JP2003027040A - Two-photon absorbing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly sensitive two-photon absorbing composition that can realize two-photon absorption by using a relatively low power laser. SOLUTION: This two-photon absorbing composition comprises a two-photon absorbing compound having a two-photon absorption cross-sectional area of >=10<2> GM (wherein 1 GM=1×10<-50> cm<4> -s-mole-cule<-1> -photon<-1> ), and a fluorescence extinction agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a two-photon absorption composition containing a compound having a large two-photon absorption cross section which is excited only by intense light. It can be used for an optical information recording medium, an optical modulation element, an optical operation element, or modeling by photopolymerization.

[0002]

2. Description of the Related Art Normally, a substance is excited by absorbing one photon having an energy corresponding to the excitation energy, and a photon having an energy less than this energy is not absorbed. However, when the intensity of light is very strong, two photons whose sum of photon energies corresponds to excitation energy may be simultaneously absorbed. By utilizing this property, a photoreaction can be caused only in the vicinity of the focus where the light is narrowed down by a lens, and an arbitrary excited position can be created by using an arbitrary position in space. However, since two-photon absorption is very unlikely to occur normally, a substance having a high two-photon excitation efficiency has been required. The two-photon absorption cross section, which indicates the likelihood of two-photon absorption, is usually very small, 1 GM (1 GM = 1 × 10 ^-50 cm ⁴ s molecule ^-1 p
It is about hoton ^-1 ), but in recent years, a substance having a relatively large two-photon absorption cross section of several hundred to several thousand GM has been found. Examples of compounds having a relatively large two-photon absorption cross section are described in the following documents, for example. That is, Reinhar
Chemistry of Materials, dt et al., 1998, Vol. 10, 1863, M. Albota et al., Science,
1998, 281, 1653, M. Rumi et al., J
Ournal of the American Chemical Society, 2000, 122, 9500, JD Bhawalkar et al.,
Optics Communications, 1996, 124, 33,
SGHe et al., Applied Physics Letters, 19
Published in 1995, 67, 2433, by PN Prasad et al.,
Nonlinear Optics Magazine, 1999, 21 volumes, 39 pages, GS
He et al., Journal of Applied Physics, 1997.
Issued 81, 2529, S. -J. Chung et al., J
ournal of Physical Chemistry B, 1999, 103
Volume, 10741, Optics Letters by SG He et al.
Journal, 1995, 20 volumes, 435 pages, JW Perry et al., Nonlinear Optics, 1999, 21 volumes, 225 pages. However, this size is still not practical because it requires a very high power laser. Also, in order to make it easier to use the excitation energy according to the purpose,
It was necessary to devise a combination of various functional substances.
Further, the compounds reported so far with a relatively large two-photon absorption cross-section emit strong fluorescence, which is inconvenient for some applications. For example, when the information is recorded by causing a change in the state of the recording layer by light irradiation, and this change is read out by the change in absorption or reflection of light, so-called optical information recording medium, fluorescence generated. And signal light are difficult to distinguish, which causes noise. When used in so-called two-photon optical modeling, which creates an arbitrary shape by curing only the area irradiated with a high-power laser in combination with a photo-curing resin, the finished product emits fluorescence and shines. There is a problem that the visibility of the shape is poor unless it is selected, and it cannot be used in the vicinity of a photosensitive material such as a photographic film. Therefore, there has been a need for a two-photon absorption composition that does not substantially emit fluorescence.

[0003]

The problem to be solved by the present invention is to provide a high-sensitivity two-photon absorption composition capable of inducing two-photon absorption using a laser of relatively low power. (EN) A two-photon absorption composition for facilitating linking of excited state energy resulting from two-photon absorption to a physical or chemical change, and particularly to a two-photon absorption composition which does not substantially emit fluorescence. Is to provide.

[0004]

Means for Solving the Problems As a result of intensive studies by the present inventors, it is important to use a compound that efficiently causes two-photon absorption and a compound that has a function of effectively utilizing its excitation energy. Focusing on that, it was found that the above problems can be solved by the following two-photon absorption composition. (1) Two-photon absorption cross section is 10 ² GM (1 GM = 1 × 10 ^-50 cm ⁴
s molecule ^-1 photon ^-1 ) or more and a two-photon absorption compound and a fluorescence quencher. (2) The two-photon absorption composition as described in (1), which contains a polymer binder. (3) The two-photon absorption composition according to (1) or (2), wherein the polymer binder is crosslinked with a crosslinking agent. (4) The two-photon absorbing compound according to any one of (1) to (3), wherein the two-photon absorbing compound is at least one of compounds represented by the following general formulas (1) to (5). Absorption composition. (5) The fluorescence quencher is at least one compound selected from the group of compounds having a strong electron accepting property, the group of compounds having a strong electron donating property and the group of heavy metal complex compounds.
The two-photon absorption composition according to any one of (1) to (4).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the two-photon absorbing composition of the present invention will be described in detail below. The operation principle of the composition used in the two-photon absorption composition of the present invention that exerts a function in response to only strong light will be described. When a substance is exposed to light, it is usually 1
Energy corresponding to photons is absorbed. Even with light having a wavelength at which this one-photon absorption does not occur, two photons whose sum of photon energies corresponds to excitation energy may be simultaneously absorbed when the intensity is very strong. The two-photon absorption cross section, which indicates the likelihood of two-photon absorption, is usually very small, 1 GM (1 GM = 1 × 10 ^-50 cm ⁴ s molecule ^-1 photon
It is about ^-1 ), but in recent years, a substance having a relatively large two-photon absorption cross section of several hundred to several thousand GM has been found.
When such a substance is used, even light in a wavelength range having no light absorption band absorbs energy of two photons if a light source having a very strong intensity such as a high power laser is used. For example 40
By irradiating a compound with an absorption maximum wavelength of 1 photon at 0 nm and no absorption band at 800 nm with a high power laser with a wavelength of 800 nm, an excited state close to the excited state generated when irradiated with 400 nm light is created. be able to. If this compound emits, for example, 430 nm fluorescence when excited with 400 nm light, it also emits 430 nm fluorescence even when absorbing 800 nm light. Furthermore, when a compound that absorbs 430 nm light and emits 460 nm fluorescence coexists, it emits 460 nm fluorescence upon irradiation with 800 nm high power laser. When the laser beam is focused by a lens and irradiated, the entire optical path does not emit light, but fluorescence is emitted only in the vicinity of the focal point where the photon density is high. If a polymerization initiator and a polymerizable monomer or a polymerizable oligomer are mixed and used in place of the compound that emits fluorescence, polymerization can occur only near the focal point, and thus a solid polymer having an arbitrary shape can be produced. Also, the intensity of the focused laser beam decreases as it moves away from the center of the beam, so the portion with sufficient light intensity to cause two-photon excitation is smaller than the beam diameter and is approximately 1 / √2.
Times, that is, about 0.7 times. Therefore, there is an advantage that only a region finer than the minimum value of the beam diameter determined by the wavelength of light can be excited. The composition of the present invention thus exerts its function.

However, to the extent that it is suitable for the purposes of the present invention,
Moreover, in order for two-photon absorption to occur more efficiently than the two-photon absorption of coexisting substances such as a binder and a support, the two-photon absorption cross section is GM (Goppert-Mayers unit, ie, 1
When expressed as a unit of × 10 ^-50 cm ⁴ s molecule ^-1 photon ^-1 ), it is preferably 100 GM or more, more preferably 1,000 GM or more, and particularly preferably 100,000.
GM to 1,000,000 GM.

Examples of the two-photon absorption compound used in the present invention include the compounds described in the above-mentioned documents cited in the prior art and compounds represented by the following general formulas (1) to (5). General formula (1)

[0008]

[Chemical 1]

(Wherein R ¹ , R ² and R ⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, And a heterocyclic group, R ⁵ represents a substituent, h represents an integer of 0 to 4, and h represents
When is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different, and may combine with each other to form a ring. R ⁶ represents a substituent on two benzene rings, j is 0 to 6
When j is an integer of 2 or more, a plurality of R ^{6 s} may be the same or different, and may combine with each other to form a ring. R ⁷ represents a substituent on the benzene ring bonded to N, i represents an integer of 0 to 10, and when i is an integer of 2 or more, a plurality of R ^7's may be the same or different, and They may be linked to each other to form a ring. R ⁸ represents a substituent on the methine group, p represents an integer of 0 to 2, and p is 2
In this case, plural R ⁸ may be the same or different,
Further, they may be linked to each other to form a ring. m represents an integer of 0-5. ^XY- represents a Y-valent organic or inorganic anion, and Y represents an integer of 1 to 5. ) General formula (2)

[0010]

[Chemical 2]

(Wherein R ¹ , R ² , R ⁴ and R ⁹ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted Represents a group selected from an aryl group and a heterocyclic group, R ⁵ and R ¹⁰ represent a substituent, and h and k
Each independently represent an integer of 0 to 4, and when h and k are integers of 2 or more, a plurality of R ⁵ and R ¹⁰ may be the same or different, and are linked to each other to form a ring. Good. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ⁶ may be the same or different, and are linked to each other to form a ring. May be. m and n each independently represent an integer of 0 to 5, R ¹¹
And R ¹² represent a substituent, and s and t are each independently 0.
Represents an integer of 2 and when s and t are 2, a plurality of R ¹¹ and R ¹² may be the same or different, and may be linked to each other to form a ring. ^XY- represents a Y-valent organic or inorganic anion, and Y represents an integer of 1 to 5. ) General formula (3)

[0012]

[Chemical 3]

(Wherein R ¹ represents a group selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, and a heterocyclic group. R ¹³ and R ¹⁴ are each independently selected from a substituted and unsubstituted alkyl group, a substituted and unsubstituted alkenyl group, a substituted and unsubstituted alkynyl group, a substituted and unsubstituted aryl group, and a heterocyclic group. Represents a group, R ⁵ represents a substituent, and h represents 0 to
Represents an integer of 4, and when h is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different, and may combine with each other to form a ring. R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ^6's may be the same or different, and are linked to each other to form a ring. May be. R ⁸ represents a substituent, p represents an integer of 0 to 2 m, and when p is 2 or more, a plurality of R ⁸ may be the same or different and may be linked to each other to form a ring. . m represents an integer of 0-5. ) General formula (4)

[0014]

[Chemical 4]

(Wherein R ¹ represents a group selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, and a heterocyclic group. R ⁵ and R ¹⁰ represent a substituent, h and k each independently represent an integer of 0 to 4, and when h and k are integers of 2 or more, a plurality of R ⁵ and R ¹⁰ are the same. Or may be different from each other or may be linked to each other to form a ring, R ⁶ represents a substituent, and j is 0.
Represents an integer of ~ 6, and when j is an integer of 2 or more, a plurality of R ⁶
May be the same or different, and may be linked to each other to form a ring. m and n are independently 0 to 5
Represents an integer, R ¹¹ and R ¹² represent a substituent, and s and t
Each independently represent an integer of 0 to 2n and 0 to 2m, and s and t
When is 2 or more, a plurality of R ¹¹ and R ¹² may be the same or different and may be linked to each other to form a ring. ) General formula (5)

[0016]

[Chemical 5]

(Wherein R ¹³ and R ¹⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or a heterocycle Represents a group selected from the group, R ⁶ represents a substituent, j represents an integer of 0 to 6, and when j is an integer of 2 or more, a plurality of R ⁶ may be the same or different, and R ⁸ represents a substituent, p represents an integer of 0 to 2 m, and p is 2
In the above case, a plurality of R ⁸ may be the same or different, and may be linked to each other to form a ring. m is 0-5
Represents the integer. R ¹⁵ represents a substituted or unsubstituted heterocyclic group. )

Specific examples of the two-photon absorption compound are shown below, but the scope of the present invention is not limited to these.

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

A compound having a large two-photon absorption cross section is likely to be in a two-photon excited state, but it is necessary to devise a device that makes it easy to utilize the excitation energy according to the purpose. For example, in the case of initiating polymerization by two-photon excitation, if a compound having a large two-photon absorption cross-section is excited and the excited state has a low ability to initiate polymerization, the polymerization initiation efficiency becomes low. Therefore, either the compound having a large two-photon absorption cross section is designed to have a high polymerization initiation ability when excited, or the compound having a large two-photon absorption cross section is excited to receive the excited state energy and to be excited. It is necessary to devise a method such as imparting a high polymerization initiation ability to the compound. The properties of the two-photon absorption compound, for example, liquid or solid, or viscosity may be adjusted by using a suitable polymer binder, solvent, plasticizer and the like.
Therefore, in a preferred embodiment of the composition of the present invention, various functional compounds are used in combination with a compound having a large two-photon absorption cross section.

The fluorescence quencher used in the present invention is a compound that deactivates the excited state of the two-photon absorption compound by some mechanism. For example, (1) a compound that is excited by energy transfer from an excited state of a two-photon absorption compound, but does not substantially emit fluorescence, and (2) an electron is injected into the excited state of a two-photon absorption compound to generate excited electrons. Compounds that emit light and inhibit the return to the original state, or (3) Compounds that inhibit the excitation electron from emitting the light and returning to the original state by accepting an electron from the excited state of the two-photon absorption compound . In (1), to be excited by energy transfer from the excited state of a two-photon absorption compound, the so-called Folste
It is preferable that the requirement for r-type energy transfer to occur, that the fluorescence spectrum of the two-photon absorption compound overlaps with the absorption spectrum of the compound that emits visible fluorescence in a certain wavelength range, and 1 of these compounds is satisfied.
It is necessary that the photon excitation energy is smaller than the one-photon excitation energy of the two-photon absorption compound. In (2),
In order to be able to inject electrons into the excited state of the two-photon absorption compound, it is preferable to have an occupied orbital having a higher energy than the energy level of the highest occupied orbital of the two-photon absorption compound. In (3), in order to be able to accept an electron from the excited state of the two-photon absorption compound, it is preferable that the two-photon absorption compound has an empty orbital having a lower energy than the lowest empty orbital energy level. A compound that emits fluorescence alone can be combined to create a situation in which substantially no harmful fluorescence is emitted. For example, a compound that meets the requirements for Folster type energy transfer to occur is repeatedly subjected to multi-step energy transfer, and the compound excited at the final step of the energy transfer chain is substantially functional in the present two-photon absorption composition. If fluorescence is emitted in the wavelength range where there is no problem, a substantially non-fluorescent state can be achieved.

The fluorescence quencher used in the present invention includes:
Various ones can be used. The compound capable of receiving the excitation energy of the two-photon absorption compound has a wavelength at which the fluorescence spectrum of the two-photon absorption compound and the absorption spectrum of the compound emitting the visible fluorescence, which are requirements for so-called Folster-type energy transfer to occur. Compounds satisfying overlapping in the range are preferred. Compounds in which the excited singlet resulting from energy transfer rapidly changes into excited triplets or undergoes a chemical change such as electron transfer are preferable, but the former is more preferable because it does not cause unnecessary chemical change. As the fluorescence quencher, various compound groups can be mentioned, but as a typical example, a compound group having a strong electron accepting property (for example, nitro compounds, quinones, tetracyanoquinodimethanes, aminiums, diimmoniums), Strong electron-donating compounds (eg, hydrazines, hydrazides, hydroxylamines, hydroquinones, tetrasubstituted boron anions), compounds containing high-period elements such as heavy metal complexes (eg, metallocenes such as ferrocene, Examples thereof include bis (1,2-benzenedithiolato) nickels, heavy metal complexes of azo dyes, dipyrromethene metal complexes, porphyrin heavy metal complexes, heavy metal phthalocyanines, and heavy metal naphthalocyanines). These fluorescence quenchers may have other functions, for example, functions as a photopolymerization initiator.

Although examples of the fluorescence quencher will be given, the scope of the present invention is not limited to these.

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

In the present invention, if necessary, a polymerizable monomer or oligomer may be used in combination for imparting photocurability. Examples of the polymerizable monomer or polymerizable oligomer used include radical polymerizable compounds such as acrylic acid esters and acrylonitrile compounds, and cationic polymerizable compounds such as vinyl ethers, methylenedioxolanes and epoxides.
In particular, as the liquid photocurable resin for stereolithography, an epoxy compound is preferable because of its relatively small volume shrinkage, and a urethane acrylate resin is preferable from the viewpoint of thermal characteristics and mechanical characteristics.

Specific examples of the photocurable resin include HS-681 manufactured by Asahi Denka Kogyo, SMS manufactured by DMS-SOMOS, and SOM.
Epoxy resins such as OS8100, Japan Synthetic Rubber, SCR-8100 series, Vantico, SL-7540, etc., DEMEC, SCR-701 and Teijin Ltd., urethane acrylates such as TSR-1938. .

The polymerization initiator used in the present invention includes
Examples thereof include a radical generator that is an initiator of radical polymerization and an acid generator and a cation generator that are cationic polymerization initiators. Examples of the radical generator include halides (α-haloacetophenones, trichloromethyl and lyazines, etc.), azo compounds (azobisisobutyronitrile, etc.), aromatic carbonyl compounds (benzoin esters, ketals, acetophenone). , O-acyloxyimino ketones, acylphosphine oxides, etc.), hexaarylbisimidazoles, peroxides,
Metal arene complexes (ferrocenes, titanocenes, etc.)
Is mentioned.

As examples of the cationic polymerization initiator, compounds capable of generating an acid by light are mainly used, and examples thereof include aromatic diazonium salts (4-dodecyloxybenzenediazonium hexafluorophosphate, etc.), aromatic iodonium salts. (Di (p-tert-butylphenyl) iodonium hexafluorophosphate, trilycumyl iodonium tetrakis (pentafluorophenyl) borate, etc.), aromatic sulfonium salts (triphenylsulfonium hexafluorophosphate, etc.), metal arene complexes (Ferrocenes, titanocenes, etc.).

Examples of various photo-curable resins and various polymerization initiators are described in, for example, “Photo-curing Technology” published by Technical Information Company, 2000. Moreover, examples of radical initiators are described in JP-A-10-60296 and references cited therein.

The composition of the present invention may be liquid or solid depending on the use.

The composition of the present invention may further contain a polymer binder and a solvent, if desired. Examples of the solvent, butyl acetate, ethyl lactate, esters such as cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform; N, Amides such as N-dimethylformamide; sulfoxides such as dimethysulfoxide;
Sulfones such as sulfolane; Hydrocarbons such as cyclohexane and toluene; Ethers such as tetrahydrofuran, ethyl ether, dioxane; Ethanol, alcohols such as n-propanol, isopropanol, n-butanol / diacetone alcohol; 2,2 Fluorine-based solvents such as 3,3,3-tetrafluorobropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether. The above solvents may be used alone or in combination of two or more in consideration of the solubility of the compound used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be added to the composition of the present invention depending on the purpose.

When a polymer binder is used together as a material for the recording layer of the optical information recording medium, the amount of the polymer binder used is generally 0.01 to 50 times the amount of the two-photon absorption compound.
It is in the range of (mass ratio), preferably 0.1 to 5 times amount (mass ratio)
Is in the range. 2 in the composition thus prepared
The concentration of the photon absorbing compound is generally in the range of 0.01 to 10% by mass, preferably 0.1 to 5% by mass.

As the binder used in the two-photon absorbing composition of the present invention, conventionally known thermoplastic resins, thermosetting resins, reactive resins, electron beam curable resins, ultraviolet curable resins, visible light curable resins are used. Resins and mixtures of these are used. The thermoplastic resin has a softening temperature of 150 ° C. or lower, an average molecular weight of 10,000 to 300,000, and a degree of polymerization of about 50.
To about 2000, more preferably 200 to 700
For example, vinyl chloride vinyl acetate copolymer, vinyl chloride copolymer, vinyl chloride vinyl acetate vinyl alcohol copolymer, vinyl chloride vinyl alcohol copolymer,
Vinyl chloride vinylidene chloride copolymer, vinyl chloride acrylonitrile copolymer, acrylic ester acrylonitrile copolymer, acrylic ester vinylidene chloride copolymer, acrylic ester styrene copolymer, methacrylic ester acrylonitrile copolymer, methacrylic acid Ester vinylidene chloride copolymer, methacrylic acid ester styrene copolymer, urethane elastomer, nylon-silicone resin, nitrocellulose-polyamide resin, polyfucca vinyl, vinylidene acrylonitrile copolymer, butadiene acrylonitrile copolymer, polyamide Resin, polyvinyl butyral, cellulose derivative (cellulose acetate butyrate, cellulose diacetate, cellulose triacetate, cellulose propionate, nit Cellulose - vinegar, ethyl cellulose - vinegar,
Methyl cellulose, propyl cellulose, methyl ethyl cellulose, carboxymethyl cellulose, acetyl cellulose, etc.), styrene butadiene copolymer, polyester resin, polycarbonate resin, chlorovinyl ether acrylate copolymer, Amino resins, various synthetic rubber thermoplastic resins, and mixtures thereof are used.

Further, the thermosetting resin or the reactive resin has a molecular weight of 200,000 or less in the state of the coating liquid, and by heating and humidifying after coating and drying, the molecular weight is infinite due to reactions such as condensation and addition. Become. Further, among these resins, those which do not soften or melt before the resin is thermally decomposed are preferable. Specifically, for example, phenol resin, phenoxy resin, epoxy resin, polyurethane resin, polyester resin, polyurethane polycarbonate resin, urea resin, melamine resin, alkyd resin, silicon resin, acrylic reaction resin (electron beam curing resin), epoxy -Polyamide resins, nitrocellulosmelamine resins, mixtures of high-molecular-weight polyester resins and isocyanate prepolymers, mixtures of methacrylate copolymers and diisocyanate prepolymers, mixtures of polyester polyols and polyisocyanates, urea formaldehyde resins , Low molecular weight glycol / high molecular weight diol / triphenylmethane triisocyanate mixtures, polyamine resins, polyimine resins and mixtures thereof.
These thermoplastic, thermosetting resins, and reactive resins include carboxylic acid (COOM), sulfinic acid, sulfenic acid, sulfonic acid (SO ₃ M), as functional groups in addition to the main functional groups.
Phosphoric acid (PO (OM) (OM)), phosphonic acid, sulfuric acid (O
SO ₃ M) and acidic groups such as ester groups (M is H, alkali metal, alkaline earth metal, hydrocarbon group),
Amino acids; amphoteric groups such as aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols, sulfobetaines, phosphobetaines, alkylbetaines, amino groups, imino groups, imide groups, amide groups, etc., and hydroxyl groups, Alkoxyl group, thiol group, alkylthio group, halogen group (F, Cl, Br, I), silyl group, siloxane group,
Epoxy group, isocyanato group, cyano group, nitrile group,
An oxo group, an acryl group, and a phosphine group are usually contained in one type or more and 6 types or less, and each functional group is 1 × 10 6 per 1 g of the resin.
^-6 eq to 1 x 10 ^-2 eq is preferable. These binders may be used alone or in combination, and other additives may be added. The mixing ratio of the two-photon absorption composition of the present invention and the binder is 10 in terms of mass ratio.
The binder is preferably used in the range of 5 to 50,000 parts by mass with respect to 0 parts by mass. Dispersant as an additive,
Lubricants, antistatic agents, antioxidants, antifungal agents, colorants, solvents and the like may be added as necessary.

It is preferable to add a cross-linking agent to the two-photon absorption composition to cross-link the polymer binder to improve the morphological stability or the adherence to the support. As the cross-linking agent, a compound having a plurality of functional groups having active hydrogen atoms such as a hydroxyl group, an amino group or a carboxyl group in the polymer binder is preferable. Examples thereof include polyaldehyde, polyacid halide, polyacid anhydride, polyvinyl sulfone, cyanuric acid chloride derivative, and polyisocyanate. Of these, particularly preferred polyisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and naphthylene.
Isocyanates such as 1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate, and the isocyanate. Products of polyalcohols and polyalcohols, diisocyanate polyisocyanates formed by the condensation of isocyanates, and polyisocyanates and polyurethanes having terminal functional groups of isocyanates. The thing etc. can be used. The average molecular weight of these polyisocyanates is 100.
Those of up to 20000 are suitable. Commercially available product names of these polyisocyanates include Coronet L, Coronet HL, Coronet 2030, Coronet 2031, Millionate MR, Millionate MTL (manufactured by Nippon Polyurethane Co., Ltd.), Takenate D-102, Takenate D-110N, Takenate D-200, Takenate D-202, Takenate 300S, Takenate 500
(Manufactured by Takeda Pharmaceutical Co., Ltd.), SUMIJOUR T-80, SUMIJU
44S, Sumidule PF, Sumidule L, Sumidule N Death module L, Death module IL, Death module N, Death module HL, Death module T
65, Death Module 15, Death Module R, Death Module RF, Death Module SL, Death Module Z
4273 (manufactured by Sumitomo Bayer Co., Ltd.) and the like, and these can be used alone or in combination of two or more by utilizing the difference in curing reactivity. Further, for the purpose of accelerating the curing reaction, a compound having a hydroxyl group (butanediol, hexanediol, polyurethane having a molecular weight of 1,000 to 10,000, water, etc.), an amino group (monomethylamine, dimethylamine, trimethylamine, etc.) or a metal oxide. It is also possible to use a substance catalyst or a catalyst such as iron acetylacetonate together. It is desirable that these compounds having a hydroxyl group or an amino group are polyfunctional. These polyisocyanates are preferably used in an amount of 2 to 70 parts by weight, more preferably 5 to 5 parts by weight, per 100 parts by weight of the total amount of the polymer binder and the polyisocyanate in the two-photon absorbing composition.
It is 0 part by mass.

[0042]

EXAMPLES The present invention will be described more specifically below with reference to examples. It is easily understood by those skilled in the art that the components, ratios, operation sequences and the like shown herein can be changed without departing from the spirit of the present invention. Therefore, the present invention should not be limited to the examples below. In addition, the part in an Example represents a mass part.

Example 1 Two-photon absorption compound (14) 1 part Fluorescent quencher (Q10) 10 parts Binder (MR110T manufactured by Zeon Corporation) 200 parts Binder (UR-5500 30% manufactured by Toyobo) 280 parts Diluent (methyl ethyl ketone / cyclohexanone) = 2 /
1) 100 parts or more of 5000 parts crosslinking agent (Coronate 3041 50%) was mixed to obtain a uniform transparent liquid composition. This composition had no absorption band in the near infrared region around 780 nm. When this composition was placed in a 1 cm square quartz cell and irradiated with a laser having a wavelength of 780 nm, an average power of 10 mW, a peak power of 5 kw, a pulse width of 100 fs and a repetition frequency of 48 MHz, a change in the refractive index was observed in the irradiated part. That is, it can be seen that the change occurred due to the absorption of the near infrared laser light. When this coated product was irradiated with an ultraviolet lamp, the remarkable fluorescent color as in Comparative Example 2 was not recognized. Comparative Example 1 A liquid composition was obtained in the same manner as in Example 1 except that the two-photon absorption compound (14) was not added. This was coated on a TAC film in the same manner as in Example 1, dried and irradiated with a laser, but no change in the refractive index was observed in the irradiated portion, and the near infrared laser light was not sufficiently absorbed. I understand. When this coated product was irradiated with an ultraviolet lamp, the remarkable fluorescent color as in Comparative Example 2 was not recognized.

Comparative Example 2 Example 1 except that no fluorescence quencher was added in Example 1.
A liquid composition was obtained in the same manner as in. This was coated on a TAC film in the same manner as in Example 1, dried, and irradiated with a laser. A change in the refractive index in the irradiated portion was observed, but when irradiated with an ultraviolet lamp, the entire coating film glowed in a fluorescent color. It was observed with the naked eye.

[0045]

It can be seen that the composition of the present invention has a preferable effect that it causes a change by two-photon absorption and, at the same time, significantly suppresses the generation of fluorescence.

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[Procedure amendment]

[Submission date] August 19, 2002 (2002.8.1)
9)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

The fluorescence quencher used in the present invention is a compound that deactivates the excited state of the two-photon absorption compound by some mechanism. For example, (1) a compound that is excited by energy transfer from an excited state of a two-photon absorption compound, but does not substantially emit fluorescence, and (2) an electron is injected into the excited state of a two-photon absorption compound to generate excited electrons. Compounds that emit light and inhibit the return to the original state, or (3) Compounds that inhibit the excitation electron from emitting the light and returning to the original state by accepting an electron from the excited state of the two-photon absorption compound . In (1), in order to be excited by energy transfer from the excited state of the two-photon absorption compound, the so-called Fel
It is preferable that the requirement for star- type energy transfer to occur, that the fluorescence spectrum of the two-photon absorption compound overlaps with the absorption spectrum of the compound that emits visible fluorescence in a certain wavelength range, and 1 of these compounds It is necessary that the photon excitation energy is smaller than the one-photon excitation energy of the two-photon absorption compound. In (2), in order to be able to inject electrons into the excited state of the two-photon absorption compound, it is preferable to have an occupied orbital having a higher energy than the energy level of the highest occupied orbital of the two-photon absorption compound. In (3), in order to be able to accept an electron from the excited state of the two-photon absorption compound, it is preferable that the two-photon absorption compound has an empty orbital having a lower energy than the lowest empty orbital energy level. A compound that emits fluorescence alone can be combined to create a situation in which substantially no harmful fluorescence is emitted. For example, a compound satisfying the requirement for Forster- type energy transfer to be combined is repeatedly subjected to multi-step energy transfer, and a compound excited at the final step of the energy transfer chain is substantially functional in the present two-photon absorption composition. If fluorescence is emitted in a wavelength range that does not interfere with the above, a substantially non-fluorescent state can be achieved.

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[Document name to be amended] Statement

[Correction target item name] 0043

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Example 1 Two-photon absorption compound (14) 1 part Fluorescent quencher (Q10) 10 parts Binder (MR110T manufactured by Zeon Corporation) 200 parts Binder (UR-5500 30% manufactured by Toyobo) 280 parts Diluent (methyl ethyl ketone / cyclohexanone) = 2 /
1) 100 parts or more of 5000 parts crosslinking agent (Coronate 3041 50%) was mixed to obtain a uniform transparent liquid composition. This composition had no absorption band in the near infrared region around 780 nm. When this composition was placed in a 1 cm square quartz cell and irradiated with a laser having a wavelength of 780 nm, an average power of 40 mW, a peak power of 7 kw, a pulse width of 100 fs and a repetition frequency of 48 MHz, a change in the refractive index was observed in the irradiated part. That is, it can be seen that the change occurred due to the absorption of the near infrared laser light. When this coated product was irradiated with an ultraviolet lamp, the remarkable fluorescent color as in Comparative Example 2 was not recognized. Comparative Example 1 A liquid composition was obtained in the same manner as in Example 1 except that the two-photon absorption compound (14) was not added. This was coated on a TAC film in the same manner as in Example 1, dried and irradiated with a laser, but no change in the refractive index was observed in the irradiated portion, and the near infrared laser light was not sufficiently absorbed. I understand. When this coated product was irradiated with an ultraviolet lamp, the remarkable fluorescent color as in Comparative Example 2 was not recognized.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H111 EA03 EA04 EA21 EA33 EA37                       FA04 FB41 FB42 FB63                 4J011 QA03 QA05 QA08 QA19 QA26                       QA34 QA37 QA38 QA39 QA40                       QA46 SA01 SA07 SA31 SA51                       SA76 SA78 SA79 SA84 SA86                       SA87 UA02 WA07 WA10                 5D029 JA04

Claims (3)

[Claims] 1. A two-photon absorption cross section is 10²GM (1GM = 1 ×
Ten^-50cm^Four s mole cule ^-1 photon^-1) Two or more photon absorption
Characterized by containing a collecting compound and a fluorescence quencher 2
Photon absorption composition. 2. The two-photon absorbing composition according to claim 1, which contains a polymer binder. 3. The two-photon absorption composition according to claim 1, wherein the polymer binder is crosslinked with a crosslinking agent.