JP2001282082A - Hologram recording material composition, hologram recording medium and producing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram recording material composition which exhibits excellent transparency and resolution, etc., the same as the conventional one and enables recording transmission type and reflection type holograms in the high efficiency of refraction. SOLUTION: This recording material composition is prepared by mixing diallylorthophthalate prepolymer 5 g, an acrylic acid adduct of 9,9-bis(4- hydroxyphenyl)fluorene glycydilether 1 g, 3,3',4,4'-tetra(tert-butylperoxyphenyl) benzophenone 3.5 g, merocyanine pigment 0.01 g, diethylsebacate 4 g and acetone 6 g at ordinary temperature. The composition is applied on a glass substrate in such a manner that the thickness after drying gets to 20 μm, solvent is removed from the coated layer under vacuum and the recording medium of a two-layer structure which is composed of the substrate and the recording layer is formed. Further, a glass substrate which is the same as above described one is covered on the recording layer and thus a photosensitive plate of a three- layer structure for hologram recording is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel hologram recording material composition, and more particularly to a hologram recording material composition capable of producing a recording medium having excellent diffraction efficiency, which is one of the basic characteristics required for holograms. Furthermore, the present invention relates to a hologram recording medium obtained therefrom and a method for producing the same.

[0002]

2. Description of the Related Art A hologram is a hologram in which an interference pattern of coherent light of a laser is recorded on a photosensitive material or the like. It has been used throughout.

As typical conventional hologram recording material compositions, there are known a dichromated gelatin photosensitive material and a bleached silver salt photosensitive material (for example, "Display Holography Handbook", pp. 66-67, Dawn Stamp Library (1985), "Optical Engineering Handbook", No. 351
-353 pages, Asakura Shoten (1986)).

However, although dichromated gelatin has a high diffraction efficiency and bleached silver salt photographic materials have high sensitivity, all of these are complicated in the processing of hologram production, and particularly require wet development. There was a disadvantage that it was required.

A hologram recording material composition containing a photopolymerizable monomer has been proposed as a photosensitive material for overcoming such disadvantages. This is to record a hologram by photopolymerizing a photopolymerizable monomer in a portion of the interference pattern where the amount of light is large, thereby causing a refractive index modulation in that portion. For example, a photopolymerizable recording material containing cyclohexyl methacrylate as a photopolymerizable monomer, N-vinylcarbazole and a photopolymerization initiator as main components, or
Photopolymerizable recording materials containing butyl methacrylate and ethylene glycol dimethacrylate as photopolymerizable monomers, 1-phenylnaphthalene as an inactive component not involved in polymerization and a photoinitiator as main components (Applied Optics (Applied Optics) Appl. Opt.), Volume 15, 534
P. (1976)).

However, since these materials are liquid, the composition flows between the two surface materials during hologram recording, which hinders good recording. Further, even after the hologram recording, a portion having a small amount of light remains as an unreacted monomer, and it is necessary to stabilize the recording by performing a whole-surface exposure process again.

Incidentally, JP-A-3-36582 and JP-A-3-249885 disclose holograms containing, as main components, an allyl monomer and an acrylic monomer having different polymerization reactivity and refractive index of the obtained polymer. A recording material composition is described. After the composition is injected between two surface materials, the composition is subjected to a heat treatment to suppress the fluidity of the composition and solve the above problems.

However, these hologram recording material compositions require a heat treatment as described above in order to fix them between two surface materials, and thus the film forming operation is complicated. There was a disadvantage.

Japanese Patent Application No. 11-225446 discloses an allyl prepolymer (A) having at least one allyl group in the molecule and a (meth) acrylate having at least one polymerizable unsaturated group in the molecule. It describes a hologram recording material composition comprising a compound (B) and a photopolymerization initiator (C). This material did not require fixing by heating or the like before recording, the film forming operation was easy, and the recording property was not unclear due to re-diffusion after recording.

However, when a (meth) acrylate-based compound having a refractive index of a simple substance lower than that of an allyl-based prepolymer is used, the transmission hologram has high sensitivity, high diffraction efficiency, and high transparency. Although holograms were obtained, reflection holograms have the disadvantage of low sensitivity and low diffraction efficiency.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hologram material comprising an allyl-based prepolymer, a radical polymerizable compound and a photopolymerization initiator. Is to provide a hologram recording material composition capable of recording transmission holograms and reflection holograms with high diffraction efficiency while exhibiting the same as conventional products.

[0012]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found the following novel hologram recording material composition and completed the present invention.

That is, the hologram recording material composition according to the present invention comprises an allyl prepolymer (A) soluble in a solvent having at least one allyl group in the molecule, a radical polymerizable compound (B), Agent (C) and photopolymerization initiator
(D).

The radical polymerizable compound (B) includes a fluorene compound [I] and a sulfide cyclic compound [I
I], 10 to 100% by weight of at least one radical polymerizable compound (B1) selected from the group consisting of a halogenated cyclic compound [III] and a carbazole compound [IV], a fluorene compound [I] and a sulfide compound Cyclic compound [I
I], at least one radical polymerizable compound (B2) other than the halogenated cyclic compound [III] and the carbazole compound [IV], in an amount of 0 to 90% by weight.

The fluorene compound [I] has the general formula

Embedded image [Wherein, R ₁ and R ₂ represent the same or different monovalent organic groups, and at least one of them has a radical polymerizable group at a terminal. M ₁ and M ₂
Are the same or different from each other and are represented _by- (OR) _n1- (R
Represents a hydroxyl group and / or a lower alkylene group optionally having an oxygen atom, and n1 represents a divalent organic group or a single bond represented by 0 or an integer of 1 to 5). X ₁ and X ₂ are the same or different from each other and represent a halogen atom, a hydroxyl group, or a lower alkyl group. ].

The sulfide-based cyclic compound [II] has the general formula

Embedded image [In the formula, R ₃ and R ₄ represent the same or different monovalent organic groups, and at least one of them has a radical polymerizable group at a terminal. M ₃ and _{M 4}
Are the same or different from each other and are represented _by- (OR) _n2- (R
Represents a hydroxyl group and / or a lower alkylene group optionally having an oxygen atom, and n2 represents 0 or an integer of 1 to 5) or a divalent organic group or a single bond. X ₃ is a substituent of a ring, the same or different from each other, a halogen atom, a hydroxyl group or a lower alkyl group, 1 represents the number 0 to 6 of X ₃ , Y ₁ represents a plurality of atoms constituting the ring, It is a carbon atom or some are carbon atoms and the rest are heteroatoms. m is 5-8 ring members. ].

The halogenated cyclic compound has the general formula [III]

Embedded image [In the formula, X ₄ is a substituent of a ring, the same or different from each other, at least one is a halogen atom, and the other is a hydroxyl group or a lower alkyl group. q is an integer of 2 to 6, and R ₅ is the same or different monovalent organic group, at least one of which has a radical polymerizable group at the terminal. M ₅ is - (OR) n3 _(R is hydroxyl group and / or substituted lower alkylene group optionally having an oxygen atom, n3 is 0 or an integer of 1 to 5) a divalent organic group or a single bond represented by means. p is an integer of 1-4, Y
₂ is a plurality of atoms constituting a ring, all of which are carbon atoms, or a portion of which is a carbon atom, and the remainder are heteroatoms. k has 5 to 8 ring members. ].

The carbazole compound has the general formula [IV]

Embedded image [Wherein, R ₆ , R ₇ and R ₈ represent the same or different monovalent organic groups, and at least one of them has a radical polymerizable group at a terminal. M ₆ , M ₇
And M ₈ are the same or different from each other, and-(O
R) _n4- (R is a hydroxyl group and / or a lower alkylene group optionally having an oxygen atom, n4 is 0 or 1 to 5
An integer) or a divalent organic group or a single bond. X ₅ and X ₆ are ring substituents, which are the same or different from each other, and represent a halogen atom, a hydroxyl group or a lower alkyl group. ].

The weight ratio of the allylic pull polymer (A), the radical polymerizable compound (B) and the viscosity reducing agent (C) is (A):
(B) :( C) = 80-20: 3-60: 3-60, preferably (A) :( B) :( C) = 75-30: 5-50: 5-5
0, and the viscosity reducing agent (C) is an allyl-based pull polymer.
A compound (C1) that is non-reactive with (A) and the radically polymerizable compound (B), or a compound (C2) having a (meth) allyl group in the molecule, and the radically polymerizable compound (B
The weighted average of the refractive indices of 1) and the radical polymerizable compound (B2) is the refractive index and viscosity reducing agent of the allylic prepolymer (A) (C)
Is greater than the weighted average of the refractive indices.

Allyl prepolymer used in the present invention
(A) is a prepolymer having at least one allyl group in the molecule, and a typical example thereof is a diallyl phthalate prepolymer. The allyl-based prepolymer (A) may be a homopolymer of an allyl-based monomer, or may be a copolymer of the same monomer with another monomer copolymerizable with the same monomer.

The starting material diallyl phthalate monomer of the diallyl phthalate prepolymer is a compound selected from the group consisting of diallyl orthophthalate monomer, diallyl isophthalate monomer and diallyl terephthalate monomer, or a combination of two or more thereof. To obtain a diallyl phthalate-based prepolymer by homopolymerization of a diallyl phthalate-based monomer, for example,
A known polymerization reaction described in JP-A-16035 may be performed. Further, in order to obtain a diallyl phthalate-based prepolymer by copolymerizing a diallyl phthalate-based monomer with a diallyl phthalate-based monomer and another monomer copolymerizable with the same monomer, for example, Industrial Chemistry Magazine, Vol. 70, No. 3, pages 360 to 364 (1967)
) May be performed.

As the other monomer copolymerizable with the diallyl phthalate monomer, an aromatic compound having an ethylenic double bond, an aliphatic compound having an ethylenic double bond, or a (meth) allyl compound can be used. it can.

Examples of the aromatic compound having an ethylenic double bond include styrene, α-methylstyrene, divinylbenzene, vinyl biphenylcarboxylate, benzyl methacrylate, phenoxyethyl methacrylate, phenoxyethyl acrylate, and 2-hydroxy-3-acrylate. Phenoxypropyl acrylate is exemplified.

Examples of the aliphatic compound having an ethylenic double bond include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, and n-lauryl methacrylate.
-Stearyl methacrylate, methoxydiethylene glycol methacrylate, cyclohexyl methacrylate,
Tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl Methacrylate, tert
-Butyl methacrylate, isostearyl methacrylate, n-butoxyethyl methacrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxyethylene glycol acrylate, methoxytriethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2- Mono (meth) acrylates such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, and vinyl acetate are exemplified. .

Examples of (meth) allyl compounds include (meth) allyl alcohol, (meth) allyl chloride, (meth) allyl acetate, (meth) allyl benzoate, (meth) allyl isovalerate, and (meth) allyl compound. ) Allyl, (meth) allyl caproate, (meth) allyl formate, (meth) allyl cinnamate, (meth) allyl salicylate, (meth) allyl dihydrojasmate, (meth) allyl phenylacetate, (meth) propionate Allyl, (meth) allyl butyrate, mono (meth) allyl adipate, mono (meth) allyl sebacate, mono (meth) phthalate
Allyl ester, mono (meth) allyl isophthalate, mono (meth) allyl terephthalate, mono (meth) allyl succinate, trimellitate mono (meth) allyl ester, mono (meth) allyl succinate, ricinoleic acid Mono (meth) allyl ester, mono (meth) allyl maleate, di (meth) allyl adipate, di (meth) allyl sebacate, di (meth) allyl phthalate, di (meth) allyl isophthalate, terephthalic acid Di (meth) allyl, di (meth) allyl succinate, trimellitdi (meth) allyl, di (meth) allyl succinate, di (meth) allyl ricinoleate,
Examples thereof include di (meth) allyl maleate, tri (meth) allyl phosphate and tri (meth) allyl isocyanurate.

In the above-mentioned copolymer, usually, a diallyl phthalate-based structural unit is mainly used.

The allylic prepolymer (A) is, in addition to the above,
A homopolymer of a triallyl isocyanurate monomer or a copolymer of the same monomer with another monomer copolymerizable with the same monomer may be used. Examples of other monomers copolymerizable with the triallyl isocyanurate monomer include the above-described aromatic compounds having an ethylenic double bond, aliphatic compounds having an ethylenic double bond, and (meth) allyl compounds. Is done.

Allyl prepolymer used in the present invention
Examples of (A) include a diallyl orthophthalate prepolymer which is a homopolymer, for example, "Disodap" (registered trademark) manufactured by Daiso Corporation, a diallyl isophthalate prepolymer such as "Isodap" (registered trademark) manufactured by Daiso Corporation, diallyl Terephthalate prepolymers are preferred. The diallyl terephthalate prepolymer may be a modified product thereof, for example, “Daprene” (registered trademark) manufactured by Daiso Corporation or “Taike Prepolymer” manufactured by Nippon Kasei Co., Ltd. Further, a terpolymer of epichlorohydrin, ethylene oxide, and allyl glycidyl ether, such as "Epichromer CG series" manufactured by Daiso, a terpolymer of diethylene glycol glycidyl methyl ether, ethylene oxide, and allyl glycidyl ether, [1,3-bis (2-methoxyethoxyethoxy)
Terpolymer of propyl glycidyl ether, ethylene oxide and allyl glycidyl ether
-269263 and JP-A-11-345628).

Further, the allyl-based prepolymer (A) is a compound having a metal atom, a group having an aromatic ring, and a group represented by the following general formula in the presence of a diallyl phthalate monomer and / or a diallyl phthalate polymer. A transparent homogeneous organic-inorganic composite, which is a metal oxide polymer obtained by dehydrating and condensing a metal alkoxide having a hydrolyzable group by, for example, a sol-gel method (W
O99 / 14274).

The metal alkoxide is a substance represented by the general formula ^{_{X m M (Ar) n R}} 2 p.

Wherein X is a general formula R ¹ O (R ¹ is 1
An alkoxyl group represented by (valent organic group), M is silicon,
A metal atom selected from the group consisting of titanium, zirconium, germanium, and aluminum, Ar is a group having an aromatic ring, R ² is a monovalent organic group, m and n are 1 or more, and p is 0 or more ( Here, m + n + p is the valence of the metal atom M). Examples of metal alkoxides having a tetravalent metal atom (Si, Ti, Zr or Ge) include the following.

(CH₃ O)₃ MPh, (C₂ H₅
 O)₃ M (CH₂ Ph), (C ₂ H₃ O)₃
 M (C₂ H₄ OPh), (C₃ H₈ NO)₃
 MPh, (C₄ H₉ O)₃ M (C₃ H₄ P
h), (CH₄ NO)₂ MPh₂ , (C₂ H₅
 O)₂ M (CH₃ MPh)₂ , (C₃ H
₅O)₂ M (C₄ H₈ Ph)₂ , (C₄ H
₁₀NO)₂ M (C₂ H ₂ O₂ Ph)₂ ,
(CH₃ O)₂ M (C₄ H₉ NPh) (C₄H
₉ ), (C₂ H₅ O)₂ M (C₄ H₆ O₂
 Ph) (C₃ H₅), (C₂ H₃ O)₂ M
(C₂ H₄ Ph) (C₂ H₅ O), (C₃ H
₈ NO)₂ M (CH₂ Ph) (CH₄ N),
(C₄ H₉ O)₂ MPh (CH₃ ), (CH₄
 NO)₂ MPh (C₂ H₅ ), (C₂ H₅ 
O)₂ M (CH₂ Ph) (C₃ H₇ O), (C
₃ H₅O)₂ M (C₂ H₂ Ph) (C₅ H₉
 O₂ ), (C₄ H₁₀NO)₂ MPh (C₄ 
H₁₀N), (CH₃ O)₂ M (CH₂ OPh)
(C₃ H₇ ), (C₂ H₅ O)₂ M (C₅ 
H₈ O₂ Ph) (C₄H₉ ), (C₂ H₃ 
O)₂ MPh (C₃ H₈ N), (C₃ H₈N
O)₂ M (C₂ H₄ Ph) (C₂ H₅ ),
(C₄ H₉ O)₂MPh (C₂ H₃ O₂ ),
(CH₄ NO)₂ MPh (C₃ H₇), (C₂ 
H₅ O)₂ M (CH₃ NPh) (C₃ H₅ O
₂ ), (C₃ H₅ O)₂ M (C₄ H₈ P
h) (C₂ H₃ ), (C₄ H_{1 0}NO)₂ M
(C₂ H₂ O₂ Ph) (CH₃ ).

As the metal alkoxide, (CH₃ O)
₃ MPh, (C₂ H₅ O)₃MPh, (C₃ H
₇ O)₃ MPh, (C₄ H₉ O)₃ MPh,
(CH₃ O)₂ MPh₂ , (C₂ H₅ O)₂
 MPh₂ , (C₃ H ₇ O)₂ MPh₂ ,
(C₄ H₉ O)₂ MPh₂ Phenyl alcohol
Xysilanes are preferred, of which phenyltrimethoxy
Silanes are most preferred.

Preferred examples of the aluminum alkoxide include the following.

(CH ₃ O) ₂ AlPh, (C ₂ H
₅ O) ₂ AlPh, (C ₃ H ₇ O) ₂ AlP
h, (C ₄ H ₉ O) ₂ AlPh, (CH ₃ O)
AlPh ₂ , (C ₂ H ₅ O) AlPh ₂ , (C
_{3 H 7 O) AlPh 2,} (C 4 H 9 O) Al
Ph ₂ .

The allylic prepolymer (A) may have a thioether group and / or a halogen atom bonded to the main chain. The introduction of a thioether group and / or a halogen atom can be performed by adding a thiol compound and / or a halogen to a polymerization system of an allylic monomer,
It is carried out by a method of adding a thiol compound and / or halogen to the allylic prepolymer (A). Examples of the thiol compound used for introducing a thioether group include thiophenols such as thiophenol, 2-chlorothiophenol, 4-chlorothiophenol, 4-tert-butylthiophenol, and 4-mercaptophenol; Examples thereof include dithiols such as thiodibenzenethiol; and aliphatic thiols such as n-butylmercaptan and n-laurylmercaptan. Examples of the halogen used for introducing a halogen atom include bromine and chlorine.

The above allyl-based monomer homopolymer or copolymer, the above-mentioned organic-inorganic composite transparent homogeneous material, and the thioether group (halogen) -containing allyl-based prepolymer may be used alone or in combination of two or more. May be used. Further, the organic-inorganic composite transparent homogeneous material and / or the thioether group (halogen) -containing allyl prepolymer may be used in combination with the allyl monomer homopolymer or copolymer.

The diallyl phthalate prepolymer has a softening temperature of 50 to 110 ° C., an iodine value of 50 to 95 as measured by a Wijs method, a 50% by weight methyl ethyl ketone solution viscosity (30 ° C.) of 50 to 300 centipoise and a GPC ( The average molecular weight in terms of polystyrene measured by gel permeation chromatography) is 10
000 to 100,000, preferably 30,000 to 600
It is particularly preferred that the prepolymer is a postpolymerizable prepolymer that is 00.

Radical polymerizable compound used in the present invention
(B) is 10 to 100% by weight, preferably 30 to 100% by weight, of the radical polymerizable compound (B1) and 0 to 90% by weight, preferably 0 to 70% by weight of the radically polymerizable compound (B2).
The weighted average of the refractive indices of the radical polymerizable compound (B1) and the radical polymerizable compound (B2) is calculated from the weighted average of the refractive index of the allylic prepolymer (A) and the refractive index of the viscosity reducing agent (C). Is also big.

Hereinafter, the radical polymerizable compound (B) will be described.

The radically polymerizable compound (B1) is preferably solid at room temperature. The compound (B1) may be used alone or in combination of two or more.

Among the radically polymerizable compounds (B1), first,
The fluorene compound [I] is as follows.

In the general formula [I] of the fluorene compound, the radical polymerizable group in the organic groups R ₁ and R ₂ is a vinyl group, a (meth) acryloyl group or a (meth) acryloyl group.
It may be a functional group such as an acryloyloxy group. Organic groups R ₁ and R ₂ having no radical polymerizable group
May be a lower alkyl group having 1 to 5 carbon atoms.

In — (OR) _n1 — of M ₁ and M ₂ , the carbon number of the lower alkylene group R is preferably 1 to
5, more preferably 1-3. Examples of OR include oxymethylene, oxyethylene, oxypropylene, oxybutylene and the like, and (OR) _n1 (where n1 is 2 to 5)
) Are dioxymethylene, dioxyethylene, dioxypropylene, dioxybutylene, trioxymethylene, trioxyethylene, trioxypropylene, trioxybutylene, tetraoxymethylene, tetraoxyethylene, tetraoxypropylene, Tetraoxybutylene and the like are exemplified. When the lower alkylene group R has a hydroxyl group, the hydroxyl group may be located at any position of the alkylene group, but the alkylene having a hydroxyl group is, for example, (2-hydroxy) propylene.

The organic groups X ₁ and X ₂ may be alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl and propyl.

Hereinafter, the fluorene compound [I] will be exemplified. As fluorene (meth) acrylates, 9,
9-bis (4- (meth) acryloyloxyphenyl)
Fluorene, 9,9-bis (4- (meth) acryloyloxymethoxyphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy) phenyl) fluorene, 9,9-bis (4- (3- (meth) acryloyloxypropoxy) phenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydimethoxy) Phenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydiethoxyphenyl) fluorene, 9,9-
Bis (4- (meth) acryloyloxydipropoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytrimethoxyphenyl) fluorene,
9,9-bis (4- (meth) acryloyloxytriethoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytripropoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyl Oxytetramethoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytetraethoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytetrapropoxyphenyl) fluorene,
9,9-bis (4- (meth) acryloyloxy-3-
Methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxymethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl ) Fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (3- (meth) acryloyloxypropoxy) -3- Methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydimethoxy-3-methylphenyl) fluorene, 9,9-
Bis (4- (meth) acryloyloxydiethoxy-3
-Methylphenyl) fluorene, 9,9-bis (4-
(Meth) acryloyloxydipropoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytrimethoxy-3-methylphenyl)
Fluorene, 9,9-bis (4- (meth) acryloyloxytriethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytripropoxy-3-methylphenyl) fluorene, 9,
9-bis (4- (meth) acryloyloxytetramethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytetraethoxy-3
-Methylphenyl) fluorene, 9,9-bis (4-
(Meth) acryloyloxytetrapropoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxymethoxy) -3-ethylphenyl) fluorene, 9,9-
Bis (4- (2- (meth) acryloyloxyethoxy) -3-ethylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy)
-3-ethylphenyl) fluorene, 9,9-bis (4
-(3- (meth) acryloyloxypropoxy) -3
-Ethylphenyl) fluorene, 9,9-bis (4-
(Meth) acryloyloxydimethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydiethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy Dipropoxy-3-ethylphenyl) fluorene,
9,9-bis (4- (meth) acryloyloxytrimethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytriethoxy-3)
-Ethylphenyl) fluorene, 9,9-bis (4-
(Meth) acryloyloxytripropoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth)
Acryloyloxytetramethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytetraethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytetrapropoxy) -3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-
3-propylphenyl) fluorene, 9,9-bis (4
-(Meth) acryloyloxymethoxy-3-propylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-propylphenyl) fluorene, 9,9-bis (4- ( 2- (meta)
(Acryloyloxypropoxy) -3-propylphenyl) fluorene, 9,9-bis (4- (3- (meth) acryloyloxypropoxy) -3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyl Oxydimethoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydiethoxy-3-propylphenyl) fluorene,
9-bis (4- (meth) acryloyloxydipropoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytrimethoxy-3-)
Propylphenyl) fluorene, 9,9-bis (4-
(Meth) acryloyloxytriethoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth)
(Acryloyloxytripropoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytetramethoxy-3-propylphenyl)
Fluorene, 9,9-bis (4- (meth) acryloyloxytetraethoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytetrapropoxy-3-propylphenyl) fluorene, 9, 9-bis (4- (meth) acryloyloxy-
(2-hydroxy) propoxyphenyl) fluorene,
9,9-bis (4- (meth) acryloyloxy- (2
-Hydroxy) propoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy- (2-hydroxy) propoxyethoxyphenyl)
Fluorene, bisphenol fluorene hydroxyacrylate, that is, an acrylic acid adduct of glycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Nippon Steel Chemical Co., Ltd.), bisphenol fluorene methacrylate (manufactured by Nippon Steel Chemical Co., Ltd.), bisphenoxyethanol fluorene orange acrylate (Osaka Gas, B
PEF-A), bisphenoxyethanol full orange methacrylate (BPEF-MA, manufactured by Osaka Gas Co., Ltd.),
Bisphenoxyethanol full orange epoxy acrylate (manufactured by Osaka Gas, BPEF-GA), bisphenol full orange epoxy acrylate (manufactured by Osaka Gas, BPF-GA), biscresol full orange epoxy acrylate (manufactured by Osaka Gas, BCF-GA), etc. Is mentioned.

Particularly preferred fluorene compounds are bisphenol fluorene hydroxyacrylate, that is, acrylic acid adduct of glycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Nippon Steel Chemical Co., Ltd.) and bisphenol fluorene methacrylate (manufactured by Nippon Steel Chemical Co., Ltd.) ), Bisphenoxyethanol full orange acrylate (manufactured by Osaka Gas, BPEF-A), bisphenoxyethanol full orange methacrylate (manufactured by Osaka Gas, BPEF-MA), bisphenoxyethanol full orange epoxy acrylate (manufactured by Osaka Gas, BPEF-GA) ), Bisphenol full orange epoxy acrylate (BPF-G, manufactured by Osaka Gas Co., Ltd.)
A), biscresol full orange epoxy acrylate (BCF-GA, manufactured by Osaka Gas Co., Ltd.) and the like.

The fluorene compound may be a dimer or trimer oligomer of the above-exemplified compound.

These exemplified compounds may be used alone or in combination of two or more.

Next, the sulfide cyclic compound [II] will be described.

In the general formula [II] of the sulfide-based cyclic compound, the ring represents a cyclic structure, Y ₁ represents a plurality of atoms constituting the ring, m represents the number of atoms Y ₁ constituting the ring,
That is, it means the number of members in the ring. m is preferably 5 to 8,
More preferably, it is 5-6, most preferably 6. A plurality of Y ₁ may be all carbon atoms (in this case,
A ring is a carbocycle), a part of the plurality of Y ₁ is a sulfur atom,
It may be a heteroatom such as a nitrogen atom and / or an oxygen atom, with the remainder being carbon atoms (in which case the ring is a heterocycle). The ring may be saturated or unsaturated,
It preferably has an unsaturated bond. n is preferably 1 to 5,
More preferably, it is 1-3, most preferably 2-3.
X ₃ is a substituent of a ring, which is the same or different and is a halogen atom, a hydroxyl group or a lower alkyl group. L is preferably 0 to 6 representing the number of X _3, more this 0-4, most preferably n = 0 to 2.

In the organic groups R ₃ and R ₄ , the radically polymerizable group may be a functional group such as a vinyl group, a (meth) acryloyl group or a (meth) acryloyloxy. Organic groups R ₃ and R having no radical polymerizable group
₄ may be a lower alkyl group having 1 to 5 carbon atoms.
Heteroatoms may be nitrogen, oxygen and / or sulfur atoms.

In — (OR) _n2 — of M ₃ and M ₄ , the carbon number of the lower alkylene group R is preferably 1 to
5, more preferably 1-3. Examples of OR include oxymethylene, oxyethylene, oxypropylene, oxybutylene and the like, and (OR) _n2 (where n2 is 2 to 5)
) Are dioxymethylene, dioxyethylene, dioxypropylene, dioxybutylene, trioxymethylene, trioxyethylene, trioxypropylene, trioxybutylene, tetraoxymethylene, tetraoxyethylene, tetraoxypropylene, Tetraoxybutylene and the like are exemplified. When the lower alkylene group R has a hydroxyl group, the hydroxyl group may be located at any position of the alkylene group, but the alkylene having a hydroxyl group is, for example, (2-hydroxy) propylene.

Examples of the sulfide-based cyclic compound [II] are described below.

Functional groups at positions 2, 3, and 4 of the phenyl ring
Bis (2- (meth) acryloylthiophenyl) sulfide, bis (2-vinylthiophenyl) sulfide, bis (acrylic, methacrylic, vinyl)
(3- (meth) acryloylthiophenyl) sulfide, bis (3-vinylthiophenyl) sulfide, bis (4- (meth) acryloylthiophenyl) sulfide, bis (4-
(Vinylthiophenyl) sulfide A compound having a functional group (acryl, methacryl, vinyl) at positions 2, 3, and 4 of the phenyl ring, and asymmetrical 2- (meth) acryloylthiophenyl-3 '-(meth) acryloyl Thiophenyl sulfide, 2- (meth) acryloylthiophenyl-4 '-(meth) acryloylthiophenyl sulfide, 3- (meth) acryloylthiophenyl-4'-(meth) acryloylthiophenyl sulfide, 2-vinylthiophenyl- 3'-vinylthiophenyl sulfide, 2-vinylthiophenyl-4'-vinylthiophenyl sulfide, 3-vinylthiophenyl-
4'-vinylthiophenyl sulfide, 2- (meth) acryloylthiophenyl-3'-vinylthiophenyl sulfide, 2- (meth) acryloylthiophenyl-4'-
Vinylthiophenyl sulfide, 3- (meth) acryloylthiophenyl-4′-vinylthiophenyl sulfide,

Bis (3-bromo-2- (meth) acryloylthio) having a functional group (acryl, methacryl, vinyl) and a substituent (halogen, lower alkyl, hydroxyl group) at positions 2, 3, and 4 of the phenyl ring Phenyl) sulfide, bis (4-chloro-2- (meth) acryloylthiophenyl) sulfide, bis (3-hydroxy-
2-vinylthiophenyl) sulfide, bis (2-methyl-3- (meth) acryloylthiophenyl) sulfide,
Bis (4-propyl-3- (meth) acryloylthiophenyl) sulfide, bis (2-ethyl-3-vinylthiophenyl) sulfide, bis (2-butyl-4- (meth) acryloylthiophenyl) sulfide, bis ( 3-pentyl-4- (meth) acryloylthiophenyl) sulfide,
Bis (2-hydroxy-4-vinylthiophenyl) sulfide, 3-bromo-2- (meth) acryloylthiophenyl-3 ′-(meth) acryloylthiophenyl sulfide, 3-ethyl-2- (meth) acryloylthiophenyl -4 '-(meth) acryloylthiophenyl sulfide,
2-hydroxy-3- (meth) acryloylthiophenyl-4 ′-(meth) acryloylthiophenyl sulfide,
3-bromo-2- (meth) acryloylthiophenyl-
2'-butyl-3 '-(meth) acryloylthiophenyl sulfide, 3-ethyl-2- (meth) acryloylthiophenyl-3'-hydroxy-4'-(meth) acryloylthiophenyl sulfide, 2-hydroxy-3 -(Meth) acryloylthiophenyl-2'-chloro-4'-
(Meth) acryloylthiophenyl sulfide, 3-bromo-2-vinylthiophenyl-2'-butyl-3'-vinylthiophenyl sulfide, 3-ethyl-2-vinylthiophenyl-3'-hydroxy-4'-vinyl Thiophenyl sulfide, 2-hydroxy-3-vinylthiophenyl-2′-chloro-4′-vinylthiophenyl sulfide, 3-bromo-2- (meth) acryloylthiophenyl-2′-butyl-3 ′-(meta ) Acryloylthiophenyl sulfide, 3-ethyl-2- (meth) acryloylthiophenyl-3′-hydroxy-4 ′-(meth) acryloylthiophenyl sulfide, 2-hydroxy-3
-(Meth) acryloylthiophenyl-2'-chloro-
4 '-(meth) acryloylthiophenyl sulfide, 3
-Bromo-2- (meth) allyloylthiophenyl-2'-
Butyl-3'-vinylthiophenyl sulfide, 3-ethyl-2- (meth) acryloylthiophenyl-3'-hydroxy-4'-vinylthiophenyl sulfide, 2-
Hydroxy-3- (meth) acryloylthiophenyl-
2'-chloro-4'-vinylthiophenyl sulfide

Having a functional group (acryl, methacryl, vinyl), a substituent (halogen, lower acryl, hydroxyl group) and an organic group M ₃ M ₄ at positions 2, 3, 4 of the phenyl ring 3-bromo-2- (Meth) acryloyloxymethoxythiophenyl-2'-butyl-3'-vinylthiophenylsulfide, 2-hydroxy-2- (meth) acryloyloxyethoxythiophenyl-3'-hydroxy-4 '
-Vinylthiophenyl sulfide, 3-ethyl-3-
(Meth) acryloyloxypoloxythiophenyl-
2'-chloro-4'-vinylthiophenyl sulfide,
3-bromo-2- (meth) acryloyloxydimethoxythiophenyl-2′-butyl-3 ′-(meth) acryloyloxydiethoxythiophenylsulfide, 3-ethyl-2- (meth) acryloyloxydiethoxythiophenyl- 3'-hydroxy, 4 '-(meth) acryloyloxydimethoxythiophenyl sulfide, 2-hydroxy-3- (meth) acryloyloxydipropoxythiophenyl-2'-chloro-4'-(meth) acryloyloxydimethoxythiophenyl Sulfide saturated cyclic hydrocarbon compound 1,3-di (meth) acryloylthiocyclopentane,
1,4-di (meth) acryloylthiocyclohexane,
1,4-di (meth) acryloylthiocycloheptane,
1,6-di (meth) acryloylthiocyclooctane, bis (3- (meth) acryloylthiocyclopentyl) sulfide, bis (4- (meth) acryloylthiocyclohexyl) sulfide, bis (4- (meth) acryloylthiocycloheptyl) ) Sulfide, bis (5- (meth) acryloylthiocyclooctyl) sulfide unsaturated cyclic hydrocarbon compound bis (4- (meth) acryloylthio-2-cyclohexen-1-yl) sulfide, bis (4- (meth) acryloyl) Thio-2-cyclopenten-1-yl) sulfide,
Bis (5- (meth) acryloylthio-2-cyclohepten-1-yl) sulfidebis (5- (meth) acryloylthio-2-cycloocten-1-yl) sulfide heterocyclic compound bis (2- (meth) acryloyl Thienyl) sulfide, bis (3- (meth) acryloylthiopyridyl) sulfide,
Bis (5- (meth) acryloylthiopyranyl) sulfide, bis (5- (meth) acryloylthio-1,4-dithianyl) sulfide

Any of the above exemplified compounds may be used alone or in combination of two or more.

Of the above compounds, bis (4-methacryloylthiophenyl) sulfide, bis (4-acryloylthiophenyl) sulfide, bis (4-vinylthiophenyl) sulfide and the like are particularly preferred.

Next, the halogenated cyclic compound [III] will be described.

In the general formula [III] of the halogenated cyclic compound,
The ring means a cyclic structure, Y ₂ Form a ring
K means a plurality of ring-constituting atoms Y₂ The number of
That is, it means the number of members in the ring. k is preferably 5 to 8,
More preferably, it is 5-6, most preferably 6. plural
Y₂ May be all carbon atoms (in this case, the ring
Is a carbocycle);₂ Some of them are sulfur atoms, nitrogen
A heteroatom such as an elementary atom and / or an oxygen atom,
The remainder may be carbon atoms (in which case the ring is hetero
Ring). The ring may be saturated or unsaturated, but is preferably
Or an unsaturated bond, particularly preferably a benzene ring.
is there.

X ₄ is a substituent of a ring, which is the same or different from each other, at least one of which is a halogen atom,
Others are a hydroxyl group or a lower alkyl group. Substituent X ₄
Q representing the number of is 2 to 6.

[0063] radical polymerizable group in the organic group R ₅ is a vinyl group may be a functional group such as (meth) acryloyl group or (meth) acryloyloxy. The organic group R ₅ does not have a radical polymerizable group can be a lower alkyl group of 1 to 5 carbon atoms.

In — (OR) _n3 — of M ₅ , the carbon number of the lower alkylene group R is preferably 1 to 5, more preferably 1 to 3. As OR, oxymethylene,
Oxyethylene, oxypropylene, oxybutylene and the like are exemplified, and (OR) _n3 (n3 is an integer of 2 to 5) includes dioxymethylene, dioxyethylene, dioxypropylene, dioxybutylene, trioxymethylene,
Examples thereof include trioxyethylene, trioxypropylene, trioxybutylene, tetraoxymethylene, tetraoxyethylene, tetraoxypropylene, and tetraoxybutylene. When the lower alkylene group R has a hydroxyl group, the hydroxyl group may be located at any position of the alkylene group.
Hydroxy) propylene.

P representing the number of groups (M ₅ -R ₅ ) is 1
~ 4.

The halogenated cyclic compound [III], for example, a trihalophenol compound may be as follows.

Functional groups (acryl, methacryl, vinyl)
Having one and two substituents (halogen, hydroxyl group, lower alkyl group) 2,4-dibromophenyl (meth) acrylate, 2,6
-Dibromophenyl (meth) acrylate, 4,6-dichloro-1-vinylbenzene, 2,4-dibromo-5-ethyl-3- (meth) acryloyloxybenzene, 2,6
-Dibromo-3-hydroxy-phenyl acrylate,
4,6-dibromo-2-propyl-1-vinylbenzene, 2,4-dichloro-3-methylphenyl (meth) acrylate, 2,6-dibromo-5-hydroxyphenyl
(Meth) acrylate, 4,6-dibromo-2-butyl-
1-vinylbenzene, 2,4-dibromophenoxy (meth) acrylate, 2,6-dibromophenoxy (meth)
Acrylate, 2,4-dichloro-3-methylphenoxy (meth) acrylate, 2,6-dibromo-5-hydroxyphenoxy (meth) acrylate, 2,6-dichlorophenoxy (meth) acrylate, 2,4-dibromo-5
-Ethyl-1,3-di (meth) acryloylbenzene,
2,6-dichloro-3-hydroxy-phenoxy (meth)
Acrylate having one functional group (acryl, methacryl, vinyl) and three substituents (halogen, hydroxyl group, lower alkyl group) 2,4,6-tribromophenyl (meth) acrylate,
2,4,6-trichloro-1-vinylbenzene, 2,
4,6-tribromophenoxyethyl (meth) acrylate, 2,3,6-tribromophenyl (meth) acrylate, 2,5,6-tribromophenyl (meth) acrylate, 2,4,5-trichloro-1 -Vinyl benzene,
2,4,6-tribromophenoxydiethylene glycol (meth) acrylate, 2,4,6-tribromophenoxytriethylene glycol (meth) acrylate, 2,
4,6-tribromophenoxytetraethylene glycol (meth) acrylate, 2,4,6-trichlorophenoxymethyl (meth) acrylate, 2- (2,4,6-tribromophenoxy) -ethyl (meth) acrylate, 2
-(2,4,6-tribromophenoxy) -propyl (meth) acrylate, 3- (2,4,6-tribromophenoxy) -propyl (meth) acrylate, 2- (2,4,6
-Tribromophenoxy) -3-hydroxypropyl (meth) acrylate, 3- (2,4,6-tribromophenoxy) -3-hydroxypropyl (meth) acrylate Two functional groups (acryl, methacryl, vinyl) and substituents (Halogen, hydroxyl group, lower acrylic group) 2,4-dibromo-1,3-di (meth) acryloyloxybenzene, 5- (meth) acryloyloxy-2,4-
Dibromo-3- (meth) acryloyloxybenzene, 5
-(Meth) acryloyloxy-2-bromo-4-chloro-3- (meth) acryloyloxybenzene, 1- (meth)
Acryloyloxy-2,5-dibromo-4-hydroxy-3-methyl-6- (meth) acryloyloxybenzene, 1- (meth) acryloyloxy-2-bromo-3-
Chloro-4-hydroxy-3-methyl-6- (meth) acryloyloxybenzene Having two functional groups (acryl, methacryl, vinyl) and three substituents (halogen, hydroxyl, lower acryl) 2,4- Dibromo-6-methyl-1,3,5-tri (meth) acryloyloxybenzene, 1,5-dibromo-
3-hydroxy-2,4,6-tri (meth) acryloyloxybenzene, 1,5-dichloro-3-hydroxy-
2,4,6-tri (meth) acryloyloxybenzene having three functional groups (acryl, methacryl, vinyl) and three substituents (halogen, hydroxyl group, lower alkyl group) 2,4,6-tribromo-1 , 3,5-tri (meth) acryloyloxybenzene, 2,4,6-trichloro-
1,3,5-tri (meth) acryloyloxybenzene having a functional group (acryl, methacryl, vinyl), a substituent (halogen, hydroxyl group, lower alkenyl group) and an organic group M ₅ 1,4-di (meth) Acryloyloxytrimethoxy-
2,6-dibromobenzene, 1- (meth) acryloyloxyethoxy-2,3,6-tribromobenzene, 1-
(Meth) acryloyloxydipropoxy-2,4,6-
Trichlorobenzene, 2,4-dibromo-1,3-di
(Meth) acryloyloxymethoxybenzene, 2,4-
Dibromo-6-methyl-1,3,5-tri (meth) acryloyloxydiethoxybenzene These exemplified compounds may be used alone or in combination of two or more.

Among the above compounds, tribromophenol acrylate, tribromophenol methacrylate,
Particularly preferred are tribromophenoxyethyl acrylate, tribromophenoxyethyl methacrylate and the like.

Next, the carbazole compound [IV] will be described.

Organic group R _{6 of} carbazole compound [IV]
, R ₇ and R ₈ the radically polymerizable group may be a functional group such as a vinyl group, a (meth) acryloyl group or a (meth) acryloyloxy. Organic groups R ₆ , R ₇ and R ₈ having no radical polymerizable group are
It may be a lower alkyl group having 1 to 5 carbon atoms.

-(OR) of M ₆ , M ₇ and M _{8
In n4-} , the number of carbon atoms of the lower alkylene group R is preferably 1 to 5, more preferably 1 to 3. Examples of OR include oxymethylene, oxyethylene, oxypropylene, oxybutylene and the like, and (OR) _n4 (n4
Is an integer of 2 to 5) as dioxymethylene, dioxyethylene, dioxypropylene, dioxybutylene,
Trioxymethylene, trioxyethylene, trioxypropylene, trioxybutylene, tetraoxymethylene, tetraoxyethylene, tetraoxypropylene,
Tetraoxybutylene and the like are exemplified. When the lower alkylene group R has a hydroxyl group, the hydroxyl group may be located at any position of the alkylene group, but the alkylene having a hydroxyl group is, for example, (2-hydroxy) propylene.

X ₅ and X ₆ are ring substituents;
The same or different from each other, it means a halogen atom, a hydroxyl group or a lower alkyl group.

The carbazole compound [IV] may be as follows.

Functional groups (acryl, methacryl, vinyl)
1-vinylcarbazole, 2-vinylcarbazole, 3
-Vinyl carbazole, 4-vinyl carbazole, 9-
Vinylcarbazole, 1- (meth) acryloyloxycarbazole, 2- (meth) acryloyloxycarbazole, 3- (meth) acryloyloxycarbazole, 4-
(Meth) acryloyloxycarbazole, 9- (meth) acryloyloxycarbazole 2 or 3 functional groups (acryl, methacryl, vinyl)
Having 1,9-divinylcarbazole, 1,5,9-trivinylcarbazole, 2,7-di (meth) acryloyloxycarbazole, 2,8,9-tri (meth) acryloyloxycarbazole, 1,9- Di (meth) acryloyloxycarbazole, 3,6,9-tri (meth) acryloyloxycarbazole, 2- (meth) acryloyloxy-
1-vinylcarbazole, 6- (meth) acryloyloxy-2-vinylcarbazole, 2- (meth) acryloyloxy-9- (meth) acryloyloxycarbazole,
1- (meth) acryloyloxy-5- (meth) acryloyloxycarbazole functional group (acryl, methacryl, vinyl) and substituent
(Halogen, lower alkyl, hydroxyl group) 2-methyl-1,9-divinylcarbazole, 3-hydroxy-1,5,9-trivinylcarbazole, 1-chloro-2,7-di (meth) acryloyloxy Carbazole, 3,7-dibromo-2,8,9-tri (meth) acryloyloxycarbazole, 1,9-di (meth) acryloyloxy-4-butylcarbazole, 3,6,9-tri (meth) acryloyloxy -1-hydroxycarbazole, 2- (meth) acryloyloxy-5-propyl-
1-vinylcarbazole, 6- (meth) acryloyloxy-9-ethyl-2-vinylcarbazole, 2- (meth)
Acryloyloxy-9- (meth) acryloyloxycarbazole, 1- (meth) acryloyloxy-9-hydroxy-5- (meth) acryloyloxycarbazo

Functional groups (acryl, methacryl, vinyl)
And those having a substituent (halogen, lower alkyl, hydroxyl group) and an organic group M ₆ M ₇ 2-methyl-1,9-divinylmethoxycarbazole,
3-hydroxy-1,5,9-trivinylethoxycarbazole, 1-chloro-2,7-di (meth) acryloyloxyethoxycarbazole, 3,7-dibromo-2,
8,9-tri (meth) acryloyloxydiethoxycarbazole, 1,9-di (meth) acryloyloxytrimethoxy-4-butylcarbazole, 3,6,9-tricarb
(Meth) acryloyloxytetramethoxy-1-hydroxycarbazole, 2- (meth) acryloyloxymethoxy-5-propyl-1-vinylcarbazole, 6-
(Meth) acryloyloxydimethoxy-9-ethyl-2
-Vinylcarbazole, 2- (meth) acryloyloxytripropoxy-9- (meth) acryloyloxymethoxycarbazole, 1- (meth) acryloyloxyethoxy-9-hydroxy-5- (meth) acryloyloxyethoxycarbazole Any of these may be used alone or in combination of two or more.

Among the above compounds, N-vinylcarbazole, 3,6-dibromo-9-vinylcarbazole, 9-vinylcarbazole
Vinyl carbazole is particularly preferred.

The fluorene compound [I], the sulfide ring compound [II], the halogenated ring compound [III] and the carbazole compound [IV] can be used in combination.

Of the fluorene compound [I], sulfide ring compound [II], halogenated ring compound [III] and carbazole compound [IV], fluorene compound [I], sulfide ring compound [II] and The halogenated cyclic compound [III] is preferable, and the fluorene-based compound [I] and the halogenated cyclic compound [III] are most preferable.

The radical polymerizable compound (B2) is a radical polymerizable compound having no fluorene skeleton, bis (phenyl) sulfide skeleton, trihalophenyl skeleton, or carbazole skeleton in the molecule. The number of functional groups is 1 to 6. Hereinafter, specific examples thereof will be described.

As the aromatic compound, styrene, 2-
Chlorostyrene, 2-bromostyrene, vinyltoluene, divinylbenzene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, divinylbiphenyl, 4,4′-divinylbiphenyl, vinylnaphthalene, divinylnaphthalene, 2,2- Bis [3,5-dibromo-4- (2-methacryloyloxyethoxy) phenyl] propane, 2,2-bis [3,5-dibromo-
4- (2-acryloyloxyethoxy) phenyl] propane, phenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenolethoxylate mono (meth) acrylate, p-chlorophenyl ( (Meth) acrylate, 2- (p-chlorophenoxy) ethyl (meth) acrylate, p-bromophenyl (meth) acrylate, 2- (p-bromophenoxy) ethyl (meth)
Acrylate, 1,4-benzenediol di (meth) acrylate, 1,3,5-triisopropenylbenzene, 2- (1-naphthyloxy) ethyl (meth) acrylate, ethoxylate bisphenol A di (meth) acrylate, bisphenol And di (2- (meth) acryloxyethyl) ether of A.

Examples of the aliphatic compound include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate,
Methoxydiethylene glycol methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-
Hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tert-butyl methacrylate, isostearyl methacrylate, n-butoxyethyl methacrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, Ethoxyethylene glycol acrylate, methoxytriethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid , Isooctyl acrylate Isomyristyl acrylate,
Mono (meth) acrylates such as isostearyl acrylate and vinyl acetate are exemplified.

These aromatic and aliphatic exemplified compounds may be used alone or in combination of two or more.

The viscosity reducing agent (C) used in the present invention is a compound (C1) that is non-reactive with the allylic pull polymer (A) and / or the radical polymerizable compound (B), (C2) having a (meth) allyl group.

As the non-reactive compound (C1) among the viscosity reducing agents, phthalic esters represented by dimethyl phthalate and diethyl phthalate; dimethyl adipate, dibutyl adipate, dimethyl sebacate and diethyl succinate Aliphatic dibasic acid esters; orthophosphates represented by trimethyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate; acetate esters represented by glyceryl triacetate and 2-ethylhexyl acetate; triphenyl phosphate Inactive compounds such as phosphites represented by phyte and dibutyl hydrogen phosphite are exemplified. Further, an alkylene glycol alkyl ether represented by the following general formula is exemplified.

Embedded image [In the formula, R ₁₁ and R ₁₂ represent an alkyl group having 1 to 5 carbon atoms, a hydroxyl group or an acetyl group, and n represents an integer of 1 to 5. Examples of the alkylene glycol alkyl ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl. Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, triethylene glycol dimethyl ether,
Triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, cellosolve ethylene glycol diacetyl ether, ethylene glycol monoacetyl ether, diethylene glycol diacetyl ether, Examples thereof include diethylene glycol monoacetyl ether, triethylene glycol diacetyl ether, and triethylene glycol monoacetyl ether.

Further, polyethylene glycol or silicone oil having a weight average molecular weight of 10,000 or less can also be used.

The viscosity reducing agent (C1) is preferably selected to have a refractive index as small as possible than that of the allylic prepolymer (A).

Among the viscosity reducing agents (C), (meth)
As the compound (C2) having an allyl group, (meth) allyl alcohol, (meth) allyl chloride, acetic acid (meth)
Allyl, (meth) allyl benzoate, isovaleric acid (meth)
Allyl, (meth) allyl caprylate, (meth) allyl caproate, (meth) allyl formate, (meth) allyl cinnamate, (meth) allyl salicylate, (meth) allyl dihydrojasmate, (meth) allyl phenylacetate (Meth) allyl propionate, (meth) allyl butyrate, mono (meth) allyl adipate, mono (meth) allyl sebacate, mono (meth) allyl phthalate, mono (meth) allyl isophthalate, Mono (meth) allyl terephthalate, mono (meth) allyl succinate, mono (meth) allyl trimellitate, mono (meth) allyl succinate, mono (meth) allyl ricinoleate, mono (meth) maleate ) Mono (meth) allyl compounds such as allyl esters; (Meth) allyl, di (meth) allyl sebacate, di (meth) allyl phthalate, di (meth) allyl isophthalate, di (meth) allyl terephthalate, di (meth) allyl succinate, trimellitium (meta) Di (meth) allyl compounds such as allyl, di (meth) allyl succinate, di (meth) allyl ricinoleate, di (meth) allyl maleate, tri (meth) allyl phosphate and tri (meth) allyl isocyanurate Is exemplified.

The above compounds may be used alone or in combination of two or more.

As the photopolymerization initiator (D) in the composition of the present invention, He—Ne (wavelength 633 nm), Ar (wavelength 5
Those that absorb laser light such as 15,488 nm) and He-Cd (wavelength 442 nm) to generate radicals are preferably used. Such photopolymerization initiators include, for example, carbonyl compounds, amine compounds, arylaminoacetic acid compounds, organotin compounds, alkylaryl boron salts, onium salts, iron arene complexes, trihalogenomethyl-substituted triazine compounds, organic peroxides , Bisimidazole derivatives, titanocene compounds and combinations of these initiators with photosensitizing dyes are preferably used.

Examples of the carbonyl compound include benzyl, benzoin ethyl ether, benzophenone,
Diethoxyacetophenone and the like can be exemplified.

Examples of the amine compound include triethanolamine, triisopropanolamine, 2-dimethylaminobenzoic acid and the like.

Examples of the arylaminoacetic acid compound include N-phenylglycine.

As an organic tin compound, tributylbenzyltin can be exemplified.

Examples of the alkylaryl boron salt include tetrabutylammonium triphenylbutyl borate and triphenyl-n-butyl borate.

Examples of the onium salts include diphenyliodonium salts.

Examples of the iron arene complex include η ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluorophosphate (1-).

The trihalogenomethyl-substituted triazine compound is exemplified by tris (trichloromethyl) triazine.

As an organic peroxide, 3,3 ', 4,4'-
Tetra (tert-butylperoxycarbonyl) benzophenone can be exemplified.

As a bisimidazole derivative, 2,2′-
Bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-biimidazole, bis (2
4,5-triphenyl) imidazolyl can be exemplified.

As the titanocene compound, bis (η ^5-
2,4-cyclopentadien-1-yl) -bis (2,4-
6-difluoro-3- (1H-pyrrol-1-yl)-
(Phenyl) titanium.

These may be used alone or in combination of two or more.

As the photosensitizing dye, Michella ketone, acridine yellow, merocyanine, methylene blue, camphorquinone, eosin, decarboxylated rose bengal and the like are preferably used. The photosensitizing dye may be any as long as it absorbs light in the visible region.In addition to the above, for example, a cyanine derivative, a merocyanine derivative, a phthalocyanine derivative, a xanthene derivative, a thioxanthene derivative, an acridine derivative, a porphyrin derivative, a coumarin derivative , Base styryl derivatives, ketocoumarin derivatives,
A quinolone derivative, a stilbene derivative, an oxazine derivative, a thiazine dye, and the like can also be used. Further, “Dye Handbook” (edited by Shin Okawara et al., Kodansha, 1986)
Photosensitizing dyes described in "Functional Dye Chemistry" (Nobuo Ogawara et al., CMC, 1983) and "Specially Functional Materials" (Ikedori Chuzaburo et al., CMC, 1986) Can be used. These may be used alone or in combination of two or more.

As coumarin derivatives, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin,
(2-benzothiazolyl) -7- (dibutylamino) coumarin, 3- (2-benzothiazolyl) -7- (dioctylamino) coumarin, 3- (2-benzimidazolyl)
And -7- (diethylamino) coumarin and the like.

As ketocoumarin derivatives, 3,3'-carbonylbis (7-diethylaminocoumarin), 3,3
'-Carbonylbis-7-diethylaminocoumarin-7
'-Bis (butoxyethyl) aminocoumarin, 3,3'
-Carbonylbis (7-dibutylaminocoumarin) and the like.

As the base styryl derivative, 2- [p-
(Dimethylamino) styryl] benzothiazole, 2-
[p- (Dimethylamino) styryl] naphtho [1,2-
d] thiazole, 2-[(m-hydroxy-p-methoxy) styryl] benzothiazole and the like.

The merocyanine derivatives include 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolylidene) ethylidene] -2-thioxo-4-oxazolidinone, 5-[(1,3-dihydro -1,3,3-trimethyl-2H-indole-2-ylidene) ethylidene]
Examples thereof include -3-ethyl-2-thioxo-4-oxazolidinone.

Specific examples of the combination of an organic peroxide and a photosensitizing dye include 3,3 ′, 4,4′-tetra (ter
t-butylperoxycarbonyl) benzophenone;
NKX65, a photosensitizing dye manufactured by Japan Photographic Dye Laboratories
3, NKX3883, NKX1880, NKX159
5, NKX1695, NK4256, NK1886, N
K1473, NK1474, NK4795, NK427
6, NK4278, NK91, NK1046, NK12
37, NK1420, NK1538, NK3590 and the like are preferable.

Specific examples of the combination of the carbonyl compound and the photosensitizing dye include benzyl-Michler's ketone, benzyl-acridine yellow and the like. As the photosensitizing dye to be combined with the amine compound, decarboxylated rose bengal is preferable. As the photosensitizing dye to be combined with the borate compound, a cyanine dye such as a cyanine, an isocyanine, and a pseudocyanine is preferable.

In the composition of the present invention, the photopolymerization initiator (D) is added in the case of using a carbonyl compound, when the allylic prepolymer (A), the radical polymerizable compound (B) and the viscosity reducing agent (C) are used. To 100 parts by weight in total,
It is about 1 to 15% by weight, preferably about 0.3 to 10% by weight.

The hologram recording material composition according to the present invention may contain additives such as a viscosity modifier, a thermal polymerization inhibitor, a chain transfer agent, etc., and a solvent, if necessary.

As the viscosity modifier, inorganic fine particles such as silica gel fine particles such as "DAISOGOL SP series" manufactured by Daiso Co., Ltd., "Silycia" and "Fuji Silica Gel" manufactured by Fuji Silysia Chemical Ltd., and "Carplex" manufactured by Shionogi Pharmaceutical Co., Ltd. "," Aerosil "manufactured by Japan Aerosil Co., Ltd.
Tokuyama's "Leo Seal", "Toku Seal",
"Fine seal" can be used. Or organic fine particles, for example, JP-A-10-72510, JP-A-10-31
0684, a diallyl phthalate-based polymer that can be produced by the method described in each of the gazettes, or a product of Kao Corporation described in “New Material Series“ Advanced Technology of Ultrafine Particle Polymer ”” (CMC, supervised by Soichi Muroi, 1991) "PB, 2
00 Series, Kanebo's Bell Pearl Series, Sekisui Plastics' Techpolymer Series, Sekisui Fine Chemical's Micropearl Series, Soken Chemical's MR Series, MP Series, etc. .
The particle size of these fine particles may be smaller than the film thickness of the hologram, and is usually preferably in the range of 0.1 to 20 μm.

The amount of the viscosity modifier added depends on the amount of the allylic prepolymer (A), the radical polymerizable compound (B) and the viscosity reducing agent.
(C) preferably 0.5 to 3 parts by weight based on 100 parts by weight in total.
It is about 0 parts by weight.

The solvent is effective not only for adjusting the viscosity and the compatibility but also for improving the film forming property. Examples thereof include acetone, xylene, toluene, methyl ethyl ketone, tetrahydrofuran, benzene, methylene chloride, dichloromethane, chloroform, methanol , Etc. are often used. The amount of the solvent used is 10 in total of the allyl prepolymer (A), the radical polymerizable compound (B) and the viscosity reducing agent (C).
It is about 0.5 to 1000 parts by weight relative to 0 parts by weight.

Examples of the thermal polymerization inhibitor include, for example, hydroquinone,
Examples include p-methoxyphenol, tertiary butylcatechol, naphthylamine, diphenylpicrylhydrazine, diphenylamine and the like.

Examples of the chain transfer agent include α-methylstyrene dimer, 2-mercaptobenzoxazole,
Examples include mercaptobenzothiazole, tert-butyl alcohol, n-butanol, isobutanol, isopropylbenzene, ethylbenzene, chloroform, methyl ethyl ketone, propylene, and vinyl chloride.

To prepare the hologram recording material composition, for example, an allylic prepolymer (A), a radical polymerizable compound (B), a viscosity reducing agent (C) and a photopolymerization initiator (D) or any of the above optional components Is placed in an organic solvent-resistant container such as a glass beaker, and the whole is stirred. In this case, in order to promote the dissolution of the solid component, the composition may be heated to, for example, about 40 to 90 ° C. as long as the composition is not denatured.

In order to prepare a hologram recording medium using the hologram recording material composition according to the present invention, the recording material composition is applied to one surface of a substrate, and the resulting coating film, that is, a two-layered film composed of a recording layer and a substrate is formed. Obtain a recording medium with a structure. Also,
If necessary, a three-layer structure is obtained by covering the recording layer on the substrate with a film-like, sheet-like or plate-like protective material.
It is preferable to use a solvent in the step of preparing the composition. In this case, the allylic prepolymer (A), the radical polymerizable compound (B), the viscosity reducing agent (C) and the photopolymerization initiator (D) are dissolved or suspended in a solvent, and the resulting solution or suspension is obtained. Is applied onto a substrate, and then the solvent is volatilized to form a recording layer. When covering the recording layer with a protective material, it is preferable to remove the solvent by air drying or evaporation under reduced pressure before coating the protective material. The substrate is an optically transparent material, for example, a glass plate, a polyethylene terephthalate plate, a polycarbonate plate,
It is made of a plastic plate such as a polymethyl methacrylate plate. The thickness of the substrate is preferably 0.5 to 10 mm
It is. The substrate does not need to be flat, but may be bent or curved, or have an uneven structure on the surface. The protective material is also made of an optically transparent material like the substrate. The thickness of the protective material is preferably 0.01 to 10 mm. The application method includes gravure application, roll coating application, bar coating application, spin coating application and the like. It is preferable to apply the recording layer so that the thickness of the recording layer after removing the solvent is preferably 1 to 100 μm.

For recording a hologram on a hologram recording medium, a usual recording method can be adopted. That is, the laser light is split into two parts by a beam splitter or the like, and one is irradiated to an object to be photographed. The other is reflected by the reflecting mirror as it is. The recording medium is set at a position where a stripe pattern formed by interference between the reference light reflected from the reflecting mirror and the object light reflected from the object can be captured.
In this state, when laser light irradiation is performed for several seconds to several minutes, interference fringes serving as holograms are recorded on the recording medium. The amount of the laser light used is represented by the product of the light intensity and the irradiation time, and is preferably 1 to 10,000 mJ / cm ^2.
It is about. If the amount of light is less than this range, recording is difficult, and if it exceeds this range, the diffraction efficiency of the hologram tends to decrease.

After the hologram is formed, post-processing such as development and fixing is not indispensable.
The remaining unreacted monomer and allyl group may be post-polymerized.

The allylic prepolymer (A) remains in the recording medium even after producing a hologram on the recording medium obtained by using the recording material composition according to the present invention. Therefore, it is conceivable to use this functionally. For example,
The recording material composition according to the present invention is firmly fixed to the substrate by forming the substrate from an unsaturated polyester resin and chemically bonding the remaining allyl groups of the prepolymer (A) to the unsaturated groups of the substrate resin. be able to. Further, by post-curing unreacted allyl groups, heat resistance can be improved. Thus, the allylic prepolymer (A)
By utilizing the function of the remaining allyl group of the hologram, various variations can be given to the material characteristics of the hologram, and a hologram having physical properties that can be used in various applications can be obtained.

[0121]

The recording material composition of the present invention has a composition in which the allyl prepolymer (A), the radical polymerizable compound (B), the viscosity reducing agent (C) and the photopolymerization initiator (D) are compatible before exposure. However, the radical polymerizable compound (B) is preferentially photopolymerized to polymerize with the irradiation of the laser beam, and finally becomes a hologram recording layer.

That is, when an interference pattern is exposed to a two-layer structure obtained by coating the recording material composition according to the present invention on a substrate or a three-layer structure obtained by covering a protective material on this recording layer, The radical polymerizable compound (B), which has high photopolymerization reactivity in a portion having a large amount of light, starts photopolymerization, and the portion undergoes volume shrinkage. The unpolymerized material flows from the portion having a small amount of light into the recess formed by this, and the allyl-based prepolymer (A) is phase-separated from the radically polymerizable compound (B) and is eliminated to the portion having a small amount of light.

The photopolymerization of the radical polymerizable compound (B) which has diffused and moved to a portion having a large amount of light proceeds further. on the other hand,
In the portion where the amount of light is small, the photopolymerization proceeds with the allyl-based prepolymer (A) alone or with the polymer of the radical polymerizable compound (B) with a slight delay. As a result, the polymer of the radical polymerizable compound (B), which has a high refractive index, accumulates in the portion with a large amount of light, and the allylic prepolymer (A), which has a low refractive index, accumulates in the portion with a small amount of light. And a structure in which both are bonded to each other by radical copolymerization is formed.

The viscosity reducing agent (C) is a component for adjusting the viscosity and compatibility of the system, and is a component for promoting the separation of the allylic prepolymer (A) and the radical polymerizable compound (B). Functions as an ingredient. This is uniformly present in the system at the early stage of exposure, but is eventually removed to a portion where the amount of light is small, that is, to the allylic prepolymer (A) side. Thus, the interference distribution based on the composition distribution according to the light amount, that is, the interference pattern based on the difference in the refractive index between the portion having a large amount of the allyl-based prepolymer (A) and the viscosity reducing agent (C) and the portion having a large amount of the radical polymerizable compound (B) is obtained. Formed as a hologram.

[0125]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described with reference to several embodiments of the present invention. However, these examples do not limit the present invention.

[0126]

Example 1 1) As an allyl prepolymer (A), diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd.)
5 g of “Daiso Dap, DAPA”) and 1 g of acrylic acid adduct of glycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene as a radical polymerizable compound (B1) (“ASF400” manufactured by Nippon Steel Chemical Co., Ltd.) And 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone (manufactured by NOF CORPORATION, “BT
TB-25 ") 3.5 g, a merocyanine dye as a sensitizing dye (manufactured by Nippon Kogaku Dyestuffs Co., Ltd.," NK4795 ") 0.01
g, 4 g of diethyl sebacate ("SDE", manufactured by Wako Pure Chemical Industries, Ltd.) as a viscosity reducing agent (C1) and acetone 6 as a solvent.
g at room temperature to prepare a recording material composition.

2) This composition was applied to one side of a 60 mm × 60 mm glass substrate so that the thickness after drying became 20 μm, the solvent was removed from the coated layer under reduced pressure, and the two layers consisting of the substrate and the recording layer were formed. A recording medium with a structure was created.

3) A hologram recording photosensitive plate having a three-layer structure was formed by covering the recording layer of this recording medium with the same glass as described above.

4) Next, the 488 nm Ar ion laser was split by a beam splitter, the angles of which were changed by a reflecting mirror, and the two were combined again to cause interference to obtain interference fringes. The photosensitive plate was set at a position where the interference fringes could be captured.

5) Examples of the transmission hologram and the reflection hologram are shown in FIGS. 1 and 2, respectively. In the figure, (1)
Denotes a photosensitive plate, and (2) denotes a laser beam.

6) The photosensitive plate was exposed in this state, and interference fringes serving as holograms were recorded on the photosensitive plate.

The exposure of the transmission hologram and the reflection hologram is performed by changing one light intensity on the photosensitive plate to 1.0 mW.
/ Cm ² , exposure amount 1 for 10 seconds to 100 seconds
The measurement was performed at mJ / cm ² to 100 mJ / cm ² .

Examples 2 to 5 Allyl-based prepolymer (A) and radically polymerizable compound (B1)
A hologram recording photosensitive plate having a three-layer structure was prepared in the same manner as in Example 1, except that the amount of the viscosity reducing agent (C1) shown in Table 1 was used, and hologram recording was performed using this.

Examples 6 to 7 As an allyl-based prepolymer (A), diallyl isophthalate prepolymer (manufactured by Daiso Co., Ltd., “Daiso Isodap,
DAIP "), triallyl isocyanurate prepolymer (Nippon Kasei Co., Ltd.," Tyke prepolymer, TAIC ")
As a radical polymerizable compound (B1), bisphenoxyethanol full orange acrylate (manufactured by Osaka Gas Co., Ltd., "B
PEFA ”) and SDE as the viscosity reducing agent (C1) in the same manner as in Example 1 except that the amounts shown in Table 1 were used.
A hologram recording photosensitive plate having a three-layer structure was prepared, and hologram recording was performed using this.

Examples 8 to 9 Except that ASF400 was used as the radical polymerizable compound (B1) and divinyl biphenyl (DBVP manufactured by Nippon Steel Chemical Co., Ltd.) was used as the radical polymerizable compound (B2) in the amounts shown in Table 1, respectively. In the same manner as in Example 1, a hologram recording photosensitive plate having a three-layer structure was formed, and hologram recording was performed using this.

Examples 10 to 17 As radical polymerizable compounds (B1), ASF400, bis (4-methacryloylthiophenyl) sulfide ("MPSMA", manufactured by Sumitomo Seika Co., Ltd.), and tribromophenol acrylate (Daiichi Kogyo Seiyaku) Manufactured by "BR-30"), tribromophenol methacrylate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "SR
-804 "), N-vinylcarbazole (manufactured by Tokyo Chemical Industry Co., Ltd.,
NVC) as DBV as a radical polymerizable compound (B2).
A hologram recording photosensitive plate having a three-layer structure was prepared in the same manner as in Example 1 except that P was used as the non-reactive viscosity reducing agent (C1) in the amounts shown in Table 1, respectively. Was used to perform hologram recording.

Examples 18 to 27 ASF400 was used as the radical polymerizable compound (B1), and diethyl adipate (ADE, manufactured by Kanto Chemical Industry Co., Ltd.) and dibutyl adipate were used as the non-reactive viscosity reducing agent (C1) instead of SDE. ADB), dibutyl sebacate (SDB, manufactured by Wako Pure Chemical Industries), dimethyl phthalate
(Manufactured by Wako Pure Chemical Industries, PDM), dibutyl phthalate (manufactured by Kanto Chemical Co., PDB), dioctyl phthalate (manufactured by Wako Pure Chemical Industries, PDO) as (meth) allyl-based viscosity reducing agent (C2) The diallyl orthophthalate monomer (DASO, DAPM), the diallyl isophthalate monomer (DAIM, DAIM), the diallyl terephthalate monomer (DATM, DATM), the diallyl adipate (Tokyo Kasei Kogyo, ADA) A hologram recording photosensitive plate having a three-layer structure was prepared in the same manner as in Example 1 except that the amounts shown in Table 2 were used, and hologram recording was performed using this.

Comparative Examples 1 to 8 Holographic recording of a three-layer structure was performed in substantially the same manner as in Example 1 except that the following compounds were used as radical polymerizable compounds in the amounts shown in Table 3 and no viscosity reducing agent was used. A photosensitive plate was prepared, and hologram recording was performed using the photosensitive plate. These radical polymerizable compounds have a lower refractive index than the allyl-based prepolymer (A).

Comparative Example 1: Ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester 1G”) Comparative Example 2: triethylene glycol dimethacrylate (manufactured by Shin Nakamura Chemical Co., “NK Ester 3G”) Comparative Example 3: Neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-NPG”) Comparative Example 4: tetraethylene glycol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., “NK Ester A-200”) Comparative Example 5: Nonaethylene Glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-400”) Comparative Example 6: Trimethylolpropane trimethacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., “NK Ester TMPT”) Comparative Example 7: tetramethylol methane tetraacrylate ( "NK ester A-TMMT" manufactured by Shin-Nakamura Chemical Co., Ltd.) Comparative Example 8 : Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester ADP-6”) Comparative Examples 9 to 13 As radical polymerizable compounds, ASF400, MPSM
A, BP-30, SR-804, NVC, DBVP were used in the amounts shown in Table 4, and no viscosity reducing agent was used.
In substantially the same manner as in Example 1, a hologram recording photosensitive plate having a three-layer structure was prepared, and hologram recording was performed using this. Each of these radical polymerizable compounds has a higher refractive index than the allyl-based prepolymer (A).

Performance Evaluation The diffraction efficiency of the transmission holograms obtained in the above Examples and Comparative Examples was measured using an optical power meter (OPTICA, manufactured by PHOTODYNE).
L POWER / ENERGYMETER, MODEL 66XLA), the ratio of the value of the incident light to the value of the diffracted light was calculated, and calculated by the following equation.

Diffraction efficiency (%) = (diffraction light intensity / incident light intensity) × 100 Further, the diffraction efficiency of the reflection hologram was measured by a transmittance using an ultraviolet-visible spectrophotometer (“V-550” manufactured by JASCO Corporation). Was determined.

Tables 1 to 4 show the evaluation of the obtained measured values.

Each of the holograms obtained in the examples was free of coloring, and was a transmission hologram and a reflection hologram having a diffraction efficiency of 30% or more without any development or fixing operation. Further, the hologram maintained its image stability for a long period of 3 months or more even when the glass was peeled off. This recording was performed not by the unevenness of the recording layer but by the refractive index modulation, and the recording was transparent with little absorption in the visible part.

On the other hand, the holograms obtained in the comparative examples all showed a diffraction efficiency of less than 10%.

[0145]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[0146]

According to the present invention, a viscosity reducing agent is added to a composition comprising an allyl-based prepolymer having at least one allyl group in the molecule, a radical polymerizable compound which is solid at ordinary temperature, and a photopolymerization initiator. Then, a combination of a radical polymerizable compound that is solid at room temperature and a liquid that is liquid as necessary is used, and the weighted average of the refractive indices of the radical heavy compound is the weighted average of the refractive indices of the allyl-based prepolymer and the viscosity reducing agent. A hologram that can record transmission holograms and reflection holograms with high diffraction efficiency while exhibiting the required properties of holograms, such as good transparency and resolution, in the same way as conventional products. A recording material composition can be provided. Further, since the hologram recording material composition according to the present invention is close to a solid and does not require a heat treatment for solidifying a fluid composition as in a conventional product, a film forming operation in the production of a hologram recording medium can be performed. It can be simplified and workability is good.

Furthermore, the recording medium after the hologram recording is:
Transparency is high, and the polymer of the allyl-based prepolymer (A) and the polymer of the radical polymerizable compound (B) are both present as a sufficient high molecular weight by only one exposure, so that they are re-diffused. There is no disadvantage that the record becomes unclear. Also, it has excellent long-term heat resistance, weather resistance, solvent resistance and the like. Therefore, development and fixing operations for stabilizing the recorded image are not essential, and a hologram can be produced in real time.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a transmission hologram.

FIG. 2 is a schematic diagram illustrating an example of a reflection hologram.

[Explanation of symbols]

 1: photosensitive plate 2: laser beam

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 20/36 C08F 20/36 4J027 20/38 20/38 4J100 212/00 212/00 220/18 220 / 18 263/08 263/08 290/02 290/02 C08K 5/00 C08K 5/00 C08L 31/08 C08L 31/08 55/00 55/00 101/00 101/00 101/02 101/02 G03F 7 / 004 501 G03F 7/004 501 7/027 502 7/027 502 7/029 7/029 7/038 501 7/038 501 (71) Applicant 000108993 Daiso Corporation 1-10-8 Edobori, Nishi-ku, Osaka-shi, Osaka (74) The above three agents 100060874 Patent Attorney Enosuke Kishimoto (four others) (72) Inventor Taichi Ichihashi 3-16-16 Kofudai, Toyono-cho, Toyono-gun, Osaka Prefecture (72) Inventor Hideo Tanigawa Ikeda-shi, Osaka Midorioka 1-chome 8-31 Industrial Technology Inside the Osaka Institute of Technology (72) Inventor Akira Hashimoto 1-10-8 Edobori, Nishi-ku, Osaka-shi, Osaka Daiso Corporation (72) Inventor Naohiko Sakashita 1-10-8 Edobori, Nishi-ku, Osaka-shi, Osaka Daiso Corporation (72) Inventor Takashi Matsuo 1-10-8 Edobori, Nishi-ku, Osaka-shi, Osaka Daiso Co., Ltd. (72) Inventor Kazunori Yokoyama 1-10-8 Edobori, Nishi-ku, Osaka-shi, Osaka Daiso Co., Ltd. F-term ( Reference) 2H025 AA01 AA04 AB14 AB20 AC08 AD01 BC13 BC19 BC42 BC83 BC92 BJ10 CA00 CC05 CC20 2K008 AA00 DD13 4J002 BF051 CP032 CQ032 EA046 EB126 ED038 EE039 EH048 EH076 EH106 EH107 EH118 EH147 EV009 EA010E0E0148 PA30 PA68 PB23 PC02 QA03 QA09 QA11 QA18 QA19 QA32 QA34 QA39 QA40 QB01 QC01 SA01 SA21 SA31 SA76 SA78 SA82 SA84 SA85 SA86 UA06 WA01 4J026 AA40 BA05 BA06 BA07 BA27 BA29 BA30 BB03 DB06 DB03 AC03 BA03 BA03 18 BA19 CA01 CA05 CA24 CA31 CB03 CB04 CB08 CB10 CC04 CD10 4J100 AB02Q AB03Q AB08P AB08Q AB09P AB09Q AB16Q AG04Q AL03Q AL04Q AL05Q AL08P AL09Q AL66P AL66Q AL67P AP01P AQ26P BA02P BA03P03 BA03 BA03 BA03 BA03 BA03 BA03 BA03 BA03 BA03 BA03 BA03 BA04 BA03P BC53Q BC54P BC65P CA01 CA04 FA03 JA38

Claims (14)

[Claims] 1. An allyl-based prepolymer (A) soluble in a solvent having at least one allyl group in the molecule, a radical polymerizable compound (B), a viscosity reducing agent (C), and a photopolymerization initiator.
(D), and the radically polymerizable compound (B) is represented by the general formula [I]: [Wherein, R ₁ and R ₂ represent the same or different monovalent organic groups, and at least one of them has a radical polymerizable group at a terminal. M ₁ and M ₂
Are the same or different from each other and are represented _by- (OR) _n1- (R
Represents a hydroxyl group and / or a lower alkylene group optionally having an oxygen atom, and n1 represents a divalent organic group or a single bond represented by 0 or an integer of 1 to 5). X ₁ and X ₂ are the same or different from each other and represent a halogen atom, a hydroxyl group, or a lower alkyl group. A fluorene compound represented by the general formula [II]: [In the formula, R ₃ and R ₄ represent the same or different monovalent organic groups, and at least one of them has a radical polymerizable group at a terminal. M ₃ and _{M 4}
Are the same or different from each other and are represented _by- (OR) _n2- (R
Represents a hydroxyl group and / or a lower alkylene group optionally having an oxygen atom, and n2 represents 0 or an integer of 1 to 5) or a divalent organic group or a single bond. X ₃ is a substituent of a ring, the same or different from each other, a halogen atom, a hydroxyl group or a lower alkyl group, 1 represents the number 0 to 6 of X ₃ , Y ₁ represents a plurality of atoms constituting the ring, It is a carbon atom or some are carbon atoms and the rest are heteroatoms. m is 5-8 ring members. A sulfide-based cyclic compound represented by the general formula [III]: [In the formula, X ₄ is a substituent of a ring, the same or different from each other, at least one is a halogen atom, and the other is a hydroxyl group or a lower alkyl group. q is an integer of 2 to 6, and R ₅ is the same or different monovalent organic group, at least one of which has a radical polymerizable group at the terminal. M ₅ is - (OR) n3 _(R is hydroxyl group and / or substituted lower alkylene group optionally having an oxygen atom, n3 is 0 or an integer of 1 to 5) a divalent organic group or a single bond represented by means. p is an integer of 1-4, Y
₂ is a plurality of atoms constituting a ring, all of which are carbon atoms, or a portion of which is a carbon atom, and the remainder are heteroatoms. k has 5 to 8 ring members. A halogenated cyclic compound represented by the general formula [IV]: [Wherein, R ₆ , R ₇ and R ₈ represent the same or different monovalent organic groups, and at least one of them has a radical polymerizable group at a terminal. M ₆ , M ₇
And M ₈ are the same or different from each other, and-(O
R) _n4- (R is a hydroxyl group and / or a lower alkylene group optionally having an oxygen atom, n4 is 0 or 1 to 5
An integer) or a divalent organic group or a single bond. X ₅ and X ₆ are ring substituents, which are the same or different from each other, and represent a halogen atom, a hydroxyl group or a lower alkyl group. At least one radical polymerizable compound (B1) selected from the group consisting of carbazole compounds represented by the following formula: fluorene compound [I], sulfide ring compound [II], halogenated ring compound At least one radically polymerizable compound (B2) other than [III] and the carbazole compound [IV]
0% by weight, and the weight ratio of the allylic pull polymer (A), the radical polymerizable compound (B) and the viscosity reducing agent (C) is (A) :( B) :( C) = 80-20: 3-60: 3-6
0, and the viscosity reducing agent (C) is an allyl-based pull polymer.
A compound (C1) that is non-reactive with (A) and the radically polymerizable compound (B), or a compound (C2) having a (meth) allyl group in the molecule, and the radically polymerizable compound (B
The weighted average of the refractive indices of 1) and the radical polymerizable compound (B2) is the refractive index and viscosity reducing agent of the allylic prepolymer (A) (C)
A hologram recording material composition, wherein the hologram recording material composition has a refractive index greater than a weighted average. 2. The weight ratio of the allylic prepolymer (A), the radical polymerizable compound (B) and the viscosity reducing agent (C) is as follows:
2. The recording material composition according to claim 1, wherein (B) :( C) = 75-30: 5-50: 5-50. 3. The recording material composition according to claim 1, wherein the allyl prepolymer (A) is a diallyl phthalate prepolymer. 4. The diallyl phthalate prepolymer comprises:
The recording material composition according to any one of claims 1 to 3, wherein the recording material composition is a homopolymer of a diallyl phthalate-based monomer or a copolymer of the same monomer and another copolymerizable monomer. 5. The diallyl phthalate-based prepolymer comprises:
The recording material composition according to claim 4, which is a prepolymer selected from the group consisting of diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer and diallyl terephthalate prepolymer, or a combination of two or more thereof. 6. The allylic prepolymer (A) having a molecular weight of 1
The recording material composition according to any one of claims 1 to 5, wherein the composition is 0000 to 100,000. 7. An allylic prepolymer (A) comprising a metal alkoxide having a metal atom, a group having an aromatic ring, and a hydrolyzable group in the presence of a diallyl phthalate monomer and / or a diallyl phthalate polymer.
The recording material composition according to any one of claims 1 to 6, which is an organic-inorganic composite transparent homogeneous material obtained by dehydration-condensation by a sol-gel method. 8. The recording material composition according to claim 1, wherein the allylic prepolymer (A) has a thioether group and / or a halogen atom bonded to a main chain. 9. The recording material composition according to claim 1, wherein the radical polymerizable compound (B1) is a fluorene compound [I]. 10. The recording material composition according to claim 1, wherein the radical polymerizable compound (B1) is a sulfide-based cyclic compound [II]. 11. The recording material composition according to claim 1, wherein the radical polymerizable compound (B1) is a halogenated cyclic compound [III]. 12. The recording material composition according to claim 1, wherein the radical polymerizable compound (B1) is a carbazole compound [IV]. 13. A hologram recording medium wherein a recording layer comprising the hologram recording material composition according to claim 1 is formed on a substrate. 14. In producing the hologram recording medium according to claim 13, an allylic prepolymer (A), a radical polymerizable compound (B), a viscosity reducing agent (C) and a photopolymerization initiator (D) are used as a solvent. A hologram recording medium in which a recording layer is formed by dissolving or suspending in a solvent, applying the resulting solution or suspension on a substrate, and then volatilizing the solvent.