JP5780919B2 - Base generator - Google Patents

Description

The present invention relates to a base generator that generates a base by heat or light irradiation. More specifically, use a material that is cured using a base generated by heat or light irradiation (for example, a coding agent or paint), or a difference in solubility in a developing solution between a heated part, a non-heated part, an exposed part, and an unexposed part. It is related with the base generator used suitably for manufacture of the product or member (for example, an electronic component, an optical product, the formation material of an optical component, a layer formation material, or an adhesive agent) formed through the patterning performed.

In the photobase generator (Patent Document 1 and Non-Patent Document 1) that generates a primary amine or a secondary amine, the basicity of the generated primary amine or secondary amine is low (pKa <8), It is not suitable as a catalyst for polymerization reaction or crosslinking reaction because of its low activity. In addition, since these amines have active hydrogen atoms, if they are used for polymerization reaction or crosslinking reaction of epoxides or isocyanates, they react with each other, so that a large amount of photobase generator is required to perform a sufficient reaction. There was a problem of becoming.

In order to solve such problems, photobase generators that generate strong bases (tertiary amines, pKa8-11) and super strong bases (guanidine, amidine, etc., pKa11-13) have been proposed (patents). Documents 2 to 5 and Non-Patent Document 2).

However, it is described in Patent Documents 2 to 4 and Non-Patent Document 2 for i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a high-pressure mercury lamp that is a light source that is generally widely used. The photobase generator thus produced has a problem that absorption at 365 nm is particularly small and sensitivity is insufficient.

In the field of paints and the like, pigments (for example, titanium oxide) and binders having an aromatic ring may be blended with the photocurable composition. Therefore, for example, titanium oxide absorbs light of 380 nm or less, and an aromatic ring absorbs light of around 365 nm. Therefore, there is a problem that it cannot be cured by a conventional photobase generator.

  Moreover, in the photobase generator described in Patent Document 4, halogen ions are used as counter anions, but there is a concern of metal corrosion depending on the application. Moreover, since the basicity of the photobase generator described in Patent Document 5 is not blocked, there is a problem in that the storage stability of the reactive composition is lowered when it is contained in the reactive composition. is there.

As means for solving the above problems, a quaternary ammonium salt type photobase generator (Patent Document 6) has been reported, and the reported photobase generator sensitizes light having a wavelength of 350 to 500 nm. An amine (tertiary amine or amidine) having high catalytic activity can be efficiently generated.
However, its solubility in a solvent (such as ethyl lactate) is low, making it difficult to use it as a patterning member, and improvement has been demanded.

  Urea derivatives described in Patent Document 7 and phosphonium borate salts described in Patent Document 8 have been reported as thermal base generators used as curing accelerators for epoxy resins. Although it is excellent, it has a problem that it has low fast curability and requires heating at a high temperature for a long time. In addition, an organic acid salt of 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU; “DBU” is a registered trademark of San Apro Co., Ltd.) described in Patent Document 9 has been reported. However, storage stability and fast curability are in a trade-off relationship, and there is nothing that satisfies both.

  As means for solving the above problems, quaternary ammonium borate salts described in Patent Document 10 have been reported, but the fast curability is somewhat low, and the solubility in a solvent (such as ethyl lactate) is low, The use for a patterning member is difficult, and improvement has been demanded.

Japanese Patent Laid-Open No. 10-7709 JP 2005-107235 A JP 2005-264156 A JP 2007-119766 A JP 2009-280785 A WO2005-014696 Japanese Examined Patent Publication No. 62-1650 JP-A-8-269167 JP-A-7-188395 JP 62-246925 A

Encyclopedia of applied optical technology and materials, Industrial Technology Service Center Co., Ltd., 2006, p. 130 J.Photopolym.Sci.Tech., Vol.19., No.1 (81) 2006

The present invention has been made in view of the above-mentioned problems, and can be used for, for example, a crosslinking reaction of an epoxy compound, the strength of a generated base is high, and when applied to an epoxy compound or the like, Provided are a base generator in which base generation reactions are performed in a chain, excellent reaction efficiency, high solubility in a solvent, and one-pack storage stability, and a curable resin composition containing the base generator. There is.

As a result of intensive studies to solve the above problems, the present inventors have found a base generator having excellent characteristics.
That is, this invention is a base generator characterized by being represented by General formula (1).

In Expression ^(1), R 1 ~R ⁵ represent 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, 6 to 14 carbon atoms Aryl group, nitro group, hydroxyl group, cyano group, alkoxy group represented by —OR ⁶ , amino group represented by —NR ⁷ R ⁸ , acyl group represented by R ⁹ CO—, represented by R ¹⁰ COO— acyloxy groups, an alkylthio group or an arylthio group represented by -SR ^11. The alkyl group, alkenyl group, alkynyl group and aryl group may have a substituent, and the substituent is the same as R ^{1 to} R ⁵ described above, and these substituents can have a ring structure. . R ⁶ , R ⁹ , R ¹⁰ and R ¹¹ are alkyl groups having 1 to 8 carbon atoms or aryl groups having 6 to 12 carbon atoms, R ⁷ and R ⁸ are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or carbon atoms. 6 to 12 aryl groups. The Ar group is an aryl group having 6 to 14 carbon atoms, and these aryl groups may have a substituent, and the substituent is the same as R ^{1 to} R ⁵ described above, and these substituents are A ring structure can be formed with an aryl group. Y ⁺ is a quaternary ammonio group represented by any one of the general formulas (2) to (5), Q is a nitrogen atom or a methine group (—CH—), t and u are 2 or 3, and w is An integer of 0 to 2, A is a hydrogen atom, a hydroxyl group or a halogen atom, R ^{12 to} R ¹⁴ are an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms. . ]

  Furthermore, this invention is a curable composition characterized by containing the said base generator and a base reactive compound.

  Furthermore, this invention is a hardening body obtained by hardening | curing the said curable composition.

The base generator of the present invention can generate amines (tertiary amines or amidines) with high catalytic activity efficiently by light irradiation or heating.
Moreover, since the base 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 base generator of the present invention is not basic before light irradiation or heating, the storage stability of the reactive composition is reduced even if it is contained in the reactive composition. Absent.
In addition, the base generator of the present invention is soluble in ethyl lactate, 2-methoxy-1-methylethyl acetate and the like, and can be used for a patterning member in which those solvents are essential.
In addition, according to the method for producing a cured product using the curable resin composition of the present invention, the above base generator is used for light irradiation or heating, so that an amine having high catalytic activity (tertiary amine or amidine) can be efficiently used. ) Can be generated, and a cured product can be produced efficiently.

  Hereinafter, embodiments of the present invention will be described in detail.

The base generator means a base (amine) that is decomposed by light irradiation or heating to generate a base (amine). The generated base can act as a catalyst for epoxy resin curing reaction, polyimide resin curing reaction, isocyanate and polyol urethanization reaction, acrylate crosslinking reaction, and the like.

In the general formula (1), among R ^{1 to} R ⁵ , the alkyl group having 1 to 18 carbon atoms (preferably 1 to 12 and 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, n-octadecyl, etc.), branched alkyl group (isopropyl, isobutyl, sec- Butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc., cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl) and bridges Cyclic alkyl groups (such as norbornyl, adamantyl and pinanyl) are included. 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 or the like may be used.

Among R ^{1 to} R ⁵ , the 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 Nyl and the like), cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl) and arylalkenyl groups (such as styryl and cinnamyl). 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. A substituted alkenyl group substituted with may be used.

Among R ^{1 to} R ⁵ , as the alkynyl group having 2 to 18 carbon atoms (preferably 2 to 12 and more preferably 2 to 8), 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) and arylalkynyl groups (phenylethynyl etc.) ) Is included. As the alkynyl group, in addition to the above, some 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, etc. A substituted alkynyl group substituted with may be used.

Among R ^{1 to} R ⁵ , the aryl group having 6 to 14 carbon atoms includes a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and Aromatic heterocyclic hydrocarbon groups {thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9- Oxoxanthenyl (a group derived from xanthone) and 9-oxothioxanthenyl (a group derived from thioxanthone) and the like} and benzophenolyl (a group derived from benzophenone). As the aryl group, in addition to the above, a part 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, and / or an alkylthio group having 1 to 18 carbon atoms, etc. A substituted aryl group substituted with may be used.

Among R ^{6 to} R ¹¹ , the alkyl group having 1 to 8 carbon atoms (preferably 1 to 4) includes an alkyl group having 1 to 8 carbon atoms among the above alkyl groups. 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 8 carbon atoms or the like may be used.

Among R ^{6 to} R ¹¹ , the aryl group having 6 to 12 carbon atoms includes an aryl group having 6 to 12 carbon atoms among the above aryl groups. As the aryl group, in addition to the above, a part 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, and / or an alkylthio group having 1 to 8 carbon atoms, etc. A substituted aryl group substituted with may be used.

Examples of the alkoxy group represented by —OR ⁶ include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and 2- Examples include methylbutoxy.
Examples of the amino group represented by —NR ⁷ R ⁸ include methylamino, ethylamino, propylamino, dimethylamino, diethylamino, methylethylamino, dipropylamino, dipropylamino and piperidino.
Examples of the acyl group represented by R ⁹ CO— include acetyl, propanoyl, butanoyl, pivaloyl and benzoyl.
Examples of the acyloxy group represented by R ¹⁰ COO— include acetoxy, butanoyloxy and benzoyloxy.
The alkylthio group or an arylthio group represented by -SR ^11, methylthio, ethylthio, butylthio, hexylthio, cyclohexylthio, benzylthio, phenylthio and 4-methylphenylthio, and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The aryl group having 6 to 14 carbon atoms of Ar includes the above aryl group. As the aryl group, in addition to the above, a part 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, and / or an alkylthio group having 1 to 8 carbon atoms, etc. A substituted aryl group substituted with may be used.

The quaternary ammonio group (Y ⁺ ) is eliminated as a corresponding amine by light irradiation and functions as various reaction catalysts. On the other hand, since the quaternary ammonio group (Y ⁺ ) has no basicity before light irradiation, the storage stability of the reactive composition is lowered even if it is contained in the reactive composition. Absent.

As the quaternary ammonio group represented by the general formula (4), 1-azabicyclo [2.2.2] octan-1-yl {group derived from quinuclidine, group represented by the chemical formula (12)} 3-hydroxy-1-azabicyclo [2.2.2] octan-1-yl {a group derived from 3-quinuclidinol, a group represented by the chemical formula (13)} and 1,4-diazabicyclo [2.2 .2] octan-1-yl {group represented by chemical formula (14)} and the like.

  Examples of the quaternary ammonio group represented by the general formula (5) include triethylammonio, tributylammonio, trioctylammonio, octyldimethylammonio and dodecyloctylmethylammonio.

  Among these ammonio groups, 1,8-diazabicyclo [5.4.0] -7-undecen-8-yl {group represented by the chemical formula (2)}, 1,5-diazabicyclo [4.3.0]. ] -5-nonen-5-yl {group represented by chemical formula (3)}, 1-azabicyclo [2.2.2] octan-1-yl {group represented by chemical formula (12)}, 3- Hydroxy-1-azabicyclo [2.2.2] octane-1-yl {group represented by the chemical formula (13)} and 1,4-diazabicyclo [2.2.2] octane-1-yl {chemical formula (14 A group represented by formula (2)}, and more preferably 1,8-diazabicyclo [5.4.0] -7-undecen-8-yl {a group represented by chemical formula (2)} and 1,5-diazabicyclo [5.4.0] -5-Nonen-5-yl {in the chemical formula (3) A is the group}.

In the general formula (1), R ^{1 to} R ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Ar is an aryl group having 6 to 14 carbon atoms. In addition, these aryl groups may have a substituent, and the substituent is the same as R ^{1 to} R ⁵ described above, and these substituents can take a ring structure with the aryl group.
Ar is more preferably a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, an anthraquinolyl group, an oxothioxanthenyl group or a benzophenolyl group, and particularly preferably a phenyl group, an anthracenyl group or an oxothixanthenyl group.
R ^{1 to} R ⁵ are more preferably a hydrogen atom.
In the general formula (1), the sulfonic acid that is an anionic component is preferably methanesulfonic acid.

Preferred examples of the cation structure of the base generator represented by the general formula (1) include those represented by the following chemical formulas (2-1) to (2-10).

The base generator of the present invention can be produced by a known method. For example, when the cation component is benzylammonium and the anion component is methanesulfonic acid, benzyl alcohol and methanesulfonyl chloride are reacted in an organic solvent using triethylamine as a base, as shown in the chemical reaction formula below. To obtain an intermediate. Next, the target base generator can be obtained by reacting with an amine corresponding to the quaternary ammonio group (Y ⁺ ) in an organic solvent.

  Examples of the amine include an amine {1,8-diazabicyclo [5,4,0] -undecene-7 (DBU)} represented by the chemical formula (15) and an amine {1,5-diazabicyclo [4] represented by the chemical formula (16). , 3,0] -Nonene-5 (DBN)}, an amine represented by chemical formula (17) {each symbol is the same as chemical formula (4). For example, 1-azabicyclo [2.2.2] octane, 3-hydroxy-1-azabicyclo [2.2.2] octane and 1,4-diazabicyclo [2.2.2] octane} and the chemical formula (18) Represented by the formula: {each symbol is the same as in chemical formula (5). For example, trialkylamines (such as triethylamine, tributylamine, trioctylamine, octyldimethylamine and dodecyloctylmethylamine), trialkenylamines (such as triallylamine) and triarylamines (triphenylamine, tri-p-tolylamine and diphenyl p) -Tolylamine etc.) etc.}.

  Organic solvents include cyclic ethers (such as tetrahydrofuran and dioxane), chlorinated solvents (such as chloroform and dichloromethane), alcohols (such as methanol, ethanol and isopropyl alcohol), ketones (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), and nitriles (acetonitrile). And polar organic solvents (such as dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone). These solvents may be used alone or in combination of two or more.

The reaction temperature (° C.) between benzyl alcohol and methanesulfonyl chloride is preferably −25 to 30 and more preferably −10 to 10.
It is preferable to dissolve benzyl alcohol and triethylamine in an organic solvent and add methanesulfonyl chloride thereto. The method of adding methanesulfonyl chloride may be added dropwise, or may be added dropwise after diluting with an organic solvent. The triethylamine hydrochloride produced by the reaction is a precipitate and may be separated and removed from the organic solvent phase by filtration, or may be removed by washing the reaction solution with water and separating the organic solvent phase.

The reaction temperature (° C.) between the intermediate and the amine corresponding to the quaternary ammonio group (Y ⁺ ) is preferably 10 to 100, more preferably 20 to 60.
It is preferable to dissolve the intermediate in an organic solvent and add the amine thereto. The amine may be added dropwise, or may be added dropwise after diluting with an organic solvent.
In addition, after obtaining the intermediate, the reaction with the amine may be continued, or the intermediate may be isolated and purified, and then dissolved again in the organic solvent and reacted with the amine. .

  The base generator obtained as described above may be purified after being separated from the organic solvent. Separation from the organic solvent can be carried out by adding a poor solvent directly to the organic solvent solution containing the base generator (or after concentration) to precipitate the base generator. Examples of the poor solvent used here include chain ethers (such as diethyl ether and dipropyl ether), esters (such as ethyl acetate and butyl acetate), aliphatic hydrocarbons (such as hexane and cyclohexane), and aromatic hydrocarbons (toluene and Xylene and the like).

  When the base generator is an oily substance, the precipitated oily substance is separated from the organic solvent solution, and the organic solvent contained in the oily substance is distilled off to obtain the base generator of the present invention. On the other hand, when the base generator is a solid, the precipitated solid is separated from the organic solvent solution, and the organic solvent contained in the solid is distilled off to obtain the base generator of the present invention.

  Purification can be performed by recrystallization (a method using a difference in solubility due to cooling, a method of adding a poor solvent to precipitate, and a combination thereof). Further, when the base generator is an oily substance (when it is not crystallized), it can be purified by a method of washing the oily substance with water or a poor solvent.

The base 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 or heated, but develops an action of a basic catalyst by being irradiated with light or heated). For example, it can be used as a curing catalyst for a photosensitive resin composition such as a photocurable resin composition, a thermosetting resin composition, etc., and is used for a photocurable resin composition that cures when irradiated with light of 350 to 500 nm. It is suitable as a curing catalyst or a curing catalyst for a thermosetting resin composition that is cured by heating.
For example, a basic resin whose curing is accelerated by a base and the base generator of the present invention, and, if necessary, a light or thermosetting resin composition containing a solvent and / or an additive can be easily constituted. Since such a light or thermosetting resin composition contains the base generator of the present invention, it is excellent not only in storage stability but also in curability. That is, a base is generated by irradiating or heating light having a wavelength of 350 to 500 nm to the light or thermosetting resin composition containing the base generator of the present invention, and the curing reaction is promoted to obtain a cured product. be able to. Therefore, the method for producing such a cured product preferably includes a step of generating a base by irradiating or heating light having a wavelength of 350 to 500 nm to the base generator of the present invention. In addition, you may heat as needed in the case of a photocuring reaction.
Further, the base generator of the present invention is soluble in ethyl lactate and 2-methoxy-1-methylethyl acetate, and can be used for a patterning member in which those solvents are essential.

The photosensitive resin composition and the thermosetting resin composition whose curing is accelerated by a base generated by light irradiation or heating is not limited as long as it is a curable resin curable by a base. For example, a curable urethane resin {(polyethylene ) Resin comprising isocyanate and curing agent (polyol, thiol, etc.)}, curable epoxy resin {resin comprising (poly) epoxide and curing agent (acid anhydride, carboxylic acid, (poly) epoxide, thiol, etc.) And resins composed of epichlorohydrin and carboxylic acid}, curable acrylic resins {acrylic monomers and / or acrylic oligomers and curing agents (such as thiols, malonic esters and acetylacetonates)}, polysiloxanes (cured and crosslinked poly Siloxane), a polyimide resin, and a resin described in Patent Document 3.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not intending to be limited to this. Unless otherwise specified, “%” means “% by weight”.

Example 1
8-Anthracenyl-1,8-diazabicyclo [5.4.0] -7-undecenium methanesulfonate: Synthesis of (1-1) (1) Synthesis of Intermediate 1 (8-anthracenylmethanesulfonate) In a 200 mL four-necked flask equipped with a dropping funnel, 17.0 g of anthracenyl alcohol (manufactured by Tokyo Chemical Industry) and 13.3 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 100 ml of dichloromethane. The reaction solution was cooled to 5 ° C. Thereafter, a solution prepared by dissolving 10.0 g of methanesulfonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in 10 ml of dichloromethane was dropped from the dropping funnel over 1 hour so that the reaction solution did not exceed 10 ° C. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and then the reaction solution was poured into 100 g of ice water to separate the organic layer. The organic layer was washed 3 times with 100 g of water, 3 times with 100 g of 10% hydrochloric acid solution, and further 3 times with 100 g of water, and then dichloromethane was distilled off to obtain 20.0 g of a yellow solid. Results of analysis by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 8.5 (s, 1H
), 8.1 (d, 2H), 8.0 (d, 2H), 7.5-7.4 (m, 4H), 5.6 (s, 2H), 3.0 (s, 3H) } This yellow solid was confirmed to be Intermediate 1.

(2) Synthesis of 8-anthracenyl-1,8-diazabicyclo [5.4.0] -7-undecenium methanesulfonate: (1-1) In a 100 mL eggplant flask, 20.0 g of (Intermediate 1) was dichloromethane. A solution in which 100 g was dissolved was added, and 8.5 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU, San Apro Co., Ltd.) was added dropwise (heated after the addition), and room temperature ( The mixture was stirred at about 25 ° C. for 2 hours, and dichloromethane was distilled off to obtain 28.0 g of a yellow viscous product. This yellow viscous product was subjected to solvent washing with 10 mL of tetrahydrofuran five times to obtain 25.0 g of the base generator (1-1) (yellow solid) of the present invention. Results of analysis by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 8.5 (s, 1H), 8.1 (d, 2H), 8.0 (d, 2H), 7.5- 7.4 (m, 4H), 5.6 (s, 2H), 3.8-3.5 (m, 6H), 3.0 (s, 3H), 2.8 (m, 2H), 2 2-2.1 (m, 2H), 1.8-1.5 (m, 6H)}, this yellow viscous product is 8-anthracenyl-1,8-diazabicyclo [5.4.0] -7. -Undecenium methanesulfonate: It was confirmed to be (1-1).

Example 2
8-Benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium methanesulfonate: Synthesis of (1-2) (1) Synthesis of intermediate 2 (benzylmethanesulfonate) A dropping funnel is attached. In a 200 mL four-necked flask, 8.6 g of benzyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) and 13.3 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) are dissolved in 100 ml of dichloromethane. Cooled to ° C. Thereafter, a solution prepared by dissolving 10.0 g of methanesulfonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in 10 ml of dichloromethane was dropped from the dropping funnel over 1 hour so that the reaction solution did not exceed 10 ° C. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and then the reaction solution was poured into 100 g of ice water to separate the organic layer. The organic layer was washed 3 times with 100 g of water, 3 times with 100 g of 10% hydrochloric acid solution, and further 3 times with 100 g of water, and then dichloromethane was distilled off to obtain 12.0 g of a yellow viscous product. Results of analysis by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 7.5-7.3 (m, 5H), 5.2 (s, 2H), 2.8 (s, 3H)} This yellow viscous product was confirmed to be Intermediate 2.

(2) Synthesis of 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium methanesulfonate: (1-2) In a 100 mL eggplant flask, 12.0 g of (Intermediate 2) was added to dichloromethane. A solution in which 100 g was dissolved was added, and 8.5 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU, San Apro Co., Ltd.) was added dropwise (heated after the addition), and room temperature ( The mixture was stirred at about 25 ° C. for 2 hours, and dichloromethane was distilled off to obtain 19.0 g of a yellow viscous product. The yellow viscous product was washed with 10 mL of tetrahydrofuran five times to obtain 16.0 g of the base generator (1-1) (yellow viscous product) of the present invention. Analysis results by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 7.3-7.2 (m, 3H), 7.0 (d, 2H), 4.7 (s, 2H), 3.6-3.5 (m, 6H), 2.8 (m, 2H), 2.6 (s, 3H), 2.1-2.0 (m, 2H), 1.7-1. 5 (m, 6H)}, this yellow viscous product was confirmed to be 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium methanesulfonate: (1-2). .

Comparative Example 1
The following base generator (H-1) described in Patent Document 6 (WO 2005-014696) was prepared.

Comparative Example 2
The following base generator (H-2) described in Patent Document 10 (JP 62-246925 A) was prepared.

<Evaluation of solubility in organic solvents>
The base generator (1-1) of Example 1, the base generator (1-2) of Example 2, the comparative base generator (H-1) of Comparative Example 1, and the comparative base generator (H of Comparative Example 2) -2) was visually observed and 3% by weight added to an organic solvent (methyl lactate, 2-methoxy-1-methylethyl acetate), and evaluated according to the following criteria.

(Criteria)
○: Uniform, transparent △: Slightly turbid ×: White turbidity or phase separation

  From the results in Table 1, the base generator of the present invention has high solubility in ethyl lactate and 2-methoxy-1-methylethyl acetate. When a base generator is used for the patterning member, the base generator of the present invention is preferred because of its high solubility in ethyl lactate, 2-methoxy-1-methylethyl acetate, and the like. On the other hand, the base generators of Comparative Examples 1 and 2 have low solubility and are difficult to use for patterning members.

(Photodegradability evaluation)
<Preparation of base generator-containing solution>
2.62 mg of the base generator (1-1) of Example 1 was dissolved in 0.75 g of chloroform to obtain a base generator-containing solution. The concentration was 7.0231 × 10 ⁻⁶ mol / g.
Moreover, 3.37 mg of the comparative base generator (H-1) of Comparative Example 1 was dissolved in 0.75 g of chloroform to obtain a comparative photobase generator-containing solution. The concentration was 7.0231 × 10 ⁻⁶ mol / g.

<Photodegradability evaluation>
The above-obtained base generator-containing solution of the present invention was filled in an NMR tube and exposed ( ² J / cm ² with an integrated light amount of 365 nm) with a belt conveyor type UV irradiation device (Eye Graphics Co., ECS-151U). . In addition, in order to control the exposure wavelength, a filter (I Graphics Co., Ltd., 365 filter) that transmits light having a wavelength of 300 to 450 nm was used.
Thereafter, 10 mg of dichloromethane was added as an internal standard, and ¹ H-NMR (300 MHz) analysis was performed, and it was confirmed that the base generator (1-1) of the present invention was decomposed {the —CH ₂ — adjacent to the base. Confirmed decrease in proton signal of 4.60 ppm (s, 2H)}.
As a result, the decomposition rate was 50.0%. In addition, the decomposition rate of the unexposed one was 0%. The decomposition rate was based on the following calculation formula.
Similarly, the comparative base generator-containing solution was also evaluated, and it was confirmed that the comparative base generator (H-1) was decomposed {the signal of proton of -CH _2- adjacent to the base 5.40 ppm (s 2H) decrease}.
As a result, the decomposition rate was 40.0%. In addition, the decomposition rate of the unexposed one was 0%.

The decomposition rate was obtained by the following calculation formula. In addition, the integral value used the value obtained on the basis of the dichloromethane which is an internal standard.
Decomposition rate (%) = [{(-CH 2 adjacent to the base of the unexposed solution _- integrated value of protons of) - (-CH 2 adjacent to the base of the exposure solutions _- integrated value of protons)} / (Not Integrated value of protons of —CH ₂ — adjacent to the base of the exposure solution)] × 100

  From the above results, it was confirmed that the base generator (1-1) of Example 1 was efficiently decomposed by light as compared with the base generator (H-1) of Comparative Example 1.

[Confirmation of base generation]
The BTB solution was added to the base generator-containing solution, and the presence or absence of base generation was confirmed. As a result, the exposed base generator-containing solution turned blue, confirming the generation of base. On the other hand, it was found that the unexposed solution was yellow and did not generate a base.
From this result, the base generator (1-1) of Example 1 and the base generator (H-1) of Comparative Example 1 are decomposed by light to generate a base.

[Evaluation of pot life characteristics in acid anhydride / epoxy resin curing system]
<Preparation of formulation liquid>
In a 100 ml wide-mouthed sample bottle, 100 parts of bisphenol A type liquid epoxy resin (JER828), 90 parts of methylhexahydrophthalic anhydride (HN5500) and 2 parts of the base generator (1-2) of Example 2 were uniformly mixed. .
Further, instead of 2 parts of the base generator (1-2), 3.2 parts of the base generator (H-2) of Comparative Example 2 was used, and the others were mixed uniformly in the same manner as described above.
The addition amount of the base generator was added so that the amine component was equal.

<Pot life characteristics evaluation>
The blended solution prepared above was placed in a constant temperature and humidity chamber at 40 ° C., and the time (pot life characteristics) for the initial viscosity to double was measured (Viscolite L-type viscometer).

From the results in Table 2, the base generator (1-2) of Example 2 has pot life characteristics equivalent to those of the base generator (H-2) of Comparative Example 2, and has a high one-part storage stability.

[Evaluation of curing characteristics with acid anhydride / epoxy resin curing system]
Each gel time (150 degreeC / test-tube method) was measured with the liquid mixture adjusted above.

From the results of Table 3, the base generator (1-2) of Example 2 has excellent curing characteristics as compared with the base generator (H-2) of Comparative Example 2.

  The base generator of the present invention is a patterning that utilizes a difference in solubility in a developer (such as a coding agent or a paint) that is cured by using a base generated by light irradiation or heating, or an exposed portion and an unexposed portion. It is suitably used for the manufacture of products or members (for example, electronic components, optical products, optical component forming materials, layer forming materials, or adhesives) formed through the above.

Claims (6)

A base generator represented by the general formula (1).

In Expression ^(1), R 1 ~R ⁵ represent 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, 6 to 14 carbon atoms Aryl group, nitro group, hydroxyl group, cyano group, alkoxy group represented by —OR ⁶ , amino group represented by —NR ⁷ R ⁸ , acyl group represented by R ⁹ CO—, represented by R ¹⁰ COO— acyloxy groups, an alkylthio group or an arylthio group represented by -SR ^11. The alkyl group, alkenyl group, alkynyl group and aryl group may have a substituent, and the substituent is the same as R ^{1 to} R ⁵ described above, and these substituents can have a ring structure. . R ⁶ , R ⁹ , R ¹⁰ and R ¹¹ are alkyl groups having 1 to 8 carbon atoms or aryl groups having 6 to 12 carbon atoms, R ⁷ and R ⁸ are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or carbon atoms. 6 to 12 aryl groups. The Ar group is an aryl group having 6 to 14 carbon atoms, and these aryl groups may have a substituent, and the substituent is the same as R ^{1 to} R ⁵ described above, and these substituents are A ring structure can be formed with an aryl group. Y ⁺ is a quaternary ammonio group represented by any one of the general formulas (2) to (5), Q is a nitrogen atom or a methine group (—CH—), t and u are 2 or 3, and w is An integer of 0 to 2, A is a hydrogen atom, a hydroxyl group or a halogen atom, R ^{12 to} R ¹⁴ are an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms. . ] R ^{1 to} R ⁵ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar is an aryl group having 6 to 14 carbon atoms, and these aryl groups may have a substituent. Is the same as R ^{1 to} R ⁵ described above, and these substituents can have a ring structure with an aryl group. The base generator according to claim 1 or 2, wherein Ar is any one of a phenyl group, an anthracenyl group, and an oxothioxanthenyl group, and R ^{1 to} R ⁵ are hydrogen atoms. Y ^<+> is General formula (2) or (3), The base generator in any one of Claims 1-3. A curable composition comprising the base generator according to any one of claims 1 to 4 and a base-reactive compound. A cured product obtained by curing the curable composition according to claim 5.