JP2576712B2 - Near-infrared photosensitive resin composition and optical molded body using the composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel composition which can be rapidly cured by irradiation with near-infrared rays or heating, and an optical molded article using the composition.

[0002]

2. Description of the Related Art Highly polymerizable polymer materials, which are polymerized by energy rays, particularly light, have been actively studied, especially in the field of paints, because of demands for energy saving, space saving and pollution-free. However, most of these studies have been based on the principle of radical polymerization of compounds containing double bonds by ultraviolet irradiation. Although epoxy resin is a physically excellent material, it is difficult to perform radical polymerization, and a method of introducing a double bond by acrylic modification or the like has been employed for a long time.

[0003] Thereafter, US Pat. No. 3,794,576 proposed a high-performance photopolymerizable epoxy resin composition having favorable rheological properties and curability. This composition uses a photosensitive aromatic diazonium salt as a photopolymerization initiator. The aromatic diazonium salt is decomposed by ultraviolet irradiation, and the epoxy resin monomer is cationically polymerized by the generated Lewis acid. However, the aromatic diazonium salt releases nitrogen gas by photolysis, and when the epoxy resin obtained by polymerization becomes 15 μm or more, the coating film foams and is not suitable for thick coating.

In order to improve this point, the use of an onium salt compound such as an aromatic iodonium salt or an aromatic sulfonium salt as a photopolymerization initiator has been proposed in Japanese Patent Publication No. Sho 52 (1988).
No. -14277, Japanese Patent Publication No. 52-14278,
JP-B-54-53181, JP-B-59-1958
No. 1 publication. The composition of these onium salts and epoxy resin gives a cured product having appropriate storage stability without being foamed by ultraviolet irradiation upon photocuring. Also, by using a composite initiator of two or more components to which a sensitizer is added, the spectral sensitivity in the visible region can be increased, and a cured product can be given by irradiation with visible light.

However, a composition comprising an onium salt and an epoxy resin is disclosed in JP-A-2-24120 to JP-A-2-2412.
In the case where a molded article is produced by an optical molding method as described in Japanese Patent Publication No. 7 (1994), the ultraviolet or visible light laser required to be used as a light source is a helium-cadmium laser or an argon laser, and these are very Due to their high cost and size, the cost and size of the device are dominated by the laser light source, which makes it impossible to reduce the size of the device. The life of these lasers is as short as 2000 hours.

Thereafter, an iron allene complex is used as a one-component initiator for visible light capable of curing an epoxy resin by argon laser light. Reported by Meier et al. The iron allene complex can perform ligand exchange with an epoxide by light irradiation and initiate cationic polymerization.
However, since the efficiency of photocuring is not good due to a small molar extinction coefficient, a high-power laser light source is required, and it can be used only in a field where irradiation with a high-power laser is acceptable.

In Japanese Patent Application Laid-Open No. 2-252765, a three-dimensional structure is obtained by thermally curing a composition comprising an onium salt and an epoxy resin using a YAG laser or a carbon dioxide laser as an infrared laser. However, in order to perform thermosetting using these lasers, carbon black must be used as a laser light energy absorber and 3
Requires a high output of W or more. As a result, only a black cured product is obtained, and thermal runaway may fail to obtain a molded product having a desired shape. In addition, there was a problem in handling safety due to high output.

Therefore, if a semiconductor laser can be used, an inexpensive desktop type solid model producing apparatus can be realized. However, there is no known photopolymerization initiator capable of polymerizing and curing a cationically polymerizable organic compound such as an epoxy resin with near-infrared light having an output of the order of a semiconductor laser. Not obtained. Therefore, an optical shaping method using a semiconductor laser could not be developed.

[0009]

In view of the above situation, an object of the present invention is to polymerize and cure a cationically polymerizable organic compound such as epoxy by irradiation with near-infrared light having an output of the order of a semiconductor laser, so that heat and light are stable. It is to provide a durable cured product.

[0010]

An object of the present invention is to provide a near-infrared light sensitive composition comprising a cationically polymerizable organic compound and an aminium compound represented by the following general formula (1) or a diimmonium compound represented by the following formula (2): Achieved by the conductive resin composition.

[0011]

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[0012]

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(Where A is

[0014]

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B is

[0016]

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[K represents 1 or 2], and the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, a halogen atom or a hydroxyl group. X ^- represents an anion. R ₁ to R ₈ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkynyl group, R ₁ and R ₂ , R ₃
And R ₄ , R ₅ and R ₆ and R ₇ and R ₈ together with N to form a substituted or unsubstituted 5-membered ring, substituted or unsubstituted 6-membered ring, substituted or unsubstituted 7-membered ring Is also good. The substituents of R _{1 to} R ₈ may be the same or different).

The compound represented by the formula (1) or (2) is a known compound and is disclosed in US Pat.
No. 71 and U.S. Pat. No. 3,557,012, the optical disk has a maximum absorption wavelength of 900 nm or more, a large absorption peak having a molar extinction coefficient of about tens of thousands to hundreds of thousands, and utilizes these high near-infrared absorptivity. It has been known that it can be used for materials for laser recording, heat insulating films, sunglasses and the like.

The present inventors have studied these compounds. As a result, the aminium salt compound represented by the general formula (1) and the diimmonium salt compound represented by the formula (2) generate cations by absorbing near-infrared rays. It has been found that cationically polymerizable organic compounds such as epoxy can be polymerized and cured. Therefore, the general formula (1) or (2) is a cationic photopolymerization initiator using near infrared rays.

Further, it has been found that these compounds give a sufficiently cured product upon irradiation with light of the order of a semiconductor laser, thereby completing the present invention.

The curing sensitivity can be increased by adding an onium salt to the composition of the present invention.

According to the present invention, there is provided a near-infrared photosensitive resin composition comprising a combination of a cationically polymerizable organic compound such as epoxy and a near-infrared absorbing compound represented by the general formula (1) or (2). As a result, the composition is polymerized by light of an infrared laser such as a semiconductor laser or a YAG laser to obtain a cured product. Further, these compositions are polymerized by heating, and a cured product is obtained.

Further, a colored cured product can be obtained by adding a leuco dye having a lactone ring to the composition of the present invention.

In the above general formulas (1) and (2), R ₁
To R ₈ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkynyl group, and R ₁ and R ₂ , R ₃ and R ₄ , R ₅
A substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring with N in the combination of R ₆ and R ₇ and R ₈ ,
A substituted or unsubstituted 7-membered ring may be formed. R ₁ ~
The substituents of R ₈ may be the same or different.

For example, as the halogen atom, fluorine,
Shows chlorine, bromine, iodine, etc. For example, as the alkyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-
Butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group and the like, and further other alkyl groups, for example, substituted alkyl groups, , 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl, 2-carboxymethyl, 3-carboxypropyl, methoxyethyl, ethoxyethyl, methoxypropyl, 2 And -chloroethyl and the like. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group.Examples of the aralkyl group include a benzyl group, a p-chlorobenzyl group, a p-methylbenzyl group, and 2-phenyl. Methyl group, 2-phenylpropyl group,
3-phenylpropyl group, α-naphthylmethyl group, β-
Examples of the alkynyl group such as a naphthylethyl group include a propargyl group, a butynyl group, a benchinyl group, and a hexynyl group. As a substituted or unsubstituted 5-membered heterocyclic ring,
A substituted or unsubstituted 6-membered ring such as a pyrrolidine ring or the like is a piperidine ring, a morpholine ring, a tetrahydropyridine ring or the like, and a substituted or unsubstituted 7-membered ring is a cyclohexylamine ring or the like.

X ^- is a non-nucleophilic anion and has the formula MQ _n
^- (M is an atom selected from B, P, As, Sb, Fe, Al, Sn, Zn, Ti, Cd, Mo, W, Zr, preferably B, P, As, Sb. Q Is a halogen atom, and n is a number of 1 to 6.) Preferred _{^{anions, BF 4 -, PF 6 -}} , A
sF ₆ ^-, SbF ₆ ^-, and the like. Particularly preferred are
SbF ₆ ^- is. Also, the formula MQ _n-1 (OH) ^- (where M,
X, n SbF ₅ as the anion represented by the same) and the
(OH) ^-, and the like.

Other anions include perchlorate ion, trifluoromethyl sulfite ion, fluorosulfonate ion, p-toluenesulfonate ion, trinitrobenzenesulfonate ion and the like.

In the present invention, the general formula (1) or (2)
The method for producing the compound represented by
No. 81, U.S. Pat. No. 3,484,467, U.S. Pat.
75871 and JP-A-61-69991 can be used. For example, it can be manufactured as follows.

[0029]

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After selectively alkylating the amino compound obtained by the above-mentioned Ullmann reaction and reduction, a final product can be obtained by oxidation.

Next, specific examples of the compounds used in the general formulas (1) and (2) will be given. For the sake of simplicity, compounds represented by the general formula (1) are represented by A, X, (R ₁ R ₂ ) (R
Compounds represented by ₃ R ₄ ) (R ₅ R ₆ ) (R ₇ R ₈ ) and the general formula (2) are represented by B, X, (R ₁ R ₂ ) (R ₃ R ₄ )
_{(R 5 R 6) (R} 7 R 8), to the title.

For example, in the general formula (1), A is

[0033]

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Where k = 1, X ⁻ is SbF ₆ ⁻ , and R _{1 to} R
_{When 8} is an iso-propyl group,

[0035]

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SbF ₆ ⁻ , (iso-C ₃ H ₇ iso
−C ₃ H ₇ ) ₄ .

In the general formula (1), B is

[0038]

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Where k = 1, X ⁻ is SbF ₆ ⁻ , and R ₁ and R
_{When 2} is an ethyl group and R _{3 to} R ₈ are n-butyl groups,

[0040]

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SbF ₆ ⁻ , (nC ₄ H ₉ nC ₄ H
₉ ) ₃ (C ₂ H ₅ C ₂ H ₅ ).

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The cationically polymerizable organic compound capable of being polymerized to a high molecular weight state used in the present invention includes, for example, an epoxy compound, a cyclic ether compound, a cyclic lactone compound,
Examples thereof include one or a mixture of two or more of a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, and a vinyl compound. Among these cationically polymerizable organic compounds, compounds having at least two or more epoxy groups in one molecule are preferable, and examples thereof include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Resins.

Preferred as the aromatic epoxy resin are polyphenols having at least one aromatic nucleus or polyglycidyl ethers of an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F or alkylene oxide thereof. Glycidyl ether resins produced by the reaction of the adduct with epichlorohydrin are exemplified.

Preferred examples of the alicyclic epoxy resin include polyglycidyl ether or cyclohexene of a polyhydric alcohol having at least one alicyclic ring,
Alternatively, a cyclohexene oxide-containing compound or a cyclopentene oxide-containing compound obtained by epoxidizing a cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid can be used. Representative examples of the alicyclic epoxy resin include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene Examples include diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, and di-2-ethylhexyl epoxy hexahydrophthalate.

Preferred examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. Typical examples are diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and diglycidyl ether of polyethylene glycol. Examples include glycidyl ether and diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxystearic acid Butyl, octyl epoxystearate, epoxidized linseed oil, epoxidized polybutadiene and the like.

Examples of cationic polymerizable organic compounds other than epoxy compounds include: oxetane compounds such as trimethylene oxide and 3,3-dichloromethyloxetane; oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; trioxane; Cyclic acetal compounds such as 1,3-dioxolan and 1,3,6-trioxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; ethylene sulfide, thioepichlorohydrin, and the like. Thiirane compounds; thiethane compounds such as 1,3-propyl sulfide and 3,3-dimethylthiethane; and vinyl ether compounds such as ethylene glycol divinyl ether.

These cationically polymerizable compounds can be used alone or in combination of two or more kinds according to desired performance.

Particularly preferred among these cationically polymerizable organic compounds are alicyclic epoxy resins having at least two or more epoxy groups in one molecule, which are cationically polymerizable, have low viscosity, and have high UV transmittance. And good properties in terms of thick film curability, volume shrinkage, and resolution.

As the onium salt used in the present invention, a compound which releases the Lewis acid ion by the heat of the above-mentioned general formula (1) or (2) absorbing and emitting near-infrared light, or simply heat by external heating is used. Can be Such onium salts are divided into three groups: sulfonium salts, ammonium salts and halonium salts.

The sulfonium salt type is represented by the general formula: [(R ₉ ) _a (R ₁₀ ) _b (R ₁₁ ) _c Z] ⁺ _m [MQ _n ] ^-(np) (wherein R ₉ is a monovalent aromatic compound ⁾ R ₁₀ is a monovalent aliphatic organic group selected from an alkyl group, a cycloalkyl group and a substituted alkyl group; R ₁₁ is a heterocyclic group selected from an aliphatic group and an aromatic group; Z is a group VIa element selected from sulfur, selenium and tellurium; M is a metal or metalloid which is a central atom of a halide complex; B, P, As, Sb, Fe, Sn, Bi, Al, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc .; Q is a halogen atom; a is 0, 1, 2, or B is an integer of 0, 1 or 2;
c is an integer of 0 or 1; a + b + c is 3 or Z
M = n−p; p is the valency of M and is an integer from 2 to 7; and n is an integer greater than p and having a value up to 8. Is). Consistent with the name given herein, Z
Is preferably sulfur.

The ammonium salt type is represented by the general formula: [(R ₁₂ ) _d (R ₁₃ ) _e (R ₁₄ ) _f Z ′] ⁺ _m [MQ _n ] ^-(np) (where R ₁₂ is a carbocyclic group And R ₁₃ is a monovalent aliphatic organic group selected from an alkyl group, an alkoxy group, a cycloalkyl group and a substituted derivative thereof; and R ₁₄ is Z ′ is a polyvalent organic group forming an aromatic heterocyclic or fused ring structure;
'Is a Va group element selected from N, P, As, Sb and Bi; M is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe , Sn, Bi, Al, I
n is Ti, Zn, Sc, V, Cr, Mn, Co, etc .; Q is a halogen atom; d is an integer from 0 to 4; e is an integer from 0 to 2; D + e + f is a valence of 4 or X; m = n−p; p is a valency of M and is an integer of 2 to 7; and n is greater than p And an integer having a value of up to 8). Among them, Z 'is preferably a pyridinium salt of nitrogen. The halonium salt type has a general formula: [(R ₁₅ ) _g (R ₁₆ ) _h Z ″] ⁺ _m [MQ _n ] ^{− (np)} (wherein R ₁₅ is a monovalent aromatic organic group; R ₁₆ is a divalent aromatic organic group; Z ″ is a halogen atom such as I, Br, Cl 2, M is a metal or metalloid which is the central atom of the halide complex, , P, As, Sb, Fe, Sn, B
i is Al, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc .; Q is a halogen atom; g is an integer of 0 or 2; h is an integer of 0 or 1; g + h is a valence of 2 or X; m = n−p; p is a valence of M and is an integer from 2 to 7; and n is greater than p and up to 8 Is an integer having a value). Among them, Z ″ is preferably an iodonium salt of iodine. MQ _n ^{− in the} above general formula is a non-nucleophilic anion, and specific examples thereof include tetrafluoroborate ion (BF ₄ ⁻ ) and hexafluorophosphate ion (PF
₆ ^-), hexafluoroarsenate ion (AsF ₆ ^-), hexafluoroantimonate ion (SbF ₆ ^-), hexachloroantimonate salt ions (SbCl ₆ ^-) and the like. Further, an anion represented by the general formula MQ _n-1 (OH) ^- (M, Q and n are the same as above) can also be used.

Other anions include perchlorate ion, trifluoromethyl sulfite ion, fluorosulfonate ion, p-toluenesulfonate ion, trinitrobenzenesulfonate ion and the like.

The aromatic onium salt is disclosed in JP-A-50-151.
No. 996, JP-A-50-158680, aromatic halonium salts described in JP-A-50-151997, JP-A-52-14278, JP-A-52-30899,
JP-A-56-55420, JP-A-55-125105
Aromatic VI described in JP-A-56-15261 and the like.
Group a onium salts, aromatic Va group onium salts described in JP-A-50-151997 and the like, JP-A-56-8428.
JP-A-56-149402, JP-A-57-192
Oxo-sulfoxonium salts described in JP-A-429-429, etc .; triarylsulfonium salts and diaryliodonium salts described in JP-A-1-311103;
The aromatic sulfonium salt or the aromatic ammonium salt described in JP-A-94088 and the pyridinium salt described in JP-A-2-43202 can be exemplified.
It is not limited to these. The following are exemplified as these specific examples. Of course, two or more of these onium salts may be used in combination.

Benzyltetrahydrothiophenium hexafluoroantimonate benzyltetrahydrothiophenium hexafluoroarsenate benzyltetrahydrothiophenium hexafluorophosphate benzyltetrahydrothiophenium tetrafluoroborate benzyltetrahydrothiophenium perchlorate Benzyltetrahydrothiophenium / trifluoromethanesulfonate 2-methylbenzyltetrahydrothiophenium / hexafluoroantimonate 2-methylbenzyltetrahydrothiophenium / hexafluorophosphate 4-methylbenzyltetrahydrothiophenium / hexafluoroantimonate 4- Methylbenzyltetrahydrothiophenium hexafluorop Sulfate 2-methoxybenzyltetrahydrothiophenium hexafluoroantimonate 2-methoxybenzyltetrahydrothiophenium hexafluoroarsenate 4-methoxybenzyltetrahydrothiophenium hexafluoroantimonate 4-methoxybenzyltetrahydrothiophenium hexa Fluoroarsenate 4-methoxybenzyltetrahydrothiophenium hexafluorophosphate 2-chlorobenzyltetrahydrothiophenium hexafluoroantimonate 2-chlorobenzyltetrahydrothiophenium hexafluorophosphate 4-chlorobenzyltetrahydrothiophenium・ Hexafluoroantimonate 4-chlorobenzyltetrahydrothiophenium Fluorophosphate 2-nitrobenzyltetrahydrothiophenium hexafluoroantimonate 2-nitrobenzyltetrahydrothiophenium hexafluorophosphate 4-nitrobenzyltetrahydrothiophenium hexafluoroantimonate 4-nitrobenzyltetrahydrothiophenium・ Hexafluorophosphate 2-methylbenzyltetrahydro-2H-thiopyranium ・ Hexafluorophosphate 4-methylbenzyltetrahydro-2H-thiopyranium ・ Hexafluoroantimonate 2-methoxybenzyltetrahydro-2H-thiopyranium ・ Hexafluoroarsenate 4-methoxy Benzyltetrahydro-2H-thiopyranium hexafluoroantimonate α, α'-bis [Tetrahydrothiophenium] 4-xylylene bishexafluoroantimonate α, α'-bis [tetrahydro-2H-thiopyranium] 4-xylylene bishexafluoroantimonate dimethyl-4-thiophenoxyphenylsulfonium.
Hexafluoroantimonate diisopropyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate bis [4- (dimethylsulfonio) phenyl] sulfide bishexafluoroantimonate bis [4- (diphenylsulfonio) phenyl] sulfide bishexa Fluoroantimonate benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate benzyl-4-methoxyphenylmethylsulfonium
Hexafluoroantimonate brenyltetramethylenesulfonium / hexafluoroantimonate brenyltetramethylenesulfonium / hexafluoroarsenate brenyltetramethylenesulfonium / hexafluorophosphate dimethylbrenylsulfonium / hexafluoroarsenate t-butyltetramethylenesulfonium Hexafluoroantimonate 1-benzyl-2-chloropyridinium hexafluoroantimonate 1-benzyl-2-chloropyridinium hexafluoroarsenate 1-benzyl-2-chloropyridinium hexafluorophosphate 1-benzyl-2-chloro Pyridinium tetrafluoroborate 1-benzyl-2-chloropyridinium perchlorate 1-benzyl -2-chloropyridinium trifluoromethanesulfonate 1- (4-methoxybenzyl) -2-chloropyridinium hexafluoroantimonate 1- (4-methylbenzyl) -2-cyanopyridinium hexafluoroantimonate 1-benzyl-2 -Cyanopyridinium hexafluoroantimonate 1-benzyl-2-cyanopyridinium hexafluoroarsenate 1-benzyl-2-cyanopyridinium hexafluorophosphate 1-benzyl-3-cyanopyridinium hexafluoroantimonate 1-benzyl -3-cyanopyridinium hexafluorophosphate 1-benzyl-4-cyanopyridinium hexafluoroantimonate 1-benzyl-4-cyanopyridinium hexaflur Orophosphate 1-benzyl-2-vinylpyridinium hexafluoroantimonate 1-benzyl-4-vinylpyridinium hexafluoroantimonate 1-benzyl-2-styrylpyridinium hexafluoroantimonate 1-benzyl-4-styrylpyridinium Hexafluoroantimonate 1-benzyl-3,5-dichloropyridinium hexafluoroantimonate 1,1 '-[1,4-phenylenebis (methylene)] bis-2-cyanopyridinium hexafluoroantimonate 1-benzyl -Quinolinium hexafluoroantimonate 1-benzyl-quinolinium hexafluorophosphate 1-benzyl-2-chloroquinolinium hexafluoroantimonate 1-benzyl-2- Loloquinolinium hexafluorophosphate 1- (4-methoxybenzyl) -quinolinium hexafluoroantimonate 1- (4-methoxybenzyl) -quinolinium hexafluorophosphate 1- (4-methoxybenzyl) -2-chloroquinoli Hexafluoroantimonate 1- (4-methoxybenzyl) -2-chloroquinolinium hexafluorophosphate

The leuco dye having a lactone ring used in the present invention is not particularly limited, but one or more of the following compounds may be used in combination.

Triphenylmethane leuco dye 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide [also known as crystal violet lactone]

Fluoran leuco dye 3-Diethylamino-6-methyl-7-anilinofluoran 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran 3- (N-ethyl -P-toluidino) -6-methyl-
7-anilinofluoran 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran 3-pyrrolidino-6-methyl-7-anilinofluoran 3-piperidino-6-methyl-7- Anilinofluoran 3- (N-cyclohexyl-N-methylamino) -6
Methyl-7-anilinofluoran 3-N, N-dibutylamino-7 (o-chloroanilino) anilinofluoran 3-diethylamino-7- (m-trifluoromethylanilino) fluoran 3- (N-ethyl- N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran 3- (N-ethyl-N-propylamino) -6-methyl-7-anilinofluoran 3-dibutylamino-6-methyl- 7- (o, p-dimethylanilino) fluoran 3-diethylamino-6-chloro-7-anilinofluoran 3-diethylamino-7- (o-chloroanilino) fluoran 3-dibutylamino-7- (o-chloroanilino) Fluoran 3-diethylamino-6-methylfluoran 3-cyclohexylamino-6-chlorofluoran

Azaphthalide leuco dye 3- (4-diethylamino-2-ethoxyphenyl)-
3- (1-ethyl-2-methylindol-3-yl)
-4-azaphthalide 3- (4-diethylamino-2-ethoxyphenyl)-
3- (1-ethyl-2-methylindol-3-yl)
-7-Azaphthalide 3- (4-diethylamino-2-ethoxyphenyl)-
3- (1-octyl-2-methylindol-3-yl) -4-azaphthalide 3- (4-N-cyclohexyl-N-methylamino-2
-Methoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 3,3-bis (2-methyl-1-octyl-indol-3-yl) phthalide 3,3- Bis (2-methyl-1-ethyl-indole-
3-yl) phthalide

Fluorene leuco dye 3,6,6'-tris (dimethylamino) spiro [fluorene-9,3'-phthalide] 3,6,6'-tris (diethylamino) spiro [fluorene-9,3'- Phthalide]

In the near-infrared photosensitive resin composition of the present invention, the compound represented by the general formula (1) or (2), which functions as a near-infrared absorbing cationic polymerization initiator, is a cationically polymerizable organic compound 100 0.5 parts by weight
It is sufficient to add about 10 to 10 parts by weight, preferably about 1 to 5 parts by weight. When adding, use an appropriate solvent,
The near-infrared absorbing cationic polymerization initiator can be used by dissolving it in a solvent.

Further, when the onium salt is added, the compound represented by the general formula (1) or (2), 0.1 to 10 parts by weight per 100 parts by weight of the cation polymerizable organic compound is added.
The onium salt is added in an amount of 0.05 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, based on the weight, preferably 0.5 to 5 parts by weight.

When a leuco dye having a lactone ring is added, the compound represented by the general formula (1) or (2) is added to 100 parts by weight of the cationically polymerizable organic compound.
05 to 10 parts by weight, preferably 0.1 to 5 parts by weight,
0.05 to 10 parts by weight of onium salt, preferably 0.1 to 10 parts by weight.
To 1 to 5 parts by weight, 0.01 to 5 parts by weight, preferably 0.05 to 1 part by weight of a leuco dye having a lactone ring is added.

The near-infrared photosensitive resin composition of the present invention comprises
As long as the curing of the present invention is not impaired, various resin additives such as coloring agents such as pigments and paints, defoaming agents, leveling agents, thickeners, flame retardants, antioxidants, silica, and glass, if necessary. Fillers such as powders, ceramic powders, metal powders and the like, modifying resins and the like can be used in appropriate amounts.

The energy source used for curing the near-infrared photosensitive resin composition of the present invention has an output of 10 to 50.
In the range of 0 mW and a wavelength in the range of 600 to 1500 nm, a semiconductor laser beam converged by a lens is sufficient. However, a semiconductor laser or a YAG laser having a higher output may be used. When heating, a hot plate, a thermostat, hot air, or the like can be used.

As one specific example of the use of the near-infrared photosensitive resin composition of the present invention, a molded article may be formed by the method described in JP-A-60-247515 and JP-A-2-24121.
-As described in JP-A-2-24127, etc., the light guide is relatively moved at a fixed distance from the curable composition of the present invention contained in a container or discharged from a nozzle. While irradiating the semiconductor laser light necessary for curing through the light guide, it can be performed.

In addition, it has been difficult to distinguish the molded body and the resin composition from each other because they have been colorless or transparent in the same color. However, a leuco dye having a lactone ring was added to the near-infrared photosensitive resin composition of the present invention. When a semiconductor laser beam is applied to the object, a colored cured product is obtained, and the appearance of the molded body can be determined by vivid hue, and finally, a colorful and cured molded body having a desired shape can be obtained. .

The curing of the near-infrared photosensitive resin composition of the present invention is promoted by cationic polymerization using near-infrared light. By heating to about 60 ° C., the cross-linking reaction can be effectively promoted, and furthermore, the obtained molded article is post-cured at a temperature of 50 to 150 ° C., whereby more excellent mechanical strength is obtained. A shaped object can be obtained.

[0073]

The near-infrared photosensitive resin composition of the present invention comprises 700
By irradiation or heating of near-infrared light of ~ 1500 nm,
Provides a durable cured product that is stable to heat and light. These mechanisms are considered to be as follows. The compound represented by the general formula (1) or (2) is dissociated by irradiation with near-infrared light or heating, and the generated Lewis acid ion polymerizes and cures the cationically polymerizable organic compound. Further, when an onium salt is added, the onium salt is decomposed by the near-infrared radiation, the near-infrared ray is absorbed by the above-mentioned general formula (1) or (2), and the generated onium salt is decomposed. The compound represented by the general formula (1) or (2) is dissociated, and the resulting Lewis acid salt ion cooperates to polymerize and cure the cationically polymerizable organic compound, thereby improving the curing sensitivity. When a leuco dye having a lactone ring is added, Lewis acid ions generated by irradiation with near-infrared rays open the lactone ring to form a color. The lactone ring becomes a free carboxylic acid, which reacts with the cationically polymerizable organic compound, and the colored leuco dye is incorporated into the polymer to give a durable colored cured product that is stable to heat and light . The composition is similarly polymerized and cured by heating. Hereinafter, the effectiveness of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[0074]

【Example】

Example 1 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate was used as a cationically polymerizable organic compound, and bis (p-di-n-n- was used as a near-infrared-absorbing cationic polymerization initiator. Butylaminophenyl) [N, N-bis (p-di-n-butylaminophenyl) -p-
[Aminophenyl] aminium hexafluoroantimonate (3 parts) was mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

The near-infrared photosensitive resin composition was placed in the container 1 of the photocurable three-dimensional structure system shown in FIG. 1, and the base 9 moved by the elevator 10 was provided at the bottom of the container 1 . It is set slightly above the light-transmitting window 3 and a semiconductor laser (output: 150 mW, wavelength: 810 nm) is guided by the optical fiber 6 , and the horizontal cross-sectional shape of the target object is converted to X by a computer.
Controlling the -Y moving device 7 to irradiate this composition with the light beam 4 emitted from the light emitting portion 5 through the light transmitting window 3 ;
The composition between the base and the translucent window is cured. Then, the base 9 was slightly pulled up together with the cured product by the elevator 10 ,
The composition is newly introduced between the cured product and the transparent window. This operation was repeated to obtain a bottom surface having a diameter of 20 from the resin composition.
mm, a height of 10 mm, and a thickness of 0.2 mm A cup-shaped molded article was produced. This molded article had no distortion and the molding time was 120 minutes.

Comparative Example 1 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as a cationically polymerizable organic compound, and a cyanine compound NK-2014 as a near-infrared absorbing dye
3 parts) were mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional molded object system shown in FIG. 1 to cure the above composition in the same manner as in Example 1, no molded object could be produced.

Comparative Example 2 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as a cationic polymerizable organic compound, and a polymethine compound IR-820 (Nippon Kayaku) as a near infrared absorbing dye 3 parts) was mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional molded object system shown in FIG. 1 to cure the above composition in the same manner as in Example 1, no molded object could be produced.

Comparative Example 3 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as a cationic polymerizable organic compound, and a pyrylium-based compound NK-3027 as a near-infrared absorbing dye
3 parts) were mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

The composition was cured in the same manner as in Example 1 using the photocurable three-dimensional object system shown in FIG. 1, but no object could be produced.

Example 2 3,4-Epoxy-6-methylcyclohexylmethyl-3,4 as a cationically polymerizable organic compound
-Epoxy-6'-cyclohexanecarboxylate 80
Parts, 1,4-butanediol diglycidyl ether 20 parts,
Bis (p-di-n) as a near infrared absorbing cationic polymerization initiator
-Butylaminophenyl) [N, N-bis (p-di-n-butylaminophenyl) -p-aminophenyl] aminium hexafluoroantimonate (1 part) A composition was obtained.

Using the photocurable three-dimensional structure system shown in FIG. 1, from the above resin composition, in the same manner as in Example 1, a cup having a bottom diameter of 10 mm, a height of 5 mm, and a thickness of 0.2 mm was formed. A model was created. This molded article had no distortion and the molding time was 180 minutes.

Example 3 60 parts of vinylcyclohexene oxide, 20 parts of bisphenol A diglycidyl ether and 20 parts of triethylene glycol divinyl ether were used as the cationically polymerizable organic compound, and bis (p) was used as the near infrared absorbing cationic polymerization initiator. -Di-n-butylaminophenyl) [N, N-bis (p-di-n-butylaminophenyl)-
3′-Aminobiphenylyl] aminium hexafluoroantimonate was mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional structure system shown in FIG. 1, from the above resin composition, in the same manner as in Example 1, a cup having a bottom diameter of 10 mm, a height of 10 mm, and a thickness of 0.2 mm was formed. A model was created. This molded article had no distortion and the molding time was 120 minutes.

Example 4 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether as a cationic polymerizable organic compound, near-infrared absorbing property Bis (p-di-n-butylaminophenyl) [N, N-bis (p-di-n-butylaminophenyl) as a cationic polymerization initiator
-p-aminophenyl] aminium hexafluoroantimonate 1 part, as onium salt, brenyltetramethylenesulfonium hexafluoroantimonate 2
The parts were mixed and dissolved to obtain a near infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional structure system shown in FIG. 1, from the above resin composition, in the same manner as in Example 1, a cup having a bottom diameter of 20 mm, a height of 12 mm and a thickness of 0.2 mm was formed. A model was created. This molded article had no distortion and the molding time was 90 minutes.

Comparative Example 4 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether as a cationic polymerizable organic compound, a near-infrared absorbing dye 1 part of a cyanine-based compound NK-2014 (manufactured by Japan Photographic Dye Laboratories Co., Ltd.) and 2 parts of brenyltetramethylenesulfonium hexafluoroantimonate as an onium salt are mixed and dissolved, A resin composition was obtained.

Using the photo-curable three-dimensional structure system shown in FIG. 1, an attempt was made to produce a cup-shaped structure from the above composition in the same manner as in the example. Because of its inferiority, it was not possible to create the desired object.

Example 5 3,4-Epoxy-6-methylcyclohexylmethyl-3,4 as a cationically polymerizable organic compound
-80 parts of epoxy-6'-methylcyclohexanecarboxylate, bisphenol A diglycidyl ether 20
Part, bis (p-
1 part of di-n-butylaminophenyl) [N, N-bis (p-di-n-butylaminophenyl) -p-aminophenyl] aminium hexafluoroantimonate, 4-methoxybenzyl-2 as an onium salt -Cyanopyridinium
By mixing and dissolving 2 parts of hexafluoroantimonate, a near-infrared photosensitive resin composition of the present invention was obtained.

Using the photocurable three-dimensional structure system shown in FIG. 1, from the above resin composition, in the same manner as in Example 1, a cup having a bottom diameter of 20 mm, a height of 10 mm, and a thickness of 0.2 mm was formed. A model was created. This molded article had no distortion and the molding time was 90 minutes.

Example 6 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of bisphenol A diglycidyl ether as a cationic polymerizable organic compound, and near-infrared absorbing cationic polymerization started N, N, N ', N'-tetrakis (p-di-n-
3 parts of (butylaminophenyl) -p-benzoquinone-bis (immonium hexafluoroantimonate) were mixed and dissolved to obtain a near infrared photosensitive resin composition of the present invention.

The semiconductor laser shown in FIG. 1 (output: 150 mW,
Instead of a wavelength of 810 nm, a YAG laser (output 8
Example 1 was prepared from the above resin composition using a photocurable three-dimensional object system using 0 mW and a wavelength of 1060 nm.
In the same manner as described above, a cup-shaped molded article having a bottom surface of 20 mm in diameter, 10 mm in height, and 0.5 mm in thickness was prepared. This molded article had no distortion and the molding time was 50 minutes.

Example 7 3,4-Epoxy-6-methylcyclohexylmethyl-3,4 as a cationically polymerizable organic compound
-50 parts of epoxy-6'-methylcyclohexanecarboxylate, 30 parts of vinylcyclohexene oxide, 1,
20 parts of 4-butanediol diglycidyl ether, N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-benzoquinone as a near infrared absorbing cationic polymerization initiator
-One part of bis (immonium hexafluoroantimonate) was mixed and dissolved to obtain a near infrared photosensitive composition of the present invention. Using the photocurable three-dimensional structure system shown in Example 6, from the above resin composition, in the same manner as in Example 1, a cup-shaped structure having a bottom surface diameter of 10 mm, a height of 10 mm, and a thickness of 0.5 mm It was created. This model has no distortion,
The molding time was 60 minutes.

Example 8 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether as a cationic polymerizable organic compound, near-infrared absorbing property N, N, N ', N'-tetrakis (p-di-n
-Butylaminophenyl) -p-benzoquinone- 1 part of bis (immonium hexafluoroantimonate) and 2 parts of brenyltetramethylenesulfonium hexafluoroantimonate as onium salt are mixed and dissolved.
A near-infrared photosensitive composition of the present invention was obtained.

Using the photocurable three-dimensional structure system shown in Example 6, from the above resin composition, in the same manner as in Example 1, a cup having a bottom diameter of 20 mm, a height of 15 mm, and a thickness of 0.5 mm A shaped object was created. This model has no distortion,
The modeling time was 40 minutes.

Example 9 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether as a cationic polymerizable organic compound, near-infrared absorbing property Bis (p-di-n-butylaminophenyl) [N, N-bis (p-di-n-butylaminophenyl) as a cationic polymerization initiator
-p-aminophenyl] aminium hexafluoroantimonate 1 part, as onium salt, brenyltetramethylenesulfonium hexafluoroantimonate 2
Parts, 0.5 part of crystal violet lactone as a leuco dye having a lactone ring was mixed and dissolved to obtain a near infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional structure system shown in FIG. 1, a blue-violet color having a bottom diameter of 20 mm, a height of 12 mm and a thickness of 0.2 mm was obtained from the above resin composition in the same manner as in Example 1. Was made. This molded article had no distortion and the molding time was 120 minutes.

[Example 10] 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of bisphenol A diglycidyl ether as a cationic polymerizable organic compound, near infrared absorbing cationic polymerization started N, N, N ', N'-tetrakis (p-di-n
-Butylaminophenyl) -p-benzoquinone-bis (immonium hexafluoroantimonate), 1 part as onium salt, 4-methoxybenzyl-2-cyanopyridinium hexafluoroantimonate, 3 parts, leuco dye having a lactone ring 3,3-bis (2-methyl-1-octyl-indol-3-yl) phthalide 1
The parts were mixed and dissolved to obtain a near infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional structure system shown in FIG. 1, a red color with a bottom diameter of 10 mm, a height of 10 mm and a thickness of 0.2 mm was obtained from the above resin composition in the same manner as in Example 1. A cup-shaped object was created. This molded article had no distortion and the molding time was 120 minutes.

[Example 11] 3,4-Epoxy-6-methylcyclohexylmethyl- as a cationic polymerizable organic compound
3,4-epoxy-6'-methylcyclohexanecarboxylate 50 parts, bisphenol A diglycidyl ether 3
0 parts, triethylene glycol divinyl ether 20
Part, bis (p-
1 part of di-n-butylaminophenyl) [N, N-bis (p-di-n-butylaminophenyl) -p-aminophenyl] aminium hexafluoroantimonate, 4-methoxybenzyltetrahydrothio as onium salt 3 parts of phenium hexafluoroantimonate, 3-diethylamino-6-methyl- as a leuco dye having a lactone ring
0.8 parts of 7-anilinofluoran was mixed and dissolved to obtain a near-infrared photosensitive resin composition of the present invention.

Using the photocurable three-dimensional structure system shown in FIG. 1, a black base material having a bottom diameter of 10 mm, a height of 8 mm and a thickness of 0.2 mm was obtained from the above resin composition in the same manner as in Example 1. A cup-shaped object was created. This molded article had no distortion and the molding time was 120 minutes.

[Examples 12 to 12] The compositions of Examples 1 and 6 were heat-cured at 180 ° C. Also, instead of the near infrared absorbing cationic polymerization initiator of Example 1, bis (p-di-n-butylaminophenyl) [N, N
-Bis (p-di-n-butylaminophenyl) -p-aminophenyl] aminium perchlorate was prepared in the same manner as in Example 1 except that the near-infrared absorbing cationic polymerization initiator of Example 6 was used.
At 0 and N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-benzoquinone-bis (immonium.
Percolate), and heat-cured similarly. Table 1 shows the results.

Similarly, the compositions of Comparative Examples 1 to 3 were
Thermal curing was performed at 80 ° C.

[0105]

[Table 1]

The highest sensitivity in thermal curing was obtained when a diimmonium-based (SbF ₆ ⁻ ) was used. The curing sensitivity was affected by the type of counter anion, and SbF ₆ ⁻ > ClO ₄ ⁻ .

The compositions of Comparative Examples 1 to 3 were heat-cured at 180 ° C., but the cyanine-based NK-2014, polymethine-based IR-820, and pyrylium-based NK-302 were used.
When the near-infrared absorbing dye No. 7 was used, it did not heat cure.

[0108]

The effect of the present invention is to provide a near-infrared photosensitive resin composition which gives a cured product by irradiation with near-infrared rays. In particular, the near-infrared photosensitive resin composition of the present invention is capable of performing three-dimensional curing molding using a semiconductor laser, which has not been possible so far. Thereby, in the future, in the field of three-dimensional molding, an inexpensive three-dimensional model producing apparatus using a semiconductor laser can be realized.

Another object of the present invention is to provide a novel near-infrared absorbing cationic polymerization initiator in the near-infrared photosensitive resin composition, wherein one compound absorbs near-infrared rays and further generates cations, It has become possible to polymerize and cure a polymerizable organic compound.

Further, when the near-infrared photosensitive resin composition to which the leuco dye having a lactone ring has been added is irradiated with near-infrared rays, the curing start and the completion of curing can be clearly grasped without physically touching and clear. It has become possible to obtain a colored cured product having an appropriate hue.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of an apparatus for performing an optical molding method. DESCRIPTION OF SYMBOLS 1 ... Container, 2 ... Near infrared photosensitive resin composition, 3 ... Transparent window, 4 ... Light flux, 5 ... Light emitting part, 6 ... Optical fiber, 7 ...
XY moving device, 8 light source, 9 base, 10 elevator, 11 computer, 12 cured product.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H01L 21/027 H01L 21/30 502R

Claims (5)

(57) [Claims] A near-infrared photosensitive resin composition comprising a cationically polymerizable organic compound and a compound represented by the following general formula (1) or (2) as main components, and cured by near-infrared irradiation or heating. Embedded image Embedded image (Where A is B is [K represents 1 or 2], and the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, a halogen atom or a hydroxyl group. R ₁ to R ₈ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkynyl group, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ and R ₇ and R
The combination of ₈ may form a substituted or unsubstituted 5-membered ring, a substituted or unsubstituted 6-membered ring, or a substituted or unsubstituted 7-membered ring together with N. The substituents of R _{1 to} R ₈ may be the same or different. X ^- is a non-nucleophilic anion, wherein MQ _n ^- can be represented by. M is B, P, A
An atom selected from s, Sb, Fe, Al, Sn, Zn, Ti, Cd, Mo, W and Zr, preferably B, P, As and Sb. Q is a halogen atom,
n is a number from 1 to 6). 2. A near-infrared photosensitive resin composition comprising a cationically polymerizable organic compound, a compound represented by the above formula (1) or (2) and an onium salt as main components and being cured by irradiation with near-infrared light or heating. 3. A cured product obtained by curing the near-infrared photosensitive resin composition of claim 1 or the near-infrared photosensitive resin composition of claim 2 by irradiation with near-infrared light or heating. 4. An optical molded article obtained by irradiating the near-infrared photosensitive resin composition of claim 1 or the near-infrared photosensitive resin composition of claim 2 with a semiconductor laser beam and curing the composition. 5. A color-formed cured product comprising the near-infrared photosensitive resin composition according to claim 2 and a leuco dye having a lactone ring as main components and being colored and cured by irradiating a semiconductor laser beam.