JP2005195922A - Non-resonance two-photon absorbing material and non-resonance two-photon absorption method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic material which efficiently absorbs two photons, i.e., an organic material, having a large two-photon absorption cross section. <P>SOLUTION: The non-resonance two-photon absorption compound has a plurality of chromophores, performing non-resonance two-photon absorption within the molecule, where these chromophores are coupled through coupling groups of a non-resonance structure and performs non-resonance two-photon absorption. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a material that exhibits a nonlinear optical effect, and more particularly to an organic nonlinear optical material that has a large non-resonant two-photon absorption cross-section and a large luminous efficiency from an excited state generated by non-resonant two-photon absorption.

  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, simultaneous 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 and non-resonant two-photon emission have 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 addition, non-resonant two-photon emission refers to light emitted by an excited molecule generated by non-resonant two-photon absorption in the process of radiation deactivation in its excited state. In the following description, two-photon absorption and two-photon emission refer to non-resonant two-photon absorption and non-resonant two-photon emission, unless otherwise 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 is longer than the wavelength region in which the (linear) absorption band of the compound exists and does not have absorption, is often used. Because so-called transparent near-infrared light that does not have a (linear) absorption band of the compound is used, excitation light can reach the inside of the sample without being absorbed or scattered, and because of the square characteristic of non-resonant two-photon absorption In addition, since one point inside the sample can be excited with extremely high spatial resolution, non-resonant two-photon absorption and non-resonant two-photon emission are expected in applications such as two-photon contrast and two-photon photodynamic therapy (PDT) of biological tissues. ing. In addition, when non-resonant two-photon absorption and two-photon emission are used, a photon with an energy higher than the energy of the incident photon can be extracted. Therefore, research on upconversion lasing has been reported from the viewpoint of a wavelength conversion device.

  A so-called stilbazolium derivative is known as an organic compound that efficiently exhibits two-photon emission and upconversion lasing (He, GS et al., Appl. Phys. Lett. 1995, 67, 3703 [Non-patent Document 1]. Zhou, G. et al., Jpn. J. Appl. Phys. 2001, 40, 1250 [Non-patent Document 2]). Various applications using two-photon emission of a stilbazolium compound having a specific structure are described in WO9709043 [Patent Document 1].

When non-resonant two-photon emission is used for imaging of biological tissue, photodynamic therapy, up-conversion lasing, etc., it is caused by the two-photon absorption efficiency (two-photon absorption cross section) and two-photon absorption of the organic compound used. The luminous efficiency from the excited state needs to be high. In order to obtain the doubled two-photon emission intensity using the same organic compound, the excitation light intensity of four times is required due to the square characteristic of the two-photon absorption. However, excessively strong laser light irradiation is not desirable because, for example, there is a high possibility that the biological tissue will be damaged by light, or that the two-photon luminescent dye itself will be photodegraded. Therefore, in order to obtain strong two-photon emission with weak excitation light intensity, it is necessary to develop an organic compound that efficiently absorbs two-photons and emits two-photon emission. The two-photon emission efficiency of the stilbazolium derivative is not yet sufficient for practical use.
He, G.G. S. et al. , Appl. Phys. Lett. 1995, 67, 3703. Zhou, G .; et al. , Jpn. J. et al. Appl. Phys. 2001, 40, 1250 International Publication No. 97/09043 Pamphlet

  As described above, the use of non-resonant two-photon absorption and non-resonant two-photon emission enables various applications characterized by extremely high spatial resolution. Since the photon absorption ability is low and the two-photon emission efficiency is poor, a very high-power laser is required as an excitation light source for inducing two-photon absorption and two-photon emission.

  An object of the present invention is to provide an organic material that efficiently absorbs two-photons, that is, an organic material having a large two-photon absorption cross section, and a two-photon light-emitting material, two-photon optical recording material, and two-photon polymerization using the same. It is to provide a composition, a two-photon image display material and respective methods.

As a result of intensive studies by the inventors, when a plurality of two-photon absorption chromophores (chromophores) are connected so as not to be conjugated with each other, a two-photon absorption cross-section at a certain wavelength is obtained as a simple sum of the two-photon absorption cross-sections of the constituent chromophores. It was found that it is possible to make it larger.
The present invention has been achieved by the following means.
(1) A non-resonant two-photon absorption material comprising a non-resonant two-photon absorption compound represented by the following general formula (1).
General formula (1)

In the general formula (1), TPAD ¹ and TPAD ² each independently represent a group containing a non-resonant two-photon absorption chromophore (chromophore), L represents a linking group, a simple bond or an atom, and n represents 1 to 7 Represents an integer. When n is 2 or more, the plurality of TPADs ² may be the same or different.
(2) The linking group represented by L in the general formula (1) connects a plurality of two-photon absorption chromophores without taking a resonance contribution structure. Resonant two-photon absorption material.
(3) In the compound represented by the general formula (1), TPAD ¹ and TPAD ² are each independently represented by a cyanine dye, a streptocyanine dye, a merocyanine dye, an oxonol dye, a stilbazolium dye, or the following general formula (2). The non-resonant two-photon absorption material according to (1) or (2), which is a group containing a compound to be produced.
General formula (2)

In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and some of R ¹ , R ² , R ³ and R ⁴ are bonded to each other to form a ring. May be formed. n and m each independently represent an integer of 0 to 4, and when n and m are 2 or more, a plurality of R ¹ , R ² , R ³ and R ⁴ may be the same or different. However, n and m are not 0 simultaneously. Y represents an oxygen atom or an atomic group containing at least one of the partial structures represented by the following general formula (3), and X ¹ and X ² independently represent an aryl group, a heterocyclic group, or a general formula (4 ) Represents a group represented by
General formula (3)

In the formula, * represents a bonding position with the general formula (2). When two atomic groups represented by the general formula (3) are contained, they may be different from each other or may be bonded to form a ring. When one atomic group represented by the general formula (3) is included, other necessary atoms or atomic groups may be arbitrary.
General formula (4)

In the formula, R ⁵ represents a hydrogen atom or a substituent, and R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Z ¹ represents an atomic group forming a 5- or 6-membered ring and may be condensed.
The general formula (2) is a group obtained by removing any hydrogen atom from R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² .
(4) In the compound represented by the general formula (2), a “group” is formed by removing any hydrogen atom of either X ¹ or X ^2. Non-resonant two-photon absorption material.
(5) In the compound represented by the general formula (1), TPAD ¹ and TPAD ² are each independently represented by a cyanine dye, a merocyanine dye, an oxonol dye, a streptocyanine dye, a stilbazolium dye, or the general formula (2). The non-resonant two-photon absorption material according to any one of (1) to (4), which is a group containing a compound.
(6) In the compound represented by the general formula (1), TPAD ¹ and TPAD ² are groups containing a cyanine dye, a merocyanine dye or a streptocyanine dye, A non-resonant two-photon absorption material as described above.
(7) The non-resonant two-photon according to (5), wherein in the compound represented by the general formula (1), TPAD ¹ and TPAD ² are groups including the compound represented by the general formula (2) Absorbing material.
(8) In the compound represented by the general formula (2), R ¹ and R ³ are connected to form a ring, and any one of (3) to (5) and (7) Non-resonant two-photon absorption material.
(9) The nonresonant two-photon according to (8), wherein in the compound represented by the general formula (2), R ¹ and R ³ are linked to form a cyclopentanone ring together with a carbonyl group. Absorbing material.
(10) In the compound represented by the general formula (2), X ¹ and X ² are substituted or unsubstituted aryl groups (3) to (5) and (7) to (9) The non-resonant two-photon absorption material according to any one of the above.
(11) The non-resonant two-photon absorption material according to (11), wherein in the compound represented by the general formula (2), X ¹ and X ² are aryl groups substituted with an amino group at the 4-position .
(12) In the compound represented by the general formula (2), X ¹ and X ² are represented by the general formula (3), R ⁶ is an alkyl group, and the ring formed by Z ¹ is indolenine. A ring, an azaindolenin ring, a pyrazoline ring, a benzothiazole ring, a thiazole ring, a thiazoline ring, a benzoxazole ring, an oxazole ring, an oxazoline ring, a benzimidazole ring, a thiadiazole ring, or a quinoline ring The non-resonant two-photon absorption material according to any one of (3) to (5) and (7) to (9).
(13) In the compound represented by the general formula (2), X ¹ and X ² are represented by the general formula (3), R ⁶ is an alkyl group, and the ring formed by Z ¹ is indolenine. The nonresonant two-photon absorption material according to (12), which is represented by any one of a ring, an azaindolenine ring, a benzothiazole ring, a benzoxazole ring, and a benzimidazole ring.
(14) In the compound represented by the general formula (2), X ¹ and X ² are represented by the general formula (3), R ⁶ is an alkyl group, and the ring formed by Z ¹ is a halogen atom. The nonresonant according to (13), which is represented by any one of an indolenine ring, an azaindolenine ring, a benzothiazole ring, a benzoxazole ring and a benzimidazole ring substituted with (preferably a chlorine atom) Two-photon absorbing material.
(15) The compound represented by the general formula (2) includes a compound in which Y is an oxygen atom, and is described in any one of (3) to (5) and (7) to (14) Non-resonant two-photon absorption material.
(16) The compound represented by the general formula (2) includes a compound in which at least one of Ys represented by the general formula (3) has a structure represented by (3-1). The nonresonant two-photon absorption material according to any one of (3) to (5) and (7) to (14).
(17) A two-photon absorption compound represented by the general formula (1), wherein a non-resonant two-photon absorption cross-section at a certain wavelength of the two-photon absorption compound has a two-photon absorption chromophore constituting the compound. The non-resonant two-photon absorption material according to claim 1, wherein the non-resonant two-photon absorption material is larger than a sum of two-photon absorption cross sections.
(18) The non-resonant two-photon light-emitting material according to any one of (1) to (17) is irradiated with laser light having a wavelength longer than the linear absorption band of the non-resonant two-photon absorption compound included in the material. A non-resonant two-photon absorption inducing method characterized by inducing two-photon absorption.
(19) A non-resonant two-photon absorption material according to any one of (1) to (17), which emits light by non-resonant two-photon absorption.
(20) The non-resonant two-photon light-emitting material described in (19) is irradiated with laser light having a wavelength longer than the linear absorption band of the non-resonant two-photon absorption compound included in the material, thereby causing non-resonant two-photon absorption. A light emission generation method characterized by inducing light emission.
(21) A non-resonant two-photon optical recording material comprising the non-resonant two-photon absorbing material according to any one of (1) to (17).
(22) The information is written by irradiating the non-resonant two-photon optical recording material according to (21) with laser light having a wavelength longer than the linear absorption band of the non-resonant two-photon absorption compound included in the material. A characteristic non-resonant two-photon optical recording method.
(23) A non-resonant two-photon polymerization composition comprising the non-resonant two-photon absorption material according to any one of (1) to (17).
(24) A polymer is obtained by irradiating the non-resonant two-photon polymerization composition according to (23) with a laser beam having a wavelength longer than the linear absorption band of the non-resonant two-photon absorption compound contained in the composition. A non-resonant two-photon polymerization method.
(25) A non-resonant two-photon image display material comprising the non-resonant two-photon absorbing material described in (1) to (17).
(26) An image is displayed by irradiating the non-resonant two-photon image display material according to (25) with a laser beam having a wavelength longer than the linear absorption band of the non-resonant two-photon absorption compound included in the material. A non-resonant two-photon image display method characterized by the above.

  By connecting multiple two-photon absorption chromophores in the molecule through a non-conjugated bridge structure, the two-photon absorption cross-section at a certain wavelength is larger than the chromophore several times the two-photon absorption cross-section of the constituent chromophore used Can be obtained.

The non-resonant two-photon absorption compound and material of the present invention will be described in detail below.
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. In addition, the substituent that can be used in the compound in the present invention may be any substituent.
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 non-resonant two-photon absorption compound contained in the non-resonant two-photon absorption material of the present invention has two or more chromophores (chromophores) that absorb two-photons in the molecule, and a linking group or atom is connected between the chromophores. It is a molecule characterized by having the above structure, and is preferably represented by the general formula (1).

In general formula (1), L represents a linking group, a simple bond or an atom, and preferably a linking group. When L is a linking group, L represents a linking group or a mere bond that links a conjugated system of a plurality of two-photon absorption chromophores without going through a resonance contribution structure. That is, there is no electronic interaction due to the resonance contribution structure between a plurality of two-photon absorption chromophore conjugated systems connected by L. L may be any linking group as long as it satisfies these conditions, but is preferably an alkylene group (preferably having 1 to 20 carbon atoms (hereinafter referred to as C number), for example, methylene, ethylene, propylene. ), Amide group, ester group, sulfoamide group, sulfonate group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether Represents a linking group having 0 to 100 carbon atoms, preferably 1 or more and 20 or less, constituted by combining one or more groups and carbonyl groups.
When L is an atom, L is preferably a transition metal ion, more preferably a platinum group ion, and still more preferably Pt, Pd, Ni, Os, Ru, Fe, Ir, and Rh ions.

TPAD ¹ and TPAD ² each independently represent a group containing a chromophore that performs non-resonant two-photon absorption. The two-photon absorption cross-section of the two-photon absorption chromophore represented by TPAD ¹ and TPAD ² is preferably 500 GM or more, more preferably 1,000 GM or more in a compound obtained by adding a hydrogen atom to the chromophore as a molecule. And most preferably 5,000 GM or more.
n represents an integer of 1 to 7. When n is 2 or more, the plurality of TPADs ² may be the same or different.

Compounds such as TPAD ¹ and TPAD ² in the general formula (1), which are groups including chromophores (chromophores) that perform non-resonant two-photon absorption of the present invention (compounds that do not remove hydrogen atoms for constituting groups) In this specification, when TPAD ¹ is expressed as “cyanine dye” or the like, “a group obtained by removing a hydrogen atom from a cyanine dye” is preferably a dye. Here, the dye is a general term for compounds having a part of absorption in the visible light region (400 to 700 nm).
Any dye may be used as the above-described dye in the present invention. 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, poly Emissions dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, stilbazolium dyes and 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, stilbazolium dyes, metal complex dyes, and more preferably cyanine dyes, hemicyanine dyes, streptocyanine dyes, styryl dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, oxonol dyes, Examples include methine dyes such as squalium dyes and arylidene dyes, and more preferably cyanine dyes, streptocyanine dyes, merocyanine dyes, oxonols. Is hydrogen, and most preferred are cyanine dyes, merocyanine dyes, stilbazolium dyes or streptavidin cyanine dye.

  For more information on these dyes, see FMHarmer, “Heterocyclic Compounds-Cyanine Dyes and Related Compounds”, John Willie &・ John Wiley & Sons-New York, London, 1964, DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special topics in repeating chemistry), Chapter 18, 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 to 422, published by Elsevier Science Publishing Company Inc., New York, and the like.

  When a cyanine dye is used as the chromophore that performs non-resonant two-photon absorption of the present invention, it is preferably represented by the following general formula (4).

In the formula, Za ₁ and Za ₂ each represent a group of atoms forming a 5-membered or 6-membered nitrogen-containing heterocycle, and these include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring, etc. It may be condensed.
Ra ₁ and Ra ₂ are each a hydrogen atom or an alkyl group (preferably having a C number of 1 to 20, 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 C 2-20, for example, vinyl, allyl), aryl group (preferably C number 6-20, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic group (preferably C number 1-20, for example, pyridyl, thienyl, furyl, thiazolyl Imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), preferably a hydrogen atom, an alkyl group, Represents a phoalkyl group, more preferably an alkyl group or a sulfoalkyl group.
Ma _{1 to} Ma ₇ each represent a methine group and may have a substituent, and the substituent is preferably, for example, an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, i-propyl), a halogen atom (Eg, chlorine, bromine, iodine, fluorine), nitro group, C 1-20 alkoxy group (eg, methoxy, ethoxy), C 6-26 aryl group (eg, phenyl, 2-naphthyl), C Heterocyclic groups of 0 to 20 (for example, 2-pyridyl, 3-pyridyl), aryloxy groups of 6 to 20 carbons (for example, phenoxy, 1-naphthoxy, 2-naphthoxy), acylamino having 1 to 20 carbon atoms Group (for example, acetylamino, benzoylamino), carbamoyl group having 1 to 20 carbon atoms (for example, N, N-dimethylcarbamoyl), sulfo group, hydroxy group, carboxy group, alkyl group having 1 to 20 carbon atoms. Thio (e.g., methylthio) and a cyano group. Further, it may form a ring with another methine group, or it can form a ring with an auxiliary color group. An unsubstituted, ethyl group-substituted, or methyl group-substituted methine group is preferred.
na ¹ and na ² are 0 or 1, preferably 0. ka ¹ represents an integer from 0 to 3. Preferably it is an integer from 0 to 2, more preferably 0 or 1. When ka ¹ is 2 or more, Ma ₃ and Ma ₄ may be the same or different.
CI represents an ion that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.

In general formula (4), Za ₁ , Za ₂ , Ra ₁ , Ra ₂ , and any one of Ma _{1 to} Ma ₇ are removed to form a “group” in general formula (1). be able to.

  When a merocyanine dye is used as the chromophore that performs non-resonant two-photon absorption of the present invention, it is preferably represented by the following general formula (5).

In the formula, Za ₃ represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocycle, and these are further condensed with a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, a thiophene ring, or the like. May be. Za ₄ represents an atomic group forming an acidic nucleus. Ra ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as Ra ₁ and Ra _{2 above} ). Ma _{8 to} Ma ₁₁ each represent a methine group (preferred examples are the same as Ma ₁ to Ma ₇ ). na ³ is 0 or 1. ka ² represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 1 or 2.
When ka ² is 2 or more, Ma ₁₀ and Ma ₁₁ may be the same or different.
CI represents an ion that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.
In the general formula (5), a “group” in the general formula (1) can be formed by removing any hydrogen atom from Za ₃ , Za ₄ , Ra ₃ , and Ma _{8 to} Ma _11. .

  When an oxonol dye is used as the chromophore that performs non-resonant two-photon absorption of the present invention, it is preferably represented by the following general formula (6).

In the formula, Za ₅ and Za ₆ each represent an atomic group forming an acidic nucleus. Ma _{12 to} Ma ₁₄ each represent a methine group (preferred examples are the same as Ma ₁ to Ma ₇ ). ka ³ represents an integer of 0 to 3, preferably an integer of 0 to 2. When ka ³ is 2 or more, Ma ₁₂ and Ma ₁₃ may be the same or different.
CI represents an ion that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.
Incidentally, in the general formula (6) may be a "group" in the general formula (1) in the form of removal of any hydrogen atom of _{Za 5, Za 6, Ma 12} ~Ma 14.

  When a streptocyanine dye is used as the chromophore that performs non-resonant two-photon absorption of the present invention, it is preferably represented by the following general formula (7).

Ra _{4 to} Ra ₇ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as Ra ₁ and Ra ₂ ). Ra ₄ and Ra ₅ , Ra ₆ and Ra ₇ may be linked to each other to form a ring, and the ring to be formed is preferably a 5- or 6-membered hetero ring, and preferably, for example, a pyrrolidine ring or piperidine A ring, a morpholine ring, a thiazine ring, and a piperazine ring.
Ma _{15 to} Ma ₁₇ each represent a methine group (preferred examples are the same as Ma ₁ to Ma ₇ ). ka ⁴ represents an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably 2. When Ka ² is 2 or more, Ma ₁₅ and Ma ₁₆ may be the same or different.
CI represents an ion that neutralizes the electric charge, and y represents a number necessary for neutralizing the electric charge.
Incidentally, in the general formula (7) may be a "group" in the general formula (1) in the form of removal of any hydrogen atom of _{Ra 4 ~Ra 7, Ma 15 ~Ma} 17.

Za ₁ , Za ₂ and Za ₃ are oxazole nuclei having 3 to 25 carbon atoms (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl, 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropylbenzoxazolyl, 2-3-methylthioethylbenzox Zolyl, 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- (3-naphthoxyethyl) benzoxazolyl, 2-3,5- Methylbenzoxazolyl, 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) A thiazole nucleus 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-ethylbenzo Azolyl, 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- Ethyl benzothiazolyl, 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, etc.), charcoal A imidazole nucleus having a number of 3 to 25 (e.g., 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), an indolenine nucleus having 10 to 30 carbon atoms (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-sulfoethylquinolyl, 4-1-methyl-7-chloroquinolyl , 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.), C 3-25 selenazole nucleus (for example, 2- 3-methylbenzoselenazolyl), pyridine nuclei having 5 to 25 carbon atoms (for example, 2-pyridyl etc.) and the like, and thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellrazolin Nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quinoxaline] nucleus, oxadiazole nucleus, thiadia It can be exemplified Lumpur nucleus, a tetrazole nucleus, a pyrimidine nucleus.
These may be substituted. As the substituent, for example, an alkyl group (for example, methyl, ethyl, propyl), a halogen atom (for example, chlorine, bromine, iodine, fluorine), a nitro group, an alkoxy group (for example, methoxy, ethoxy) ), Aryl groups (eg phenyl), heterocyclic groups (eg 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-thienyl), aryloxy groups (eg phenoxy), acylamino groups (eg acetylamino, benzoylamino) ), Carbamoyl group (for example, N, N-dimethylcarbamoyl), sulfo group, sulfonamide group (for example, methanesulfonamide), sulfamoyl group (for example, N-methylsulfamoyl), hydroxy group, carboxy group, alkylthio group (for example, methylthio group) ), A cyano group, and the like.
Of these, an oxazole nucleus, an imidazole nucleus, and a thiazole nucleus are preferable. These heterocycles may be further condensed. 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.

Za ₄ , Za ₅ , and Za ₆ each represent an atomic group necessary for forming an acidic nucleus, and are defined by James, The Theory of the Photographic Process, 4th edition, Macmillan, 1977, p. 198. The Specifically, 2-pyrazolin-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, indazolin-2-one, pyrido [1,2-a] Rimijin-1,3-dione, pyrazolo [1,5-b] quinazolone pyrazolopyridone, 3 nuclei such dicyanomethylidene Ride-3- phenylpropionitrile the like.
Hydantoin, rhodanine, barbituric acid, 2-oxazolin-5-one, and 3-dicyanomethylidenyl-3-phenylpropionitrile are preferable.

  Specific examples of cyanine chromophore, merocyanine chromophore, oxonol chromophore and streptocyanine chromophore include those described in FM Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds, John & Wiley & Sons, New York, London, 1964. It is done.

  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 number of n12 and n15 is not limited and is an integer of 0 or more) (Preferably an integer of 0 to 4)).

  The chromophore that performs non-resonant two-photon absorption of the present invention is also preferably represented by the following general formula (2).

In the general formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (preferably having a C number of 1 to 20, for example, Methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl, carboxymethyl, 5-carboxy Pentyl), an alkenyl group (preferably C 2-20, such as vinyl, allyl), a cycloalkyl group (preferably C 3-20, such as cyclopentyl, cyclohexyl), an aryl group (preferably C 6-20, For example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably C number 1-20, for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino).
R ¹ , R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group. Some (preferably two) of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring. In particular, R ¹ and R ³ 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 A 4-membered ring is more preferable, and a 5-membered ring is most preferable.

In General formula (2), 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 R ¹ , R ² , R ³ and R ⁴ may be the same or different.

X ¹ and X ² are each independently an aryl group (preferably having a C number of 6 to 20, preferably a substituted aryl group (for example, a substituted phenyl group, a substituted naphthyl group, a substituent having preferably Ma ₁ to Ma ₇ as an example of the substituent). And more preferably 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, and more preferably an alkyl group Represents an aryl group substituted with an amino group, 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, wherein a plurality of substituents are linked. Ring may be formed, and a preferred ring to be formed includes a julolidine ring), a heterocyclic group (preferably Is a C 1-20, preferably 3-8 membered ring, more preferably 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, the heterocycle may be substituted, and preferred substituents are the same as those in the case of the aryl group), or a group represented by the general formula (4) .

In the general formula (4), R ⁵ represents a hydrogen atom or a substituent (preferred examples are the same as those of R ^{1 to} R ⁴ ), preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
R ⁶ 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 R ^{1 to} R ⁴ ), preferably an alkyl group (preferably having a C number of 1 to 6 alkyl groups).

Z ¹ 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 or 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 A ring, or a quinoline ring, and most preferably an indolenine ring, an azaindolenine ring, a benzothiazole ring, a benzoxazole ring, or a benzimidazole ring.
The heterocyclic ring formed by Z ¹ may have a substituent, and the substituent is preferably an alkyl group (preferably having a 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, such as vinyl, allyl, 2-butenyl, 1,3- Butadienyl), 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), a heterocyclic group (preferably having 1 to 20 carbon atoms, such as pyridyl, thienyl, furyl, thiazo Lyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, eg ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atom (eg F , Cl, Br, I), amino group (preferably C 1-20, for example, dimethylamino, diethylamino, dibutylamino), cyano group, nitro group, hydroxyl group, carboxyl group, sulfo group, acyl group (preferably C number 1-20, for example, acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C number 1-20, for example, methoxy, butoxy, cyclohexyloxy), aryloxy group (preferably C number 6-26, For example, phenoxy, 1-naphthoxy), alkylthio group (preferably Or an arylthio group (preferably having a C number of 6 to 20, such as phenylthio, 4-chlorophenylthio), an alkylsulfonyl group (preferably having a C number of 1 to 20, such as, for example, Methanesulfonyl, butanesulfonyl), arylsulfonyl group (preferably C number 6-20, for example, benzenesulfonyl, paratoluenesulfonyl), carbamoyl group (preferably C number 1-20, for example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (preferably C number 1-20, such as acetylamino, benzoylamino), imino group (preferably C number 2-20, such as phthalimino), acyloxy group (preferably C number 1-20) For example, acetyloxy, benzoyloxy), a Coxycarbonyl group (preferably C 2-20, for example, methoxycarbonyl, phenoxycarbonyl), more preferably alkyl group, aryl group, heterocyclic group, halogen atom (especially chlorine atom, bromine atom), carboxyl A group, a sulfo group, an alkoxy group, a carbamoyl group, and an alkoxycarbonyl group.

X ¹ and X ² are each preferably an aryl group or a group represented by the general formula (4), more preferably an aryl group substituted with a dialkylamino group or a diarylamino group at the 4-position, or a general formula (4) Represented by the group represented.

Y represents an oxygen atom or an atomic group containing at least one of the partial structures represented by the following general formula (3).
General formula (3)

  In the formula, * represents a bonding position. When two atomic groups represented by the general formula (3) are contained, they may be different from each other, or they may be bonded to form a ring.

In the general formula (3), examples of the atomic group including the partial structures of (3-1) to (3-6) include a structure represented by the following general formula (5).
General formula (5)

R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁵¹⁰ , R ⁵¹¹ , R ⁵¹² , R ⁵¹³ , R ⁵¹⁴ , R ^{515 in the} general formula (5) , R ⁵¹⁶ , R ⁵¹⁷ , R ⁵¹⁸ , R ⁵¹⁹ , R ⁵²⁰ , R ⁵²¹ , R ⁵²² and R ⁵²³ each independently represents a hydrogen atom or a substituent, and the substituent is preferably R ¹¹ in the general formula (2), The group quoted as a substituent of the group represented by R < ¹² >, R <^13> , R < ¹⁴ > can be mentioned. ^{R 51, R 52, R 53} , R 54, R 55, R 56, R 57, R 58, R 59, R 510, R 511, R 512, R 513 in formula ^{(5), R 514, R} 515 R ⁵¹⁶ , R ⁵¹⁷ , R ⁵¹⁸ , R ⁵¹⁹ , R ⁵²⁰ , R ⁵²¹ , R ⁵²² and R ⁵²³ are preferably substituted or unsubstituted alkyl groups (more preferably having 1 to 20 carbon atoms, eg, methyl , Ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), a substituted or unsubstituted cycloalkyl group (more preferably carbon And a substituted or unsubstituted aryl group (more preferably 6 to 20 carbon atoms such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3- Butylphenyl, 1-naphthyl) and the like. In the general formula (5), when R ⁵⁶ and R ⁵⁷ and R ⁵¹⁴ and R ⁵¹⁵ are alkyl groups, they may be bonded to each other to form a ring.

  Y in the general formula (2) is preferably a structure containing any two of an oxygen atom or an atomic group represented by the general formula (3), more preferably an oxygen atom or the general formula (5). (5-1), (5-17), (5-18) and (5-19), most preferably an oxygen atom or an atomic group represented by (5-1).

In the general formula (2), the “group” in the general formula (1) is obtained by removing any hydrogen atom from R ¹ , R ² , R ³ , R ⁴ , X ¹ or X ^2. It is more preferable to form a “group” by removing either hydrogen atom from X ¹ or X ² . When X ¹ or X ² is represented by the general formula (4), it is preferable to a "group" in the form of removal of any hydrogen atom of R ⁶ or Z ^1,, from Z ¹ It is more preferable that the “group” is formed by removing a hydrogen atom.

  The two-photon absorption cross section of the two-photon absorption compound represented by the general formula (1) contained in the two-photon absorption material of the present invention is 1,000 GM of the two-photon absorption chromophore constituting the compound. It is preferable that at any wavelength within the above-described wavelength region, it has a value that is at least 1.1 times larger than the sum of the two-photon absorption cross-sectional areas of the two-photon absorption chromophore constituting it. It has a value that is 5 times or more larger, more preferably has a value that is 2 times or more, and most preferably has a value that is 3 times or more.

  The preferred specific examples of the compound that performs non-resonant two-photon absorption used in the present invention are listed below, but the present invention is not limited to these.

The two-photon absorption optical recording material and the two-photon absorption optical recording / reproducing method of the present invention will be described in detail below.
A two-photon absorption optical recording material of the present invention is an optical recording material comprising the above-described non-resonant two-photon absorption material and writing information using non-resonant two-photon absorption of the non-resonant two-photon absorption material. is there.

  The two-photon absorption optical recording material of the present invention has a non-resonant two-photon absorption compound, and utilizes the non-resonant two-photon absorption of the two-photon absorption compound, 1) a polymerization reaction, 2) a color reaction, and 3) Latent image coloring-coloring body self-sensitized amplification coloring reaction, 4) latent image coloring-coloring body sensitized polymerization reaction, 5) orientation change of compound having intrinsic birefringence, 6) decoloring reaction, 7) foaming, A two-photon absorption optical recording material is preferable, in which information is recorded by any one of A) refractive index modulation, B) absorptance modulation, and C) luminous intensity modulation. The two-photon absorption optical recording material of the present invention is preferably not subjected to wet processing in the process of information recording and fixing. Moreover, it is preferable that the two-photon absorption optical recording material of the present invention is a system that cannot be rewritten. Here, the method that cannot be rewritten means a method in which information is recorded by an irreversible reaction, and once recorded information is not rewritten even if it is overwritten and rewritten. Therefore, it is suitable for storing important information that needs long-term storage. Needless to say, however, it is possible to newly record and record in an area that has not yet been recorded, and in that sense, it is generally called a “write-once type” or “write-once type”.

  The two-photon absorption optical recording medium of the present invention preferably has a light-shielding cartridge, and the medium is stored in the cartridge. Further, inside the optical recording apparatus, even if the medium goes out of the cartridge and receives recording and reading, recording is performed through the irradiation port inside the cartridge having a light irradiation port that can be opened and closed such as a shutter, It may be read out.

  The two-photon absorption optical recording medium of the present invention may have a filter layer for preventing linear absorption. The wavelength of the light that is transmitted without being absorbed by the filter layer is preferably a wavelength region having a longer wavelength than the wavelength at the longest wavelength end of the linear absorption band of the non-resonant two-photon absorbing material included in the optical recording medium. .

Information is recorded on the two-photon absorption optical recording medium of the present invention at an absorption wavelength longer than the linear absorption band derived from the longest-wavelength electronic transition of the non-resonant two-photon absorption compound contained in the medium. It is preferable to use laser light having a wavelength that does not exist.
Irradiation with light having such a wavelength induces non-resonant two-photon absorption of the non-resonant two-photon absorption compound, and information is recorded using the obtained excited state. More preferably, it is a laser beam having a wavelength in a wavelength region shorter than a wavelength obtained by adding 200 nm to the linear absorption maximum wavelength existing at the longest wavelength of the non-resonant two-photon absorption compound, and more preferably, the wavelength range. Among them, the laser beam has a wavelength with the maximum two-photon absorption cross-section.

The laser that can be used for information recording of the optical recording medium of the present invention is not particularly limited, and specifically, a solid laser or a fiber laser such as Ti-sapphire having an oscillation wavelength in the vicinity of the central wavelength of 1000 nm, or near 780 nm. Semiconductor lasers and solid-state lasers, which are also used in CD-Rs having a lasing wavelength, fiber lasers, semiconductor lasers and solid-state lasers which are also used in DVD-Rs having a lasing wavelength in the range of 620-680 nm, 400- A GaN laser having an oscillation wavelength near 415 nm can be preferably used.
In addition, a solid SHG laser such as a YAG / SHG laser having an oscillation wavelength in the visible light region, a semiconductor SHG laser, or the like can be preferably used.
The laser used in the present invention may be a pulsed laser or a CW laser.

As a two-photon optical recording / reproducing method of the present invention, recording by refractive index modulation or absorptivity modulation was performed on a two-photon absorption optical recording material having a two-photon absorption compound by utilizing two-photon absorption of the two-photon absorption compound. Thereafter, a method of reproducing by irradiating the recording material with light and detecting the difference in reflectance is preferable.
On the other hand, after recording is performed on the two-photon absorption optical recording material having the two-photon absorption compound by using the two-photon absorption of the two-photon absorption compound, the light emission is performed by irradiating the recording material with light. A method of reproducing by detecting a difference in intensity is preferred. In this case, the light emission may be fluorescence or phosphorescence, but fluorescence is preferable from the viewpoint of light emission efficiency.

The light used for reproduction is preferably the above laser light, for example. Further, although the power or pulse shape is the same or different, it is more preferable to reproduce by using a laser having the same wavelength as that at the time of recording.
Examples of the light used for reproduction include carbon arc, high-pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, LED, and organic EL.
In order to irradiate light in a specific wavelength range, it is also preferable to use a sharp cut filter, a band pass filter, a diffraction grating, or the like as necessary.

In the two-photon absorption optical recording material of the present invention, the size of the reaction part or color development part produced by recording is preferably in the range of 10 nm to 100 μm, more preferably in the range of 50 nm to 5 μm, and 50 nm to More preferably, it is in the range of 2 μm.
Further, in order to enable reproduction of the recording material, the size of the reaction part or the color development part is preferably 1/20 to 20 times the irradiation light wavelength, and is 1/10 to 10 times as large. It is more preferable that the size is 1/5 to 5 times.

In the two-photon absorption optical recording material of the present invention, after the two-photon recording, a fixing step may be performed by light (ordinary one-photon), heat, or both.
In particular, when an acid proliferating agent or a base proliferating agent is used in the two-photon absorption optical recording material of the present invention, it is preferable to use heating for fixing in order to make the acid proliferating agent or base proliferating agent function effectively.
In the case of photofixing, the entire surface of the two-photon absorption optical recording material is irradiated with ultraviolet light or visible light (non-interference exposure). Preferably, the light source used includes a visible light laser, an ultraviolet light laser, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an LED, an organic EL, and the like.
It is also preferable to use a laser used for recording as a light source for light fixing as it is or by changing the power, pulse, condensing degree, wavelength and the like.
In the case of thermal fixing, the fixing step is preferably performed at 40 ° C to 160 ° C, more preferably 60 ° C to 130 ° C.
When both photofixing and heat fixing are performed, light and heat may be applied simultaneously, or light and heat may be added separately.

In the two-photon absorption optical recording material of the present invention, the chemical reaction, color development reaction, and the like that occur by performing two-photon absorption are reactions that do not involve thermal decomposition, that is, the photon mode, particularly in terms of high sensitivity. preferable.
That is, it is preferable to record with a mechanism different from the method that is practically used in the existing CD-R and DVD-R, particularly when considering the writing transfer speed in the recording material.

The two-photon absorption optical recording / reproducing method of the present invention includes an optical recording / reproducing method such as DVD-R and DVD-BL (BR), a near-field optical recording / reproducing method, a three-dimensional optical recording / reproducing method (three-dimensional volume display recording). It is preferably used for a three-dimensional optical recording / reproducing method. That is, the two-photon absorption optical recording / reproducing method of the present invention is preferably used for a two-photon absorption three-dimensional optical recording / reproducing method (or a two-photon absorption three-dimensional volume display recording / reproducing method).
Similarly, the two-photon absorption optical recording material of the present invention includes optical recording media such as DVD-R and DVD-BL (BR), near-field optical recording media, three-dimensional optical recording media (three-dimensional volume display recording materials). ) Etc., but more preferably it is used for a three-dimensional optical recording material or medium. That is, the two-photon absorption optical recording material of the present invention is preferably used for a two-photon absorption three-dimensional optical recording medium (or a two-photon absorption three-dimensional volume display recording material).

  Further, the two-photon absorption compound and the two-photon absorption optical recording material of the present invention may perform multiphoton absorption of three or more photons.

As described above, the two-photon absorption optical recording material of the present invention has a two-photon absorption compound and uses the two-photon absorption of the two-photon absorption compound to 1) polymerization reaction, 2) color reaction, and 3) latent Image development-Color development body self-sensitized amplification color development reaction, 4) Latent image color development-Color development body sensitized polymerization reaction, 5) Orientation change of compound having intrinsic birefringence, 6) Decolorization reaction, 7) Foaming It is preferable to perform recording by causing any one of A) refractive index modulation, B) absorptance modulation, and C) emission intensity modulation.
Then, next, a preferable recording method 1) to 7) for causing any one of A) refractive index modulation, B) absorption rate modulation, and C) emission intensity modulation will be described.
Here, A) recording by refractive index modulation can be performed by any of the above methods 1) to 7). Recording by B) absorption rate modulation and C) emission intensity can be recorded by the methods 2), 3), 5) and 6).

  The above recording methods will be described below.

  1) Recording by polymerization reaction

  Preferably, it has at least a two-photon absorption compound, a polymerization initiator, a polymerizable compound, and a binder, and the refractive index of the polymerizable compound and the binder is different, and the laser focal portion and the non-focal point are formed by photopolymerization caused by non-resonant two-photon absorption. In this part, the composition ratio of the polymerizable compound and its polymerization reaction product to the binder is made nonuniform in the part, thereby performing refractive index modulation.

It is preferable that either one of the polymerizable compound or the binder contains at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or sulfur atom, and the other one does not contain them.
Preferred polymerization initiators are ketones, organic peroxides, trihalomethyl-substituted triazines, diazonium salts, diaryliodonium salts, sulfonium salts, borates, diaryl iodonium organic boron complexes, sulfonium organic boron Radical polymerization initiator (radical generator) or cationic polymerization of complex, cationic two-photon absorption compound, organic boron complex, anionic two-photon absorption compound, onium salt complex, metal arene complex, or sulfonate ester Examples include initiators (acid generators) or those having both functions.
Specific examples of preferred polymerization initiators, polymerizable compounds, and binders include those described in Japanese Patent Application No. 2003-146527.
An anionic polymerization and an anionic polymerization initiator (base generator) are also preferably used. In this case, specific examples include those described in Japanese Patent Application No. 2003-178083.
When using a radical polymerization initiator, it is preferable to have an ethylenically unsaturated group such as an acryloyl group, a methacryloyl group, a styryl group, or a vinyl group as the polymerizable compound, and when using a cationic polymerization initiator or an anionic polymerization initiator. It preferably has an oxirane ring, an oxetane ring or a vinyl ether group.
Specific examples of preferred polymerization initiators in the present invention are listed below, but the present invention is not limited thereto.

  2) Recording by color reaction

  In the present invention, the color development reaction refers to a reaction in which the shape of the absorption spectrum changes in the ultraviolet light, visible light, and infrared light regions of 200 to 2000 nm, and more preferably λmax has a longer wavelength in the absorption spectrum. , Indicates a reaction in which either increase in ε occurs, and more preferably indicates a reaction in which both occur. Moreover, it is more preferable that the color development reaction occurs in a wavelength region of 200 to 1000 nm, and it is more preferable that the color development reaction occurs in a wavelength region of 300 to 900 nm.

When the recording is based on a color development reaction, preferably, the two-photon absorption compound capable of absorbing at least two photons and generating an excited state and a color reaction by electron transfer or energy transfer from the two-photon absorption compound excited state, It is preferable to include a recording component capable of recording a refractive index difference, an absorptivity difference, or a light emission intensity difference.
Further, it is more preferable that the recording component contains a dye precursor capable of becoming a color former whose absorption has been extended from the original state by electron transfer or energy transfer from the excited state of the two-photon absorption compound.

Here, the refractive index of the dye generally takes a high value in the region having a wavelength longer than that from the vicinity of the linear absorption maximum wavelength (λmax), and particularly takes a very high value in a region having a wavelength as long as 200 nm from λmax to λmax, Some dyes have high values exceeding 2 and in some cases exceeding 2.5. On the other hand, organic compounds which are not pigments such as binder polymers usually have a refractive index of about 1.4 to 1.6.
Therefore, it can be seen that coloring the dye precursor by two-photon absorption of the two-photon absorption compound can preferably form not only an absorption difference but also a large refractive index difference.
When recording using a difference in refractive index in the two-photon absorption optical recording material of the present invention, the refractive index of the dye formed from the recording component is preferably maximized in the vicinity of the laser wavelength used for reproduction.
Further, when recording using a difference in light emission intensity, it is preferable that there is a difference in light emission intensity when the color former and the dye precursor are irradiated with light having a certain wavelength during reproduction.

  As the recording component, the following combinations are preferable. About these, the example described in Japanese Patent Application No. 2003-284959 is preferably mentioned as a specific example.

i) A combination comprising at least an acid color-forming dye precursor as a dye precursor and an acid generator. A combination further containing an acid proliferating agent if necessary.
As the acid generator, diaryl iodonium salts, sulfonium salts and sulfonic acid esters are preferable, and the above-mentioned acid generator (cationic polymerization initiator) can be preferably used.
The color former generated from the acid color-formable dye precursor is preferably a xanthene dye, a fluorane dye or a triphenylmethane dye. Particularly preferred specific examples of the acid coloring dye precursor are listed below, but the present invention is not limited thereto.

ii) A combination including at least a base color-forming dye precursor as a dye precursor, a base generator, and, if necessary, a base proliferating agent.
As the base generator, the aforementioned base generator (anionic polymerization initiator) is preferably mentioned, and as the base color-forming dye precursor, a dissociation azo dye, a dissociation azomethine dye, a dissociation oxonol dye, a dissociation xanthene dye , Dissociated fluorane dyes, and non-dissociated isomers of dissociated triphenylmethane dyes.
Particularly preferred specific examples of the base color-forming dye precursor are listed below, but the present invention is not limited thereto.

  iii) an organic compound portion having a function of breaking a covalent bond by electron transfer or energy transfer with an excited state of a two-photon absorption compound, and an organic compound having a feature that becomes a color former when covalently bonded and released Including compounds where the moiety is covalently bonded. A combination further containing a base if necessary. Particularly preferred specific examples are listed below, but the present invention is not limited thereto.

  iV) When a compound that reacts by electron transfer with an excited state of a two-photon absorption compound to change the absorption form is included. So-called electrochromic compounds can be preferably used.

  3) Latent image color development—Recording by color former self-sensitized amplification color reaction

  Preferably, at least a first step of generating a color former having an absorption form different from that of the two-photon absorption compound as a latent image by two-photon absorption exposure, and two-photon absorption compound linear (one-photon) absorption in the color former latent image Is irradiated with light in a wavelength range of 5,000 or less to cause linear absorption of the color former, and the color former is generated by self-sensitizing amplification to form a difference in refractive index, difference in absorbance, or difference in emission intensity. A two-photon absorption optical recording method having a second step of recording, which is preferable in terms of high-speed writing, high S / N ratio reproduction, and the like.

  Here, the “latent image” means “a refractive index difference, an absorptivity difference, or a luminescence intensity difference formed after the second step, preferably a refractive index difference, an absorptance difference, or a luminescence intensity that is preferably 1/5 or less. Difference ”(that is, preferably an amplification step of 5 times or more is performed in the second step), more preferably 1/10 or less, and even more preferably 1/30 or less of refractive index and absorption. It is a rate or emission intensity difference image (that is, an amplification step of 10 times or more, more preferably 30 times or more is performed in the second step).

Here, the second step is preferably light irradiation, heat application, or both, more preferably light irradiation, and the light to be irradiated is the entire surface exposure (so-called solid exposure, blanket exposure, non-image). Wise exposure) is preferable.
Preferred examples of the light source to be used include a visible light laser, an ultraviolet light laser, an infrared light laser, a carbon arc, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an LED, and an organic EL. In order to irradiate light in a specific wavelength range, it is also preferable to use a sharp cut filter, a band pass filter, a diffraction grating, or the like as necessary.

Furthermore, as a two-photon absorption optical recording material capable of such a two-photon absorption optical recording method, at least,
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state in the first step;
2) including a dye precursor that can be a color former that has a wavelength longer than that of the original state and has absorption in a wavelength range different from the linear absorption of the two-photon absorption compound, and from the excited state of the two-photon absorption compound or the color former It is preferable to include a recording component that can be recorded as a difference in refractive index, a difference in absorption rate, or a difference in light emission intensity by electron transfer or energy transfer.
Preferred examples of the recording component are the same as those described in 2) Color development reaction.
In the wavelength range of the light irradiated in the second step, the molar absorption coefficient of linear absorption of the two-photon absorption compound is more preferably 1000 or less, and further preferably 500 or less.
Further, in the wavelength range of the light irradiated in the second step, the molar extinction coefficient of the color former is more preferably 5000 or more, and further preferably 10,000 or more.

The concept of “latent image color development—colored body self-sensitized amplification color reaction system” will be described below.
For example, a two-photon absorption optical recording material is irradiated with a 780 nm laser, and a two-photon absorption compound absorbs two photons to generate an excited state. By transferring energy or electrons from the excited state of the two-photon absorption compound to the recording component, the dye precursor contained in the recording component is changed to a color former to form a latent image by color development (the first step). Next, light in a wavelength range of 680 to 740 nm is irradiated to cause linear absorption of the color former, and the color former is amplified and generated by self-sensitization of the color former (the second step). Since the latent image is not generated in the non-recorded portion where the laser is not irradiated in the first step, the self-sensitized coloring reaction hardly occurs even in the second step, and as a result, the recording portion and the non-recording portion are largely refracted. Rate modulation, absorption rate modulation, or emission intensity modulation can be formed. For example, by using a 780 nm laser again and irradiating the recorded two-photon absorption optical recording material, it becomes possible to reproduce the light by the difference in the reflectance of the light based on the large difference in refractive index between the recording part and the non-recording part. A two-photon absorption (three-dimensional) optical recording medium by recording and reproduction can be provided.

  As a specific example of the latent image color development-chromogen self-sensitized amplification color development reaction, an example described in Japanese Patent Application No. 2003-300058 is preferable.

  4) Latent image color development—Recording by color development sensitized polymerization reaction

Preferably, at least the first step of generating a color developing body as a latent image by two-photon absorption and the polymerization based on the linear absorption of the color developing body by irradiating the color developing latent image with light to cause a refractive index It is a two-photon absorption optical recording method characterized by having a second step of recording by forming a difference, and is excellent in high-speed writing, storability and the like.
In the second step, a method in which polymerization is caused while self-sensitizing amplification production is performed is also preferable.

Furthermore, as a two-photon absorption optical recording material capable of such a two-photon absorption optical recording method, at least,
1) a two-photon absorption compound capable of absorbing two photons and generating an excited state in the first step;
2) Absorption is increased in wavelength from the original state by transferring electrons or energy from the excited state of the two-photon absorption compound in the first step or from the excited state of the color former in the second step, and two-photon absorption. A dye precursor capable of becoming a color former having absorption in a wavelength region where the molar absorption coefficient of linear absorption of the compound is 5000 or less,
3) a polymerization initiator capable of initiating polymerization of the polymerizable compound by electron transfer or energy transfer from the excited state of the two-photon absorption compound in the first step;
4) a polymerizable compound,
5) binder,
It is preferable to contain.
Preferred examples of the recording component are the same as those described in 2) Color development reaction.
Preferred examples of the polymerization initiator, the polymerizable compound and the binder are the same as those described in 1) polymerization reaction.
In the wavelength range of the light irradiated in the second step, the molar absorption coefficient of linear absorption of the two-photon absorption compound is more preferably 1000 or less, and further preferably 500 or less.
Further, in the wavelength range of the light irradiated in the second step, the molar extinction coefficient of the color former is more preferably 5000 or more, and further preferably 10,000 or more.

  In the two-photon absorption optical recording method of the present invention and the two-photon absorption optical recording material capable of such recording, the first step, the second step, or subsequent light irradiation, heat application, or both It is preferable that the two-photon absorption dye is decomposed and fixed in any one of the fixing steps from the viewpoint of storage stability and non-destructive regeneration. Furthermore, the first step, the second step, or subsequent light irradiation, heat application The two-photon absorbing dye is decomposed and fixed by either the second step or the subsequent fixing step by light irradiation, heat application, or both by the fixing step by either or both. Is more preferable.

The concept of “latent image color development-colored material sensitized polymerization reaction method” will be described below.
For example, a two-photon absorption optical recording material is irradiated with a 780 nm laser, and the two-photon absorption compound absorbs the two-photon absorption optical recording material to generate an excited state. By transferring energy or electrons from the excited state of the two-photon absorption compound to the dye precursor, the dye precursor is changed to a color former to form a latent image by color development (the first step). Next, irradiation with a laser beam of 780 nm causes linear absorption of the color former, and the polymerization initiator is activated by electron transfer or energy transfer to initiate polymerization. For example, when the refractive index of the polymerizable compound is larger than that of the binder, the refractive index increases because the polymerizable compound gathers at the portion where the polymerization occurs (second step). In the first step, a latent image is not generated in the unrecorded portion that has not been irradiated with the laser. Therefore, polymerization does not occur so much in the second step, and the abundance ratio of the binder is increased. Thus, refractive index modulation can be formed. Provided a two-photon absorption optical recording material that is excellent in non-destructive reproduction and storability and is colorless and transparent if the two-photon absorption compound and the colored body can be decomposed and decolored by the first and second steps or further fixing step. can do.
For example, by using a 780 nm laser again and irradiating the recorded two-photon absorption optical recording material, it is possible to reproduce the light based on the difference in the refractive index between the recording portion and the non-recording portion, and the two-photon absorption A (three-dimensional) optical recording medium can be provided.
In this case, a 780 nm laser can be used for recording in the first step, photopolymerization amplification in the second step, and reproduction.

  Preferable examples of the latent image color development-colored material sensitization polymerization reaction include those described in Japanese Patent Application No. 2003-31744.

  5) Recording by changing the orientation of a compound having an intrinsic birefringence

  Preferably, it is a method of recording as refractive index modulation in a non-rewritable manner by causing an orientation change of a compound having an intrinsic birefringence by two-photon absorption and fixing it as it is by a chemical reaction. As the compound having an intrinsic birefringence, a liquid crystal compound is preferable, a low molecular liquid crystal compound is more preferable, and a low molecular liquid crystal compound having a polymerizable group is further preferable. A specific example is preferably the example described in Japanese Patent Application No. 2003-327594.

  6) Recording by decoloring reaction

Preferably, there is a method in which the two-photon absorption compound is decolored by two-photon absorption in the recording portion by the following method i) or ii).
i) a two-photon absorption optical recording material in which the two-photon absorption compound erases itself by two-photon absorption in the recording unit;
ii) At least a two-photon absorption compound and a decolorant precursor different from the two-photon absorption compound, and after the two-photon absorption compound generates an excited state by two-photon absorption, the decolorant precursor and energy transfer Or a two-photon absorption optical recording material in which a decolorant is generated from the decolorizer precursor by electron transfer, and the decolorizer decolors the two-photon absorption compound,
In this case, the decolorizer precursor is preferably a radical generator, acid generator, base generator, nucleophile generator, electrophile generator, triplet oxygen, particularly a radical generator, An acid generator and a base generator are preferable, and in this case, the examples given in 1) Polymerization reaction are preferably used.
Specific examples of the decoloring method, decoloring agent precursor, decoloring agent and the like of i) and ii) preferably include the examples described in Japanese Patent Application No. 2003-276684.

  7) Recording by foaming

Preferably, there is a method of causing foaming by two-photon absorption in the recording portion by the following method i) or ii).
i) A two-photon compound having a two-photon absorption compound having at least a foamable portion and being excited by two-photon absorption, whereby the foamable portion generates a gas and creates bubbles to reduce light-emitting components. Absorbing optical recording material,
ii) At least a two-photon absorption compound and a foamable compound different from the two-photon absorption compound, and after the two-photon absorption compound generates an excited state by two-photon absorption, energy transfer or electron transfer with the foamable compound Thus, a two-photon absorption optical recording material in which the foamable compound generates a gas to form bubbles to reduce the light-emitting component is exemplified.
At that time, the gas generated from the foamable portion of i) or the foamable compound of ii) is any of N ₂ , CO ₂ , SO ₂ , SO ₃ , NO ₂ , O ₂ , and iC ₄ H _8. preferable.
Specific examples of the foaming method, foamable site and foamable compound of i) and ii) are preferably the examples described in Japanese Patent Application No. 2003-274096.

  In addition to the sensitizing dye, interference fringe recording component, polymerization initiator, polymerizable compound, binder and the like as described above, the two-photon absorption optical recording material of the present invention further comprises an electron donating compound, an electron accepting agent as necessary. Additives such as a chemical compound, a chain transfer agent, a crosslinking agent, a heat stabilizer, a plasticizer, and a solvent can be used.

  The electron-donating compound has the ability to reduce the radical cation of the two-photon absorption compound or color former, and the electron-accepting compound has the ability to oxidize the radical anion of the two-photon absorption compound or color former. It has a function of regenerating a compound or color former. Specifically, for example, an example described in Japanese Patent Application No. 2003-284959 can be given as a preferable example.

  Specific examples of the chain transfer agent, the crosslinking agent, the heat stabilizer, the plasticizer, the solvent and the like include the examples described in Japanese Patent Application No. 2003-146527.

  Next, the two-photon polymerization composition and the two-photon polymerization method of the present invention will be described. The two-photon polymerization composition of the present invention includes at least a two-photon absorption compound represented by the general formula (1), a polymerizable compound that is polymerized by a radical or a cation, a radical or a cationic polymerization initiator that generates a radical or an acid, If necessary, a binder, a chain transfer agent, a heat stabilizer, a plasticizer, a solvent and the like can be added and used.

The polymerizable compound of the present invention refers to a compound that can be oligomerized or polymerized by addition polymerization by a radical or 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: Kaprorad-modified dipentaerythritol poly (meth) acrylates, such as Nippon Kayaku Kayrad D-310, 320, 330, etc .: 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 per molecule described in Japanese Patent Publication No. 48-41708, general formula CH ₂ ═C (R) COOCH ₂ CH (R ′) OH ( In the formula, R and R ′ represent hydrogen or a methyl group.) And 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 .

  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.

  Further, TSR-1920B, TSR-1938 (manufactured by Teijin Ltd.), and SCR-500 (manufactured by Nippon Synthetic Rubber Co., Ltd.) are also preferable as polymerizable urethane acrylate resins in terms of thermal properties and mechanical properties.

  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, page 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 cationically 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, polyester Lenglycol diglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether, phenyl glycidyl ether, p-t-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-dimethylol perfluorohexane diglycidyl ether, 4,4 '-Bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, vinylcyclohexenedioxide, 3,4-epoxycyclohexyl Methyl-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-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, Examples include compounds such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, p-bromostyrene oxide, bisphenol-A-diglycidyl ether, tetrabromobisphenol-A-diglycidyl ether, and bisphenol-F-diglycidyl ether. .

  In addition, 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 (die 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 cationically 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, the polymerization initiator 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 organoboron complex polymerization initiator
10) Sulphonium organoboron complex polymerization initiator
11) Cationic two-photon absorption compound organoboron 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), a thioxanthone derivative (e.g., thioxanthone, 2-chlorothioxanthone), ketocoumarin derivatives.

  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 (eg, 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-tetrahydronaphthacene Non, as well as 1,2,3,4-tetrahydrobenz (a) anthracene-7,12-dione).

  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

  Preferable bisimidazole-based polymerization initiators are bis (2,4,5-triphenyl) imidazole derivatives, such as bis (2,4,5-triphenyl) imidazole, 2- (o-chlorophenyl)- 4,5-bis (m-methoxyphenyl) -imidazole dimer (CDM-HABI), 1,1′-biimidazole, 2,2′-bis (o-chlorophenyl) -4,4′5,5′-tetra Phenyl (o-Cl-HABI), 1H-imidazole, 2,5-bis (o-chlorophenyl) -4- [3,4-dimethoxyphenyl] -dimer (TCTM-HABI) and the like can be mentioned.

  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 the general formula (6), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a halogen atom, preferably a chlorine atom. R ₂₄ and R ₂₅ each independently represent a hydrogen atom, —CR ₂₁ R ₂₂ R ₂₃ , or a substituent (preferred examples are the same as those for Za ¹ ). R ₂₄ preferably represents —CR ₂₁ R ₂₂ R ₂₃ , more preferably —CCl ₃ group, and R ₂₅ is preferably —CR ₂₁ R ₂₂ R ₂₃ , 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, etc. . 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).

R ₂₆ represents an aryl group or a heterocyclic group (the above preferred examples are the same as the substituents on Za ¹ ), preferably an aryl group, more preferably a phenyl group.
R ₂₇ represents a substituent (preferred examples are the same as the substituents on Za ¹ ), and a 21 represents an integer of 0 to 5, preferably an integer of 0 to 2. a21 is when 2 or more, the plurality of R ₂₇ may be the same or different and may form a ring.
X ₂₁ ⁻ is an anion in which HX ₂₁ becomes an acid having a pKa of 4 or less (in water, 25 ° C.), preferably 3 or less, more preferably 2 or less, preferably, for example, chloride, bromide, iodide, tetrafluoroborate, hexa Fluorophosphate, hexafluoroarsenate, hexafluoroantimonate, perchlorate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, tetra ( Pentafluorophenyl) borate and the like.

Specific examples of the diazonium-based polymerization initiator such as benzene diazonium, 4-methoxy diazonium, 4-methyl aforementioned X ₂₁ of diazonium ^- such salts.

  6) Diaryliodonium salt polymerization initiator

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

In the general formula (8), X ₂₁ ^- has the same meaning as in the general formula (7). R ₂₈ and R ₂₉ each independently represent a substituent (preferred examples are the same as the substituents on Za ¹ ), and preferably represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a nitro group.
a22 and a23 each independently represents an integer of 0 to 5, preferably an integer of 0 to 1. When a22 and a23 are each 2 or more, the plurality of R ₂₈ and R ₂₉ 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, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethane Examples include tilbenzene sulfonate, tosylate, and tetra (pentafluorophenyl) borate.
Further, compounds described in “Macromolecules”, Vol. 10, p1307 (1977), Japanese Patent Application Laid-Open No. 58-29803, Japanese Patent Application Laid-Open No. 1-287105, 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 general formula (9), X ₂₁ ^- has the same meaning as in general formula (7). R ₃₀ , R ₃₁ , and R ₃₂ each independently represents an alkyl group, an aryl group, or a heterocyclic group (preferred examples are the same as the substituents on Za ¹ ), preferably an alkyl group, a phenacyl group, or an aryl group Represents a 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 L-methanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoro Methylbenzenesulfonate, tosylate, etc. tetra (pentafluorophenyl) borate.

8) Borate polymerization initiator

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

In the general formula (10), in each of _{R 33, R 34, R 35} , R 36 independently represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group (preferred examples of the substituent on Za ¹ The same as the group), preferably an alkyl group or an aryl group. However, R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ are not all aryl groups at the same time. X ₂₂ ⁺ represents a cation.
More preferably, R ₃₃ , R ₃₄ and R ₃₅ are all aryl groups and R ₃₆ is an alkyl group, most preferably R ₃₃ , R ₃₄ and R ₃₅ are phenyl groups, and R ₃₆ is n- It is a 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), R ₂₈ , R ₂₉ , a22 and a23 have the same meaning as in general formula (8), and R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ have the same meaning as in general formula (10).

  Specific examples of the diaryliodonium organic boron 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 the general formula (12), R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ have the same _{meaning as} in the 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 (more preferred examples) Is the same as the substituent on Za ¹ ), more preferably an alkyl group, a phenacyl group, an aryl group or an alkenyl group. R ₃₇ , R ₃₈ and R ₃₉ may be connected to each other to form a ring. R ₄₀ represents an oxygen atom or a lone electron pair.

  Specific examples of the sulfonium organic boron complex-based 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. R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ have the same _{meaning as} in general formula (10).

  Specific examples of the cationic two-photon absorption compound organoboron complex polymerization initiator include I-11, I-12, I-13 and the like 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. X ₂₃ ⁺ represents a cation moiety of the diazonium salt of the general formula (7), a cation moiety of the diaryliodonium salt of the general formula (8), and a cation moiety of the sulfonium salt of the general formula (9) (all preferred examples are described above). 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-14 to I-25 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.)”, Volume 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 organoboron complex polymerization initiator
10) Sulphonium organoboron complex polymerization initiator
11) Cationic two-photon absorption compound organoboron 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 polymerization initiator 3) Bisimidazole polymerization initiator 4) Trihalomethyl-substituted triazine polymerization initiator 6) Diaryliodonium salt polymerization initiator 7) Sulfonium salt 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 polymerization initiator 6) Diaryliodonium salt polymerization initiator 7) Sulfonium salt polymerization initiator
11) Cationic two-photon absorption compound organoboron complex polymerization initiator
12) Anionic two-photon absorption compound onium salt complex polymerization initiator.

  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, A TECHNOLOGY MARKING PUBLICATION] and "Comments Inorg. Chem." [B. Klingelt, M.M. Reedy Car and A. Rolov (B. KLINGERT, M. RIEDICER and A. ROLOFF), Volume 7, No. 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 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. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. 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 High molecular weight polyethylene glycol of polyglycol 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-methoxymethyl) Rihexamethylene 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 include those disclosed in US Pat. No. 3,458,311 and US Pat. No. 4,273,857. To do. Polystyrene polymers, and copolymers such as 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 copolymer), polyvinyl chloride and copolymers (eg, polyvinyl chloride / acetate, vinyl chloride / acrylonitrile copolymer), polyvinyl benzal synthetic rubber (eg, butadiene / acrylonitrile copolymer, acrylonitrile) / Butadiene / styrene copolymer, methacrylate / acrylonitrile / butadiene / styrene copolymer, 2-chlorobutadiene-1,3 polymer, chlorinated rubber, styrene / butadiene / styrene, styrene / isopre / Styrene block copolymer), copolyesters (for example, polymethylene glycol of the formula HO (CH ₂ ) nOH (where n is an integer from 2 to 10), and (1) hexahydroterephthalic acid, sebacin Acid and terephthalic acid, (2) terephthalic acid, isophthalic acid and sebacic acid, (3) terephthalic acid and sebacic acid, (4) produced from the reaction product of terephthalic acid and isophthalic acid, and (5) the glycol And (i) a mixture of terephthalic acid, isophthalic acid and sebacic acid and (ii) a copolyester prepared from terephthalic acid, isophthalic acid, sebacic acid and adipic acid), poly N-vinylcarbazole and copolymers thereof, and H . A carbazole-containing polymer as disclosed by Kamogawa et al. In Journal of Polymer Science: Polymer Chemistry Edition, Vol. 18, pages 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, organic solvent-soluble fluorine atom-containing polymers are also marketed by 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 0.1 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 USP No. 4414312 and JP-A No. 64-13144 Thiols, disulfides described in JP-A-2-291561, thiones described in USP 3,558,322 and JP-A 64-17048, O-acylthiohydroxamates and N-alkoxy described in JP-A-2-291560 Also included are pyridinethiones.
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 thermal 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 present photopolymerizable composition can be applied directly onto the substrate, can be spin-coated, or can be cast as a film and then laminated to the substrate by conventional methods. 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.
[Example 1]

  [Synthesis of D-25]

  Compound D-25 of the present invention can be synthesized by the following method.

  Raw material compound (1) 1.2 g (4.2 mmol) and cyclopentanone 7.1 g (85 mmol) were dissolved in 50 ml of methanol, 1.6 g (8.5 mmol) of 28% sodium methoxide methanol solution was added, and the mixture was stirred at 50 ° C. for 5 hours. . Saturated aqueous NaCl solution was added to the reaction solution, and the mixture was extracted twice with ethyl acetate. The organic layer was evaporated, and purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/2). Intermediate compound (2 ) 1.2g (yield 80%) was obtained.

  Intermediate compound (2) 0.4 g (1.1 mmol) and starting compound (3) 0.3 g (1.1 mmol) were dissolved in 20 ml of methanol, and sodium methoxide 28% methanol solution 0.2 g (1.1 mmol) was added at 50 ° C. Stir. The solid obtained by distilling off the solvent from the reaction solution was purified by silica gel column chromatography (eluent: chloroform / methanol = 20/1) to obtain 0.41 g of intermediate compound (4) (yield 62%). .

Intermediate compound (4) 100 mg (0.17 mmol), hydroquinone 7.5 mg (0.07 mmol), 4-dimethylaminopyridine (DMAP) 8.6 mg (0.07 mmol), 1-hydroxy-1-benztriazole (HOBT) 27 mg (0.2 mmol) ), WSC 38 mg (0.2 mmol) was stirred in DMF at room temperature, saturated aqueous NaCl solution was added, and the mixture was extracted twice with ethyl acetate, and the organic layer was evaporated to dryness. The obtained crude product was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 3/4) and recrystallized from ethyl acetate / n-hexane to obtain 45 mg of D-25 green-purple crystals (yield). Rate: 52%). The structure of the compound was confirmed by NMR spectrum and MS spectrum.
[Example 2]

[Synthesis of D-25]
Compound D-28 of the present invention can be synthesized by the following synthesis method.

Intermediate compound (4) 100 mg (0.17 mmol), 1,2-cyclohexanediamine 7.8 mg (0.07 mmol), 4-dimethylaminopyridine (DMAP) 8.6 mg (0.07 mmol), 1-hydroxy-1-benztriazole (HOBT After stirring 27 mg (0.2 mmol) and WSC 38 mg (0.2 mmol) in DMF at room temperature, a saturated aqueous NaCl solution was added and the mixture was extracted twice with ethyl acetate, and the organic layer was evaporated to dryness. The obtained crude product was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 3/4) and recrystallized from ethyl acetate / n-hexane to obtain 22 mg of dark purple crystals of D-28 (yield). Rate: 25%). The structure of the compound was confirmed by NMR spectrum and MS spectrum.
In addition, the synthesis method of the compound of this invention is not necessarily limited to this.
Example 3

[Method for evaluating two-photon absorption cross section]
The evaluation of the two-photon absorption cross section of the compound of the present invention was performed with reference to the method described in MA Albota et al., Appl. Opt. 1998, 37, p. Ti: sapphire pulse laser (pulse width: 100 fs, repetition rate: 80 MHz, average output: 1 W, peak power: 100 kW) is used as the light source for measuring the two-photon absorption cross section, and two-photon absorption is performed in the wavelength range from 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 measured using rhodamine B and C. Xu et al., J. Opt. Soc. Am. B 1996, vol. 13, page 481. The two-photon absorption cross section of each compound was obtained by correcting using the value of the two-photon absorption cross section of fluorescein.

As a sample for two-photon absorption measurement, a 10 ⁻⁴ M chloroform solution of the two-photon absorption compounds D-25, D-26, D-27, D-28 of the present invention and the comparative monomer compound R-1 was used.

The two-photon absorption cross sections of the two-photon absorption compound of the present invention and its comparative monomer compound were measured by the above method, and the obtained results are shown in Table 1 in GM units (1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s / photon).

Among the two-photon absorption cross sections at each wavelength of each two-photon absorption compound shown in Table 1, the value larger than twice the two-photon absorption cross-section at each wavelength of the comparative compound R-1 Underlined, parentheses for small values.
From Table 1, the two-photon absorption cross section of the two-photon absorption compound of the present invention can be larger than twice the two-photon absorption cross-section of the constituent chromophore at a certain wavelength.

Claims (13)

A non-resonant two-photon absorption material comprising a non-resonant two-photon absorption compound represented by the following general formula (1):
General formula (1)

In general formula (1), TPAD ¹ and TPAD ² each independently represent a group containing a non-resonant two-photon absorption chromophore, L represents a linking group, a simple bond, or an atom, and n represents an integer of 1 to 7 Represent. When n is 2 or more, the plurality of TPADs ² may be the same or different.   The non-resonant two-photon according to claim 1, wherein the linking group represented by L in the general formula (1) connects a plurality of two-photon absorption chromophores without taking a resonance contribution structure. Absorbing material. In the compound represented by the general formula (1), TPAD ¹ and TPAD ² are each independently a cyanine dye, streptocyanine dye, merocyanine dye, oxonol dye, stilbazolium dye or a compound represented by the following general formula (2) The non-resonant two-photon absorption material according to claim 1, wherein the non-resonant two-photon absorption material is a group containing
General formula (2)

In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and some of R ¹ , R ² , R ³ and R ⁴ are bonded to each other to form a ring. May be formed. n and m each independently represent an integer of 0 to 4, and when n and m are 2 or more, a plurality of R ¹ , R ² , R ³ and R ⁴ may be the same or different. However, n and m are not 0 simultaneously. Y represents an oxygen atom or an atomic group containing at least one of the partial structures represented by the following general formula (3), and X ¹ and X ² independently represent an aryl group, a heterocyclic group, or a general formula (4 ) Represents a group represented by
General formula (3)

In the formula, * represents a bonding position with the general formula (2). When two atomic groups represented by the general formula (3) are contained, they may be different from each other or may be bonded to form a ring. When one atomic group represented by the general formula (3) is included, other necessary atoms or atomic groups may be arbitrary.
General formula (4)

In the formula, R ⁵ represents a hydrogen atom or a substituent, and R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Z ¹ represents an atomic group forming a 5- or 6-membered ring and may be condensed.
The general formula (2) is a group obtained by removing any hydrogen atom from R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² .   The two-photon absorption compound represented by the general formula (1), wherein the non-resonant two-photon absorption cross-section at a certain wavelength of the two-photon absorption compound constitutes the compound at the same wavelength. The non-resonant two-photon absorption material according to any one of claims 1 to 3, wherein the non-resonant two-photon absorption material is larger than a sum of two-photon absorption cross sections of chromophores.   Two-photon absorption is performed by irradiating the non-resonant two-photon absorption material according to any one of claims 1 to 4 with laser light having a longer wavelength than the linear absorption band of the non-resonant two-photon absorption compound contained in the material. A non-resonant two-photon absorption inducing method characterized by inducing.   The non-resonant two-photon absorption material according to any one of claims 1 to 4, wherein the non-resonant two-photon light-emitting material emits light by non-resonant two-photon absorption.   The non-resonant two-photon light-emitting material according to claim 6 is irradiated with laser light having a longer wavelength than the linear absorption band of the non-resonant two-photon absorption compound included in the material to induce non-resonant two-photon absorption, A light emission generation method characterized by generating light emission.   A non-resonant two-photon optical recording material comprising the non-resonant two-photon absorbing material according to claim 1.   The information is written by irradiating the non-resonant two-photon optical recording material according to claim 8 with laser light having a longer wavelength than the linear absorption band of the non-resonant two-photon absorption compound included in the material. Non-resonant two-photon optical recording method.   A non-resonant two-photon polymerization composition comprising the non-resonant two-photon absorption material according to claim 1.   A polymer is obtained by irradiating the non-resonant two-photon polymerization composition according to claim 10 with laser light having a longer wavelength than the linear absorption band of the non-resonant two-photon absorption compound contained in the composition. A non-resonant two-photon polymerization method.   A non-resonant two-photon image display material comprising the non-resonant two-photon absorption material according to claim 1.   The non-resonant two-photon image display material according to claim 12 is irradiated with a laser beam having a wavelength longer than the linear absorption band of the non-resonant two-photon absorption compound included in the material, thereby displaying an image. Non-resonant two-photon image display method.