JP6974045B2 - Photosensitive composition - Google Patents

Description

The present invention relates to a photosensitive composition that is exposed to and cured by light rays in the visible to infrared region. More specifically, it is a photosensitive composition that is cured by irradiating it with light rays in the visible to infrared region, and is used, for example, in coating agents, paints, lithographic printing plates, and the like. Further, in the present invention, a product or member (for example, an electronic component, an optical product, a material for forming an optical component, a layer forming material or an adhesive) formed through patterning utilizing the difference in solubility of an exposed portion and an unexposed portion in a developing solution is used. The present invention relates to a photosensitive composition suitably used for the production of (agents, etc.).

The range of application of UV curing technology, which cures a liquid substance by irradiation with ultraviolet rays (UV), is expanding from the viewpoint of workability (fast curing) and low VOC, such as coating agents, paints, and printing inks.
Generally, the photosensitive composition comprises a photopolymerization initiator and a sensitizer, a radical (or cationic) polymerizable monomer, an oligomer or a polymer, and a colorant and an additive depending on the application. Colorants are roughly classified into pigments and dyes, and are blended to color the coating film, but they not only block light but also have light absorption characteristics according to the color and part of the light to be irradiated. Since it is absorbed, the light may not reach the deep part of the coated coating film in the photosensitive composition containing the colorant. On the other hand, it has been proposed to use a specific photopolymerization initiator (see, for example, Patent Document 1).

Further, in order to use a small and inexpensive semiconductor laser used as a recording material as a light source, sensitivity to a long wavelength, particularly a near infrared region is required. However, known photosensitive compositions do not have sensitivity to the near-infrared region, or even if they do, they are not sufficiently sensitive, and if they have high sensitivity, the photosensitive composition is preserved. It has the drawback of not being sufficiently sex.
Therefore, a specific initiator has been proposed as a highly sensitive initiator in the long wavelength region (see, for example, Patent Documents 2 to 3).

However, even in the photosensitive composition using the specific initiator described in Patent Documents 1 to 3, if a substance such as a colorant that attenuates or shields the irradiated light is present at a high concentration, the photosensitive composition When the light irradiated with a thick film is attenuated, or when the light source is in the long wavelength region, the curability is not sufficient, and the solubility of the initiator or the like in the composition is low. The development of a sensitivity initiator is desired.

Japanese Unexamined Patent Publication No. 2009-19142 Japanese Unexamined Patent Publication No. 2-157760 Japanese Unexamined Patent Publication No. 5-247110

The problem to be solved by the present invention is
(1) When a substance such as a colorant that attenuates or shields the irradiated light is present in the photosensitive composition at a high concentration;
(2) When the film thickness of the photosensitive composition is thick and the irradiated light is attenuated;
(3) When the light source irradiates visible light to infrared light, especially infrared light having low energy;
An object of the present invention is to provide a photosensitive composition having excellent curability in any case.

As a result of diligent research to solve the above problems, the present inventors have found a photosensitive composition having excellent sensitivity to visible light to infrared light.
That is, the present invention
(A) A photosensitive composition comprising an onium salt (B) sensitizer (C) radically polymerizable compound represented by the general formula (1) as an essential component.

[In the formula (1), Rf is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and carbon atoms of each group independently of each other. It is a group in which a hydrogen atom bonded to is substituted with a fluorine atom by 80% or more, and A ⁺ is a monovalent onium cation. ]

Further, the present invention is a curing method comprising a step of irradiating the above-mentioned photosensitive composition with light in a visible light to infrared light region having a wavelength of 400 nm to 1500 nm.

Further, the present invention is a cured product obtained by curing the photosensitive composition.

The photosensitive composition of the present invention can be exposed to light in the visible to infrared light region having a wavelength of 400 nm to 1500 nm to efficiently generate radicals and be cured. Further, even in a composition containing an additive and a colorant having absorption in the ultraviolet light to visible light region, the transmission of energy rays is not hindered, so that a cured product can be efficiently produced.

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

The photosensitive composition of the present invention is characterized by containing an onium salt (A) represented by the general formula (1).

In the formula (1), Rf is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and each group has a carbon atom. It is a group in which the bonded hydrogen atom is replaced with a fluorine atom by 80% or more, and A ⁺ is a monovalent onium cation.

Alkyl groups having 1 to 8 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and tert-. Examples thereof include branched alkyl groups such as pentyl and isohexyl, and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Examples of the alkenyl group having 2 to 8 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl. 2-Methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2-butenyl, 3- Examples thereof include linear or branched ones such as methyl-2-butenyl and 1,2-dimethyl-1-propenyl.

Aryl groups having 6 to 10 carbon atoms (excluding the carbon number of the substituents below) include phenyl groups, naphthyl groups and aromatic heterocyclic hydrocarbon groups (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl and pyridyl). , Pyrimidyl, pyrazinyl and other monocyclic heterocycles; and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl and other fused polycyclic heterocycles).
As the aryl group, in addition to the above, a part of the hydrogen atom in the aryl group may be substituted with an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 2 to 8 carbon atoms.

In the formula (1), the hydrogen atom bonded to the carbon atom in the alkyl group having 1 to 8 carbon atoms, the alkenyl group having 2 to 8 carbon atoms, and the aryl group having 6 to 10 carbon atoms is usually 80. It has been replaced by% or more. It is preferably 90% or more, more preferably 100%. If the substitution rate of the fluorine atom is less than 80%, the polymerization initiation ability of the photosensitive composition of the present invention is lowered.
Among Rf, an alkyl group having 1 to 8 carbon atoms, a phenyl group and a naphthyl group are preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable, from the viewpoint of easy availability of raw materials. A particularly preferable Rf is an alkyl group having 1 to 4 carbon atoms and a substitution rate of a fluorine atom of 100%, and specific examples thereof include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, and CF ₃ CF. _{2 CF 2, CF 3 CF 2} CF 2 CF 2, include _{(CF 3) 2 CFCF 2,} CF 3 CF 2 (CF 2) CF and _{(CF 3)} 3 C.

Specific examples of preferred anions include [(CF ₃ SO ₂ ) ₃ C] ⁻ , [(CF ₃ CF ₂ SO ₂ ) ₃ C] ⁻ , [(CF ₃ CF ₂ CF ₂ ) SO ₂ ) ₃ C] ⁻ , [((CF ₃ ) ₂ CFSO ₂ ) ₃ C] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C] ^- , [((CF ₃ ) ₂ CFCF ₂ SO ₂ ) ₃ C] ^- , [(CF ₃ SO ₂ ) ₂ (CF ₃ CF ₂ SO ₂ ) C] ⁻ , [(CF ₃ SO ₂ ) ₂ (CF ₃ CF ₂ CF ₂ ) SO ₂ ) C] ⁻ , [(CF ₃ SO ₂ ) ₂ (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) C] ^- , [(CF ₃ SO ₂ ) (CF ₃ CF ₂ SO ₂ ) ₂ C] ^- , [(CF ₃ SO ₂ ) (CF ₃ CF ₂ CF) _{2) SO 2) 2 C]} - and _{[(CF 3 SO 2) (} CF 3 CF 2 CF 2 CF 2 SO 2) 2 C] - , and the like, among these in terms of ease availability [( ^{_{CF 3 SO 2) 3 C]}} -, [(CF 3 CF 2 SO 2) 3 C] -, [(CF 3 CF 2 CF 2) SO 2) 3 C] - and _{[(CF 3 CF 2 CF 2} CF ₂ SO ₂ ) ₃ C] ⁻ is preferred, and [(CF ₃ SO ₂ ) ₃ C] ⁻ and [(CF ₃ CF ₂ SO ₂ ) ₃ C] ⁻ are particularly preferred.

In formula (1), A ⁺ is a monovalent onium cation.
The monovalent onium cation means a cation generated by coordinating a proton or a cation type atomic group (alkyl group, etc.) to a compound containing an element having an unshared electron pair, and means a monovalent onium cation. Examples include the following cations.

Oxonium cations (trimethyloxonium cations, triethyloxonium, tetramethylenemethyloxonium cations, etc.);
Pyrrilinium cations (4-methylpyrrilinium cations and 2,6-diphenylpyrilinium cations, etc.);
Chromenium cations (2,4-dimethylchromenium cations, etc.);
Isochromenium cations (1,3-dimethylisochromenium cations, etc.);
Ammonium cations [ammonium cations, primary ammonium cations (n-butylammonium cations, etc.), secondary ammonium cations (diethylammonium cations, etc.), tertiary ammonium cations (triethylammonium cations, etc.), quaternary ammonium cations (tetramethylammonium cations, etc.) , Phenyltrimethylammonium cations and tetrabutylammonium cations, etc.)];
Pyrrolidinium cations (N, N-dimethylpyrrolidinium cations and N, N-diethylpyrrolidinium cations, etc.);
Imidazolinium cations (N, N'-dimethylimidazolinium cations and N-ethyl-N'-methylimidazolinium cations, etc.);
Amidinium cations (N, N'-dimethyltetrahydropyrimidinium cations, N-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium cations and N-benzyl-1,5-diazabicyclo [4.3.0] -5-nonenium cation, etc.);
Morphorinium cations (N, N'-dimethylmorpholinium cations, etc.), piperidium cations (N, N'-diethylpiperidinium cations, etc.);
Pyridinium cations (N-methylpyridinium cations, N-methoxypyridinium cations, N-butoxypyridinium cations, N-benzyloxypyridinium cations, N-benzylpyridinium cations, etc.).
Imidazole cations (N, N'-dimethylimidazolium cations, 1-ethyl-3-methylimidazolium cations, etc.);
Kinolium cations (N-methylquinolium cation cations, N-benzyl quinolium cations, etc.);
Isoquinolium cations (N-methylisoquinolium, etc.);
Thiazonim cation (benzylbenzothiazonium cation, etc.);
Acridium cations (benzylacrydium cations, phenacylacrydium, etc.);
Diazonium cations (phenyldiazonium cations, 2,4,6-triethoxyphenyldiazonium cations, 2,4,6-trihexyloxyphenyldiazonium cations, 4-anilinophenyldiazonium cations, etc.);
Guazinium cations (hexamethylguanidinium cations and 2-benzyl-2-tert-butyl-1,1,3,3-tetramethylguanidinium cations, etc.).
Phosphonium cations [tertiary phosphonium cations (triphenylphosphonium cations and tritert-butylphosphonium cations, etc.) and quaternary phosphonium cations (tetraphenylphosphonium cations, tetra-p-tolylphosphonium cations, triphenylbenzylphosphonium cations, triphenylbutyl cations, etc.) , Tetraethylphosphonium cations and tetrabutylphosphonium cations, etc.)].
Sulfonium cations {triphenylsulfonium cations, 4- (phenylthio) phenyldiphenylsulfonium cations, bis [4- (diphenylsulfonate) phenyl] sulfides, 4-hydroxyphenylmethylbenzylsulfonium cations, etc.};
Sulfoxonium cation (triphenylsulfoxonium, etc.);
Cianthrenium cations [5- (4-methoxyphenyl) thianthrenium, 5-phenylthianthrenium, 5-trilucianthrenium cations, etc.];
Thiophenium cation (2-naphthyltetrahydrothiophenium, etc.);
Iodonium cations [diphenyliodonium cations, di-p-tolyl iodonium cations, 4-isopropylphenyl (p-tolyl) iodonium cations, etc.].

Among the above-mentioned onium cations, sulfonium cations, iodonium cations, diazonium cations and pyridinium cations are preferable from the viewpoint of reactivity, and sulfonium cations and iodonium cations are particularly preferable from the viewpoint of thermal stability.

Specific examples of preferred iodonium cations include diphenyliodonium cation, di-p-triliodonium cation and 4-isopropylphenyl (p-tolyl) iodonium cation, as well as di- (4-tert-butyl) phenyliodonium cation, 4-. Octyloxyphenylphenyliodonium cation, di-4-isopropylphenyliodonium cation, bis (2,4-diisopropylphenyl) iodonium cation, 4-hexylphenyl (p-tolyl) iodonium cation, 4-cyclohexylphenyl (p-tolyl) iodonium Examples thereof include cations, bis (4-dodecylphenyl) iodonium cations, bis (4-methoxyphenyl) iodonium cations, bis (4-decyloxy) phenyliodonium cations, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium cations and the like. ..

Specific examples of preferable sulfonium cations include the above-mentioned triphenylsulfonium cation, 4- (phenylthio) phenyldiphenylsulfonium cation, bis [4- (diphenylsulfonio) phenyl] sulfide and 4-hydroxyphenylmethylbenzylsulfonium cation, and Tris. Examples thereof include (4-chlorophenyl) sulfonium cation, tris (4-fluorophenyl) sulfonium cation, 4-tert-butylphenyldiphenylsulfonium cation, diphenylphenacil sulfonium cation and the like.

Specific examples of preferable iodonium salts include the following.

Specific examples of preferable sulfonium salts include the following.

The onium salt represented by the general formula (1) of the present invention can be produced by a metathesis method. The multiple decomposition method is, for example, New Experimental Chemistry Course 14-I (1978, Maruzen) p-448; Advance in Composer Science, 62, 1-48 (1984); New Experimental Chemistry Course 14-III (1978, Maruzen). ) Pp1838-1846; Organic Sulfur Chemistry (Synthetic Reaction Edition, 1982, Chemistry), Chapter 8, pp237-280; Nihon Kagaku Journal, 87, (5), 74 (1966); Japanese Patent Application Laid-Open No. 61-212554, Japanese Patent Application Laid-Open No. 61-1005557, Japanese Patent Application Laid-Open No. 5-4996, Japanese Patent Application Laid-Open No. 7-82244, Japanese Patent Application Laid-Open No. 7-82245, Japanese Patent Application Laid-Open No. 58-21904 Although it is described in Japanese Patent Application Laid-Open No. 6-184170, etc., first, halogen ion salts such as ^{F −} , Cl ⁻ , Br ⁻ , I ^{− of onium cations; OH −} salt; ClO ₄ ⁻ salt; FSO ₃ ^- , Salts with sulfonic acid ions such as _{ClSO 3} ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ ; with sulfate ions such as _{HSO 4} ⁻ , SO ₄ ^{2- _{salt; HCO 3 -, CO 3 2-}} , salts of carbonate ion such _{^{as; H 2 PO 4 -, HPO}} 4 2-, manufactures and salts with phosphate ions such as _PO ^{4 3-,} this And an anion alkali metal salt, an alkaline earth metal salt or a quaternary ammonium salt constituting the onium salt represented by the formula (1) are added to a solvent and an aqueous solution containing a theoretical amount or more and compoundly decomposed. As the solvent, water or an organic solvent can be used. Examples of the organic solvent include hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetratetra, dioxane, etc.), chlorine-based solvents (chloroform, dichloromethane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones (methanol, ethanol, isopropyl alcohol, etc.), ketones ( Includes acetone, methyl ethyl ketone and methyl isobutyl ketone, etc.), nitriles (acetohydrate, etc.) and polar organic solvents (dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, etc.). These solvents may be used alone or in combination of two or more.

The desired onium salt thus produced is separated by crystals or oil. In the case of an oily substance, it is obtained by separating the precipitated oily substance from the organic solvent solution and further distilling off the organic solvent contained in the oily substance. In the case of crystals, it is obtained by separating the precipitated solid from the organic solvent solution and further distilling off the organic solvent contained in the solid. The desired onium salt thus obtained can be purified by a method such as recrystallization or washing with water or a solvent, if necessary.

Purification by recrystallization dissolves the target onium salt in a small amount of organic solvent, and separation from the organic solvent is performed by directly (or after concentrating) the poor solvent in the organic solvent solution containing the target onium salt. In addition, it can be carried out by precipitating the desired onium salt. Examples of the poor solvent used here include chain ethers (diethyl ether, dipropyl ether, etc.), esters (ethyl acetate, butyl acetate, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), and aromatic hydrocarbons (toluene and cyclohexane, etc.). Xylene, etc.) is included. Purification can also be performed by utilizing the difference in solubility depending on the temperature. Purification can be performed by recrystallization (a method utilizing the difference in solubility due to cooling, a method of adding a poor solvent to precipitate, and a combination thereof). When the photobase generator is an oil (when it does not crystallize), the oil can be purified by washing with water or a poor solvent.

The structure of the thus obtained onium salts generally analytical techniques, for ^{example, 1 H, 13 C, 19} F, the nuclear magnetic resonance spectrum, such as that identified by like infrared absorption spectrum or elemental analysis Can be done.

As the anion salt used in the above-mentioned metathesis reaction, an alkali metal salt is preferable from the viewpoint of reactivity. This salt can be produced by a known method. For example, a non-patent document (Inorgan. Chem., Vol. 27, pp. 2135-2137, 1988) or a patent document (Japanese Unexamined Patent Publication No. 05-503808) can be referred to.

The photosensitive composition of the present invention contains a sensitizer (B) that absorbs light having a wavelength in the visible region to the infrared region (400 nm to 1500 nm) and causes decomposition of the onium salt (A) by energy or electron transfer. include.

As the sensitizer (B), a compound having absorption in the visible region to the infrared region, which contains the sensitizer described in publicly known (Japanese Patent Laid-Open Nos. 11-279212 and Japanese Patent Laid-Open No. 09-183960, etc.), is used. Be done. In particular, a sensitizer having absorption in the infrared region of 700 nm to 1500 nm is also called an “IR absorber” or an “IR dye”.

Specific examples of the sensitizer (B-1) having absorption in the visible region (400 nm to 700 nm) include benzoquinone {1,4-benzoquinone, 1,2-benzoquinone, etc.}; naphthoquinone {1,4-naphthoquinone, 1 , 2-Naftquinone, etc.}; Anthracene {2-methylanthracene, 2-ethylanthracene, etc.}; Anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2, -Ethl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronen; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2 -Chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone}; phenothiazine {phenothracene, N-methylphenothracene, N-ethylphenothracene, N-phenylphenothiazine, etc.}; (Trifluoromethyl) coumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 10-acetyl-2,3,6,7-tetrahydro- 1,1,7,7-Tetramethyl-1H, 5H, 11H,-[1] benzopyrano [6,7,8-ij] quinolidine-11-one, 10- (2-benzothiazolyl) -2,3,6 , 7-Tetrahydro-1,1,7,7-Tetramethyl-1H, 5H, 11H,-[1] benzopyrano [6,7,8-ij] quinolidine-11-one, etc.}; Ketone {2-hydroxy- 2-Methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4'-methyldiphenylsulfide, bis (4,4'-dimethylamino) Benzophenone and bis (4,4'-diethylamino) benzophenone, etc.}; Carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.}; 1,4-di-α-methylbenzyloxythracene, etc.}; Phenantren {9-hydroxyphenanthracene, 9-methoxyphenanthracene, 9-hydroxy-10-meth Xyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.} and the like.
In particular, from the viewpoint of electron acceptability, a high sensitizing effect can be obtained when a naphthoquinone-based, benzophenone-based, xanthone-based, anthraquinone-based, or thioxanthone-based sensitizer is used, which is preferable.

Examples of the sensitizer (B-2) having absorption in the infrared region (700 nm to 1500 nm) include cyanine dye, (thio) porphyrinium dye, polymethine dye such as squalium dye, aminium dye, diimonium dye and the like, N, N-. Dyes having a diarylimino cation skeleton, phthalocyanines, naphthalocyanines, porphyrins and complexes having their central metals can be used.
In particular, a polymethine dye is preferable from the viewpoint of easy availability of raw materials and solubility in a photosensitive composition.

Specific examples of preferable polymethine dyes include the following compounds.

These sensitizers (B) may be used alone or in combination of two or more. The content of the sensitizer (B) is usually 0.005 to 20% by weight, preferably 0, based on the total weight of the sensitizer (B), the onium salt and the radically polymerizable compound (C). It is 01 to 10% by weight.

As the radically polymerizable compound (C) contained in the photosensitive composition of the present invention, any known compound can be used without particular limitation as long as it is a compound that polymerizes by radicals.
For example, an acrylamide compound (C11) having 3 to 35 carbon atoms, a (meth) acrylate compound (C12) having 4 to 35 carbon atoms, an aromatic vinyl compound (C13) having 6 to 35 carbon atoms, and a vinyl ether having 3 to 20 carbon atoms. Examples include compound (C14) and other radically polymerizable compounds (C15).
In the above and below, when referring to both or either of "acrylate" and "methacrylate", "(meth) acrylate" and when referring to both or either of "acrylic" and "methacryl", "(meth) acrylic". ", Each may be described.

Examples of the (meth) acrylamide compound (C11) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylic ad, N-propyl (meth) acrylamide, and N. -N-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl ( Examples include meth) acrylamide, N, N-diethyl (meth) acrylamide and (meth) acryloylmorpholin.

Examples of the (meth) acrylate compound (C12) having 4 to 35 carbon atoms include the following monofunctional to hexafunctional (meth) acrylates.
Examples of the monofunctional (meth) acrylate include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl. (Meta) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) Meta) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxy Methyl (meth) acrylate, methoxypropylene monoacrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2) -Methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl ( Meta) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (Meta) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, diethylene glycol monovinyl ether monoacrylate, tetrahydrofurfuryl (meth) Acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Meta) acrylate, dimethylaminoethyl (meth) acrylic Rate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene Oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether ( Meta) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloxyhexahydrophthale Acid, 2-methacryloyloxyethyl-2-hydroxypropylphthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Examples thereof include acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, and EO-modified -2-ethylhexyl (meth) acrylate.

Examples of the bifunctional (meth) acrylate include 1,4-butanedi (meth) acrylate, 1,6-hexanediacrylate, polypropylene diacrylate, 1,6-hexanediol di (meth) acrylate, and 1,10-decanediol di. (Meta) acrylate, neopentyl diacrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonandi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate and tricyclodecandi (meth) acrylate. ) Acrylate and the like can be mentioned.

Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, alkyleneoxide-modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, and di. Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide-modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meth) ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin triacrylate and the like.

The tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, and ethoxylated pentaerythritol tetra. Examples thereof include (meth) acrylate.

Examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Be done.

Examples of the aromatic vinyl compound (C13) having 6 to 35 carbon atoms include vinylthiophene, vinylfuran, vinylpyridine, styrene, methylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chlormethylstyrene, methoxystyrene, acetoxystyrene, and chlor. Styrene, dichlor styrene, brom styrene, vinyl benzoic acid methyl ester, 3-methyl styrene, 4-methyl styrene, 3-ethyl styrene, 4-ethyl styrene, 3-propyl styrene, 4-propyl styrene, 3-butyl styrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, isopropenylstyrene, Examples thereof include butenyl styrene, octenyl styrene, 4-tert-butoxycarbonyl styrene, 4-methoxy styrene and 4-tert-butoxy styrene.

Examples of the vinyl ether compound (C14) having 3 to 35 carbon atoms include the following monofunctional or polyfunctional vinyl ethers.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether and 4-methyl. Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydro Frifuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chlorethyl vinyl ether, chlorbutyl vinyl ether, chlorethoxyethyl vinyl ether , Phenylethyl vinyl ether and phenoxypolyethylene glycol vinyl ether.

Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: Trimethylol ethanetrivinyl ether, Trimethylol propanetrivinyl ether, Ditrimethylol propanetetravinyl ether, Glycerin trivinyl ether, Pentaerythritol tetravinyl ether, Dipentaerythritol pentavinyl ether, Dipentaerythritol hexavinyl ether, Ethyleneoxide-added trimethylol. Propane trivinyl ether, propylene oxide-added trimethylol propantrivinyl ether, ethylene oxide-added ditrimethylol propanetetravinyl ether, propylene oxide-added ditrimethylol propanetetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added Examples thereof include dipentaerythritol hexavinyl ether and propylene oxide-added dipentaerythritol hexavinyl ether.

Other radically polymerizable compounds (C15) include acrylonitrile, vinyl ester compounds (vinyl acetate, vinyl propionate, vinyl versaticate, etc.), maleimide compounds (1-methyl-2,4-bismaleimidebenzene, N, N'. -M-Phenylene bismaleimide, etc.), allyl ester compounds (allyl acetate, etc.), halogen-containing monomers (vinylidene chloride, vinyl chloride, etc.), olefin compounds (ethylene, propylene, etc.), etc., as well as (meth) acrylate groups. A plurality of oligomers are also included. Examples of the polyfunctional (meth) acrylate oligomer include oligomers such as epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polysiloxane (meth) acrylate oligomer, and polyester (meth) acrylate oligomer. Can be mentioned.

Of these, acrylamide compounds (C11) having 3 to 35 carbon atoms, (meth) acrylate compounds (C12) having 4 to 35 carbon atoms, and aromatic vinyl compounds having 6 to 35 carbon atoms are preferable from the viewpoint of curing rate. (C13) and a vinyl ether compound (C14) having 3 to 20 carbon atoms, more preferably an acrylamide compound (C11) having 3 to 35 carbon atoms and a (meth) acrylate compound (C12) having 4 to 35 carbon atoms. ..

In the photosensitive resin composition of the present invention, the content of the onium salt represented by the general formula (1) is 0.5% by weight to 30% by weight based on the total weight of the onium salt and the radically polymerizable compound (C). By weight%, preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight. The onium salt represented by the general formula (1) may be used in combination of two or more.

The photosensitive resin composition of the present invention may contain another additive (J) generally used for controlling the appearance and physical properties of the cured product of the photosensitive resin composition. Other additives (J) include colorants (Ja), metal oxide particles (Jb), metal particles (Jc) and the like.

As the colorant (Ja) in the present invention, pigments and dyes such as inorganic pigments and organic pigments conventionally used for paints and inks can be used.

Examples of the inorganic pigment include chrome yellow, zinc yellow, dark blue, barium sulfate, cadmium red, titanium oxide, zinc flower, red iron oxide, alumina, calcium carbonate, ultramarine, carbon black, graphite and titanium black.

Examples of organic pigments include soluble azo pigments such as β-naphthol type, β-oxynaphthoic acid type anilide type, acetoacetic acid anilide type and pyrazolone type, β-naphthol type, β-oxynaphthoic acid type and β-oxynaphthoic acid type. Insoluble azo pigments such as anilide, acetoacetate anilide monoazo, acetoacetate anilide dysazo, pyrazolone, copper phthalocyanine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine and other phthalocyanine pigments, iso Examples thereof include polycyclic or heterocyclic compounds such as syndrinone-based, quinacridone-based, dioxandin-based, perinone-based and perylene-based compounds.

As a specific example of the dye, as the yellow dye, an aryl or heteryl azo dye having phenols, naphthols, aniline, pyrazolones, pyridones or open chain active methylene compounds as a coupling component, and open chain active as a coupling component. Examples thereof include azomethine dyes having methylene compounds, methine dyes such as benziliden dyes and monomethine oxonoll dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acrydin dyes and acridinone dyes.

As the magenta dye, phenols, naphthols, aniline, pyrazolones, pyridones, pyrazorotriazoles, ring-closed active methylene compounds or heterocycles (pyrrole, imidazole, thiophene, thiazole derivatives, etc.) are used as coupling components. Aryl or heteryl azo dyes, azomethine dyes having pyrazolones or pyrazorotriazoles as coupling components, allylidene dyes, styryl dyes, methine dyes such as merocyanine dyes and oxonoll dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes and the like. Examples thereof include quinone dyes such as carbonium dyes, naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

Cyan dyes include azomethine dyes such as Indian aniline dyes and Indian phenol dyes, polymethine dyes such as cyanine dyes, oxonoll dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes and anthraquinone dyes. Examples of the coupling component include phenols, naphthols, anilins, aryl or heteryl azo dyes (CI Direct Blue 14 and the like) having a pyrolopyrimidinone or pyrorotriadinone derivative, and indigo / thioindigo dyes.

The particle size of the colorant (Ja) is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm, as an average particle size from the viewpoint of the vividness of the coating film.

The amount of the colorant (Ja) added is not particularly limited, but is preferably 1 to 60% by weight based on the total weight of the photosensitive composition.

When a pigment is used, it is preferable to add a pigment dispersant in order to improve its dispersibility and storage stability of the photosensitive composition.
Examples of the pigment dispersant include pigment dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184 or 2020, etc. ), Pigment dispersants manufactured by Ajinomoto Fine Techno Co., Ltd. (Azispar PB711, PB821, PB814, PN411, PA111, etc.), and pigment dispersants manufactured by Lubrizol (Solspurs 5000, 12000, 32000, 33000, 39000, etc.). These pigment dispersants may be used alone or in combination of two or more. The amount of the pigment dispersant added is not particularly limited, but it is preferably used in the range of 0.1 to 10% by weight in the photosensitive composition.

By containing the metal oxide particles (Jb) or the metal particles (Jc), the photosensitive composition of the present invention can be used, for example, for forming a green sheet and forming an electrode layer of a ceramic electronic component.

The metal oxide particles (Jb) are used in forming the dielectric layer. Examples of (Jb) include titanium oxide, aluminum oxide, barium titanate, calcium zirconate, niobium oxide, lead zirconate titanate and the like, and barium titanate is preferable. Further, aluminum oxide, silicon oxide, titanium oxide and the like are used when forming a coating layer for protecting the base material.

From the viewpoint of the dielectric constant, the particle size of (Jb) is preferably 0.01 μm to 2.0 μm as an average particle size, and more preferably 0.01 μm to 1.0 μm.

The metal powder (Jc) is a noble metal and a base metal used when forming a conductor layer, and specific examples thereof include palladium, nickel, copper, silver and gold, and palladium, nickel and copper are preferable. Is.
The average particle size of (Jc) is preferably 0.01 μm to 10 μm.

The photosensitive composition of the present invention may contain a solvent, an adhesion-imparting agent (silane coupling agent, etc.) and the like, if necessary.
Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether, etc.). Acetates and propylene glycol alkyl ether acetates, etc.), aromatic hydrocarbons (toluene, xylene, mesitylen, limonene, etc.), alcohols (methanol, ethanol, normalpropanol, isopropanol, butanol, geraniol, linalol, citronellol, etc.) and ethers. (Tetratetra and 1,8-cineole, etc.) can be mentioned. These may be used alone or in combination of two or more.
The content of the solvent in the photosensitive composition is preferably 0 to 99% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 90% by weight, based on the total weight of the photosensitive resin composition. Is.

Adhesion-imparting agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and ureapropyltri. Examples thereof include ethoxysilane, tris (acetylacetonate) aluminum and acetylacetate aluminum diisopropylate. When the adhesion-imparting agent is used, the content is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight based on the total weight of the photosensitive composition.

Further, the photosensitive composition of the present invention further comprises inorganic fine particles, a dispersant, an antifoaming agent, a leveling agent, a thixotropic agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant and ultraviolet rays according to the purpose of use. It can contain an absorbent or the like.

The photosensitive composition of the present invention comprises an onium salt represented by the general formula (1), a radically polymerizable compound (C), a sensitizer (B), a colorant (Ja) used if necessary, and a metal oxidation used if necessary. Uniform particles (Jb), metal particles (Jc) used if necessary, solvent used if necessary, and adhesion imparting agent used if necessary are uniformly mixed using a known stirring and mixing device (mixing container with a stirrer, paint shaker, etc.). It can be obtained by a method of mixing and a method of kneading using a known kneader (ball mill, 3-roll mill, etc.). The uniform mixing temperature and kneading temperature are usually 10 ° C to 40 ° C, preferably 20 ° C to 30 ° C.

The photosensitive composition of the present invention can irradiate energy rays in the visible region to the infrared region using an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, a xenon lamp, or an LED light source. A light source can be used. Further, depending on the application, in addition to the generally used high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp, and the like can also be used because energy rays are generated at 400 nm or more.

The photosensitive composition of the present invention can generate a radical by irradiating it with light to accelerate the curing reaction and obtain a cured product. Therefore, as a method for producing such a cured product, is it possible to select a sensitizer (B) according to the wavelength of light as a light source and irradiate the light with the one contained in the photosensitive composition? It is preferable to include a step of irradiating light with a light source corresponding to the absorption wavelength of the sensitizer (B) used. In addition, in the case of a curing reaction, it may be heated if necessary. The heating temperature is usually 30 ° C. to 200 ° C., preferably 35 ° C. to 150 ° C., and more preferably 40 ° C. to 120 ° C.

As a method for applying the photosensitive composition of the present invention to a substrate, known coating methods such as spin coat, roll coat and spray coat, as well as slab printing, carton printing, metal printing, offset printing and screen printing, depending on the application. And known printing methods such as gravure printing can be applied. It can also be applied to an inkjet method of coating in which fine droplets are continuously ejected.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not intended to be limited thereto. Unless otherwise specified below,% means% by weight.

Production Example 1 Synthesis of Tris (Trifluoromethanesulfonyl) Lithium Metidenate (AN-1) 2.8 g of methyl iodide and 100 mL of diethyl ether are added to a dry reaction vessel, and 2.5 g of trifluoromethanesulfonyl chloride is added thereto-78. Cooled to ° C. 44 mL of tert-butyllithium pentane solution (1.9 molL ^-1 ) was added dropwise thereto while maintaining the liquid temperature at −50 ° C. or lower. After the dropping, the temperature was gradually raised to room temperature and the mixture was stirred for 6 hours. Then, the mixture was further stirred under reflux for 10 hours.
Under an ice bath, 1N hydrochloric acid was added to the reaction solution, and the solid produced after stirring for 1 hour was filtered, the filtrate was extracted with diethyl ether, and washed with saturated brine. The organic layer was concentrated to give a white solid.
¹⁹ FNMR confirmed that this was tris (trifluoromethanesulfonyl) lithium methideate (AN-1).

Production Example 2 Synthesis of Tris (Pentafluoroethanesulfonyl) Lithium Metidenate (AN-2) In Production Example 1, the same as Production Example 1 except that 2.5 g of trifluoromethanesulfonyl chloride is 3.3 g of pentafluoroethanesulfonyl chloride. To obtain tris (pentafluoroethanesulfonyl) lithium methidenate (AN-2).

Production Example 3 Synthesis of Tris (Nonafluorobutanesulfonyl) Lithium Metidate (AN-3) In Production Example 1, the same as Production Example 1 except that 2.5 g of trifluoromethanesulfonyl chloride is 4.8 g of nonafluorobutanesulfonyl chloride. To obtain lithium tris (nonafluorobutanesulfonyl) methidenate (AN-3).

Production Example 4 Onium salt (A1-1): 4.3 g of diphenyliodonium trifluoromethanesulfonate (manufactured by Tokyo Kasei) and 30 g of dichloromethane were added to a synthetic reaction vessel of diphenyliodonium tris (trifluoromethanesulfonyl) methide. While stirring, 4.2 g of the lithium salt (AN-1) synthesized in Production Example 1 and 50 mL of water were added, and the mixture was stirred at room temperature for 18 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was further washed 5 times with 50 mL of water. The organic solvent was distilled off under reduced pressure to obtain 5.5 g of a white solid. The ^{1 H, 19 F,} this compound was confirmed to be an onium salt (A1-1).

Production Example 5 Onium salt (A1-2): Synthesis of diphenyliodonium tris (pentafluoroethanesulfonyl) methide In Production Example 4, the lithium salt (AN-2) was replaced with 4.2 g of the lithium salt (AN-1). 8.0 g of the target product was obtained according to the method described in Production Example 4 except that the weight was 7 g. ^{1 H, 19} F from the white solid was confirmed to be an onium salt (A1-2).

Production Example 6 Onium Salt (A1-3): Synthesis of Diphenyliodonium Tris (Nonafluorobutanesulfonyl) Metide In Production Example 4, the lithium salt (AN-3) was replaced with 4.2 g of the lithium salt (AN-1). 9.3 g of the target product was obtained according to the method described in Production Example 4 except that the weight was 7 g. ^{1 H, 19} F from the white solid was confirmed to be an onium salt (A1-3).

Production Example 7 Onium salt (A1-4): (4-isopropylphenyl) Trilliodonium Tris (trifluoromethanesulfonyl) Methyl synthesis Add 2 g of 4-methyliodobenzene to a reaction vessel, and add 5 mL of acetic acid and 1 mL of sulfuric acid to dissolve. Then, 1 g of potassium persulfate was added little by little at 15 ° C. or lower while cooling in an ice water bath. The reaction was carried out at 20 ° C. for 4 hours, and 2.4 g of cumene was added dropwise thereto so as not to exceed 20 ° C. Then, it was reacted at room temperature for 20 hours. The reaction mixture was added to a solution prepared by dissolving 4.2 g of lithium salt (A-1) in 50 mL of water, and the mixture was further stirred for 3 hours. 50 mL of dichloromethane was added thereto. After standing, the aqueous layer was removed by liquid separation, and the organic layer was washed 5 times with 50 mL of water. Dichloromethane was concentrated and recrystallized from cyclohexane to obtain 6.8 g of a white solid. ^By 1H, ¹⁹ F-NMR, it was confirmed that this was an onium salt (A1-4).

Production Example 8 Onium Salt (A1-5): Synthesis of (4-isopropylphenyl) Trilliodonium Tris (Pentafluoroethanesulfonyl) Metide In Production Example 7, a lithium salt (AN-1) was replaced with 4.2 g. AN-2) The target product was obtained according to the method described in Production Example 7 except that the weight was 5.7 g. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A1-5).

Production Example 9 Onium Salt (A1-6): Synthesis of Di (tert-butylphenyl) Iodonium Tris (Trifluoromethanesulfonyl) Metide In Production Example 4, diphenyliodonium trifluoromethanesulfonate (tert-tert) was used instead of 4.3 g. -The target product was obtained according to the method described in Production Example 4 except that the amount was 5.4 g of (butylphenyl) iodonium hexafluorophosphate (manufactured by Tokyo Kasei). The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A1-6).

Production Example 10 Onium Salt (A1-7): Synthesis of Di (tert-butylphenyl) iodoniumtris (pentafluoroethanesulfonyl) methide In Production Example 9, a lithium salt (AN-1) was replaced with 4.2 g. AN-2) The target product was obtained according to the method described in Production Example 9 except that the weight was 5.7 g. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A1-7).

Production Example 11 Onium Salt (A1-8): Synthesis of Di (tert-butylphenyl) iodoniumtris (nonafluorobutanesulfonyl) methide In Production Example 9, a lithium salt (AN-1) was replaced with 4.2 g. AN-3) The target product was obtained according to the method described in Production Example 9 except that the weight was 8.7 g. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A1-8).

Production Example 12 Synthesis of onium salt (A1-9): (4-octyloxyphenyl) phenyliodonium tris (trifluoromethanesulfonyl) methide According to the method described in Patent Document (Japanese Unexamined Patent Publication No. 06-184170), the desired product is obtained. rice field. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A1-9).

Production Example 13 Onium Salt (A1-10): Synthesis of (4-octyloxyphenyl) Phenyliodonium Tris (Nonafluorobutanesulfonyl) Metide A desired product was obtained according to the method described in Patent Document (Japanese Patent Laid-Open No. 06-184170). .. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A1-10).

Production Example 14 Onium salt (A2-1): To a synthetic reaction vessel of triphenylsulfonium tris (trifluoromethanesulfonyl) methide, 3.4 g of triphenylsulfonium bromide (manufactured by Tokyo Kasei) and 50 mL of dichloromethane were added. While stirring, 4.2 g of the lithium salt (AN-1) synthesized in Production Example 1 and 50 mL of water were added, and the mixture was stirred at room temperature for 8 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was further washed 5 times with 50 mL of water. The organic solvent was distilled off under reduced pressure to obtain 5.9 g of a white solid. ^By 1H, ¹⁹ F-NMR, it was confirmed that this was an onium salt (A2-1).

Production Example 15 Onium Salt (A2-2): Synthesis of Triphenylsulfonium Tris (Pentafluoroethanesulfonyl) Metide In Production Example 14, the lithium salt (AN-2) 5 is replaced with 4.2 g of the lithium salt (AN-1). The target product was obtained according to the method described in Production Example 14 except that the weight was 0.7 g. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-2).

Production Example 16 Onium Salt (A2-3): Synthesis of Triphenylsulfonium Tris (Nonafluorobutanesulfonyl) Metide In Production Example 14, the lithium salt (AN-3) 8 is replaced with 4.2 g of the lithium salt (AN-1). The target product was obtained according to the method described in Production Example 14 except that the weight was 0.7 g. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-3).

Production Example 17 Synthesis of onium salt (A2-4): (4-phenylthio) phenyldiphenylsulfonium tris (trifluoromethanesulfonyl) methide According to the method of Patent Document (WO2005-116038), the desired product was obtained. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-4).

Production Example 18 Synthesis of onium salt (A2-5): (4-phenylthio) phenyldiphenylsulfonium tris (pentafluoroethanesulfonyl) methide According to the method of Patent Document (WO2005-116038), the desired product was obtained. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-5).

Production Example 19 Synthesis of (4-phenylthio) phenyldiphenylsulfonium tris (nonafluorobutanesulfonyl) methide onium salt (A2-6) The desired product was obtained according to the method of Patent Document (WO2005-116038). The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-6).

Production Example 20 Onium salt (A2-7): Tris (4-tert-butylphenyl) Sulfonium Tris (trifluoromethanesulfonyl) methide synthesis in a reaction vessel Tris (4-tert-butylphenyl) sulfonium triflate (manufactured by Aldrich) 5. 8 g and 50 mL of dichloromethane were added. While stirring, 4.2 g of the lithium salt (AN-1) synthesized in Production Example 1 and 50 mL of water were added, and the mixture was stirred at room temperature for 8 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was further washed 5 times with 50 mL of water. The organic solvent was distilled off under reduced pressure to obtain 8.2 g of a white solid. The ^{1 H,} 19 ^F-NMR, this product was confirmed to be an onium salt (A2-7).

Production Example 21 Onium Salt (A2-8): Synthesis of Tris (4-tert-butylphenyl) Sulfonium Tris (Pentafluoroethanesulfonyl) Metide In Production Example 20, lithium is used instead of 4.2 g of the lithium salt (AN-1). The desired product was obtained according to the method described in Production Example 20 except that the amount of salt (AN-2) was 5.7 g. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-8).

Production Example 22 Onium salt (A2-9): Synthesis of tris (4-fluorophenyl) sulfonium tris (trifluoromethanesulfonyl) methide 2.4 g of bis (4-fluorophenyl) sulfoxide was added to the reaction vessel, and 50 mL of THF was further added. .. The mixture was cooled to 0 ° C. under an ice bath, and 5.0 g of trimethylsilyl chloride was added dropwise thereto. The mixture was stirred for 2 hours, and 25 mL of a 1.0 mol / L THF solution prepared by a conventional method was added dropwise from 4-fluorobromobenzene while maintaining a temperature of 10 ° C. or lower. After completion of the dropping, the reaction was carried out at room temperature for 8 hours. The reaction solution was poured into 100 mL of water and washed twice with 50 mL of toluene. 4.2 g of lithium salt (AN-1) was added to the aqueous layer, and the mixture was further stirred for 4 hours. 70 mL of dichloromethane was added, the aqueous layer was removed by separation, and washing was performed 5 times with 50 mL of water. The dichloromethane layer was concentrated and crystallized with cyclohexane to give 6.2 g of a white solid. The ^{1 H,} 19 ^F-NMR, the white solid was confirmed to be an onium salt (A2-9).

Production Example 23 Onium salt (A2-10): Synthesis of tris (4-fluorophenyl) sulfonium tris (pentafluoroethanesulfonyl) methide In Production Example 22, a lithium salt (AN-1) was replaced with 4.2 g. AN-2) The target product was obtained according to the method described in Production Example 22 except that the weight was 5.7 g. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-10).

Production Example 24 Onium salt (A2-11): Synthesis of thiodi-p-phenylenebis (diphenylsulfonium) bis [tris (trifluoromethanesulfonyl) methide] According to the method of Patent Document (Japanese Patent Laid-Open No. 2013-227368), the desired product. Got The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-11).

Production Example 25 Onium salt (A2-12): Synthesis of thiodi-p-phenylene bis (diphenylsulfonium) bis [tris (pentafluoroethanesulfonyl) methide] I got something. The ^{1 H,} 19 ^F-NMR, it was confirmed that an onium salt (A2-12).

Comparative Production Example 1 Production of the following onium salt (A'-1) in Synthetic Production Example 10 except that 4.2 g of lithium salt (AN-1) is replaced with 3.5 g of tetraphenylborate sodium (manufactured by Nacalai Tesque). The desired product was obtained according to the method described in Example 10. ¹ It was confirmed by 1 H-NMR that it was an onium salt (A'-1).

Comparative Production Example 2 In Synthetic Production Example 14 of the following photobase generator (A'-2), tetraphenylborate sodium (manufactured by Nacalai Tesque) was used instead of 4.2 g of the lithium salt (AN-1), except for 3.5 g. Obtained the desired product according to the method described in Production Example 14. ¹ It was confirmed by 1 H-NMR that it was an onium salt (A'-2).

<Examples 1-37 and Comparative Examples 1-16>
[Preparation of photosensitive composition]
100 g of the radically polymerizable compound (C), 3 g of the onium salt (A), and 0.3 g of the sensitizer (B) were uniformly mixed, and compared with the photosensitive compositions (Q-1) to (Q-37) of the present invention. Photosensitive resin compositions (Q'-1) to (Q'-16) were prepared. The types of raw materials used are shown in Table 1. This photosensitive composition is applied to a glass substrate (76 mm × 52 mm) using an applicator (40 μm), exposed using an irradiation device LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics) as a light source, and the following evaluation method is performed. The curability was confirmed in. The results are shown in Table 1.
[Raw materials used]
A1-1 to A2-12 (onium salt described above)
A'-1: Onium salt of Comparative Production Example 1 A'-2: Onium salt of Comparative Production Example 2 A'-3: Di (tert-butylphenyl) iodonium hexafluorophosphate (manufactured by Tokyo Kasei)
A'-4: Triphenylsulfonium bromide (manufactured by Tokyo Kasei)
B-1: B-201 (described above as a specific example of the polymethine dye)
B-2: B-204 (described above as a specific example of the polymethine dye)
B-3: 3,3'-carbonylbis (7-diethylaminocoumarin)
B-4: 2,4-diethylthioxanthone C-1: Dipentaerythritol pentaacrylate (“Neomer DA-600” manufactured by Sanyo Chemical Industries, Ltd.)
C-2: Trimethylolpropane triacrylate ethoxylated ("Neomer TA-401" manufactured by Sanyo Chemical Industries, Ltd.)
C-3: Polypropylene glycol diacrylate ("Neomer PA-305" manufactured by Sanyo Chemical Industries, Ltd.)
[Curability]
Curability-1: Exposure was performed through an infrared transmission filter (manufactured by HOYA) R72 (cut below 700 nm), and the curability was confirmed.
Curability evaluation: ◎ There is no tack on the surface and it will not be scratched even if scratched with a nail.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
× It does not cure in liquid form.

<Examples 38 to 42 and Comparative Examples 17 to 20>
[Preparation of photosensitive composition]
The photosensitive compositions (Q-38) to (Q-42) of the present invention are uniformly mixed with 100 g of a radically polymerizable compound (C), 3 g of an onium salt (A), and 0.3 g of a sensitizer (B-3). And comparative photosensitive resin compositions (Q'-17) to (Q'-20) were prepared. The types of raw materials used are shown in Table 1. This photosensitive composition is applied to a glass substrate (76 mm × 52 mm) using an applicator (40 μm), exposed using an irradiation device LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics) as a light source, and the following evaluation method is performed. The curability was confirmed in. The results are shown in Table 2. The raw materials used are as described above.
[Curability]
Curability-2: Exposure was performed through a sharp cut filter (manufactured by HOYA) Y44 (cut of 430 nm or less), and the curability was confirmed.
Curability evaluation: ◎ There is no tack on the surface and it will not be scratched even if scratched with a nail.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
× It does not cure in liquid form.

<Examples 43 to 47 and Comparative Examples 21 to 24>
[Preparation of photosensitive composition]
The photosensitive compositions (Q-43) to (Q-47) of the present invention are uniformly mixed with 100 g of a radically polymerizable compound (C), 1 g of an onium salt (A), and 0.1 g of a sensitizer (B-4). And comparative photosensitive resin compositions (Q'-21) to (Q'-24) were prepared. The types of raw materials used are shown in Table 1.
[Curability]
Curability-3: This photosensitive composition is applied to a glass substrate (76 mm × 52 mm) using an applicator (40 μm), and exposed using a UV-LED irradiator OMUNICURE LX405-S (manufactured by LumenDynamics) as a light source. The curability was confirmed by the following evaluation method. The results are shown in Table 2. The raw materials used are as described above.
Curability evaluation: ◎ There is no tack on the surface and it will not be scratched even if scratched with a nail.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
× It does not cure in liquid form.

From Tables 1 to 3, it can be seen that the photosensitive composition of the present invention has higher sensitivity than the comparative photosensitive composition. It is also understood that it is important to select an appropriate sensitizer for the wavelength of the irradiated light.

<Examples 48 to 52 and Comparative Examples 25 to 28: Examples of photosensitive compositions containing pigments>
[Preparation of photosensitive composition]
<Preparation of high-concentration dispersion liquid (1)>
43 parts of titanium oxide (“Typake R-930” manufactured by Ishihara Sangyo Co., Ltd.) as a pigment, 4 parts of a pigment dispersant (“Sol Spurs 32000” manufactured by Lubrizol Co., Ltd.) and tetrahydrofurryl acrylate (Kyoeisha Co., Ltd.) as a radically polymerizable compound (C). A mixture consisting of 53 parts of "Light Aacrylate THF-A" manufactured by Chemical Co., Ltd.) was kneaded for 3 hours using a ball mill to prepare a pigment dispersant solution having a pigment concentration of 43%.
<Preparation of photosensitive composition>
47 parts of the high-concentration pigment dispersant solution, 46 parts of dipentaerythritol pentaacrylate (“Neomer DA-600” manufactured by Sanyo Chemical Industries, Ltd.), 0.5 part of the sensitizer (B-2), and the onium salt shown in Table 2 ( A) or 5 parts of the comparative onium salt (A') were kneaded at 25 ° C. for 3 hours using a ball mill, and the photosensitive compositions (Q-48) to (Q-52) of the present invention and comparative photosensitive were obtained. The resin compositions (Q'-25) to (Q'-28) were produced, the coating film curability (curability -3) was evaluated by the following method, and the results are shown in Table 4.
[Curability]
Curability-3: These photosensitive compositions were applied to a surface-treated 100 μm-thick PET (polyethylene terephthalate) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.] so as to have a film thickness of 20 μm using an applicator. Applied. Exposure was performed using an irradiation device LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics Co., Ltd.) as a light source, and the curability was confirmed by the following evaluation method.
Curability evaluation: ◎ There is no tack on the surface and it will not be scratched even if scratched with a nail.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
× It does not cure in liquid form.

<Examples 53 to 57 and Comparative Examples 29 to 32: Examples of photosensitive compositions containing a dye>
[Preparation of photosensitive composition]
<Preparation of high-concentration dispersion liquid (2)>
A dye dispersion was prepared by performing the same operation as the preparation of the high-concentration dispersion (1) except that the dye was replaced with Direct Blue 14 (manufactured by Tokyo Kasei).
<Preparation of photosensitive composition>
47 parts of the high-concentration dye dispersant solution, 46 parts of dipentaerythritol pentaacrylate (“Neomer DA-600” manufactured by Sanyo Chemical Industries, Ltd.), 0.5 part of the sensitizer (B-2), and the onium salt shown in Table 2 ( A) or 5 parts of the comparative onium salt (A') were kneaded at 25 ° C. for 3 hours using a ball mill, and the photosensitive compositions (Q-53) to (Q-57) of the present invention and comparative photosensitive were obtained. The resin compositions (Q'-29) to (Q'-32) were produced, the coating film curability (curability-4) was evaluated by the following method, and the results are shown in Table 5.
[Curability]
Curability-4: These photosensitive compositions were applied to a surface-treated 100 μm-thick PET (polyethylene terephthalate) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.] so as to have a film thickness of 20 μm using an applicator. Applied. Exposure was performed using an irradiation device LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics Co., Ltd.) as a light source, and the curability was confirmed by the following evaluation method.
Curability evaluation: ◎ There is no tack on the surface and it will not be scratched even if scratched with a nail.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
× It does not cure in liquid form.

From the results in Tables 4 and 5, the photosensitive composition of the present invention can be efficiently cured even in the presence of a substance such as a colorant that attenuates or shields the irradiated light at a high concentration, and is comparatively photosensitive. It can be seen that the sensitivity is higher than that of the sex composition.

The photosensitive composition of the present invention utilizes light (particularly in the visible region to the infrared region) to provide a coating material, a coating agent, and various coating materials (hard coat, stain-resistant coating material, anti-fog coating material, and touch-resistant coating material). , Optical fiber, etc.), adhesive tape back treatment agent, adhesive label release sheet (release paper, release plastic film, release metal foil, etc.) release coating material, printing board, dental material (dental formulation, dental composite) ) Ink, inkjet ink, positive resist (connection terminals for manufacturing electronic parts such as circuit boards, CSP, MEMS elements, wiring pattern formation, etc.), resist film, liquid resist, negative resist (semiconductor element and transparent electrode for FPD (transparent electrode for semiconductor element and FPD) Surface protective film such as ITO, IZO, GZO), interlayer insulating film, permanent film material such as flattening film, etc.), resist for MEMS, positive photosensitive material, negative photosensitive material, various adhesives (various electronic parts) Temporary fixing agent for HDD, adhesive for pickup lens, adhesive for functional film for FPD (deflecting plate, antireflection film, etc.), insulating film for circuit formation and semiconductor encapsulation, weird conductive adhesive Agent (ACA), film (ACF), paste (ACP), etc.), holographic resin, FPD material (color filter, black matrix, partition material, photospacer, rib, liquid crystal alignment film, FPD sealant, etc.), Optical members, molding materials (for building materials, optical parts, lenses), casting materials, putties, glass fiber impregnants, sealing materials, sealing materials, flip chips, chip encapsulants such as COF, CSP or BGA, etc. It is suitably used for packaging encapsulants, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, optical molding materials, micro-optical modeling materials and the like.

Claims (4)

(A) The onium salt (B) sensitizer (C) radically polymerizable compound represented by the general formula (1) is contained as an essential component, and the sensitizer (B) is a polymethine-based dye. Photosensitive composition.

[In the formula (1), Rf is an alkyl group having 1 to 8 carbon atoms independently of each other, and is a group in which a hydrogen atom bonded to a carbon atom of each group is replaced with a fluorine atom by 80% or more. A ⁺ is a monovalent onium cation. ] The photosensitive composition according to claim 1, wherein ^{A +} in the general formula (1) is sulfonium or iodonium. The photosensitive composition according to claim 1 or 2, wherein Rf in the general formula (1) is an alkyl group having 1 to 8 carbon atoms in which a hydrogen atom is substituted with a fluorine atom by 90% or more independently of each other. A method for curing a photosensitive composition, which comprises a step of irradiating the photosensitive composition according to any one of claims 1 to 3 with light in a near infrared light region having a wavelength of 700 nm to 1200 nm.