JPH03148686A - Composition for hologram recording material and photosensitive body for hologram recording - Google Patents

Abstract

PURPOSE:To obtain the compsn. for hologram recording material which is stable and is hardly gelatinized by incorporating a polymer having a carbazole ring and a dye consisting of a compd. having N-phenyl glycine and a cumarine structure in the molecule into the compsn. CONSTITUTION:The compsn. components for hologram recording materials contain at least the polymer having the carbazole ring and the dye consisting of the compd. having the N-phenyl glycine and the cumarine structure in the molecule. The weight of the N-phenyl glycine is preferably 1 to 30% of the weight of the polymer and the weight of the above-mentioned dye is preferably 0.1 to 20% of the weight of the polymer. The hologram photosensitive body is formed with a film 2 consisting of the compsn. for hologram recording materials constituted in the above-mentioned manner on a transparent substrate 1. Since the hologram photosensitive body of this constitution does not contain gelatin, the photosensitive body has the high environmental resistance and the high sensitivity to visible light.

Description

[Detailed description of the invention]

[Summary] The present invention relates to a composition for a hologram recording material used in a method of recording a hologram using a photochemical crosslinking reaction in a polymer, and a photoreceptor for hologram recording formed using the composition, which has excellent moisture resistance and heat resistance. It is used as a photoreceptor for hologram recording, which has excellent environmental resistance such as light resistance and light resistance, is highly sensitive to visible light, and has high light transmittance when producing holograms, and is chemically stable and is used as a recording material. The purpose of the present invention is to provide a composition for a hologram recording material that is difficult to gel and is difficult to gel. Among the above objects, the composition for a hologram recording material contains at least a polymer having a carbazole ring, N-phenylglycine, and a coumarin structure. A photoreceptor for hologram recording is composed of a composition containing a dye consisting of a compound contained in the molecule, and among the above purposes, a photoreceptor for hologram recording is formed by forming a film made of the composition on a transparent substrate. It is composed of a hologram recording photoreceptor.

[Industrial application field]

The present invention relates to a composition for a hologram recording material used in a method of recording a hologram using a photochemical crosslinking reaction in a polymer, and a photoreceptor for hologram recording formed using the composition. [Prior Art] A hologram is a recording of an interference pattern of multiple coherent lights. During reproduction, by irradiating one beam of light that was incident during recording, a hologram is irradiated with the beam of light incident on the other beam during recording. It is a technology that reproduces Holograms were originally
Although it has been developed as a three-dimensional photographic technology, since the mechanical parts of conventional optical components such as lenses, prisms, and mirrors can be integrated into a hologram film, it has recently been used as a new optical element in barcode leagues, laser scanning systems such as laser printers, and heads. The conditions required for the recording material constituting the hologram optical element, which is being applied to combiners of up-displays, etc., are: (a) It must be capable of recording with a visible light laser. (b) High sensitivity. (c) High diffraction efficiency. (d) Colorless and transparent with high light transmittance. (e) Excellent environmental resistance. (f) There should be no defects such as cracks in the film. can be mentioned. Initially, hologram recording materials used were bleached silver salts used in ordinary photographic materials and dichromate gelatin. These photosensitive materials have high sensitivity across the entire range of visible light, but because they use a gelatin film as a binder, they have low environmental resistance such as moisture resistance, heat resistance, and light resistance. There's a problem. In order to solve these problems, polymer hologram recording materials have been proposed in recent years, in which an organic halogen compound is used as a photoreaction initiator and a polymer containing a carbazole ring is used as a base resin (for example, 55-31453 etc.). Incidentally, the process for producing holograms of polymers containing carbazole rings is similar to the process for conventional dichromate gelatin. First, by interference exposure, the molecular weight of a polymer containing a carbazole ring is changed in accordance with the interference fringes.
A molecular weight distribution corresponding to interference fringes is formed within the hologram recording material. Prior to developing this, a decoloring process is performed to remove the crosslinking agent, sensitizer, and photoreaction initiator in the hologram recording material using a solvent that has appropriate solubility for the polymer containing a carbazole ring. Execute. Examples of solvents used for decolorization include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, l,2-dichloroethane, tetrahydrofuran, acetone, methyl alcohol, ethyl alcohol, butyl alcohol, propyl alcohol, isopropyl alcohol, etc. , these can be used alone or in combination. Next, development is carried out using two solutions with different properties. First, a first solvent having good solubility that can swell a polymer containing a carbazole ring, such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, cumene, or a mixture of the above solutions, is used. After swelling the film of the polymer containing exposed carbazole rings using a solution of pentane, hexane, heptane, octane, cyclohexane, acetone, methyl alcohol, ethyl alcohol, butyl alcohol, propyl alcohol, isopropyl alcohol, acetic acid By treating with a second solution that is a poor solvent for polymers containing carbazole rings such as methyl and ethyl acetate,
The swollen film contracts, causing a refractive index change corresponding to the interference exposure pattern, and a phase-type hologram is formed. As a development processing method different from the above, there is a method in which development is completed by IH processing using a mixed solution of a good solvent with a low boiling point and a poor solvent with a high boiling point. First, the exposed film of the polymer containing carbazole rings is swollen using a mixture of a good solvent and a poor solvent for the polymer containing carbazole rings. The degree of swelling can be adjusted by adjusting the types and composition ratios of good and poor solvents. After moistening with 1M, slowly lift the substrate on which the recording material film is formed from the mixed solution. If a good solvent with a low boiling point is used, the good solvent will vaporize first and the poor solvent will remain. A polymer containing a carbazole ring precipitates and separates from the poor solvent.Then, the poor solvent evaporates, leaving voids and forming a hologram.Good low boiling point solvents used in the developer include, for example: Dichloromethane, chloroform, back tetrachloride, 1,2-dichloroethane, 1゜2-dichloroethylene, trichloroethylene, benzene, tetrahydrofuran, tetrahydrobyran, etc. are used alone or in combination.As a high boiling point poor solvent. There are paraffin hydrocarbons such as heptane, octane, nonane, and decane, and alcohols such as butyl alcohol, propyl alcohol, and isopropyl alcohol, and these are used alone or in combination. Decolorization treatment is performed before development as described above. However, it is possible to create a hologram even if the decolorization treatment is omitted.In this case, the crosslinking agent, sensitizer, and photoinitiator are removed at the same time as development. It turns out.
A transparent hologram cannot be produced unless the crosslinking agent, sensitizer, and photoreaction initiator are sufficiently removed during the decolorization and development steps. (Problem to be solved by the invention) When using bleached silver salt or dichromate gelatin as a hologram recording material, moisture resistance,
It has the disadvantage of low environmental resistance such as heat resistance and light resistance. On the other hand, when a polymer hologram recording material is used and an organic halogen compound is used as a photoreaction initiator, the following problems occur. (a) Carbon tetraiodide (C1,) as an organic halogen compound
When using this material, it is difficult to handle it in the process of forming a film of the recording material on the substrate because this material tends to gel when irradiated with light. (b) Iodoform (CHI) as an organic halogen compound
When using s), there is a problem that the photosensitive region of this material is in the ultraviolet region and the sensitivity is low to visible light. (c) When an iodine compound is used as an organic halogen compound, it decomposes as the amount of light irradiation during exposure increases, and the compound takes on a green color, reducing the transparency of the produced hologram. The reason for this is thought to be that iodine, which is a decomposition product of the photoinitiator, forms a charge transfer complex (CT complex) with a polymer containing a carbazole ring, resulting in coloring of the hologram. The details of the structure of the CTR structure of a polymer containing a carbazole ring and iodine are unknown, but the nitrogen of the carbazole ring is sufficiently polarized to form a complex with the iodide ion (t), or the iodine -amylose CT
Complex (Poly@er Preprints, Jap
an Vo1.36. p 1799.19B? ), it is thought that the iodide ion has a structure between adjacent benzene rings. The purpose of the present invention is to eliminate these drawbacks, and has excellent environmental resistance such as moisture resistance, heat resistance, and light resistance, high sensitivity to visible light, and low light transmission when manufacturing holograms. An object of the present invention is to provide a photoreceptor for hologram recording with a high yield rate, and a composition for a hologram recording material that is chemically stable and difficult to gel, which is used as a recording material for the photoreceptor. [Means for Solving the Problems] Among the above objects, the composition for holographic recording material contains at least a dye comprising a polymer having a carbazole ring, N-phenylglycine, and a compound having a coumarin structure in the molecule. This is achieved by the composition for hologram recording material containing the following. The weight of the N-phenylglycine is 1 to 30% of the weight of the polymer, and the weight of the dye is 1 to 30% of the weight of the polymer.
It is preferably 0.1 to 20% by weight of the polymer. Among the above objects, the photoreceptor for hologram recording is achieved by a photoreceptor for hologram recording in which a film (2) made of the above composition is formed on a transparent substrate (1). [Function] As a result of research on a photoreaction initiator that can photocrosslink a polymer containing a carbazole ring, the inventor of the present application found that
We have discovered that N-phenylglycine, which is well known as a radical generator, can photocrosslink a polymer containing a carbazole ring, making hologram recording possible. However, N-phenylglycine alone does not absorb visible light and cannot record holograms using argon laser light, which is visible light. However, by adding a dye as a sensitizer, argon laser light can be recorded. It has high sensitivity to light. It has been found that compounds having a coumarin structure in the molecule, such as coumarin dyes and ketocoumarin dyes, which can act as sensitizers for N-phenylglycine, are effective as dyes. By the way, in a hologram recording material containing a dye made of N-phenylglycine and a compound having a coumarin structure in the molecule, the N-phenylglycine and the dye can be easily removed by decolorization treatment or development treatment, so the manufactured hologram is transparent. becomes. Further, unlike a polymer containing an organic halogen compound and a carbazole ring, it does not form a CTji body and cause absorption in the visible region. Note that examples of the polymer containing a carbazole ring include polyvinyl carbazole, carbazole copolymer, halogen-substituted polyvinyl carbazole, and the like. In addition, N-
It is effective to add phenylgutsucin in an amount of 1 to 30% by weight, and to add the pigment in an amount of 0.1 to 20% by weight. [Examples] Hereinafter, compositions for holographic recording materials and photoreceptors for holographic recording according to three examples of the present invention will be described with reference to the drawings. 1] Refer to FIGS. 2 and 3. The composition of the composition for hologram recording material is as follows. M material FMM: Polyvinylcarbazole (weight average molecular weight 730,000)...10.0 g Photoreaction initiator 2 N-phenylglycine (the structural formula is
) ... l,og Sensitizer = 3- (2"-Benzothiazo
lyl) Fu N, N -diatbylasia
Ocommarin (Structural formula is shown in Figure 3)...0.8g Solvent: Dioxane...80.0g Monochlorobenzene...40.0g See Figure 1 On a 70x7G garden, 1 inch thick glass substrate l Next, the above composition was spin-coded and dried to form 1]2 made of the above composition having a thickness of 5 μm, thereby producing a photoreceptor for hologram recording. A transmission hologram was recorded on the above hologram recording photoreceptor by irradiating it with an argon laser (wavelength: 488 ns) at an exposure dose of 180 mJ/cJ using a two-beam interference exposure optical system. Next, the photoreaction initiator and sensitizer were removed by immersion in a xylene-〇-dichlorobenzene-isopropanol mixture for 4 minutes (decolorization treatment), and the humidity was 20%.
Then, in an atmosphere with a humidity of less than 20%, it was first immersed in a xylene-toluene mixture for 1 minute, then pulled out, slowly dipped in n-pentane, and then slowly pulled up again. Development was completed and a transparent hologram with no defects such as cracks was created.The above hologram was exposed to helium-neon laser light (wavelength 6
331Im), the transmission diffraction efficiency was 68%, and the light transmittance measured using a helium-neon laser beam was 95%, which is lower than the conventional light transmittance of about 90%. improved compared to %. Furthermore, in order to examine moisture resistance, the sample was left in a constant temperature bath at 70 DEG C. and 95% R, H-, but no decrease in diffraction efficiency or light transmittance was observed even after 10 days. ] See Figures 2 and 4. The composition of the composition for hologram recording material is as follows. Base resin: Vinyl carbazole-styrene copolymer (8:2) (weight average molecular weight 750,000) --- 10.0 g Photoinitiator 2 N-phenylglycine (with structural formula 2)
)... 1.2g sensitizer = 3. 3”-Carbonylbis
(Food diethylaminocous+ari
n) (The structural formula is shown in Figure 4)...0.6g Solvent: o-dichlorobenzene...80-0g dichloromethane...-40.0gRefer to Figure 170x70 size, thickness 1 glass The above composition is spin-coded and dried on the substrate 1 to form a thin film 2 made of the above composition, thereby producing a photoreceptor for hologram recording. A transmission hologram was recorded on the above hologram recording photoreceptor by irradiating it with an argon laser (wavelength: 488 nm) at an exposure dose of 140 mJ/d using a two-beam interference exposure optical system. Next, xylene-〇-dichlorobenzene-
After removing the photoreaction initiator and sensitizer by immersing it in a tetrahydrofuran-acetone mixture for 5 minutes (decolorization treatment),
It was left in an atmosphere with a humidity of less than 20% for 2 hours, and then, in an atmosphere with a humidity of less than 20%, it was first immersed in a xylene solution for 30 seconds, then taken out and slowly immersed in n-hebutane (
The above hologram was reproduced using helium-neon laser light (wavelength 633n+++). As a result, the transmission diffraction efficiency was 69%, and the result of measuring the light transmittance using a helium-neon laser beam was 94%.
%Met. ]'' IK See FIGS. 2 and 5 Hologram 5 The composition of the recording material composition is as follows. Base resin: Vinylcarbazole-methyl acrylate copolymer (9:l) (weight average molecular weight 670,000)...10.0g Photoinitiator 2 N-phenylglycine (with structural formula 2)
)...1.5 g Sensitizer = 3- (2--B6Hzisidazol
yl) Fu N, N-diethylaminoc
ou ■ Revised in (Structural formula is shown in Figure 5) ...0.5g Additive: Polycarbonate ...0.4gn agent:
O-dichlorobenzene...40.0 g Monochlorobenzene...40-0 g Tetrahydrofuran...40.0 g See Figure 1. Spin the above composition onto a 70x70m glass substrate l with a thickness of 2. It is coated and dried to form a film 2 of the above composition having a thickness of 8 μm, thereby producing a photoreceptor for hologram recording. A reflection hologram was recorded on the above hologram recording photoreceptor by irradiating it with an argon laser (wavelength: 488 nm) at an exposure dose of 160 mJ/d using a two-beam interference exposure optical system. Then, xylene-〇-dichlorobenzene-
The photoreaction initiator and sensitizer were removed by immersion in a seven-ton isopropyl alcohol mixture for 5 minutes (decolorization treatment).
After that, it was left in an atmosphere with a humidity of less than 20% for 2 hours, and then, in an atmosphere with a humidity of less than 20%, it was first immersed in a di-chloromethane-n-octane-isopropyl alcohol mixture for 30 seconds, and slowly After pulling it up and completing development, we were able to create a transparent hologram with no defects such as cracks. The above hologram was exposed to argon laser light (wavelength 514.5
ns), the reflection diffraction efficiency was 70%.
In addition, helium-neon laser light (633ns
) was used to measure the light transmittance, and the result was 92%. [Effects of the Invention] As explained above, the composition for a hologram recording material according to the present invention is composed of a polymer having a carbazole ring, N-phenylglycine, and a dye made of a compound having a coumarin structure in the molecule. It is chemically stable and does not gel, making it easy to manufacture photoreceptors for hologram recording. In addition, the photoreceptor for hologram recording according to the present invention, in which a film made of the above-mentioned acid is formed on a substrate, has environmental resistance such as moisture resistance, heat resistance, and light resistance, since it does not contain gelatin.
It has excellent sensitivity to visible light such as argon laser, and furthermore, since the dye can be easily removed by decolorization treatment after exposure, the light transmittance of the manufactured hologram becomes high.

[Brief explanation of the drawing]

FIG. 1 is a side view of a hologram recording photoreceptor according to an embodiment of the present invention. FIG. 2 is the structural formula of N-phenylglycine. Figure 3 shows 3- (2”-Bemzotbiaxol
yl)? -N, N-diethylaminoc
This is the structural formula of oumarin. Figure 4 shows 3*3”-Carboaylbis
(Food diethylaminocousarin
) is the structural formula. 5t5i1] is 3- (2”-Beazimid
azolyl) - Fu N, N - diethyla
This is the structural formula of minocoumarin. l...Transparent substrate, 2... Film made of a composition for hologram recording material.

Claims (1)

[Scope of Claims] [1] At least a polymer having a carbazole ring and N
- A composition for a hologram recording material, comprising phenylglycine and a dye made of a compound having a coumarin structure in its molecule. [2] The weight of the N-phenylglycine is 1 to 30% of the weight of the polymer, and the weight of the dye is 0.1 to 20% of the weight of the polymer. Composition for hologram recording material. [3] A photoreceptor for hologram recording, characterized in that a film (2) made of the composition according to claim 1 or 2 is formed on a transparent substrate (1).