JP2019003122A - Photosensitive composition - Google Patents

Abstract

To provide a photosensitive composition excellent in curability even in such cases that a substance such as a colorant which attenuates or blocks irradiation light is present at a high concentration, that a thick film is formed, and that a light source emitting visible light to infrared light, particularly infrared light at a low energy is used.SOLUTION: The photosensitive composition comprises (A) an onium salt represented by general formula (1), (B) a sensitizer and (C) a radical polymerizable compound, as essential components. In formula (1), Rf each independently represents an alkyl group having 1 to 8 carbon atom, an alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms, in which a hydrogen atom bonded to a carbon atom in the group is replaced by a fluorine atom by 80% or more; and Arepresents a monovalent onium cation.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive composition that is exposed to light in the visible to infrared region and cured. More specifically, it is a photosensitive composition that is cured by irradiation with light in the visible to infrared region, and is used, for example, in coating agents, paints, lithographic printing plates and the like. In addition, the present invention is a product or member formed through patterning using a difference in solubility in a developer in an exposed area and an unexposed area (for example, an electronic component, an optical product, an optical component forming material, a layer forming material, or an adhesive). It is related with the photosensitive composition used suitably for manufacture of an agent etc.).

The UV curing technology for curing a liquid substance by ultraviolet (UV) irradiation is expanding the application range of coating agents, paints, printing inks and the like from the viewpoint of workability (rapid curing) and low VOC.
Generally, the photosensitive composition comprises a photopolymerization initiator and a sensitizer, a radical (or cation) polymerizable monomer, an oligomer or a polymer, and a colorant and an additive depending on the application. Colorants are roughly divided into pigments and dyes, and are blended to color the coating, but they not only block light, but also have a light absorption characteristic according to the color, and part of the irradiated light. In order to absorb, light may not reach the deep part of the coated 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).

In addition, in order to use a small and inexpensive semiconductor laser used in a recording material or the like as a light source, sensitivity to a long wavelength, particularly the near infrared region is required. However, the known photosensitive composition does not have sensitivity to the near infrared region or is not sufficiently sensitive even if it has, and if it has high sensitivity, the photosensitive composition is stored. It has the disadvantage of not being sufficient.
Thus, specific initiators have been proposed as highly sensitive initiators in the long wavelength region (see, for example, Patent Documents 2 to 3).

  However, even in a photosensitive composition using the specific initiator described in Patent Documents 1 to 3, if a substance such as a colorant that attenuates or blocks irradiated light is present in a high concentration, the photosensitive composition When the irradiated light is attenuated by a large film thickness, or when the light source is in the long wavelength region, there are problems such as insufficient curability and low solubility of the initiator in the composition. Development of a sensitive initiator is desired.

JP 2009-19142 A Japanese Patent Laid-Open No. 2-157760 JP-A-5-247110

The problem to be solved by the present invention is:
(1) When a substance such as a colorant that attenuates or blocks irradiated light is present in a high concentration in the photosensitive composition;
(2) When the photosensitive composition is thick and the irradiated light attenuates;
(3) When the light source emits visible light to infrared light, particularly infrared light with low energy;
The object is to provide a photosensitive composition having excellent curability in any case.

As a result of intensive studies 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) and a radical polymerizable compound represented by formula (1) as an essential component.

[In Formula (1), Rf is mutually independently a C1-C8 alkyl group, a C2-C8 alkenyl group, a C6-C10 aryl group, and carbon atom of each group. A ⁺ is a group obtained by substituting 80% or more of the hydrogen atom bonded to with a fluorine atom, and A ⁺ is a monovalent onium cation. ]

Furthermore, this invention is a hardening method characterized by including the process of irradiating the light of the visible light-infrared region of wavelength 400nm-1500nm to the said photosensitive composition.

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

The photosensitive composition of the present invention can efficiently generate radicals by being exposed to light in the visible light to infrared light region having a wavelength of 400 nm to 1500 nm, and can be cured. Moreover, even if it is a composition which mix | blended the additive and colorant which have absorption in a ultraviolet light-visible region, since transmission of an energy ray is not prevented, a hardened | cured material can be manufactured efficiently.

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

The photosensitive composition of this invention contains the onium salt (A) represented by General formula (1), It is characterized by the above-mentioned.

In formula (1), Rf is independently 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 a carbon atom of each group. It is a group obtained by substituting 80% or more of bonded hydrogen atoms with fluorine atoms, and A ⁺ is a monovalent onium cation.

Examples of the alkyl group having 1 to 8 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 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 include linear or branched ones such as methyl-2-butenyl and 1,2-dimethyl-1-propenyl.

Examples of the aryl group having 6 to 10 carbon atoms (not including the carbon number of the following substituents) include a phenyl group, a naphthyl group, and an aromatic heterocyclic hydrocarbon group (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl). , Pyrimidyl, pyrazinyl and the like monocyclic heterocycles; and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl and the like condensed polycyclic heterocycles).
As the aryl group, in addition to the above, a part of hydrogen atoms in the aryl group may be substituted with an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

In formula (1), Rf is a fluorine atom in which a hydrogen atom bonded to a carbon atom in the alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms is usually 80 % Or more is substituted. Preferably it is 90% or more, More preferably, it is 100%. When the substitution rate of fluorine atoms is less than 80%, the polymerization initiating ability of the photosensitive composition of the present invention decreases.
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 because of availability of raw materials. Particularly preferred Rf is an alkyl group having 1 to 4 carbon atoms and a substitution rate of 100% of fluorine atoms. Specific examples 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 , (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) (} C _{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] ⁻ are preferred, and [(CF ₃ SO ₂ ) ₃ C] ⁻ and [(CF ₃ CF ₂ SO ₂ ) ₃ C] ⁻ are particularly preferable.

In the formula (1), A ⁺ is a monovalent onium cation.
The monovalent onium cation means a cation produced by coordination of a proton or a cation type atomic group (alkyl group, etc.) to a compound containing an element having an unshared electron pair. The following cations are mentioned.

Oxonium cations (trimethyloxonium cation, triethyloxonium and tetramethylenemethyloxonium cations, etc.);
Pyririnium cations (such as 4-methylpyrrinium cation and 2,6-diphenylpyrrinium cation);
Chromenium cation (2,4-dimethylchromenium cation, etc.);
Isochromenium cation (such as 1,3-dimethylisochromenium cation);
Ammonium cation [ammonium cation, primary ammonium cation (n-butylammonium cation, etc.), secondary ammonium cation (diethylammonium cation, etc.), tertiary ammonium cation (triethylammonium cation, etc.), quaternary ammonium cation (tetramethylammonium cation) , Phenyltrimethylammonium cation and tetrabutylammonium cation, etc.)];
Pyrrolidinium cations (N, N-dimethylpyrrolidinium cation and N, N-diethylpyrrolidinium cation, etc.);
Imidazolinium cations (N, N′-dimethylimidazolinium cation and N-ethyl-N′-methylimidazolinium cation, etc.);
Amidinium cations (N, N′-dimethyltetrahydropyrimidinium cation, N-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium cation and N-benzyl-1,5-diazabicyclo [4.3.0] -5-Nonenium cation etc.);
Morpholinium cation (N, N′-dimethylmorpholinium cation, etc.), piperidinium cation (N, N′-diethylpiperidinium cation, etc.);
Pyridinium cation (N-methylpyridinium cation, N-methoxypyridinium cation, N-butoxypyridinium cation, N-benzyloxypyridinium cation, N-benzylpyridinium cation, etc.).
Imidazolium cations (N, N′-dimethylimidazolium cation and 1-ethyl-3-methylimidazolium cation, etc.);
Quinolium cations (N-methyl quinolium cation cation, N-benzyl quinolium cation, etc.);
Isoquinolium cations (N-methylisoquinolium, etc.);
Thiazonium cations (such as benzylbenzothiazonium cations);
Acridium cation (such as benzylacridium cation and phenacylacridium);
Diazonium cations (phenyldiazonium cation, 2,4,6-triethoxyphenyldiazonium cation, 2,4,6-trihexyloxyphenyldiazonium cation, 4-anilinophenyldiazonium cation, etc.);
Guazinium cations (such as hexamethylguanidinium cation and 2-benzyl-2-tert-butyl-1,1,3,3-tetramethylguanidinium cation).
Phosphonium cation [tertiary phosphonium cation (triphenylphosphonium cation, tritert-butylphosphonium cation, etc.) and quaternary phosphonium cation (tetraphenylphosphonium cation, tetra-p-tolylphosphonium cation, triphenylbenzylphosphonium cation, triphenylbutyl cation) , Tetraethylphosphonium cation and tetrabutylphosphonium cation, etc.)].
Sulfonium cations {triphenylsulfonium cation, 4- (phenylthio) phenyldiphenylsulfonium cation, bis [4- (diphenylsulfonio) phenyl] sulfide, 4-hydroxyphenylmethylbenzylsulfonium cation, etc.};
Sulfoxonium cations (such as triphenylsulfoxonium);
Thianthrenium cation [5- (4-methoxyphenyl) thianthrenium, 5-phenylthianthrenium and 5-tolylthanthrhenium cation, etc.];
A thiophenium cation (such as 2-naphthyltetrahydrothiophenium);
Iodonium cations [diphenyl iodonium cation, di-p-tolyl iodonium cation, 4-isopropylphenyl (p-tolyl) iodonium cation, etc.].

Among the 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-tolyliodonium cation and 4-isopropylphenyl (p-tolyl) iodonium cation, 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 Cation, bis (4-dodecylphenyl) iodonium cation, bis (4-methoxyphenyl) iodonium cation, bis (4-decyloxy) phenyliodonium Thione, 4- (2-hydroxy-tetradecyloxy) phenyl iodonium cation and the like.

Specific examples of preferred sulfonium cations include the above triphenylsulfonium cation, 4- (phenylthio) phenyldiphenylsulfonium cation, bis [4- (diphenylsulfonio) phenyl] sulfide and 4-hydroxyphenylmethylbenzylsulfonium cation, as well as tris (4-chlorophenyl) sulfonium cation, tris (4-fluorophenyl) sulfonium cation, 4-tert-butylphenyldiphenylsulfonium cation, diphenylphenacylsulfonium cation, and the like.

Specific examples of preferred iodonium salts include the following.

Specific examples of preferred 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 metathesis method is, for example, New Experimental Chemistry Course 14-I (1978, Maruzen) p-448; Advance in Polymer Science, 62, 1-48 (1984); New Experimental Chemistry Course 14-III (1978, Maruzen). ) Pp 1838-1846; Organosulfur Chemistry (Synthetic Reactions, 1982, Kagaku Dojin), Chapter 8, pp 237-280; Nihon Kagaku Kagaku, 87, (5), 74 (1966); JP-A 64-45357 JP, 61-212554, JP 61-100557, JP 5-4996, JP 7-82244, JP 7-82245, JP 58-21904. No. 1, JP-A-6-184170 and the like, but first, onium cations such as F ⁻ , Cl ⁻ , Br ⁻ , I ^−, etc. Halogen ion salt; OH ⁻ salt; ClO ₄ ⁻ salt; salt with sulfonate ions such as FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ and CF ₃ SO ₃ ⁻ ; Salts with sulfate ions such as HSO ₄ ⁻ and SO ₄ ²⁻ ; Salts with carbonate ions such as HCO ₃ ⁻ and CO ₃ ²⁻ ; H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ and PO ₄ ³⁻ And the like, and an alkali metal salt, alkaline earth metal salt or quaternary ammonium salt of the anion constituting the onium salt represented by the formula (1) above the theoretical amount In addition to the solvent and aqueous solution it contains, it decomposes. As the solvent, water or an organic solvent can be used. Organic solvents include hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahydrofuran, dioxane, etc.), chlorinated solvents (chloroform, dichloromethane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones ( Acetone, methyl ethyl ketone and methyl isobutyl ketone), nitriles (acetonitrile, etc.) and polar organic solvents (dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, etc.). These solvents may be used alone or in combination of two or more.

The target onium salt thus produced is separated as 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, the precipitated solid is separated from the organic solvent solution, and further, the organic solvent contained in the solid is distilled off. The target onium salt thus obtained can be purified by a method such as recrystallization or washing with water or a solvent, if necessary.

In purification by recrystallization, the target onium salt is dissolved in a small amount of organic solvent, and separation from the organic solvent is performed directly (or after concentration) on the organic solvent solution containing the target onium salt. In addition, the target onium salt can be precipitated. Examples of the poor solvent used here include chain ethers (such as diethyl ether and dipropyl ether), esters (such as ethyl acetate and butyl acetate), aliphatic hydrocarbons (such as hexane and cyclohexane), and aromatic hydrocarbons (toluene and Xylene and the like). Further, purification can be performed by utilizing the difference in solubility depending on temperature. Purification can be performed by recrystallization (a method using a difference in solubility due to cooling, a method of adding a poor solvent to precipitate, and a combination thereof). Further, when the photobase generator is an oily substance (when it is not crystallized), it can be purified by a method of washing the oily substance with water or a poor solvent.

The structure of the onium salt thus obtained should be identified by a general analytical method, for example, each nuclear magnetic resonance spectrum such as ¹ H, ¹³ C, and ¹⁹ F, infrared absorption spectrum, or elemental analysis. Can do.

As the salt of an anion used for the above metathesis reaction, an alkali metal salt is preferable from the viewpoint of reactivity. This salt can be produced by a known method. For example, non-patent literature (Inorg. Chem., 27, 2135-2137, 1988) or patent literature (Japanese Patent Laid-Open No. 05-503808) can be referred to.

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

As the sensitizer (B), a compound having absorption in the visible region to the infrared region, including a sensitizer described in the publicly known (Japanese Patent Laid-Open Nos. 11-279212 and 09-183960, etc.) is used. It is done. In particular, a sensitizer having absorption in the infrared region of 700 nm to 1500 nm is also called “IR absorber” or “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-naphthoquinone, etc.}; anthraquinone {2-methylanthraquinone, 2-ethylanthraquinone, etc.}; anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2 -Ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2 -Chlorothioxa Phenothiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine, etc.}; xanthone; coumarin {7- (diethylamino) 4- (tri Fluoromethyl) 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] quinolizin-11-one, 10- (2-benzothiazolyl) -2,3,6,7 -Tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H,-[1] benzopyra [6,7,8-ij] quinolidin-11-one etc.}; ketone {2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpro Piophenone, 4-benzoyl-4′-methyldiphenyl sulfide, bis (4,4′-dimethylamino) benzophenone and bis (4,4′-diethylamino) benzophenone, etc.}; carbazole {N-phenylcarbazole, N-ethylcarbazole , Poly-N-vinylcarbazole and N-glycidylcarbazole etc.}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene etc.}; phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene 9-hydroxy-10-methoxyphenanthrene and 9-hydroxy-10-ethoxy phenanthrene and the like}.
In particular, from the viewpoint of electron acceptability, when a naphthoquinone, benzophenone, xanthone, anthraquinone, or thioxanthone sensitizer is used, a high sensitization effect is obtained, which is preferable.

Examples of the sensitizer (B-2) having absorption in the infrared region (700 nm to 1500 nm) include cyanine dyes, polymethine dyes such as (thio) pyrrinium dyes, squalium dyes, aminium dyes, diimonium dyes, and the like. A dye having a diaryliminocation skeleton, phthalocyanine, naphthalocyanine, porphyrin, a complex having these central metals, and the like 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 0.00, based on the total weight of the sensitizer (B), the onium salt and the radical polymerizable compound (C). 01 to 10% by weight.

As the radically polymerizable compound (C) contained in the photosensitive composition of the present invention, known compounds can be used without particular limitation as long as they are compounds that are polymerized by radicals.
For example, C3-C35 acrylamide compound (C11), C4-C35 (meth) acrylate compound (C12), C6-C35 aromatic vinyl compound (C13), C3-C20 vinyl ether A compound (C14) and another radically polymerizable compound (C15) are mentioned.
In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.

  Examples of the (meth) acrylamide compound (C11) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylate, N-propyl (meth) acrylamide, 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 ( Mention may be made of (meth) acrylamide, N, N-diethyl (meth) acrylamide and (meth) acryloylmorpholine.

Examples of the (meth) acrylate compound (C12) having 4 to 35 carbon atoms include the following monofunctional to hexafunctional (meth) acrylates.
Monofunctional (meth) acrylates include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( (Meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate Relate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene monoacrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexyl carbitol ( (Meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meta) ) Acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxy Propyl (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 (meth) acrylate, dimethylaminoethyl (meth) acrylate 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 ( (Meth) acrylate, dipropylene glycol (meth) acrelane , Polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2- Hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) 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.

  As the bifunctional (meth) acrylate, 1,4-butanedi (meth) acrylate, 1,6-hexanediacrylate, polypropylene diacrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanedioldi (Meth) 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) a Relate, hydroxypivalate 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-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate and tri And cyclodecanedi (meth) acrylate.

  Trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate , Propoxylated trimethylolpropane tri (meth) acrylate and ethoxylated glycerol triacrylate, and the like.

  Tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionate dipentaerythritol tetra (meth) acrylate and ethoxylated pentaerythritol tetra. (Meth) acrylate etc. are mentioned.

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

  Examples of hexafunctional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) acrylate. It is done.

  Examples of the aromatic vinyl compound having 6 to 35 carbon atoms (C13) include vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro. Styrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, Seo propenyl styrene, butenylstyrene, octenyl styrene, 4-tert-butoxycarbonyl styrene, 4-methoxystyrene and 4-tert-butoxystyrene, and the like.

As a C3-C35 vinyl ether compound (C14), the following monofunctional or polyfunctional vinyl ether is mentioned, for example.
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, cyclohexyl methyl vinyl ether, 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, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloro Mention may be made of ethoxyethyl 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, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added penta Examples include erythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

  Other radical polymerizable compounds (C15) include acrylonitrile, vinyl ester compounds (vinyl acetate, vinyl propionate, vinyl versatate, etc.), maleimide compounds (1-methyl-2,4-bismaleimide benzene, N, N ′ -M-phenylene bismaleimide etc.), allyl ester compounds (eg allyl acetate), halogen containing monomers (vinylidene chloride and vinyl chloride etc.) and olefin compounds (ethylene and propylene etc.) Multiple oligomers are also included. Polyfunctional (meth) acrylate oligomers include oligomers such as epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polysiloxane (meth) acrylate oligomers, and polyester (meth) acrylate oligomers. Can be mentioned.

  Among these, the acrylamide compound (C11) having 3 to 35 carbon atoms, the (meth) acrylate compound (C12) having 4 to 35 carbon atoms, and the aromatic vinyl compound having 6 to 35 carbon atoms are preferable from the viewpoint of the curing rate. (C13) and a C3-C20 vinyl ether compound (C14), more preferably a C3-C35 acrylamide compound (C11) and a C4-C35 (meth) acrylate compound (C12). .

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% based on the total weight of the onium salt and the radical polymerizable compound (C). % By weight, preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight. In addition, the onium salt represented by General formula (1) may use 2 or more types together.

The photosensitive resin composition of the present invention can contain other additives (J) generally used for controlling the appearance and physical properties of the cured product of the photosensitive resin composition. Other additives (J) include a colorant (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 in paints and inks can be used.

  Examples of inorganic pigments include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

  Organic pigments include β-naphthol, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone and other soluble azo pigments, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid Insoluble azo pigments such as anilide, acetoacetanilide monoazo, acetoacetate anilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, iso Examples thereof include polycyclic or heterocyclic compounds such as sindrinone, quinacridone, dioxazine, perinone, and perylene.

Specific examples of dyes include yellow dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones or open-chain active methylene compounds as coupling components, open-chain activity as coupling components Examples thereof include azomethine dyes having a methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes.

  For magenta dyes, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) are used as coupling components. Aryl or heteryl azo dyes having, azomethine dyes having pyrazolones or pyrazolotriazoles as coupling components, arylidene dyes, styryl dyes, merocyanine dyes such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes Examples thereof include carbonium dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes Examples of the coupling component include phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives, aryl or heteryl azo dyes (such as CI Direct Blue 14), and indigo / thioindigo dyes.

  The particle diameter 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 diameter, from the viewpoint of the sharpness of the coating film.

  Although the addition amount of a coloring agent (Ja) is not specifically limited, It is preferable that it is 1 to 60 weight% based on the total weight of a photosensitive composition.

When using a pigment, it is preferable to add a pigment dispersant in order to improve the dispersibility and the storage stability of the photosensitive composition.
Pigment dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184, 2020, etc.) ), Pigment dispersants manufactured by Ajinomoto Fine Techno Co. (Ajisper PB711, PB821, PB814, PN411, PA111, etc.) and pigment dispersants manufactured by Lubrizol (Solspers 5000, 12000, 32000, 33000, 39000, etc.). These pigment dispersants may be used alone or in combination of two or more. Although the addition amount of a pigment dispersant is not specifically limited, It is preferable to use in the range of 0.1 to 10 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 green sheets and electrode layers of ceramic electronic components.

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

  The particle diameter of (Jb) is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm as an average particle diameter from the viewpoint of dielectric constant.

The metal powder (Jc) is a noble metal and a base metal used when forming the conductor layer, and specifically includes palladium, nickel, copper, silver, gold, and the like, preferably palladium, nickel, and copper. It is.
The average particle diameter of (Jc) is preferably 0.01 μm to 10 μm.

The photosensitive composition of the present invention can contain a solvent, an adhesion-imparting agent (such as a silane coupling agent) and the like as 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). Acetate and propylene glycol alkyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, mesitylene, limonene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (Tetrahydrofuran and 1,8-cineole etc.). 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. It is.

  Adhesion imparting agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltri Examples include ethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. The content in the case of using an 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 based on the total weight of the photosensitive composition.

  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 an ultraviolet ray in accordance with the purpose of use. An absorbent or the like can be contained.

  The photosensitive composition of the present invention comprises an onium salt represented by the general formula (1), a radical polymerizable compound (C), a sensitizer (B), a colorant (Ja) used if necessary, and a metal oxide used if necessary. Object particles (Jb), optionally used metal particles (Jc), optionally used solvents, and optionally used adhesion imparting agents are uniformly mixed using a known stirring and mixing device (such as a mixing container with a stirrer and a paint shaker). It can be obtained by a mixing method and a kneading method using a known kneader (such as a ball mill and a three-roll mill). 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. Depending on the application, in addition to the commonly 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 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 light to accelerate the curing reaction to obtain a cured product. Therefore, as a method for producing such a cured product, is it possible to select a sensitizer (B) corresponding to the wavelength of light serving as a light source, and irradiate light using the one contained in the photosensitive composition? It is preferable to include a step of irradiating light using a light source corresponding to the absorption wavelength of the used sensitizer (B). In addition, you may heat as needed in the case of hardening reaction. The heating temperature is usually 30 ° C to 200 ° C, preferably 35 ° C to 150 ° C, 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 coating, roll coating, and spray coating, and lithographic printing, carton printing, metal printing, offset printing, and screen printing are used depending on the application. In addition, a known printing method such as gravure printing can be applied. In addition, the present invention can also be applied to ink jet type coating in which fine droplets are continuously discharged.

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

Production Example 1 Synthesis of lithium tris (trifluoromethanesulfonyl) methydate (AN-1) 2.8 g of methyl iodide and 100 mL of diethyl ether were added to a dry reaction vessel, and 2.5 g of trifluoromethanesulfonyl chloride was added thereto to add -78. Cooled to ° C. Thereto, 44 mL of tert-butyllithium pentane solution (1.9 mol L ⁻¹ ) was added dropwise while keeping the liquid temperature at −50 ° C. or lower. After dropping, the temperature was gradually raised to room temperature and stirred for 6 hours. Thereafter, the mixture was further stirred for 10 hours under reflux.
1N Hydrochloric acid was added to the reaction solution in an ice bath, and the resulting solid was stirred for 1 hour. The resulting solid was filtered, and the filtrate was extracted with diethyl ether and washed with saturated brine. The organic layer was concentrated to give a white solid.
This was confirmed by ¹⁹ FNMR to be lithium tris (trifluoromethanesulfonyl) methidoate (AN-1).

Production Example 2 Synthesis of lithium tris (pentafluoroethanesulfonyl) methydate (AN-2) In Production Example 1, the same as Production Example 1 except that 2.5 g of trifluoromethanesulfonyl chloride was changed to 3.3 g of pentafluoroethanesulfonyl chloride. Thus, lithium tris (pentafluoroethanesulfonyl) methidoate (AN-2) was obtained.

Production Example 3 Synthesis of lithium tris (nonafluorobutanesulfonyl) methydate (AN-3) Same as Production Example 1 except that 2.5 g of trifluoromethanesulfonyl chloride was changed to 4.8 g of nonafluorobutanesulfonyl chloride in Production Example 1. Thus, tris (nonafluorobutanesulfonyl) methydate lithium (AN-3) was obtained.

Production Example 4 Synthesis of Onium Salt (A1-1): Diphenyliodonium Tris (trifluoromethanesulfonyl) methide 4.3 g of diphenyliodonium trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry) and 30 g 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 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. ^{By 1} H and ¹⁹ F, this was confirmed to be an onium salt (A1-1).

Production Example 5 Synthesis of Onium Salt (A1-2): Diphenyliodonium Tris (pentafluoroethanesulfonyl) methide In Production Example 4, lithium salt (AN-2) was used instead of 4.2 g of lithium salt (AN-1). 8.0 g of the desired product was obtained according to the method described in Production Example 4 except that the amount was 7 g. ^{From 1} H and ¹⁹ F, it was confirmed that this white solid was an onium salt (A1-2).

Production Example 6 Onium Salt (A1-3): Synthesis of Diphenyliodonium Tris (Nonafluorobutanesulfonyl) methide In Production Example 4, lithium salt (AN-3) was used instead of 4.2 g of lithium salt (AN-1) 8. 9.3 g of the target product was obtained according to the method described in Production Example 4 except that the amount was 7 g. ^{From 1} H and ¹⁹ F, it was confirmed that this white solid was an onium salt (A1-3).

Production Example 7 Synthesis of Onium Salt (A1-4) :( 4-Isopropylphenyl) Tolyliodonium Tris (trifluoromethanesulfonyl) methide 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. 1 g of potassium persulfate was added little by little at 15 ° C. or lower while cooling in an ice water bath. It was made to react at 20 degreeC for 4 hours, and 2.4 g of cumene was dripped there so that it might not exceed 20 degreeC. Thereafter, the reaction was allowed to proceed at room temperature for 20 hours. The reaction solution was added to a solution in which 4.2 g of lithium salt (A-1) was dissolved in 50 mL of water, and further stirred for 3 hours. Thereto was added 50 mL of dichloromethane. 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 with cyclohexane to obtain 6.8 g of a white solid. ^{By 1} H, ¹⁹ F-NMR, this was confirmed to be an onium salt (A1-4).

Production Example 8 Synthesis of Onium Salt (A1-5) :( 4-Isopropylphenyl) Tolyliodonium Tris (pentafluoroethanesulfonyl) methide In Production Example 7, lithium salt (AN-1) was replaced with 4.2 g AN-2) The target product was obtained according to the method described in Preparation Example 7 except that 5.7 g was used. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A1-5).

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

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

Production Example 11 Synthesis of Onium Salt (A1-8): Di (tert-butylphenyl) iodonium tris (nonafluorobutanesulfonyl) methide In Production Example 9, lithium salt (AN-1) was replaced with 4.2 g of lithium salt (AN-1). AN-3) The target product was obtained according to the method described in Preparation Example 9 except that the amount was 8.7 g. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be 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 Patent Laid-Open No. 06-184170), the desired product was obtained. It was. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A1-9).

Production Example 13 Synthesis of Onium Salt (A1-10) :( 4-Octyloxyphenyl) phenyliodoniumtris (nonafluorobutanesulfonyl) methide According to the method described in Patent Literature (JP 06-184170), the desired product was obtained. . ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A1-10).

Production Example 14 Synthesis of Onium Salt (A2-1): 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 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 1} H, 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) methide In Production Example 14, lithium salt (AN-2) 5 instead of 4.2 g of lithium salt (AN-1) The target product was obtained according to the method described in Production Example 14 except that the amount was 0.7 g. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A2-2).

Production Example 16 Onium Salt (A2-3): Synthesis of Triphenylsulfonium Tris (Nonafluorobutanesulfonyl) methide In Production Example 14, lithium salt (AN-3) 8 instead of 4.2 g of lithium salt (AN-1) The target product was obtained according to the method described in Production Example 14 except that the amount was 0.7 g. It was confirmed by ¹ H, ¹⁹ F-NMR that it was an onium salt (A2-3).

Production Example 17 Synthesis of Onium Salt (A2-4): (4-Phenylthio) phenyldiphenylsulfonium Tris (trifluoromethanesulfonyl) methide According to the method described in Patent Document (WO2005-116038), the desired product was obtained. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A2-4).

Production Example 18 Onium Salt (A2-5): Synthesis of (4-Phenylthio) phenyldiphenylsulfonium Tris (pentafluoroethanesulfonyl) methide According to the method described in Patent Document (WO2005-116038), the desired product was obtained. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A2-5).

Production Example 19 Onium salt (A2-6): Synthesis of (4-phenylthio) phenyldiphenylsulfonium tris (nonafluorobutanesulfonyl) methide According to the method described in Patent Literature (WO2005-1116038), the desired product was obtained. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A2-6).

Production Example 20 Onium salt (A2-7): Synthesis of tris (4-tert-butylphenyl) sulfonium tris (trifluoromethanesulfonyl) methide Tris (4-tert-butylphenyl) sulfonium triflate (manufactured by Aldrich) in a reaction vessel 8 g and 50 mL of dichloromethane were added. While stirring, 4.2 g of 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. ^{By 1} H, ¹⁹ F-NMR, this 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) methide In Production Example 20, lithium instead of 4.2 g of lithium salt (AN-1) The target product was obtained according to the method described in Production Example 20 except that 5.7 g of salt (AN-2) was used. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be 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 a reaction vessel, and 50 mL of THF was further added. . The mixture was cooled to 0 ° C. in 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 from 4-fluorobromobenzene was added dropwise while maintaining the temperature at 10 ° C. or lower. After completion of dropping, the reaction was allowed to proceed 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. Dichloromethane (70 mL) was added, the aqueous layer was removed by liquid separation, and washing was performed 5 times with 50 mL of water. The dichloromethane layer was concentrated and crystallized with cyclohexane to obtain 6.2 g of a white solid. ^{By 1} H, ¹⁹ F-NMR, it was confirmed that this white solid was 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, lithium salt (AN-1) was replaced with 4.2 g of lithium salt (AN-1). AN-2) The target product was obtained according to the method described in Production Example 22 except that the amount was 5.7 g. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A2-10).

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

Production Example 25 Synthesis of Onium Salt (A2-12): Thiodi-p-phenylenebis (diphenylsulfonium) bis [tris (pentafluoroethanesulfonyl) methide] According to the method described in Patent Document (JP 2013-227368 A) I got a thing. ^{By 1} H, ¹⁹ F-NMR, it was confirmed to be an onium salt (A2-12).

Comparative Production Example 1 Synthesis of the following onium salt (A′-1) Production Example 10 except that in place of 4.2 g of lithium salt (AN-1), tetraphenylborate sodium (manufactured by Nacalai Tesque) is used in an amount of 3.5 g. The target product was obtained according to the method described in Example 10. It was confirmed by ¹ H-NMR that it was an onium salt (A′-1).

Comparative Production Example 2 Synthesis of Production Example 14 of the following photobase generator (A′-2) In Example 14 except that 4.2 g of lithium salt (AN-1) is replaced with sodium tetraphenylborate (manufactured by Nacalai Tesque). Was obtained according to the method described in Preparation Example 14. ^{By 1} H-NMR, it was confirmed to be an onium salt (A′-2).

<Examples 1-37 and Comparative Examples 1-16>
[Preparation of photosensitive composition]
100 g of radically polymerizable compound (C), 3 g of onium salt (A), 0.3 g of sensitizer (B) were uniformly mixed, and the photosensitive compositions (Q-1) to (Q-37) and comparison of the present invention were compared. 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), and exposure is performed using an irradiation apparatus LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics) as a light source. The curability was confirmed. 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 Chemical Industry Co., Ltd.)
A'-4: Triphenylsulfonium bromide (manufactured by Tokyo Chemical Industry)
B-1: B-201 (described above as a specific example of polymethine dye)
B-2: B-204 (described above as a specific example of 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)
C-2: Ethoxylated trimethylolpropane triacrylate (“Neomer TA-401” manufactured by Sanyo Chemical Industries)
C-3: Polypropylene glycol diacrylate (“Neomer PA-305” manufactured by Sanyo Chemical Industries)
[Curing property]
Curability-1: Exposed through an infrared transmission filter (manufactured by HOYA) R72 (cut below 700 nm) to confirm curability.
Curability evaluation: ◎ There is no tack on the surface, and even if scratched with a nail, it will not be damaged.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
X It does not cure in the liquid state.

<Examples 38 to 42 and Comparative Examples 17 to 20>
[Preparation of photosensitive composition]
100 g of radically polymerizable compound (C), 3 g of onium salt (A), and 0.3 g of sensitizer (B-3) are uniformly mixed, and the photosensitive compositions (Q-38) to (Q-42) of the present invention are mixed. 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), and exposure is performed using an irradiation apparatus LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics) as a light source. The curability was confirmed. The results are shown in Table 2. The raw materials used are as described above.
[Curing property]
Curability-2: Exposed through a sharp cut filter (manufactured by HOYA) Y44 (cut below 430 nm) to confirm curability.
Curability evaluation: ◎ There is no tack on the surface, and even if scratched with a nail, it will not be damaged.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
X It does not cure in the liquid state.

<Examples 43 to 47 and Comparative Examples 21 to 24>
[Preparation of photosensitive composition]
100 g of radically polymerizable compound (C), 1 g of onium salt (A), and 0.1 g of sensitizer (B-4) are uniformly mixed, and the photosensitive compositions (Q-43) to (Q-47) of the present invention are mixed. And comparative photosensitive resin compositions (Q′-21) to (Q′-24) were prepared. The types of raw materials used are shown in Table 1.
[Curing property]
Curability-3: This photosensitive composition was applied to a glass substrate (76 mm × 52 mm) using an applicator (40 μm), and exposed using a UV-LED irradiation apparatus 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 even if scratched with a nail, it will not be damaged.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
X It does not cure in the liquid state.

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 can also be seen that it is important to select an appropriate sensitizer for the wavelength of light to be irradiated.

<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 (1)>
43 parts of titanium oxide (“Taipek R-930” manufactured by Ishihara Sangyo Co., Ltd.) as a pigment, 4 parts of pigment dispersant (“Solspers 32000” manufactured by Lubrizol) and tetrahydrofurryl acrylate (Kyoeisha) as a radical polymerizable compound (C) A pigment dispersant solution having a pigment concentration of 43% was prepared by kneading a mixture of 53 parts of “light acrylate THF-A” (chemical product) for 3 hours using a ball mill.
<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), 0.5 part of the sensitizer (B-2) and onium salts shown in Table 2 ( A) or 5 parts of comparative onium salt (A ′) was kneaded for 3 hours at 25 ° C. using a ball mill, respectively, and the photosensitive compositions (Q-48) to (Q-52) and comparative photosensitive properties of the present invention were used. Resin compositions (Q′-25) to (Q′-28) were produced, and the coating film curability (curability-3) was evaluated by the following method. The results are shown in Table 4.
[Curing property]
Curability-3: A surface-treated PET (polyethylene terephthalate) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.] having a thickness of 20 μm was applied to the photosensitive composition using an applicator. Applied. Exposure was performed using an irradiation apparatus LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics) as a light source, and curability was confirmed by the following evaluation method.
Curability evaluation: ◎ There is no tack on the surface, and even if scratched with a nail, it will not be damaged.
○ There is no tack on the surface, but it is damaged by the nails.
△ Tack remains on the surface.
X It does not cure in the liquid state.

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

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

The photosensitive composition of the present invention utilizes light (especially visible region to infrared region), paints, coating agents, various coating materials (hard coat, antifouling coating material, antifogging coating material, touchproof 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 plate, dental material (dental compound, dental composite) ) Ink, inkjet ink, positive resist (formation of connection terminals and wiring patterns for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (semiconductor elements and transparent electrodes for FPD ( Surface protection film such as ITO, IZO, GZO), permanent film materials such as interlayer insulation film, flattening film, etc.), MEMS resist, positive photosensitive material, G-type photosensitive materials, various adhesives (various electronic component temporary fixing agents, HDD adhesives, pickup lens adhesives, FPD functional film (deflecting plates, antireflection films, etc.) adhesives, circuit formation Insulating film for semiconductor encapsulation, anisotropic conductive adhesive (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 components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, flip chips, Chip sealing material such as COF, packaging sealing material such as CSP or BGA, optical semiconductor (LED) sealing material, optical waveguide material, nanoimprint material, optical construction , And it is preferably used in micro-stereolithography material or the like.

Claims (7)

(A) The photosensitive composition characterized by containing the onium salt (B) sensitizer (C) radical polymerizable compound represented by General formula (1) as an essential component.

[In Formula (1), Rf is mutually independently a C1-C8 alkyl group, a C2-C8 alkenyl group, a C6-C10 aryl group, and carbon atom of each group. A ⁺ is a group obtained by substituting 80% or more of the hydrogen atom bonded to with a fluorine atom, and 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 independently an alkyl group having 1 to 8 carbon atoms in which 90% or more of hydrogen atoms are substituted with fluorine atoms. The photosensitive composition according to any one of claims 1 to 3, wherein the sensitizer (B) is a polymethine dye. A method for curing a photosensitive composition comprising irradiating the photosensitive composition according to any one of claims 1 to 4 with light having a wavelength of 400 nm to 1500 nm in a visible light to infrared light region. . A method for curing a photosensitive composition, comprising a step of irradiating the photosensitive composition according to claim 1 with light in a near-infrared light region having a wavelength of 700 nm to 1200 nm. A cured product obtained by curing the photosensitive composition by the method according to claim 5.