JPH03259176A - Volume phase type hologram recording material - Google Patents

Abstract

PURPOSE:To obtain characteristics which are excellent in photosensitive speed and resolution by providing a photosensitive material formed of a specific compd., a polymn. initiator which generates radical species by irradiation with radiations, a spectral sensitizer and a polymer having a 2-oxazolidone ring on a base. CONSTITUTION:The photosensitive material is constituted of the acrylic or methacrylate compd. which has at least one ethylenic unsatd. bond and can be addition-polymerized, the polymn. initiator which generates the radical species by irradiation with radiations, the spectral sensitizer, and the polymer (binder) having the 2-oxazolidone ring. Such photosensitive material is formed on a base to constitute the material 5 for volume phase type hologram recording. The recording material which can produce the volume phase type hologram having the high sensitivity and high resolution is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the recording of 11 grams using a photochemical polymerization reaction, and is a volume phase type recording method using a photosensitive material that records interference fringes as a refractive index difference. Concerning 11-gram recording materials.

[Prior Art 1] With the development of holography technology, the required characteristics of photosensitive materials for hologram recording have become quite clear.

At present, many materials have been proposed, such as silver salt photosensitive materials, moldy romic acid geladine, photochromic materials, photopolymers, and photoreactive crystals. Research is being conducted on the properties of many of these materials.

Photosensitive materials for hologram recording are required to have unique characteristics, but the most required characteristics are high image density and high sensitivity in order to record ζ images as interference patterns.

Among these photosensitive materials, a material using dichromate gelatin has been used as a material for recording volume phase type photograms. Although this material has low diffraction efficiency, etc. There is a problem with stability, which is a major drawback as a material.Also, there are high-sensitivity materials that use silver salt, but they have a problem with diffraction efficiency.

For example, 5. JP-A-60-2
58579 M publication describes a material based on a polymer containing a carbazole ring and using an iodine I sandwich, JP-A-60
JP-A No. 6170-258580 discloses a material mainly composed of polysaccharides and containing a metal element that causes coordinate bonding.
In JP 573, poly-N-biJ and lucarbazole are used as main materials, 2,3-bornadione is used as a crosslinking agent, and 4
-(4'Butoxyphenyl) -2,6-Syphenylthiovirylium fluoroCl borate is used as a spectral sensitizer, and in JP-A-64-40876, a water-soluble Feeds based on polymers have been proposed.

All of these materials utilize a crosslinking reaction that cannot be caused by radiation irradiation, and there are considerable theoretical limits to the sensitivity improvement value.

- Materials using photopolymerization reactions are expected to have a sensitivity 1.000 times higher than those using crosslinking reactions, and are considered the most promising materials11.

[Problems to be Solved by the Invention] The present invention relates to a recording material that can produce a hologram by using a photochemical polymerization reaction, particularly by being exposed to visible light, among materials for recording volume phase holograms. The purpose of this invention was to provide a photosensitive material that also has excellent photosensitive speed and resolution.

[Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive research to obtain a recording material capable of producing a volume phase type hologram with high sensitivity and high resolution. 1.

That is, the present invention provides an acrylate or methacrylate-1 compound having at least one ethylenically unsaturated bond and capable of polymerization, a polymerization initiator that generates C radical species upon irradiation with radiation, and a spectral increaser. This is a volume phase type hologram recording device 44, which is composed of a photosensitive material and a polymer (binder) having a 2-oxazolidone ring, and is formed by forming the photosensitive material on a carrier.

As the polymerization initiator, general formula (1) (wherein R+
R2 are the same or different and represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group, an 11-cy group, or a nitro group, and X- is a halogen, BF4-P
F6- represents AsFi- or sb F&-. ) can be used as a polymerization initiator.

(Left below) ii'l The sensitizer toshiteha, general formula (jib(Ill
)○ (wherein R and R4 represent a hydrogen atom, an alkoxy group or a dialkylamino group, and l represents a lower alkyl group or an aryl group).

Compounds selected from 3-kel coumarins can be used.

"Detailed Description of the Invention 1. 1 of the present invention, the compound having at least one gotylenic unsaturated bond constituting the volume-phase bologram recording material is formed by the plowing start plate. The photosensitive material E contains C as a component that polymerizes in the photosensitive material E.

Specifically, pentaerythritol triacrylate, 5 pentaerythritol trimethacrylate, pen 4
1 erythritol acrylate, pentaerythritol methacrylate L-1, ff, narenguli methacrylate, I rimebro lp I3
Examples include pantriacrylate, dipentaerythrithoric droxypentaacrylate, hexanedimer-1,6-dimethacrylate, di-11.5singlycol dimethacrylate, triethyleneglycol didacrylate, etc. .

Diaryliodonium salts can be used as initiators that cause a polymerization reaction upon irradiation with radiation.

As the compound used in the present invention, Macromo! ee
ules, -3,,,0,4307 (1977)
Compounds described in Schiff 3. ,:'Luyo F, ditolyl iodo 4: -ram, phenyl (p-anisyl) iodo; um, bis (m-nitropherol) 3-
doum, bis(p-1-)'chirnoe,'-ru)
Examples include chlorides of iodonium such as iodine, electrocomide or fluoroborate salts, hexafluoride salts, and hexafluoroarsene salts.

Spectral sensitizer and 1. In this case, 3-ke1 coumarin is preferable, and it is desirable that the benzene nucleus of the coumarin is substituted with an alkoxy group or a dialkylamino group. Specific examples of the compound represented by the general formula (n) include 3-acetyl-7diethylminocumarin, 3-acetyl-5,
7-diethoxykumari2,3-cinnamoyl-7-dinithylaminocou? Phosphorus, 3-"(p-diethyl'aminocy;/chomoyl) ~7-dinitylaminocoumarin,
Compound 1 (, “C
Examples include 1343 carbonylbis(7-sidiylaminocoumarin) and 3.3"-carbonylbis(5,7-?/methoxycarbonylrin).

Furthermore, by using a polymer having a lJ, 2-oxazolidone ring as a binder, the rate at which 9-tumer changes into a heavy color substance can be accelerated.

During this photopolymerization reaction, a difference in molecular weight occurs between the exposed and non-exposed areas, and a difference in refractive index appears. As a result, it became possible to record interference fringes as a difference in refractive index, and realized a material for volume phase type hologram recording with a high degree of 58 degrees.11. It is something that

Diarylyo1 contained in the photopolymerizable material of the present invention
The amount of the dimeryl leadonium salt can range from about 1:3 to 1:50 in terms of the weight ratio of the dimeryl leadonium salt to the polymeric compound, preferably from 1:5 to 1:5. 1=1
It is in the range of 0. Additionally, the weight ratio of diaryliodonium salt to spectral sensitizer ranges from about 5021 to 1.1, preferably from 4:1 to 221.

The photopolymerizable material of the present invention may also contain additives such as a desired amount of G, a dihydric compound, and a known plasticizer.

Examples of rice grains that can be used in the photopolymerizable material of the present invention include high-pressure mercury lamps, ultra-high-pressure mercury lamps, XB1-xenon lamps, halogen lamps, and laser light sources such as helium-cadmium and argon. Preferably, visible light lasers are used. Good.

[Example 1 Hereinafter, with examples, visible l! The present invention, which realizes a material sensitive to I-length cS light, will be described in more detail, but the present invention is not limited thereto.

[Practice, Example 1] Pentaerythritol triacrylate) IOg diphenyliodonium borofluoride salt 2g 3-get Coumarin dye (-Fee 1 (■), R1: H, R6: N (C
Zl(S)2) 015g Poly-N-vinyloxazolidone 10g Methylce1” solder
50g.

The film thickness of the above photosensitive liquid after drying on the glass substrate is 10 μm.
1.8 after coating using the spin code method so that
After heating and drying at 0°C for 20 minutes, overcoat with polyvinyl alcohol) Ml! :L7171m was coated and air-dried to prepare a photosensitive plate for hologram recording.

This photosensitive plate was processed using Ar
A hologram was recorded using a laser (wavelength: 514.degree. 5 nm) as a light source, developed with vapor of a mixed solution of benzene and toluene, immersed in heptane, and further air-dried to obtain a hologram.

When the characteristics of this hologram were evaluated, the spatial frequency was 2000 lines/mm, the diffraction efficiency was 80%, and the exposure amount was 30 mJ/c IT+''.

[Example 2] In place of the 6-tocoumarin dye of Example 1, a 3-kel coumarin yarn dye (-in freight (I[l), R,,:H5R6:
N (C1lHs)t Rt: C00CH,
l) Example 1 except that 0.5 g was used. ! -The same procedure was performed to obtain a volume phase hologram. In the characteristic evaluation, the spatial frequency was 1500 lines/n+m, and the diffraction efficiency was 75%.
and exposure i: 40 mJ/cm”
So 1. Ta.

[Effects of the Invention] The volume phase type hologram recording material of the present invention has excellent sensitivity to visible light, and can be applied not only to hologram production but also to a wide range of fields such as photocurable materials. It is possible.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram schematically showing an example of an apparatus used for creating a bologram using the recording material of the present invention. ... Laser oscillation device 2 ... Laser 3 ... Beam splitter 4 ... Reflection mirror 5 ... Hologram recording material patent Applicant Toppan Printing Co., Ltd. Representative Kazuo Suzuki No. 1 figure

Claims (3)

[Claims] (1) A photosensitive material that records interference fringes caused by interference between a reference beam emitted from a laser light source and an object beam is made of an addition-polymerizable acrylate or methacrylate compound having at least one ethylenically unsaturated bond and a radiation-polymerizable material. A volume phase type hologram recording comprising a polymerization initiator that generates radical species upon irradiation, a spectral sensitizer, and a polymer (binder) having a 2-oxazolidone ring, and formed by forming the photosensitive material on a support. Materials for use. (2) The polymerization initiator has the general formula (I) ▲mathematical formula, chemical formula, table, etc.▼(I) (wherein R_1 and R_2 are the same or different, hydrogen atom, halogen atom, lower alkyl group, Represents an alkoxy group or a nitro group, X^- is a halogen, BF_
4^-, PF_6^-, AsF_6^- or SbF_
Represents 6＾-. 2. The volume phase type hologram recording material according to claim 1, characterized in that a diaryliodonium salt represented by: ) is used. (3) As the sensitizer, the general formula (II) (III) ▲ mathematical formula,
Chemical formulas, tables, etc. are available▼(II) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(III) (In the formula, R_3 and R_4 represent a hydrogen atom, an alkoxy group, or a dialkylamino group, and R_5 represents a lower alkyl group or an aryl group. The volume phase type hologram recording material according to claim 1, characterized in that a compound represented by the following formula is used.