JP5662929B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition having excellent thick film curability. Photosensitive resin composition suitably used for paints, printing inks, coating agents, casting materials (for example, materials for MEMS), resist materials, nanoimprint materials, adhesives, sealing agents, or molding materials for optical members or building materials It is.

  In recent years, in the fields of paints, printing inks, coating agents, casting materials (for example, materials for MEMS), resist materials, nanoimprint materials, adhesives, sealants or molding materials, active rays such as electron beams, ultraviolet rays, and visible rays A photosensitive resin that is cured by irradiation with a glass has been studied. This is because it has characteristics that are not found in thermosetting resins, such as short-time curing and solvent-free.

  When paints, printing inks, resist materials, coating agents, and the like contain coloring materials such as dyes and pigments and fillers such as inorganic particles, there is a problem that actinic rays are attenuated and do not cure sufficiently to the depth. In addition, when a thick film is required for casting materials (e.g., MEMS materials), nanoimprint materials, adhesives, sealants, or molding materials, actinic rays do not reach the depths. There is a problem of not curing.

  In order to solve such problems, a cationic polymerizable adhesive that cures at a low temperature by generating an acid from a photoacid generator by ultraviolet irradiation has been proposed (for example, Patent Document 1). In comparison, the curing rate was slow, and the metal member was corroded. Further, although a radical polymerizable adhesive that promotes radical generation from a thermal radical polymerization initiator by generating a base from a photobase generator by ultraviolet irradiation and cures quickly at a low temperature has been proposed (for example, Patent Document 2). ), The photobase generator described above has a small absorption of 365 nm light, and is generally used for a wavelength of a high-pressure mercury lamp (i-line: 365 nm, h-line: 405 nm, g-line: 436 nm) which is a widely used light source. There is a problem that the sensitivity is insufficient. For example, in paints and printing inks, pigments (for example, titanium oxide) and binders with aromatic rings may be added to the photosensitive resin composition. However, binders with pigments and aromatic rings absorb the irradiation light. Therefore, for example, titanium oxide absorbs light of 380 nm or less, and an aromatic ring absorbs light near 365 nm. Therefore, a conventional photobase generator cannot generate a base.

JP 2000-169821 A JP 2007-45900 A

An object of the present invention is to provide a photosensitive resin composition that is efficiently exposed to light having a wavelength of 350 nm to 500 nm and is excellent in thick film curability and deep part curability.

The present inventors diligently studied to solve the above problem and arrived at the present invention. That is, the present invention relates to a compound represented by the general formula (1) or the general formula (2), which generates a base by irradiation with actinic rays (A), a thermal radical polymerization initiator (B), and A photosensitive resin composition comprising a radically polymerizable substance (C).

[In the formula, Ar has at least one benzene skeleton, halogen atom, alkoxy group having 1 to 20 carbon atoms, nitro group, carboxyl group, hydroxyl group, mercapto group, alkylthio group having 1 to 20 carbon atoms, carbon number 1 Substituted with a group selected from the group consisting of ˜20 alkylsilyl groups, C 1-20 acyl groups, amino groups, cyano groups, C 1-20 alkyl groups, phenyl groups, naphthyl groups, phenoxy groups, and phenylthio groups. An aromatic hydrocarbon group or a heterocyclic group which may be substituted; R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, an alkoxy group having 1 to 20 carbon atoms, Nitro group, carboxyl group, hydroxyl group, mercapto group, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino Group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, a phenyl group which may be substituted with a group selected from the group of phenoxy group and a phenylthio group, R ¹ and R ² are each ^{May be} bonded to form a ring structure; m is an integer of 2 to 4; R ^{3 to} R ⁵ are each independently a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, Substituted with a group selected from the group consisting of mercapto group, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, phenoxy group and phenylthio group Or an alkyl group having 1 to 20 carbon atoms, a phenyl group or a naphthyl group, and R ^{3 to} R ⁵ may be bonded to each other to form a ring structure; X ⁻ represents an anion. . ]

The photosensitive resin composition of the present invention exhibits an effect that it is efficiently exposed to light having a wavelength of 350 nm to 500 nm and is excellent in deep part curability.

BEST MODE FOR CARRYING OUT THE INVENTION

The photosensitive resin composition of the present invention contains a photobase generator (A), a thermal radical polymerization initiator (B), and a radical polymerizable substance (C).
The photobase generator (A) is a compound represented by the general formula (1) or the general formula (2), and Ar in the formula has at least one benzene skeleton, a halogen atom, a carbon number of 1 to 20 alkoxy groups, nitro groups, carboxyl groups, hydroxyl groups, mercapto groups, C1 - C20 alkylthio groups, C1-C20 alkylsilyl groups, C1-C20 acyl groups, amino groups, cyano groups, An aromatic hydrocarbon group or a heterocyclic group which may be substituted with a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, a phenoxy group and a phenylthio group.
Ar is preferably an aromatic hydrocarbon group or a heterocyclic group having 1 to 4 benzene ring skeletons. More preferable ones will be described later.
R ¹ and R ² in the formula are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, carbon C1-C20 alkylthio group, C1-C20 alkylsilyl group, C1-C20 acyl group, amino group, cyano group, C1-C20 alkyl group, phenyl group, naphthyl group, phenoxy group And a phenyl group which may be substituted with a group selected from the group of phenylthio groups, R ¹ and R ² may be bonded to each other to form a ring structure.
M in the formula is an integer of 2 to 4, preferably 2 or 4.
R ^{3 to} R ⁵ in the formula are each independently a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, a mercapto group, an alkylthio group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. A silyl group, an acyl group having 1 to 20 carbon atoms, an amino group, a cyano group, a phenoxy group, and a phenylthio group, which may be substituted with a group selected from the group selected from the group of phenylthio group, phenyl group or naphthyl group And R ^{3 to} R ⁵ may be bonded to each other to form a ring structure.
Among these, Preferably it is a C1-C10 alkyl group, Most preferably, it is a C1-C5 alkyl group.
X ⁻ in the formula represents an anion. Specifically, halide ion, hydroxide ion, carbonate ion, bicarbonate ion, aliphatic carboxy ion, aromatic carboxy ion (benzoate anion, phenylglyoxylate anion, etc.), aliphatic sulfoxy ion, Aromatic sulfoxy ions, halides of aliphatic sulfoxy ions, halides of aromatic sulfoxy ions, hexafluoroantimonate ions (SbF ₆ ⁻ ), phosphorus hexafluoride ions (PF ₆ ⁻ ) and borate anions (tetra Phenyl borate, butyltriphenyl borate anion, etc.). From the viewpoint of photodegradability, aliphatic carboxy ions, aromatic carboxy ions and borate anions are preferred.
By the actinic ray, the bond portion of carbon and nitrogen to which Ar, R ¹ and R ^{2 of the} photobase generator (A) are bonded is cleaved, which is represented by the general formula (6) or the general formula (7). A base is generated.

M in the general formula (6) is the same as m in the general formula (1), and preferable ones are also the same. Similarly, ^R 3 to R ⁵ in the general formula (7) are the same as ^R 3 to R ⁵ in the general formula (2), it is preferable also the same.

  A photobase generator (A) may be used independently and may use 2 or more types together.

In the photosensitive resin composition of the present invention, a base generated from the photobase generator (A) by irradiation with actinic rays (a tertiary amidine represented by the general formula (6) or a tertiary represented by the general formula (7) The amine) forms a redox initiator with the thermal radical polymerization initiator (B), so that decomposition of (B) proceeds rapidly. Radical generation from the redox initiator proceeds in a dark reaction, and as the base diffuses, photocuring is difficult with general photoradical initiators, where active light is attenuated or where it does not reach. Can be cured.

The general formula (6) will be described. The general formula (6) is a compound having an amidine skeleton, and m is an integer of 2 to 4. Particularly preferred are 1,8-diazabicyclo [5.4.0] -7-undecene in which m is 4, and 1,5-diazabicyclo [4.3.0] -5-nonene in which m is 2.

The general formula (7) will be described. The general formula (7) is a tertiary amine, particularly preferably triethylamine, tributylamine and 1-azabicyclo [2.2.2] octane.

As Ar in the general formula (1) or the general formula (2), an aromatic hydrocarbon group or a heterocyclic group having 1 to 4 benzene ring skeletons is preferable, and a general formula (3) is particularly preferable. A monovalent residue obtained by removing any one of R ^{6 to} R ¹⁵ from the compound represented by the formula: any one of R ^{16 to} R ²³ from the compound represented by the general formula (4) it is a monovalent residue and monovalent residue obtained by removing any one of the general formula (5) R ²⁴ ~R ³³ from the compounds represented by excluding.

The residue (Ar1) represented by the general formula (3) will be described. (Ar1) is a residue having an anthracene skeleton, and is an example of a residue having a maximum absorption wavelength in the vicinity of i-line (365 nm). The substituents R ^{6 to} R ¹⁵ are modified in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc., and include a hydrogen atom, a halogen atom, an alkoxy group (1 to 1 carbon atoms). 20), nitro group, carboxyl group, hydroxyl group, mercapto group, silyl group (1-20 carbon atoms), acyl group (1-20 carbon atoms), amino group, cyano group, alkyl group (1-20 carbon atoms), A functional group selected from the group consisting of a phenyl group and a naphthyl group is modified depending on the purpose.

Examples of the alkoxy group (having 1 to 20 carbon atoms) include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, pentyloxy group, iso-pentyloxy group, neo- A pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like can be mentioned.
Examples of the silyl group (having 1 to 20 carbon atoms) include a trialkylsilyl group such as a trimethylsilyl group and a triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

Examples of the acyl group (having 1 to 20 carbon atoms) include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.
Examples of the alkyl group (having 1 to 20 carbon atoms) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and iso-pentyl group. , Neo-pentyl group, hexyl group, heptyl group, octyl group and the like.
As the halogen atom, fluorine and chlorine are preferable.

Preferred examples of the substituent include a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, a phenyl group, and carbon. Examples thereof include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, and an acyl group having 1 to 15 carbon atoms. Particularly preferred are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. The alkyl moiety may be linear, branched or cyclic.

The residue (Ar2) represented by the general formula (4) will be described. (Ar2) is a residue having a thioxanthone skeleton, and is an example of a compound having a maximum absorption wavelength in the vicinity of i-line (365 nm). Examples of the substituents R ^{16 to} R ²³ include the same ones as the substituents R ^{6 to} R ¹⁵ of the above (Ar1), and preferable ones are also the same.

The residue (Ar3) represented by the general formula (5) will be described. (Ar3) is a residue having a benzophenone skeleton, and is an example of a residue having a maximum absorption wavelength near the i-line (365 nm). Examples of the substituents R ^{24 to} R ³³ are the same as those of the substituents R ^{6 to} R ^{15 of} (Ar1), and preferable ones are also the same.

Of these Ar, from the viewpoint of photodegradability, the residue (Ar1) and the residue (Ar2) are preferable.

Next, the thermal radical polymerization initiator (B) contained in the photosensitive resin composition of the present invention will be described. The thermal radical polymerization initiator (B) represents a compound that generates radicals by heat, unlike a photo radical initiator that generates radicals by irradiation with actinic rays such as electron beams, ultraviolet rays, and visible rays. It is preferable to use known compounds such as organic peroxides (hydroperoxides, dialkyl peroxides, diacyl peroxides, etc.) known from azo compounds and azo compounds. From the viewpoint of stability and reactivity, a thermal radical polymerization initiator having a 10-hour half-life temperature of 70 ° C. to 250 ° C. is more preferable. Specifically, the following (B1) and (B2) are mentioned. (B) may be used alone or in combination of two or more.

Examples of the thermal radical polymerization initiator (B1) having a 10-hour half-life temperature of 70 ° C. or higher and lower than 150 ° C. include the following.
(B11) Peroxide-based polymerization initiator: benzoyl peroxide (half-life temperature 74 ° C.), t-butyl peroxyacetate (half-life temperature 102 ° C.), 2,2-di- (t-butylperoxy) butane ( Half-life temperature 103 ° C), t-butyl peroxybenzoate (half-life temperature 104 ° C), n-butyl 4,4-di- (t-butylperoxy) valerate (half-life temperature 105 ° C), di- (2 -T-butylperoxyisopropyl) benzene (half-life temperature 119 ° C), dicumyl peroxide (half-life temperature 116 ° C), di-t-hexyl peroxide (half-life temperature 116 ° C), 2,5, -dimethyl -2,5, -di (t-butylperoxy) hexane (half-life temperature 118 ° C.), t-butylcumyl peroxide (half-life temperature 120 ° C.), di-t- Chill peroxide (half life temperature 124 ° C.), diisopropylbenzene hydroperoxide (half-life temperature 145 ° C.), p-menthane hydroperoxide (half-life temperature 128 ° C.) and the like.
(B12) Azo polymerization initiator: 1-[(1-cyano-1-methylethyl) azo] formamide (half-life temperature 104 ° C.), 2,2′-azobis (N-butyl-2-methylpropionamide) (Half-life temperature 110 ° C.), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) (half-life temperature 111 ° C.), 2,2′-azobis (2,4,4-trimethylpentane) ( Half-life temperature 110 ° C.) and the like.

Examples of the thermal radical polymerization initiator (B2) having a 10-hour half-life temperature of 150 ° C. or higher and 250 ° C. or lower include the following.
(B21) Peroxide-based polymerization initiator: 1,1,3,3-tetramethylbutyl hydroperoxide (half-life temperature 153 ° C.), cumene hydroperoxide (half-life temperature 158 ° C.), t-butyl hydroper Oxide (half-life temperature of 167 ° C.), t-butyltrimethylsilyl peroxide (half-life temperature of 176 ° C.) and the like.
(B22) Others: 2,3-dimethyl-2,3-diphenylbutane (half-life temperature 210 ° C.) and the like.

Next, the radically polymerizable substance (C) contained in the photosensitive resin composition of the present invention will be described. As (C), any known compound can be used as long as it is a compound that is polymerized by radicals, but an N-vinyl compound, a monofunctional (meth) acrylate monomer, a (meth) acryloyl group (hereinafter, Polyfunctional (meth) acrylate oligomers and maleimide compounds having two or more (meth) acryloyl groups) in the molecule are preferred, and (meth) acrylate monomers and polyfunctional (meth) acrylate oligomers are more preferred.

  Examples of the N-vinyl compound include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide and the like.

As the (meth) acrylate monomer, an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.]; alicyclic group-containing (meth) acrylate [dicyclopentanyl (meth) acrylate, sicyclopentenyl (meth) Acrylate and isobornyl (meth) acrylate, etc.], hydroxyalkyl (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc. ] And the like.

Polyfunctional (meth) acrylate oligomers include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and trimethylolpropane tri (meth) acrylate. , Polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, 2,2′-di (meth) a Leroy b carboxymethyl diethyl phosphate, a polyfunctional (meth) acrylate compounds such as 2- (meth) acryloyloxyethyl acid phosphate.

The maleimide compound contains at least two maleimide groups in the molecule. For example, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N, N′— p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4-biphenylene bismaleimide, N, N′-4,4- (3,3′-dimethyl-biphenylene) Bismaleimide, N, N′-4,4- (3,3′-dimethyldiphenylmethane) bismaleimide, N, N′-4,4- (3,3′-diethyldiphenylmethane) bismaleimide, N, N′- 4,4-diphenylmethane bismaleimide, N, N′-4,4-diphenylpropane bismaleimide, N, N′-4,4-diphenyl ether bismaleimide, N, N′-3,3 ′ Diphenylsulfone bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-4-8 (4-maleimidophenoxy) phenyl) propane, 1, 1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene-bis (1- (4maleimidophenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4 -Maleimidophenoxy) phenyl) hexafluoropropane etc. These can be used alone or in combination.
These can be used alone or in combination. If necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be appropriately used.

  The addition amount of the thermal radical polymerization initiator (B) is 0.05 to 30 parts with respect to 100 parts of the radical polymerizable substance (C) from the viewpoint of photocurability and storage stability, and preferably is 0.00. 1 to 20 parts. The addition amount of the photobase generator (A) is preferably 1 to 150 parts by weight, preferably 5 to 100 parts by weight with respect to 100 parts by weight of the thermal radical initiator (B), from the viewpoint of radical generation efficiency and physical properties of the cured product. Is more preferable.

If necessary, the photosensitive resin composition in the present invention may contain a solvent, a sensitizer, an adhesion-imparting agent (such as a silane coupling agent) and the like.

Solvents include glycol ethers (such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone), and esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether). Acetate and propylene glycol alkyl ether acetate), aromatic hydrocarbons (toluene, xylene and the like), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol and the like) and ethers (tetrahydrofuran and the like). These may be used alone or in combination. The solvent is preferably added so that the solid content concentration of the photosensitive resin composition is 1 to 100% by weight, more preferably 5 to 80% by weight, and particularly preferably 10 to 60% by weight.

Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The content of the sensitizer is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive resin composition.

Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea Examples thereof include propyltriethoxysilane, tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like. The content of the adhesion-imparting agent is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive resin composition.

In the photosensitive resin composition of the present invention, inorganic fine particles, pigments, dispersants, antifoaming agents, leveling agents, thixotropy imparting agents, slip agents, flame retardants, antistatic agents, oxidations are further selected according to the purpose of use. An inhibitor and an ultraviolet absorber may be added and contained.

Since the photosensitive resin composition of the present invention can be photocured by irradiation with an actinic ray of 350 to 500 nm, 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, and the like (UV・ Latest trends in EB curing technology, edited by Radtech Research Association, CM Publishing, 138 pages, 2006) can be used. Heating may be performed at the time of irradiation with actinic rays and / or for the purpose of diffusing the base generated from the photobase generator after irradiation. Although heating temperature changes with uses, it is 30 to 200 degreeC normally, Preferably it is 35 to 150 degreeC, More preferably, it is 40 to 120 degreeC.

The photosensitive resin composition of the present invention is hard to be photocured with a general photoradical initiator due to generation of radicals from a redox initiator, and cures at a portion where active light is attenuated or does not reach. Therefore, it can be used for paints, printing inks, coating agents, casting materials (for example, materials for MEMS), resist materials, nanoimprint materials, adhesives or sealants, or molding materials for optical members or building materials.

EXAMPLES Hereinafter, although an Example and a manufacture example demonstrate this invention concretely, this invention is not limited to these. Hereinafter, parts represent parts by weight.

[Production of photobase generator (A)]
<Production Example 1>
Synthesis of 1- (9-anthrylmethyl) -1-azabicyclo [2.2.2] octanium tetraphenylborate (A1-1)
In a 50 ml eggplant flask, 2.0 g of 9-chloromethylanthracene (Aldrich) was dissolved in chloroform, and 1.3 g of 1,8-diazabicyclo [5.4.0] -7-undecene was added in small portions ( A slight exotherm was observed after the addition.) The reaction solution was obtained by stirring at room temperature (about 25 ° C.) for 1 hour. The reaction solution was added dropwise to an aqueous solution consisting of 4.0 g of sodium tetraphenylborate salt and 40 g of water in a 100 ml eggplant flask, and the mixture was further stirred for 1 hour at room temperature (about 25 ° C.). And the organic layer was washed three times with water. The organic layer was concentrated with an evaporator to obtain 5.4 g of a white solid. This white solid was recrystallized from acetonitrile to obtain 4.7 g of a photobase generator (A1-1) (white solid). Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.8 (s, 1H), 8.3-8.1 (m, 4H), 7.8-7.5 ( m, 4H), 7.2-7.1 (m, 8H), 7.0-6.8 (m, 8H), 6.8-6.7 (m, 4H), 5.9 (s, 2H), 3.8-3.7 (m, 2H), 3.5-3.2 (m, 6H), 2.8 (m, 2H), 2.0-1.6 (m, 8H) } This white solid was confirmed to be 8- (9-anthrylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate (A1-1).

<Production Example 2>
Synthesis of 1- (9-anthryl) methyl-1-azabicyclo [2.2.2] octanium tetraphenylborate (A1-2)
Except that “1,8-diazabicyclo [5.4.0] -7-undecene 1.3 g” was changed to “1-azabicyclo [2.2.2] octane 1.0 g”, the same as in Production Example 1. Thus, 4.4 g of a photobase generator (A1-2) (white solid) was obtained. Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.9 (s, 1H), 8.7 (d, 2H), 8.2 (d, 2H), 7.7 (T, 2H), 7.6 (t, 2H), 7.3-7.1 (m, 8H), 7.0-6.9 (m, 8H), 6.9-6.8 (m 4H), 5.6 (s, 2H), 3.6-3.4 (m, 6H), 1.9 (m, 1H), 1.8-1.6 (m, 6H)}, this It was confirmed that the white solid was 9-anthrylmethyl-1-azabicyclo [2.2.2] octanium tetraphenylborate (A1-2).

<Production Example 3>
Synthesis of 5- (9-anthrylmethyl) -1,5-diazabicyclo [4.3.0] -5-nonenium tetraphenylborate (A1-3)
Manufactured except that “1-azabicyclo [2.2.2] octane 2.0 g” is changed to “1,5-diazabicyclo [4.3.0] -5-nonene (San Apro Co., Ltd.) 1.1 g”. In the same manner as in Example 1, 4.6 g of a photobase generator (A1-3) (white solid) was obtained. Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.8 (s, 1H), 8.3-8.1 (m, 4H), 7.8-7.5 ( m, 4H), 7.2-7.1 (m, 8H), 7.0-6.8 (m, 8H), 6.8-6.7 (m, 4H), 5.7 (s, 2H), 3.8-3.7 (t, 2H), 3.5 (t, 2H), 3.4-3.2 (m, 2H), 2.7 (m, 2H), 2.2 (M, 2H), 1.7 (m, 2H)}, this white solid is 5- (9-anthrylmethyl) -1,5-diazabicyclo [4.3.0] -5-nonenium tetraphenylborate It was confirmed that it was (A1-3).

<Production Example 4>
Synthesis of 8- (9-anthrylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium phenylglyoxylate (A1-4)
(1) Preparation of silver phenylglyoxylate 3.9 g of phenylglyoxylic acid (Aldrich) was dissolved in 20 g of methanol, and 0.9 g of sodium hydroxide (Wako Pure Chemical Industries, Ltd.) was added little by little (by neutralization). Exotherm was observed.) After stirring for 1 hour and adding 10.4 g of 1 mol / L silver nitrate aqueous solution (Wako Pure Chemical Industries, Ltd.), the precipitated gray solid was filtered off and washed with methanol. After drying, 4.4 g of silver phenylglyoxylate (gray solid) was obtained.

(2) Synthesis of 8- (9-anthrylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium phenylglyoxylate:
In a 50 ml eggplant flask, 2.0 g of 9-chloromethylanthracene (Aldrich) was dissolved in 40 g of methanol, and 1.3 g of 1,8-diazabicyclo [5.4.0] -7-undecene was added in small portions. (Slight exotherm was observed after the addition.) The reaction solution was obtained by stirring at room temperature (about 25 ° C.) for 1 hour. The reaction solution was added dropwise to a dispersion composed of 3.0 g of silver phenylglyoxylate and 20 g of methanol placed in a 100 ml eggplant flask, and further stirred for 1 hour at room temperature (about 25 ° C.). The filtrate removed by the above step was concentrated with an evaporator to obtain 4.5 g of a brown solid. This brown solid was recrystallized with ether / hexane to obtain 2.6 g of the photobase generator (A1-4) (yellow solid) of the present invention. Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.8 (s, 1H), 8.3 (d, 2H), 8.2 (d, 2H), 7.8 (D, 2H), 7.7 (t, 2H), 7.6 (t, 2H), 7.5 (d, 1H), 7.4 (t, 2H), 5.9 (s, 2H) 3.8-3.7 (m, 2H), 3.5-3.4 (m, 4H), 2.8-2.7 (m, 2H), 2.0-1.6 (m, 8H)}, this yellow solid was confirmed to be 8- (9-anthrylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium phenylglyoxylate (A1-4). did.

<Production Example 5>
Synthesis of N- (9-anthrylmethyl) -N, N, N-trioctylammonium tetraphenylborate (A1-5)
Photobase generation in the same manner as in Production Example 1, except that “1-azabicyclo [2.2.2] octane 1.0 g” was changed to “trioctylamine (Wako Pure Chemical Industries, Ltd.) 3.1 g”. 6.2 g of agent (A1-5) (white solid) was obtained. Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.9 (s, 1H), 8.7 (d, 2H), 8.2 (d, 2H), 7.7 (T, 2H), 7.6 (t, 2H), 7.2-7.0 (m, 8H), 7.0-6.9 (m, 8H), 6.9-6.8 (m 4H), 5.8 (s, 2H), 3.4-3.2 (m, 6H), 1.9-1.6 (m, 6H), 1.4-1.2 (m, 30H) ), 1.0-0.8 (t, 9H)}, this white solid is N- (9-anthrylmethyl) -N, N, N-trioctylammonium tetraphenylborate (A1-5) It was confirmed.

<Production Example 6>
Synthesis of 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate (A2-1)
(1) Synthesis of methylthioxanthone (intermediate 10) 139 g of sulfuric acid was charged into an Erlenmeyer flask, 10 g of dithiosalicylic acid (Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at room temperature (about 25 ° C.) for 1 hour. Cooling in an ice bath gave a cooled solution. Next, 25 g of toluene was dropped little by little while keeping the liquid temperature of this cooling solution at 20 ° C. or lower, and then dropped to room temperature (about 25 ° C.), and further stirred for 2 hours to obtain a reaction solution. The reaction solution was added little by little while stirring 815 g of water placed in a beaker, and the precipitated yellow solid was filtered off. This yellow solid was dissolved in 260 g of dichloromethane, 150 g of water was added, and further 6.7 g of a 24% KOH aqueous solution was added to make the aqueous layer alkaline. After stirring for 1 hour, the aqueous layer was removed by a liquid separation operation, The organic layer was washed 3 times with 130 g of water. The organic layer was then dried over anhydrous sodium sulfate, and then the solvent (dichloromethane) was distilled off to obtain 8.7 g of intermediate (10) (yellow solid). Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.4 (d, 1H), 8.2 (s, 1H), 7.8-7.7 (m, 2H) 7.7-7.5 (m, 3H), 2.4 (s, 3H)}, this intermediate (10) is a mixture of 2-methylthioxanthone and 3-methylthioxanthone (molar ratio 2: 1) It was confirmed that.

(2) Synthesis of 2-bromomethylthioxanthone (intermediate 11) 2.1 g of intermediate (10) (methylthioxanthone mixture) was dissolved in 120 ml of cyclohexane, and N-bromosuccinimide (Wako Pure Chemical Industries, Ltd.) 8 .3 g and 0.1 g of benzoyl peroxide (Wako Pure Chemical Industries, Ltd.) were added and reacted for 4 hours under reflux (3-methylthioxanthone did not react), and then the solvent (cyclohexane) was distilled off. The residue was redissolved by adding 50 ml of chloroform to obtain a chloroform solution. The chloroform solution was washed 3 times with 30 g of water, and the aqueous layer was removed by a liquid separation operation. Then, the solvent (chloroform) was distilled off to obtain 1.7 g of a brown solid. This was recrystallized using ethyl acetate to obtain 1.5 g of intermediate (11) (yellow solid). Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.6 (s, 2H), 7.8-7.5 (m, 5H), 4.6 (s, 2H) } This intermediate (11) was confirmed to be 2-bromomethylthioxanthone.

(3) Synthesis of 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide (Intermediate 12) Intermediate ( 11) 1.0 g of (2-bromomethylthioxanthone) was dissolved in 85 g of dichloromethane, and 0.5 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU, San Apro Co., Ltd.) was added dropwise thereto. Then (heated after dropping), the mixture was stirred at room temperature (about 25 ° C.) for 1 hour, and dichloromethane was distilled off to obtain 2.2 g of a white solid. This white solid was dissolved in tetrahydrofuran / dichloromethane and recrystallized to obtain 1.2 g of intermediate (12) (white solid). Results of analysis by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 8.6 (d, 1H), 8.3 (d, 1H), 7.8 (d, 1H), 7.8- 7.6 (m, 3H), 7.5 (t, 1H), 5.1 (s, 2H), 3.9-3.8 (m, 6H), 3.0 (m, 2H), 2 4-2.2 (m, 2H), 2.0-1.7 (m, 6H)}, this intermediate (12) is 8- (9-oxo-9H-thioxanthen-2-yl) methyl It was confirmed to be -1,8-diazabicyclo [5.4.0] -7-undecenium bromide.

(4) Synthesis of 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate Sodium tetraphenylborate salt ( (Nacalai Tesque Co., Ltd.) Intermediate (12) (8- (9-oxo-9H-thioxanthen-2-yl) methyl-1) previously dissolved in 50 g of chloroform in an aqueous solution in which 0.8 g of water was dissolved in 17 g of water , 8-diazabicyclo [5.4.0] -7-undecenium bromide) 1.0 g dropwise, and then stirred for 1 hour at room temperature (about 25 ° C.), and the aqueous layer was removed by a liquid separation operation. The organic layer was washed 3 times with 30 g of water. The organic layer was concentrated with an evaporator to obtain a yellow solid. This yellow solid was recrystallized from acetonitrile / ether to obtain 1.3 g of a photobase generator (A1-6) (slightly yellow powder). Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.5 (d, 1H), 8.4 (s, 1H), 8.0-7.6 (m, 5H) 7.2-7.1 (m, 8H), 7.0-6.8 (m, 8H), 6.8-6.7 (m, 4H), 5.1 (s, 2H), 3 .8-3.7 (m, 2H), 3.7-3.5 (m, 4H), 3.0-2.9 (m, 2H), 2.1-2.0 (m, 2H) 1.8-1.5 (m, 6H)}, this pale yellow powder was 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,8-diazabicyclo [5.4.0]. It was confirmed that it was -7-undecenium tetraphenylborate (A2-1).

<Production Example 7>
Synthesis of 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate (A3-1)
(1) Synthesis of 4-bromomethylbenzophenone (intermediate 20) In a 200 mL flask equipped with a reflux condenser, 25.1 g of 4-methylbenzophenone (Aldrich), 22.8 g of N-bromosuccinimide (Wako Pure Chemical Industries, Ltd.) Benzoyl peroxide (containing 20% water, Wako Pure Chemical Industries, Ltd.) 0.54 g and acetonitrile 80 g were added, heated to 80 ° C., reacted for 2 hours under reflux, cooled, and then the solvent was distilled off to give 160 g of methanol. To give 26 g of intermediate (20) (white crystals). Results of analysis by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 7.9-7.7 (m, 4H), 7.6 (t, 1H), 7.55-7.4 (m 4H), 4.5 (s, 2H)} and this intermediate (H10) was confirmed to be 4-bromomethylphenylbenzophenone.

(2) Synthesis of 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide (intermediate 21) 25.8 g of intermediate (20) was added to 100 g of acetonitrile. 14.6 g of 1,8-diazabicyclo [5.4.0] -7-undecene (San Apro Co., Ltd.) was added dropwise to the solution (heated after the addition), and at room temperature (about 25 ° C.), The mixture was stirred for 18 hours, and acetonitrile was distilled off to obtain a brown solid. This brown solid was dissolved in acetonitrile and recrystallized to obtain 28.2 g of intermediate (21) (white solid). Results of analysis by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 7.9-7.7 (d, 4H), 7.6-7.3 (m, 5H), 5.0 (s 2H), 3.9-3.6 (m, 6H), 3.0-2.9 (m, 2H), 2.3-2.2 (m, 2H), 1.9-1.7 (M, 6H)} and this intermediate (H11) was confirmed to be 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide.

(3) Synthesis of 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate Sodium tetraphenylborate salt (Nacalai Tesque, Inc.) 0.8 g Intermediate (21) (8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undece) previously dissolved in 50 g of chloroform in an aqueous solution in which 17 g of water was dissolved. 6.8 g of (nium bromide) was added dropwise little by little, and then stirred at room temperature (about 25 ° C.) for 2 hours to obtain a reaction solution. The reaction solution was filtered, and the yellow oil obtained by concentrating the filtrate was dissolved in acetonitrile and recrystallized to obtain 7.6 g of a photobase generator (A3-1) (white solid). Results of analysis by ¹ H-NMR {300 MHz, CDCl ₃ , δ (ppm): 7.8-7.7 (d, 4H), 7.6 (t, 1H), 7.5-7.3 (m 10H), 7.1-6.8 (m, 14H), 4.8 (s, 2H), 3.9-3.8 (m, 2H), 3.7-3.5 (m, 4H) ), 2.0 (m, 2H), 1.5-1.1 (m, 8H)}, this white solid is 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0]. It was confirmed that it was -7-undecenium tetraphenylborate (A3-1).

<Production Example 8>
{Synthesis of 8- (2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate (A4-1)}

(1) Synthesis of 8- (2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium bromide [intermediate (30)]:
“2-Bromomethylnaphthalene [manufactured by Tokyo Chemical Industry Co., Ltd.] 1.1 g” was dissolved in 100 g of acetonitrile, and 1,8-diazabicyclo [5.4.0] -7-undecene [manufactured by San Apro Co., Ltd.] DBU ”] was added dropwise (heated after the addition), and the mixture was stirred at room temperature (about 25 ° C.) for 18 hours, and acetonitrile was distilled off to obtain a white powder. This white powder was dissolved in acetonitrile and recrystallized to obtain 1.3 g of intermediate (30) (white powder). Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.0-7.4 (m, 7H), 5.0 (s, 2H), 3.7-3.2 ( m, 6H), 3.0-2.9 (m, 2H), 2.1 (m, 2H), 1.7-1.5 (m, 8H)}, this intermediate (30) is 8- It was confirmed that it was (9-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium bromide.

(2) Synthesis of 8- (2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate (A4-1):
Intermediate (30) {8- (9-naphthalylmethyl) -1, previously dissolved in 50 g of chloroform in an aqueous solution prepared by dissolving 0.8 g of sodium tetraphenylborate salt [manufactured by Nacalai Tesque Co., Ltd.] with 17 g of water, 0.8 g of 8-diazabicyclo [5.4.0] -7-undecenium bromide} was added dropwise little by little, and then stirred at room temperature (about 25 ° C.) for 2 hours to obtain a reaction solution. The reaction solution was filtered, and the yellow oil obtained by concentrating the filtrate was dissolved in acetonitrile and recrystallized to obtain 1.3 g of a photobase generator photobase generator (A4-1) (slightly yellow powder). . Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.0-7.4 (m, 7H), 7.2-7.1 (m, 8H), 7.0- 6.8 (m, 8H), 6.8-6.7 (m, 4H), 5.1 (s, 2H), 3.8-3.3 (m, 6H), 2.9-2. 8 (m, 2H), 1.9-1.5 (m, 8H)}, this slightly yellow powder is 8- (2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7. -It was confirmed to be undecenium tetraphenylborate.

<Production Example 9>
{Synthesis of 8- (t-butyl-2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate (A4-2)}

(1) Synthesis of t-butyl-2-methylnaphthalene [intermediate (31)]:
To a 200 mL flask, 7.1 g of 2-methylnaphthalene [manufactured by Wako Pure Chemical Industries, Ltd.] and 4.8 g of t-butyl chloride [manufactured by Wako Pure Chemical Industries, Ltd.] are added, and aluminum chloride [manufactured by Wako Pure Chemical Industries, Ltd.] 0 .2 g was added dropwise little by little, and then stirred at room temperature (about 25 ° C.) for 2 hours to obtain a reaction solution. 100 ml of dichloroethane was added to the reaction solution, and the organic layer was washed 3 times with water. The organic layer was concentrated with an evaporator to obtain 9.7 g of a brown oil. Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.0-7.4 (m, 6H), 2.6 (s, 2H), 1.4 (s, 9H) } This brown oil was confirmed to be t-butyl-2-methylnaphthalene.

(2) Synthesis of t-butyl-2-bromomethylnaphthalene [intermediate (32)]:
In a 200 mL flask equipped with a reflux condenser, 9.7 g of intermediate (31) {t-butyl-2-methylnaphthalene}, 9.6 g of N-bromosuccinimide [Wako Pure Chemical Industries, Ltd.], benzoyl peroxide [20% Water content: Wako Pure Chemical Industries, Ltd.] 4.8 g and chlorobenzene 100 ml were added, heated to 70 ° C. and reacted for 6 hours under reflux to obtain a reaction solution. 50 ml of dichloroethane was added to the reaction solution, and the organic layer was washed 3 times with water. This organic layer was concentrated with an evaporator to obtain 10.1 g of a white solid. Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.0-7.4 (m, 6H), 4.5 (s, 2H), 1.4 (s, 9H) } This brown oil was confirmed to be t-butyl-2-bromomethylnaphthalene.

(3) Synthesis of 8- (t-butyl-2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium bromide [intermediate (33)]
Intermediate (33) (white) in the same manner as in Production Example 8 (1) except that “2-bromomethylnaphthalene [manufactured by Tokyo Chemical Industry Co., Ltd.] 1.1 g” was changed to 2.5 g of intermediate (32). 2.6 g of powder) was obtained. Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.0-7.4 (m, 6H), 5.0 (s, 2H), 3.7-3.2 ( m, 6H), 3.0-2.9 (m, 2H), 2.1 (m, 2H), 1.7-1.5 (m, 8H), 1.4 (s, 9H)}, This intermediate (33) was confirmed to be 8- (t-butyl-9-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium bromide.

(4) Synthesis of 8- (t-butyl-2-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate (A4-2):
"Intermediate (30) {8- (9-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium bromide} 0.8 g" intermediate (33) 1.1 g Except having changed into, it carried out similarly to manufacture example 8 (2), and obtained 1.6 g of photobase generators (A4-2) (slightly yellow powder). Results of analysis by ¹ H-NMR {300 MHz, DMSO-d6, δ (ppm): 8.0-7.4 (m, 6H), 7.2-7.1 (m, 8H), 7.0- 6.8 (m, 8H), 6.8-6.7 (m, 4H), 5.1 (s, 2H), 3.8-3.3 (m, 6H), 2.9-2. 8 (m, 2H), 1.9-1.5 (m, 8H), 1.4 (s, 9H)}, this slightly yellow powder is 8- (2-naphthalylmethyl) -1,8-diazabicyclo. [5.4.0] -7-Undecenium tetraphenylborate was confirmed.

[Production of photobase generator used in comparative example]
<Comparative Production Example 1>
As a photobase generator, {[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine (abbreviated as DNCDP) is described in Non-Patent Document 1 (Macromolecules A. Mochizuki, Vol. 28, No. 1, 1995), and recrystallized with n-pentane and benzene to obtain a photobase generator (H-1). The obtained DNCDP had a yield of 65% and a melting point of 132.8 ° C., and the elemental analysis results were C; 58.12, H; 6.90, N; 7.94, O; . DNCDP is a compound that generates a secondary amine when irradiated with actinic rays.

<Comparative Production Example 2>
A quaternary ammonium salt as a photobase generator was synthesized in the same manner as in the production example of Patent Document 2. That is, p-nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g), and N, N-dimethylbenzylamine (1.10 g, 8.8) dissolved in acetone (5 g) was dissolved therein. 2 mmol) was slowly added, and then stirred at room temperature for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain white crystals (yield 1.59 g).
The above-mentioned white crystal (1.00 g, 2.65 mmol as ammonium bromide salt) was dissolved in a methanol / water (15 g / 15 g) solution, and sodium tetraphenylborate dissolved in water (5.0 g) ( 0.94 g, 2.65 mmol) solution was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired quaternary ammonium salt (H-2) (yield 1.22 g).

[Production of photosensitive resin composition]
Examples 1-7
Photobase generators (A1-1) to (A1-5), (A2-1), 3 parts (A3-1), dipentaerythritol pentaacrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), 100 parts, oxidation After mixing 40 parts of titanium (made by Ishihara Sangyo, Type A-200) and 0.5 part of a pigment dispersant (Bic Chemie, Disperyk-111) to obtain a pigment dispersion, benzoyl peroxide (manufactured by NOF Corporation, 3 parts of Niper BW) were mixed to produce photosensitive resin compositions Q-1 to Q-7.

Examples 8-9
Photobase generator (A4-1), 3 parts of (A4-2), 1 part of diethylthioxanthone (Wako Pure Chemical Industries, Ltd., 2,4-diethyl-9H-thioxanthen-9-one), dipentaerythritol penta Mix 100 parts of acrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), 40 parts of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Tyco A-200), 0.5 part of pigment dispersant (manufactured by Big Chemie, Disperryk-111), After obtaining the pigment dispersion, 3 parts of benzoyl peroxide (manufactured by NOF Corporation, Nyper BW) was mixed to prepare photosensitive resin compositions Q-8 to Q-9.

[Production of comparative photosensitive resin composition]
Comparative Examples 1-3
Comparative photobase generators (H-1) to (H-2) 3 parts, dipentaerythritol pentaacrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), titanium oxide (Ishihara Sangyo, Tyco A-200) 40 parts of pigment dispersant (Bic Chemie, Disperyk-111) 0.5 part was mixed to obtain a pigment dispersion, and then mixed with 3 parts of benzoyl peroxide (manufactured by NOF Corporation, Nyper BW) for photosensitivity. Resin compositions Q′-1 to Q′-2 were produced.
100 parts of dipentaerythritol pentaacrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), 40 parts of titanium oxide (manufactured by Ishihara Sangyo, Type A-200), 0.5 part of pigment dispersant (manufactured by Big Chemie, Disperyk-111) Were mixed to obtain a pigment dispersion, and then 3 parts of benzoyl peroxide (manufactured by NOF Corporation, Nyper BW) was mixed to produce a photosensitive resin composition Q′-3.

Comparative Examples 4-6
Comparative photobase generators (H-1) to (H-2) 3 parts, diethylthioxanthone (Wako Pure Chemical Industries, Ltd., 2,4-diethyl-9H-thioxanthen-9-one) 1 part, dipentaerythritol 100 parts of pentaacrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), 40 parts of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Type A-200), 0.5 part of pigment dispersant (manufactured by Big Chemie, Disperyk-111) are mixed. After obtaining the pigment dispersion, 3 parts of benzoyl peroxide (manufactured by NOF Corporation, NIPPER BW) was mixed to prepare photosensitive resin compositions Q′-4 to Q′-5.
1 part of diethylthioxanthone (Wako Pure Chemical Industries, Ltd., 2,4-diethyl-9H-thioxanthen-9-one), 100 parts of dipentaerythritol pentaacrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), titanium oxide ( Ishihara Sangyo, Type A-200 (40 parts) and a pigment dispersant (Big Chemie, Disperyk-111) 0.5 part were mixed to obtain a pigment dispersion, and then benzoyl peroxide (Nissan, Nyper BW). ) 3 parts were mixed to produce a photosensitive resin composition Q′-6.

[Measurement of molar extinction coefficient of photobase generator]
For the photobase generators (A1-1) to (A4-2) and (H-1) to (H-2) used in the photosensitive resin compositions of Examples and Comparative Examples, the molar extinction coefficient ε (365 nm, 405 nm). It was found that the photobase generators (A1-1) to (A3-1) efficiently absorb light with wavelengths of 365 nm and 405 nm. On the other hand, the photobase generators used in the photobase generators (A4-1) to (A4-2) and the photosensitive resin compositions of the comparative examples were barely absorbed at 365 nm. The results are shown in Table 1.

Measurement method About 50 mg of a measurement sample (photobase generator) was precisely weighed into a 50 mL volumetric flask, about 20 g of acetonitrile was added and dissolved, and then acetonitrile was added to match the marked line. 1 mL of this solution was taken into a 20 mL volumetric flask with a measuring pipette, and acetonitrile was added to the marked line for dilution to obtain an acetonitrile solution having a predetermined concentration.
This solution was put in a quartz cell (optical path length 1 cm), and an absorption spectrum in a wavelength range of 200 to 500 nm was measured with a spectrophotometer (Shimadzu Corporation, UV-2550). From the absorbance obtained from the spectrum, the molar extinction coefficient was calculated by the following equation.

Molar extinction coefficient (ε) = (absorbance) / molar concentration (mol / L)

[Evaluation of thick film curability]
Using an applicator, each photosensitive resin composition obtained in the examples and comparative examples was applied to a PET steel plate obtained by thermocompression bonding of a 12 μm thick homo-PET (polyethylene terephthalate) sheet to a 0.20 mm thick tin-free steel plate. The film thickness was changed and applied, photocured under the following irradiation conditions, the pencil hardness (JIS K5400 (1990)) of the coating film was measured, and the film thickness at which the pencil hardness could be maintained at 2H or higher was measured. The results are shown in Table 1.

Irradiation condition With a belt conveyor type UV irradiation device (I Graphics, ECS-151U), a filter (I Graphics, 365 filter) that transmits light with a wavelength of 300 to 450 nm is used to control the exposure wavelength. Used for exposure. Exposure was about 12 J / cm ² as approximately 0.6 J ^/ cm 2, 405 nm as 365 nm.

From Table 1, the photosensitive resin compositions Q-1 to Q-9 of the present invention have good film thicknesses of 50 μm or more that maintain a pencil hardness of 2H or more, and the photosensitive resin composition Q ′ of the comparative example. -1 to Q′-6 were found to have a film thickness of 25 μm or less maintaining a pencil hardness of 2H or more. In order to maintain the pencil hardness of 2H or more, the coating film needs to be deeply cured to the surface of the PET steel plate.

As can be seen from this example, it can be seen that a photosensitive resin composition having excellent thick film curability can be obtained by using the photosensitive resin composition of the present invention. Paints, printing inks, coating agents, resist materials, etc. containing fillers such as coloring materials such as dyes and pigments and inorganic particles that attenuate actinic light and do not cure sufficiently to the deep part. It is particularly useful for adhesives, casting materials (for example, materials for MEMS), nanoimprint materials, sealing agents, or molding materials that need to be cured with a thick film that does not reach and do not fully cure deep.

The photosensitive resin composition of the present invention is a paint, printing ink, coating agent, casting material (for example, a material for MEMS), resist material, nanoimprint material, adhesive or sealing agent, in which thick film curability and deep curability are useful. Or it is used suitably for the molding material of an optical member or a building material.

Claims (8)

A compound represented by the general formula (1) or the general formula (2), which generates a base upon irradiation with actinic rays (A), a thermal radical polymerization initiator (B), and a radical polymerizable substance ( A photosensitive resin composition comprising C).

[In the formula, Ar has at least one benzene skeleton, halogen atom, alkoxy group having 1 to 20 carbon atoms, nitro group, carboxyl group, hydroxyl group, mercapto group, alkylthio group having 1 to 20 carbon atoms, carbon number 1 Substituted with a group selected from the group consisting of ˜20 alkylsilyl groups, C 1-20 acyl groups, amino groups, cyano groups, C 1-20 alkyl groups, phenyl groups, naphthyl groups, phenoxy groups, and phenylthio groups. An aromatic hydrocarbon group or a heterocyclic group which may be substituted; R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, an alkoxy group having 1 to 20 carbon atoms, Nitro group, carboxyl group, hydroxyl group, mercapto group, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino Group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, a phenyl group which may be substituted with a group selected from the group of phenoxy group and a phenylthio group, R ¹ and R ² are each ^{May be} bonded to form a ring structure; m is an integer of 2 to 4; R ^{3 to} R ⁵ are each independently a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, Substituted with a group selected from the group consisting of mercapto group, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, phenoxy group and phenylthio group Or an alkyl group having 1 to 20 carbon atoms, a phenyl group or a naphthyl group, and R ^{3 to} R ⁵ may be bonded to each other to form a ring structure; X ⁻ represents an anion. . ] The photosensitive resin composition according to claim 1, wherein Ar in the general formula (1) or the general formula (2) has 1 to 4 benzene ring skeletons. Ar in General Formula (1) or General Formula (2) is a monovalent residue obtained by removing any one of R ^{6 to} R ¹⁵ from the compound represented by General Formula (3), General Formula ( 4) a monovalent residue obtained by removing any one of R ^{16 to} R ²³ from the compound represented by 4), or any one of R ^{24 to} R ³³ from the compound represented by the general formula (5) The photosensitive resin composition according to claim 1, which is a monovalent residue excluding one.

[In the formula, substituents R ^{6 to} R ¹⁵ are a hydrogen atom, a halogen atom, an alkoxy group (1 to 20 carbon atoms), a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, a silyl group (1 to 20 carbon atoms), an acyl. It is a group selected from the group consisting of a group (C1-20), amino group, cyano group, alkyl group (C1-20), phenyl group and naphthyl group. ]

[In the formula, substituents R ^{16 to} R ²³ are a hydrogen atom, a halogen atom, an alkoxy group (1 to 20 carbon atoms), a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, a silyl group (1 to 20 carbon atoms), an acyl. It is a group selected from the group consisting of a group (C1-20), amino group, cyano group, alkyl group (C1-20), phenyl group and naphthyl group. ]

[In the formula, substituents R ^{24 to} R ³³ are a hydrogen atom, a halogen atom, an alkoxy group (1 to 20 carbon atoms), a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, a silyl group (1 to 20 carbon atoms), an acyl. It is a group selected from the group consisting of a group (having 1 to 20 carbon atoms), an amino group, a cyano group, an alkyl group (having 1 to 20 carbon atoms), a phenyl group and a naphthyl group. ] In the general formula (1), m is 2 or 4, The photosensitive resin composition in any one of Claims 1-3.   The photosensitive resin composition according to claim 1, wherein the thermal radical polymerization initiator (B) is an organic peroxide and / or an azo compound. The photosensitive resin composition according to claim 1, wherein the radical polymerizable substance (C) is an N-vinyl compound, a monofunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate oligomer, or a maleimide compound. object. Further, selected from the group consisting of inorganic fine particles, pigments, dispersants, antifoaming agents, leveling agents, adhesion promoters, thixotropic agents, slip agents, flame retardants, antistatic agents, antioxidants and UV absorbers. The photosensitive resin composition according to any one of claims 1 to 6, which contains at least one additive (D). The photosensitive property according to any one of claims 1 to 7, which is used as a paint, a printing ink, a coating agent, a casting material, a resist material, a nanoimprint material, an adhesive, a sealing agent, or a molding material for an optical member or a building material. Resin composition.