WO2015068839A1

WO2015068839A1 - Polymerizable compound, resin composition using same, cured resin, and optical material

Info

Publication number: WO2015068839A1
Application number: PCT/JP2014/079728
Authority: WO
Inventors: 一嘉正木; 清水　健博; 敏男安藤
Original assignee: 新日鉄住金化学株式会社
Priority date: 2013-11-11
Filing date: 2014-11-10
Publication date: 2015-05-14
Also published as: JP6870054B2; TW201533068A; JP2020037693A; JPWO2015068839A1; JP6869636B2

Abstract

　Provided are a polymerizable compound having a high refractive index, high light transmittance, and low viscosity, a resin composition using the same, a cured resin, and an optical material. A polymerizable compound represented by general formula (1). Here, R¹-R⁵ are a hydrogen atom or a monovalent group such as an arylthio group, alkyl group, or the like, but 1-3 thereof are arylthio groups represented by –S-Ar¹; X¹ is a direct bond, oxygen atom, or a divalent group such as an alkylene group or the like; R⁶ is a polymerizable group such as a glycidyl group, acryloyl group, or the like; and the Ar¹ of -S-Ar¹ is an aryl group or heteroaryl group.

Description

Polymerizable compound, resin composition, resin cured product and optical material using the same

The present invention relates to a polymerizable compound having a high refractive index and excellent in transparency, handling properties, and the like, a resin composition using the same, a cured resin and an optical material, particularly a holographic recording material and a holographic recording medium It is about.

Recently, optical resins have been actively used in various optical fields, and (meth) acrylic resins such as polymethylmethacrylate are well known as materials thereof. In general, optical resin materials typified by (meth) acrylic resins have lightness, safety, and design properties, but have a disadvantage of low refractive index. Therefore, in recent years, there has been an increasing demand for optical resins having a high refractive index, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, TFT prism lens sheets, aspherical lenses, optical fibers, Studies on optical waveguides, optical recording materials, and the like have been actively conducted. In particular, for optical recording materials, particularly holographic recording materials, the development of high refractive index materials for achieving a high degree of refractive index modulation, a large M # (M number), and high sensitivity has become a major issue.

In order to increase the refractive index of the optical resin, it is advantageous to use a high refractive index monomer as a raw material polymerizable compound (hereinafter also referred to as a monomer). It is theoretically known that introduction of halogen atoms (chlorine, bromine, iodine), sulfur atoms and heavy metal atoms is effective.

As monomers having an aromatic ring in the molecular structure, for example, those having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene and anthracene in addition to a benzene ring are known (

Patent Documents

1 and 2, etc.). However, the refractive index of a monomer having a single benzene ring in the molecular structure is not sufficient. In addition, monomers having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, and anthracene in the molecular structure are expected to have a high refractive index, but in most cases become a high-viscosity liquid or a crystalline solid. There is a problem that handling property is lowered. Furthermore, there is a problem that not only the transparency is lowered but also the photocurability and the weather resistance are lowered by increasing the absorption wavelength.

On the other hand, a monomer having a diphenyl sulfide structure in the molecular structure has a higher refractive index than a monomer having a single benzene ring. In addition, the higher the viscosity and the longer the absorption wavelength, the less the monomer having a polycyclic aromatic ring such as biphenyl, naphthalene, fluorene, anthracene, etc., handling properties such as solubility, transparency, photocurability, weather resistance The advantage that there are few problems of the fall of can be expected.

So far, several polymerizable compounds having a diphenyl sulfide structure in the molecular structure have been synthesized (Patent Documents 3 to 6, etc.). However, even the polymerizable compounds disclosed in the patent documents listed here are insufficient in terms of high refractive index, transparency and handling properties, and further creation of improved polymerizable compounds is required. ing.

Holographic recording is performed by recording interference fringes generated by simultaneously irradiating reference light together with signal light having image information on a recording medium as a diffraction grating (hereinafter also referred to as a grating). The reproduction from the recording medium is performed by irradiating the recording medium on which the image information is recorded with reference light and reading out the image information as reproduction signal light from the diffraction grating.
In holographic recording, the above-mentioned image information can be recorded and reproduced as a single page in a batch, and multiple pages can be recorded at the same location on the medium. Therefore, bit-by-bit used in conventional CDs, DVDs, and Blu-ray discs. This technology is expected as a high transfer rate and large capacity optical recording system that replaces the bit recording system.

As a holographic recording material, a photopolymer in which a recording polymerizable compound and a photopolymerization initiator are dispersed in a matrix resin is used in consideration of the convenience of recording medium production and diversity of raw material selection. There are many cases. In a holographic recording medium using a photopolymer, a write-once type in which interference fringes are recorded as a refractive index modulation diffraction grating is generally used.

In a holographic recording medium, a large M # is necessary for increasing the capacity. M # is an index representing the multiplex recording performance, and is a numerical value represented by the following formula (I) when the diffraction efficiency of the i-th page is η _{i in} the m-multiplex recorded signal.

Further, in a holographic recording medium, a high recording sensitivity is required because it is necessary to obtain a sufficient diffraction efficiency with a short recording exposure in order to achieve a high transfer rate.

Holographic recording is performed by irradiating a photopolymer with interference fringes (light contrast) obtained by crossing coherent light. Photopolymerization occurs in the bright part of the interference fringes during light irradiation, and the polymerizable compound is consumed to produce a polymer. The polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes so as to compensate for the concentration gradient of the polymerizable compound generated at this time. In this way, the interference fringe pattern is fixed in the photopolymer as a refractive index distribution (Non-Patent Document 1).

It is advantageous to select the matrix resin and the polymerizable compound so that the difference in refractive index is as large as possible. When a matrix resin having a low refractive index is used, the polymerizable compound should have a refractive index as high as possible. It is desirable to use it.

Conventionally, examples of the high refractive index polymerizable compound include condensed (hetero) aryl groups and bromine-substituted aryl groups such as N-vinylcarbazole, bromostyrene, and tribromophenyl acrylate described in Patent Documents 7 to 9. There are those that have.

Patent Documents 10 to 12 report that a holographic recording material and a recording medium having high diffraction efficiency and sensitivity can be obtained by using a polymerizable compound having a sulfur-containing fused ring structure. However, in general, the difference in refractive index and the compatibility are in a trade-off relationship. When the refractive index of the polymerizable compound is improved to improve the diffraction efficiency, the matrix resin and the polymerizable compound or a polymer thereof are not affected. Compatibility is deteriorated. Even the polymerizable compounds disclosed in the patent documents listed here are insufficient from the viewpoint of diffraction efficiency, light transmittance, and compatibility, and the creation of further improved polymerizable compounds is demanded.

JP-A-5-170702 JP 2004-83855 A Japanese Patent Laid-Open No. 2-113005 JP 2005-145861 A JP 2010-186979 A Korean Patent No. 1254325 (KR2012-40799A) JP-A-10-105030 Japanese Patent Laid-Open No. 11-352303 JP 2005-502918 A JP 2005-43507 A JP 2005-114848 A JP 2010-18606 A

The diffraction efficiency of the holographic recording medium is proportional to the recording density per medium surface, and the value can be expressed by the refractive index modulation degree from the Kogelnik theory of the following equation (II). Here, η is the diffraction efficiency, Δn is the refractive index modulation degree, λ is the reproduction wavelength, and θ _B is the reproduction angle.

The degree of modulation of the refractive index is the difference in refractive index between the light irradiated part and the non-irradiated part. The holographic recording medium before recording is uniformly dispersed in a state where the polymerizable compound is compatible with the matrix resin. When this holographic recording medium is irradiated with interference fringes for recording, photopolymerization starts in the bright part of the interference fringes, and the polymerizable compound is consumed to produce a polymer. In order to compensate for the concentration gradient of the polymerizable compound generated at this time, the polymerizable compound is supplied by diffusion transfer from the dark part to the bright part of the interference fringes, and the polymerization continues, and the polymerization causes an increase in density. On the other hand, the concentration of the polymerizable compound decreases in the dark part of the interference fringes.

Therefore, when the refractive index of the polymerizable compound is higher than the refractive index of the matrix resin, the refractive index increases with respect to the non-irradiated portion due to the increase in density due to polymerization and the concentration of the polymerizable compound in the light irradiated portion. On the other hand, in the non-irradiated portion, the refractive index is further lowered than the state before recording due to the decrease in the polymerizable compound concentration. Therefore, a refractive index difference is formed between the light irradiation part and the non-irradiation part.

When the refractive index of the polymerizable compound is lower than the refractive index of the matrix resin, the refractive index increases in the light-irradiated part than in the non-irradiated part due to polymerization. The width is suppressed. Furthermore, since the refractive index increases due to a decrease in the concentration of the polymerizable compound in the non-irradiated part, the difference in refractive index between the light-irradiated part and the non-irradiated part is larger than that when the polymerizable compound has a higher refractive index than the matrix resin. Smaller. Therefore, in order to increase the refractive index difference between the light irradiated portion and the unirradiated portion, it is important that the refractive index of the polymerizable compound is larger than the refractive index of the matrix resin and that the difference is large.

From the above formula (I), M # increases as the multiplicity increases. Further, M # is calculated from the diffraction efficiency, and it can be seen from the formula (II) that the diffraction efficiency increases as the refractive index modulation degree increases. From these facts, the diffraction efficiency can be increased as the difference in the refractive index between the light-irradiated portion and the non-irradiated portion is increased, and further, improvement in M # can be achieved.

Therefore, the present invention provides a polymerizable compound having a high refractive index, a high light transmittance, and a low viscosity, and a resin composition, a cured resin and an optical material using the polymerizable compound, and further when used as a holographic recording material. It is an object to provide a holographic recording material containing the polymerizable compound capable of obtaining a large M # and high sensitivity, and a holographic recording medium capable of realizing a large capacity (high density) and a high transfer rate using the material. To do.

Generally, as means for increasing the refractive index of organic substances, introduction of aromatic rings and introduction of heavy atoms such as sulfur atoms and bromine atoms can be mentioned. Therefore, the present inventors have created a compound that can achieve both high refractive index and high compatibility by introducing an aromatic ring through a sulfur atom into a benzene ring having a polymerizable group. By using this, it has been found that a high-performance holographic recording material exhibiting a large M # and high sensitivity can be obtained, and the present invention has been completed.

That is, the present invention is a polymerizable compound represented by the following general formula (1).

here,
R ¹ to R ⁵ are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a carbon atom having 6 to 10 carbon atoms. Represents a monovalent group selected from the group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an arylthio group represented by —S—Ar ¹ , one of which Two or three are the arylthio groups.
X ¹ is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms, wherein the alkylene group, oxyalkylene group, thioalkylene group, alkyleneoxy group and alkylenethio group may have a substituent, The substituent of is a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a carbon number 6 to 10 arylthio groups.
R ⁶ is a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, an optionally substituted vinylaryl group or a vinylaryloyl group.
The -S-Ar Ar ¹ of ¹ represents an aryl group or ring members 5-14 heterocyclic aryl group ring members 6-14, also may have combined two or more rings are condensed, substituted It may be. In the case of having a substituent, the substituent is chlorine atom, bromine atom, alkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, phenyloxy group or phenylthio group. In the case where these are a phenyloxy group or a phenylthio group, they may further have a substituent similar to the substituent.

In the general formula (1), one of R ₁ ~ R ^5, it is -S-Ar ^1, or two or but three R ¹ ~ R ^5, more excellent If it is -S-Ar ¹ It becomes a polymerizable compound.

The present invention also includes a resin composition characterized by containing the polymerizable compound, a resin cured product obtained by curing the resin composition, and the resin composition or resin cured product. It is an optical material characterized by this.

Furthermore, the present invention relates to a holographic recording material containing the polymerizable compound. The holographic recording material may be a holographic recording material containing A) the polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator.

In the general formula (1), one of R ¹ to R ⁵ is —S—Ar ¹ , two or three of R ¹ to R ⁵ are —S—Ar ¹ , or the polymerizable property A refractive index n _D at 25 ° C. of the compound of 1.60 or more gives a better holographic recording material.

Examples of the matrix resin include isocyanate-hydroxyl polyadducts, and examples of the matrix resin forming material include materials containing polyisocyanate and polyol.

The present invention also provides a holographic recording medium comprising a recording layer containing the holographic recording material.

The polymerizable compound of the present invention is higher in refractive index, transparency and handling than conventional polymerizable compounds, glass substitute materials for lens applications, and protective film materials for color filters for liquid crystal displays. Resin compositions useful for various optical materials such as coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, and curing Can give things.

The optical material as used in the present invention means a material used for light transmitting or reflecting light, and is preferably an optical material for light transmission such as for lenses and light transmission films. More preferably, it is an optical material for lens use.

In addition, the polymerizable compound used in the holographic recording material of the present invention is compatible with the refractive index modulation and compatibility, and without causing turbidity or scattering, the holographic recording material using the polymerizable compound is , Large M #, high sensitivity.

It is an ultraviolet-visible absorption spectrum of the polymeric compound of this invention. It is an infrared absorption spectrum of the polymeric compound of this invention. It is a schematic block diagram of the optical system for multiple recording. It is a schematic block diagram of the reproduction | regeneration optical system. It is a graph which shows the integrated value of M # with respect to recording exposure energy. It is a graph which shows the sensitivity with respect to recording exposure energy.

Hereinafter, the details and other features of the present invention will be described in detail in connection with the embodiments. However, the present invention is not limited to the following embodiments, and variously within the scope of the gist of the present invention. It can be changed and implemented.

First, the polymerizable compound of the present invention will be described.
The polymerizable compound of the present invention is represented by the general formula (1).

In the general formula (1), R ¹ to R ⁵ are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms. A monovalent group selected from the group consisting of an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an arylthio group represented by -S-Ar ¹ And one, two or three of R ¹ to R ⁵ are the arylthio group.

The number of monovalent groups other than hydrogen atoms or arylthio groups in R ¹ to R ⁵ is 0 to 4, preferably 0 to 2, and more preferably 0 or 1. In the case of a monovalent group other than a hydrogen atom or an arylthio group, for example, a chlorine atom, a bromine atom, an alkyl group having 1 to 2 carbon atoms, an alkyloxy group having 1 to 2 carbon atoms, or an alkylthio group having 1 to 2 carbon atoms And an aryloxy group having 6 to 7 carbon atoms, an aryloxy group having 6 to 7 carbon atoms, or an aralkyl group having 7 to 9 carbon atoms, preferably a bromine atom, methyl group, methoxy group, methylthio group, phenyl group, phenoxy A group, a benzyl group, a 1-phenylethyl group, or a 2-phenylpropan-2-yl group is more preferable.

X ¹ is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms. Here, the oxyalkylene group, thioalkylene group, alkyleneoxy group or alkylenethio group is represented by YC _n H _2n or C _n H _2n Y, Y is O or S, and n is a number from 1 to 4. It is. The alkylene group, oxyalkylene group (or alkyleneoxy group), and thioalkylene group (or alkylenethio group) may have a substituent.
In the case of having a substituent, preferred substituents include a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aryloxy group or arylthio group having 6 to 10 carbon atoms, and the aryl group, aryloxy group or arylthio group may have a substituent which Ar1 described later may have.

R ⁶ represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinyl aryl group which may have a substituent, or a vinyl aryloyl group. The vinyl aryl group preferably has 8 to 20 carbon atoms, and the vinyl aryloyl group preferably has 9 to 20 carbon atoms. Further, a vinyl aryl group Preferred examples of the substituent for the case of having a substituent include the substituents cited as preferred substituents in the description of X ^1.

It said Ar ¹ of -S-Ar ¹ represents a ring members 6-14 aryl group or ring members 5-14 heterocyclic aryl group may have a substituent, and two or more rings condensed You may do it. Ar ¹ may be a monocyclic structure or a condensed ring structure, and the number of rings constituting Ar ¹ is 1 to 4, preferably 1 to 3, and more preferably 1 to 2. In addition, when used for optical resin applications, particularly for holographic recording, it is preferable that the coloring is small in order to ensure not only a decrease in transparency but also photocurability and weather resistance. From this point, Ar ¹ is an aryl group. It is preferable that The substituent in the case of having a substituent will be described later.

However, in the general formula (1), when —S—Ar ¹ is one, (d) R ¹ , R ² , R ⁴ , R ⁵ are hydrogen atoms, and (e) R ³ is — When S-Ar ¹ and (f) Ar ¹ is a phenyl group, those satisfying the following (a), (b) or (c) are preferably excluded.
(A) X ¹ is a direct bond and R ⁶ is a vinyl group,
(B) X ¹ is an oxygen atom, and R ⁶ is an acryloyl group or a methacryloyl group,
(C) X ¹ is an oxymethylene group having no substituent, and R ⁶ is an acryloyl group or a methacryloyl group.

However, in the general formula (1), when the number of —S—Ar ¹ is 2 or 3, the above (d) to (f) and (a), (b) or (c) are satisfied. It is not excluded even if it is something to do.

When used as a holographic recording material, the number of —S—Ar ¹ is one, R ¹ , R ² , R ⁴ , R ⁵ are hydrogen atoms, and R ³ is —S—Ar ¹ . When Ar ¹ is a phenyl group, it is desirable to exclude those in which X ¹ is a direct bond and R ⁶ is a vinyl group.

The terms used in this specification have the following meanings unless otherwise specified.

<Aryl group>
6-16, preferably 6 carbon atoms such as benzene, indene, naphthalene, azulene, fluorene, acenaphthene, anthracene, phenanthrene, fluoranthene, pyrene, and the like -14 aryl groups. From the viewpoint of avoiding coloring and compatibility, the number of carbon atoms is more preferably 6 to 10, and particularly preferably a benzene ring group and a naphthalene ring group. The benzene ring group is a group formed by taking one H from benzene, and the other groups are the same.

<Heteroaryl group>
The heteroatom contained in the heteroaryl group is not particularly limited, and each atom such as S, O, N, and P can be used, but each atom of S, O, and N is preferable from the viewpoint of ensuring compatibility, Each atom of S or O is more preferable, and S atom is particularly preferable from the viewpoint of improving the refractive index. From the viewpoint of high transmittance and compatibility, the number of heteroatoms is preferably 1 to 3, more preferably 1 to 2, in the heteroaryl group.

Specifically, pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, oxazole ring group, thiazole ring group, pyridine ring group, pyrazine ring group, pyrimidine ring group, triazine ring group, indole ring group, benzofuran Ring group, benzothiophene ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, quinoline ring group, isoquinoline ring group, carbazole ring group, dibenzofuran ring group, dibenzothiophene ring group, acridine ring group, benzocarbazole Examples thereof include heteroaryl groups having 5 to 17 carbon atoms, preferably 5 to 14 carbon atoms, such as a cyclic group, a benzonaphthofuran ring group, and a benzonaphththiophene ring group. Of these, a thiophene ring group, a benzothiophene ring group, and a dibenzothiophene ring group are preferable.

<Substituent Ar ¹ may have>
Ar ¹ may have a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group, an alkylthio group, a phenyloxy group, and a phenylthio group. Preferred substituents are a chlorine atom, a bromine atom, an alkylthio group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms. However, from the viewpoint of ease of synthesis, it is advantageous that it is unsubstituted.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to these unless it exceeds the gist.

The polymerizable compound represented by the general formula (1) can be produced by a known method. A compound in which R ⁶ is a vinyl group can be produced, for example, by a dehydration reaction using a compound having a hydroxyethyl group as a precursor. A compound in which R ⁶ is a (meth) acryloyl group can be produced, for example, by a reaction between a compound having active hydrogen and (meth) acrylic acids. A compound in which R ⁶ is a glycidyl group can be produced, for example, by a reaction between a compound having active hydrogen and epichlorohydrin.

The molecular weight of the polymerizable compound represented by the general formula (1) described above is usually 1000 or less, preferably 800 or less, from the viewpoint of shrinkage reduction due to crosslinking during light irradiation or recording sensitivity and compatibility. More preferably, it is 600 or less, especially 500 or less, and is usually 200 or more, preferably 220 or more, more preferably 250 or more.

The polymerizable compound represented by the general formula (1) has a refractive index n _{D at} 25 ° C. of 1.50 or more, preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1.62 or more. It is. When used for a holographic recording material or a holographic recording medium, if the refractive index is excessively low, the diffraction efficiency does not increase and sufficient multiplicity cannot be obtained, so the refractive index n _D is 1.60 or more. It is preferable. On the other hand, if the refractive index is excessively high, the difference in refractive index from the matrix resin becomes too large, which may cause scattering. In addition, although a refractive index shows a large value when evaluated at a short wavelength, a sample showing a relatively large refractive index at a short wavelength shows a relatively large refractive index even at a long wavelength, and its order is not reversed. . Therefore, the refractive index can be evaluated at a wavelength other than the recording wavelength, and the value at the recording wavelength can be predicted.

When the polymerizable compound is solid and it is difficult to directly measure the refractive index, the compound is dissolved in an appropriate solvent to form a solution, and the refractive index of this solution is measured. The refractive index can be obtained by extrapolation.

The polymerizable compound represented by the general formula (1) has a viscosity at 60 ° C. of 5000 mPa · s or less, preferably 3000 mPa · s or less, more preferably 1000 mPa · s or less, and particularly preferably 500 mPa · s or less. is there.

The resin composition of the present invention contains the polymerizable compound, but preferably contains a polymerization initiator. The polymerization initiator may be a known polymerization initiator and is not particularly limited as long as the polymerization is initiated by heating or irradiation with ultraviolet rays.

For example, when a compound having a radical polymerizable group such as a (meth) acryloyl group or a vinyl group is used as the polymerizable compound of the present invention, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc. may be mentioned. A radical photopolymerization initiator is preferred because it can be rapidly cured at room temperature.

Examples of the thermal radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert -Butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1 -Peroxyketals such as bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, hydroperoxides such as p-menthane hydroperoxide, α, α'-bis (tert-butylperoxy) ) Diiso Dialkyl peroxides such as propylbenzene, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, distearyl peroxide, dibenzoyl peroxide Diacyl peroxides, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutylperoxydi Peroxydicarbonates such as carbonate, tert-butyl peroxyisopropyl monocarbonate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl Peroxycarbonates such as oxy-2-ethylhexyl monocarbonate, tert-butyl peroxypivalate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexano 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxybenzoate, tert-hexylperoxybenzoate, 2, 5-dimethyl-2 Peroxyesters such as 5-bis (benzoylperoxy) hexane and tert-butylperoxyacetate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) And azo compounds such as 2,2′-azobis (4-methoxy-2′-dimethylvaleronitrile).

Of these, diacyl peroxides, peroxycarbonates, peroxyesters, and azo compounds are preferable from the viewpoints of curability, transparency, and heat resistance.

Examples of the photo radical polymerization initiator include benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl. Α-hydroxyacetophenones such as propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1 Α-aminoacetophenones such as-(4-morpholinophenyl) -butan-1-one and 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1- [ Oxime esters such as 4- (phenylthio) phenyl] -1,2-octadione and 2- (O-benzoyl) oxime Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine oxides such as fin oxide, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer, benzo Benzophenones such as enone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2- Ethyl anthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2- Quinones such as methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether Benzoin ethers such as benzoin phenyl ether, benzoins such as benzoin, methylbenzoin, and ethylbenzoin, acridines such as 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, N-phenylglycine, coumarin, etc. Is mentioned.

Among these, α-hydroxyacetophenones and phosphine oxides are preferable from the viewpoints of curability, transparency and heat resistance. These thermal and photo radical polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

The photosensitizer is not particularly limited, and specifically, tertiary amines such as triethylamine and triethanolamine, alkylphosphine such as triphenylphosphine, β-thiodiglycol and the like Thioethers are exemplified, and the blending amount is recommended to be about 0.01 to 5% by weight with respect to the total amount of the resin composition.

Further, when a compound having a cationic polymerizable group such as a glycidyl group is used as the polymerizable compound of the present invention, examples of the polymerization initiator include a thermal cationic polymerization initiator and a photo cationic polymerization initiator. A photocationic polymerization initiator is preferred because it can be rapidly cured at room temperature.

Examples of the thermal cationic polymerization initiator include benzylsulfonium salts such as p-alkoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-p-cyanopyridinium hexafluoroantimonate, 1-naphthylmethyl-o-cyanopyridinium hexafluoroantimonate. And pyridinium salts such as cinnamyl-o-cyanopyridinium hexafluoroantimonate and benzylammonium salts such as benzyldimethylphenylammonium hexafluoroantimonate.

Of these, benzylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance.

Examples of the cationic photopolymerization initiator include aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfone Triarylsulfonium such as phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate Salts, triphenyl acetate Triarylselenonium salts such as nonium hexafluorophosphate, triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroantimonate, dialkyl such as dimethylphenacylsulfonium hexafluoroantimonate, diethylphenacylsulfonium hexafluoroantimonate Dialkyl-4-hydroxy salts such as phenacylsulfonium salts, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate, α-hydroxymethylbenzoin sulfonate, N-hydroxyimide sulfonate , Α-sulfonyloxy ketone, β-sulfonyloxy ketone, etc. An acid ester.

Of these, triarylsulfonium salts are preferred from the viewpoints of curability, transparency, and heat resistance. These thermal and photocationic polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

The amount of the polymerization initiator used is 0.01 to 10% by weight based on the total amount of the resin composition, although it varies depending on the presence or absence of the polymerization inhibitor and the type and amount of the polymerization inhibitor used. More preferably, it is 0.02 to 5% by weight, and further preferably 0.03 to 3% by weight. However, since the amount used varies greatly depending on the type of polymerization initiator used, it is necessary to appropriately determine the optimum conditions.

In the resin composition of the present invention, a known polymerization inhibitor can be added for storage of the resin composition. However, since the type and amount of addition vary greatly depending on the type and amount of polymerization initiator and polymerizable compound to be used, it is necessary to appropriately determine the optimum conditions.

Moreover, the resin composition of this invention can contain other polymeric compounds (henceforth other polymeric compounds) other than the polymeric compound represented by General formula (1) as needed. . Even when other polymerizable compounds are included, the polymerizable compound represented by the general formula (1) is preferably 10% by weight or more, more preferably 50% by weight based on the total amount of the resin composition. % Or more.

As the other polymerizable compound, a known polymerizable compound may be used, and any of monofunctional, bifunctional, polyfunctional, and polymerizable oligomers may be used. You may use together. As the polymerizable compound by heat or light, it is preferable to use either a thermally polymerizable compound or a photopolymerizable compound depending on the application.

When a compound having a radical polymerizable group such as a (meth) acryloyl group or a vinylaryl group is used as the polymerizable compound of the present invention, a known radical polymerizable compound can be used as the other polymerizable compound. (Meth) acrylate compounds, vinylidene halide compounds, vinyl ether compounds, vinyl ester compounds, vinyl pyridine compounds, vinyl amide compounds, vinyl aryl compounds, and the like. Of these, a (meth) acrylate compound and a vinylaryl compound are preferable from the viewpoint of transparency.

Examples of monofunctional (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and butoxyethyl (meth) acrylate. , Isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, Allyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Fats such as acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, mono (2- (meth) acryloyloxyethyl) succinate Group (meth) acrylates, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopenta Ru (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate Alicyclic (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthoxyethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, phenoxypolyethylene Lenglycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl Aromatic (meth) acrylates such as (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate, 2- Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (meth) acryloyloxyethyl-N-carbazole, Such Rorakuton modified products thereof.

Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth). ) Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated polypropylene glycol Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ne Pentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, ethoxylated 2-methyl-1,3-propanediol di Aliphatic di (meth) acrylates such as (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, propoxylated cyclohexanedimethanol di (meth) acrylate, ethoxylated propoxylation Cyclohexane Methanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethoxylated tricyclodecane dimethanol di (meth) acrylate, propoxylated tricyclodecane dimethanol di (meth) acrylate, ethoxylated propoxylated tricyclo Decandimethanol di (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated water Cycloaliphatic di (meth) acrylates such as bisphenol F di (meth) acrylate, propoxylated hydrogenated bisphenol F di (meth) acrylate, ethoxylated propoxy hydrogenated bisphenol F di (meth) acrylate Ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, propoxylated bisphenol F Di (meth) acrylate, ethoxylated propoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol AF di (meth) acrylate, propoxylated bisphenol AF di (meth) acrylate, ethoxylated propoxylated bisphenol AF di (meth) acrylate, Fragrances such as ethoxylated fluorene type di (meth) acrylate, propoxylated fluorene type di (meth) acrylate, ethoxylated propoxylated fluorene type di (meth) acrylate Heterocyclic di (meth) acrylates such as di (meth) acrylates, ethoxylated isocyanuric acid di (meth) acrylate, propoxylated isocyanuric acid di (meth) acrylate, ethoxylated propoxylated isocyanuric acid di (meth) acrylate, These modified caprolactones, aliphatic epoxy di (meth) acrylates such as neopentyl glycol type epoxy di (meth) acrylate, cyclohexanedimethanol type epoxy di (meth) acrylate, hydrogenated bisphenol A type epoxy di (meth) acrylate, hydrogenated bisphenol Alicyclic epoxy di (meth) acrylates such as F type epoxy di (meth) acrylate, resorcinol type epoxy di (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, Phenol F type epoxy di (meth) acrylate, bisphenol AF type epoxy di (meth) acrylate, and aromatic epoxy di (meth) acrylates such as fluorene epoxy di (meth) acrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxy. Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated propoxylated pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol Aliphatic polyfunctional (meth) such as tiger (meth) acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Heterocyclic polyfunctional (meth) acrylates such as acrylates, ethoxylated isocyanuric acid tri (meth) acrylate, propoxylated isocyanuric acid tri (meth) acrylate, ethoxylated propoxylated isocyanuric acid tri (meth) acrylate, and these caprolactones Modified products, aromatic epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, etc. And the like.

(Meth) acrylate-based polymerizable oligomers include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polybutadiene oligomer (meth) acrylate, polyamide-type (meth) acryl oligomer, melamine (meth) acrylate , Cyclopentadiene oligomer (meth) acrylate, silicone oligomer (meth) acrylate, and the like.

Another polymerizable oligomer is a copolymer obtained by copolymerizing a bifunctional compound having two unsaturated double bonds and a chain transfer agent, and a reaction derived from the bifunctional compound in the side chain. An oligomer having a pendant structure having a sex group can be mentioned. Preferred functional groups at this time are a vinyl group and an allyl group, and the bifunctional compound includes a branched structure, an alicyclic structure, or a substituent having an unsaturated double bond in a monocyclic or condensed aromatic ring. May be partially substituted with oxygen, nitrogen, or sulfur atoms.

When a compound having a cationic polymerizable group such as a glycidyl group is used as the polymerizable compound of the present invention, a known cationic polymerizable compound can be used as the other polymerizable compound.

Examples of the cationic polymerizable compound used as the other polymerizable compound include alkenyl ethers such as vinyl ether compounds and propenyl ether compounds, alkenyl thioethers such as vinyl thioether compounds and propenyl thioether compounds, vinyl ester compounds, and O-propenyl ester compounds. N-alkenylamides such as N-vinylamide compounds and N-propenylamide compounds, cyclic ethers such as epoxy (oxirane) compounds, oxetane compounds and oxolane compounds, and cyclic compounds such as ethylene sulfide (thiirane) compounds Thioethers, cyclic acetal compounds, lactone compounds, spiroorthoester compounds, N-vinylimidazole compounds, N-vinylcarbazole compounds, etc. Rukoto can. Among these cationically polymerizable compounds, vinyl ether compounds, epoxy compounds, and oxetane compounds are preferable.

Particularly preferable other polymerizable compounds include a resin composition having a high refractive index and a low viscosity, which contains a polymerizable functional group capable of copolymerization and is a compound represented by the following general formula (2). It is suitable for giving.

In the general formula (2), Y represents an n-valent ring-containing group having 2 to 7, preferably 2 to 5, 5- or 6-membered rings, where n is an integer of 2 to 4. The plurality of rings of the ring-containing group are (a) those directly connected to each other by a single bond, (b) an alkylene group having 1 to 3 carbon atoms, an oxygen atom (ether group), a sulfur atom (sulfide group) There are those in which the rings are bonded via any of the above, or (c) the rings are condensed, and have two or more types of bonds (a), (b) and (c) above. It may be what you are doing.

The structure of Y is not particularly limited, but an n-valent ring-containing group having a structure represented by the following formulas (Y-1) to (Y-17) is preferable. The compound represented by the general formula (2) is obtained by substituting these n-valent ring-containing groups with n atomic groups -ZA.

In the resin composition of the present invention, n-valent ring-containing groups having the structures of the above formulas (Y-1) to (Y-11) are preferable from the viewpoint of improving the refractive index, and the above formulas (Y-12) to (Y An n-valent ring-containing group having the structure of Y-17) is preferred from the viewpoint of reducing the viscosity.

In the general formula (2), Z represents a direct bond, an oxygen atom, a sulfur atom, or an alkylene group having 1 to 4 carbon atoms, an oxyalkylene group, a thioalkylene group, an alkyleneoxy group, or an alkylenethio group. A represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinylaryl group or a vinylaryloyl group.

In the general formula (2), n is an integer of 2 to 4, but a compound in which n is 2 is more preferable because of the availability of materials.

The type and content of the other polymerizable compound represented by the general formula (2) can be appropriately determined depending on the type and amount of the other constituents in the resin composition, but preferably to obtain a sufficient effect. In addition, 5% by weight, preferably 10% by weight or more is added to the total amount of the resin composition.

Other components such as fillers, fibers, coupling agents, flame retardants, mold release agents, and foaming agents can be added to the resin composition of the present invention as necessary. The filler used in this case is polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorite, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, iron powder. , Talc, mica, kaolin clay and the like. Examples of the fiber include cellulose fiber, glass fiber, carbon fiber, and aramid fiber. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent. Examples of the flame retardant include brominated bisphenol A, antimony trioxide, and phosphorus compounds. Examples of the release agent include stearates, silicones, waxes and the like. As the blowing agent, Freon, dichloroethane, butane, pentane, dinitropentamethylenetetramine, p-toluenesulfonyl hydrazide, or freon, dichloroethane, butane, pentane, etc. are vinyl chloride-vinylidene chloride copolymer or styrene- (meth) acrylic. Examples thereof include expandable thermoplastic resin particles filled in an acid ester copolymer shell.

The resin composition of the present invention can be dissolved in a solvent and diluted for use. In this case, specific examples of the diluent solvent that can be used include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, etc., and the amount used is based on the total amount of the resin composition and the diluent solvent. It is preferable that it is 70 weight% or less, More preferably, it is 60 weight% or less.
In addition, other polymerizable compounds having a low viscosity can also be used as a reactive diluent for reducing the viscosity of the resin composition. Here, the low viscosity is 500 mPa · s or less, preferably 200 mPa · s or less.

The resin composition of the present invention can be easily made into a cured resin or molded product by a method similar to a conventionally known method. For example, a thermal polymerization initiator or a photopolymerization initiator is added to the polymerizable compound of the present invention, and other polymerizable compounds and other additives are further added as necessary, and an extruder, kneader, roll, stirrer, etc. And mixed well to obtain a resin composition. The resin composition is molded using a roll coater, a cast after casting or a transfer molding machine, and further heated to 60 to 200 ° C. or irradiated with light. A cured product can be obtained.

In addition, a prepreg obtained by impregnating the resin composition of the present invention into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding to obtain a cured product. You can also For example, a thermal polymerization initiator is added to the polymerizable compound of the present invention, another polymerizable compound or other additive is further added as necessary, a solvent is further added, and the resin composition diluent is stirred. A glass cloth laminate can be produced by impregnating a glass cloth and heating and semi-drying (devolatilization) and prepressing the prepreg obtained by heating at 60 to 200 ° C. However, when the optical material of the present invention is used for an application of transmitting light, the substrate is preferably a transparent material. On the other hand, when the optical material of the present invention is used for the purpose of reflecting / diffusing light, it is preferable that the substrate is opaque with respect to the wavelength of the light to be reflected / diffused.

The resin composition thus obtained and its cured product are excellent in high refractive index, excellent in transparency, handling properties, etc., glass substitute materials for lens applications, protective film materials for color filters for liquid crystal displays, optical It is suitably used for various optical materials such as coating materials for product protection, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, and optical recording materials for hologram recording media.

Next, the holographic recording material of the present invention will be described. The holographic recording material of the present invention comprises A) a polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator. As the polymerizable compound, the polymerizable compound represented by the general formula (1) is used. Hereinafter, A) polymerizable compound, B) matrix resin or matrix resin forming component, and C) photopolymerization initiator are also referred to as A component, B component, and C component, respectively.

(B component: Matrix resin)
As the matrix resin, a resin that can be dissolved in a solvent may be used, or a three-dimensionally cross-linked resin may be used, and a three-dimensional cross-linked resin is preferably used from the viewpoint of recording characteristics. The holographic recording material may be blended with a matrix resin, but may be blended as a matrix resin forming component (such as a monomer) that forms the matrix resin. When the matrix resin forming component is blended, it is preferable that polymerization of the polymerizable compound does not occur when forming the matrix resin.

Examples of the three-dimensional crosslinked resin include isocyanate-hydroxyl polyadducts, isocyanate-amine polyadducts, isocyanate-thiol polyadducts, epoxy-amine polyadducts, epoxy-thiol polyadducts, episulfide-amine polyadducts, and Episulfide-thiol polyadduct, etc. can be mentioned, and it is an isocyanate-hydroxyl polyadduct capable of reacting under a relatively mild temperature condition, having excellent optical characteristics of the resulting matrix resin, and having a relatively low odor. It is preferable.

As the polyisocyanate component constituting the isocyanate-hydroxyl polyadduct, a compound having two or more isocyanate groups in one molecule or a mixture thereof is used. For example, tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthylene-1,5-diisocyanate (NDI), triphenyl Methane-4,4 ′, 4 ″ -triisocyanate, dicyclohexylmethane-4,4′-diisocyanate (H12MDI), hydrogenated xylylene diisocyanate (H6XDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), Isophorone diisocyanate (IPDI), norbornane diisocyanate (NBDI), cyclohexane-1,3,5-triisocyanate and their isocyanateation Trimers obtained from products, biurets, adducts, prepolymers, etc. These compounds having two or more isocyanate groups in one molecule may be used alone or in combination of two or more. Also good.

As the polyol component constituting the isocyanate-hydroxyl polyadduct, a compound having two or more hydroxyl groups in one molecule or a mixture thereof is used. For example, diols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, butanediol, pentanediol, hexanediol, heptanediol, tetramethylene glycol; bisphenols; Examples include triols such as methylolpropane, butanetriol, pentanetriol, hexanetriol and decanetriol; compounds obtained by modifying the hydroxyl group of these compounds with a polyethyleneoxy chain or a polypropyleneoxy chain. These compounds having two or more hydroxyl groups in one molecule may be used alone or in combination of two or more.

As another preferred embodiment, the matrix resin may contain a unit derived from a reactive aromatic compound having an aromatic ring and having a polymerization reactive group and a hydroxyl group as a part of the constituent unit of the matrix resin.
In this case, it can be part of the structural unit of the matrix resin via the hydroxyl group, and an aromatic ring is present in the matrix resin, so that the hollow resin containing the high refractive index polymerizable compound having the aromatic ring is present. Even in the case of graphic recording materials, it has been experimentally confirmed that the compatibility is high and turbidity hardly occurs, and a relatively large amount of polymerizable compound can be contained. As a result, the refractive index difference between the matrix resin and the polymerizable compound or polymer thereof can be increased, and as a result, the refractive index modulation can be increased.

Further, in this case, since a polymerization reactive group is present in the matrix resin, at the time of light irradiation, at least a part of the polymerizable compound reacts with the polymerization reactive group present in the matrix resin and is copolymerized. It is thought that there is. As a result, compatibility is improved and transparency is improved, and it is presumed that the formed refractive index modulation structure is stabilized.

Therefore, when the reactive aromatic compound is added to the holographic recording material, a plurality of diffraction gratings can be formed with high contrast by the refractive index modulation structure, and a plurality of page information corresponding to the plurality of diffraction gratings can be obtained. It can be recorded and played back with a high SNR.

Examples of the reactive aromatic compound include those represented by the formula (5), (6) or (7).

In the formula (5), Ar5 represents a monovalent or divalent group having one or more aromatic rings, Z ¹ and Z ² each independently represents a hydrogen atom or a methyl group, and L 1 represents an oxygen atom, a sulfur atom or — (OZ ³ ) nO— (Z ³ is an alkylene group having 1 to 4 carbon atoms, n is an integer of 1 to 4), and L ² is a divalent divalent alkyl group which may have an aromatic ring. Represents a group, and m represents an integer of 1 to 2.
In formula (6), Z ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and L ³ represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or an alkylene group having 1 to 4 carbon atoms. Or represents a 9,9-fluorenylene group. Z ¹ and L ¹ are the same as in formula (5).
In formula (7), L ² represents a single bond or a divalent group which may have an aromatic ring. Z ¹ , Z ² , and L ¹ are the same as in formula (6).

Examples of the reactive aromatic compound represented by the formula (5) or (6) include (meth) acrylic acid adducts, 3-butenoic acid adducts, and vinyl benzoic acid adducts of bisphenol A type epoxy resins. , Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, bisphenol F type epoxy resin (meth) acrylic acid adduct, 3-butenoic acid adduct, vinyl benzoic acid adduct, Vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, (meth) acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether, 3-butenoic acid adduct, Vinyl benzoic acid adduct, vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, 9,9- (Meth) acrylic acid adducts, 3-butenoic acid adducts, vinyl benzoic acid adducts, vinyl phenol adducts, vinyl thiophenol adducts of bis (4-hydroxy-3-methylphenyl) fluorenediglycidyl ether , Vinyl aniline adduct, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorenediglycidyl ether (meth) acrylic acid adduct, 3-butenoic acid adduct, vinyl benzoic acid addition Products, vinyl phenol adducts, vinyl thiophenol adducts, vinyl aniline adducts, and the like.

The reactive aromatic compound is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, based on the total of the matrix resin or the matrix resin forming component (including the reactive aromatic compound), More preferably, it is 0.3-5% by mass. If the content of the reactive aromatic compound is too high, the viscosity of the precursor becomes high and the production of the holographic recording material may become complicated. On the other hand, if the reactive aromatic compound is not contained or if the content is too low, the compatibility between the matrix resin and the polymerizable compound or polymer thereof is lowered, and the holographic recording material may be turbid. .

Examples of the compound having a polymerization reactive group and a hydroxyl group represented by the formula (7) include 9,9-bis (4-hydroxy) among the reactive aromatic compounds represented by the formula (5) or (6). (Meth) acrylic acid adduct, phenyl 3-butenoic acid adduct, vinyl benzoic acid adduct, vinyl phenol adduct, vinyl thiophenol adduct, vinyl aniline adduct, 9 , 9-Bis (4-hydroxy-3-methylphenyl) fluorenedin glycidyl ether, (meth) acrylic acid adduct, 3-butenoic acid adduct, vinylbenzoic acid adduct, vinylphenol adduct, vinyl Thiophenol adduct, vinylaniline adduct, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorange glycidyl a (Meth) acrylic acid adduct of Le, the 3-butenoic acid adduct, the vinyl benzoic acid adducts, the vinyl phenol adduct, the vinylthiophenol adducts, such as the vinyl aniline adduct.

The main component of the acrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is that R ¹ in formula (7) is a hydrogen atom, R ² is a hydrogen atom, L ¹ is an oxygen atom, L ² is a compound represented by a single bond.
The main components of the methacrylic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether are as follows: R ¹ in formula (7) is a methyl group, R ² is a hydrogen atom, L ¹ is an oxygen atom, L ² is a compound represented by a single bond.
The main components of the 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct are: R ¹ in formula (7) is a hydrogen atom, R ² is a hydrogen atom, and L ¹ is an oxygen atom , L ² is a compound represented by a methylene group.
The main component of the vinyl benzoic acid adduct of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether is as follows: R ¹ in formula (7) is a hydrogen atom, R ² is a hydrogen atom, L ¹ is an oxygen atom, L ² is a compound represented by a phenylene group.

(Component A: polymerizable compound)
The blending amount of the polymerizable compound is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1.5 to 10% by mass with respect to the entire holographic recording material. Moreover, if necessary, a small amount of other polymerizable compounds can be used in combination for the purpose of adjusting the refractive index.

(C component: photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it initiates polymerization of the polymerizable compound of component A by irradiation with ultraviolet rays or the like. For example, when a compound having an ethylenically unsaturated group is used as the polymerizable compound, a radical photopolymerization initiator can be used. As the radical photopolymerization initiator, any known radical radical polymerization initiator can be used. Examples include azo compounds, azide compounds, organic peroxides, organoborates, onium salts, bisimidazole derivatives, titanocene compounds, iodonium salts, organic thiol compounds, halogenated hydrocarbon derivatives, α-hydroxyketone compounds. , Α-aminoketone compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are used. Any one of these may be used alone, or two or more may be used in any combination and ratio. Of these, titanocene compounds, acylphosphine oxide compounds, oxime ester compounds, and the like are preferable because a polymerization reaction occurs in the visible light region without requiring a sensitizer.

The type of titanocene compound is not particularly limited, but specific examples thereof include biscyclopentadienyl-Ti-dichloride, biscyclopentadienyl-Ti-diphenyl, biscyclopentadienyl-Ti-bis (2 , 3,4,5,6-pentafluorophenyl), biscyclopentadienyl-Ti-bis (2,3,5,6-tetrafluorophenyl), biscyclopentadienyl-Ti-bis (2,4 , 6-trifluorophenyl), biscyclopentadienyl-Ti-bis (2,6-difluorophenyl), biscyclopentadienyl-Ti-bis (2,4-difluorophenyl), bis (methylcyclopentadi) Enyl) -Ti-bis (2,3,4,5,6-pentafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,3,5,6-tetrafluorophenyl), bis (methylcyclopentadienyl) -Ti-bis (2,6-difluorophenyl), biscyclopentadienyl-Ti-bis (2 , 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) and the like.

The acyl phosphine oxide compound is not particularly limited, but specific examples include triphenyl phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 2,6-dichlorobenzoyl diphenyl. Phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichloro) And benzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and the like.

The type of the oxime ester compound is not particularly limited, but specific examples thereof include 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) -1,2-octanedione, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -2- (O-benzoyloxime) -3-cyclopentyl-1,2-propanedione, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] And -2- (O-acetyloxime) -4-cyclopentyl-1,2-butanedione.

Any one of these various photo radical polymerization initiators may be used alone, or two or more of them may be used in any combination and ratio.

In addition, when a cationically polymerizable compound such as a compound having a glycidyl group is used as the polymerizable compound, a photocationic polymerization initiator can be used as the photopolymerization initiator.

Any known cationic photopolymerization initiator can be used as the cationic photopolymerization initiator. Examples include aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenonium salts, dialkylphenacyl sulfonium salts, dialkyl-4-hydroxy salts, sulfonic acid esters, and the like. Any one of these may be used alone, or two or more may be used in any combination and ratio.

(Other ingredients)
The holographic recording material of the present invention includes a photosensitizer, a plasticizer, a compatibilizer, a chain transfer agent, a polymerization accelerator, a polymerization inhibitor, a polymerization inhibitor, a radical scavenger, and a surfactant as necessary. , A silane coupling agent, an antifoaming agent, a release agent, a stabilizer, an antioxidant, a flame retardant and the like may be further included. These additives may be used alone, or two or more of them may be used in any combination and ratio.

(Manufacture of holographic recording materials)
The method for producing the holographic recording material of the present invention will be described. First, a matrix resin forming component, for example, a polyisocyanate component and a polyol component constituting an isocyanate-hydroxyl polyadduct, a polymerizable compound, a photopolymerization initiator, and, if necessary, represented by the formula (5) A reactive aromatic compound is blended. Next, a matrix resin is formed by causing polymerization by a reaction other than a reaction in which the polymerizable reactive group of the polymerizable compound or the reactive aromatic compound is polymerized with respect to the matrix resin forming component. In this case, the matrix resin can be formed by polymerizing a matrix resin forming component in the presence of a polymerizable compound and a photopolymerization initiator.

A holographic recording material contains a high refractive index polymerizable compound in addition to a low refractive index matrix resin, and forms a diffraction grating as a refractive index modulation structure in the medium by polymerizing the polymerizable compound during recording. It is preferable. The holographic recording material includes (1) matrix forming components (isocyanate, polyol, reaction catalyst (tin-containing catalyst), etc.), (2) polymerizable compound, (3) photopolymerization initiator, (4) other components, Are mixed and dissolved as appropriate, and (1) only the matrix-forming components are allowed to react independently. At this time, (2) a polymerizable compound, (3) a photopolymerization initiator, (4) other components Is basically unaffected and is preferably dispersed in the matrix resin as it is. A material in which the holographic recording material is sandwiched between two substrates is called a holographic recording medium. When information is recorded on this holographic recording material or holographic recording medium, when irradiated with light, (3) a photopolymerization initiator is cleaved to form polymerization initiation species (radicals, etc.), and (2) polymerization Compound is polymerized.

On the other hand, when the polymerizable compound or the photopolymerization initiator decreases due to reaction, the performance as a holographic recording material is lowered. Therefore, it is preferable to form a matrix resin without reducing these. Therefore, it is preferable to mix a reaction catalyst or adjust the reaction temperature so that polymerization in a reaction form different from the reaction in which the polymerizable compound is polymerized preferentially occurs.

As the reaction catalyst, for example, as a catalyst for isocyanate-hydroxyl polyaddition reaction, a tin-containing catalyst, a titanium-containing catalyst, a zinc-containing catalyst, a zirconium-containing catalyst, an aluminum-containing catalyst, a cobalt-containing catalyst, a nickel-containing catalyst, a copper-containing catalyst, and Various metal-containing catalysts such as iron-containing catalysts can be used. Of these, tin-containing catalysts are preferred from the viewpoint of reaction rate. As the tin-containing catalyst, for example, a tin-containing catalyst such as dimethyltin dilaurate or dibutyltin dilaurate can be used. Non-metal-containing catalysts include 1,4-diazabicyclo [2,2,2] octane (DABCO), imidazole derivatives, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylbenzylamine. Tertiary amine compounds such as can be used. These catalysts may be used alone or in combination of two or more.

(Holographic recording medium)
The holographic recording medium of the present invention includes a recording layer containing the holographic recording material described above. The holographic recording medium of the present invention can have other layers such as an upper substrate, a lower substrate, and a reflective film as necessary.
The holographic recording medium of the present invention may be either a transmission type or a reflection type.

The following is a detailed introduction of each substrate and recording layer that can be included in the holographic recording medium of the present invention.
As the substrate material, glass, ceramics, resin and the like are usually used, but resin is preferable from the viewpoint of moldability and cost. Examples of the resin include polycarbonate resin, acrylic resin, polycycloolefin resin, epoxy resin, polystyrene resin, acrylonitrile-styrene copolymer, ABS resin, polyethylene resin, polypropylene resin, silicone resin, fluorine resin, and urethane resin. Can be mentioned. Among these, polycarbonate resin, acrylic resin, and polycycloolefin resin are particularly preferable in terms of moldability, optical characteristics, and cost. Further, those obtained by subjecting the substrate surface to a hard coat treatment with a UV curable resin or the like and those subjected to an antireflection treatment can be used as appropriate. A substrate provided with a reflective layer in advance can also be used according to the recording / reproducing method.

The recording layer is made of the holographic recording material, and information can be recorded using the holographic recording. There is no restriction | limiting in particular as thickness of a recording layer, According to the objective, it can select suitably. If the thickness of the recording layer is in the range of 1 to 3000 μm, the transmittance in the recording wavelength region of 350 to 800 nm is high, which is advantageous. In the case where the substrate is not used, those obtained by subjecting the surface of the recording layer to a hard coat treatment with a UV curable resin or the like and those subjected to an antireflection treatment can be used as appropriate.

The holographic recording medium of the present invention is preferably used for holographic recording / reproduction, but any method can be used for the holographic recording / reproduction method. For example, a holographic recording / reproducing method based on the two-beam interference method, a coaxial holographic recording / reproducing method in which reference light and information light are arranged on the same axis and condensed are preferably used.

An example of the holographic recording / reproducing apparatus will be described with reference to FIGS.
FIG. 3 shows a schematic configuration diagram of an optical system for multiple recording. Laser light emitted from a laser generator (a semiconductor laser having a wavelength of 405 nm) 1 is reflected by a mirror 2 and is a half-wave plate (HWP). After the power is adjusted at 3, a part thereof is reflected downward by the polarizing beam splitter (PBS) 4, the beam diameter is enlarged by the beam expander 5, and then passed through the shutter 6 to be stopped. The beam diameter is narrowed by 7 (opening diameter 6 mmφ), and reaches the PBS 9 through the HWP 8. In the PBS 9, the laser light is divided into two, and one of the divided lights passes through the shutter 10, is reflected by the mirror 11, and is applied to the holographic recording medium S as the recording signal light Ls. The other light split by the PBS 9 passes through the quarter wave plate (QWP) 12 and is reflected by the mirror 13, and then passes through the QWP 12 and PBS 9 again to irradiate the holographic recording medium S as the recording reference light Lw. Is done.
At this time, the angle θ of the rotary stage 14 to which the holographic recording medium S is attached is set to a predetermined value, the shutter 6 is opened for a predetermined time and exposed, and the first hologram is recorded on the holographic recording medium S. . Next, θ is set to the next predetermined value, the shutter 6 is opened for a predetermined time and exposed, and a second hologram is recorded in the same location of the holographic recording medium S. Thereafter, multiplex recording can be performed by repeating the above operation until a predetermined multiplicity is reached.
HWP3 is for adjusting the power of the entire optical system, and HWP8 is for adjusting the power ratio of the signal light and the reference light. The QWP 12 is for adjusting the polarization axis of the recording reference light Lw (or reproduction reference light Lr described later).

FIG. 4 is a schematic configuration diagram of the reproducing optical system, and the same symbols as those in FIG. 3 have the same meaning. Laser light emitted from the laser generator 1 reaches the PBS 9 via the mirror 2, the HWP 3, the PBS 4, the beam expander 5, the shutter 6, and the diaphragm 7. In the PBS 9, the laser light is divided into two, and one of the divided lights is blocked by the shutter 10. The other light divided by the PBS 9 is reflected by the mirror 13 through the QWP 12, and then passes again through the QWP 12 and the PBS 9, and the beam diameter is narrowed by the aperture 15 (opening diameter 2.7 mmφ), and the reproduction reference light Lr To the holographic recording medium S.
At this time, the angle θ of the rotary stage 14 to which the holographic recording medium S is attached is set to a value corresponding to a predetermined (reproduced) hologram, the shutter 6 is opened for a predetermined time, and the reproduction reference light Lr is irradiated onto the medium. To do. The intensity of the light (reproduced signal light) diffracted by the recorded hologram is measured by the optical power meter 16, and the intensity of the light transmitted through the medium (transmitted light) is measured by the optical power meter 17.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.

Example 1
1- (I): Synthesis of 4-acetyldiphenyl sulfide 25.0 g (0.136 mol) of diphenyl sulfide was dissolved in 300 ml of dichloromethane and cooled to 0 ° C. under a nitrogen atmosphere. 149 mol) was added slowly and the mixture was stirred for 15 minutes. A solution prepared by dissolving 11.9 g (0.149 mol) of acetyl chloride in 50 ml of dichloromethane was added dropwise, stirred for 30 minutes, warmed to room temperature, and further stirred for 1 hour. After completion of the reaction, the mixture was poured into ice water (200 ml), stirred for 10 minutes, and extracted three times with dichloromethane (100 ml each). The organic layers were combined, washed with water (100 ml) and saturated brine (100 ml), and dried over anhydrous magnesium sulfate. The desiccant was filtered off and the solvent was distilled off under reduced pressure to obtain 28.5 g of a crude product. The obtained crude product was used in the next reaction without further purification.

1- (II): Synthesis of 4- (1-hydroxyethyl) diphenyl sulfide 28.2 g (0.124 mol) of 4-acetyldiphenyl sulfide obtained by the above reaction was dissolved in 150 ml of methanol and cooled to 0 ° C. To the mixture, 9.3 g (0.247 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture and extracted with ethyl acetate (250 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 26.6 g of a crude product. The obtained crude product was used in the next reaction without further purification.

1- (III): Synthesis of 1- [4- (phenylthio) phenyl] ethyl acrylate

A solution obtained by dissolving 5.0 g (0.022 mol) of 4- (1-hydroxyethyl) diphenyl sulfide obtained in the above reaction and 8.8 g (0.087 mol) of triethylamine in 50 ml of dichloromethane and cooling to 0 ° C. was obtained by adding acryloyl Chloride was added dropwise and the mixture was stirred for 30 minutes, then warmed to room temperature and stirred for an additional hour. After completion of the reaction, water (100 ml) was added and extracted with dichloromethane (100 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 3.0 g of the objective compound as a colorless transparent liquid (yield 48%).
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.25-7.36 (m, 9H); 6.42 (dd = 18.0 Hz & 1.2 Hz, 1H); 6.14 (dd = 17 .4 Hz & 10.2 Hz, 1 H); 5.92-5.95 (q, 1 H); 5.83 (dd = 10.8 Hz & 1.2 Hz, 1 H); 1.56 (d = 6.6 Hz, 3 H)

Example 2
2- (I): Synthesis of 2,4-bis (phenylthio) acetophenone 16.1-g (0.103 mol) 2,4-difluoroacetophenone, 25 g (0.227 mol) thiophenol, 31.5 g (0.227 mol) potassium carbonate ) Was dissolved in 250 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 34.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.

2- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis (phenylthio) benzene 34.0 g (0.103 mol) of 2,4-bis (phenylthio) acetophenone obtained by the above reaction Was dissolved in 300 ml of methanol and cooled to 0 ° C., 5.9 g (0.155 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 27.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.

2- (III): Synthesis of 2,4-bis (phenylthio) styrene

In a reaction vessel equipped with a Dean-Stark trap, 10.0 g (0.030 mol) of 1- (1-hydroxyethyl) -2,4-bis (phenylthio) benzene obtained by the above reaction, p-toluenesulfonic acid 0.014 g (0.070 mmol) of monohydrate and 100 ml of toluene were added, and the mixture was stirred for 7 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 7.5 g of the objective compound as a colorless transparent liquid.
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.50-7.52 (m, 1H); 7.15-7.33 (m, 12H); 5.69 (d = 18.0 Hz) , 1H); 5.30 (d = 10.8 Hz, 1H).

Example 3
Synthesis of 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate

1- (1-Hydroxyethyl) -2,4-bis (phenylthio) benzene (5.0 g, 0.015 mol) and triethylamine (6.0 g, 0.059 mol) obtained by the above 2- (II) reaction were mixed with dichloromethane. Acryloyl chloride was added dropwise to the solution dissolved in 50 ml and cooled to 0 ° C., and the mixture was stirred for 30 minutes, then warmed to room temperature and further stirred for 1 hour. After completion of the reaction, water (100 ml) was added and extracted with dichloromethane (100 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 2.9 g of the objective compound as a colorless transparent liquid (yield 49%).
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.14-7.39 (m, 13H); 6.38-6.41 (q, 1H); 6.13 (dd = 18.6 Hz & 10 .2 Hz, 1 H); 5.82 (dd = 10.2 Hz & 1.2 Hz, 1 H); 1.51 (d = 6.0 Hz, 3 H)

Example 4
Synthesis of 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate

3.39 g (0.010 mol) of 1- (1-hydroxyethyl) -2,4-bis (phenylthio) benzene obtained by the reaction of 2- (II) above, 1.8 g (0. 10 mol) of 4-vinylbenzoic acid. 012 mol), 2.5 g (0.012 mol) of N, N′-dicyclohexylcarbodiimide and 1.5 g (0.012 mol) of N, N-dimethylaminopyridine were dissolved in 100 ml of dichloromethane, and the mixture was stirred at room temperature for 8 hours. . After completion of the reaction, water (100 ml) was added and extracted with dichloromethane (100 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 3.9 g of the target compound as a white solid (powder) (yield 83%). This white solid became a colorless and transparent liquid in a hot bath at 60 ° C.
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.50-7.52 (m, 2H); 7.24-7.46 (m, 15H); 6.75 (dd = 15.0 Hz & 10 8.53, 6.57 (q, 1H); 5.86 (d = 18 Hz, 1H); 5.38 (d = 10.8 Hz, 1H); 1.59 (d = 7) .2Hz, 3H)

Example 5
5- (I): Synthesis of 2,4-bis (2-naphthylthio) acetophenone 12.4-g (0.078 mol) 2,4-difluoroacetophenone, 25.0 g (0.156 mol) 2-naphthalenethiol, potassium carbonate 21 0.6 g (0.156 mol) was dissolved in 250 ml of DMF and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 33.9 g of a crude product. The obtained crude product was used in the next reaction without further purification.

5- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis (2-naphthylthio) benzene 33.9 g of 2,4-bis (2-naphthylthio) acetophenone obtained by the above reaction ( 0.078 mol) was dissolved in 300 ml of methanol and cooled to 0 ° C., and 4.4 g (0.117 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower. Stir for hours. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 28.0 g of a crude product. The obtained crude product was used in the next reaction without further purification.

5- (III): Synthesis of 2,4-bis (2-naphthylthio) styrene

In a reaction vessel equipped with a Dean-Stark trap, 15.0 g (0.034 mol) of 1- (1-hydroxyethyl) -2,4-bis (2-naphthylthio) benzene obtained by the above reaction, p-toluene 0.016 g (0.08 mmol) of sulfonic acid monohydrate and 150 ml of toluene were added, and the mixture was stirred for 7 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 11.8 g of the target compound as a white solid (powder). This white solid became a colorless and transparent liquid in a hot bath at 60 ° C.
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.20-7.81 (m, 17H); 5.71 (d = 17.4 Hz, 1H); 4.13 (d = 7.2 Hz) , 1H)

Example 6
6- (I): Synthesis of 2,4-bis [4- (methylthio) phenylthio] acetophenone 2,4-difluoroacetophenone 7.1 g (0.45 mol), 4- (methylthio) benzenethiol 10 g (0.091 mol) 12.5 g (0.091 mol) of potassium carbonate was dissolved in 150 ml of DMF and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (200 ml) and ethyl acetate (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 16.5 g of a crude product. The obtained crude product was used in the next reaction without further purification.

6- (II): Synthesis of 1- (1-hydroxyethyl) -2,4-bis [4- (methylthio) phenylthio] benzene 2,4-bis [4- (methylthio) phenylthio obtained by the above reaction A solution of 16.5 g (0.039 mol) of acetophenone in 300 ml of methanol and cooling to 0 ° C. slowly added 2.2 g (0.058 mol) of sodium borohydride so that the liquid temperature was kept at 15 ° C. or lower. And the mixture was stirred for 1 hour. After completion of the reaction, water (300 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 15.6 g of a crude product. The obtained crude product was used in the next reaction without further purification.

6- (III): Synthesis of 2,4-bis [4- (methylthio) phenylthio] styrene

In a reaction vessel equipped with a Dean-Stark trap, 13.6 g (0.032 mol) of 1- (1-hydroxyethyl) -2,4-bis [4- (methylthio) phenylthio] benzene obtained in the above reaction, 0.014 g (0.075 mmol) of p-toluenesulfonic acid monohydrate and 150 ml of toluene were added, and the mixture was stirred under toluene reflux for 7 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 1.0 g of the objective compound as a colorless transparent liquid (yield 7%).
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 6.84-7.45 (m, 10H); 5.77 (d = 18.0 Hz, 1H); 5.67 (d = 18.0 Hz) , 1H).

Example 7
7- (I): Synthesis of 2,4,6-tris (phenylthio)

acetophenone

25,4,6-trifluoroacetophenone 25. 4 (0.144 mol), 47.5 g thiophenol (0.430 mol), potassium carbonate 59. 5 g (0.430 mol) was dissolved in 500 ml of DMF and stirred at 130 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (400 ml) and ethyl acetate (400 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 68.7 g of a crude product. The obtained crude product was used in the next reaction without further purification.

7- (II): Synthesis of 1- (1-hydroxyethyl) -2,4,6-tris (phenylthio) benzene 66.0 g of 2,4,6-tris (phenylthio) acetophenone obtained by the above reaction ( 0.148 mol) was dissolved in 500 ml of methanol and cooled to 0 ° C., and 16.8 g (0.445 mol) of sodium borohydride was slowly added so that the liquid temperature was kept at 15 ° C. or lower. Stir for hours. After completion of the reaction, water (500 ml) was added to the mixture and extracted with ethyl acetate (200 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 56.7 g of a crude product. The obtained crude product was used in the next reaction without further purification.

7- (III): Synthesis of 2,4,6-tris (phenylthio) styrene

In a reaction vessel equipped with a Dean-Stark trap, 20.0 g (0.448 mol) of 1- (1-hydroxyethyl) -2,4,6-tris (phenylthio) benzene obtained by the above reaction, p-toluene 0.204 g (0.107 mmol) of sulfonic acid monohydrate and 300 ml of toluene were added, and the mixture was stirred for 7 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 14.5 g of the objective compound as a colorless transparent viscous liquid (yield 78%).
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.10-7.41 (m, 17H); 5.71 (d = 18.0 Hz, 1H); 5.32 (d = 10.8 Hz) , 1H).

Example 8
8- (I): Synthesis of 4,4′-bis (phenylthio)

benzophenone

4,4′-difluorobenzophenone 50.0 g (0.229 mol), thiophenol 53.0 g (0.481 mol), potassium carbonate 66.5 g (0.481 mol) was dissolved in 250 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (300 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 101.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.

8- (II): Synthesis of 4,4′-bis (phenylthio) benzhydrol 80.0 g (0.200 mol) of 4,4′-bis (phenylthio) benzophenone obtained by the above reaction was dissolved in 500 ml of methanol. Then, 9.2 g (0.241 mol) of sodium borohydride was slowly added to the solution cooled to 0 ° C. so that the liquid temperature was kept at 15 ° C. or lower, and the mixture was stirred for 1 hour. After completion of the reaction, water (1000 ml) was added to the mixture and extracted with ethyl acetate (300 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 77.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.

8- (III): Synthesis of 4,4'-bis (phenylthio) phenylmethyl acrylate

46.5 g (0.116 mol) of 4,4′-bis (phenylthio) benzhydrol obtained by the above 8- (II) reaction and 24.7 g (0.232 mol) of triethylamine were dissolved in 300 ml of dichloromethane, and 0 ° C. To the cooled product, acryloyl chloride was added dropwise, and the mixture was stirred for 30 minutes, then warmed to room temperature and further stirred for 1 hour. After completion of the reaction, water (300 ml) was added and extracted with dichloromethane (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 38.8 g of the target compound as a colorless transparent liquid (yield 74%).
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.25-7.38 (m, 18H); 6.87 (s, 1H); 6.48 (d = 16.2 Hz, 1H); 6.21 (dd = 8.4 Hz & 10.8 Hz, 1 H); 5.82 (dd = 16.2 Hz & 1.2 Hz, 1 H)

Example 9
9- (I): Synthesis of 4- (2-naphthylthio) -2-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), 2-naphthalenethiol 25 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Subsequently, after 17.2 g (0.156 mol) of thiophenol was added little by little, the mixture was further stirred at 130 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 20.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.

9- (II): Synthesis of 1- (1-hydroxyethyl) -4- (2-naphthylthio) -2-phenylthiobenzene 4- (2-naphthylthio) -2-phenylthioacetophenone obtained by the above reaction To 20.0 g (0.052 mol) dissolved in 200 ml of THF and cooled to 0 ° C., 3.91 g (0.104 mol) of sodium borohydride was added and slowly added so that the liquid temperature was kept at 15 ° C. or lower. And 50 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (250 ml) was added to the mixture, and the mixture was extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 21.3 g of a crude product. The obtained crude product was used in the next reaction without further purification.

9- (III): Synthesis of 4- (2-naphthylthio) -2-phenylthiostyrene

In a reaction vessel equipped with a Dean-Stark trap, 20.0 g (0.052 mol) of 1- (1-hydroxyethyl) -4- (2-naphthylthio) -2-phenylthiobenzene obtained in the above reaction, p -Toluenesulfonic acid monohydrate 0.079 g (0.41 mmol) and toluene 200 ml were added and the mixture was stirred for 4 hours under toluene reflux. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 4.2 g of the desired compound.
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.80-7.82 (m, 2H); 7.71-7.73 (m, 2H); 7.48-7.51 (m , 3H); 7.35 (d = 8.7 Hz, 1H); 7.04-7.21 (m, 7H); 5.69 (d = 16.9 Hz, 1H); 5.30 (d = 11) .4Hz, 1H).

Example 10
10- (I): Synthesis of 2- (2-naphthylthio) -4-phenylthioacetophenone 2,4-difluoroacetophenone 24.4 g (0.156 mol), thiophenol 17.2 g (0.156 mol), potassium carbonate 43 .13 g (0.312 mol) was dissolved in 300 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Next, 25 g (0.156 mol) of 2-naphthalenethiol was added little by little, and the mixture was further stirred at 130 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 48.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.

10- (II): Synthesis of 1- (1-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene 2- (2-naphthylthio) -4-phenylthioacetophenone obtained by the above reaction 48.1 g (0.124 mol) was dissolved in 400 ml of THF, and cooled to 0 ° C., 14.2 g (0.375 mol) of sodium borohydride was added, and the solution temperature was slowly kept so as to be kept at 15 ° C. or lower. And 200 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (400 ml) was added to the mixture and extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 50.8 g of a crude product. The obtained crude product was used in the next reaction without further purification.

10- (III): Synthesis of 2- (2-naphthylthio) -4-phenylthiostyrene

In a reaction vessel equipped with a Dean-Stark trap, 40.0 g (0.052 mol) of 1- (1-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene obtained in the above reaction, p -Toluenesulfonic acid monohydrate (0.157 g, 0.82 mmol) and toluene (400 ml) were added, and the mixture was stirred under toluene reflux for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 6.3 g of the desired compound.
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 7.78-7.80 (m, 1H); 7.67-7.73 (m, 3H); 7.46-7.52 (m 7.04-7.28 (m, 8H); 5.70 (d = 16.2 Hz, 1H); 5.30 (d = 11.4 Hz, 1H).

Example 11
11- (I): Synthesis of 2- (2-naphthylthio) -4-phenylthiobenzophenone 4,4-difluorobenzophenone 48.7 g (0.312 mol), thiophenol 34.4 g (0.312 mol), potassium carbonate 43 .13 g (0.614 mol) was dissolved in 500 ml of dimethylformamide (DMF) and stirred at 130 ° C. for 1 hour. Next, 50 g (0.312 mol) of 2-naphthalenethiol was added little by little, and the mixture was further stirred at 130 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, and extracted by adding a saturated aqueous ammonium chloride solution (500 ml) and ethyl acetate (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 94.1 g of a crude product. The obtained crude product was used in the next reaction without further purification.

11- (II): Synthesis of 1- (2-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained by the above reaction To 94.1 g (0.243 mol) dissolved in 400 ml of THF and cooled to 0 ° C., 27.6 g (0.73 mol) of sodium borohydride is added and slowly added so that the liquid temperature is kept at 15 ° C. or lower. And 200 ml of methanol were added and the mixture was stirred for 1 hour. After completion of the reaction, water (400 ml) was added to the mixture and extracted with ethyl acetate (125 ml). The organic layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain 101.2 g of a crude product. The obtained crude product was used in the next reaction without further purification.

11- (III): Synthesis of 2- [2- (2-naphthylthio) -4-phenylthiophenyl] ethyl acrylate

100.0 g (0.267 mol) of 1- (2-hydroxyethyl) -2- (2-naphthylthio) -4-phenylthiobenzene obtained by the reaction of 2- (II) and 108.1 g (1. (07 mol) was dissolved in 500 ml of dichloromethane and cooled to 0 ° C., 81.2 ml (1.07 mmol) of acryloyl chloride was added dropwise, and the mixture was stirred for 30 minutes, then warmed to room temperature and further stirred for 1 hour. After completion of the reaction, water (500 ml) was added and extracted with dichloromethane (500 ml). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography to obtain 25.4 g of the target compound.
¹ H-NMR (CDCl ₃ , 600 MHz) δ (ppm): 6.90-7.52 (m, 15H); 6.37-6.45 (m, 1H); 6.13 (dd = 18.6 Hz & 10 .2 Hz, 1 H); 5.82 (dd = 10.2 Hz & 1.2 Hz, 1 H); 5.20 (s, 2 H)

The refractive index of each of the compounds obtained in Examples 1 to 11 was determined according to the following procedure. For measurement, an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm. Since the compound obtained in Example 4 was a solid, the refractive index of a compound dissolved in a solvent having a known refractive index was measured using the above apparatus, and the value extrapolated to 100% of the substrate The refractive index of the compound was used. In this case, N-methylpyrrolidone was used as a solvent, and the substrate concentrations were 10% by mass, 20% by mass, and 30% by mass. The results of refractive index measurement are shown in Table 1.

For the compounds obtained in Examples 1 to 11, ultraviolet / visible absorption spectra were measured according to the following procedures. The above compound was dissolved in acetonitrile to make a 0.001% by weight solution, and an absorption spectrum was measured in a wavelength region of 500 to 200 nm using an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation. FIG. 1 is an ultraviolet / visible absorption spectrum of the compounds obtained in Examples 1 to 3, 9, and 11. In any sample, it was confirmed that there was no absorption in the visible region of 400 nm or more, and the transparency was high.

The compounds obtained in Examples 1 to 11 were measured for absorption spectra in the region of wave numbers of 500 to 4000 cm ⁻¹ using a Perkin Elmer infrared spectrophotometer Frontier. FIG. 2 is an infrared absorption spectrum of the compounds obtained in Examples 1 to 3. The inset in FIG. 2 is an enlarged view of the wave number range of 500 to 1000 cm ⁻¹ .

Example 12
99.5 parts by weight of 2,4-bis (phenylthio) styrene obtained in Example 2 as a polymerizable compound and 0.5 parts by weight of azobisisobutyronitrile as a thermal radical polymerization initiator are stirred and mixed at 40 ° C. Thus, a resin composition was obtained. Furthermore, this resin composition was introduced into a gap formed by bonding two glass substrates (50 mm × 50 mm) coated with a release agent through silicon film spacers (thickness 1.0 mm). After heat treatment at 60 ° C. for 15 hours, the glass substrate was peeled off to obtain a colorless and transparent sheet-like resin cured product.

Example 13
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 1- [2,4-bis (phenylthio) phenyl] ethyl acrylate obtained in Example 3 was used as the polymerizable compound. It was.

Example 14
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 4,4′-bis (phenylthio) phenylmethyl acrylate obtained in Example 8 was used as the polymerizable compound.

Example 15
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12, except that 2- (2-naphthylthio) -4-phenylthiostyrene obtained in Example 10 was used as the polymerizable compound.

Example 16
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 12 except that 2- (2-naphthylthio) -4-phenylthiobenzophenone obtained in Example 11 was used as the polymerizable compound.

Comparative Example 1
A pale yellow transparent sheet-like cured resin was obtained in the same manner as in Example 9 except that phenylthioethyl acrylate (manufactured by BIMAX, BX-PTEA) was used as the polymerizable compound.

Comparative Example 2
A colorless and transparent sheet-like cured resin product was obtained in the same manner as in Example 9, except that benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester BZ) was used as the polymerizable compound.

Comparative Example 3
A light yellow transparent sheet-like resin cured product was obtained in the same manner as in Example 9 except that ethoxylated o-phenylphenol acrylate (Miramer M1142 manufactured by MIWON) was used as the polymerizable compound.

Samples having a length of 20 mm, a width of 5 mm, and a thickness of 1.0 mm were cut out from the sheet-like resin cured products obtained in Examples 12 to 16 and Comparative Examples 1 to 3, and the refractive index was measured. The results are shown in Table 2. For measurement, an Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. was used, and the temperature was adjusted to 25 ° C. at a wavelength of 589 nm.

As described above, the polymerizable compound of the present invention, the resin composition using the same, and the cured product thereof are excellent in high refractive index and excellent in transparency, and are used for glass substitute materials for lens applications, liquid crystal displays, and the like. Suitable for various optical materials such as protective film materials for color filters, coating materials for protecting optical products, fine particles for spacers such as electronic paper and liquid crystal displays, adhesives for optical disks and optical fibers, optical recording materials for hologram recording media, etc. Used for.

Examples of holographic recording materials are shown below. The abbreviations and the like in the preparation examples of the holographic recording material are as follows.
HMDI: Hexamethylene diisocyanate (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.453)
G-400: Polyether triol (manufactured by ADEKA, G-400, average molecular weight 430, refractive index nD = 1.469)
OFHDO: 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.342)
Matrix resin forming catalyst: Dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -2- (O-acetyloxime) -3-cyclopentyl-1,2-propanedione plastic Agent: O-acetyl tributyl citrate (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.443)

Example 17
Compound having a polymerizable reactive group containing 34.2 parts (parts by mass) of HMDI, 45.8 parts of G-400, 10.0 parts of OFHDO, and 0.06 parts of matrix resin-forming catalyst as matrix resin-forming components 9 parts of 9,9-bis (4-hydroxyphenyl) fluorenediglycidyl ether 3-butenoic acid adduct (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 2 parts obtained as a polymerizable compound in Example 2 , 4-bis (phenylthio) styrene (3.0 parts by mass), photopolymerization initiator (0.05 parts), and plasticizer (6.0 parts) were blended to prepare a holographic recording material.

This holographic recording material was introduced into the gap between two glass substrates (30 mm × 30 mm) bonded together via a silicon film spacer (thickness 0.5 mm). Holographic recording medium in which a matrix resin is formed by heat treatment at 60 ° C. for 2 hours in a nitrogen atmosphere, and a recording layer made of a holographic recording material is formed between two glass substrates to a thickness of 0.5 mm Got.

Example 18
As a matrix resin forming component, 33.7 parts of HMDI, 44.9 parts of G-400, and 1- [2,4-bis (phenylthio) phenyl] ethyl 4-vinylbenzoate obtained in Example 4 as a polymerizable compound A holographic recording medium was obtained in the same manner as in Example 17 except that 4.4 parts were used.

Example 19
As the matrix resin forming component, 33.9 parts of HMDI, 45.2 parts of G-400, and 4.0 parts of 2,4-bis (2-naphthylthio) styrene obtained in Example 5 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as Example 17 except for the above.

Example 20
As a matrix resin forming component, 33.8 parts of HMDI, 45.5 parts of G-400, and 3.5 parts of 4- (2-naphthylthio) -2-phenylthiostyrene obtained in Example 9 as a polymerizable compound were used. A holographic recording medium was obtained in the same manner as in Example 17 except that it was used.

Comparative Example 4
As a matrix resin forming component, 34.8 parts of HMDI, 46.7 parts of G-400, and 4-vinylphenyl acetate as a polymerizable compound (Tokyo Chemical Industry Co., Ltd., refractive index nD = 1.538) 1.5 A holographic recording medium was obtained in the same manner as in Example 17 except that the part was used.

Comparative Example 5
As a matrix resin forming component, 34.7 parts of HMDI, 46.6 parts by mass of G-400, and 4-bromostyrene (refractive index nD = 1.594, manufactured by Tokyo Chemical Industry Co., Ltd.) 1.7 as a polymerizable compound. A holographic recording medium was obtained in the same manner as in Example 17 except that the part was used.

Table 3 shows the compositions of the holographic recording material precursors of Examples 17 to 20 and Comparative Examples 4 and 5. The number of the compounding amount in Table 3 is part by mass.

Holographic recording / reproduction evaluation was performed using a holographic recording / reproduction evaluation machine based on the two-beam interference method. Multiple recording was performed using angle multiplexing.

(Plane wave recording and playback method)
Evaluation of M # and recording sensitivity was performed using the recording / reproducing optical system shown in FIGS. For recording and reproduction, a continuous wave (CW) semiconductor laser having a wavelength of 405 nm was used. The light intensity of the recording light on the recording medium (total of the ^two light beams) was 18 mW / cm ^2, and angle multiplex recording (101 multiplex) was performed so that the total exposure energy was 600 mJ / cm ² . The diffraction efficiency of the recorded hologram was calculated by the following equation using values obtained by reading the intensity of each of the diffracted light and transmitted light during reproduction with an optical power meter.
Diffraction efficiency (η) = [diffracted light intensity / (transmitted light intensity + diffracted light intensity)] × 100 (%)
Using this diffraction efficiency value, the value of M # (M number) was calculated by the above-mentioned formula (I) as an index of the multiple recording property of the hologram recording medium.
Further, using the obtained diffraction efficiency value, the recording sensitivity was calculated by the formula (III), and the maximum value was defined as the maximum sensitivity.

Where η is diffraction efficiency E is exposure energy [mJ / cm ² ]
L is the media thickness [cm]
Represents.

(Plane wave recording conditions)
Exposure before recording: None Recording scheduling: None Multiplicity: 100 multiplexing Angular direction: 100 multiplexing (−29.7 to + 29.7 °, step 0.6 °)
Recording light intensity: 18 mW / cm ²
Total exposure energy for recording: 600 mJ / cm ²
Exposure energy after recording: 90 J / cm ^{2 with} LED

<Evaluation results>
(Plane wave recording characteristics)
FIG. 5 is an integrated value of M # with respect to the recording exposure energy. It can be seen that the media according to Examples 17 to 20 all have a higher M # than the media according to Comparative Examples 4 and 5 and are excellent in multiplex recording properties.
FIG. 6 shows the sensitivity to the recording exposure energy. All the media according to Examples 17 to 20 have higher sensitivity than the media according to Comparative Examples 4 and 5, and a high data transfer rate can be realized.

Table 4 shows the results of numerical comparison of M # obtained by plane wave measurement, maximum sensitivity, refractive index of polymerizable compound, and number of molecules per gram of material.

Here, since the polymerizable compound is responsible for forming a refractive index modulation structure when holographic recording is performed, increasing the content improves M # and sensitivity, but on the other hand, it tends to cause polymerization shrinkage. Become. Generally, it is known that the polymerization shrinkage of vinyl monomers is proportional to the inverse of the molecular weight. By aligning the number of molecules of the polymerizable compound contained in the material, it is possible to polymerize with the same shrinkage of the recording medium. The performance between compounds can be compared.
It can be seen from Table 4 that when the shrinkage ratios are set to the same level, the medium according to the example clearly has higher M # and sensitivity than the medium according to the comparative example.

1:

Laser generator

2, 11, 13: Mirror 3, 8: 1/2 wavelength plate (HWP)
4, 9: Polarization beam splitter (PBS)
5: Beam expander 6, 10: Shutter 7, 15: Aperture 12: 1/4 wavelength plate (QWP)
14: Rotation stage 16, 17: Optical power meter Ls: Recording signal light Lw: Recording reference light Lr: Reproduction reference light S: Holographic recording medium

Claims

The polymeric compound represented by following General formula (1).

R 1 to R 5 are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a carbon atom having 6 to 10 carbon atoms. Represents a monovalent group selected from the group consisting of an aryl group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an arylthio group represented by —S—Ar 1 , one of which Two or three are the arylthio groups.
X 1 is a direct bond, oxygen atom, sulfur atom, alkylene group having 1 to 4 carbon atoms, oxyalkylene group having 1 to 4 carbon atoms, thioalkylene group having 1 to 4 carbon atoms, alkyleneoxy group having 1 to 4 carbon atoms Or an alkylenethio group having 1 to 4 carbon atoms, wherein the alkylene group, oxyalkylene group, thioalkylene group, alkyleneoxy group and alkylenethio group may have a substituent, The substituent of is a chlorine atom, a bromine atom, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or a carbon number 6 to 10 arylthio groups.
R 6 represents a glycidyl group, an acryloyl group, a methacryloyl group, a vinyl group, a vinyl aryl group which may have a substituent, or a vinyl aryloyl group.
The -S-Ar Ar 1 of 1 represents an aryl group or ring members 5-14 heterocyclic aryl group ring members 6-14, also may have combined two or more rings are condensed, substituted It may be. In the case of having a substituent, the substituent is chlorine atom, bromine atom, alkyl group having 1 to 4 carbon atoms, alkyloxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, phenyloxy group or phenylthio group. In the case where these are a phenyloxy group or a phenylthio group, they may further have a substituent similar to the substituent.
The polymerizable compound according to claim 1 , wherein one of R 1 to R 5 is -S-Ar 1 .
The polymerizable compound according to claim 1 , wherein two or three of R 1 to R 5 are -S-Ar 1 .
A resin composition comprising the polymerizable compound according to any one of claims 1 to 3.
A cured resin obtained by curing the resin composition according to claim 4.
5. An optical material comprising the resin composition according to claim 4 or a cured resin obtained by curing the resin composition.
A holographic recording material comprising the polymerizable compound according to claim 1.
A holographic recording material comprising A) a polymerizable compound, B) a matrix resin or a matrix resin forming component, and C) a photopolymerization initiator, wherein the polymerizable compound is the polymerizable compound according to claim 1. A holographic recording material characterized by the above.
The holographic recording material according to claim 7, wherein the polymerizable compound has a refractive index n D at 25 ° C. of 1.60 or more.
The holographic recording material according to claim 8, wherein the matrix resin is an isocyanate-hydroxyl polyadduct.
A holographic recording medium comprising a recording layer containing the holographic recording material according to claim 7.