JP2003029404A - Multiple photon excited photosensitive photopolymer composition and method for exposing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive photopolymer composition capable of a photoreaction by multiple photon excitation in a transparent region. SOLUTION: The photosensitive photopolymer composition has a composition containing at least a titanocene compound sensitized by multiple photon excitation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive photopolymer composition that can be used for photocuring by irradiation with laser light and a method for exposing the same, and specifically, it utilizes multiphoton excitation in a transparent region. The present invention relates to a photosensitive photopolymer composition capable of realizing optical recording, stereolithography, photoforming, and the like, and an exposure method thereof.

[0002]

2. Description of the Related Art (1) Multiphoton absorption Normally, photoreaction is basically the irradiation light energy (light intensity).
Is a linear phenomenon, the amount of change is also constant if the irradiation light energy is constant, the so-called reciprocity law is established. However, when the light intensity increases, the deviation from the reciprocity law occurs. Among them, the most common one is that the amount of change tends to be saturated by strong exposure, which is caused by the deactivation due to the interaction between the photoexcited states.

On the other hand, there is also a phenomenon that the change becomes larger as the light intensity becomes stronger. The typical one is based on excitation by multiphoton absorption. This is due to the stepwise excitation that the electronic state exists in the intermediate state,
There is no electronic state in the intermediate state, and it can be directly classified into two types of processes, that is, excitation by a multiphoton process. The former is a phenomenon in which excitation occurs with light having a wavelength contained in the light absorption wavelength band of the irradiated substance, and the latter is a phenomenon in which excitation occurs with light in a wavelength band outside the light absorption band (this is called a transparent region). is there.

Many useful applications are conceivable if it is possible to induce the polymerization or crosslinking reaction of the photopolymer by multiphoton excitation in the transparent region.

First, if multi-photon excitation in the transparent region is used for optical shaping and optical processing, optical shaping and optical processing different from conventional ones can be performed. This is because, when the laser light is strongly focused and irradiated, the photoreaction is induced only in the strong light area near the focal point, and the light reaction does not occur in the weak light area where other light hits. To use.
In photolithography and optical processing that combines ordinary photopolymers and lasers, it is necessary to first pattern two-dimensionally and then stack them to form a three-dimensional object, while using excitation in the multiphoton process. Then, an image can be directly drawn in three dimensions by focusing a laser in the monomer, and a three-dimensional object can be directly formed without two-dimensional patterning.

Secondly, when multiphoton excitation in the transparent region is used for optical recording / storage, a photon mode recording excellent in stability and a storage medium using the same can be obtained. In so-called photon mode optical recording / memory using photochemical reaction,
Since a photochemical reaction occurs even with weak light irradiation, there is a problem that the medium changes when the medium before recording is exposed to light or when the recorded information is read after recording. On the other hand, in multi-photon excitation in the transparent region, since the light intensity has a large dependency, irradiation with weak light causes no substantial change, so that the above-mentioned difficulties can be improved.

Thirdly, when multiphoton excitation in the transparent region is used for optical recording / storage, it is expected that the resolution will be improved. This is because the sensitivity greatly depends on the light intensity, so that the change occurs more rapidly than the light distribution. For example, if the light intensity has a Gaussian distribution, its spatial extent is

[Formula 1] Can be expressed as Where Ip is the peak intensity, x is the distance, σ is the degree of spread of the distribution, and x (1 / e) = σ
Is the distance from the center where the light intensity is 1 / e. Since the n-photon process (n is an integer of 2 or more) depends on the nth power of the light intensity, its spatial distribution is

[Formula 2] And its width is 1 / n to 1/2 compared to the one-photon process.
Becomes smaller. That is, if the excitation in the multi-photon process is used, it is possible to record at a higher resolution than in the one-photon process.

As described above, if the photochemical reaction in the multiphoton process can be controlled, various merits can be considered. However, the actually confirmed photopolymer system is Nature 398, Vol.
51 (1999), J. Micromechanica1 Systems Volume 7, 411 (19
98), Optics Letters, Vol. 23, p. 1745 (1998), etc., and only a few kinds are known.

(2) Technology of Photopolymer Photopolymer is a material that has been widely used for paints, adhesives, printing plates, etc. for a long time, and has a property that a polymerization reaction or a crosslinking reaction proceeds by irradiation with light. The exposure of a normal photopolymer uses light having a wavelength existing in an absorption band corresponding to a one-photon transition to an excited state, and is a one-photon process as described above.

The photopolymer basically contains a monomer molecule responsible for a polymerization reaction, a polymerization initiator that initiates polymerization by generating active species such as radicals by light, and the like, if necessary. A binder for this purpose, a sensitizer that absorbs light to activate the polymerization initiator, and the like are also included. Further, a hydrogen donating compound component may be included for the purpose of improving the photopolymerization initiation ability.

As a photopolymerization initiator in the ordinary one-photon process, it is known that titanocene compounds are effective, as disclosed in JP-A-59-152396 and JP-A-61-151197.
No. 63-160602 and 63-4148.
No. 4 and Japanese Patent Application Laid-Open No. 3-12403. In addition, examples of the use as a combination system of titanocene compounds include titanocene and 3-ketocoumarin dye system (JP-A-63-221110), titanocene and xanthene dye, and addition polymerization containing amino group or urethane group. Systems combining ethylenically unsaturated compounds (JP-A-4-221958 and JP-A-4-219)
No. 756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061), and the like.

However, it has not yet been confirmed whether or not the titanocene compound can effectively function as a photopolymerization initiator in the multiphoton process and cause a photoreaction.

[0013]

SUMMARY OF THE INVENTION The present invention was created in view of the above-mentioned prior art. That is, the present invention is a photoreaction (photopolymerization, etc.) by multiphoton excitation in the transparent region.
It is an object of the present invention to provide a light-sensitive photopolymer composition capable of being exposed to light and a method for exposing the composition.

[0014]

Therefore, the present inventors have
As a result of intensive studies to achieve the above-mentioned object, the inventors have found that a photosensitive photopolymer composition containing a titanocene compound as a photopolymerization initiator can effectively achieve the above-mentioned object, and arrived at the present invention.

That is, the gist of the present invention resides in a photopolymer composition containing a titanocene compound and exposed to light by multiphoton excitation. Further, another gist of the present invention is to provide the photopolymer composition with pulsed laser light having a wavelength on the longer wavelength side (transparent region) than the longest absorption wavelength band in the ultraviolet and visible light regions of the photopolymer composition. A method of exposing a multiphoton excited photosensitive photopolymer composition, which comprises irradiating and exposing.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The photopolymer composition as one embodiment of the present invention is one that is exposed to light by multiphoton excitation,
(A) contains a titanocene compound as a photopolymerization initiator, and further contains (B) monomer, (C) binder, (D)
It contains a sensitizer, (E) a hydrogen donating compound, and other additives. Each of these components contained in the photopolymer composition of the present embodiment will be described in detail below.

(1) (A) Photopolymerization Initiator (Titanocene Compound) The photopolymer composition of the present embodiment generates a radical species when irradiated with an actinic ray to generate a monomer of the component (B) described later. It is characterized by containing a titanocene compound as a photopolymerization initiator for initiating the photoreaction (mainly a polymerization reaction).

Here, the titanocene compound is a compound in which two pentadiene rings and two aromatic rings other than the pentadiene ring (particularly a benzene ring or a naphthalene ring) are bonded to titanium, and in the present embodiment, the above aromatic ring is used. It is desirable that a fluorine atom be bonded to the 4th ortho position.

As the titanocene compound in this embodiment, for example, known compounds described in JP-A-59-152396 and JP-A-61-151197 can be appropriately selected and used. is there. Specifically, di-cyclopentadienyl-Ti-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,3.
4,5,6-Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-triple Oropheny
1-yl, di-cyclopentadienyl-Ti-bis-
2,6-difluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,4-difluorophenyl-
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Di-methylcyclopentadienyl-Ti-bis-
2,3,5,6-Tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-
Difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-
Il) phenyl) titanium and the like can be mentioned.
In particular, the compounds shown below are preferable. The titanocene compounds represented by these exemplified compounds may be used alone or in combination of two or more.

[0020]

[Chemical 1]

The amount of the titanocene compound used in this embodiment is usually 0.5 to 1 with respect to 100 parts by weight of the monomer (ethylenically unsaturated compound) of the component (B) described later.
A range of 00 parts by weight, preferably 1 to 80 parts by weight, more preferably 2 to 50 parts by weight is suitable.

(2) (B) Monomer The photopolymer composition of the present embodiment contains an ethylenically unsaturated compound as a monomer that polymerizes when exposed to actinic rays. This ethylenically unsaturated compound is
At least 1 radical-polymerizable ethylenically unsaturated bond in the molecule, which is capable of addition polymerization by the action of the photopolymerization initiation system containing the photopolymerization initiator, and which is crosslinked and cured in some cases, is included in the molecule.
It is a compound that has an individual.

The ethylenically unsaturated compound in the present embodiment is a compound having only one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid [here, "(meth “Acrylic” means acrylic or methacrylic, and the same applies hereinafter. ], Unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, maleic acid, itaconic acid and citraconic acid, and alkyl esters thereof, (meth) acrylonitrile,
Although it may be (meth) acrylamide, styrene, etc., the ethylenically unsaturated bond is a molecule from the viewpoint that the polymerizability and the crosslinkability and the difference in the solubility between the exposed part and the unexposed part in the developing solution can be expanded. A compound having two or more of them is preferable, and an acrylate compound whose unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferable.

Typical examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, hydroxy (meth) acrylate compounds and polyisocyanate compounds. Urethane (meth) acrylates, epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound, and (meth) acryloyloxy group-containing phosphates.

Specific examples of the esters include unsaturated carboxylic acids as described above, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol and tetra. Methylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane,
Trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, reaction products with aliphatic polyhydroxy compounds such as triethanolamine, specifically, For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth ) Acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Propane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerine Lumpur propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth)
Acrylate and the like, and cohabiting crotonate, incrotonate, maleate, itaconate, citraconeate and the like are included.

Further, as the ester thereof, a reaction product of an unsaturated carboxylic acid as described above and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F and bisphenol A, specifically, for example, hydroquinone Di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth)
Reaction products of acrylates and the like, unsaturated carboxylic acids as described above, and heterocyclic polyhydroxy compounds such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, tris (2-hydroxyethyl) Isocyanurate di (meth) acrylate, tri (meth) acrylate and the like, and reaction products of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, specifically, for example, (meth) acrylic acid and phthalate. Condensate of acid and ethylene glycol, condensate of (meth) acrylic acid and maleic acid and diethylene glycol, condensate of (meth) acrylic acid and terephthalic acid and pentaerythritol, (meth) acrylic acid and adipic acid and butane Examples thereof include a condensate of diol and glycerin.

Specific examples of the urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate. Hydroxy (meth) acrylate compounds such as tetramethylolethane tri (meth) acrylate and hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1 , 6,11-Undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octa Aliphatic polyisocyanates and the like,
Alicyclic polyisocyanates such as cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, xylylene diisocyanate,
Tetramethylxylylene diisocyanate, 4,4'-
Aromatic polyisocyanates such as diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenylmethane), tris (isocyanatophenyl) thiophosphate, and heterocyclic polyisocyanates such as isocyanurate, and polyisocyanate compounds such as And the like.

Specific examples of the epoxy (meth) acrylates include (meth) acrylic acid or the above-mentioned hydroxy (meth) acrylate compound, and (poly) ethylene glycol polyglycidyl ether, ( (Poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethyleglycol polyglycidyl ether, ( Aliphatic polyepoxy compounds such as (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novo Kkuporiepokishi compounds, brominated phenol novolac polyepoxy compound, (o-,
m-, p-) Cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds and other aromatic polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) Examples include heterocyclic polyepoxy compounds such as isocyanurate, and reaction products with polyepoxy compounds such as.

Specific examples of the (meth) acryloyloxy group-containing phosphates include:
(Meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate,
(Meth) acryloyloxyethylene glycol phosphate and the like can be mentioned.

As the other ethylenically unsaturated compound, in addition to the above, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl groups such as divinyl phthalate are included. Examples thereof include compounds. The ethylenically unsaturated compounds represented by the above exemplified compounds may be used alone or in combination of two or more kinds.

Among the above ethylenically unsaturated compounds, in the present embodiment, (meth) acryloyloxy group-containing phosphates, urethane (meth) acrylates,
Alternatively, it is preferable to use ester (meth) acrylates. The ratio of these compounds to the whole ethylenically unsaturated compound is preferably 1 to 60% by weight in the case of (meth) acryloyloxy group-containing phosphates and 10 to 10 in the case of urethane (meth) acrylates.
60% by weight is preferable, and in the case of ester (meth) acrylates, 10 to 60% by weight is preferable.

(3) (C) Binder The photopolymer composition of the present embodiment contains, in addition to the above-mentioned core components (photopolymerization initiator and monomer), modification of the composition and improvement of physical properties after photocuring. Therefore, it is preferable to further contain an organic polymer substance as a binder.

The binder in this embodiment may be appropriately selected depending on the purpose of improvement such as compatibility, film forming property, developability and adhesiveness. For example, when developing with an alkaline aqueous solution, a binder containing a carboxyl group in its side chain is used.

Specifically, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, cinnamic acid, etc. Homopolymers of carboxyl group-containing monomers such as unsaturated carboxylic acids,
And these carboxyl group-containing monomers, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) ) Acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide,
(Meth) such as N, N-dimethyl (meth) acrylamide
Acrylic acid derivatives, vinyl heterocyclic compounds such as N-vinylpyrrolidone, styrene, α-methylstyrene, vinyl aromatic compounds such as vinyltoluene, vinyl acetate,
Examples thereof include copolymers with other vinyl compounds such as vinyl chloride and the like, and comonomer such as. Two or more kinds of these carboxyl group-containing monomers and the comonomer in the copolymer may be used in combination.

Among these, (meth) acrylic acid is preferable as the carboxyl group-containing monomer. Further, the copolymer is preferably a copolymer containing (meth) acrylic acid, and the comonomer in the copolymer is (meth) acrylic such as methyl (meth) acrylate or butyl (meth) acrylate. Acid esters are preferred.

Further, the binder in this embodiment is
It is preferable to have a group that reacts with the above-mentioned monomer, such as a (meth) acrylic acid group, a vinyl group, or an allyl group, as a side chain.

That is, as a specific example of the binder in this embodiment, from the viewpoint of improving film strength and adhesiveness, a polyether of epichlorohydrin and bisphenol A; soluble nylon; polymethacrylic acid such as polymethylmethacrylate. Alkyl and alkyl polyacrylate; alkyl methacrylate and acrylonitrile, acrylic acid,
Copolymers with methacrylic acid, vinyl chloride, vinylidene chloride, styrene, etc .; Acrylonitrile with vinyl chloride, vinylidene chloride copolymers; Vinylidene chloride, chlorinated polyolefins, vinyl chloride with vinyl acetate copolymers; Polyacetic acid Vinyl; acrylonitrile / styrene copolymer; acrylonitrile / butadiene / styrene copolymer; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyamide; polyurethane;
Examples thereof include polyethylene terephthalate isophthalate; acetyl cellulose and polyvinyl butyral.

The weight ratio of the binder in this embodiment to the ethylenic compound of the component (A) is preferably 500% or less, more preferably 200%.
It can be added and mixed within the following range. Further, 10 to 4 parts by weight with respect to 100 parts by weight of the monomer of the component (B).
It is preferably 00 parts by weight, particularly preferably 20 to 200 parts by weight.

(4) (D) Sensitizer The photopolymer composition of this embodiment preferably further contains an organic dye as a sensitizer.

Examples of the sensitizer in this embodiment include dialkylaminobenzene dyes.
Sialkylaminobenzophenone dyes represented by the following general formula (I) are preferable.

[0041]

[Chemical 2]

[In the above general formula (I), R_{twenty three}, R_{twenty four},
R_{twenty five}, And R₂₆Each independently represents an alkyl group,
R₂₇, R₂₈, R₂₉, And R₃₀Each independently, Archi
Represents a hydrogen atom or a hydrogen atom. R_{twenty three}And R_{twenty four}, R_{twenty five}When
R₂₆, Or R_{twenty three}And R₂₇, R_{twenty four}And R ₂₈, R_{twenty five}And R₂₉,
Or R₂₆And R₃₀Are each independently linked to each other and condensed
It may form a ring. ]

In the above general formula (I), R ₂₃ ,
The alkyl group of R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ preferably has 1 to 6 carbon atoms. Examples of suitable sialylaminobenzophenone dyes represented by the general formula (I) include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Further, the sensitizer (organic dye) in this embodiment has a structure in which hetero atoms such as nitrogen atom, oxygen atom and sulfur atom are bonded by polymethine (—CH =) _n chain, In general, the heteroatom forms a heterocycle,
A so-called cyanine dye in a broad sense having a structure in which a heterocycle is bound via a polymethine chain as a basic structure, specifically, for example, a quinoline dye (so-called cyanine dye), an indole dye (so-called indocyanine dye), Benzothiazole-based (so-called thiocyanine-based), pyrylium-based, thiopyrylium-based, squarylium-based, croconium-based, azulenium-based, etc., and so-called polymethine having a basic structure in which an acyclic heteroatom is bonded via a polymethine chain Examples thereof include cyan dyes such as quinoline dyes, indole dyes, benzothiazole dyes, pyrylium dyes, and thiopyrylium dyes, and polymethine dyes.

In the present embodiment, among the cyanine dyes, as the quinoline dye, those represented by the following general formula (IIa), (IIb) or (IIc) are particularly preferable.

[0046]

[Chemical 3]

[In the above general formulas (IIa), (IIb), and (IIc), R ₁ and R ₂ are each independently an alkyl group which may have a substituent or a substituent. And an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent. L ₁ represents an optionally substituted tri, penta, hepta, nona, or undecamethine group. Two substituents on the penta, hepta, nona or undecamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms. The condensed benzene ring may have a substituent, and in this case, two adjacent substituents may be linked to each other to further form a condensed benzene ring. Xa ^- represents a counter anion. ]

Here, the above general formulas (IIa) and (II
When R ₁ and R _{2 in} b) and (IIc) are alkyl groups, the carbon number thereof is usually 1 to 15, preferably 1
When it is -10, an alkenyl group or an alkynyl group, its carbon number is usually 2 to 15, preferably 2 to 10.
In addition, examples of those substituents including a phenyl group include an alkoxy group having a carbon number of usually 1 to 15, preferably 1 to 10, a phenoxy group, a hydroxy group, a phenyl group, and the like, L ₁ and a condensed group. Examples of the substituent on the benzene ring include an alkyl group having the same carbon number as above.

As the indole and benzothiazole dyes, those represented by the following general formula (III) are particularly preferable.

[0050]

[Chemical 4]

[In the general formula (III), Y ₁ and Y ₂ each independently represent a cyalkylmethylene group or a sulfur atom. R ₃ and R ₄ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent Represents a phenyl group which may have. L
₂ represents a tri, penta, hepta, nona or undecamethine group which may have a substituent. Two substituents on the penta, hepta, nona or undecamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms. The condensed benzene ring may have a substituent, and in this case, two adjacent substituents may be linked to each other to further form a condensed benzene ring. Xa ^- represents a counter anion. ]

When R ₃ and R ₄ in the above general formula (III) are alkyl groups, the number of carbon atoms is usually 1 to
15, preferably 1 to 10, the number of carbon atoms in the case of an alkenyl group or an alkynyl group is usually 2 to 15, preferably 2
It is -10. Examples of those substituents including a phenyl group include an alkoxy group having usually 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, a phenoxy group, a hydroxy group, a phenyl group, and the like, L ₂ and a condensed benzene ring. Examples of the substituent in the above include an alkyl group having the same number of carbon atoms and the like.

As the pyrylium-based and thiopyrylium-based dyes, the following general formulas (IVa) and (IV
Those represented by b) or (IVc) are preferable.

[0054]

[Chemical 5]

[In the above general formulas (IVa), (IVb), and (IVc), Z ₁ and Z ₂ each independently represent an oxygen atom or a sulfur atom. R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom or an alkyl group. R ₅ and R ₇ , and R ₆ and R ₈ may be linked to each other to form a cycloalkene ring having 5 or 6 carbon atoms. L ₃ represents a mono-, tri-, penta-, or heptamethine group which may have a substituent. The two substituents on the tri, penta, or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms. The pyrylium ring and thiapyrylium ring may have a substituent, and in this case, two adjacent substituents may be linked to each other to form a condensed benzene ring. Xa ^- represents a counter anion. ]

Here, the above general formulas (IVa) and (IV
b), and R in (IVc)_Five, R₆, R ₇, And R₈But
When it is an alkyl group, its carbon number is usually 1 to 15,
It is preferably 1 to 10. Also, L₃Substituents on
Include an alkyl group having the same number of carbon atoms as above.
As Substituents on the Ring and Thiopyrylium Ring
Examples include aryl groups such as phenyl groups.

As the polymethine dye,
What is represented by the following general formula (V) is preferable.

[0058]

[Chemical 6]

[In the above general formula (V), R ₉ , R ₁₀ ,
R ₁₁ and R ₁₂ each independently represent an alkyl group.
R ₁₃ and R ₁₄ each independently represent an aryl group, a furyl group, or a thienyl group which may have a substituent.
L ₄ is optionally substituted mono, tri, penta,
Alternatively, it represents a heptamethine group. The two substituents on the tri, penta, or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms.
The quinone ring and the benzene ring may have a substituent. Xa ^- represents a counter anion. ]

Here, R ₉ , R ₁₀ , R ₁₁ in the formula (V),
And the carbon number of the alkyl group of R ₁₂ is usually 1 to 15,
Preferably, the number of carbon atoms when 1 to 10, R ₁₃ and R ₁₄ are aryl groups is usually 6 to 20, and preferably 6 to 1.
It is 5. Specific examples of R ₁₃ and R ₁₄ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-furyl group, a 3-furyl group, a 2-thienyl group, and a 3-thienyl group. Examples of the substituent include an alkyl group having the same number of carbon atoms, an alkoxy group having the same number of carbon atoms, a dialkylamino group, a hydroxy group, and a halogen atom. Examples of the substituents on L ₄ , the quinone ring, and the benzene ring include alkyl groups having the same carbon number as above.

The above general formulas (IIa-c) and (II
Specific examples of the counter anion Xa ⁻ in I), (IVa to c), and (V) include Cl ⁻ , Br ⁻ ,
Inorganic acid anions such as I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , and inorganic boronic acids such as BF ₄ ⁻ and BCl ₄ ⁻ ,
And benzene sulfonic acid, toluene sulfonic acid,
Naphthalene sulfonic acid, acetic acid, and methyl, ethyl,
Examples thereof include organic acid anions such as organic boric acid having an organic group such as propyl, butyl, phenyl, methoxyphenyl, naphthyl, fluorophenyl, difluorophenyl, pentafluorophenyl, thienyl and pyrrolyl.

The sensitizer in this embodiment is preferably a compound having a ketone conjugated with a π-electron conjugated system and an amino group bonded with a methylene group.
The photopolymer composition of the present embodiment, in addition to the above-described titanocene-based compound as a photopolymerization initiator, also has such a compound as a sensitizer, so that a photoreaction by multiphoton excitation can be more efficiently generated. Become. Therefore,
The quinoline type represented by the general formula (IIa to c), the indole type or benzothiazole type represented by the general formula (III), and the pyrylium type or thiopyrylium represented by the general formula (IVa to c) described above. Among the cyanine-based dyes such as those of the system and the polymethine-based dyes represented by the general formula (V), the polymethine-based dye represented by the general formula (V) is particularly preferable in the present embodiment.

Specific examples of the cyanine dye or the polymethine dye which are particularly preferable as the sensitizer in the present embodiment are shown below.

[0064]

[Chemical 7]

[0065]

[Chemical 8]

[0066]

[Chemical 9]

[0067]

[Chemical 10]

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

In the above specific example, the counter anion X
a ⁻ is specifically Cl ⁻ , Br ⁻ , I ⁻ , CO ₄ ⁻ , PF
₆ ^-, BF ₄ ^-, a p- toluenesulfonic acid or 1-naphthalenesulfonic acid.

Further, the above-mentioned general formulas (IIa to c) and (II
I), (IVa-c), and L ₁ , L ₂ in (V),
_On the polymethine chain of L ₃ and L ₄ , the following general formula (VI)
By having a barbituric acid anion group or a thiobarbituric acid anion group represented by as a substituent, or in the polymethine chain of L ₁ , L ₂ , L ₃ and L ₄ represented by the following general formula (VII) It is also preferable that a square acid anion group or a thiosquare acid anion group, or a croconate anion group or a thiocroconate anion group represented by the following general formula (VIII) is formed to form an inner salt. .

[0075]

[Chemical 16]

[The above general formulas (VI), (VII), and
Z in (VIII)₃, Z_Four, Z_Five, Z₆, Z₇, And Z₈Is each
Each independently represent an oxygen atom or a sulfur atom, R₁₉And
And R ₂₀Each independently have a hydrogen atom and a substituent.
Alkenyl which may be substituted, Alkeni which may have a substituent
Group, an alkoxy group which may have a substituent, or
The phenyl group which may have a substituent is shown. ]

When R ₁₉ and R ₂₀ in the above general formula (VI) are an alkyl group or an alkoxy group, the number of carbon atoms is usually 1 to 15, preferably 1 to 5, and an alkenyl group. The carbon number of is usually 2 to 15, preferably 2 to 5, but is preferably an alkyl group, and specific examples of the alkyl group include a methyl group, an ethyl group,
Examples thereof include a propyl group and a butyl group.

Further, as the sensitizer in this embodiment, a so-called phthalocyanine dye having a basic structure of a heterocycle bonded through an azapolymethine chain can also be mentioned. As the phthalocyanine dye, the following general formula (I
Those represented by X) are preferred.

[0079]

[Chemical 17]

[In the above general formula (IX), R ₂₁ and R ₂₂
Each independently represents an alkoxy group, a thioalkoxy group, an aryloxy group, a thioaryloxy group, an alkylamino group, an arylamino group, a halogen atom, or a hydrogen atom, and M represents Zn, Cu, Ni, SnCl ₂ , Al
Indicates Cl or a hydrogen atom. Two adjacent substituents on the benzene ring may be linked to each other to form a condensed ring. ]

When R ₂₁ and R ₂₂ in the general formula (IX) are an alkoxy group, a thioalkoxy group or an alkylamino group, the carbon number thereof is usually 1 to 1.
It is 0, preferably 1-4. As the aryloxy group, thioaryloxy group, or arylamino group,
Examples thereof include a phenoxy group, a thiophenoxy group, a phenylamino group, and the like, and M is Zn or S.
It is preferably nCl ₂ .

Further, as the sensitizer in this embodiment, for example, triphenylmethane type leuco dyes such as leuco crystal violet and leuco malachite green disclosed in US Pat. No. 3,479,185, erythrosine and eosin Y, etc. Dyes, aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in US Pat. Nos. 3,549,367 and 3,652,275, and US Pat. No. 38,447.
Β-diketones disclosed in Japanese Patent No. 90, indanones disclosed in US Pat. No. 4,162,162, JP-A-6-301208, JP-A-8-129258,
JP-A-8-129259, JP-A-8-146605
And the coumarin dyes disclosed in JP-A-8-212605, the ketocoumarin dyes disclosed in JP-A-52-112681, and JP-A-59-56.
Aminostyrene derivatives and aminophenylbutadiene derivatives disclosed in Japanese Patent No. 403, U.S. Pat. No. 4,594.
310, aminophenyl heterocycles,
Julolidine heterocycles disclosed in U.S. Pat. No. 4,966,830, JP-A-5-241338, JP-A-7
Compounds such as the pyrromethene dyes disclosed in JP-A-5685 and JP-A-10-144242 can be mentioned.

The content of the sensitizer in this embodiment is usually 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the monomer of the component (B), and further, A range of 0.2 to 10 parts by weight is preferable.

(5) (E) Hydrogen Donating Compound The photopolymer composition of the present embodiment has a hydrogen donating property for the purpose of improving the photopolymerization initiation ability in addition to the components (A) to (D). It preferably contains a compound.

The hydrogen-donating compound is, for example,
2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole,
3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate. And other mercapto group-containing compounds, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate and other multifunctional thiol compounds, N, N-dialkylaminobenzoic acid esters, N-phenylglycine, Or a salt thereof such as ammonium or sodium salt, a derivative such as an ester of the same as above,
Examples thereof include phenylalanine, salts thereof such as ammonium and sodium salts thereof, amino acids having an aromatic ring such as derivatives such as esters, and derivatives thereof.

As the hydrogen donating compound in this embodiment, aminobenzoic acid ester is preferable. In the photopolymer composition of the present embodiment, in addition to the above-described titanocene-based compound as a photopolymerization initiator, by using an aminobenzoic acid ester in combination as a hydrogen-donating compound, the photoreaction by multiphoton excitation can be performed more efficiently. Will occur. Therefore, among the exemplified compounds described above, N, N
-Dialkylaminobenzoic acid esters are preferred.

As the hydrogen donating compound in this embodiment, the following compounds are specifically preferable.

[Chemical 18]

(6) Other Additives In addition to the above components, the photopolymer composition of the present embodiment may further contain various additives such as hydroquinone, p-methoxyphenol, 2,6-di-, and the like, if necessary. Thermal polymerization inhibitor such as t-butyl-p-cresol, dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, dioctyl adipate, plasticizer such as triethylene glycol dicaprylate, adhesion improver such as silane coupling agent The coating composition may contain various commonly used additives such as a coating property improver, a developability improver, a sensitivity improver and an oil sensitizer.

(7) Form of Use The form of use of the photopolymer composition of the present embodiment as a photosensitive material is, for example, without solvent or diluted with a suitable solvent and applied on the surface of a support. , A dried form, or a form in which an overcoat layer for blocking oxygen is further provided thereon, a form in which droplets are dispersed in a heterophasic medium and applied in multiple layers as a plurality of types of photosensitive materials, and encapsulated in microcapsules The photopolymer composition of the present embodiment may be applied on the surface of the support as a solution prepared by dissolving the composition in a suitable solvent, and then heated and dried. Therefore, the use form in which the layer of the photopolymer composition of the present embodiment is formed on the surface of the support is preferable.

The solvent is not particularly limited as long as it has a sufficient solubility for the components used and gives a good coating property. For example, methyl cellosolve,
Cellosolve solvents such as ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate , Propylene glycol solvents such as dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, Ester solvent such as methyl 3-methoxypropionate, heptanol Hexanol, diacetone alcohol, alcohol solvents such as furfuryl alcohol, cyclohexanone, ketone solvents such as methyl amyl ketone,
Examples thereof include highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, mixed solvents thereof, and further aromatic hydrocarbons added thereto. The proportion of the solvent used is usually 1 to 20 by weight with respect to the total amount of the photopolymer composition of the present embodiment.
It is about double the range.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used.

The photosensitive material using the photopolymer composition of the present embodiment can be exposed to an image and then the unexposed portion of the photosensitive layer can be removed with a developing solution to obtain a desired image. As a preferable developing solution, Japanese Patent Publication No. 57-7427
Examples of the developer include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, and tribasic phosphoric acid. Aqueous solutions of inorganic alkaline agents such as ammonium, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkaline agents such as monoethanolamine or diethanolamine are suitable. These organic alkaline agents are added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

The above alkaline aqueous solution may contain a small amount of a surfactant and an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol, if necessary. For example, US Pat.
Nos. 71 and 3615480 can be mentioned. Furthermore, JP-A-50-
No. 26601, No. 58-54341, Japanese Patent Publication No. 56-3
The developing solutions described in Japanese Patent Nos. 9464 and 56-42860 are also excellent.

Depending on the intended use of the photopolymer composition of this embodiment, it is possible to directly irradiate the liquid photopolymer composition with a laser beam instead of forming a thin film. In this case, the composition in the coating liquid is sandwiched between containers or substrates, or fixed by lowering the fluidity by making it a highly viscous composition and irradiating it with laser light to induce a photochemical reaction. Let For example, a three-dimensional shape directly scanned with a laser beam and cured can be taken out by washing away the unirradiated non-solidified portion.

(8) Example of Utilization The photopolymer composition of the present embodiment and the photosensitive material such as a film formed by using the composition are various in the wavelength range from ultraviolet to visible light depending on the type. However, in order to cause multiphoton excitation in the transparent region of the present composition and photosensitive material, it is necessary to use a laser having a relatively large optical power.

Suitable as such a laser is a mode-locked laser, a Q-switched laser, a combination thereof, and a laser obtained by further amplifying the light of these pulsed lasers by an optical amplifier. Examples of such things are mode-locked titanium sapphire laser, mode-locked YAG laser, Q-switched YAG laser, Q-switched ruby laser, mode-locked Q-switched YAG.
A laser etc. are mentioned. Further, in order to increase the light intensity, it is preferable to focus the light with a lens, but in the case of light having a temporally high power such as a femtosecond laser, it is not necessary to focus strongly.

When the present composition and the light-sensitive material undergo multiphoton absorption by the above-mentioned exposure using a laser, an excited state is generated, and fluorescence is observed. In the case of normal fluorescence, light emission occurs on the longer wavelength side than the excitation light, whereas fluorescence due to this multiphoton absorption often shows fluorescence on the shorter wavelength side than the excitation light. Observation is easy.

Therefore, when the composition or the photosensitive material is irradiated with the pulsed laser light for exposure, the laser light of the composition or the photosensitive material is irradiated under the condition that fluorescence is observed at the irradiation position of the laser light. Irradiation is preferred. This makes it possible to perform the exposure operation while easily confirming that the multiphoton excitation is surely generated in the transparent region during the exposure operation by the laser light irradiation.

Specifically, the fluorescence is observed at the irradiation position by directly changing the intensity of the irradiation laser light or by changing the focal position to change the focusing degree of the laser light at the irradiation position. The irradiation conditions of the laser light are determined, and the exposure is performed under the conditions. Fluorescence can be visually confirmed in some cases, but it can be more sensitively and quantitatively confirmed by using a photodetector such as a photomultiplier tube.

When an image is formed by exciting the composition or the light-sensitive material by multiphoton excitation in the transparent region, at least the laser beam irradiated during exposure and the composition or the light-sensitive material to be exposed. A desired image can be formed by scanning one side. In the case of a laser that can obtain a sufficient intensity without focusing light, it is possible to expose an image in a certain range or expose an interference fringe.
Three-dimensional scanning is also possible using the non-linearity of photochemical reaction sensitivity due to multiphoton absorption. In this case, a thick film having a thickness of 10 μm or more is formed in the composition or the photosensitive material, and exposure is performed by controlling the position in the film thickness (Z) direction in addition to the in-plane (X, Y) direction. It is possible to perform complicated three-dimensional processing. Examples of applications of such three-dimensional processing include production of three-dimensional optical waveguide elements, production of photonic crystals, production of parts for micromachines, three-dimensional information recording, production of volume holograms, and the like.

As described above, according to this embodiment, laser light (especially pulsed laser light) having a wavelength on the longer wavelength side (transparent region) than the longest absorption wavelength of the light absorption band is irradiated for exposure. As a result, it is possible to efficiently and surely cause a photoreaction (photopolymerization or the like) due to multiphoton excitation, and to cause photocuring only in a target portion with high accuracy. Therefore, when the composition and the light-sensitive material are applied to the fields of stereolithography, photoforming, optical recording, etc., various effects based on multiphoton excitation in the transparent region can be enjoyed.

For example, when the present composition or photosensitive material is used in the field of stereolithography or photoforming, a desired image can be directly drawn in three dimensions by focusing a laser, and two-dimensional patterning can be performed. It is possible to directly form a three-dimensional object without intervention. Further, when used in the field of optical recording / storage, the problem of photon mode recording / storage due to ultraviolet light or visible light can be improved, and photon mode optical recording / storage with excellent stability becomes possible. Optical recording / storage with high resolution is realized.

When the photopolymer composition of this embodiment or a photosensitive material using the same is exposed,
It is preferable to use pulsed laser light having a wavelength on the longer wavelength side of 100 nm (nanometers) or more than the longest absorption wavelength of the light absorption band, and irradiate the composition or the photosensitive material with the pulsed laser light. By using such pulsed laser light, it is possible to reliably generate only multiphoton excitation in the transparent region without single-photon excitation or stepwise multiphoton excitation based on light in the ultraviolet / visible region. .

[0104]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded, and does not depart from the gist of the present invention. Can be variously modified and implemented. (1) Manufacturing example

[Table 1]

A coating solution of the multiphoton-excited photosensitive photopolymer composition of the present invention was prepared on the basis of the composition shown in Table 1 above, and the coating solution was coated on a slide glass with a wire bar to give a thickness of 1.5 μm. A photopolymer film having a thickness of 100 nm was formed.

(2) Example Using a mode-locked titanium sapphire laser manufactured by Spectra Physics, Inc., 800 nm, 80 MHz, 150
A femtosecond laser beam was generated and an exposure experiment was performed using this laser beam.

After placing the slide glass on which the above-mentioned photopolymer film was formed on the stage of the optical microscope, the intensity of the laser beam was adjusted to 15 mW and the laser beam was introduced into the optical microscope. The light was collected on the photopolymer film on the slide glass. When the stage was moved up and down (parallel to the incident angle of laser light),
When the focus of the laser beam was close to the photopolymer film, bluish white fluorescence was visually observed, and it was recognized that the photopolymer film was photoexcited by multiphoton absorption.

The stage was fixed in a state where the above-mentioned bluish white fluorescence was observed, the laser beam was focused on the photopolymer film, and the stage was moved horizontally at a speed of 250 μm / sec (with respect to the incident angle of the laser beam). Vertical) 5
Lines with a length of mm were drawn in parallel at intervals of 0.1 mm. FIG. 1 shows an image obtained by exposing and drawing a photopolymer composition on a slide glass using a laser beam.

After that, 3% by weight of potassium silicate A and an anionic surfactant (Perex NBL, manufactured by Kao Corporation)
When it was immersed in a 5 wt% aqueous solution and developed at room temperature for 30 seconds and then washed with water, it was visually confirmed that the laser-exposed portion of the photopolymer film was cured and remained on the slide glass.

With respect to the curing pattern of the photopolymer film remaining on the slide glass, the step difference existing in the direction perpendicular to the surface of the slide glass was measured by using Alpha step manufactured by Tencor. The measurement result between the line segment AB on the slide glass shown in FIG. 1 is shown in the graph of FIG. The horizontal axis of the graph represents coordinates in the horizontal direction of the slide glass surface (unit: μm), and the vertical axis of the graph represents coordinates in the vertical direction with respect to the surface of the slide glass (unit: μm). The abscissa coordinates are over 200 μm, over 300 μm, and 4
In the vicinity of a little over 00 μm, there is a step of about 1.5 μm in the direction perpendicular to the surface of the slide glass. That is,
It was confirmed that the photopolymer film on the image drawn by laser exposure was cured and remained on the slide glass.

(3) Comparative Example A photopolymer film on a slide glass was prepared under the same conditions as in the above example except that the position of the focal point of the irradiation laser beam was shifted so that the fluorescence was not observed as described above. After exposure, drawing and development, nothing was left on the slide glass. Therefore, photocuring does not occur under the condition that multiphoton absorption does not occur.

[0112]

As described above in detail, according to the multiphoton-excited photosensitive photopolymer composition of the present invention, a composition containing a titanocene compound as a photopolymerization initiator and exposed to multiphoton excitation is provided. Therefore, the multi-photon excitation in the transparent region is achieved by irradiating the composition with pulsed laser light having a wavelength longer than the longest absorption wavelength band in the ultraviolet and visible light regions (transparent region). A light reaction utilizing is realized.

Therefore, by using the composition and the exposure method of the present invention, various effects based on multiphoton excitation in the transparent region can be enjoyed in the fields of stereolithography, photoforming, optical recording and the like. For example, if the present invention is applied to stereolithography or photoshaping, it is possible to directly fabricate a three-dimensional object without using two-dimensional patterning. Further, when the present invention is used for optical recording / storage by using multiphoton excitation in the transparent region, the drawbacks of the photon mode recording / storage can be improved, and the photon mode optical recording / storage with excellent stability can be realized. Optical recording / storage at high resolution is realized.

[Brief description of drawings]

FIG. 1 is a schematic diagram for explaining an image obtained by exposing a photopolymer composition on a slide glass with a laser beam in an example of the present invention.

FIG. 2 is a graph showing the presence of a photopolymer composition photocured on a slide glass by exposure in an example of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA01 AB14 AB20 AC08 AD01                       BC13 BC42 CA00 CA39 CC20                 2H097 CA17 FA02 GB04 LA20                 4J011 AC04 QA01 QA02 QA03 QA04                       QA05 QA06 QA09 QA14 QA21                       QA22 QA23 QA24 QA25 QA33                       SA21 SA25 SA72 SA75 SA78                       SA83 SA85 SA88 UA02 WA01                       WA02

Claims (6)

[Claims] 1. A photopolymer composition comprising a titanocene compound and is exposed to light by multiphoton excitation. 2. The photo according to claim 1, wherein the photopolymer composition further contains a compound having a ketone conjugated to a π-electron conjugated system and an amino group to which a methylene group is bonded. Polymer composition. 3. The photopolymer composition according to claim 1, wherein the photopolymer composition further contains an aminobenzoic acid ester compound. 4. A pulsed laser beam having a wavelength on the longer wavelength side than the longest absorption wavelength in the ultraviolet and visible light regions of the photopolymer composition according to claim 1. A method for exposing a multiphoton-excited photosensitive photopolymer composition, which comprises irradiating an object to be exposed. 5. The multiphoton excitation according to claim 4, wherein the photopolymer composition is irradiated with a pulsed laser beam having a wavelength longer than the longest absorption wavelength by 100 nm (nanometer) or more. A method for exposing a photosensitive photopolymer composition. 6. The multiphoton-excited photosensitivity according to claim 5, wherein the photopolymer composition is irradiated with the pulsed laser light under the condition that fluorescence is observed at an irradiation position with respect to the photopolymer composition. A method for exposing a photopolymer composition.