JPH03278082A - Photosensitive material for hologram recording - Google Patents

Abstract

PURPOSE:To provide the photosensitive material which has excellent chemical stability, high resolution, high diffraction efficiency, etc., and has an excellent photosensitive characteristic to long-wavelength laser beams by combining poly-N-vinyl carbazole, a compd. having polymerizable ethylenic unsatd. bonds and a specific photopolymn. initiator. CONSTITUTION:The photopolymn. initiator, consisting of the combination of the tetrabenzoporphyrins expressed by formula I or metal complex thereof and an electron-accepting radical generator, the poly-N-vinyl carbazole as a supporting material having a refractive index as high as 1.68 and the compd. having at least >=1 pieces of the polymerizable ethylenic unsatd. bonds are combined. In the formula I, R denotes a hydrogen atom, alkyl group or a residual arom. group which may have a substituent; the respective benzene rings may have an alkyl group or alkoxy group as a substituent. The photosensitive material for hologram recording which has the excellent chemical stability, the high resolution and the high diffraction efficiency based on high-refractive index modulation and has the excellent photosensitive material to the long- wavelength laser beams of >=600nm is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel photosensitive material for hologram recording. More specifically, it is a photosensitive material for hologram recording suitable for hologram recording using a long wavelength laser beam of 600 nm or more, such as a He-Ne laser (633 nm), a Kr laser (647 nm and 676 nm), or a ruby laser (694 nm). Pause.

[Prior Art] Traditionally, as hologram recording materials for long wavelength light, yellow-sensitive dichromate-gelatin-based materials spectrally sensitized with a silver salt emulsion, methylene blue, etc. have been generally used. . However, these photosensitive materials for hologram recording,
All of them require complicated wet processing for manufacturing photosensitive plates, post-recording processing, etc., or have environmental resistance properties such as moisture resistance, etc.
It had the problem of poor weather resistance.

To solve these problems, metal acrylate, acrylamide, methylene blue, p-) sodium luenesulfonate, p-
A photopolymerizable recording material consisting of sodium nitrophenylacetate was proposed [Photogr.
SciEng, )” Volume 12, Page 177 (1968
), and Applied Physics Letters (Ap.
pl, Phys, Lett,) J Vol. 14 No. 5, No. 1
Page 59 (1969), However, this recording material has a problem in that the properties of the material deteriorate due to the progress of dark reactions during storage, so it is of little practical use.

Materials with excellent environmental resistance, high resolution, high diffraction efficiency, and other properties that a photosensitive material for hologram recording should have, such as poly-N-vinylcarbazole, a cyclic cis-α-dicarbonyl compound, and a sensitizer. hologram recording material f1
(Japanese Unexamined Patent Publication No. 60-45283), from poly-N-vinylcarbazole, 1.4.4.5.6.7.7-hexachloro-5-norbornene-anhydride-2,3-dicarboxylic acid, and a dye. Hologram recording material
227280), hologram recording material consisting of poly-N-vinylcarbazole and frill (Japanese Patent Laid-Open No. 6
0-227281), hologram recording material consisting of poly-N-vinylcarbazole, 2,3-bornanedione, and thioflavin (JP-A-60-260080), poly-N-vinylcarbazole, thioflavin T, and iodoform A hologram recording material (Japanese Unexamined Patent Publication No. 62-123489) consisting of the following has been proposed.

These photosensitive materials for hologram recording are photopolymer-based materials based on poly-N-vinylcarbazole, so they are chemically stable and have high resolution, moisture resistance, heat resistance, and weather resistance. It has an important problem that it is not sensitive at all to laser light sources having an oscillation wavelength in the red light region of 600 nm or more, such as Ne laser, Kr laser, and ruby laser.

A photocurable resin composition consisting of a compound having a polymerizable ethylenically unsaturated bond, a tetrabenzoporphyrin derivative, and an electron-accepting radical generator as a material that can be photocured with a long wavelength laser of 600 nm or more.
No. 63-243102) was proposed. However, this photocurable resin composition did not have a sufficient refractive index difference which is important in hologram recording, and therefore its performance for hologram recording was not satisfactory.

[Problems to be Solved by the Invention] The present invention not only has excellent chemical stability, such as environmental resistance, high resolution, and high diffraction efficiency, but also has 60%
Provided is a photosensitive material for hologram recording that has excellent photosensitivity to long wavelength laser light of 0 nm or more.

[Means for Solving the Problems] The present invention provides poly-N-vinylcarbazole, a compound having at least one polymerizable ethylenically unsaturated bond, and the following photopolymerization initiator formula (I) (in the formula, R represents a hydrogen atom, an alkyl group, or an aromatic residue that may have a substituent; each benzene ring may have an alkyl group or an alkoxy group as a substituent; each R in the formula is independently tetrabenzoporphyrins (which can be a hydrogen atom, an alkyl group, or an aromatic residue, and the substituents of the aromatic residues can also be independent for each R) or metal complexes thereof and electrons. Provided is a photosensitive material for hologram recording, which is characterized by comprising a combination of a receptive radical generator and a receptive radical generator.

The present invention provides a photopolymerization initiator consisting of a combination of tetrabenzoporphyrins with a specific structure or a metal complex thereof and an electron-accepting radical generator, and poly-N-vinylcarbazole as a supporting material with a large refractive index of 1.68. By combining a compound having at least one polymerizable ethylenically unsaturated bond, it has chemical stability, high resolution, high diffraction efficiency based on high refractive index modulation, and a long wavelength laser beam of 600 nm or more. It was discovered that a photosensitive material for hologram recording having excellent photosensitive properties could be obtained, and the work was completed based on this knowledge.

The poly-N-vinylcarbazole used in the present invention may be substituted with a halogen, an alkyl group, an amino group, a nitro group, a thiocyano group, or the like.

The compound having at least one polymerizable ethylenically unsaturated bond used in the present invention includes an oligomer in addition to a monofunctional vinyl monomer, and may also be a high molecular weight compound. A mixture of these may be used.

Next, these compounds will be illustrated.

Acrylic acid, methacrylic acid, itaconic acid, maleic acid,
High boiling point vinyl monomers such as acrylamide, methacrylamide, diacetone acrylamide, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, N-vinylcarbazole, ethylene glycol, diethylene glycol, polyethylene glycol, 1.3-propanediol, 1.4- Di- or poly(meth)acrylic esters such as butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, polypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, incyanur Ethylene oxide-modified acid (meth)acrylates, (meth)acrylated epoxy resins, polyester acrylate oligomers, (meth)acrylated urethane oligomers, acroleinated polyvinyl alcohol, etc. These compounds can be mixed as appropriate and used. It's okay.

R in the tetrabenzoporphyrins of formula (I) used in the present invention represents a hydrogen atom, an alkyl group, or an aromatic residue such as a phenyl group, a naphthyl group, or a pyridyl group. , which may have a substituent, such as a halogen atom, a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group, an alkoxycarbonyl group,
Examples include a carboxy group, nitro group, amino group, and sulfone group. One or more of these substituents may be independently introduced into each benzene ring.

Specific examples of tetrabenzoporphyrins are given below.

Unsubstituted tetrabenzoporphyrin, meso-phenyltetrabenzoporphyrin in which at least one men's position is substituted with a phenyl group, meso-naphthyltetrabenzoporphyrin in which at least one men's position is substituted with a naphthyl group, at least one men's position meso-pyridyltetrabenzoporphyrin substituted with a pyridyl group, 2.9,
16゜23-tetra-t-butyltetrabenzoporphyrin, 1,4,8.11,15.18,22.25-octamethyltetrabenzoporphyrin, 2゜9.16.
23-tetramethoxytetrabenzoporphyrin, 2.
3,9,10.16.17,23.24-octamethoxytetrabenzoporphyrin, meso-tolyltetrabenzoporphyrin substituted with tolyl group at least one meso position, meso-tolyltetrabenzoporphyrin substituted with anisyl group at least one meso position mesoanisyltetrabenzoporphyrin, etc.

Examples of metal complexes of tetrabenzoporphyrins include the tetrabenzoporphyrins and Mg, Zn, Cd, Pd.
, complexes with trivalent metal atoms such as Pb, Ni, Co, Cu, etc., AI, In, in which hydroxyl groups, halogen groups, etc. are coordinated in the vertical direction (in the structural formula of Formula 1, the front and back directions of the paper).
Trivalent metal atoms such as Ga, Fe, Cr or Si, S
Complexes with tetravalent metal atoms such as n, V, T coordinated with oxygen
Examples include complexes with tetravalent metal atoms such as i.

The tetrabenzoporphyrins or metal complexes thereof of the present invention can be produced by any known method, one of which is exemplified below.

Benzylidenephthalimidine and various metal salts are reacted using a solid phase method. The obtained product is extracted into a solvent such as tetrahydrofuran, and then a column purification method is used to produce tetrabenzoporphyrin Wt or its metal complex.

Examples of compounds preferably used as the electron-accepting radical generator, which is the other component of the photopolymerization initiator, are shown below.

Formula (II) (wherein R' and R2 are each a hydrogen atom, a halogen atom, a lower alkyl group, a methoxy group, a cyano group, or a nitro group, and X- is a halogen ion, BF, -1PF@-
Diaryliodonium salt of 1AsF, -1sbpps-1CIO<-) [Macromolecules, No. 1O, No. 13
07 page (1977)], formula (III) (wherein R3 and R4 each represent an alkyl group,
R1 and R2 represent the same meanings as in formula (II)) [Journal of Polymers]
Science (J, Polym, Sci.

) Volume 17, Page 2877 (1979)] Formula (1ν) (In the formula, R4 and Ra each represent an alkyl group or an aryl group, and R1 and X- represent the same meaning as in formula (I)) phenacylsulfoxonium salt [European Patent No. 4]
Publication No. 4,274 Sulfoxonium salt of formula (v) (wherein R1 and No. 44,274), iron arene complexes of the formula (Vl) (wherein R7 is an alkyl group and X- has the same meaning as in formula (1)) [European Patent No. 109,851, European Patent Publication No. 126,712, Journal of Imaging Science (J, I
Mag, Sci,) J Vol. 30, No. 4, Page 174 (1986)], and the formula (Vll) 9 (wherein, R1, R and R O are each a methyl group or trihalogenated methyl triazine compounds (indicating groups), etc.

Examples of the diaryliodonium salt of formula (II) include diphenyliodonium, ditolyliodonium, bis(m-nitrophenyl)iodonium, bis(ter
Examples include chlorides, bromides, boron tetrafluoride salts, phosphorous hexafluoride salts, arsenic hexafluoride salts, and perchlorates of t-butylphenyl)iodonium and bis(p-cyanophenyl)iodonium.

Examples of the phenacylsulfonium salt of formula (III) include chlorides, bromides, boron tetrafluoride salts, phosphorous hexafluoride salts, and hexafluoride salts such as dimethylphenacylsulfonium, phenacyltetramethylenesulfonium, and p-cyanophenacylsulfonium. Examples include arsenic salts, phosphorus antimony hexafluoride salts, perchlorates, and the like.

As the phenacylsulfoxonium salt of formula (IV),
For example, chloride, bromide, boron tetrafluoride salt, phosphorus hexafluoride salt, arsenic hexafluoride salt, antimony phosphorus hexafluoride salt, perchlorate, etc. of diphenyl phenacylsulfoxonium, dimethylphenacylsulfoxonium, etc. is exemplified.

Examples of the sulfoxonium salt of formula (V) include chlorides, bromides, boron tetrafluoride salts such as dimethylphenoxysulfoxonium, tetramethylenephenoxysulfoxonium, and diphenylphenoxysulfoxonium;
Examples include phosphorus hexafluoride, arsenic hexafluoride, antimony phosphorus hexafluoride, and perchlorate.

The iron-alene complexes of formula (vr) include (η6-benzene) (ηS-cyclopentadienyl)iron, (η6-cumene) (η5-cyclopentagenyl)iron, (η6-
Examples include chloride, bromide, boron tetrafluoride, phosphorus hexafluoride, arsenic hexafluoride, perchlorate, etc. of iron (η5-cyclopentagenyl) (naphthalene).

As the triazine compound of formula (Vll), 2°4.6
Examples include -tris(trichloromethyl)-1,3°5-triazine, 2,4,6-)-dimethyl-1°3,5-triazine, and the like.

In the present invention, examples of electron-accepting radical generators that are particularly preferably used include onium salt compounds, iron allene compounds, and S triazines substituted with at least one mono-, di-, or trihalomethyl group.

The photosensitive material for hologram recording of the present invention is a photopolymerization initiator comprising poly-N-vinylcarbazole, a compound having at least one polymerizable ethylenically unsaturated bond, a tetrabenzoporphyrin, and an electron-accepting radical generator. It can be obtained by dissolving the agent at an arbitrary concentration in a suitable solvent and applying the resulting solution in the form of a film on a substrate such as a glass plate. Although there is no specific restriction on the blending ratio of each of the above components, it is preferable to adjust the concentration of tetrabenzoporphyrins so that the transmittance of the laser beam for irradiation is 1% or more. Additives such as plasticizers, antioxidants, thermal polymerization inhibitors, etc. may be added.

The amount of poly-N-vinylcarbazole in the total photosensitive material is 10 to 90% by weight, preferably 30 to 70% by weight in order to perform hologram recording with high diffraction efficiency. The amount of the compound having at least one unsaturated bond is determined based on the poly-N-
The amount is 10 to 200 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of vinylcarbazole. If it deviates from the above range, it will be difficult to maintain high diffraction efficiency and improve photosensitivity, which is not preferable.

Among the photopolymerization initiators used in the present invention, tetrabenzoporphyrins of formula (I) or metal complexes thereof are poly-N-
0.1 to 30 parts by weight of vinyl carbazole
It is used in parts by weight, preferably in the range of 0.5 to 15 parts by weight. The amount used is limited by the thickness of the photosensitive layer and the optical density of the thickness.
-0.1 to 2 parts per 100 parts by weight of vinylcarbazole
It is used in an amount of 0 parts by weight, preferably in the range of 1 to 15 parts by weight.

[Function] The photosensitive material for hologram recording of the present invention comprises poly-N-vinylcarbazole as a support, a compound having at least one polymerizable ethylenically unsaturated bond, and 60
It consists of a combination of tetrabenzoporphyrins that can generate radicals by irradiation with red laser light of 0 nm or more and an electron-accepting radical generator.

In hologram recording, when the photopolymerizable photosensitive material is irradiated with laser light, a polymerization reaction of a compound having at least one polymerizable ethylenically unsaturated bond occurs in the region where the laser beam irradiation site has a strong Sino-American interference effect. It forms a network together with poly-N-vinylcarbazole as a support, and becomes insoluble in organic solvents for development processing. In the laser irradiation area where the Central America interference effect is weak, the polymerization reaction of the compound having at least one polymerizable ethylenically unsaturated bond does not occur or the degree of polymerization is low, so the organic solvent for development processing The compound having at least one polymerizable ethylenically unsaturated bond is dissolved and removed from the photosensitive layer. It is presumed that this causes a density difference between the two parts, resulting in a refractive index difference and hologram recording. At that time, by using poly-N-vinylcarbazole, a material with a high refractive index, as a support, it was possible to increase the difference in refractive index, and it is assumed that hologram recording with high diffraction efficiency was achieved. Ru.

(Example) The present invention will be explained in more detail based on the following example. In each side below, parts represent parts by weight unless otherwise specified.

Example 1 100 parts of poly-N-vinylcarbazole (trade name Tubicol T-210, manufactured by Anan Fragrance Industry Co., Ltd.) Incyanuric acid ethylene oxide modified triacrylate (trade name Aronix M-315, manufactured by Toagosei Chemical Industry Co., Ltd.) 700 parts meso-diphenyltetrabenzoporphyrin lead
4-part diphenyliodonium hexafluorophosphate
5 part dioxane
900 parts of the photosensitive liquid having the above composition were mixed into 50×50×2
A photosensitive plate for hologram recording was prepared by applying the photosensitive liquid onto a 4 mm glass plate using a 4MIL applicator so that the film thickness after drying would be 10 μm.

After performing hologram recording on this photosensitive plate using the hologram production optical system shown in Fig. 1 using He-Ne laser 633 nm light, it was immersed for 2 minutes in a mixed solvent consisting of xylene and toluene in a volume ratio of 1:1. The photosensitive layer was then subjected to development and swelling treatment. Then, it was immersed in n-hebutane for shrinkage treatment to produce a Lippmann hologram.

FIG. 2 shows the relationship between the exposure amount and the diffraction efficiency when holograms were produced by varying the exposure amount.

Diffraction efficiency 60% at exposure dose 50 mJ/cm'
A hologram was created. This hologram was heated to 25 degrees Celsius.
No decrease in diffraction efficiency was observed even after being left in an environment of 60% RH for 180 days.

Examples 2 to 4 In Example 1, the central metals of meso-diphenyltetrabenzoporphyrin were changed to cadmium, magnesium, and palladium, respectively, and photosensitive solutions were prepared.
Table 1 shows the exposure amount required to achieve a diffraction efficiency of 60% for a Tubmann type hologram obtained by the same operation as above.

Table 1
J / cm 2) I Zn 50 2 Cd 40 3 Mg 70 4 Pd 70 Examples 5 to 7 In Example 1, diphenyliodonium hexafluorophosphate was used as the electron-accepting radical generator,
2.4.6-tris(trichloromethyl)-1 respectively
, 3,5-) riazine, (η6-cumene) (η“-dichloropentagenyl) iron hexafluorophosphate, and dimethylphenacylsulfonium hexafluorophosphate were used to prepare a photosensitive solution, and in the same manner as in Example 1. The diffraction efficiency of the Tubmann type hologram obtained by operation is 60
% is shown in Table 2.

Table 2 Phantom l Motion 011 -IuL-1 (mJ/cm") 5 A 80 5 B 200 7 C140 Note: A: 2,4.6-) Lis(trichloromethyl)-1
,3,5-) riazine, B; (η locumene) (η6-dichloropentadienyl) iron hexafluorophosphate, C; dimethylphenacylsulfonium hexafluorophosphate Example 8.9 Tetrabenzoporphyrin in Example 1 Meso-tetraphenyltetrabenzoporphyrin, 2.9.16
．． A photosensitive solution was prepared using 23-tetra-tert-butyltetrabenzoporphyrin magnesium. He-Ne laser - Kr laser instead of 633 nm
A Lippmann hologram was produced in the same manner as in Example 1 except that 647 nm was used.

Table 3 shows the exposure amount required to reach a diffraction efficiency of 60%.

Table 3 Kyoho 1 Mogura 11 -1 Yu 1-1- (mJ/cm
') 8 D 1009
E 80 Note: D; Meso-tetraphenyltetrabenzoporphyrin, E, 2.9.16.23-Tetra-tert-butyltetrabenzoporphyrin Magnesium Comparative Example 1 Poly-N-vinylcarbazole in Example 1 has a refractive index of Hologram recording was performed in the same manner as in Example 1, except that polymethyl methacrylate having a molecular weight of 1.49 was used and ethanol was used as the developing and swelling solvent.

Although hologram recording was possible at an exposure dose of 80 mJ/cm', the diffraction efficiency was 10%.

Comparative Example 2 Same as Example 1 except that the poly-N-vinylcarbazole in Example 1 was changed to polystyrene with a refractive index of 1.59, and the developing/swelling solvent was changed to a 1=1 mixed solvent of benzene/ethanol. The hologram was recorded using the following operations.

Although hologram recording was possible with an exposure dose of 80 mJ/cm'', the diffraction efficiency was 40%.

Comparative Example 3 A hologram was produced in the same manner as in Example 1, except that the poly-N-vinylcarbazole in Example 1 was changed to polyvinylpyrrolidone with a refractive index of 1.53, and the developing/swelling solvent was changed to ethyl acetate. Recorded.

Hologram recording was possible with an exposure dose of 40 mJ/c rri 2, but the diffraction efficiency was 20%.

Further, due to the poor moisture resistance of the polyvinylpyrrolidone support, the hologram recording completely disappeared after one day of storage.

Comparative Example 4 Hologram recording was performed in the same manner as in Example 1 except that a composition excluding poly-N-vinylcarbazole was used, but hologram recording was not possible at all.

Table 4 shows the measurement results of Example 1 and Comparative Examples 1 to 4.

Table 4 Subcondylar Body Hoshichikaza Exposure 1 Sarachinmokutei Yasujugo-(Suzuki J/e
m2) ($) Example I A 1.59 50 60 1
After 80 days Comparative Example I B 1.49 80 1
0 180 days or more Comparative Example 2 C1,59803018
Comparative example 3 after 0 days D 1.53 40 20
1 Comparison Example 4 E - Hologram recording impossible Note: A: Bory-N-vinylcarbazole B: Polymethyl methacrylate C: Polystyrene D: Polyvinylpyrrolidone Storage stability: Halving of rotation efficiency in an environment of 25°C and 60% RH [Effects of the Invention] According to the present invention, the material has excellent photosensitivity to Naganuma long laser light of 600 nm or more, which could not be achieved with conventional sensitive materials for hologram recording, and is chemically stable. A photosensitive material for hologram recording is provided which has high resolution and high diffraction efficiency.

[Brief explanation of the drawing]

FIG. 1 shows a block diagram of a two-beam exposure apparatus for producing a hologram, and FIG. 2 is a graph showing the relationship between the laser exposure amount and the diffraction efficiency of the produced hologram. 1: Laser 2: Beam splitter - 3, 4, 5
: Mirror 6.7, 8.9: Lens 10.11: Pinhole 12: Photosensitive plate

Claims (2)

[Claims] (1) Poly-N-vinylcarbazole, a compound having at least one polymerizable ethylenically unsaturated bond, and the following photopolymerization initiator formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom, an alkyl group, or an aromatic residue which may have a substituent, and each benzene ring may have an alkyl group or an alkoxy group as a substituent) or its metal A photosensitive material for hologram recording, comprising a combination of a complex and an electron-accepting radical generator. (2) The electron-accepting radical generator is at least one type of electron-accepting radical generator selected from onium salt compounds, iron allene compounds, and s-triazines substituted with at least one mono-, di-, or trihalomethyl group. The photosensitive material for hologram recording according to claim 1, which is a photosensitive material for hologram recording.