JP2005029725A - Polymerizable composition and photopolymerization method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly sensitive, 2-photon polymerizable composition, which can be photopolymerized by 2-photon absorption and whose polymerization product can be colored into a desired color simultaneously with the polymerization. <P>SOLUTION: The 2-photon absorption polymerizable composition contains at least (A) a polymerizable compound, (B) a 2-photon absorption compound, (C) a polymerization initiator, and (D) a colorant. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a material that exhibits a nonlinear optical effect, and in particular, has a large non-resonant two-photon absorption cross-section, enables efficient photopolymerization from an excited state generated by non-resonant two-photon absorption, and colors a polymer. The present invention relates to a photopolymerizable composition and a photopolymerization method that can be polymerized with high sensitivity regardless of the concentration of the colorant.

  In general, the nonlinear optical effect is a non-linear optical response proportional to the square of the applied photoelectric field, the third power or more, and a second-order nonlinear optical effect proportional to the square of the applied photoelectric field. For example, second harmonic generation (SHG), optical rectification, photorefractive effect, Pockels effect, parametric amplification, parametric oscillation, optical sum frequency mixing, and optical difference frequency mixing are known. The third-order nonlinear optical effect proportional to the cube of the applied photoelectric field includes third harmonic generation (THG), optical Kerr effect, self-induced refractive index change, two-photon absorption, and the like.

  Many inorganic materials have been found so far as nonlinear optical materials exhibiting these nonlinear optical effects. However, inorganic materials are very difficult to put into practical use because so-called molecular design for optimizing desired nonlinear optical characteristics and various physical properties necessary for device fabrication is difficult. On the other hand, organic compounds can be optimized not only for the desired nonlinear optical properties by molecular design, but also for other physical properties, so they are highly practical and attract attention as promising nonlinear optical materials. Collecting.

  In recent years, the third-order nonlinear optical effect has attracted attention among the nonlinear optical characteristics of organic compounds, and among these, non-resonant two-photon absorption has attracted attention. Two-photon absorption is a phenomenon in which a compound is excited by simultaneously absorbing two photons, and the case where two-photon absorption occurs in an energy region where there is no (linear) absorption band of the compound is called non-resonant two-photon absorption. . In the following description, two-photon absorption refers to non-resonant two-photon absorption even if not specified.

By the way, the efficiency of non-resonant two-photon absorption is proportional to the square of the applied photoelectric field (square characteristic of two-photon absorption). For this reason, when a two-dimensional plane is irradiated with a laser, two-photon absorption occurs only at a position where the electric field strength is high in the central portion of the laser spot, and two-photon absorption is completely absent in a portion where the electric field strength is weak in the peripheral portion. Does not happen. On the other hand, in the three-dimensional space, two-photon absorption occurs only in the region where the electric field strength at the focal point where the laser light is collected by the lens is large, and no two-photon absorption occurs in the region outside the focal point because the electric field strength is weak. . Compared with linear absorption where excitation occurs at all positions in proportion to the intensity of the applied photoelectric field, non-resonant two-photon absorption results in excitation at only one point inside the space due to this square characteristic. , The spatial resolution is significantly improved.
Usually, when inducing non-resonant two-photon absorption, a short pulse laser in the near infrared region, which has a longer wave and no absorption than the wavelength region in which the (linear) absorption band of the compound exists, is often used. Since near infrared light in a so-called transparent region is used, the excitation light can reach the inside of the sample without being absorbed or scattered. That is, photopolymerization can be performed to a spatially deep region regardless of the absorption position of the colorant coexisting for coloring the polymer and its optical density. Further, because of the square characteristic of non-resonant two-photon absorption, one point inside the sample can be excited with extremely high spatial resolution, so that a finer and finer polymer can be obtained.

  An example in which two-photon photopolymerization using a non-resonant two-photon absorption compound is applied to optical modeling or the like is described in the following literature (BH Cumpston et al., Nature. 1999, 398, 51 pages). [Non-Patent Document 1], KD Belfield et al., J. Phys. Org. Chem., 2000, 13, pp. 837 [Non-Patent Document 2], C. Li et al., Chem. Phys. Lett., 2001, 340, 444 [Non-Patent Document 3], KD Belfield et al., J. Am. Chem. Soc., 2000, 122, 1217 [Non-Patent Document 4]. S. Maruo et al., Opt. Lett., 1997, 22, 132 [Non-Patent Document 5]). However, there is no example in which the polymer or molded article obtained in these examples shown above is colored in an arbitrary color.

On the other hand, in ordinary photopolymerization using one-photon absorption, a method of coloring a polymer by photopolymerization using a resin in which a pigment or the like is dispersed has been proposed. However, in this method, if a pigment having a higher concentration is dispersed in order to increase the color density of the polymer, the light used for photopolymerization is absorbed by the pigment dispersion. There have been various problems such as a decrease in performance.
B. H. Cumpston et al. , Nature. 1999, 398, 51 K. D. Belfield et al. , J .; Phys. Org. Chem. 2000, vol. 13, p. 837 C. Li et al. , Chem. Phys. Lett. 2001, 340, 444 K. D. Belfield et al. , J .; Am. Chem. Soc. 2000, 122, 1217 S. Maruo et al. , Opt. Lett. 1997, Vol. 22, p. 132

  If two-photon absorption can be used to induce polymerization at an arbitrary location in a three-dimensional space with extremely high spatial resolution and simultaneously color the polymer (without the need for post-processing), a fine three-dimensional stereolithography material, a three-dimensional image Application to recording, color filter manufacturing, etc. becomes possible. However, as described above, several methods for polymerizing a polymerizable compound using excitation energy absorbed by non-resonant two-photon absorption have been disclosed, and there are methods for coloring a desired color on a polymer or a modeled object. do not do.

  An object of the present invention is to provide a highly sensitive two-photon polymerizable composition capable of photopolymerization by two-photon absorption and capable of coloring a polymer to a desired color simultaneously with polymerization (without requiring post-treatment). It is to be. Another object of the present invention is to provide a photopolymerization method capable of realizing good photopolymerization regardless of the concentration of the colorant to be dispersed.

As a result of intensive studies by the inventors of the present invention, it has been found that the object of the present invention can be achieved by the following means.
(1) A two-photon absorption polymerizable composition comprising at least a polymerizable compound (A), a two-photon absorption compound (B), a polymerization initiator (C), and a colorant (D).
(2) The two-photon absorption polymerization composition according to (1), wherein the two-photon absorption compound (B) according to (1) has a two-photon absorption cross-sectional area of 500 GM or more.
(3) The polymerization initiator is 1) a ketone polymerization initiator, 2) an organic peroxide polymerization initiator, 3) a bisimidazole polymerization initiator, 4) a trihalomethyl-substituted triazine polymerization initiator, 5) Diazonium salt polymerization initiator, 6) diaryliodonium salt polymerization initiator, 7) sulfonium salt polymerization initiator, 8) triphenylalkylborate polymerization initiator, 9) diaryliodonium organic boron complex polymerization initiator 10) Sulphonium organic boron complex polymerization initiator, 11) Cationic two-photon absorption compound, organic boron complex polymerization initiator, 12) Anionic two-photon absorption compound, onium salt complex polymerization initiator, 13) Metal arene complex system The two-photon absorption according to (1) or (2), which is any one of a polymerization initiator and 14) a sulfonate ester polymerization initiator Polymerizable composition.
(4) In (3), the polymerization initiator is 1) a ketone polymerization initiator, 3) a bisimidazole polymerization initiator, 4) a trihalomethyl-substituted triazine polymerization initiator, 6) a diaryliodonium salt polymerization start 7) a sulfonium salt-based polymerization initiator, 11) a cationic two-photon absorption compound, an organic boron complex-based polymerization initiator, and 12) an anionic two-photon absorption compound, an onium salt complex-based polymerization initiator. (2) The two-photon absorption polymerizable composition as described in (3).
(5) The polymerization initiator is a polymerization initiator that generates at least one radical, and the polymerizable compound is a radical polymerizable compound that is polymerized by at least one radical. (2) The two-photon collection polymerization composition according to any one of (3).
(6) In (5), the radical polymerization initiator generating at least one radical is 1) a ketone polymerization initiator, 2) an organic peroxide polymerization initiator, 3) a bisimidazole polymerization initiator, 4) Trihalomethyl-substituted triazine polymerization initiator, 5) Diazonium salt polymerization initiator, 6) Diaryliodonium salt polymerization initiator, 7) Sulfonium salt polymerization initiator, 8) Triphenylalkylborate polymerization initiator 9) Diaryliodonium organic boron complex polymerization initiator, 10) Sulfonium organic boron complex polymerization initiator, 11) Cationic two-photon absorption compound, organic boron complex polymerization initiator, 12) Anionic two-photon absorption compound, onium The two-photon absorption according to (5), which is any of a salt complex polymerization initiator and 13) a metal arene complex polymerization initiator Polymerizable composition.
(7) In (6), the radical polymerization initiator that generates at least one radical is 1) a ketone polymerization initiator, 3) a bisimidazole polymerization initiator, 4) a trihalomethyl-substituted triazine polymerization initiator, 6) diaryliodonium salt polymerization initiator, 7) sulfonium salt polymerization initiator, 11) cationic two-photon absorption compound, organic boron complex polymerization initiator, 12) anionic two-photon absorption compound, onium salt complex polymerization initiator (2) The two-photon absorption polymerizable composition as described in (6) above.
(8) The polymerization initiator is a polymerization initiator that generates an acid without generating at least one radical, and the polymerizable compound is a cationic polymerizable compound that is polymerized with at least one acid. The two-photon absorption polymerizable composition according to any one of (1) to (3).
(9) In (8), the polymerization initiator that generates acid without generating at least one radical is 14) a sulfonate ester polymerization initiator, Photon absorption polymerizable composition.
(10) The polymerization initiator is a polymerization initiator that generates both at least one radical and an acid, and the polymerizable compound is polymerized by at least one radical and at least one acid. The two-photon absorption polymerizable composition as described in any one of (1) to (3), which is one or both of cationically polymerizable compounds to be polymerized.
(11) In (10), the radical polymerization initiator that generates both at least one radical and an acid is 4) a trihalomethyl-substituted triazine polymerization initiator, 5) a diazonium salt polymerization initiator, and 6) diaryliodonium. The two-photon absorption polymerizable composition as described in (10), which is any of a salt polymerization initiator, 7) a sulfonium salt polymerization initiator, and 13) a metal arene complex polymerization initiator.
(12) In (11), the radical polymerization initiator that generates at least one kind of radical and acid is either 6) a diaryliodonium salt-based polymerization initiator or 7) a sulfonium salt-based polymerization initiator. (2) The two-photon absorption polymerizable composition according to (11).
(13) The two-photon absorption polymerizable composition according to any one of (1) to (12), wherein the colorant (D) according to (1) is a dye.
(14) The two-photon absorption polymerizable composition according to any one of (1) to (12), wherein the colorant (D) according to (1) is a pigment. The pigment is an inorganic pigment or an organic pigment, preferably an organic pigment.
(15) The two-photon absorption polymerizable composition according to any one of (1) to (14) has a longer wave length than the absorption in the ultraviolet-visible wavelength region of the polymerizable composition, and the polymerizable composition A photopolymerization method characterized in that a colored polymer is obtained by irradiating light having a wavelength at which no absorption occurs.
(16) The two-photon absorption polymerizable composition according to any one of (1) to (14) corresponds to the non-resonant two-photon absorption maximum wavelength of the (B) two-photon absorption compound contained in the polymerizable composition. The photopolymerization method according to (15), wherein a colored polymer is obtained by irradiating light.
(17) A photolithographic composition comprising the two-photon absorption polymerizable composition according to any one of (1) to (14).
(18) A resin composition for a color filter, comprising the two-photon absorption polymerizable composition according to any one of (1) to (14).
(19) A method for producing a color filter, comprising using the resin composition for a color filter according to (18).
(20) A three-dimensional image forming material comprising the two-photon absorption polymerizable composition according to any one of (1) to (14).
(21) A three-dimensional image forming method comprising the two-photon absorption polymerizable composition according to any one of (1) to (14).

  By using the photopolymerizable composition of the present invention, a polymer colored in an arbitrary color can be obtained.

  The photopolymerizable composition of the present invention will be described in detail below.

  The photopolymerizable composition of the present invention comprises at least four components: a polymerizable compound (A), a two-photon absorption compound (B), a polymerization initiator (C), and a colorant (D). If necessary, a binder, chain transfer Additives such as an agent, a heat stabilizer, a plasticizer, and a solvent can be used. Each of these components will be described in detail below.

  First, the polymerizable compound (A) in the photopolymerizable composition of the present invention will be described.

The polymerizable compound of the present invention is a compound that can be oligomerized or polymerized by causing addition polymerization with a radical or an acid (Bronsted acid or Lewis acid).
The polymerizable compound of the present invention may be monofunctional or polyfunctional, may be a single component or a multicomponent, and may be a monomer, a prepolymer (for example, a dimer or oligomer), or a mixture thereof.
Further, the form may be liquid or solid.

The polymerizable compound of the present invention is a compound that can be oligomerized or polymerized by causing addition polymerization with a radical or an acid (Bronsted acid or Lewis acid).
The polymerizable compound of the present invention may be monofunctional or polyfunctional, may be a single component or a multicomponent, and may be a monomer, a prepolymer (for example, a dimer or oligomer), or a mixture thereof.
Further, the form may be liquid or solid.

  The polymerizable compound of the present invention is roughly classified into a polymerizable compound capable of radical polymerization and a polymerizable compound capable of cationic polymerization.

  The radically polymerizable compound of the present invention is preferably a compound having at least one ethylenically unsaturated double bond in the molecule. Specifically, the following polymerizable monomers and prepolymers (dimers, oligomers, etc.) comprising them are preferred. ).

  First, non-halogen aliphatic compounds are exemplified. Specifically, as a monofunctional type, unsaturated acid compounds such as (meth) acrylic acid, itaconic acid, maleic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t- Butyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Alkyl such as 2-hydroxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, n-butoxyethyl (meth) acrylate, morpholinoethyl (meth) acrylate, etc. (Me ) Acrylate type, methoxydiethyl (propylene) glycol (meth) acrylate, methoxytriethylene (propylene) glycol (meth) acrylate, methoxytetraethylene (propylene) glycol (meth) acrylate, methoxypolyethylene (propylene) glycol (meta) ) Acrylate, ethoxydiethylene (propylene) glycol (meth) acrylate, ethoxytriethylene (propylene) glycol (meth) acrylate, ethoxypolyethylene (propylene) glycol (meth) acrylate, etc., alkoxy alkylene glycol (meth) acrylate type, cyclohexyl (Meth) acrylate, tetrahydrofuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tris Alicyclic (meth) acrylate types such as lopentanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, pinanyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl Examples include (meth) acrylates such as (meth) acrylates, (meth) acrylamides, diacetone (meth) acrylamides, and other functional group-containing (meth) acrylates such as allyl (meth) acrylates and glycidyl (meth) acrylates.

  Next, as the polyfunctional type, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, bis (acryloxyneopentyl glycol) adipate, bis (methacryloxyneopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayrad R-167, hydroxypivalate neo Pentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate neopentyl glycol di (meth) acrylate: alkyl-type (meth) acrylates such as Nippon Kayaku Kayrad HX series, ethylene glycol di (me ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -811, epichlorohydrin modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified Loren glycol di (meth) acrylate: alkylene glycol type (meth) acrylate such as Nagase Sangyo Denacol DA (M) -911, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentyl glycol modified tri Methylolpropane di (meth) acrylate: Nippon Kayaku Kayrad R-604, ethylene oxide modified trimethylolpropane tri (meth) acrylate: Sartomer SR-454, propylene oxide modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku TPA-310, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate: trimethylolpropane type (meth) acrylate such as Nagase Sangyo DA (M) -321 , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate: Toagosei Aronix M-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (Meth) acrylate, alkyl-modified dipentaerythritol poly (meth) acrylates: Nippon Kayaku Kayrad D-310, 320, 330, etc. Caprolactone-modified dipentaerythritol poly (meth) acrylates: Nippon Kayaku Kayrad DPCA- Pentaerythritol type (meth) acrylate such as 20, 30, 60, 120, glycerol di (meth) acrylate, epichlorohydrin modified glycerol tri ) Acrylate: Nagase Sangyo Denacol DA (M) -314, glycerol type (meth) acrylate such as triglycerol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyl Di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate: cycloaliphatic (meth) acrylate such as Sanyo Kokusaku Pulp CAM-200, tris (acryloxyethyl) isocyanurate: Toa Gosei Aronix M-315, Tris (methacrylic) Isocyanurate type (meth) acrelanes such as (Roxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate And the like.

  Moreover, the compound which further contains a sulfur atom in a molecule | numerator among the compounds which have a polymerizable ethylenically unsaturated group comprised only from an aliphatic group is illustrated. For example, as a monofunctional type, methoxydiethyl (propylene) glycol glycol thio (meth) acrylate, methoxytriethyl (propylene) glycol glycol thio (meth) acrylate, methoxytetraethyl (propylene) glycol thio (meth) acrylate, methoxypolyethylene ( Such as propylene) lenylene glycol thio (meth) acrylate, ethoxydiethylene (propi) lenylene glycol thio (meth) acrylate, ethoxy triethylene (propi) lenylene glycol thio (meth) acrylate, ethoxy poly (propylene) glycol thio (meth) acrylate Alkoxyalkylene glycol thio (meth) acrylate type, cyclohexylthio (meth) acrylate, tetrahydrofurylthio (meth) acrylate, isobornylthio (meth) acrylate Examples include alicyclic thio (meth) acrylate types such as dicyclopentanylthio (meth) acrylate, tricyclopentanylthio (meth) acrylate, dicyclopentadienylthio (meth) acrylate, and pinanylthio (meth) acrylate. It is done.

  Next, 1,3-propanediol dithio (meth) acrylate, 1,4-butanediol dithio (meth) acrylate, 1,6-hexanediol dithio (meth) acrylate, neopentyl glycol dithio (meth) ) Acrylate, bis (thioacryloxy neopentyl glycol) adipate, bis (thiomethacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol dithio (meth) acrylate, hydroxypivalate neopentyl glycol dithio (meth) acrylate , Caprolactone-modified hydroxypivalic acid neopentyl glycol dithio (meth) acrylate and other alkyl type thio (meth) acrylate, ethylene glycol dithio (meth) acrylate, die Lenglycol dithio (meth) acrylate, triethylene glycol dithio (meth) acrylate, tetraethylene glycol dithio (meth) acrylate, polyethylene glycol dithio (meth) acrylate, epichlorohydrin modified ethylene glycol dithio (meth) acrylate, epichlorohydrin modified diethylene glycol dithio (meta) ) Acrylate, propylene glycol dithio (meth) acrylate, dipropylene glycol dithio (meth) acrylate, tripropylene glycol dithio (meth) acrylate, tetrapropylene glycol dithio (meth) acrylate, polypropylene glycol dithio (meth) acrylate, epichlorohydrin modified prolene Alcohols such as glycol dithio (meth) acrylate Lenglycol-type thio (meth) acrylate, trimethylolpropane trithio (meth) acrylate, ditrimethylolpropane trithio (meth) acrylate, neopentyl glycol modified trimethylolpropane dithio (meth) acrylate, ethylene oxide modified trimethylolpropane trithio Trimethylolpropane type thio (meth) acrylate such as (meth) acrylate, propylene oxide modified trimethylolpropane trithio (meth) acrylate, epichlorohydrin modified trimethylolpropane trithio (meth) acrylate, pentaerythritol trithio (meth) acrylate, Pentaerythritol tetrathio (meth) acrylate, stearic acid modified pentaerythritol dithio (meth) acrylate , Dipentaerythritol hexathio (meth) acrylate, dipentaerythritol monohydroxypentathio (meth) acrylate, alkyl-modified dipentaerythritol polythio (meth) acrylate, caprolactone-modified dipentaerythritol polythio (meth) acrylates, etc. Type thio (meth) acrylate, glycerol dithio (meth) acrylate, epichlorohydrin modified glycerol trithio (meth) acrylate, glycerol type thio (meth) acrylate such as triglycerol dithio (meth) acrylate, dicyclopentanyl dithio (meth) acrylate , Tricyclopentanyldithio (meth) acrylate, cyclohexyldithio (meth) acrylate, methoxylated cyclohexyldithio Cycloaliphatic thio (meth) acrylate such as (meth) acrylate, tris (thioacryloxyethyl) isocyanurate, tris (thiomethacryloxyethyl) isocyanurate, caprolactone-modified tris (thioacryloxyethyl) isocyanurate, caprolactone-modified tris And isocyanurate type thio (meth) acrylates such as (thiomethacryloxyethyl) isocyanurate. These may be used alone or in combination.

  Among compounds having an ethylenically unsaturated group, compounds having an aromatic ring or (and) a halogen atom in the molecule include styrenes such as styrene, α-methylstyrene, 4-methyl (e) oxystyrene, phenyl ( (Meth) acrylate, 4-phenylethyl (meth) acrylate, 4-methoxycarbonylphenyl (meth) acrylate, 4-ethoxycarbonylphenyl (meth) acrylate, 4-butoxycarbonylphenyl (meth) acrylate, 4-tert-butylphenyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, 4-phenoxyethyl (meth) acrylate, 4-phenoxydiethylene glycol (meth) acrylate, 4 Phenoxytetraethylene glycol (meth) acrylate, 4-phenoxyhexaethylene glycol (meth) acrylate, EO-modified phenoxylated phosphoric acid (meth) acrylate, EO-modified phthalic acid (meth) acrylate, 4-biphenylyl (meth) acrylate, aromatic Polyhydroxy compounds such as diquinone or poly (meth) acrylate compounds such as hydroquinone, resorcin, catechol, pyrogallol, bisphenol A di (meth) acrylate, ethyl (propi) ylene oxide modified bisphenol A di (meth) acrylate, bisphenol F di (Meth) acrylate, Ethi (propi) lene oxide modified bisphenol F di (meth) acrylate, Bisphenol S di (meth) acrylate, Ethi (propi) lene oxide modification (Meth) acrylate compounds having aromatic groups, such as bisphenol S di (meth) acrylate and epichlorohydrin modified di (meth) acrylate, p-chlorostyrene, p-bromostyrene, p-chlorophenoxyethyl (meth) acrylate , P-bromophenoxyethyl (meth) acrylate, trichlorophenol ethyl (propi) ylene oxide modified (meth) acrylate, tribromophenol ethyl (propi) ylene oxide modified (meth) acrylate, tetrachlorobisphenol A ethyl (propi) lene oxide modified di ( (Meth) acrylate, tetrabromobisphenol A ethyl (prop) ylene oxide modified di (meth) acrylate, tetrachlorobisphenol S ethyl (propylene) oxide modified di (meth) acrylate, Styrenes having an aromatic group substituted with a halogen atom having an atomic weight equal to or higher than chlorine, such as trabromobisphenol S ethyl (prop) ylene oxide-modified di (meth) acrylate, and (meth) acrylate compounds, N-vinylcarbazole, 3- Vinyl compounds having a heteroaromatic group such as me (e) til-N-vinylcarbazole, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-bromo-2-hydroxypropyl (meth) acrylate, 2,3 -(Meth) acrylate compounds substituted with halogen atoms such as dichloropropyl (meth) acrylate and 2,3-dibromopropyl (meth) acrylate.

  In addition, as a compound having an aromatic ring or (and) halogen atom in the molecule and a sulfur atom in the molecule, phenylthio (meth) acrylate, 4-phenylethylthio (meth) acrylate, 4-methoxycarbonylphenylthio ( (Meth) acrylate, 4-ethoxycarbonylphenylthio (meth) acrylate, 4-butoxycarbonylphenylthio (meth) acrylate, 4-tert-butylphenylthio (meth) acrylate, benzylthio (meth) acrylate, 4-phenoxydiethylene glycolthio (Meth) acrylate, 4-phenoxytetraethylene glycol thio (meth) acrylate, 4-phenoxyhexaethylene glycol thio (meth) acrylate, 4-biphenylylthio (meth) acrylate, aromatic Polyhydroxy compounds such as dithio or polythio (meth) acrylate compounds such as hydroquinone, resorcin, catechol, pyrogallol, bisphenol A dithio (meth) acrylate, ethi (propi) ylene oxide modified bisphenol A dithio (meth) acrylate, bisphenol F dithio (Meth) acrylate, Ethi (propi) lene oxide modified bisphenol F dithio (meth) acrylate, Bisphenol S dithio (meth) acrylate, Ethi (propi) lene oxide modified bisphenol S dithio (meth) acrylate, Epichlorohydrin modified dithiophthalate (meta) ) Thio (meth) acrylate compounds having aromatic groups such as acrylate, trichlorophenol ethyl (propylene) oxide modified thio (meta) Acrylate, tribromophenol ethyl (prop) ylene oxide modified thio (meth) acrylate, tetrachlorobisphenol A ethyl (prop) alkylene oxide modified dithio (meth) acrylate, tetrabromobisphenol A ethyl (propylene) oxide modified dithio (meth) acrylate, tetra Thio having an aromatic group substituted with a halogen atom having an atomic weight equal to or greater than chlorine, such as chlorobisphenol S ethyl (propi) ylene oxide modified dithio (meth) acrylate, tetrabromobisphenol S ethyl (propi) ylene oxide modified dithio (meth) acrylate (Meth) acrylate compound, 3-chloro-2-hydroxypropylthio (meth) acrylate, 3-bromo-2-hydroxypropylthio (meth) acrylate, 2,3-dichroic Examples thereof include thio (meth) acrylate compounds substituted with halogen atoms such as ropropylthio (meth) acrylate and 2,3-dibromopropylthio (meth) acrylate.

  Examples of the compound having an ethylenically unsaturated bond include addition-polymerizable compounds that polymerize via ring-opening sigma bond cleavage. Such compounds are described in K. J. et al. Ivin and T.W. Saegusa, Elsevier, New York, 1984, Chapter 1 “General Thermodynamics and Mechanical Aspects of Ring-Opening Polymerization” pages 1 to 82, and Chapter 2 “Ring Opinion Polymer”. Pages 83-119, W.M. J. et al. Bailey et al. Macromol. Sci. -Chem. A21, pp. 1611-1639, 1984, and I.A. Cho and K.K. -D. Ahn J.M. Polym. Sci. , Polym. Lett. Ed. Volume 15, pages 751 to 753, 1977. Specific examples include vinylcyclopropane, such as 1,1-dicyano-2-vinylcyclopropane, 1,1-dichloro-2-vinylcyclopropane, diethyl-2-vinylcyclopropane-1,1-dicarboxylate (EVCD). ), Ethyl-1-acetyl-2-vinyl-1-cyclopropanecarboxylate (EAVC), ethyl-1-benzoyl-2-vinyl-1-cyclopropanecarboxylate (EBVC), and the like. These may be used alone or in combination, or may be used in combination with the (meth) acrylic compound or vinyl compound.

  Specific examples of amide monomers of unsaturated carboxylic acids and aliphatic polyvalent amine compounds include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, and 1,6-hexamethylene bismethacrylamide. , Diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, N-phenylmethacrylamide, diacetone acrylamide and the like.

Other examples include polyisocyanate compounds having two or more isocyanate groups in one molecule described in JP-B-48-41708, general formula CH ₂ ═C (R) COOCH ₂ CH (R ′) OH ( In the formula, R and R ′ represent a hydrogen atom or a methyl group.) A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group represented by It is done.

  Also, urethane acrylates described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, respectively. Polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy resins and (meth) acrylic acid can be mentioned.

  Furthermore, the Japan Adhesion Association Vol. No. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

  In addition, as a monomer containing phosphorus, mono (2-acryloyloxyethyl) acid phosphate (trade name: Light Ester PA, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), mono (2-methacryloyl ethyl) acid phosphate (Product name: Light Ester PM, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), and product name: Lipoxy VR-60 (manufactured by Showa Polymer Co., Ltd.), product name: Lipoxy VR- 90 (manufactured by Showa Polymer Co., Ltd.) and the like.

  Moreover, brand name: NK ester M-230G (made by Shin-Nakamura Chemical Co., Ltd.) and brand name: NK ester 23G (made by Shin-Nakamura Chemical Co., Ltd.) are also mentioned. Triacrylates, manufactured by Toa Synthetic Chemical Industry Co., Ltd., trade name, Aronix M-315, manufactured by Toa Synthetic Chemical Industry Co., Ltd., trade name, Aronix M-325, and 2,2′-bis (4-acryloxy)・ Diethoxyphenyl) propane (trade name, NK ester A-BPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.), tetramethylolmethane tetraacrylate (trade name, NK ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) Etc.

  Moreover, as a polymerizable urethane acrylate resin, TSR-1920B, TSR-1938 (manufactured by Teijin Limited), and SCR-500 (manufactured by Nippon Synthetic Rubber Co., Ltd.) are preferable in terms of thermal characteristics and mechanical characteristics.

  The cationically polymerizable compound of the present invention is a compound in which polymerization is initiated by an acid generated by a two-photon absorption compound and a cationic polymerization initiator. For example, “Chemtech. Oct.” [J. V. JV Crivello, p. 624, (1980)], Japanese Patent Application Laid-Open No. 62-149784, Journal of the Adhesion Society of Japan [Vol. 26, No. 5, pp. 179-187 (1990)] and the like.

The cationically polymerizable compound of the present invention is preferably a compound having at least one oxirane ring, oxetane ring or vinyl ether group site in the molecule, and more preferably a compound having an oxirane ring site.
Specific examples include the following cationically polymerizable monomers and prepolymers (for example, dimers and oligomers) composed of these monomers.

  Specific examples of the cationic polymerizable monomer having an oxirane ring include glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis ( 2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol tetraglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol di Glycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, Reethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether, phenyl glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diacid Glycidyl ester, phthalic acid diglycidyl ester, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, 4,4 '-Bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, vinylcyclohexene dioxide, 3,4 Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, 1,2,5,6 -Diepoxy-4,7-methanoperhydroindene, 2- (3,4-epoxycyclohexyl) -3 ', 4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy- Bis (3,4-epoxycyclohexylmethane), 4 ', 5'-epoxy Cis-2′-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), bis- (3,4-epoxycyclohexylmethyl) adipate, Di-2,3-epoxycyclopentyl ether, vinyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, p-bromostyrene oxide, bisphenol-A-diglycidyl ether, tetrabromobisphenol-A-diglycidyl ether And compounds such as bisphenol-F-diglycidyl ether.

  HS-681 (manufactured by Asahi Denka Kogyo Co., Ltd.), SOMOS8100 (manufactured by DMS-SOMOS), SCR-8100 series (manufactured by Nippon Synthetic Rubber Co., Ltd.), SL-7540 (manufactured by Vantico) SCR-701 (Dee) MEC, Nippon Synthetic Rubber Co., Ltd.) can also be mentioned as a polymerizable epoxy resin.

  Specific examples of the cationic polymerizable monomer having an oxetane ring include compounds in which the oxirane ring in the specific examples of the cationic polymerizable monomer having an oxirane ring is replaced with an oxetane ring.

  Specific examples of the cationic polymerizable monomer having a vinyl ether group moiety include, for example, vinyl-2-chloroethyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, propylene glycol diester. Vinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether , Trimethylolpropane trivinyl ether Diglycerol trivinyl ether, sorbitol tetravinyl ether, allyl vinyl ether, 2,2-bis (4-cyclohexanol) propane divinyl ether, 2,2-bis (4-cyclohexanol) trifluoropropane divinyl ether, 1,4-cyclohexanedi Examples include methanol divinyl ether, 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, bisphenol A divinyl ether, tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, and p-bromophenoxyethylene vinyl ether.

  Next, (B) the two-photon absorption compound in the photopolymerizable composition of the present invention will be described.

In the present invention, when a specific moiety is referred to as a “group”, unless otherwise specified, it may be substituted with one or more (up to the maximum possible) substituents. It means that it is not necessary. For example, “alkyl group” means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention may be any substituent regardless of the presence or absence of substitution.
In the present invention, when a specific moiety is referred to as “ring”, or when “group” includes “ring”, it may be monocyclic or condensed unless otherwise specified. May not be substituted.
For example, the “aryl group” may be a phenyl group, a naphthyl group, or a substituted phenyl group.

The two-photon absorption compound used in the present invention is preferably a two-photon absorption compound having a two-photon absorption cross section of 500 GM (1GM = 1.0 × 10 ⁻⁵⁰ cm ⁴ s photon ⁻¹ ) or more, more preferably It is a two-photon absorption compound having a two-photon absorption cross section of 1000 GM or more.

The two-photon absorption compound used in the present invention is not particularly limited, and examples thereof include the following dye compounds.
For example, cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, Squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, xanthene dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, Phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine Down dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes or metal complex dyes,.

  Preferably, cyanine dye, hemicyanine dye, streptocyanine dye, styryl dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, oxonol dye, squalium dye, arylidene dye, triphenylmethane dye, xanthene dye, porphyrin And dyes, phthalocyanine dyes, and metal complex dyes, more preferably cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, oxonol dyes, squalium dyes. And methine dyes such as arylidene dyes, more preferably cyanine dyes, merocyanine dyes, or oxonol dyes.

  For more information on these dyes, see F.M. Harmer, “Heterocyclic Compounds-Cyanine Dies and Related Compounds”, John. John Wiley & Sons-New York, London, 1964, by DM Sturmer, “Heterocyclic Compounds in Special Topics in Heterocyclics” Chemistry (Heterocyclic Compounds-Special topics in heterochemical chemistry) , Chapter 14, Section 14, 482-515, John Wiley & Sons-New York, London, 1977, "Rods Chemistry of Carbon Compounds (Rodd ' s Chemistry of Carbon Compounds) "2nd. Ed. vol. IV, part B, 1977, Chapter 15, pages 369-422, published by Elsevier Science Publishing Company Inc., New York, and the like.

  Specific examples of the cyanine dye, merocyanine dye, or oxonol dye include F.I. M.M. As described by Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964.

  The general formulas of cyanine dye and merocyanine dye are those shown in (XI) and (XII) on pages 21 and 22 of US Pat. No. 5,340,694 (however, the numbers of n12 and n15 are not limited, An integer of 0 or more (preferably an integer of 0 to 4) is preferable.

  When the dye of the present invention is a cyanine dye, it is preferably represented by the following general formula (1).

In the general formula (1), Za ₁ and Za ₂ each represent an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle. The 5-membered or 6-membered nitrogen-containing heterocycle formed is preferably an oxazole nucleus having 3 to 25 carbon atoms (hereinafter referred to as C number) (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl). , 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropyl Benzoxazolyl, 2-3-methylthioethylbenzoxazolyl, 2-3-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl 2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3- ( -Naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2- 3-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-3 -Dimethyl-5,6-dimethylthiobenzoxazolyl), thiazole nuclei having 3 to 25 carbon atoms (for example, 2-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2- 3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2 -3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl , 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro -3-methylbenzothiazolyl, 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl 2-5-phenyl-3-sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6- Dimethylthiobenzothiazolyl), imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2-1-methylbenzimidazolyl, 2- 1,3,4-triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-1,3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro- 1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzimidazolyl, etc.), C10-30 indolenine nucleus (for example, 3,3-dimethylindolenine) ), A quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1-methylquinolyl, 2-1-ethylquinolyl) 2-1-methyl 6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1 And sulfoethylquinolyl, 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.) , A C 3-25 selenazole nucleus (for example, 2-3methylbenzoselenazolyl etc.), a C 5-25 pyridine nucleus (for example, 2-pyridyl etc.) and the like can be mentioned. In addition, thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quino Zarin] nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, may be mentioned pyrimidine nucleus.

  These may be substituted, and the substituent is preferably, for example, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3- Sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3-20, for example cyclopentyl, cyclohexyl), aryl groups (preferably C 6-20, for example phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic groups ( Preferably C number 1-20, for example pyridyl, thienyl, furyl, thiazolyl, imida Lyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atom (for example, F, Cl Br, I), amino group (preferably C 0-20, for example, amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, Phosphonic acid group, acyl group (preferably C 1-20, such as acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C 1-20, such as methoxy, butoxy, cyclohexyloxy), aryloxy group (Preferably C number 6-26, for example, phenoxy, 1 Naphthoxy), alkylthio group (preferably C number 1-20, for example, methylthio, ethylthio), arylthio group (preferably C number 6-20, for example, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (preferably C number) 1-20, such as methanesulfonyl, butanesulfonyl), arylsulfonyl groups (preferably C number 6-20, such as benzenesulfonyl, paratoluenesulfonyl), sulfamoyl groups (preferably C number 0-20, such as sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (Preferably C number 1 -20, such as acetylamino, benzoylamino), imino group (preferably C 2-20, such as phthalimino), acyloxy group (preferably C 1-20, such as acetyloxy, benzoyloxy), alkoxycarbonyl group (preferably Is a C 2-20, such as methoxycarbonyl, phenoxycarbonyl), or a carbamoylamino group (preferably a C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), and more An alkyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group is preferable.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

Za1 (in this specification, all superscripts and subscripts in chemical formulas are expressed in full-width. For example, “ ₁ ” and “ ¹ ” are displayed as “1”) and five members formed by Za2 Or a 6-membered nitrogen-containing heterocyclic ring, more preferably an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine ring, more preferably an oxazole nucleus, an imidazole nucleus, or an indolenine ring, most preferably an oxazole nucleus. It is.

  Ra1 and Ra2 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4 -Sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C2-20, for example, vinyl, allyl), aryl group (preferably C number 6-20, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl) or a heterocyclic group (preferably C number 1-20, for example pyridyl, thienyl, furyl, Thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino) and more preferred Properly is an alkyl group (preferably an alkyl group having a C number of 1 to 6) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl).

Ma1 to Ma7 each represents a methine group and may have a substituent (examples of preferred substituents are the same as the examples of substituents on Za1 and Za2), and the substituents are preferably alkyl groups, halogen atoms, A nitro group, an alkoxy group, an aryl group, a nitro group, a heterocyclic group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group, an alkylthio group, a cyano group and the like are preferable, and a substituent is more preferable. Is an alkyl group.
Ma1 to Ma7 are preferably an unsubstituted methine group or an alkyl group (preferably having a C number of 1 to 6) substituted methine group, and more preferably an unsubstituted, ethyl group-substituted, or methyl group-substituted methine group.
Ma1 to Ma7 may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

  na1 and na2 are 0 or 1, preferably both 0.

ka1 represents an integer of 0 to 3, more preferably ka1 represents 1 to 3, and further preferably ka1 represents 1 or 2.
When ka1 is 2 or more, the plurality of Ma3 and Ma4 may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the two-photon absorption compound of the present invention is a merocyanine dye, it is preferably represented by the following general formula (2).

  In the general formula (2), Za3 represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocycle (preferred examples are the same as Za1 and Za2), and these may be substituted (examples of preferred substituents). Are the same as the examples of the substituents on Za1 and Za2, and these heterocyclic rings may be further condensed.

  The 5-membered or 6-membered nitrogen-containing heterocyclic ring formed by Za3 is more preferably an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine ring, and more preferably an oxazole nucleus or an indolenine ring.

Za4 represents an atomic group forming a 5-membered or 6-membered ring. The ring formed from Za4 is a part generally called an acidic nucleus, and is defined by James ed., The Theory of the Photographic Process, 4th edition, Macmillan, 1977, p. 198. As Za4, 2-pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5 -One, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, Indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3- Dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazoline-2- Examples include nuclei such as on, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolopyridone.
More preferably, the ring formed from Za4 is 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1. , 1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, or coumarin-2,4-dione, more preferably pyrazolidine-3,5-dione, Indan-1,3-dione, 1,3-dioxane-4,6-dione, barbituric acid, or 2-thiobarbituric acid, most preferably pyrazolidine-3,5-dione, barbituric acid, or 2-thiobarbituric acid.

  The ring formed from Za4 may be substituted (preferred examples of the substituent are the same as the examples of the substituent on Za3). More preferably, the substituent is preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, A cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group.

  These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.

  Each of Ra3 is independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as Ra1 and Ra2), more preferably an alkyl group (preferably having 1 to 6 carbon atoms). Alkyl group) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl).

Ma8 to Ma11 each represents a methine group and may have a substituent (examples of preferred substituents are the same as those of the substituents on Za1 and Za2), and the substituents are preferably alkyl groups, halogen atoms, A nitro group, an alkoxy group, an aryl group, a nitro group, a heterocyclic group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group, an alkylthio group, a cyano group and the like are preferable, and a substituent is more preferable. Is an alkyl group.
Ma8 to Ma11 are preferably unsubstituted methine groups or alkyl groups (preferably having a C number of 1 to 6) substituted methine groups, more preferably unsubstituted, ethyl group-substituted, or methyl group-substituted methine groups.
Ma8 to Ma11 may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

  na3 is 0 or 1, preferably 0.

ka2 represents an integer of 0 to 8, preferably an integer of 0 to 4, more preferably an integer of 2 to 4.
When ka2 is 2 or more, the plurality of Ma10 and Ma11 may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  When the two-photon absorption compound of the present invention is an oxonol dye, it is preferably represented by the general formula (3).

In the general formula (3), Za5 and Za6 each represent an atomic group forming a 5-membered or 6-membered ring (preferred examples are the same as Za4), and these may be substituted (preferred examples of substituents on Za4). These heterocyclic rings may be further condensed.
More preferably as a ring formed from Za5 and Za6, 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one -1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, or coumarin-2,4-dione, more preferably barbituric acid, or 2- Thiobarbituric acid, most preferably barbituric acid.

Ma12 to Ma14 each represent a methine group and may have a substituent (preferred examples of the substituent are the same as the examples of the substituent on Za5 and Za6), and the substituent is preferably an alkyl group or a halogen atom. Nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, or cyano group, more preferably An alkyl group, a halogen atom, an alkoxy group, an aryl group, a heterocyclic group, a carbamoyl group, or a carboxy group, and more preferably an alkyl group, an aryl group, or a heterocyclic group.
Ma12 to Ma14 are preferably unsubstituted methine groups.
Ma12 to Ma14 may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.

ka3 represents an integer from 0 to 3, preferably represents an integer from 0 to 2, more preferably represents 1 or 2, and most preferably represents 2.
When ka3 is 2 or more, Ma12 and Ma13 may be the same or different.

  CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.

  The two-photon absorption compound of the present invention is also preferably represented by the following general formula (4).

In the general formula (4), R 1, R 2, R 3 and R 4 each independently represent a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl, carboxymethyl, 5-carboxypentyl), alkenyl A group (preferably having 2 to 20 carbon atoms, such as vinyl, allyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), or a heterocyclic group (Preferably having 1 to 20 carbon atoms, such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino).
R1, R2, R3 and R4 are preferably a hydrogen atom or an alkyl group. Some (preferably two) of R1, R2, R3 and R4 may be bonded to each other to form a ring. In particular, R1 and R3 are preferably bonded to form a ring, and the ring formed with the carbonyl carbon atom is preferably a 6-membered ring, a 5-membered ring or a 4-membered ring, and a 5-membered ring or 4-membered ring A ring is more preferable, and a 5-membered ring is most preferable.

In General formula (4), n and m represent the integer of 0-4 each independently, Preferably the integer of 1-4 is represented. However, n and m are not 0 simultaneously.
When n and m are 2 or more, a plurality of R1, R2, R3 and R4 may be the same or different.

  X1 and X2 are independently an aryl group [preferably having 6 to 20 carbon atoms, preferably a substituted aryl group (for example, a substituted phenyl group, a substituted naphthyl group, and preferably the same as the substituents of Ma1 to Ma7 as examples of the substituent). More preferably represents an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an amino group, a hydroxyl group, an alkoxy group, an aryloxy group, an aryl group substituted by an acylamino group, more preferably an alkyl group, an amino group, An aryl group substituted with a hydroxyl group, an alkoxy group, or an acylamino group, and most preferably a phenyl group substituted with a dialkylamino group or a diarylamino group at the 4-position. In this case, a plurality of substituents may be linked to form a ring, and examples of a preferable ring to be formed include a julolidine ring], a heterocyclic group (preferably having 1 to 20 carbon atoms, preferably 3 to 8 membered ring, More preferably a 5- or 6-membered ring such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolyl, indolyl, carbazolyl, phenothiazino, pyrrolidino, piperidino, morpholino, more preferably indolyl, carbazolyl, pyrrolyl, phenothiazino. It may be substituted, and a preferable substituent is the same as the example in the case of the aryl group) or a group represented by the following general formula (5).

In general formula (5), R5 represents a hydrogen atom or a substituent (preferred examples are the same as R1 to R4), preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
R6 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferable examples of these substituents are the same as R1 to R4), preferably an alkyl group (preferably an alkyl having 1 to 6 carbon atoms). Group).

Z1 represents an atomic group forming a 5- or 6-membered ring.
The heterocycle formed is preferably an indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, imidazole ring, thiadiazole ring Quinoline ring, pyridine ring, more preferably indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, thiadiazole ring Or an quinoline ring, most preferably an indolenine ring, an azaindolenine ring, a benzothiazole ring, a benzoxazole ring, or a benzimidazole ring.
The heterocycle formed by Z1 may have a substituent (examples of preferred substituents are the same as the examples of substituents on Za1 and Za2), and more preferably alkyl groups, aryl groups, heterocycles as substituents. A ring group, a halogen atom, a carboxyl group, a sulfo group, an alkoxy group, a carbamoyl group, or an alkoxycarbonyl group.

  X1 and X2 are preferably an aryl group or a group represented by the general formula (5), more preferably an aryl group substituted with a dialkylamino group or a diarylamino group at the 4-position, or a general formula (5). It is a group.

The two-photon absorption compound of the present invention preferably has a hydrogen bonding group in the molecule. Here, the hydrogen-bonding group represents a group that donates hydrogen or a group that accepts hydrogen in a hydrogen bond, and a group having both properties is more preferable.
Further, the compound having a hydrogen bonding group of the present invention preferably has an associative interaction by the interaction between hydrogen bonding groups in a solution or in a solid state, and may be an intramolecular interaction or an intermolecular interaction. The interaction is more preferable.

As the hydrogen bonding group, —COOH, —CONHR11, —SO ₃ H, —SO ₂ NHR12, —P (O) (OH) OR13, —OH, —SH, —NHR14, —NHCOR15, —NR16C (O ) NHR17. Here, R11 and R12 are each independently a hydrogen atom or an alkyl group (preferably having a carbon atom number (hereinafter referred to as C number) of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl. Benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an alkenyl group (preferably having 2 to 20 carbon atoms, for example, vinyl, allyl), an aryl group (preferably having 6 to 20 carbon atoms, For example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms, such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino , piperidino, morpholino), - represents COR18 or -SO ₂ R19, R1 ~R19 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group (preferred examples of these R11, the same as R12).

R11 preferably represents a hydrogen atom, an alkyl group, an aryl group, a —COR18 group, or a —SO ₂ R19 group. In that case, R18 and R19 are preferably each independently an alkyl group or an aryl group.
R11 is more preferably a hydrogen atom, an alkyl group, or a —SO ₂ R19 group, and most preferably a hydrogen atom.
R12 preferably represents a hydrogen atom, an alkyl group, an aryl group, a —COR18 group, or a —SO ₂ R19 group. In that case, R18 and R19 are preferably each independently an alkyl group or an aryl group.
R12 is more preferably a hydrogen atom, an alkyl group, or a —COR18 group, and most preferably a hydrogen atom.
R13 preferably represents a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.
R14 preferably represents a hydrogen atom, an alkyl group, or an aryl group.
R15 preferably represents an alkyl group or an aryl group.
R16 preferably represents a hydrogen atom, and R17 preferably represents a hydrogen atom, an alkyl group, or an aryl group.

Hydrogen bonding group is more _{preferably, -COOH, -CONHR11, -SO 2 NHR12} , -NHCOR15, are either -NR16C (O) NHR17, either more preferably -COOH, -CONHR11, a -SO ₂ NHR12 Most preferably, it is either —COOH or —CONH 2.

The two-photon absorption compound of the present invention may be used in a monomer state or in an associated state. Here, the dye chromophores are fixed in a specific spatial arrangement by a bond such as a covalent bond or a coordinate bond, or various intermolecular forces (hydrogen bond, van der Waals force, Coulomb force, etc.) This state is generally referred to as an association (or aggregation) state.
The two-photon absorption compound of the present invention has two or more chromophores that perform two-photon absorption in a molecule even when used in an intermolecular association state, and is used in a state in which they absorb two-photons in an intramolecular association state. May be.

For reference, the meeting is explained below. As for the association, for example, James, “The Theory of the Photographic Process”, 4th edition, Macmillan Publishers, 1977, Chapter 8, 218. Pp. 222 and “J-Aggregates” written by Takabayashi Kobayashi, World Scientific Publishing Co. Pte. Ltd., published in 1996). .
A monomer means a monomer. From the viewpoint of the absorption wavelength of the aggregate, the aggregate whose absorption shifts to a short wavelength with respect to monomer absorption is defined as an H aggregate (the dimer is specially called a dimer), and the aggregate whose shift is shifted to a long wavelength. Called coalescence.

  From the viewpoint of the structure of the aggregate, in a brick-stacked aggregate, when the deviation angle of the aggregate is small, it is called a J aggregate, but when the deviation angle is large, it is called an H aggregate. Brickwork aggregates are described in detail in Chemical Physics Letters, Vol. 6, page 183 (1970). In addition, there is a ladder or staircase aggregate as an aggregate having a structure similar to that of a brickwork aggregate. Ladder or staircase structures are described in detail in Zeitschiff for Physikaliche Chemie, Vol. 49, p. 324 (1941).

Moreover, as what forms other than a brickwork aggregate | assembly, the aggregate | assembly (it can call an arrowhead aggregate | assembly) etc. which take an arrow (Herringbone) structure etc. are known.
The Herringbone association is described in Charles Reich, Photographic Science and Engineering, Vol. 18, No. 3, p. 335 (1974). Has been. The arrowhead aggregate has two absorption maxima derived from the aggregate.

Whether or not it is in an associated state can be confirmed by a change in absorption (absorption λmax, ε, absorption type) from the monomer state as described above.
The compound of the present invention may be either short-wavelength (H-association) or long-wavelength (J-association) or both by association, but it is more preferable to form a J-aggregate.

The intermolecular association state of a compound can be formed in various ways.
For example, in a solution system, an aqueous solution to which a matrix such as gelatin is added (for example, gelatin 0.5 wt% / compound 10 ⁻⁴ M aqueous solution), an aqueous solution to which a salt such as KCl is added (for example, KCl 5% · compound 2 × 10 ^−3). M aqueous solution), a method of dissolving a compound in a good solvent, a method of adding a poor solvent afterwards (for example, DMF-water system, chloroform-toluene system, etc.) and the like.
Examples of the film system include polymer dispersion systems, amorphous systems, crystal systems, and LB film systems.
Furthermore, molecules can be adsorbed, chemically bonded, or self-assembled into bulk or fine particle (μm to nm size) semiconductors (eg, silver halide, titanium oxide, etc.), bulk or fine particle metals (eg, gold, silver, platinum, etc.). Inter-association states can also be formed. Spectral sensitization by cyanine dye J-associative adsorption on silver halide crystals in a color silver salt photograph utilizes this technique.
The number of compounds involved in the intermolecular association may be two or a very large number of compounds.

  Although the preferable specific example of the two-photon absorption compound used by this invention is given to the following, this invention is not limited to these.

Next, (C) the polymerization initiator in the two-photon absorption polymerizable composition of the present invention will be described. The polymerization initiator of the present invention is a radical or acid (Bronsted acid) by performing energy transfer or electron transfer (giving or receiving electrons) from the excited state of a two-photon absorption compound generated by non-resonant two-photon absorption. Or a Lewis acid) and a compound capable of initiating polymerization of a polymerizable compound.
The polymerization initiator of the present invention is preferably a radical polymerization initiator capable of generating radicals to initiate radical polymerization of polymerizable compounds, and cationic polymerization of polymerizable compounds by generating only acids without generating radicals. Either a cationic polymerization initiator capable of initiating only radicals or a polymerization initiator capable of generating both radicals and acids to initiate both radical and cationic polymerization.

  The polymerization initiator of the present invention preferably includes the following 14 systems. In addition, you may use these polymerization initiators as 2 or more types of mixtures by arbitrary ratios as needed.

1) Ketone polymerization initiator 2) Organic peroxide polymerization initiator 3) Bisimidazole polymerization initiator 4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization Initiator 7) sulfonium salt polymerization initiator 8) borate polymerization initiator 9) diaryliodonium organic boron complex polymerization initiator 10) sulfonium organic boron complex polymerization initiator 11) cationic two-photon absorption compound organic boron Complex polymerization initiator 12) Anionic two-photon absorption compound onium salt complex polymerization initiator 13) Metal arene complex polymerization initiator 14) Sulfonic acid ester polymerization initiator

  The preferred system described above will be specifically described below.

1) Ketone-based polymerization initiator

Preferred examples of the ketone polymerization initiator include aromatic ketones and aromatic diketones.
Preferred examples include, for example, benzophenone derivatives (for example, benzophenone, Michler's ketone), benzoin derivatives (for example, benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, α-allylbenzoin, α-phenylbenzoin), acetoin derivatives (acetoin, pivaloin, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone), acyloin ether derivatives (eg diethoxyacetophenone), α-diketone derivatives (diacetyl, benzyl, 4,4′-dimethoxybenzyl, benzyldimethyl ketal) , 2,3-bornanedione (camphorquinone), 2,2,5,5-tetramethyltetrahydro-3,4-furanic acid (imidazole trione)), xanthone derivative (For example, xanthone), thioxanthone derivatives (for example, thioxanthone, 2-chlorothioxanthone), ketocoumarin derivatives, and the like.

  Examples of commercially available products include Irgacure 184, 651, and 907 represented by the following formula, which are commercially available from Ciba Geigy.

  Preferred examples include quinone polymerization initiators (for example, 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone. Quinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-methyl-1,4-naphthoquinone, 2, 3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2,3-dimethylanthraquinone, sodium salt of anthraquinone alpha-sulfonic acid, 3-chloro-2 -Methylanthraquinone, Rethenequinone, 7,8,9,10-tetra Mud naphthacene quinone, and 1,2,3,4-tetrahydrobenz (a) anthracene-7,12-dione) can be mentioned.

2) Organic peroxide polymerization initiator

  Preferable examples include benzoyl peroxide, di-t-butyl peroxide, 3,3 ′, 4,4′-tetra (t-) described in JP-A-59-189340 and JP-A-60-76503. Butylperoxycarbonyl) benzophenone and the like.

3) Bisimidazole polymerization initiator

  Preferred examples of the bisimidazole-based polymerization initiator include bis (2,4,5-triphenyl) imidazole derivatives such as bis (2,4,5-triphenyl) imidazole and 2- (o-chlorophenyl) -4. , 5-bis (m-methoxyphenyl) -imidazole dimer (CDM-HABI), 1,1'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,4'5,5'-tetraphenyl (O-Cl-HABI), 1H-imidazole, 2,5-bis (o-chlorophenyl) -4- [3,4-dimethoxyphenyl] -dimer (TCTM-HABI) and the like.

  The bisimidazole polymerization initiator is preferably used together with a hydrogen donor. Preferred examples of the hydrogen donor include 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 4-methyl-4H-1,2,4-triazole-3-thiol, and the like.

4) Trihalomethyl-substituted triazine polymerization initiator

  The trihalomethyl-substituted triazine polymerization initiator is preferably represented by the following general formula (6).

In general formula (6), R21, R22 and R23 each independently represent a halogen atom, preferably a chlorine atom. R24 and R25 each independently represent a hydrogen atom, -CR21R22R23, or other substituents (preferred examples are the same as the substituents on Za1). R24 is a preferably -CR21R22R23, more preferably represents a ₃ group -CCl, R25 is preferably, -CR21R22R23, an alkyl group, an alkenyl group or an aryl group.

  Specific examples of the trihalomethyl-substituted triazine polymerization initiator include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1, 3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4′-methoxyphenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4′-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (p -Methoxyphenylvinyl) -1,3,5-triazine, 2- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine . Preferable examples also include compounds described in British Patent No. 1388492 and JP-A No. 53-133428.

5) Diazonium salt polymerization initiator

  The diazonium salt polymerization initiator is preferably represented by the following general formula (7).

R26 represents an aryl group or a heterocyclic group (the above preferred examples are the same as the substituents on Za1), preferably an aryl group, more preferably a phenyl group.
R27 represents a substituent (preferred examples are the same as the substituents on Za1), and a21 represents an integer of 0 to 5, preferably an integer of 0 to 2. When a21 is 2 or more, the plurality of R27s may be the same or different and may be connected to each other to form a ring.
X21 ⁻ is an anion in which HX21 becomes an acid having a pKa of 4 or less (in water, 25 ° C.), preferably 3 or less, more preferably 2 or less, and preferably, for example, chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate , Hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, tetra (pentafluoro Phenyl) borate and the like.

Specific examples of the diazonium-based polymerization initiator include benzenediazonium, 4-methoxydiazonium, the above X21 ^- salt of 4-methyldiazonium, and the like.

6) Diaryliodonium salt polymerization initiator

  The diaryliodonium salt polymerization initiator is preferably represented by the following general formula (8).

In general formula (8), X21 < ^- > is synonymous with general formula (7). R28 and R29 each independently represent a substituent (preferred examples are the same as the substituents on Za1), and preferably represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a nitro group.
a22 and a23 each independently represent an integer of 0 to 5, preferably an integer of 0 to 1. When a21 is 2 or more, a plurality of R28 and R29 may be the same or different, and may be connected to each other to form a ring.

Specific examples of the diaryliodonium salt polymerization initiator include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-dimethyldiphenyliodonium, 4,4′-t- Chlorides such as butyldiphenyliodonium, 3,3′-dinitrodiphenyliodonium, phenyl (p-methoxyphenyl) iodonium, bis (p-cyanophenyl) iodonium, bromide, iodide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate , Hexafluoroantimonate, perchlorate, trifluoromethane sulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methane sulfonate, benzene sulfonate, 4-tri Le Oro methylbenzenesulfonate, tosylate, tetra (pentafluorophenyl) borate.
Further, compounds described in “Macromolecules”, Vol. 10, p1307 (1977), Japanese Patent Application Laid-Open Nos. 58-29803, 1-287105, and Japanese Patent Application No. 3-5569. And diaryliodonium salts as described in 1).

7) Sulfonium salt polymerization initiator

  The sulfonium salt polymerization initiator is preferably represented by the following general formula (9).

In the general formula (9), X21 ⁻ has the same meaning as in the general formula (7). R30, R31, and R32 each independently represent an alkyl group, an aryl group, or a heterocyclic group (preferred examples are the same as the substituents on Za1), preferably an alkyl group, a phenacyl group, or an aryl group.

  Specific examples of the sulfonium salt polymerization initiator include triphenylsulfonium, diphenylphenacylsulfonium, dimethylphenacylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 4-tertiarybutyltriphenylsulfonium, tris (4-methylphenyl). ) Sulphonium chloride such as sulfonium, tris (4-methoxyphenyl) sulfonium, 4-thiophenyltriphenylsulfonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoro Lomethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trif Oro-methylbenzenesulfonate, tosylate, etc. tetra (pentafluorophenyl) borate.

8) Borate polymerization initiator

  The borate polymerization initiator is preferably represented by the following general formula (10).

In general formula (10), R33, R34, R35, and R36 each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group (the preferred examples are the same as the substituents on Za1), An alkyl group or an aryl group is preferable. However, all of R33, R34, R35, and R36 do not become an aryl group at the same time. X22 ⁺ represents a cation.
More preferably, R33, R34 and R35 are all aryl groups, and R36 is an alkyl group, most preferably R33, R34 and R35 are phenyl groups, and R36 is an n-butyl group.

  Specific examples of the borate polymerization initiator include tetrabutylammonium n-butyltriphenylborate, tetramethylammonium sec-butyltriphenylborate and the like.

9) Diaryliodonium organoboron complex polymerization initiator

  The diaryliodonium organoboron complex salt polymerization initiator is preferably represented by the following general formula (11).

  In general formula (11), R28, R29, a22, and a23 have the same meaning as in general formula (8), and R33, R34, R35, and R36 have the same meaning as in general formula (10).

  Specific examples of the diaryliodonium organoboron complex salt polymerization initiator include I-1 to I-3 shown below.

  Furthermore, iodonium organoboron complexes such as diphenyliodonium (n-butyl) triphenylborate described in JP-A-3-704 are also preferable examples.

10) Sulfonium organoboron complex polymerization initiator

  The sulfonium organic boron complex salt polymerization initiator is preferably represented by the following general formula (12).

  In general formula (12), R33, R34, R35, and R36 have the same meaning as in general formula (10). R 37, R 38, and R 39 are each independently an alkyl group, aryl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, or amino group. The same as the substituent on Za1), more preferably an alkyl group, a phenacyl group, an aryl group, or an alkenyl group. R37, R38, and R39 may be connected to each other to form a ring. R40 represents an oxygen atom or a lone electron pair.

  Specific examples of the sulfonium organic boron complex salt polymerization initiator include I-4 to I-10 shown below.

  Furthermore, preferred examples include sulfonium organoboron complexes described in JP-A-5-255347 and JP-A-5-213861.

11) Cationic two-photon absorption compound organoboron complex polymerization initiator

When the polymerization initiator of the present invention is a cationic two-photon absorption compound organic boron complex polymerization initiator, the cationic two-photon absorption compound may serve as the two-photon absorption compound of the present invention.
The cationic two-photon absorption compound organoboron complex polymerization initiator is preferably represented by the general formula (13).

In the general formula (13), (Dye-1) ⁺ performs non-resonant two-photon absorption and is a cationic compound. Preferred examples are as described above. R33, R34, R35, and R36 have the same meaning as in the general formula (10).

  Specific examples of the cationic two-photon absorption compound organoboron complex polymerization initiator include I-11, I-12, I-13, and I-14 shown below.

  Specific examples include cationic dye-borate anion complexes described in JP-A-62-143044 and 62-150242.

  12) Anionic two-photon absorption compound onium salt complex polymerization initiator

When the polymerization initiator of the present invention is an anionic two-photon absorption compound onium salt complex polymerization initiator, the anionic two-photon absorption compound may serve as the two-photon absorption compound of the present invention.
The anionic two-photon absorption compound onium salt complex polymerization initiator is preferably represented by the general formula (14).

In the general formula (14), (Dye-2) ⁻ is an anionic compound that performs non-resonant two-photon absorption, and preferred examples are as described above. X23 ⁺ represents the cation moiety of the diazonium salt of the general formula (7), the cation moiety of the diaryliodonium salt of the general formula (8), and the cation moiety of the sulfonium salt of the general formula (9) (all preferred examples are as described above) ), Preferably a cation moiety of the diaryliodonium salt of the general formula (8) or a cation moiety of the sulfonium salt of the general formula (9).

  Specific examples of the anionic two-photon absorption compound onium salt complex polymerization initiator include I-15 to I-32 shown below.

  13) Metal arene complex polymerization initiator

  As the metal arene complex polymerization initiator, the metal is preferably iron or titanium. Specifically, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712 and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, page 174 ( 1986), an iron arene complex described in “Organometallics”, Vol. 8, page 2737 (1989), and a titanone described in JP-A-61-151197. And the like are preferable examples.

14) Sulfonic acid ester polymerization initiator

  Examples of the sulfonate ester polymerization initiator include sulfonate esters, imide sulfonates, and aryl sulfonic acid-p-nitrobenzyl esters.

  Specific examples include benzoin tosylate, pyrogallol trimesylate, o-nitrobenzyl tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide, α-cyanobenzylidene tosylamine, p-nitrobenzyl-9,10- Examples include diethoxyanthracene-2-sulfonate.

15) Other polymerization initiators

Examples of the polymerization initiator other than the above 1) to 14) include organic azide compounds such as 4,4′-diazidochalcone, aromatic carboxylic acids such as N-phenylglycine, polyhalogen compounds (CI ₄ , CHI ₃ , CBrCI _3), phenylisoserine oxazolone, silanol-aluminum complex, such as aluminate complexes described in JP-a-3-209477 and the like.

Here, the polymerization initiator of the present invention is
a) A polymerization initiator capable of activating radical polymerization b) A polymerization initiator capable of activating only cationic polymerization c) A polymerization initiator capable of simultaneously activating radical polymerization and cationic polymerization can be classified.

a) A polymerization initiator capable of activating radical polymerization means energy transfer or electron transfer from an excited state of a two-photon absorption compound generated by non-resonant two-photon absorption (giving an electron to the two-photon absorption compound or from a two-photon absorption compound) It is a polymerization initiator capable of generating radicals by performing (to receive electrons) and initiating radical polymerization of the polymerizable compound.
Among the above, the following systems are polymerization initiator systems that can activate radical polymerization.
1) Ketone polymerization initiator 2) Organic peroxide polymerization initiator 3) Bisimidazole polymerization initiator 4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization Initiator 7) sulfonium salt polymerization initiator 8) borate polymerization initiator 9) diaryliodonium organic boron complex polymerization initiator 10) sulfonium organic boron complex polymerization initiator 11) cationic two-photon absorption compound organic boron Complex polymerization initiator 12) Anionic two-photon absorption compound onium salt complex polymerization initiator 13) Metal arene complex polymerization initiator

More preferably as a polymerization initiator capable of activating radical polymerization,
1) Ketone-based polymerization initiator 3) Bisimidazole-based polymerization initiator 4) Trihalomethyl-substituted triazine-based polymerization initiator 6) Diaryliodonium salt-based polymerization initiator 7) Sulfonium salt-based polymerization initiator 11) Cationic two-photon absorption compound Organoboron complex polymerization initiator 12) anionic two-photon absorption compound onium salt complex polymerization initiator, more preferably,
3) Bisimidazole-based polymerization initiator 6) Diaryliodonium salt-based polymerization initiator 7) Sulfonium salt-based polymerization initiator 11) Cationic two-photon absorption compound Organic boron complex-based polymerization initiator 12) Anionic two-photon absorption compound onium salt A complex polymerization initiator is mentioned.

  A polymerization initiator capable of activating only cationic polymerization is an acid (Bronsted acid or Lewis) without generating a radical by performing energy transfer or electron transfer from the excited state of a two-photon absorption compound generated by non-resonant two-photon absorption. It is a polymerization initiator capable of generating an acid) and initiating cationic polymerization of the polymerizable compound with the acid.

Among the above systems, the following systems are polymerization initiator systems that can activate only cationic polymerization.
14) Sulfonic acid ester polymerization initiator

  Examples of the cationic polymerization initiator include “UV curing; science and technology (UVCURING; SCIENCEANDTECHNOLOGY)” [p. 23-76, S.M. Edited by S. PETERPAPPAS, ATECHNOLOGYMARKET PUBLICATION] and "Comments Inorg. Chem." [B. Klingelt, M.M. Reedy Car and A. Rolov (B. KLINGERT, M. RIEDICER and A. ROLOFF), Vol. 3, p109-138 (1988)] and the like can also be used.

  A polymerization initiator capable of simultaneously activating radical polymerization and cationic polymerization is a radical or acid (Bronsted acid or Lewis) by performing energy transfer or electron transfer from the excited state of a two-photon absorption compound generated by non-resonant two-photon absorption. Acid) is a polymerization initiator capable of simultaneously generating radical polymerization of the polymerizable compound by the generated radical, and cationic polymerization of the polymerizable compound by the generated acid.

Among the above systems, the following systems are polymerization initiator systems that can simultaneously activate radical polymerization and cationic polymerization.
4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization initiator 7) Sulfonium salt polymerization initiator 13) Metal arene complex polymerization initiator

As a polymerization initiator that can activate radical polymerization and cationic polymerization,
6) Diaryliodonium salt polymerization initiators 7) Sulfonium salt polymerization initiators.

  The colorant (D) of the present invention will be described. The colorant (D) of the present invention is not particularly limited as long as the polymer obtained in photopolymerization can be colored, and any one of organic colorants and inorganic colorants can be selected and used according to the desired color. can do. As the organic colorant, for example, organic pigments, dyes, natural pigments and the like (however, it is necessary to contain dyes and pigments other than the two-photon absorption compound (B)) can be used. Or an organic pigment is preferable. In addition, as the inorganic colorant, for example, inorganic pigments, extender pigments and the like can be used, but inorganic pigments are preferable. As the colorant of the present invention, an inorganic colorant or an organic pigment is preferable. The organic colorant used in the present invention is preferably an organic pigment having a high color density and high durability such as light resistance and heat resistance. Preferable examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists).

  As a specific example, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175; C.I. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73; C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38; C.I. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97, C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265; C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 8, C.I. I. Pigment blue 60; I. Pigment green 7, C.I. I. Pigment green 36; C.I. I. Pigment brown 23, C.I. I. Pigment brown 25; C.I. I. Pigment black 1, pigment black 7, and the like.

  Specific examples of the inorganic pigment or extender pigment of the present invention include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue. , Bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

In particular, as the black colorant having a high light shielding property, for example, a colorant such as carbon black, acetylene black, lamp black, graphite, iron black, aniline black, and cyanine black is preferable.
The colorant of the present invention can be used alone or in combination of two or more.

The two-photon absorption polymerizable composition of the present invention is optionally added with a dispersant, a binder, a chain transfer agent, a heat stabilizer, a plasticizer, a solvent, an ultraviolet absorber, an adhesion promoter, an antioxidant, an anti-aggregation agent, and the like. A thing can be used suitably.
The dispersant is blended as necessary in order to disperse the colorant satisfactorily. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.

  That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.

  The binder is usually used for the purpose of improving the film formability of the composition before polymerization, the uniformity of the film thickness, and the stability during storage. As the binder, those having good compatibility with the polymerizable compound, the polymerization initiator, and the two-photon absorption compound are preferable.

As the binder, a solvent-soluble thermoplastic polymer is preferable and can be used alone or in combination with each other, and the following are preferable.
Acrylate and alpha-alkyl acrylate esters and acidic polymers and interpolymers (eg, polymethyl methacrylate and polyethyl methacrylate, copolymers of methyl methacrylate and other (meth) acrylic acid alkyl esters), polyvinyl esters (eg, poly Vinyl acetate, polyacetic acid / vinyl acrylate, polyacetic acid / vinyl methacrylate and hydrolyzable polyvinyl acetate), ethylene / vinyl acetate copolymers, saturated and unsaturated polyurethanes, butadiene and isoprene polymers and copolymers and nearly Polyglycol high molecular weight polyethylene oxide having a weight average molecular weight of 4,000 to 1,000,000, epoxidized product (for example, epoxidized product having acrylate or methacrylate group), polyamide (for example, N-methoxy) Chilled polyhexamethylene adipamide), cellulose esters (eg, cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate), cellulose ethers (eg, methyl cellulose, ethyl cellulose, ethyl benzyl cellulose), polycarbonate, polyvinyl acetal (polyvinyl butyral and Polyvinyl formal), polyvinyl alcohol, polyvinylpyrrolidone, acid-containing polymers and copolymers that function as suitable binders (including those disclosed in US Pat. No. 3,458,311 and US Pat. No. 4,273,857). Polystyrene copolymers, and copolymers with, for example, acrylonitrile, maleic anhydride, acrylic acid, methacrylic acid and esters thereof, vinylidene chloride Copolymers (eg, vinylidene chloride / acrylonitrile copolymers, vinylidene chloride / methacrylate copolymers, vinylidene chloride / vinyl acetate copolymers), polyvinyl chlorides and copolymers (eg, polyvinyl chloride / acetate, vinyl chloride / Acrylonitrile copolymer), polyvinylbenzal synthetic rubber (for example, butadiene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methacrylate / acrylonitrile / butadiene / styrene copolymer, 2-chlorobutadiene-1, triple) coalescence, chlorinated rubber, styrene / butadiene / styrene, styrene / isoprene / styrene block copolymer), copolyesters (e.g., formula HO (CH ₂₎ nOH (wherein n is an integer of 2 to 10) of Polymethylene glyco And (1) hexahydroterephthalic acid, sebacic acid and terephthalic acid, (2) terephthalic acid, isophthalic acid and sebacic acid, (3) terephthalic acid and sebacic acid, (4) terephthalic acid and isophthalic acid And (5) a mixture of the glycol and (i) terephthalic acid, isophthalic acid and sebacic acid and (ii) a copolyester made from terephthalic acid, isophthalic acid, sebacic acid and adipic acid), Poly N-vinylcarbazole and copolymers thereof; Carbazole-containing polymers as disclosed by Kamogawa et al. In Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18, pp. 9-18 (1979).

  Further, a fluorine atom-containing polymer is also preferable as the binder. Preferably, fluoroolefin is an essential component, and one or more selected from alkyl vinyl ether, alicyclic vinyl ether, hydroxy vinyl ether, olefin, haloolefin, unsaturated carboxylic acid and ester thereof, and carboxylic acid vinyl ester It is a polymer soluble in an organic solvent having the unsaturated monomer as a copolymerization component. Preferably, the weight average molecular weight is 5,000 to 200,000, and the fluorine atom content is 5 to 70% by mass.

  As the fluoroolefin in the fluorine atom-containing polymer, tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, or the like is used. In addition, as other copolymerization components, alkyl vinyl ethers include ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, alicyclic vinyl ethers such as cyclohexyl vinyl ether and derivatives thereof, hydroxy vinyl ethers such as hydroxybutyl vinyl ether, olefins and halo. Examples of olefins include ethylene, propylene, isobutylene, vinyl chloride, and vinylidene chloride. Examples of carboxylic acid vinyl esters include vinyl acetate and n-vinyl butyrate. Examples of unsaturated carboxylic acids and esters include (meth) acrylic acid and crotonic acid. Unsaturated carboxylic acids and methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso (meth) acrylate C1 to C18 alkyl esters of (meth) acrylic acid such as lopyr, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, hydroxyethyl (meth) C2-C8 hydroxyalkyl esters of (meth) acrylic acid such as acrylate, hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, etc. Can be mentioned. These radical polymerizable monomers may be used alone or in combination of two or more, and if necessary, a part of the monomer may be used as another radical polymerizable monomer such as styrene, α -You may substitute with vinyl compounds, such as methylstyrene, vinyl toluene, and (meth) acrylonitrile. Further, as other monomer derivatives, carboxylic acid group-containing fluoroolefin, glycidyl group-containing vinyl ether, and the like can also be used.

  Specific examples of the fluorine atom-containing polymer include, for example, an organic solvent-soluble “Lumiflon” series having a hydroxyl group (for example, Lumiflon LF200, weight average molecular weight: about 50,000, manufactured by Asahi Glass Co., Ltd.). In addition to these, organic solvent-soluble fluorine atom-containing polymers are also commercially available from Daikin Industries, Ltd., Central Glass Co., Ltd., and Penwort Co., Ltd., and these can also be used.

In general, the proportion of each component in the two-photon absorption polymerizable composition of the present invention is preferably in the following% range based on the total mass of the composition.
Binder: preferably 0 to 90% by mass, more preferably 45 to 75% by mass,
Polymerizable compound: preferably 5 to 60%, more preferably 15 to 50% by mass,
Two-photon absorption compound: preferably 0.01 to 10% by mass, more preferably 0.02 to 7% by mass,
Polymerization initiator: preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass
Colorant: preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass

In some cases, the two-photon absorption polymerizable composition of the present invention preferably uses a chain transfer agent. Preferred chain transfer agents are thiols such as 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 4 , 4-thiobisbenzenethiol, p-bromobenzenethiol, thiocyanuric acid, 1,4-bis (mercaptomethyl) benzene, p-toluenethiol, etc., as described in U.S. Pat. No. 4,414,312 and JP-A 64-13144 Thiols, disulfides described in JP-A-2-291561, thiones described in U.S. Pat. No. 3,558,322 and JP-A-64-17048, O-acylthiohydroxamates described in JP-A-2-291560, and N -Alkoxypyridinethiones are also included.
In particular, when the polymerization initiator is 2,4,5-triphenylimidazolyl dimer, it is preferable to use a chain transfer agent.
As for the usage-amount of a chain transfer agent, 1.0-30 mass% is preferable with respect to the whole composition.

A heat stabilizer (thermal polymerization inhibitor) can be added to the two-photon absorption polymerizable composition of the present invention for the purpose of preventing polymerization during storage and maintaining storage stability.
Useful heat stabilizers include hydroquinone, phenidone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, catechol, t-butylcatechol, pyrogallol, 2-naphthol, 2,6-di-t-butyl-p. -Cresol, phenothiazine, chloranneal and the like. Also useful are dinitroso dimers described in US Pat. No. 4,168,982 to Pazos.
The heat stabilizer is preferably added in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the compound having an unsaturated bond.

  Plasticizers are used to change the adhesion, flexibility, hardness, and other mechanical properties of the two-photon polymerizable composition. Examples of the plasticizer include triethylene glycol dicaprylate, triethylene glycol bis (2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate, tris (2-ethylhexyl) phosphate, Examples include tricresyl phosphate and dibutyl phthalate.

The photopolymerizable composition of the present invention may be prepared by a usual method. For example, the above-mentioned essential components and optional components can be prepared as they are or by adding a solvent as necessary.
Examples of the solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol diacetate, ethyl lactate and cellosolve acetate, carbonization such as cyclohexane, toluene and xylene. Hydrogen solvent, ether solvents such as tetrahydrofuran, dioxane, diethyl ether, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl cellosolve, methanol, ethanol, n-propanol, 2-propanol, n-butanol, diacetone Alcohol solvents such as alcohol, fluorine solvents such as 2,2,3,3-tetrafluoropropanol, dichloromethane, chloroform, 1,2-dichloro Halogenated hydrocarbon solvents such as Roetan, N, include amide solvents such as N- dimethylformamide.
The photopolymerizable composition of the present invention can be applied directly onto a substrate, can be spin-coated, or can be cast as a film and then laminated to the substrate by a conventional method. The solvent used can be removed by evaporation during drying.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-aminopropyltriethoxysilane. 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are mentioned.

  Examples of the antioxidant include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like.

  Examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

Examples of the aggregation inhibitor include sodium polyacrylate and various surfactants.
[Example]
Hereinafter, specific embodiments of the present invention will be described based on experimental results. Of course, the present invention is not limited to these examples.

  Synthesis of the two-photon absorption compound of the present invention

(1) Synthesis of D-73

  The two-photon absorption compound D-73 of the present invention can be synthesized by the following method.

  14.3 g (40 mmol) of the quaternary salt [1] was dissolved in 50 ml of water, 1.6 g (40 mmol) of sodium hydroxide was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was extracted three times with ethyl acetate, dried over magnesium sulfate and concentrated to obtain 9.2 g (yield 100%) of methylene-based [2] oil.

  3.97 g (40 mmol) of dimethylaminoacrolein [3] was dissolved in 50 ml of acetonitrile, and 6.75 g (44 mmol) of phosphorus oxychloride was added dropwise while cooling to 0 ° C., followed by stirring at 0 ° C. for 10 minutes. Subsequently, 9.2 g of acetonitrile solution of methylene base [2] was dropped, and the mixture was stirred at 35 ° C. for 4 hours. After pouring into 100 ml of ice water, 16 g of sodium hydroxide was added and refluxed for 10 minutes. After cooling, the mixture was extracted 3 times with ethyl acetate, dried over magnesium sulfate and concentrated. Purification by silica gel column chromatography (developing solvent: ethyl acetate: hexane = 1: 10 → 1: 3) gave 4.4 g (39% yield) of aldehyde [4] as an oil.

  0.126 g (1.5 mmol) of cyclopentanone and 0.85 g (3 mmol) of aldehyde [4] were dissolved in 30 ml of dehydrated methanol and refluxed in a dark atmosphere in a nitrogen atmosphere. After becoming uniform, 0.69 g (3.6 mmol) of a 28% sodium methoxide methanol solution was added, and the mixture was further refluxed for 6 hours. After cooling, the precipitated crystals were separated by filtration and washed with methanol to obtain 0.50 g (yield 54%) of D-73 dark green crystals. The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(2) Synthesis of D-84

  The two-photon absorption compound D-84 of the present invention can be synthesized by the following method.

  33.6 g (0.4 mol) of cyclopentanone, 2 ml of DBN, and 400 g of N, N-dimethylformamide dimethyl acetal were refluxed for 5 days. After concentration, acetone was added and cooled to separate the crystals, which were then washed with cold acetone to obtain 32.4 g of crystals [5] (yield 42%).

[5] 0.78 g (4 mmol), quaternary salt [6] 2.78 g (8 mmol), and 20 ml of pyridine were refluxed in a dark place under a nitrogen atmosphere for 4 hours. After cooling, ethyl acetate was added and the crystals were separated and washed with ethyl acetate. The crystals were dispersed in methanol and separated by filtration to obtain 2.14 g (yield 56%) of the desired deep blue crystals of D-84.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

  In addition, other two-photon absorption compounds represented by the general formula (1) of the present invention can be synthesized by the synthesis methods of D-73 and D-84, Tetrahedron. Lett. 42, 6129, (2001) and the like.

(3) Synthesis of D-1

  The two-photon absorption compound D-1 of the present invention can be synthesized by the following method.

  Benzoxazole [7] 52.25 g (0.2 mol) and propane sultone [8] 45.75 g (0.375 mol) were heated and stirred at 140 ° C. for 4 hours. After cooling, acetone was added and the crystals were separated, and washed with acetone to obtain 70.42 g (yield 85%) of a quaternary salt [9].

Quaternary salt [9] 66.2 g (0.2 mol), triethyl orthopropionate [10] 200 ml, pyridine 200 ml and acetic acid 80 ml were heated and stirred at 120 ° C. for 1 hour. After cooling, decantation washing was performed 3 times with ethyl acetate. When dissolved in 100 ml of methanol and stirred, a solution of sodium acetate 4.0 g (50 mmol) / methanol 20 ml was added, and the resulting crystals were separated. Furthermore, it disperse | distributed to methanol and separated and obtained the target D-1 vermilion crystal 31.36g (yield 43.4%).
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(4) Synthesis of D-42

The two-photon absorption compound D-42 of the present invention can be synthesized by the following method.

Quaternary salt [11] 2.81 g (10 mmol), [12] 6.67 g (30 mmol), acetic anhydride 10 g, and acetonitrile 50 ml were refluxed for 30 minutes. After concentration, decantation with ethyl acetate was performed to obtain a crude product of anil form [13].
To the crude product of anil [13], 2.00 g (10 mmol) of thiobarbituric acid [14], 3.0 g (30 mmol) of triethylamine and 100 ml of ethanol were added and refluxed for 1 hour. After concentration, the residue was purified by silica gel column chromatography (developing solvent: chloroform: methanol = 20: 1 → 10: 1), and further recrystallized from methanol-isopropyl alcohol to obtain 2.55 g of the target D-42 crystal. (Total yield 41.3%) was obtained.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(5) Synthesis of D-56

  The two-photon absorption compound D-56 of the present invention can be synthesized by the following method.

Barbituric acid [15] 3.12 g (20 mmol), [16] 2.85 g (10 mmol) and triethylamine 4.1 g (40 mmol) were dissolved in DMF 30 ml, and the mixture was stirred at room temperature for 2 hours. Crystals produced by adding dilute hydrochloric acid were filtered, washed with water and dried to obtain 2.99 g (yield: 80.0%) of the desired D-56 crystals.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

(6) Synthesis of D-104

  The two-photon absorption compound D-104 of the present invention can be synthesized by the following method.

3- (9-ethylcarbazol-3-yl) propenal [17] 3.3 g (13 mmol) and cyclopentanone 0.55 g (6.6 mmol) were dissolved in dehydrated methanol 100 ml, and sodium methoxide 28% methanol solution 1 ml. Was added dropwise and stirred at room temperature for 2 hours. Precipitated crystals were separated, washed with methanol and dried to obtain 2.5 g (yield 70.0%) of the desired D-104 crystals.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.

  Further, other cyanine dyes, merocyanine dyes, oxonol dyes and the like are also described in F.I. M.M. By Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964, D.C. M.M. According to Sturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry, Chapter 18, Section 14, pages 482 to 515, according to John & Wiley & Sons, New Yor et al.

Evaluation of the two-photon absorption cross-section The evaluation of the two-photon absorption cross-section of the two-photon absorption compound of the present invention is based on the fluorescence method when the compound is fluorescent, and Z-Scan when the compound is non-fluorescent. The method was used.
<Fluorescence method>
The two-photon absorption cross section is evaluated by the fluorescence method. A. Albota et al. , Appl. Opt. 1998, 37, 7352. The description was made with reference to the method described. This measurement method is a method for comparing the intensity of light emission from an excited state induced by non-resonant two-photon absorption between a reference substance and a substance to be measured, and must be a compound that causes two-photon emission. Although it cannot be measured, it is characterized in that a simpler and relatively accurate value can be obtained as compared with other methods. A Ti: sapphire pulse laser (pulse width: 100 fs, repetition rate: 80 MHz, average output: 1 W, peak power: 100 kW) is used as a light source for measuring the two-photon absorption cross section, and two-photon absorption is performed in a wavelength range of 700 nm to 1000 nm. The cross-sectional area was measured. In addition, rhodamine B and fluorescein were measured as reference substances, and the obtained measured values were calculated as C.I. Xu et al. , J .; Opt. Soc. Am. B1996, 13, 481. Were corrected using the values of the two-photon absorption cross sections of rhodamine B and fluorescein described in 1. to obtain the two-photon absorption cross sections of the respective compounds. As a sample for two-photon absorption measurement, a solution obtained by dissolving a compound in chloroform or DMSO at a concentration of 1 × 10 ⁻³ was used.
<Z-Scan method>
The evaluation of the two-photon absorption cross section by the Z-Scan method is described in MANSOOR SHEIK-BAHAE et al. , IEEE. Journal of Quantum Electronics. 1990, 26, 760. The Z scan method described was used. The Z-scan method is widely used as a method for measuring nonlinear optical constants. The measurement sample is moved along the beam near the focal point of the focused laser beam, and the change in the amount of transmitted light is recorded. . Since the power density of incident light varies depending on the position of the sample, the amount of transmitted light attenuates near the focal point when there is nonlinear absorption. A two-photon absorption cross-sectional area was calculated by fitting a change in the amount of transmitted light with respect to a theoretical curve predicted from incident light intensity, focused spot size, sample thickness, sample concentration, and the like. A Ti: sapphire pulse laser (pulse width: 100 fs, repetition: 80 MHz, average output: 1 W, peak power: 100 kW) is used as a light source for measuring the two-photon absorption cross section, and two-photon absorption is performed in a wavelength range of 700 nm to 1000 nm. The cross-sectional area was measured. As a sample for two-photon absorption measurement, a solution in which a compound was dissolved in chloroform at a concentration of 1 × 10 ⁻³ was used.

Table 2 shows the two-photon absorption cross-sectional area of the two-photon absorption compound of the present invention evaluated by the above method.

Preparation of photopolymerizable composition of the present invention Composition of photopolymerizable composition (1) (red photopolymerizable composition)
Polymerizable compound: SCR-701 manufactured by DEMEC 100 parts by mass Two-photon absorption compound: D-104 0.5 parts by mass Polymerization initiator: diphenyliodonium tetrafluoroborate 3.0 parts by mass Colorant: C.I. I. Pigment Red 177 10 parts by mass

Composition of photopolymerizable composition (2) (green photopolymerizable composition)
Polymerizable compound: SCR-701 manufactured by DEMEC, Inc. 100 parts by mass Two-photon absorption compound: D-104 0.05 parts by mass Polymerization initiator: diphenyliodonium tetrafluoroborate 3.0 parts by mass Colorant: C.I. I. Pigment Green 36 10 parts by mass

Composition of photopolymerizable composition (3) (blue photopolymerizable composition)
Polymerizable compound: SCR-701 manufactured by DEMEC 100 parts by mass Two-photon absorption compound: D-104 0.5 parts by mass Polymerization initiator: diphenyliodonium tetrafluoroborate 3.0 parts by mass Colorant: C.I. I. Pigment Blue-15 10 parts by mass

Composition of photopolymerizable composition (4) (black photopolymerizable composition)
Polymerizable compound: SCR-701 100 parts by mass by DEMEC, Inc. Two-photon absorption compound: D-104 0.5 parts by mass Polymerization initiator: Diphenyliodonium tetrafluoroborate 3.0 parts by mass Colorant: Carbon black 15 parts by mass

Comparative Example (1)
Polymerizable compound: SCR-701 manufactured by DEMEC 100 parts by mass Polymerization initiator: 3.0 parts by mass of diphenyliodonium tetrafluoroborate Colorant: C.I. I. Pigment Red 177 10 parts by mass

[Performance evaluation]
For the performance evaluation of the photopolymerizable composition of the present invention, the photopolymerizable composition prepared in each of the above compositions was cast on a slide glass, and an evaluation sample with a cover glass on the upper surface was used. After irradiating the femtosecond laser pulse light of 820nm corresponding to the maximum two-photon absorption wavelength of the dye, the uncured part is washed away with a 5% ethyl acetate-hexane solution, and the presence or absence of polymerization and coloring is visually observed in the light irradiated part. did.
The results are shown in Table 2.

以上の評価結果より、本発明の光重合性組成物を用いることで、任意の色に着色した重合物を得ることができた。

From the above evaluation results, it was possible to obtain a polymer colored in an arbitrary color by using the photopolymerizable composition of the present invention.

  The photopolymerizable composition and photopolymerization method of the present invention are used for fine three-dimensional stereolithography materials, three-dimensional image recording, color filter production, and the like.

Claims (9)

  A two-photon absorption polymerizable composition comprising at least a polymerizable compound (A), a two-photon absorption compound (B), a polymerization initiator (C), and a colorant (D).   The two-photon absorption polymerization composition according to claim 1, wherein the two-photon absorption compound according to claim 1 has a two-photon absorption cross-sectional area of 500 GM or more.   3. The polymerization initiator according to claim 1, wherein the polymerization initiator is a polymerization initiator that generates at least one radical, and the polymerizable compound is a radical polymerizable compound that is polymerized by at least one radical. Two-photon collection polymerization composition.   The polymerization initiator is a polymerization initiator that generates an acid without generating at least one radical, and the polymerizable compound is a cationic polymerizable compound that is polymerized by at least one acid. The two-photon absorption polymerizable composition according to 1 or 2.   The polymerization initiator is a polymerization initiator that generates both at least one radical and an acid, and the polymerizable compound is polymerized by at least one radical and a cation that is polymerized by at least one acid. The two-photon absorption polymerizable composition according to claim 1 or 2, wherein the polymerizable compound is one or both of a polymerizable compound.   The two-photon absorption polymerizable composition according to any one of claims 1 to 5 has a longer wave than the absorption in the ultraviolet-visible wavelength region of the polymerizable composition and no absorption of the polymerizable composition. A photopolymerization method characterized in that a colored polymer is obtained by irradiation with light of a wavelength.   The two-photon absorption polymerizable composition according to any one of claims 1 to 5 is irradiated with light corresponding to the non-resonant two-photon absorption maximum wavelength of the two-photon absorption compound (B) contained in the polymerizable composition. 7. A photopolymerization method according to claim 6, wherein a colored polymer is obtained.   An optical modeling composition comprising the two-photon absorption polymerizable composition according to claim 1.   A resin composition for a color filter, comprising the two-photon absorption polymerizable composition according to claim 1.