by light irradiation). For example, a curable resin composition It is suitable as a curing catalyst for a curable resin composition that is cured when heated by irradiation with light of 200 to 500 nm during and / or after exposure.
For example, a curable resin composition comprising a basic resin that promotes curing with a base, the photobase generator of the present invention, and, if necessary, a solvent and / or an additive can be easily configured.

Since such a curable resin composition contains the photobase generator of the present invention, it is excellent not only in storage stability but also in curability.
That is, the curable resin composition containing the photobase generator of the present invention is irradiated with light having a wavelength of 200 to 500 nm and heated during and / or after exposure to generate a base and accelerate the curing reaction. Thus, a cured product can be obtained.
Therefore, as a method for producing such a curable resin (cured product), the curable resin composition containing the photobase generator and the curable resin is irradiated with light having a wavelength of 200 to 500 nm. After the carbamoyl group-containing primary amine is generated from the base generator, the carbamoyl group-containing primary amine is intramolecularly cyclized to amidine by heating to 50 to 250 ° C. to cure the curable resin. It is preferable to include a step of obtaining a cured resin.

  In addition, in the manufacturing method of such curable resin (hardened | cured material), it replaces with said process, or replaces said process with the said curable resin composition containing a photobase generator and curable resin. A carbamoyl group-containing primary amine is generated from a photobase generator by irradiating light having a wavelength of 200 to 500 nm, and the carbamoyl group-containing primary amine is converted into an amidine molecule by heating to 50 to 250 ° C. You may include the process of making it cyclize internally and hardening curable resin and obtaining curable resin.

  The curable resin composition whose curing is accelerated by a base generated by light irradiation is not limited as long as it is a curable resin cured by a base. For example, a curable urethane resin {(poly) isocyanate and a curing agent (polyol and thiol). Etc.}, curable epoxy resins {resins consisting of (poly) epoxides and curing agents (acid anhydrides, carboxylic acids, (poly) epoxides, thiols, etc.), and epichlorohydrins and carboxylic acids. Resin, etc.}, curable acrylic resin {acrylic monomer and / or acrylic oligomer and curing agent (thiol, malonic acid ester, acetylacetonate, etc.)} and polysiloxane (cured into a crosslinked polysiloxane).

  Since the photobase generator of the present invention is sensitive to light having a wavelength of 400 nm or more, in addition to a commonly used high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, etc. (UV / EB curing) The latest trends in technology, edited by Radtech Institute, CM Publishing, 138 pages, 2006) can be used.

<Production Example 1>
Synthesis of 4,5-dimethoxy-2-nitrobenzyl alcohol In a 500 ml Meyer flask, 9.0 g of 4,5-dimethoxy-2-nitrobenzaldehyde (Wako Pure Chemical Industries, Ltd.) and sodium tetrahydroborate (Wako Pure Chemical Industries, Ltd.) Company) 1.7 g and 400 ml of methanol were added and stirred at room temperature (about 25 ° C.) for 3 hours. It became liquid. To this yellow suspension, 200 ml of chloroform was added for extraction, the organic layer was separated, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a pale yellow solid. This solid was dissolved in 30 ml of ethyl acetate and recrystallized to obtain 8.0 g of pale yellow crystals.

  As a result of analysis by 1H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.63 (s, 1H), 7.38 (s, 1H), 5.50 (t, 1H), 4. 80 (d, 2H), 3.85 (d, 6H)}, and this pale yellow crystal was confirmed to be 4,5-dimethoxy-2-nitrobenzyl alcohol.

<Production Example 2>
Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol (1) Synthesis of 4,5-dimethoxy-2-nitroacetophenone (Intermediate 1) 90 ml of concentrated nitric acid was placed in a 200 ml Meyer flask and cooled in a cold water bath. While maintaining the temperature in the system at 18 to 22 ° C., 15.0 g of 4,5-dimethoxyacetophenone (Wako Pure Chemical Industries, Ltd.) was added over 1 hour, followed by stirring at the same temperature for 1 hour, and the reaction solution Was added dropwise to a 3 L beaker containing 1200 ml of water over 30 minutes with stirring to deposit a pale yellow solid. This solid was subjected to suction filtration to obtain a pale yellow solid. This pale yellow solid was dissolved in 250 ml of ethanol and recrystallized to obtain 8.4 g of pale yellow needle crystals (intermediate 1).

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.62 (s, 1H), 7.20 (s, 1H), 3.90 (d, 6H), 2 .50 (s, 3H)}, this pale yellow needle crystal was confirmed to be 4,5-dimethoxy-2-nitroacetophenone (intermediate 1).

(2) Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol In a 500 ml Meyer flask, 10.0 g of intermediate (1), 1.7 g of sodium tetrahydroborate and 400 ml of methanol were placed at room temperature (about After stirring at 25 ° C. for 3 hours, the obtained reaction solution was dropped into a 3 L beaker containing 400 ml of water with stirring to obtain a yellow suspension. To this yellow suspension, 200 ml of chloroform was added for extraction, the organic layer was separated, and the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a pale yellow solid. This pale yellow solid was dissolved in 30 ml of ethyl acetate and recrystallized to obtain 8.6 g of pale yellow crystals.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.55 (s, 1H), 7.35 (s, 1H), 5,50 (s, 1H), 5 .23 (t, 1H), 3.90 (d, 6H), 1.35 (d, 3H)} and the pale yellow crystals are 1- (4,5-dimethoxy-2-nitrophenyl) ethanol It was confirmed.

<Production Example 3>
Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propanol (1) Synthesis of 1- (3,4-dimethoxyphenyl) -2-methyl-propanone (Intermediate 2) Dropping funnel 4. A 500 ml three-necked glass flask equipped with a thermometer and a magnetic stirrer was purged with nitrogen, and 6.68 g of aluminum chloride (Wako Pure Chemical Industries, Ltd.), 1,2-dimethoxybenzene (Wako Pure Chemical Industries, Ltd.) 5. 52 g and 30 ml of dichloromethane were charged and cooled in an ice bath while stirring with a magnetic stirrer to obtain a mixed solution of 0 to 5 ° C.
On the other hand, 4.50 g of isobutyryl chloride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 ml of dichloromethane to obtain a dichloromethane solution of isobutyryl chloride.

  While maintaining the temperature of the previous mixture at 0 to 5 ° C. in an ice bath, the dichloromethane solution was added dropwise to the mixture over 30 minutes from the dropping funnel, and then the ice bath was removed and room temperature (about 25 ° C. ) For 2 hours. Thereafter, 40 ml of 2N hydrochloric acid, 100 ml of water and 100 g of dichloromethane were added to the reaction solution and stirred for 30 minutes, and the organic layer was separated. The organic layer was washed 3 times with 200 ml of water, the solvent was distilled off under reduced pressure with a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 7.56 g of a yellow oil (intermediate 2). It was.

As a result of analysis by ¹ H-NMR {300 MHz, chloroform-d, δ (ppm): 7.55 (d, 1H), 7.5 (s, 1H), 6.80 (d, 1H), 3 .80 (s, 6H), 3.50 (m, 1H), 1.20 (d, 6H)}, this yellow oil is 1- (3,4-dimethoxyphenyl) -2-methyl-propanone ( It was confirmed to be intermediate 2).

(2) Synthesis of 1- (3,4-dimethoxy-2-nitrophenyl) -2-methyl-propanone (intermediate 3) “4,5-dimethoxyacetophenone 15.0 g” was converted to “(intermediate 2) 17. 16.0 g of pale yellow crystals (intermediate 3) were obtained in the same manner as in Production Example 2 (1) except that the content was changed to “0 g”.

As a result of analysis by ¹ H-NMR {300 MHz, chloroform-d, δ (ppm): 7.65 (s, 1H), 7.22 (s, 1H), 3.95 (s, 6H), 2 .90 (m, 1H), 1.20 (d, 6H)}, this pale yellow crystal is 1- (3,4-dimethoxy-2-nitrophenyl) -2-methyl-propanone (Intermediate 3) It was confirmed.

(3) Synthesis of 1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propanol “Intermediate (1) 10.0 g” was changed to “(Intermediate 3) 12.0 g” Except that, 10.0 g of light yellow crystals was obtained in the same manner as in Production Example 2 (2).

As a result of analysis by ¹ H-NMR {300 MHz, chloroform-d, δ (ppm): 7.50 (s, 1H), 7.20 (s, 1H), 5.27 (d, 1H), 3 .90 (s, 3H), 3.80 (s, 3H), 2.25 (s, 1H), 1.95 (m, 1H), 0.90 (d, 6H)}, It was confirmed that it was 1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propanol.

<Production Example 4>
Synthesis of 1- (2-nitro-4.5-dimethoxyphenyl) -1- (2-nitrophenyl) -methanol A 300 ml three-necked glass flask equipped with a dropping funnel, a thermometer and a magnetic stirrer was purged with nitrogen. , 5-Dimethoxy-2-nitrobenzaldehyde (3.0 g) and tetrahydrofuran (200 ml) were added and dissolved. The solution was added dropwise from a dropping funnel so that the temperature did not exceed 5 ° C., and the solution was stirred at 5 ° C. or lower for 3 hours. Thereafter, 300 ml of a saturated aqueous ammonium chloride solution and 300 ml of diethyl ether were added to the reaction solution, and after stirring for 1 hour, the organic layer was separated. The organic layer was washed with 200 ml of water three times, the organic layer was separated, the solvent was distilled off under reduced pressure with a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 2.0 g of a yellow solid. .

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.85 (d, 1H), 7.18 (s, 1H), 7.40-7.20 (m, 2H), 7.37 (s, 1H), 7.18 (d, 1H), 6.49 (d, 1H), 3.80 (s, 6H)}, the yellow solid is 1- (2-nitro It was confirmed to be -4.5-dimethoxyphenyl) -1- (2-nitrophenyl) -methanol.

<Production Example 5>
Synthesis of 2- (4,5-dimethoxy-2-nitrophenyl) propanol (1) Synthesis of 4,5-dimethoxyethylbenzene (intermediate 4) 500 ml three-neck glass flask equipped with dropping funnel, thermometer and magnetic stirrer Was replaced with nitrogen, charged with 6.68 g of aluminum chloride (Wako Pure Chemical Industries, Ltd.), 5.52 g of 1,2-dimethoxybenzene (Wako Pure Chemical Industries, Ltd.) and 30 ml of dichloromethane, and stirred with a magnetic stirrer. The mixture was cooled in a bath to obtain a mixed solution of 0 to 5 ° C.
On the other hand, 3.0 g of ethyl chloride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 ml of dichloromethane to obtain a dichloromethane solution of ethyl chloride.

  While maintaining the temperature of the previous mixture at 0 to 5 ° C. in an ice bath, the dichloromethane solution was added dropwise to the mixture over 30 minutes from the dropping funnel, and then the ice bath was removed and room temperature (about 25 ° C. ) For 2 hours. Thereafter, 40 ml of 2N hydrochloric acid, 100 ml of water and 100 g of dichloromethane were added to the reaction solution and stirred for 30 minutes, and the organic layer was separated. The organic layer was washed with 200 ml of water three times, the organic layer was separated, the solvent was distilled off under reduced pressure using a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain a yellow oil (intermediate 4). 2.00 g was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, chloroform-d, δ (ppm): 7.55 (d, 1H), 7.5 (s, 1H), 6.80 (d, 1H), 3 .80 (s, 6H), 5.10 (q, 2H), 1.20 (t, 3H)}, confirming that the yellow oil was 4,5-dimethoxyethylbenzene (intermediate 4). .

(2) Synthesis of 2-ethyl-4,5-dimethoxy-nitrobenzene (intermediate 5) Manufactured except that “4,5-dimethoxyacetophenone 15.0 g” was changed to “(intermediate 4) 10.0 g” In the same manner as in Example 2 (1), 8.0 g of pale yellow crystals (Intermediate 5) were obtained.

As a result of analysis by ¹ H-NMR {300 MHz, chloroform-d, δ (ppm): 7.65 (s, 1H), 7.22 (s, 1H), 3.95 (s, 6H), 5 .05 (q, 2H), 1.20 (t, 3H)}, this yellow crystal was confirmed to be 2-ethyl-4,5-dimethoxy-nitrobenzene (intermediate 5).

(3) Synthesis of 2- (4,5-dimethoxy-2-nitrophenyl) propanol A 100 ml two-necked eggplant flask was purged with nitrogen. To this, 3.0 g of (Intermediate 5) and 30 ml of dimethyl sulfoxide were added. After dissolving at about 25 ° C., 1.0 g of paraformaldehyde (Wako Pure Chemical Industries, Ltd.) and 1.0 g of t-butoxypotassium (Wako Pure Chemical Industries, Ltd.) were added, and the mixture was added at room temperature (about 25). Stir for hours. The reaction solution was neutralized with a saturated aqueous solution of sodium bicarbonate, dichloromethane and water were added and stirred for 30 minutes, and then the organic layer was separated. The organic layer was washed with 200 ml of water three times, and the organic layer was separated. The solvent was distilled off under reduced pressure using a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 2.0 g of a yellow solid.

  As a result of analysis by 1H-NMR {300 MHz, chloroform-d, δ (ppm): 7.50 (s, 1H), 7.20 (s, 1H), 5.27 (d, 1H), 3. 90 (s, 3H), 3.80 (s, 3H), 3.10 (d, 2H), 2.25 (s, 1H), 1.95 (m, 1H), 1.00 (d, 3H) )}, This yellow solid was confirmed to be 2- (4,5-dimethoxy-2-nitrophenyl) propanol.

<Production Example 6>
Synthesis of N- (3-aminopropyl) -6-heptane lactam In a 100 ml Meyer flask, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, San Apro, Inc., “DBU” (Registered product) 15 g and 10 g of water were added, and the mixture was heated and stirred at 80 ° C. for 2 hours, and then the water was distilled off with a vacuum dryer to obtain 16.5 g of a transparent oily substance.

  As a result of analysis by 1H-NMR {300 MHz, DMSO-d6, δ (ppm): 3.40-3.30 (m, 4H), 2.60-2.40 (m, 4H), 1.50 −1.80 (m, 8H)}, this clear oil was confirmed to be N- (3-aminopropyl) -6-heptane lactam.

<Production Example 7>
Synthesis of N- (3-aminopropyl) -4-pentanelactam To a 100 ml Meyer flask, 15 g of 1,5-diazabicyclo [4.3.0] non-5-ene (DBN, San Apro Co., Ltd.) and 10 g of water were added. The mixture was heated and stirred at 80 ° C. for 2 hours, and then water was distilled off with a vacuum dryer to obtain 16.5 g of a transparent oily substance.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 3.60-3.50 (m, 4H), 2.80-2.60 (m, 4H), 1. 50-1.80 (m, 4H)}, and this clear oil was confirmed to be N- (3-aminopropyl) -4-pentanelactam.

<Production Example 8>
Synthesis of N- (3-aminopropyl) -N-methylacetamide (1) Synthesis of N- (3-aminopropyl) -acetamide (intermediate 6) In a 100 ml Meyer flask, propylenediamine (Wako Pure Chemical Industries, Ltd.) 3.0 g and 1.0 g of methyl acetic acid (Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature (about 25 ° C.) for 3 hours to obtain 4.0 g of a transparent oil.
This transparent oil was purified by silica gel column chromatography to obtain a transparent oil (intermediate 6).

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.00 (s, 1H), 3.30 (t, 2H), 2.05 (s, 3H), 1 .80 (m, 2H), 1.20 (t, 2H)}, this clear oil was confirmed to be N- (3-aminopropyl) -acetamide.

(2) Synthesis of N- (3-aminopropyl) -N-methylacetamide In a 100 ml Meyer flask, 4.0 g of (Intermediate 6) and 2.0 g of bis (1,1-dimethylethyl) dicarbonate (Wako Pure Chemical Industries, Ltd.) ) And stirred at room temperature (about 25 ° C.) for 3 hours to protect the amino group with the Boc group. Thereafter, 1.0 g of dimethyl sulfate (Wako Pure Chemical Industries, Ltd.) was added and stirred for 3 hours at room temperature (about 25 ° C.), then 5.0 g of 2N hydrochloric acid was added, and 1 hour at room temperature (about 25 ° C.). The transparent oily substance which agitated and settled at the bottom of the flask was separated to obtain 4.0 g of a transparent oily substance.

  As a result of analysis by 1H-NMR {300 MHz, DMSO-d6, δ (ppm): 3.40 (t, 2H), 2.90 (s, 3H), 2.00 (s, 3H), 1. 70 (m, 2H), 1.10 (t, 2H)}, and this clear oil was confirmed to be N- (3-aminopropyl) -N-methylacetamide.

<Example 1>
Synthesis of N- (N ′-(4,5-dimethoxy-2-nitrobenzyloxycarbonyl) aminopropyl) -6-heptane lactam A 100 ml three-necked glass flask equipped with a dropping funnel, thermometer and magnetic stirrer was purged with nitrogen Then, 1.78 g of N, N′-carbonyldiimidazole (Tokyo Chemical Industry Co., Ltd.) and 5 ml of N, N-dimethylformamide are added and suspended, and the suspension is cooled in an ice bath while stirring with a magnetic stirrer. To obtain a suspension at 0 to 5 ° C.
On the other hand, 2.13 g of “4,5-dimethoxy-2-nitrobenzyl alcohol” obtained in Production Example 1 was dissolved in 5 ml of N, N-dimethylformamide to obtain DMF of 4,5-dimethoxy-2-nitrobenzyl alcohol. A solution was obtained.

  While maintaining the temperature of the suspension at 0 to 5 ° C. in an ice bath, this DMF solution was added dropwise to the suspension over 30 minutes from the dropping funnel, and after aging at 0 to 5 ° C. for 30 minutes, While maintaining the reaction solution at this temperature, a solution of 2.40 g of “N- (aminopropyl) -6-heptanelactam” obtained in Preparation Example 6 in 5 ml of DMF was added dropwise from a dropping funnel over 10 minutes. It was. Next, after removing the ice bath and aging the reaction solution at room temperature (about 25 ° C.) for 4 hours, the reaction solution is concentrated with a rotary evaporator to remove DMF, and the residue is purified by silica gel column chromatography to obtain the light of the present invention. Base generator (1) (light yellow solid 3.29 g) was obtained.

  As a result of analysis by 1H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.7 (s, 1H), 7.35 (t, 1H), 7.15 (s, 1H), 5. 30 (s, 2H), 3.85 (d, 6H), 3.4-3.2 (m, 4H), 3.0 (m, 2H), 2.4 (m, 2H), 1.8 -1.3 (m, 8H)}, confirming that this pale yellow solid was N- (N ′-(4,5-dimethoxy-2-nitrobenzyloxycarbonyl) aminopropyl) -6-heptane lactam. .

<Example 2>
Synthesis of N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -6-heptanelactam “4,5-dimethoxy-2 obtained in Production Example 1 -Nitrobenzyl alcohol 2.13 g "was changed to" 2.3 g of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol obtained in Preparation Example 2 "in the same manner as in Example 1, except that Inventive photobase generator (2) (3.3 g of pale yellow solid) was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2.40 (m, 2H), 1. 70-1.40 (m, 11H)}, this pale yellow solid is N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -6-heptane Confirmed to be lactam.

<Example 3>
Synthesis of N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propoxy) carbonyl) aminopropyl) -6-heptanelactam “4 obtained in Production Example 1 Other than changing 2.13 g of “5-dimethoxy-2-nitrobenzyl alcohol” to “2.6 g of 1- (4,5-dimethoxy-2-nitrophenyl) -2-methyl-propanol obtained in Production Example 3”. The photobase generator (3) of the present invention (3.5 g of a pale yellow solid) was obtained in the same manner as in Example 1.

As a result of analysis by ¹ H-NMR {300 MHz, chloroform-d, δ (ppm): 7.60 (s, 1H), 7.00 (s, 1H), 6.25 (d, 1H), 6 .10 (t, 1H), 3.90 (d, 6H), 3.40-3.25 (m, 4H), 3.00 (m, 2H), 2.50 (m, 2H), 77-1.50 (m, 8H), 0.90 (t, 6H)}, this pale yellow solid was N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) -2 -Methyl-propoxy) carbonyl) aminopropyl) -6-heptane lactam.

<Example 4>
Synthesis of N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) -1- (2-nitrophenyl) methoxy) carbonyl) aminopropyl) -6-heptanelactam “In Production Example 1 The obtained 4,5-dimethoxy-2-nitrobenzyl alcohol 2.13 g ”was obtained as“ 1- (2-nitro-4.5-dimethoxyphenyl) -1- (2-nitrophenyl) -methanol obtained in Production Example 4. The photobase generator (4) of the present invention (4.0 g of a pale yellow solid) was obtained in the same manner as in Example 1 except that the amount was changed to “3.0 g”.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.02 (d, 1H), 7.75 (s, 1H), 7.65 (m, 2H), 7 .60 (s, 1H), 7.48 (t, 1H), 7.22 (d, 1H), 7.00 (s, 1H), 3.85 (d, 6H), 3.40-3. 20 (m, 4H), 2.90 (m, 2H), 2.40 (m, 2H), 1.70-1.40 (m, 8H)}, and this pale yellow solid is N- (N'- ((1- (4,5-dimethoxy-2-nitrophenyl) -1- (2-nitrophenyl) methoxy) carbonyl) aminopropyl) -6-heptane lactam was confirmed.

<Example 5>
Synthesis of N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -4-pentanelactam “4,5-dimethoxy-2 obtained in Production Example 1 “2.13 g of nitrobenzyl alcohol” was changed to “2.3 g of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol obtained in Production Example 2,” and “N- ( Photobase of the present invention in the same manner as in Example 1 except that “aminopropyl) -6-heptane lactam 2.40 g” was changed to “N- (3-aminopropyl) -4-pentane lactam 2.30 g”. The generator (5) (4.0 g of pale yellow solid) was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2.40 (m, 2H), 1. 70-1.40 (m, 7H)}, this pale yellow solid is N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -4-pentane. Confirmed to be lactam.

<Example 6>
Synthesis of N- (N ′-((2- (4,5-dimethoxy-2-nitrophenyl) propoxy) carbonyl) aminopropyl) -6-heptanelactam “4,5-dimethoxy-2 obtained in Production Example 1 -Nitrobenzyl alcohol 2.13 g "was changed to" 2- (4,5-dimethoxy-2-nitrophenyl) propanol 3.2 g obtained in Production Example 5 "in the same manner as in Example 1, except that The photobase generator (6) of the invention (4.0 g of a pale yellow solid) was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 4.10 (d, 2H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2. 40 (m, 2H), 1.70-1.40 (m, 11H)}, this pale yellow solid is N- (N ′-((2- (4,5-dimethoxy-2-nitrophenyl) propoxy). )) Carbonyl) aminopropyl) -6-heptane lactam.

<Example 7>
Synthesis of N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) aminopropyl) -N-methylacetamide “4,5-dimethoxy-2 obtained in Production Example 1 “2.13 g of nitrobenzyl alcohol” was changed to “2.3 g of 1- (4,5-dimethoxy-2-nitrophenyl) ethanol obtained in Production Example 2,” and “N- ( Aminopropyl) -6-heptane lactam 2.40 g "was changed to" N- (3-aminopropyl) -N-methylacetamide 2.00 g obtained in Preparation Example 8 "in the same manner as in Example 1. The photobase generator (7) of the present invention (3.0 g of a pale yellow solid) was obtained.

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.28 (t, 1H), 7.10 (s, 1H), 6 .10 (q, 1H), 3.90 (d, 6H), 3.40-3.20 (m, 4H), 2.90 (m, 2H), 2.70 (s, 3H), 2. 00 (s, 3H), 1,60 (d, 3H)}, this pale yellow solid is N- (N ′-((1- (4,5-dimethoxy-2-nitrophenyl) ethoxy) carbonyl) amino Propyl) -N-methylacetamide was confirmed.

<Comparative example>
Synthesis of N- (4,5-dimethoxy-2-nitrobenzyloxycarbonyl) -2,6-dimethylpiperidine “2.40 g of N- (aminopropyl) -6-heptanelactam obtained in Production Example 6” was changed to “2 A photobase generator (H1) for comparison (2.0 g of a pale yellow solid) was obtained in the same manner as in Example 1, except that it was changed to "1,6-dimethylpiperidine 1.50 g".

As a result of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 7.60 (s, 1H), 7.10 (s, 1H), 5.35 (s, 2H), 4 .23 (m, 2H), 3.90 (d, 6H), 1.80-1.60 (m, 1H), 1.50 (m, 4H), 1.40 (m, 1H), 1. 15 (d, 6H)}, and this pale yellow solid was confirmed to be N- (4,5-dimethoxy-2-nitrobenzyloxycarbonyl) -2,6-dimethylpiperidine.

<Evaluation>
100 g of bisphenol A type epoxy resin (JER-828, Japan Epoxy Resin Co., Ltd.), 90 g of acid anhydride (HN5500E, Hitachi Chemical Co., Ltd.) and 4.5 g of photobase generator were uniformly mixed, and a glass plate (76 mm × 52 mm) , 5 mm thick) using a bar coater (No. 10, Yasuda Seiki Seisakusho Co., Ltd.), and then exposed (365 nm integrated light intensity) with a belt conveyor type UV irradiation device (Eye Graphics Co., Ltd., ECS-151U). 10 J / cm < ² >) {In order to control the exposure wavelength, a filter (I Graphics Co., Ltd., 365 filter) that transmits light with a wavelength of 300 to 450 nm was used. }. Immediately thereafter, the sample was placed on a hot plate heated to 150 ° C., and the time (minutes) from the placement on the hot plate until the tack of the coated surface disappeared was measured and shown in the table below.

  In addition, except for changing the heating temperature on the hot plate from 150 ° C. to 80 or 115 ° C., the time (minutes) from when it was placed on the hot plate to when there was no tack on the coated surface was measured. The results are shown in the table below.

  The photobase generators (1) to (7) of the present invention required significantly less time to eliminate tack as compared with the photobase generator for comparison. When the heating temperature was increased, the photobase generator of the present invention decreased the time until tack disappeared, whereas no change was seen in the comparative photobase generator. This is because the primary amine generated by exposure of the photobase generator of the present invention is easily cyclized to amidine by increasing the heating temperature, whereas the photobase for comparison is used. This is considered to be due to the fact that 3,5-dimethylpiperidine does not change with the heating temperature in the generator.

  It was confirmed as follows that the photobase generator of the present invention generates a primary amine when exposed to light, and further generates amidine by heating the primary amine.

2.17 mg of the photobase generator (1) of the present invention and 0.75 g of heavy DMSO (DMSO-d6) were uniformly dissolved (concentration 7.02 × 10 ⁻⁶ mol / L), filled in an NMR tube, and belt Exposed (50 J / cm ² with 365 nm integrated light intensity) with a conveyor-type UV irradiation device (I Graphics Co., ECS-151U) {Filter for transmitting light with a wavelength of 300 to 450 nm to control the exposure wavelength ( Eye Graphics Co., Ltd., 365 filter) was used. }.
Thereafter, ¹ H-NMR (300 MHz) analysis was performed, and it was confirmed that the photobase generator (1) of the present invention was decomposed to produce a primary amine {N- (aminopropyl) -6-heptane lactam}. {The signal of proton at the benzyl position 5.30 ppm (s, 2H) disappeared, and the signal of N- (aminopropyl) -6-heptane lactam was confirmed. }

  Regarding the photobase generators (2) to (7) of the present invention, it was confirmed in the same manner as above that the photobase generators (2) to (7) of the present invention were decomposed to produce primary amines. {Photobase generators (2) to (5) and (7); The signal of the proton at the benzyl position disappeared, and the signal of the primary amine was confirmed. It was confirmed that the photobase generator (6): 6.10 ppm (q, 1 H) of the proton at the benzyl position was shifted to a high magnetic field of 6.50 ppm (m, 1 H). }

A primary amine (NMR tube) obtained by subjecting the photobase generators (1) to (7) of the present invention to exposure decomposition was heated in an oil bath at 120 ° C. for 1 hour, and then again ¹ H-NMR (300 MHz). ) Analysis, the primary amine signal disappeared and the amidine signal was confirmed. The NMR data of the obtained amidine are shown in the table below.

After heating the primary amine (NMR tube) obtained by exposing and decomposing the photobase generators (1) to (7) of the present invention at 80, 115, or 150 ° C. for 1 hour in an oil bath. Again, ¹ H-NMR (300 MHz) analysis was performed to determine the conversion rate (mol%) of primary amine to amidine, and the results are shown in the table below.
The conversion rate (mol%) of primary amine to amidine was calculated from the integral value of protons of primary amine and amidine.

Claims (5)

A photobase generator represented by the general formula (1) or the general formula (2).

R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n is 2 Is an integer of -3, m is an integer of 3-5, and A is a group represented by Formula (3) or Formula (4).

R ³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acyl group having 1 to 18 carbon atoms, or a carbon number Phenyl having at least one substituent selected from the group consisting of a 7-18 aroyl group, a nitro group, a cyano group, a C1-C18 alkoxy group, a C1-C18 alkylthio group, a hydroxyl group and a halogen atom Group {alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, aroyl group, nitro group, cyano group, alkoxy group, alkylthio group, hydroxyl group and halogen atom may be either singular or plural, But it may be different}, represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 8 carbon atoms, ^{R 4} is an alkyl group having 1 to 18 carbon atoms, carbon atoms 2 to 18 Alkenyl group, C2-C18 alkynyl group, C6-C12 aryl group, C1-C18 acyl group, C7-C18 aroyl group, nitro group, cyano group, C1-C18 Represents an alkoxy group, an alkylthio group, a hydroxyl group or a halogen atom, q is an integer of 1 to 4, and when q is 2 to 4, R ⁴ may be the same or different. The photobase generator of Claim 1 represented by Formula (2-1) or Formula (2-2).

A is as described in claim 1. A photobase generator in which A is a group represented by any one of formulas (3-1) to (3-4) or a group represented by any one of formulas (4-1) to (4-3) .

A curable resin composition comprising the photobase generator according to claim 1 and a curable resin. A carbamoyl group-containing material is generated from the photobase generator by irradiating light having a wavelength of 200 to 500 nm to the curable resin composition containing the photobase generator and the curable resin according to claim 1. After generating the primary amine, heating to 50 to 250 ° C. to cyclize the carbamoyl group-containing primary amine into amidine and cure the curable resin to obtain a cured resin. A method for producing a cured resin, comprising: