JP6448042B2 - Information recording material, medium and recording apparatus therefor - Google Patents

Description

  The present invention relates to an information recording material, a medium, and a recording method thereof.

Conventionally, as optical information recording media, disk-shaped optical discs such as CD (Compact Disc), DVD (Digital Versatile Disc), and Blu-ray Disc (registered trademark, sometimes referred to as BD) have been widely used. Yes.
In recent years, such optical information recording media have been required to have a large capacity, and in fact, a very large amount of data can be recorded. CD, DVD, BD, and the like are based on the principle that fine recording marks are read by laser light, but the recording marks are arranged in a two-dimensional direction. If this is arranged in a three-dimensional direction, the capacity can be further increased. With respect to such a technique, Patent Document 1 proposes an optical information recording medium in which cavities as recording marks are arranged in a three-dimensional direction.
As another method for increasing the capacity of an optical information recording medium, an optical information recording medium has been proposed in which two light beams interfere with each other to form a minute hologram in the optical information recording medium (for example, a patent). Reference 2).
When this optical information recording medium is irradiated with reading light when reproducing information, the reproduction light returns from the medium, but the reproduction light does not return from the recording mark. The principle is to recognize which value “1” is recorded. As in this example, an optical information recording medium that forms a recording mark in which reproduction light does not return by optical processing, or a method thereof, is referred to as a “negative type micro reflector” in this specification.
For example, Patent Document 3 proposes a negative microreflector using a specific polymer and a donor-acceptor type norbornadienyl derivative.

JP 2008-176902 A Japanese Patent No. 3330854 JP 2010-237621 A

However, since the optical information recording medium of Patent Document 1 uses a cavity as a recording mark, it is difficult to highly refine the recording mark, and light having a relatively large pulse energy is necessary for forming the recording mark. Is needed. Here, the light pulse energy means the energy of the light pulse that is temporally pulsed light, and is obtained by integrating the light intensity over the duration of the light pulse and the entire irradiation area. Since the two optical information recording media use two light beams, there is a problem that high-level control is required for stable information recording or reproduction. However, there was room for improvement in writing speed.
Further, the optical information recording medium described in Patent Document 3 has room for improvement in terms of writing speed.
An object of the present invention is to enable formation of extremely fine recording marks with light of small pulse energy, easy recording or reproduction of stable information, and formation of recording marks at high speed (short time). It is to provide an optical information recording medium or the like.

As a result of intensive studies, the inventors of the present invention have a specific wavelength in the range of 365 nm to 650 nm.
(1) having a non-linear absorption coefficient in the range of 5 to 10,000 cm / GW (gigawatts);
(2) The present inventors have found that the above problems can be solved by an optical information recording material in which a multilayer diffraction grating is formed, and have completed the present invention.

  In the negative type micro reflector, the optical information recording / reproducing apparatus is used to perform initialization by forming light interference fringes over the entire information recording area in the photopolymerization type photopolymer, and such interference. Although there is Form 2 that does not perform initialization by fringe formation, the present invention relates to the former Form 1. In the present invention, the recording mark can be formed by locally destroying the diffraction grating formed by the interference fringes.

  The present invention includes the following aspects.

Item 1.
At a specific wavelength whose wavelength is in the range of 365 nm to 650 nm,
(1) having a non-linear absorption coefficient in the range of 5 to 10,000 cm / GW, and
(2) An optical recording material in which a multilayer diffraction grating is formed.
Item 2.
Item 2. The optical information recording material according to Item 1, wherein the multilayer diffraction grating is a diffraction grating formed by exposure using multilayer optical interference fringes due to optical interference.
Item 3.
A non-linear absorption dye that is a photosensitive resin and has a two-photon absorption cross-section of 50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more at a specific wavelength in the range of 365 nm to 650 nm Item 3. The optical information recording material according to Item 1 or 2.
Item 4.
In a specific wavelength containing the optical information recording material according to any one of Items 1 to 3 and having a wavelength in the range of 365 nm to 650 nm,
An optical information recording medium having a visible light transmittance of 50% or more.
Item 5.
At a specific wavelength whose wavelength is in the range of 365 nm to 650 nm,
(1) a non-linear absorption dye having a two-photon absorption cross-section of 50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more,
(2) one or more polymerizable substances selected from the group consisting of diol compounds and alicyclic epoxy group-containing cationic polymerizable compounds, and
(3) A composition containing a fluorine-containing radically polymerizable compound.
Item 6.
(1) (a) a laser that generates pulsed laser light having a pulse width in the range of 0.1 to 30 nanoseconds, (b) a wavelength in the range of 365 to 650 nm, and (c) a peak output of 1000 W or less Generator,
(2) (a) a laser condensing device provided with an objective lens having a numerical aperture in the range of 0.5 to 1.0, and (b) a magnification in the range of 1 to 100 times,
(3) (a) The optical information recording material according to any one of items 1 to 3, or (b) a storage device that stores the optical information recording medium according to item 5, and
(4) A non-linear absorption type optical information recording apparatus provided with a mechanism for scanning a predetermined condensing position in the optical information recording material or the optical information recording medium with a laser beam.

  According to the present invention, it is possible to form a very fine recording mark with light of small pulse energy, and it is easy to record or reproduce stable information, and to form a recording mark at high speed (short time). A possible optical information recording medium or the like can be provided.

FIG. 1 is a sectional view showing an outline of an example of an optical information recording medium of the present invention. FIG. 2 is a schematic diagram showing an outline of an example of the nonlinear absorption type optical information recording apparatus of the present invention. FIG. 3 is a grayscale plot of the transmission image along the x direction (lateral direction) of the optical information recording medium. FIG. 4 is a plot along the Z direction (depth direction) at the in-plane center of the recording pit of the optical information recording medium. FIG. 5 is a graph of measurement results of the nonlinear absorption coefficient by the z-scan method.

<Terminology>
Unless otherwise specified, the symbols and abbreviations in the present specification can be understood within the meanings commonly used in the technical field to which the present invention belongs in accordance with the context of the present specification.
In this specification, the phrase “containing” is intended to encompass the phrase “consisting essentially of” and the phrase “consisting of”.
Unless specifically limited, the steps, processes, or operations described herein can be performed at room temperature.
In this specification, room temperature means a temperature within the range of 5 to 40 ° C.

In the present specification, unless otherwise specified, examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the present specification, unless otherwise specified, the “organic group” means a group containing one or more carbon atoms as its constituent atoms.
In the present specification, unless otherwise specified, examples of the “organic group” include a hydrocarbon group.
In the present specification, unless otherwise specified, the “hydrocarbon group” means a group containing one or more carbon atoms and one or more hydrogen atoms as its constituent atoms.
In the present specification, unless otherwise specified, examples of the “hydrocarbon group” include an aliphatic hydrocarbon group and an aromatic hydrocarbon group (aryl group).
In the present specification, unless otherwise specified, the “aliphatic hydrocarbon group” may be linear, branched, cyclic, or a combination thereof.
In the present specification, unless otherwise specified, the “aliphatic hydrocarbon group” may be saturated or unsaturated.
In the present specification, unless otherwise specified, examples of the “aliphatic hydrocarbon group” include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group.
In the present specification, unless otherwise specified, examples of the “alkyl group” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. And a linear or branched alkyl group having 1 to 10 carbon atoms.
In the present specification, unless otherwise specified, examples of the “alkenyl group” include vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2 -Ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5- Examples thereof include straight-chain or branched alkenyl groups having 1 to 10 carbon atoms such as hexenyl.
In the present specification, unless otherwise specified, examples of the “alkynyl group” include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, Linear or branched alkynyl groups having 2 to 6 carbon atoms, such as 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and 5-hexynyl Is exemplified.
In the present specification, unless otherwise specified, examples of the “cycloalkyl group” include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopentyl group, cyclohexyl group, and cycloheptyl.

  In the present specification, unless otherwise specified, the “alkoxy group” is, for example, a group represented by RO— (wherein R is an alkyl group).

In the present specification, unless otherwise specified, the “ester group” is, for example, a group represented by RCO ₂ — (wherein R is an alkyl group).

In the present specification, unless otherwise specified, the “ether group” means a group having an ether bond (—O—) and includes a polyether group. The polyether group has the formula: R ^a — (O—R ^b ) _n — (wherein R ^a is an alkyl group, R ^b is the same or different at each occurrence, is an alkylene group, and n is 1 It is an integer of the above. An alkylene group is a divalent group formed by removing one hydrogen atom from the alkyl group.

  In the present specification, unless otherwise specified, the “acyl group” includes an alkanoyl group. In the present specification, unless otherwise specified, the “alkanoyl group” is, for example, a group represented by RCO— (wherein R is an alkyl group).

In the present specification, unless otherwise specified, examples of the “5-membered heteroaryl group” include pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (eg, 2-furyl, 3-pyrrole). Furyl), thienyl (eg, 2-thienyl, 3-thienyl), pyrazolyl (eg, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (eg, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl), Isoxazolyl (eg, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (eg, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (eg, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl) , Thiazolyl (eg, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazo (Eg, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (eg, 1,2,4-oxadiazol-3-yl, 1,2 , 4-oxadiazol-5-yl), thiadiazolyl (eg, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), etc. Examples thereof include a 5-membered heteroaryl group having 1 or more (eg, 1, 2, or 3) heteroatoms selected from the group consisting of sulfur and nitrogen.
In this specification, the “acrylate monomer” includes not only an acrylate having a hydrogen atom at the α-position but also an acrylate in which the hydrogen atom at the α-position is substituted with a substituent such as an alkyl group or a halogen atom. To do.

<Optical information recording material>
The optical information recording material of the present invention has a specific wavelength in the range of 365 nm to 650 nm.
(1) having a non-linear absorption coefficient in the range of 5 to 10,000 cm / GW, and
(2) A multilayer diffraction grating is formed.

The optical information recording material of the present invention has a nonlinear absorption coefficient in the range of 5 to 10000 cm / GW, preferably in the range of 7 to 7000 cm / GW, more preferably in the range of 50 to 6000 cm / GW, still more preferably. It has a non-linear absorption coefficient in the range of 100 to 5000 cm / GW, and more preferably in the range of 250 to 4000 cm / GW.
Since the optical information recording material of the present invention has such a non-linear absorption coefficient, it is possible to form extremely fine recording marks with light of small pulse energy, and stable information recording or reproduction is easy. In addition, recording marks can be formed at high speed (short time).
When the pulse energy is small, it is difficult to form a recording mark at high speed. A larger pulse energy is advantageous in that a recording mark can be made at a higher speed, but if this is too large, (1) the recording area may be increased, leading to a decrease in information recording density, and (2) If it is too large, the medium may be destroyed undesirably.

と表される。
ここでＩ［Ｗ／ｃｍ^２］は試料透過後の光強度であり、α［ｃｍ^−１］は吸収係数である。通常は定数として扱われるこの吸収係数が実測時に光強度に依存する場合、以下のように、光強度に依存しない部分α_Ｌと、依存する部分α_ＮＬ（Ｉ_０）に分けて定義する。

ここで、α_Ｌを線形吸収係数、α_ＮＬ（Ｉ_０）を非線形吸収係数と名付ける。吸収係数が入射光強度に依存しない場合はα＝α_Ｌであり、α_ＮＬ（Ｉ_０）＝０とみなすことができる。
式２の定義において、ここではα_ＮＬ（Ｉ_０）が定数とは限らないと考える（このことを明示的に示すため、Ｉ_０の関数の形で書いている）。すなわちα_ＮＬ（Ｉ_０）自体が入射光強度Ｉ_０に依存するものも含める。この定義は現象論的なものであり、どのような機構において光強度に依存した吸収が現れるかを問わない。
一方、同様な定義であるが、入射光強度に対してベキ展開を行うことができる。

の定義が一般になされており、ここでα⁽ⁿ⁾はｎ光子吸収係数と呼ばれる。
α⁽ⁿ⁾は、ｎが２の場合は、二光子吸収係数である。
この定義においてα⁽ⁿ⁾はＩ_０に依存しない定数と考える。ここで直ちにα_Ｌ＝α^（１）であり、どちらも同一の線形吸収係数である。もしα_ＮＬ（Ｉ_０）がＩ_０に対して定数である場合は、α_ＮＬ（Ｉ_０）＝α^（２）となり非線形吸収係数α^（２）と一致するが、一般には数式３の右辺第２項以降を全て含む、

に相当するものである。In this specification, the “nonlinear absorption coefficient” is defined as follows.
The transmittance T when incident light of light intensity I ₀ [W / cm ² ] passes through a sample with a thickness of L [cm] is based on the Beer-Lambert law.

It is expressed.
Here, I [W / cm ² ] is the light intensity after passing through the sample, and α [cm ⁻¹ ] is the absorption coefficient. When this absorption coefficient, which is normally treated as a constant, depends on the light intensity at the time of actual measurement, it is defined by dividing into a part α _L that does not depend on the light intensity and a dependent part α _NL (I ₀ ) as follows.

Here, α _L is named a linear absorption coefficient, and α _NL (I ₀ ) is named a non-linear absorption coefficient. When the absorption coefficient does not depend on the incident light intensity, α = α _L and α _NL (I ₀ ) = 0 can be considered.
In the definition of Equation 2, α _NL (I ₀ ) is not necessarily a constant here (in order to express this explicitly, it is written in the form of a function of I ₀ ). That is, α _NL (I ₀ ) itself also includes those depending on the incident light intensity I ₀ . This definition is phenomenological, and it does not matter in what mechanism the absorption depending on the light intensity appears.
On the other hand, although it is the same definition, a power expansion can be performed with respect to incident light intensity.

Is generally defined, where α ⁽ⁿ⁾ is called the n photon absorption coefficient.
α ⁽ⁿ⁾ is a two-photon absorption coefficient when n is 2.
In this definition, α ⁽ⁿ⁾ is considered as a constant independent of I ₀ . Here, α _L = α ⁽¹⁾ immediately, both of which have the same linear absorption coefficient. If α _NL (I ₀ ) is a constant with respect to I ₀ , α _NL (I ₀ ) = α ⁽²⁾ , which matches the nonlinear absorption coefficient α ⁽²⁾ . Including all 2nd and later,

It is equivalent to.

In the optical information recording material of the present invention, a multilayer diffraction grating is formed.
The multilayer diffraction grating formed in the optical information recording material of the present invention preferably has a structure in which a large number of layers having a higher refractive index and layers having a lower refractive index are alternately stacked. Thus, when the optical information recording material of the present invention is irradiated with reading light, the light is diffracted and returned to a high degree as reproduction light.
In the optical information recording material of the present invention, the difference in refractive index (Δn) between a layer having a higher refractive index and a layer having a lower refractive index that are adjacent to each other is larger. In this case, when the readout light is irradiated, the reproduction light becomes stronger from the medium, and the ratio with the intensity of the background optical noise, which is always present in a certain amount, the so-called signal / noise ratio or S / N ratio is improved, and the noise is increased. Recording / reproducing light with a small amount can be obtained. At this time, the difference in refractive index (Δn) is preferably 0.001 or more, more preferably 0.005, more preferably 0.01 or more, and still more preferably 0.02 or more.
Although the upper limit is not specifically limited, For example, it can be 0.5.

The number of diffraction grating layers included in the optical information recording material of the present invention depends on the film thickness of the material layer. For example, when the film thickness of the material layer is 100 μm, it is preferably 4 or more, more preferably 10 or more, and More preferably, it is 50 or more.
Although there is no upper limit to the number of diffraction grating layers included in the optical information recording material of the present invention, the upper limit can usually be 1000 when the thickness of the material layer is 1000 μm.
The number of diffraction grating layers of the optical information recording material of the present invention can be confirmed using, for example, a phase difference TEM.
In the optical information recording material of the present invention, when the material is a layer (or a plane or a film), the direction perpendicular to this layer, in other words, the direction parallel to the direction in which the film thickness of the material layer is defined is as follows. This is called the depth direction. In the optical information recording material of the present invention having a certain film thickness, the number of recording markers that can hold information independent of each other along the depth direction is defined as the number of information recording layers. Further, the thickness obtained by dividing the film thickness by the number of information recording layers is the information recording layer thickness, and the information recording layer thickness needs to be at least equal to or greater than the layer thickness of the diffraction grating shown below. .
Although the number of information recording layers depends on the thickness of the material layer, for example, when the thickness of the material layer is 100 μm, it is preferably 4 or more, more preferably 10 or more, and still more preferably 50 or more.
Although there is no upper limit to the number of information recording layers of the optical information recording material of the present invention, the upper limit can usually be 1000 when the thickness of the material layer is 1000 μm.

The multilayer diffraction grating can be preferably formed by exposure using multilayer optical interference fringes due to optical interference.
By using the optical interference fringes, a diffraction grating having an extremely large number of layers can be formed in a short time.

On the other hand, as described above, the optical information recording material of the present invention has a multilayer diffraction grating, so that the optical information recording material of the present invention can extremely reduce the thickness of a single layer of the diffraction grating. .
The thickness of the single layer of the diffraction grating is preferably in the range of 50 to 500 nm, more preferably in the range of 60 to 400 nm, still more preferably in the range of 80 to 300 nm, and even more preferably 100 to 250 nm. Can be within the range of The thickness of the single layer of the diffraction grating can be confirmed using, for example, a phase difference TEM.
Even with this, it is possible to form extremely fine recording marks with light of small pulse energy, it is easy to record or reproduce stable information, and it is possible to form recording marks at high speed (short time). Become.
The thickness of the single layer of the diffraction grating is approximate to the wavelength length of the light source irradiated when reading the optical information of the optical information recording material of the present invention, or 1/2 or 1 / of the wavelength of the light source. 4 is desirable.

The optical information recording material of the present invention is preferably a photosensitive resin and has a wavelength of 365 × 650 nm at a specific wavelength of 50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ^−1. It contains a nonlinear absorption dye having the above two-photon absorption cross section. The two-photon absorption cross section can be determined by the method described in Non-Patent Document 1 or 2, for example.
In the present specification, the dye may be referred to as a “nonlinear absorbing dye”.
[Non-Patent Document 1]
Kenji Kamada, “Evaluation Method of Two-Photon Absorbing Materials”, “Development and Application of Highly Efficient Two-Photon Absorbing Materials”, Toshiyuki Watanabe, Chapter 2, CMC Publishing, 2011, pp.16-27.
[Non-Patent Document 2]
M. Sheik-Bahae, AA Said, TH Wei, DJ Hagan, EW Van Stryland, IEEE J. Quant. Electron., 1990, 26, 760-769.

The optical information recording material of the present invention is preferably an optical information recording material produced by a production method including the following steps (1), (2), and (3), or a production method according thereto, for example. be able to.
That is, the optical information recording material and the composition for optical information recording material of the present invention can each contain a compound described in the following production method or a compound derived therefrom.
For example, specifically, the optical information recording material of the present invention includes the compositions of the following examples.
Example 1-1)
Diol compounds,
An alicyclic epoxy group-containing cationic polymerizable compound,
Fluorine-free radically polymerizable compound,
Optional cationic polymerization catalyst,
A composition comprising a nonlinear absorbing dye and an optional photoinitiator.
Example 1-2)
Diol compounds,
An alicyclic epoxy group-containing cationic polymerizable compound,
Fluorine-free radically polymerizable compound,
Optional cationic polymerization catalyst,
A composition containing a non-linear absorbing dye and an optional photopolymerization initiator and / or a compound derived therefrom.
Example 2-1)
Diol compounds,
An alicyclic epoxy group-containing cationic polymerizable compound,
Fluorine-containing radically polymerizable compound,
Optional cationic polymerization catalyst,
A composition comprising a nonlinear absorbing dye and an optional photoinitiator.
Example 2-2)
Diol compounds,
An alicyclic epoxy group-containing cationic polymerizable compound,
Fluorine-containing radically polymerizable compound,
Optional cationic polymerization catalyst,
A composition containing a non-linear absorbing dye and an optional photopolymerization initiator and / or a compound derived therefrom.

One preferred embodiment of the composition of the present invention is:
A non-linear absorption dye having a two-photon absorption cross section of 50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more at a specific wavelength in the range of 365 nm to 650 nm;
Diol compounds,
It is a composition containing an alicyclic epoxy group-containing cationically polymerizable compound and a fluorine-containing radically polymerizable compound.
Here, the fluorine-containing radical polymerizable compound can be preferably a fluorine-containing acrylate monomer.
Since the fluorine-containing radical polymerizable compound has a low refractive index, it is possible to reduce the noise of the reproduction signal by increasing the refractive index difference of the diffraction grating during the initialization.

Step (1) Preparation of composition for optical information recording material

  Suitable examples of the preparation of examples of the composition for optical information recording material of the present invention include the following preparation method examples.

Preparation method example 1)
Diol compounds,
An alicyclic epoxy group-containing cationic polymerizable compound,
Fluorine-free radically polymerizable compound,
A preparation method comprising a step of mixing a cationic polymerization catalyst, a non-linear absorbing dye, and a photopolymerization initiator.

Preparation method example 2)
Diol compounds,
An alicyclic epoxy group-containing cationic polymerizable compound,
Fluorine-containing radically polymerizable compound,
A preparation method comprising a step of mixing a cationic polymerization catalyst, a non-linear absorbing dye, and a photopolymerization initiator.
Here, since a high refractive index difference is obtained in the diffraction grating, the method of Preparation Method Example 2) can be suitably employed.

Examples of the “diol compound” include those represented by the formula: HO— (CH ₂ ) _a1 — ((CH ₂ ) _b —O) c— (CH ₂ ) _a2 —OH, wherein a1 and a2 are the same or different Represents 0, 1, or 2, b represents 1 to 10, and c represents a number of 1 to 100. ] The compound represented by this is included.
Specific examples are:
Monohydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monobutyl ether and their alkylene oxide adducts; and ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl-1,3-hexanediol) 2-butyl-2-ethyl-1,3-propanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,2-hexadecanediol, 1,2-octadecanediol, Includes aliphatic diols such as 1,12-octadecanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.

The “alicyclic epoxy group-containing cationic polymerizable compound” is, for example, a compound containing an epoxy group-containing cycloalkyl group.
The “alicyclic epoxy group-containing cationic polymerizable compound” can be a polyfunctional epoxy compound having two or more epoxy groups.
Examples of the alicyclic epoxy resin include 3,4,3 ′, 4′-diepoxybicyclohexyl, bis (3,4-epoxycyclohexyl) adipate, and the like.

（式中、ｒは、０〜１０の数を表す。）
で表される化合物を包含する。
ここで、当該化合物は、ｒが０の化合物と、ｒが１〜１０の数である化合物との混合物（例、当量混合物）であってもよい。Examples of the “polyfunctional epoxy compound” include the following formula (1):

(In the formula, r represents a number of 0 to 10.)
The compound represented by these is included.
Here, the compound may be a mixture (eg, equivalent mixture) of a compound in which r is 0 and a compound in which r is a number of 1 to 10.

  Examples of the “polyfunctional epoxy compound” also include the following compounds.

前記式（２）中、ｓは、１以上の数を表を表す。
前記式（３）中、ｔ、およびｕは、それぞれ０以上の数を表す。

In the formula (2), s represents a number of 1 or more.
In the formula (3), t and u each represent a number of 0 or more.

［式中、Ｒ^ｂは、単結合、−Ｏ−、−ＣＯ−または−ＯＣ（Ｏ）−であり、
Ｒ^ｃは、水素原子、炭素数１〜１０のアルキル基（好ましくは、炭素数１〜３のアルキル基、より好ましくはメチル基）、ラクタム基（好ましくは、β-ラクタム、γ-ラクタムまたはδ-ラクタム基、より好ましくはγ-ラクタム基）またはフェニル基を表し、好ましくは、メチル基または水素原子である。］
で表される基である。
より好ましいラジカル重合性基は、下記式：

［式中、Ｒ^ｃは、上記と同意義である。］
で表される基である。
さらに好ましいラジカル重合性基は、アクリロイル基またはメタクリロイル基である。
本発明における当該フッ素不含有ラジカル重合性化合物の好適な例は、アクリレート単量体、およびこれに由来する構成単位を有するアクリル共重合体を包含する。
前記「フッ素不含有ラジカル重合性化合物」の例としては、
スチレン、α−メチルスチレン、
２−ブロモスチレン、酢酸ビニル、メチルビニルケトン、アクリロニトリル、Ｎ−ビニルカルバゾール、Ｎ−ビニルピロリドン、アクリレート、メチルアクリレート、ｎ−ブチルアクリレート、ラウリルアクリレート、２−エチルヘキシルアクリレート、ジシクロペンタニルアクリレート、フェニルアクリレート、ｏ−ビフェニルアクリレート、２−ナフチルアクリレート、エチレンオキシドフェノールアクリレート、フェノキシジエチレングリコールアクリレート、フェノキシ−ポリエチレングリコールアクリレート、ノニルフェノールエチレンオキシドアクリレート、ビスフェノールＡエチレンオキシドジアクリレート、エチレンオキシドテトラブロモビスフェノールＡジアクリレート、エチレンオキシドビスフェノールＡジアクリレート、プロピレンオキシドビスフェノールＡジアクリレート、プロポキシ化エトキシ化ビスフェノールＡジアクリレート、ジメチロール−トリシクロデカンジアクリレート、プロピレンオキシドトリメチロールプロパントリアクリレート、ウレタンアクリレート、ε−カプロラクトン酸トリス−（２−アクリロキシエチル）イソシアヌレート、メトキシポリエチレングリコールアクリレート、ポリプロピレングリコール４００ジアクリレート、オクトキシポリエチレングリコール−ポリプロピレングリコールモノアクリレート、トリメチロールプロパントリアクリレート、トリブロモフェニルアクリレート、エチレンオキシドトリブロモフェニルアクリレート、フェニルフェノールグリシジルエーテルアクリレート、２−メチル−２アダマンチルアクリレート、３−ヒドロキシ−１−アダマンチルアクリレート、１−アダマンチルアクリレート、フェニルエチルアクリレート、２−フェニルエチルアクリレート、２−フェノキシエチルアクリレート、２−（９−カルバゾリル）エチルアクリレート、メチルフェノキシエチルアクリレート、トリフェニルメチルチオアクリレート、２−（ｐ−クロロフェノキシ）エチルアクリレート、ノニルフェノキシエチルアクリレート、フェノールエトキシレートモノアクリレート、ｐ−クロロフェニルアクリレート、２−（１−ナフチルオキシ）エチルアクリレート、２，４，６−トリブロモフェニルアクリレート、イソボニルアクリレート、ヒドロキシエチルアクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート、２，３−ジブロムプロピルアクリレート、２−（トリシクロ［５，２，１０^２．６］ジブロモデシルチオ）エチルアクリレート、テトラメチレングリコールジアクリレート、エチレングリコールジアクリレート、ジエチレンジチオグリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、フェノキシポリエチレングリコールアクリレート、プロピレングリコールジアクリレート、メトキシプロピレングリコールアクリレート、１，３−ブタンジオールジアクリレート、ネオペンチルグリコールジアクリレート、ヘキサンジオールジアクリレート、１，４−シクロヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールトリアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、ソルビトールトリアクリレート、ソルビトールテトラアクリレート、ソルビトールペンタアクリレート、ソルビトールヘキサアクリレート、２−エチルヘキシルカルビトールアクリレート、Ｓ−（１−ナフチルメチル）チオアクリレート、β−アクリロキシエチルハイドロゲンフタレート、エトキシ化されたビスフェノールＡジアクリレート、イタコン酸、マレイン酸、Ｎ−アクリロイルモルホリン、α−シアノアクリル酸メチル、ビニル−２−クロロエチルエーテル、ビニル−ｎ−ブチルエーテル、トリエチレングリコールジビニルエーテル、トリメチロールエタントリビニルエーテル、１，４−シクロヘキサンジメタノールジビニルエーテル、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、ビスフェノールＡの（２−アクリルオキシエチル）エーテル、ビス（４−アクリロキシジエトキシフェニル）メタン、ビス（４−アクリロキシエトキシ−３，５−ジブロモフェニル）メタン、２，２−ビス（４−アクリロキシエトキシフェニル）プロパン、２，２−ビス（４−アクリロキシジエトキシフェニル）プロパン、２，２−ビス（４−アクリロキシエトキシ−３，５−ジブロモフェニル）プロパン、２，３−ナフタレンジカルボン酸（アクリロキシエチル）モノエステル、２，３−ナフタリンジカルボン酸（２−アクリロキシエチル）（３−アクリロキシプロピル−２−ヒドロキシ）ジエステル、４，５−フェナントレンジカルボン酸（２−アクリロキシエチル）（３−アクリロキシプロピル−２−ヒドロキシ）ジエステル、ジフェン酸（２−メタクリロキシエチル）モノエステル、ジフェン酸（２−アクリロキシエチル）（３−アクリロキシプロピル−２−ヒドロキシ）ジエステル、１，３−ビス［２−アクリロキシ−３−（２，４，６−トリブロモフェノキシ）プロポキシ］ベンゼン、ビス（４−アクリロキシエトキシフェニル）スルホン、ビス（４−アクリロキシジエトキシフェニル）スルホン、ビス（４−アクリロキシプロポキシフェニル）スルホン、ビス（４−アクリロキシエトキシ−３，５−ジブロモフェニル）スルホン、および４，４’−ビス（β−アクリロイルオキシエチルチオ）ジフェニルスルホン
ならびに前記化合物におけるアクリレートをメタクリレートに変えた化合物などが挙げられる。（メタ）アクリル酸とジオールとのエステル基を有する化合物としては、具体的には、下記化学式：

（化学式中、ｑ及びｐは同一又は異なり０〜６であってｑ＋ｐ＝２〜６となる数、Ｒ^３及びＲ^４は同一又は異なり水素原子又はメチル基）が挙げられる。
ｑ＋ｐが５であると、より好ましい。具体的には、
９，９−ビス（４−アクリロキシジプロポキシフェニル）フルオレン、
９，９−ビス（４−アクリロキシエトキシ−３，５−ジメチル）フルオレン、
９，９−ビス（４−アクリロキシトリエトキシフェニル）フルオレン、
９，９−ビス（４−アクリロキシエトキシ−３−メチルフェニル）フルオレン、
９，９−ビス（４−アクリロキシエトキシ−３−エチルフェニル）フルオレン、および
９，９−ビス（４−アクリロキシジエトキシフェニル）フルオレン
などが挙げられる。The fluorine-free radically polymerizable compound is a compound having a radically polymerizable group.
A preferred radical polymerizable group is represented by the following formula:

[Wherein, R ^b is a single bond, —O—, —CO— or —OC (O) —,
R ^c is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), a lactam group (preferably β-lactam, γ-lactam or δ A -lactam group, more preferably a γ-lactam group) or a phenyl group, preferably a methyl group or a hydrogen atom. ]
It is group represented by these.
More preferred radical polymerizable groups have the following formula:

[Wherein R ^c has the same meaning as described above. ]
It is group represented by these.
A more preferred radical polymerizable group is an acryloyl group or a methacryloyl group.
Suitable examples of the fluorine-free radically polymerizable compound in the present invention include an acrylate monomer and an acrylic copolymer having a structural unit derived therefrom.
Examples of the “fluorine-free radical polymerizable compound” include
Styrene, α-methylstyrene,
2-bromostyrene, vinyl acetate, methyl vinyl ketone, acrylonitrile, N-vinyl carbazole, N-vinyl pyrrolidone, acrylate, methyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, dicyclopentanyl acrylate, phenyl acrylate , O-biphenyl acrylate, 2-naphthyl acrylate, ethylene oxide phenol acrylate, phenoxydiethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, nonylphenol ethylene oxide acrylate, bisphenol A ethylene oxide diacrylate, ethylene oxide tetrabromobisphenol A diacrylate, ethylene oxide bisphenol A diacrylate , Propylene oxide bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate, dimethylol-tricyclodecane diacrylate, propylene oxide trimethylolpropane triacrylate, urethane acrylate, ε-caprolactone acid tris- (2-acryloxyethyl) isocyanate Nurate, methoxypolyethylene glycol acrylate, polypropylene glycol 400 diacrylate, octoxy polyethylene glycol-polypropylene glycol monoacrylate, trimethylolpropane triacrylate, tribromophenyl acrylate, ethylene oxide tribromophenyl acrylate, phenylphenol glycidyl ether acrylate, 2-methyl- 2 Adamantyl Acrylate, 3-hydroxy-1-adamantyl acrylate, 1-adamantyl acrylate, phenylethyl acrylate, 2-phenylethyl acrylate, 2-phenoxyethyl acrylate, 2- (9-carbazolyl) ethyl acrylate, methylphenoxyethyl acrylate, triphenylmethylthio Acrylate, 2- (p-chlorophenoxy) ethyl acrylate, nonylphenoxyethyl acrylate, phenol ethoxylate monoacrylate, p-chlorophenyl acrylate, 2- (1-naphthyloxy) ethyl acrylate, 2,4,6-tribromophenyl acrylate , Isobornyl acrylate, hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2,3-dibu Arm propyl acrylate, 2- (tricyclo [5,2,10 ^2.6] dibromo decyl thio) ethyl acrylate, tetramethylene glycol diacrylate, ethylene glycol diacrylate, diethylene dithio glycol diacrylate, triethylene glycol diacrylate, tetraethylene Glycol diacrylate, polyethylene glycol diacrylate, phenoxy polyethylene glycol acrylate, propylene glycol diacrylate, methoxypropylene glycol acrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, trimethylolpropane triacrylate, trimethylo Ruethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetra Acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, 2-ethylhexyl carbitol acrylate, S- (1-naphthylmethyl) thioacrylate, β-acryloxyethyl hydrogen phthalate, ethoxylated bisphenol A diacrylate, itaconic acid, maleic acid N-acryloylmorpholine, α-si Methyl anoacrylate, vinyl-2-chloroethyl ether, vinyl-n-butyl ether, triethylene glycol divinyl ether, trimethylolethane trivinyl ether, 1,4-cyclohexanedimethanol divinyl ether, trimethylolpropane tri (acryloyloxypropyl) Ether, (2-acryloxyethyl) ether of bisphenol A, bis (4-acryloxydiethoxyphenyl) methane, bis (4-acryloxyethoxy-3,5-dibromophenyl) methane, 2,2-bis (4 -Acryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxy-3,5-dibromophenyl) propane, 2,3-naphthalene Carboxylic acid (acryloxyethyl) monoester, 2,3-naphthalene dicarboxylic acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diester, 4,5-phenanthrene dicarboxylic acid (2-acryloxyethyl) ) (3-acryloxypropyl-2-hydroxy) diester, diphenic acid (2-methacryloxyethyl) monoester, diphenic acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diester, 1, 3-bis [2-acryloxy-3- (2,4,6-tribromophenoxy) propoxy] benzene, bis (4-acryloxyethoxyphenyl) sulfone, bis (4-acryloxydiethoxyphenyl) sulfone, bis ( 4-acryloxypropoxyphenyl) sulfone Bis (4-acryloxyethoxy-3,5-dibromophenyl) sulfone, and 4,4'-bis etc. (beta-acryloyloxyethyl) diphenylsulfone and compounds acrylate was changed to methacrylate in the compounds. Specifically, the compound having an ester group of (meth) acrylic acid and diol has the following chemical formula:

(In the chemical formula, q and p are the same or different and are 0 to 6 and q + p = 2 to 6, and R ³ and R ⁴ are the same or different and are a hydrogen atom or a methyl group).
It is more preferable that q + p is 5. In particular,
9,9-bis (4-acryloxydipropoxyphenyl) fluorene,
9,9-bis (4-acryloxyethoxy-3,5-dimethyl) fluorene,
9,9-bis (4-acryloxytriethoxyphenyl) fluorene,
9,9-bis (4-acryloxyethoxy-3-methylphenyl) fluorene,
Examples include 9,9-bis (4-acryloxyethoxy-3-ethylphenyl) fluorene and 9,9-bis (4-acryloxydiethoxyphenyl) fluorene.

および

が挙げられる。
前記「フッ素不含有ラジカル重合性化合物」の例としては、さらに、２，４−ビス（β−アクリロイルオキシエチルチオ）ジフェニルケトン、４，４’−ビス（β−アクリロイルオキシエチルチオ）ジフェニルケトン、４，４’−ビス（β−アクリロイルオキシエチルチオ）ジフェニルケトン、トリ（アクリロイルオキシエチル）イソシアヌレート、アクリルアミド、メチレンビスアクリルアミド、ジアセトンアクリルアミド、シクロヘキセンオキシド、エトキシ化プロピレングリコール７００ジアクリレート、プロポキシ化エトキシ化ジアクリレート、デンドリマー（２世代）アクリレート、および前記におけるアクリレートをメタクリレートに変えた化合物などが挙げられる。
前記「フッ素不含有ラジカル重合性化合物」の例は、前記で例示したこれらに限定されるものではなく、記録感度や多重記録性の点から、９，９−ビス（４−アクリロキシジプロポキシフェニル）フルオレン、ジアリルフタレートモノマー、プロポキシ化エトキシ化ビスフェノールＡジアクリレート、ポリプロピレングリコール７００ジアクリレート、α−フルオロアクリロイル基またはアクリロイル基を有するものおよび前記におけるアクリレートをメタクリレートに変えた化合物などが好ましい。Examples of the “fluorine-free radical polymerizable compound” are further diallyl phthalate monomers,

and

Is mentioned.
Examples of the “fluorine-free radically polymerizable compound” further include 2,4-bis (β-acryloyloxyethylthio) diphenyl ketone, 4,4′-bis (β-acryloyloxyethylthio) diphenyl ketone, 4,4′-bis (β-acryloyloxyethylthio) diphenyl ketone, tri (acryloyloxyethyl) isocyanurate, acrylamide, methylenebisacrylamide, diacetone acrylamide, cyclohexene oxide, ethoxylated propylene glycol 700 diacrylate, propoxylated ethoxy Diacrylate, dendrimer (2nd generation) acrylate, and compounds obtained by replacing acrylate with methacrylate.
Examples of the “fluorine-free radically polymerizable compound” are not limited to those exemplified above, but 9,9-bis (4-acryloxydipropoxyphenyl) from the viewpoint of recording sensitivity and multiple recording properties. ) Fluorene, diallyl phthalate monomer, propoxylated ethoxylated bisphenol A diacrylate, polypropylene glycol 700 diacrylate, those having an α-fluoroacryloyl group or acryloyl group, and compounds in which the acrylate is changed to methacrylate are preferred.

［式中、Ｒ^ｂは、単結合、−Ｏ−、−ＣＯ−または−ＯＣ（Ｏ）−であり、
Ｒ^ｃは、水素原子、フッ素原子、あるいはフッ素原子により置換されていてもよい炭素数１〜１０のアルキル基（好ましくは、炭素数１〜３のアルキル基、より好ましくはメチル基）、ラクタム基（好ましくは、β-ラクタム、γ-ラクタムまたはδ-ラクタム基、より好ましくはγ-ラクタム基）またはフェニル基を表し、好ましくは、メチル基または水素原子である。］
で表される基である。
より好ましいラジカル重合性基は、下記式：

［式中、Ｒ^ｃは、上記と同意義である。］
で表される基である。
さらに好ましいラジカル重合性基は、アクリロイル基またはメタクリロイル基である。
本発明における当該フッ素含有ラジカル重合性化合物の好適な例は、フッ素含有基を有するアクリレート単量体、およびこれに由来する構成単位を有するアクリル共重合体を包含する。The fluorine-containing radical polymerizable compound is a compound having a radical polymerizable group.
A preferred radical polymerizable group is represented by the following formula:

[Wherein, R ^b is a single bond, —O—, —CO— or —OC (O) —,
R ^c is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), a lactam group. (Preferably β-lactam, γ-lactam or δ-lactam group, more preferably γ-lactam group) or a phenyl group, preferably a methyl group or a hydrogen atom. ]
It is group represented by these.
More preferred radical polymerizable groups have the following formula:

[Wherein R ^c has the same meaning as described above. ]
It is group represented by these.
A more preferred radical polymerizable group is an acryloyl group or a methacryloyl group.
Suitable examples of the fluorine-containing radical polymerizable compound in the present invention include an acrylate monomer having a fluorine-containing group, and an acrylic copolymer having a structural unit derived therefrom.

［式中、Ｘは、水素原子、メチル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ¹Ｘ²基（但し、Ｘ¹およびＸ²は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１〜１０の脂肪族基、酸素原子を有していてもよい炭素数６〜１０の芳香族基、環状脂肪族基または芳香脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）または−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、
Ｒｆは炭素数１〜７の直鎖状または分岐状のフルオロアルキル基、炭素数２〜７のフルオロアルケニル基または、繰り返し単位：−Ｃ_３Ｆ_６Ｏ−、−Ｃ_２Ｆ_４Ｏ−および−ＣＦ_２Ｏ−からなる群から選択された少なくとも一種の繰り返し単位の合計数が１〜２００のフルオロエーテル基である。］
で示される。
好ましくは、Xは水素原子またはメチル基である。Examples of the acrylate monomer having a fluorine-containing group include a formula (4):

[Wherein, X represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² represent a hydrogen atom, a fluorine atom, a chlorine atom, bromine A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or a —CH ₂ CH (OY ¹ ) CH ₂ — group ( Y ¹ is a hydrogen atom or an acetyl group.
Rf is a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, or fluoroalkenyl group having 2 to 7 carbon atoms, repeating _{units: -C 3 F 6 O -,} - C 2 F 4 O- and - The total number of at least one repeating unit selected from the group consisting of CF ₂ O— is a fluoroether group having 1 to 200. ]
Indicated by
X is preferably a hydrogen atom or a methyl group.

In the formula (I), when the Rf group is a fluoroalkyl group, it is preferably a perfluoroalkyl group. Examples of Rf _{groups, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3 ) ₂ , —C (CF ₃ ) ₃ , — (CF ₂ ) ₄ CF ₃ , — (CF ₂ ) ₂ CF (CF ₃ ) ₂ , —CF ₂ C (CF ₃ ) ₃ , —CF (CF ₃ ) CF ₂ CF ₂ CF ₃ , — (CF ₂ ) ₅ CF ₃ , — (CF ₂ ) ₃ CF (CF ₃ ) ₂ , — (CF ₂ ) ₄ CF (CF ₃ ) ₂ , — (CF ₂ ) ₂ H, — _{CF 2 CFHCF 3, - (CF} 2) 4 H, and - _{(CF 2) 6} H, and the like. When the Rf group is a fluoroalkyl group, the number of carbon atoms of the Rf group is 1 to 7, for example 2 to 6, particularly 4 to 6, particularly 6 from the viewpoints of PFOA and functions described above. Is preferred.
When the Rf group is a fluoroalkenyl group, it is preferably a perfluoroalkenyl group. Examples of Rf _{groups, -CF = CF (CF 3)} , - CF = C (CF 3) 2, -CF = C (CF 3) (CF 2 CF 2 CF 3), - CF = C (CF 3) _{(CF (CF 3) 2)} , - C (CF 3) = CF (CF (CF 3) 2), - C (CF 2 CF 3) = C (CF 3) is _2, and the like. When the Rf group is a fluoroalkenyl group, the Rf group preferably has 2 to 7 carbon atoms, particularly 3 to 6 carbon atoms, especially 6 carbon atoms.

When the Rf group is a fluoroether group, the fluoroether group is at least one repeating unit selected from the group consisting of —C ₃ F ₆ O—, —C ₂ F ₄ O— and —CF ₂ O— (oxypar Fluoroalkylene group). -C ₃ F ₆ O- is -CF ₂ CF ₂ CF ₂ O- or -CF ₂ C (CF ₃₎ is fo-. -C ₂ F ₄ O- is generally _-CF 2 _CF 2 O- are. The total number of oxyperfluoroalkylene repeating units is 1 to 200, for example 1 to 100, in particular 5 to 50. The fluoroether group has a terminal group that is directly bonded to the oxyperfluoroalkylene repeat unit. Examples of the terminal group are a hydrogen atom, a halogen atom (for example, a fluorine atom), an alcohol group (for example, HOCH ₂ —), an amine group (for example, H ₂ N—), and a chloromethyl group (ClH ₂ C—). . The fluoroether group may have a fluoroalkylene group having 1 to 10 carbon atoms, particularly a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of fluoroalkylene group having 1 to 10 carbon atoms, -CF ₂ - and _-CF 2 CF ₂ - is.

Examples of fluoroether groups (particularly perfluoroether groups) that are examples of Rf groups are as follows.
F- (CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF _2- (n is 1 to 200)
F- (CF ₂ C (CF ₃ ) FO) _n -CF ₂ CF _2- (n is 1 to 200)
F- (CF ₂ C (CF ₃ ) FO) _n- (CF ₂ O) _m -CF ₂ CF _2- (total of n and m is 1 to 200)
F- (CF ₂ CF ₂ O) _n- (CF ₂ O) _m -CF ₂ CF _2- (total of n and m is 1 to 200)

Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or a —CH ₂ CH (OY ¹ ) CH ₂ — group ( However, Y < ¹ > is a hydrogen atom or an acetyl group.). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2). The aromatic group, cycloaliphatic group and araliphatic group may be either substituted or unsubstituted.

Examples of the acrylate monomer having a fluorine-containing group are as follows.
Rf- (CH ₂ ) ₁₀ OCOCH═CH _{2
Rf- (CH 2) 10 OCOC (} CH 3) = CH 2
Rf—CH ₂ OCOCH═CH _{2
Rf-CH 2 OCOC (CH 3} ) = CH 2
Rf- (CH ₂ ) ₂ OCOCH═CH ₂
Rf- (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH _{2
Rf-SO 2 N (CH 3} ) (CH 2) 2 OCOCH = CH 2
_{Rf-SO 2 N (C 2} H 5) (CH 2) 2 OCOCH = CH 2
_{Rf-CH 2 CH (OCOCH 3} ) CH 2 OCOC (CH 3) = CH 2
_{Rf-CH 2 CH (OH)} CH 2 OCOCH = CH 2

Wherein, Rf is a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, or fluoroalkenyl group having 2 to 7 carbon atoms, repeating _{units: -C 3 F 6 O -,} - C 2 F 4 It is a fluoroether group in which the total number of at least one repeating unit selected from the group consisting of O— and —CF ₂ O— is 1 to 200. ]

Examples of the cationic polymerization catalyst include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, aromatic phosphonium salts, mixed ligand metal salts, and aromatic onium salts. For example, Sun-Aid SI-60L, 80L, 110L (all manufactured by Sanshin Chemical Industry Co., Ltd .: trade name) can be used.
The two-photon absorption cross-section of the “nonlinear absorption dye” used in the present invention has a specific wavelength in the range of 365 nm to 650 nm.
It must be within the range of ^{50 to} 100,000 × 10 ⁻⁵⁰ cm ⁴ · s · molecule ⁻¹ · photon ⁻¹ , preferably 100 to 90000 × 10 ⁻⁵⁰ cm ⁴ · s · molecule ⁻¹ · photon ⁻¹ Within the range, more preferably within the range of 150 to 70000 × 10 ⁻⁵⁰ cm ⁴ · s · molecule ⁻¹ · photon ⁻¹ , and even more preferably 200 to 60000 × 10 ⁻⁵⁰ cm ⁴ · s · molecule ⁻¹ · Within the range of photon ^-1 .
The optical information recording medium of the present invention is based on the fact that the nonlinear fringe dye is contained, and by irradiating the pulsed light laser, the interference fringes are locally destroyed at high speed (short time), whereby the recording mark is recorded. Can be formed.

The “nonlinear absorption dye” used in the present invention is preferably a hydrocarbon having two or more benzene rings, which may have one or more substituents, based on nonlinear absorption. A condensed aromatic hydrocarbon which may have one or more substituents.
Preferred examples of the “hydrocarbon” include naphthalene, anthracene, phenanthrene, 1,4-bis (phenylethynyl) benzene, and pyrene.
Examples of the “substituent” include a halogen atom, a hydroxy group, and an organic group.
Specific examples of the “nonlinear absorbing dye” used in the present invention include 1,1,4,4-tetraphenyl-1,3-butadiene, 1,3,6,8-tetraphenylpyrene, pyrene-ethylene glycol-pyrene. 1,4-bis (phenylethynyl) benzene, 1,2,4,5-tetrakis (phenylethynyl) benzene, 9,10-diphenylanthracene, 5,6,11,12-tetraphenylnaphthacene, fluorene, 2 , 7-dibromofluorene, 1-bromopyrene, 4-bromopyrene, preferred examples of which include 1,4-bis (phenylethynyl) benzene, and pyrene.

  On the other hand, the “photosensitizer” used in the present invention is not particularly limited as long as it is based on optical interference fringes and sensitizes a photopolymerization initiator, and known ones can be used. For example, thiopyrylium salt compounds, merocyanine compounds, quinoline compounds, styrylquinoline compounds, coumarin compounds, ketocoumarin compounds, thioxanthene compounds, xanthene compounds, oxonol compounds, cyanine compounds, rhodamine compounds, pyrylium Examples thereof include salt compounds. In the case where high transparency such as an optical element is required, the photosensitizer is preferably colorless and transparent by being decomposed by a post-process after hologram recording, heating or ultraviolet irradiation. A photosensitizer can be used individually or in combination of 2 or more types.

  Typically, a styryl compound or a coumarin compound is preferable, and specifically, 2- (p-dimethylaminostyryl) quinoline, 2- (p-diethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) quinoline. 4- (p-diethylaminostyryl) quinoline, 2- (p-dimethylaminostyryl) -3,3-3H-indole, 2- (p-diethylaminostyryl) -3,3-3H-indole, 2- (p -Dimethylaminostyryl) benzoxazole, 2- (p-diethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzimidazole, 2- (p-diethylaminostyryl) benzimidazole and the like.

  Examples of the coumarin compound include 7-diethylamino-4-methylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 4,6-diethylamino-7-ethylaminocoumarin, and 3- (2-benzimidazolyl)-. 7-N, N-diethylaminocoumarin, 7-diethylaminocyclopenta (c) coumarin, 7-amino-4-trifluoromethylcoumarin, 1,2,3,4,5,3H, 6H, 10H-tetrahydro-8- Trifluoromethyl (1) benzopyrano- (9,9A, 1-gh) -quinolizin-10-one, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 1,2,3,4,5, 3H, 6H, 10H-tetrahydro-9-carbethoxy (1) benzopyrano (9,9a, 1-gh) -quinolidine-10- Such as emissions, and the like.

The photopolymerization initiator is not particularly limited as long as it is a compound that activates photoradical polymerization. For example, peroxide esters such as t-butylperoxybenzoate; t-butylhydroperoxide, di-t- Peroxides such as butyl peroxide; benzoin / benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl)- Acetophenones such as tan-1-one; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2, Thioxanthones such as 4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-isopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenones such as benzophenone; Xanthones; Benzophenones, benzoin alkyl ketals CGI-784 (manufactured by Ciba Geigy Co., Ltd .: trade name) known as a general name titanocene can be used, and these can be used alone or in combination with a photosensitizer. Kill.
The composition for optical information recording materials of the present invention, including examples of the composition for optical information recording materials of the present invention understood from these preparation methods, may contain other components.
An example of another component is a plasticizer.
Examples of such plasticizers include phthalates represented by dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, and dioctyl phthalate; dimethyl adipate, diethyl adipate, dibutyl adipate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate Aliphatic dibasic acid esters typified by Kate and diethylsuccinate; Orthophosphoric acid esters typified by trimethyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate; typified by glyceryl triacetate and 2-ethylhexyl acetate Inactive compounds such as triphenyl phosphite, phosphites such as dibutyl hydrogen phosphite, and acetic acid-2 Ethoxyethyl, and combinations of two or more of the above.

Step (2) The curing and curing of the epoxy group-containing cationic polymerizable substance of the composition may be carried out by employing a method according to the type of the epoxy group-containing cationic polymerizable substance.
For example, an epoxy group-containing cationic polymerizable material is cured by a cationic polymerization catalyst. Curing in the case of a thermal cationic polymerization catalyst can be performed by heating at an appropriate time and temperature condition.

Step (2) is, for example, a step in which the composition is applied on a base material, and the alicyclic epoxy group-containing cationic polymerizable substance is cationically polymerized and cured by heating.
Step (3) Formation of Diffraction Grating In this step, the diffraction grating is preferably formed over the entire cured product to be the optical information recording region. In this specification, this is also called initialization.

The diffraction grating layer of the optical information recording medium of the present invention is formed by optical interference exposure using two lights having coherence with each other.
The angle formed by the two lights forming the diffraction grating, that is, the crossing angle, is 90 ° to 270 ° with respect to each other in the definition that the angle formed when both are parallel and the traveling direction of the wave front is the same direction is 0 °. It is within the range, preferably within the range of 135 ° to 225 °, and more preferably within the range of 170 ° to 190 °.
Appropriate conditions can be adopted as the light irradiation condition depending on the substance contained in the optical information recording material. For example, the wavelength is in the range of 400 to 650 nm, and the range is in the range of 1 to 1000 mW / cm ² . A layer of interference fringes can be formed by irradiating with intense light and for a time in the range of 0.1 to 2000 seconds.
The number of layers of the diffraction grating can be adjusted by the film thickness and the crossing angle of the optical information recording material.

Absorption coefficient of the optical information recording material, at 405nm of the present invention, when measured by the following methods, preferably 150 cm ^-1 or less, more preferably 100 cm ^-1 or less, more preferably 50 cm ^-1 or less.
(Measurement method of absorption coefficient)
The absorption coefficient is obtained from the transmittance T of the sample and the thickness L of the sample by the method defined in the above equation 1.

The optical information recording material of the present invention has a wavelength in the range of 365 nm to 650 nm from the viewpoint that the optical information recording material can easily form a recording mark over the entire optical information recording material by the operation of step (4) described later. Preferably, it has a visible light transmittance of 50% or more, more preferably 60%, and even more preferably 70%.
In the present specification, the value of visible light transmittance is determined by the measurement method described in JIS K 7375: 2008.

The shape of the optical information recording material is not particularly limited, but may be, for example, a flat plate shape.
In the flat optical information recording material, preferably, the “multilayer diffraction grating” or the “multilayer interference fringes” can be arranged in parallel to the planar direction of the flat plate.
In the flat optical information recording material, the thickness is usually in the range of 50 to 600 μm.
Step (4) Formation of recording mark The recording mark is formed on the optical information recording material initialized in step (3).
It is formed by irradiating pulsed laser light having a pulse width in the range of 0.1 to 30 nanoseconds, a wavelength in the range of 365 to 650 nm, and a peak output of 1000 W or less.
Specifically, the recording marks can be formed by locally destroying the multilayer interference fringes formed in the step (3).
This optical information recording material is initialized by the operation in the step (3), so that when the reading light is irradiated when reproducing information, the reproduction light returns from the medium, but the recording is performed by the operation in the step (4). Since the reproduction light does not return when the mark is formed, it is possible to recognize which value “0” or “1” is recorded as information.

<Optical information recording medium>
The optical information recording medium of the present invention is
In a specific wavelength containing the optical information recording material of the present invention described above and having a wavelength in the range of 365 nm to 650 nm,
It has a visible light transmittance of 50% or more.
Although the number of layers of the optical information recording medium of the present invention depends on the thickness of the material layer, for example, when the thickness of the material layer is 100 μm, it is preferably 4 or more, more preferably 10 or more, and still more preferably. 50 or more.

The optical information recording medium of the present invention usually has a recording layer comprising the optical information recording material of the present invention, and a base material layer,
For example, one aspect of the optical information recording medium of the present invention has a structure in which a recording layer is sandwiched between two base material layers together with a spacer.
That is, the thickness of the recording layer is determined by the thickness of the spacer.

Examples of the material of the base material layer used in the optical information recording medium of the present invention include glass, polycarbonate, polymethyl methacrylate, cycloolefin polymer and the like.
The spacer used in the optical information recording medium of the present invention is not particularly limited as long as the thickness is uniform, and examples of the material include metals, ceramics, resins, and the like.
In a preferred aspect of the optical information recording medium of the present invention, examples of the material of the base material layer on the side irradiated with light among the two base material layers include glass.
In a preferred embodiment of the optical information recording medium of the present invention, examples of the material of the other substrate layer of the two substrate layers include polycarbonate.

The thickness of the recording layer is usually in the range of 50 to 1000 μm.
The thickness of each base material layer is usually in the range of 50 to 1100 μm.
The thickness of the optical information recording medium is usually in the range of 150 to 1200 μm.

Recording layer, the absorption coefficient at 405nm is preferably 150 cm ^-1 or less, more preferably 100 cm ^-1 or less, more preferably 50 cm ^-1 or less.
The transmittance of the base material layer at 405 nm is preferably 50% or more, more preferably 90% or more, and still more preferably 95% or more.

  In the optical information recording medium of the present invention, a recording mark having a diameter (major axis) of preferably 0.8 μm or less, more preferably 0.5 μm or less, and further preferably 0.4 μm or less can be formed. The diameter (major axis) is preferably small and the lower limit thereof is not limited, but in the present invention, the lower limit is, for example, 0.1 μm.

In the optical information recording medium of the present invention, recording marks can be formed at a recording speed (recording time) of preferably 50 nanoseconds (ns) or less, more preferably 30 ns or less, and even more preferably 8 ns or less. The recording speed (recording time) is preferably short, and the lower limit thereof is not limited, but in the present invention, the lower limit is, for example, 1 ns.
The recording time can be determined by forming the recording mark by one-time laser irradiation for the set pulse width in the pulse laser used for forming the recording mark.

  In the optical information recording medium of the present invention, the S / N ratio after formation of the recording mark is determined from the ratio between the base count value and the peak value of the initialized medium, preferably 1.0 or more, more preferably 2. It can be 0 or more, more preferably 2.5 or more. The S / N ratio is preferably large and the upper limit is not limited, but in the present invention, the upper limit is 10, for example.

Method for Producing Optical Information Recording Medium The optical information recording medium of the present invention can be understood from the production of the material of the present invention described above.
That is, the optical information recording medium of the present invention is, for example,
(1) The liquid of the composition constituting the optical information recording material of the present invention described above is applied to a substrate (for example, one of the base material layers),
(2) The liquid can be cured, and (3) optical interference fringes can be formed over the entire cured product to be an optical information recording area.
Curing may be performed by employing a method according to the type of the polymerizable substance.
For example, when the polymerizable substance is a thermosetting substance, the curing can be performed by heating at an appropriate time and temperature condition.

The diffraction grating layer of the optical information recording medium of the present invention is formed by light irradiation by the two-beam interference method.
The light irradiation condition by the two-beam interference method can be appropriately selected according to the substance contained in the optical information recording material. For example, the wavelength is in the range of 365 to 650 nm, and 1 to 1000 mW / cm. The layer of the diffraction grating can be formed by irradiating with light having an intensity in the range of ² and for a time in the range of 0.1 to 2000.
At this time, the reflected light from the surface of the optical information recording material layer or the base material becomes an obstacle for reading a signal from the reproduction light overlapping with the reproduction light, and acts as noise. In order to avoid the overlap, it is preferable that the incident angle of the incident light is inclined by about 5 ° to 15 ° with respect to the normal line.
The number of interference fringe layers can be adjusted by the film thickness of the optical information recording material and the angle formed by the two light beams.
The thickness of the interference fringe layer can be adjusted by the spacer of the optical information recording material.

<Nonlinear absorption dye and diffraction grating destruction accelerator>
The present invention also provides the following inventions.
[1] At a specific wavelength whose wavelength is in the range of 365 nm to 650 nm,
(1) having a non-linear absorption coefficient in the range of 5 to 10,000 cm / GW, and
(2) A non-linear absorption dye used in an optical information recording material in which a multilayer diffraction grating is formed,
A non-linear absorption dye having a two-photon absorption cross section of 100 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more.
[2] At a specific wavelength whose wavelength is in the range of 365 nm to 650 nm,
50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more, a non-linear absorbing dye having a two-photon absorption cross-section, and an optical information recording having a multilayer diffraction grating formed Material diffraction grating destruction accelerator.
These will be understood based on the detailed description of the present invention described above.

<Nonlinear Absorption Type Optical Information Recording Device>
The nonlinear absorption type optical information recording apparatus of the present invention,
(1) (a) a laser that generates pulsed laser light having a pulse width in the range of 0.1 to 30 nanoseconds, (b) a wavelength in the range of 365 to 650 nm, and (c) a peak output of 1000 W or less Generator,
(2) (a) a laser condensing device provided with an objective lens having a numerical aperture in the range of 0.5 to 1.0, and (b) a magnification in the range of 1 to 100 times,
(3) (a) the optical information recording material of the present invention, or (b) a storage device for storing the optical information recording medium of the present invention, and
(4) A mechanism for scanning a predetermined condensing position in the optical information recording material or the optical information recording medium with a laser beam is provided.

Laser generator The laser generator provided in the nonlinear absorption optical information recording apparatus of the present invention comprises (1) (a) a pulse width in the range of 0.1 to 30 nanoseconds, and (b) in the range of 365 to 650 nm. Any pulse laser beam having a wavelength and (c) a peak output of 1000 W or less may be generated, and other pulse laser beam may be generated.
The wavelength is preferably in the range of 400 to 650 nm, more preferably in the range of 400 to 532 nm, and even more preferably in the range of 400 to 410 nm.
The peak output is preferably 150 W or less, more preferably 120 W or less.
The numerical aperture is preferably 0.5 or more, more preferably 0.7 or more, and still more preferably 0.8 or more.
In a preferred embodiment of the present invention,
Preferably, the wavelength is in the range of 400 to 532 nm, the peak power is 150 W or less, and the numerical aperture is 0.5 or more;
More preferably, the wavelength is in the range of 400-410 nm, the peak power is 150 W or less, and the numerical aperture is 0.7 or more; and more preferably,
The wavelength is in the range of 400 to 410 nm, the peak output is 120 W or less, and the numerical aperture is 0.8 or more.

The nonlinear absorption type optical information recording apparatus of the present invention will be described below with reference to the drawings.
In these drawings, the same members are assigned the same reference numerals. In these drawings, the scale is appropriately changed.
In order to facilitate understanding of the present invention, reference numerals in the accompanying drawings may be added, but the present invention is not limited to the illustrated embodiments. That is, the apparatus of the present invention is not limited to this, and it goes without saying that excellent effects are exhibited in other various apparatuses. In order to simplify the explanation, only the main components are shown in the illustrated apparatus, but other known components may be adopted in a practical apparatus.
Also, for the sake of simplicity and clarity, the figure shows a general structure. Descriptions and details of well-known features may be omitted so as not to unnecessarily obscure the description of the embodiments of the invention. Also, the elements in the figures are not necessarily drawn to scale. For example, in order to facilitate an understanding of embodiments of the present invention, some elements in the figures are emphasized in size relative to other elements. The same reference numerals in different drawings denote the same elements.

FIG. 1 is a sectional view showing an outline of an example of an optical information recording medium of the present invention.
FIG. 2 is a schematic diagram showing an outline of an example of the nonlinear absorption type optical information recording apparatus of the present invention.
The optical information recording apparatus comprises (a) a pulse laser beam having a pulse width in the range of 0.1 to 30 nanoseconds, (b) a wavelength in the range of 365 to 650 nm, and (c) a peak output of 1000 W or less. Laser generating device,
(a) a laser condensing device comprising an objective lens having a numerical aperture in the range of 0.5 to 1.0, and (b) a magnification in the range of 1 to 100 times,
The optical information recording material of the present invention, or an optical information recording medium accommodating device capable of accommodating the optical information recording medium, and a mechanism for scanning a predetermined condensing position of the optical information recording medium with a laser beam, The optical information recording medium contains a non-linear absorbing dye having a two-photon absorption cross section of 50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more.

The recording arm unit 100 includes a neutral density filter 6, a first beam expander 7, and a first mirror 8.
The read arm unit 200 includes a continuous wave laser diode 12, a second beam expander 14, and a second mirror 15.
The optical readout unit 300 includes a first beam splitter 9 and a second beam splitter 16, a CCD camera 18, a fiber connection port 20, and a spectrometer 19.
The optical information recording medium 1 is composed of two antireflective coating glasses 2 and a photocrosslinkable resin doped with a non-linear absorbing dye sandwiched between them (this includes an optical information recording layer 3 which is an optical information recording region). To make up.
Before optical information recording, a diffraction grating is formed inside the optical information recording medium 1 by interference exposure.
The diffraction grating is formed by making the interference light incident on the entire optical information recording layer 3. Here, when the incident angle of the interference light is about 5 ° to 15 ° with respect to the normal, and the reading light is incident on the medium along the normal, the optical information recording layer is Since the reproduction light returning from the formed diffraction grating is emitted from the same normal by the same angle, that is, in this case with an inclination of about 5 ° to 15 °, the optical information recording that returns along the normal is recorded. It is possible to make an angle difference from the reflected light from the surface of the medium, and it is possible to avoid the reflected light acting as noise on the reproduction light.
The optical information recording medium 1 on which the diffraction grating is formed is also referred to as “initialization medium”.
In the optical information recording, the pulse laser beam 5 generated from the laser generator 4 passes through the neutral density filter 6 and the first beam expander 7 and is redirected by the first mirror 8 and the first beam. The direction is further changed by the splitter 9, and the reflected light is condensed by a laser condensing device including an objective lens 10 and irradiated onto the optical information recording layer 3 inside the recording medium 1.
The optical information recording medium 1 is accommodated in an accommodation device including a power stage 11.
Here, the pulsed laser beam is focused by the objective lens 10, is focused in the optical information recording layer 3 of the optical information recording medium 1, becomes high light intensity, and induces nonlinear absorption of the nonlinear absorbing dye. . The diffraction grating of the optical information recording layer 3 is locally destroyed by the thermal energy generated by this nonlinear absorption.
The focal point of the pulse laser beam 5 in the optical information recording layer 3 can be moved by moving the optical information recording medium 1 by the power stage 11.
By repeatedly performing the condensing operation controlled in this way, the diffraction grating can be locally broken at an arbitrary position in three dimensions. Thus, three-dimensional recording of information becomes possible.

  In the reading of optical information recording, the output beam 13 of the continuous wave laser diode 12 passes through the second beam expander 14 and is directed by the second mirror 15 and the first beam splitter 9 used only for reading. And is passed through the second beam splitter 16 and introduced into the optical readout unit 300. Of the diffraction grating formed on the optical information recording layer 3 inside the recording medium 1, the reflected reproduction light is not detected at the locally destroyed portion, whereas the reproduced light is detected at the non-destructed portion. Is done.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited to this.

The recording conditions and reading conditions employed in the following examples and the like are as follows.
<Recording and reading conditions>
Objective lens: 50x, numerical aperture (NA) 0.80
Recording light: Pulse energy 600 to 1000 nJ / pulse, center wavelength 401 nm, full width at half maximum of 5 nm, pulse width 8 ns, recording peak power 75 to 125 W, pulse repetition frequency 1 kHz
Reading light: optical power 2.1 μW, central wavelength 408 nm, full width at half maximum of 3 nm, continuous light Here, the recording peak power and the optical power of the reading light are values between the objective lens 10 and the recording medium 1. is there.

In the following examples, the recording mark size and the S / N ratio were measured by the following methods, respectively.
[Measurement method of recording mark size]
As the recording mark size, the recorded major axis was determined as the full width at half maximum of the change in the gray scale value of the image of the recording mark taken by the optical microscope.
[Measurement Method of S / N Ratio] The S / N ratio was determined from the ratio between the base count value and the peak value of the initialized medium.

［式中、ｐ, qは０〜３である。］
脂環式エポキシ基含有カチオン重合物質である下記化学式の二官能環式エポキシ ５３．０重量部、

ジオール化合物である下記化学式のポリテトラメチレンエーテルグリコール ３０．０重量部、および

さらに、
光重合開始剤として（ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム ３．０重量部（チバスペシャリテーケミカルズ社）、
カチオン重合触媒として芳香族スルホニウム塩 ５．０重量部（サンエイドＳＩ−６０Ｌ、三新化学工業株式会社）、および
非線形吸収色素としてピレン（Pyrene）５．０重量部 ５．０重量部を加えて、均一な感光性樹脂を調製した。
また、別の例として、ここでは光干渉縞を形成する色素の役割は、は光重合開始剤の役割に包含されるので、当該色素を用いないこと以外は、これと同様にして感光性樹脂を調製した場合での、均一な感光性樹脂が調製可能であった。<Example 1>
[(1) Preparation of photosensitive solution]
With respect to 17.0 parts by weight of an acrylic fluorene monomer having the following chemical formula, which is a fluorine-free radically polymerizable substance having an acrylate group,

[Wherein, p and q are 0 to 3. ]
53.0 parts by weight of a bifunctional cyclic epoxy having the following chemical formula, which is an alicyclic epoxy group-containing cationic polymerization substance,

30.0 parts by weight of a polytetramethylene ether glycol having the following chemical formula, which is a diol compound, and

further,
(Bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium 3.0 parts by weight as a photopolymerization initiator) (Ciba Special Chemicals),
Add 5.0 parts by weight of aromatic sulfonium salt as a cationic polymerization catalyst (Sun Aid SI-60L, Sanshin Chemical Co., Ltd.) and 5.0 parts by weight of Pyrene as a non-linear absorbing dye, A uniform photosensitive resin was prepared.
As another example, since the role of the dye forming the light interference fringes is included in the role of the photopolymerization initiator, the photosensitive resin is similarly used except that the dye is not used. A uniform photosensitive resin in the case of preparing can be prepared.

[(2) Preparation of optical information recording medium and cross-linking]
Next, in the prepared photosensitive solution, a glass substrate (50 × 50 mm square) having an antireflection treatment with respect to 405 nm is used as an incident side (front surface) substrate, and a back substrate is formed with a thickness of 0.9 mm. An optical information recording medium was prepared by sandwiching a glass substrate (the glass substrate was antireflection treated for 405 nm) with a spacer having a thickness of 100 μm.
The prepared optical information recording medium was crosslinked under a crosslinking condition of 90 ° C. × 2 hr. The transmittance of the optical information recording medium thus produced was 98% at 405 nm.

[(3) Initialization of optical information recording medium]
In the negative type micro reflector, the optical information recording medium is initialized by forming a diffraction grating by performing interference exposure by the two-beam interference method over the entire optical information recording area in advance before recording the optical information on the optical information recording medium. It was. The conditions at that time were a light source wavelength of 405 nm, a light intensity of 7 mW / cm ² , and an initialization time of 20 s. At this time, the incident angle of the interference light was inclined by about 5 ° to 15 ° with respect to the normal line.
Next, the optical information recording / reproducing apparatus locally collects the 8 ns pulsed light described in the <Recording / Reading Conditions> from the nanosecond pulse laser as the light source at the site where information is recorded. By doing so, the diffraction grating containing the nonlinear absorption dye in the recording region was locally destroyed.
At this time, the region where one piece of information was recorded was performed under the condition that only one relevant pulse was irradiated. This condition was performed by sufficiently moving the optical information recording medium in the direction perpendicular to the incident direction of the recording light between the irradiation of a certain light pulse and the irradiation of the next light pulse. Here, “sufficient” means an amount of movement in which the recording marker formed by the preceding light pulse does not cause a spatial overlap with the recording marker formed by the light pulse that follows in time. Specifically, the recorded marker size is 0.7 μm in full width at half maximum, and the time interval between the light pulse and the next light pulse is 1 because the repetition frequency of the pulse light used is 1 kHz. ms, and the moving speed of the optical information recording medium was 6 μm per 1 ms, so that the recording markers did not sufficiently overlap each other.
In this regard, transmission images of the optical information recording medium at different focal positions (ie different depths) were acquired [recording peak output set to 71 W (threshold output)]. Here, with respect to the x direction (lateral direction) and the Z direction (depth direction), the center of the recording pit was set to 0 μm. FIG. 3 shows a grayscale plot of the transmitted image along the x direction (lateral direction) at a focal position of Z = 0 μm. The lateral size of the pit was 0.7 μm in full width at half maximum. FIG. 4 shows a plot along the Z direction (depth direction) at the in-plane center of the recording pit, as in FIG. The depth dimension of the pit was 2.4 μm in full width at half maximum. As will be understood, the recording pits formed on the medium are certainly confined three-dimensionally.
As a result, the optical information recording / reproducing apparatus having this negative type micro-reflector can reproduce the information from the part where the reproduction light returns from the hologram when the reading light is irradiated and the hologram interference fringes are locally destroyed. Was able to recognize whether the value “1” as information was recorded based on the fact that the reproduction light hardly returned. In this case, the S / N according to the definition in reading information was 2.5 or more. The recording of information due to the destruction of the diffraction grating at the recording site is formed by irradiation with a single pulse having a duration of 8 ns. In other words, this is a quarter of the current Blu-ray recording time of 30 ns, and 100 ns (for example, Non-Patent Document 3) which is the recording time of the conventional negative type micro-reflector system. Was also confirmed to be short. The shorter recording time means that more information can be recorded per unit time, and it can be said that the recording speed is faster.
[Non-Patent Document 3] ITE Technical Vol.35, No.27 MMS2011-17 (Jul. 2011).
When the non-recording information recording medium was measured for the nonlinear absorption coefficient by the z-scan method described in Non-Patent Documents 1 and 2, the scanning time was changed twice, and as a result, the measurement time The signal intensity that appeared as a dent in the measurement result of the z-scan method increased with the passage of time, so that a reaction product was generated, and a nonlinear absorption behavior that contributed to recording by absorbing light was confirmed.
FIG. 5 shows the result of scanning with an 8 ns pulse and an excitation wavelength of 402 nm. In the figure, the upper dot indicates a forward scan, and the lower dot indicates a return scan.

  The value of the nonlinear absorption coefficient obtained from this result was 280-1750 cm / GW. Further, the refractive index difference of the diffraction grating was Δn = 0.02, and the number of information recording layers recordable in the 100 μm medium was 20 from the observed size of the recording marker in the depth direction. The recording capacity was estimated to be about 80 GB with a recording layer of 100 μm and 20 layers. On the other hand, the optical recording capacity exceeding the TB class can be improved to 10 TB recording capacity with a recording layer of 40 μm thickness and 800 μm by optimizing the optical equipment.

<Comparative Example 1>
When the same operation as in Example 1 was performed except that pyrene (Pyrene), which is a non-linear absorption dye, was not used, recording was not performed due to the destruction of the diffraction grating, or it was accidental and from Example 1. However, destruction in a large area occurred and information could not be recorded with good reproducibility.

<Example 2>
Production of optical information recording media
(1) alicyclic epoxy group-containing cationic polymerization substance (3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate (hard segment, hereinafter sometimes referred to as ECMECC) ”45 parts by weight
(2) 45 parts by weight of PTG (PTG1000S (product name), Hodogaya Chemical Co., Ltd.) as a diol compound (as a soft segment)
(3) 10 parts by weight of 1,1, -bisphenyl 4,4′-bisethoxyfluorenediacrylate (hereinafter sometimes referred to as BPEF-A) as a fluorine-free radically polymerizable compound (non-fluorine monomer),
(4) 5 parts by weight of Sun-Aid SI-60L (trade name, Sanshin Chemical Co., Ltd.) as an epoxy cationic polymerization catalyst
(5) 3 parts by weight of Irgacure784 (trade name, Ciba Specialty Chemicals) and dye pyrene were added as a photopolymerization initiator and mixed uniformly.
(6) Further, 5.0 parts by weight of 1,4-bis (phenylethynyl) benzene (BPEB) was added as a nonlinear absorbing dye to prepare a uniform photosensitive resin.
The resulting photosensitive resin composition is sandwiched between 1.2 mm thick glass substrates with two antireflection films, and spacers are used to maintain an interval (100 μm) according to the evaluation method, and thermosetting at 120 ° C. for 1 hour. A coupon media was prepared.
Next, optical interference fringes were formed by a two-beam interference method on the coupon media obtained using a tester compliant with Shottec Corporation Shot500 to prepare an optical information recording medium.
“Diol compounds (as soft segments)” include PTG, polyethylene glycol (hereinafter sometimes referred to as PEG), polypropylene glycol (hereinafter sometimes referred to as PPG), and polytetramethylene glycol (hereinafter referred to as PPG). An optical information recording medium was prepared by adding PTMG).
When the nonlinear coefficient was measured by the Z-scan method under the same conditions as in Example 1, a dent appeared in the immediate result, and the nonlinear absorption effect was confirmed.
The value of the nonlinear absorption coefficient obtained as a result was 7.3 cm / GW. The amount of the dent does not depend on the scanning direction or the number of scans. From this, it was confirmed that the absorption was a nonlinear absorption due to a pure two-photon absorption process.
However, the value of the nonlinear absorption coefficient was small, and the recording experiment was not completed.

<Comparative Example 2>
All operations were the same as in Example 2, except that 1.0 part by weight of 1,2,4,5-tetrakis (phenylethynyl) benzene was used instead of 1,4-bis (phenylethynyl) benzene (BPEB). went. Since the produced information recording medium had a transmittance of 31% at 405 nm, it was not suitable for recording experiments.

1: Optical information recording medium 2: Antireflection agent coated glass 3: Optical information recording layer 4: Laser generator 5: Pulse laser beam 6: Neutral filter 7: First beam expander 8: First mirror 9: First Beam splitter 10: Objective lens 11: Power stage 12: Continuous oscillation laser diode 13: Output beam 14: Second beam expander 15: Second mirror 16: Second beam splitter 17: Third beam splitter 18: CCD camera 19 : Spectrometer 20: Fiber connection port 100: Recording arm unit 200: Reading arm unit 300: Optical reading unit

Claims (6)

At a specific wavelength whose wavelength is in the range of 365 nm to 650 nm,
(1) having a non-linear absorption coefficient in the range of 5 to 10,000 cm / GW, and
(2) An optical information recording material in which a multilayer diffraction grating is formed. The optical information recording material according to claim 1, wherein the multilayer diffraction grating is a diffraction grating formed by exposure using multilayer optical interference fringes due to optical interference. A non-linear absorption dye that is a photosensitive resin and has a two-photon absorption cross-section of 50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more at a specific wavelength in the range of 365 nm to 650 nm The optical information recording material according to claim 1, which is contained. In the specific wavelength which contains the optical information recording material as described in any one of Claims 1-3, and a wavelength exists in the range of 365 nm-650 nm,
An optical information recording medium having a visible light transmittance of 50% or more. At a specific wavelength whose wavelength is in the range of 365 nm to 650 nm,
(1) a non-linear absorption dye having a two-photon absorption cross-section of 50 × 10 ⁻⁵⁰ cm ⁴ · sec · molecule ⁻¹ · photon ⁻¹ or more,
(2) one or more polymerizable substances selected from the group consisting of diol compounds and alicyclic epoxy group-containing cationic polymerizable compounds, and
(3) A composition containing a fluorine-containing radically polymerizable compound. (1) (a) a laser that generates pulsed laser light having a pulse width in the range of 0.1 to 30 nanoseconds, (b) a wavelength in the range of 365 to 650 nm, and (c) a peak output of 1000 W or less Generator,
(2) (a) a laser condensing device provided with an objective lens having a numerical aperture in the range of 0.5 to 1.0, and (b) a magnification in the range of 1 to 100 times,
(3) (a) the optical information recording material according to any one of claims 1 to 3, or (b) a storage device for storing the optical information recording medium according to claim 5, and
(4) A non-linear absorption type optical information recording apparatus provided with a mechanism for scanning a predetermined condensing position in the optical information recording material or the optical information recording medium with a laser beam.

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