JPH10111633A - Hologram photosensitive agent, hologram photosensitive material and hologram as well as their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the diffraction efficiency and sensitivity of a hologram by constituting triphenyl methane based dyestuff of specific dyestuff, thereby sufficiently decoloring the hologram by washing after exposure. SOLUTION: The triphenyl methane dyestuff of the hologram photosensitive agent consisting of a hexavalent chromium compd. and the triphenyl methane dyestuff consists of the plastid which is expressed by formula II and is of logP<=6 in the distribution coefft. calculated as the dye precursor expressed by formula I. In the formula I, X denotes a hydrogen atom or an aryl group having a substituent, Y denotes the hydrogen atom or the aryl group having the substuent and R1 to R6 respectively denote hydrogen atoms or 1 to 5C straight chain or branched chain alkyl groups. In the formula II, Y denotes a hydrogen atom or an aryl group having a substituent; R1 to R6 respectively denote hydrogen atoms or 1 to 5C straight chain or branched chain alkyl groups and Z<-> denotes anion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram used for a display or a filter, and more particularly to a hologram photosensitive agent capable of exhibiting excellent sensitivity to long-wavelength laser light, a hologram photosensitive material using the same, and a hologram. , As well as a method for producing them.

[0002]

2. Description of the Related Art A hologram is obtained by recording an interference surface of coherent light such as a laser on a hologram photosensitive material.

There is a demand for producing a red hologram for a hologram used for an application such as an optical element. When producing a hologram in a long wavelength region such as red, a semiconductor laser (about 780 nm) or a He-Ne laser (about 633) is used as coherent light.
nm) long laser light.

However, the above-mentioned conventional hologram photosensitive material has sensitivity to light having a relatively short wavelength of about 560 nm from the ultraviolet region, but has extremely low sensitivity to light having the long wavelength. Therefore, recording of the hologram in a long wavelength region such as red becomes unclear, and it is difficult to obtain a good hologram.

Various proposals have been made to solve this problem. One example is Japanese Patent Publication No. 54-357.
No. 68 discloses that a gelatin film is immersed in a photosensitive solution obtained by dissolving ammonium bichromate and a methylene blue sensitizer of a thiazine dye in aqueous ammonia, and then dried under an ammonia atmosphere to form a photosensitive layer. A method for making is described.

As another example, Graube, Op.
t. Commun. , 8, 251 (1973), Acid Fast Violet B as a sensitizing dye.
There is a report on a hologram photosensitive agent containing G and ammonium dichromate. Also, Japanese Patent Application Laid-Open No. 7-110648
Japanese Patent Application Publication No. JP-A-2003-26464 discloses a hologram photosensitive agent comprising a hexavalent chromium compound, a triphenylmethane dye and a binder, and having a light absorption of 7% or more for long-wavelength laser light.

[0007]

However, the conventional hologram has the following problems. First, the photosensitive layer disclosed in the former patent publication must be dried in an ammonia atmosphere, and the process is complicated. In addition, there is a problem that the pigment is easily precipitated. Furthermore, the sensitivity is still insufficient for a long wavelength semiconductor laser or the like.

[0008] In the hologram photosensitive agent disclosed in the latter document, Acid Fast contained therein is used.
The solubility product of Violet BG and ammonium bichromate is extremely small at 1 × 10 ⁻⁴ (mol / liter) ² . Therefore, they are hardly dissolved in the gelatin solution. Therefore, a hologram photosensitive material having excellent sensitivity to a long wavelength region cannot be obtained. Further, when a hologram is manufactured using such a hologram photosensitive material, a hologram having a high diffraction efficiency cannot be obtained. Also, a hologram photosensitive agent using a triphenylmethane dye described in the literature has not yet obtained sufficient sensitivity and performance.

When a triphenylmethane dye is used, the hologram photosensitive material is dyed due to the triphenylmethane dye. This is not desirable when considering a wide range of applications. Therefore, after exposing the hologram photosensitive material, the hologram photosensitive material is washed to remove the hexavalent chromium compound and the triphenylmethane dye from the inside of the photosensitive layer, and decolorize. However, when the above-mentioned conventional triphenylmethane-based dye is used, the triphenylmethane-based dye is not sufficiently removed, and decolorization is insufficient.

SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a hologram photosensitive agent capable of sufficiently decoloring by washing after exposure, and improving the diffraction efficiency and sensitivity of a hologram, and a hologram photosensitive material using the same. And a hologram, and a manufacturing method thereof.

[0011]

According to a first aspect of the present invention, there is provided a hologram photosensitive agent comprising a hexavalent chromium compound, a triphenylmethane-based dye, and a binder, wherein the triphenylmethane-based dye is a dye precursor represented by the following chemical formula (2). A hologram photosensitizer comprising a coloring matter represented by Chemical Formula 1 having a distribution coefficient calculated as log P ≦ 6.

[0012]

Embedded image

In Chemical Formula 1, Y represents a hydrogen atom or an aryl group having a substituent. R1, R2, R3, R
4, R5 and R6 each represent a hydrogen atom or a carbon atom 1
To 5 represents a linear or branched alkyl group. Z ^- represents an anion.

[0014]

Embedded image

In Formula 2, X represents a hydrogen atom or an aryl group having a substituent, and Y represents a hydrogen atom or an aryl group having a substituent. R1, R2, R3, R
4, R5 and R6 each represent a hydrogen atom or a carbon atom 1
To 5 represents a linear or branched alkyl group.

The most remarkable point in the present invention is to use a dye body corresponding to a dye precursor having a distribution coefficient LogP = 6 or less as a triphenylmethane-based dye causing dyeing of the hologram photosensitive material. .

The above dye precursor is colorless and transparent when it is simply dissolved in water, but its side chains Y, R1, R2, R
A plastid having the same 3, R4, R5, and R6 develops a blue, green, or purple color. As described above, when the distribution coefficient LogP of the dye precursor corresponding to the above-mentioned dye body is calculated, there is a correlation between the distribution coefficient LogP and the decolorizing property of the photosensitive layer. That is, when a dye corresponding to a dye precursor having a distribution coefficient LogP ≦ 6 is used, decolorization is easy. On the other hand, when a dye precursor having a distribution coefficient LogP> 6 is used, decolorization is difficult.

The distribution coefficient LogP is calculated as Roel of
F. Rekker, THE HYDROPHOBIC
FRAGMENTAL CONSTANT (1977
), Etc., as described in “Formula 4” below.

[0019]

Embedded image

In the chemical formula 4, f is Hydropho
In the bic fragmental constant,
a is the number of fragments contained in the chemical structure.

For example, as shown in the calculation formula of the following chemical formula 5, the dye precursor (HS) shown in the chemical formula of the chemical formula 6
When the distribution coefficient LogP of D-9) is calculated, LogP =
4.9 (f used here is HYDRO described above)
PHOBIC FRAGMENTAL CONSTAN
The value described in T was used. The same applies hereinafter. ).

[0022]

Embedded image

[0023]

Embedded image

Similarly, one of the various dye precursors or plastids shown in Chemical formulas 7 to 21 as Lo as a dye precursor.
gP was calculated. The results are shown in Table 1.

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

[Table 1]

Of the above dye precursors or dye bodies, those having a distribution coefficient of LogP ≦ 6 as the dye precursor (“Chemical Formula 6”)
To “Chemical formula 18”), a hologram photosensitive material is prepared from a hologram photosensitive agent comprising a hexavalent chromium compound and a binder, and a desired portion of the hologram photosensitive material is exposed,
By washing, the triphenylmethane dye can be removed from the inside of the photosensitive layer of the hologram photosensitive material, and the dyeing of the photosensitive layer caused by the triphenylmethane dye can be decolorized. Thereby, a colorless and transparent hologram can be obtained.

On the other hand, a photosensitive material was prepared and washed in the same manner as described above using a dye precursor ("Chemical Formula 19" to "Chemical Formula 21") having a distribution coefficient LogP> 6, but decolorization was difficult. Further, a hologram manufactured using the hologram photosensitive agent has high diffraction efficiency and sensitivity. When a hologram photosensitive material is manufactured using the above-mentioned dye precursor, it is necessary to subject the above-mentioned dye precursor to an acid treatment to obtain a dye body corresponding to the dye precursor.

Next, a second aspect of the present invention provides a distribution coefficient log
Preparing a triphenylmethane-based dye by subjecting a dye precursor represented by the following chemical formula 3 with P ≦ 6 to acid treatment, and then mixing the triphenylmethane-based dye with a hexavalent chromium compound and a binder; A method for producing a hologram photosensitive agent, characterized by the following.

[0044]

Embedded image

In Formula 3, X represents a hydrogen atom or an aryl group having a substituent, and Y represents a hydrogen atom or an aryl group having a substituent. R1, R2, R3, R
4, R5 and R6 each represent a hydrogen atom or a carbon atom 1
To 5 represents a linear or branched alkyl group.

The above-mentioned dye precursor is colorless and transparent when simply dissolved in water. However, the solution is subjected to an acid treatment such as addition of an acid, for example, by adjusting the pH to 2 to 4 to obtain the dye precursor. The precursor changes to a plastid, and the solution develops a blue, green, or purple color.

As the acid to be added to the above solution, for example,
Mineral acids such as hydrochloric acid, oxalic acid, nitric acid or sulfuric acid can be used. According to the method for producing a hologram photosensitive agent,
The hologram can be sufficiently decolorized by washing after exposure, and has high diffraction efficiency and high sensitivity.

Next, a third aspect of the present invention is a hologram photosensitive material in which the surface of a transparent member is covered with a photosensitive layer, wherein the photosensitive layer is provided with the hologram photosensitive agent of the first aspect on the surface of the transparent member. A hologram photosensitive material characterized by being applied and dried.

[0049] The hologram photosensitive material is characterized in that:
Because it has a photosensitive layer composed of a hologram photosensitive agent,
Decoloring can be sufficiently achieved by washing after exposure.
A hologram manufactured using the hologram photosensitive material has high diffraction efficiency and sensitivity.

According to a fourth aspect of the present invention, there is provided a hologram photosensitive material in which the surface of a transparent member is covered with a photosensitive layer, wherein the photosensitive layer comprises the hologram photosensitive agent obtained by the second aspect. A hologram photosensitive material which is applied to a surface and dried.

Since the hologram photosensitive material uses the hologram photosensitive agent obtained according to claim 2, the photosensitive layer has good decolorization, good diffraction efficiency and high sensitivity, as in the case of claim 3.

Next, a fifth aspect of the present invention relates to the third or fourth aspect.
The hologram photosensitive material is irradiated with a laser beam to expose a desired portion of the photosensitive layer, and then the hologram photosensitive material is washed to remove a hexavalent chromium compound and a triphenylmethane dye from the inside of the photosensitive layer. And a method for producing a hologram, which comprises developing the photosensitive layer.

The invention of claim 6 is the invention of claim 3 or 4
The hologram photosensitive material is irradiated with a laser beam to expose a desired portion of the photosensitive layer, and then the hologram photosensitive material is washed to remove a hexavalent chromium compound and a triphenylmethane dye from the inside of the photosensitive layer. And a hologram obtained by developing the photosensitive layer.

In the hologram and the method for producing the hologram, since the hologram photosensitive material is used, the hologram is sufficiently decolorized by washing, and has high diffraction efficiency and sensitivity. Therefore, it can be used as an excellent optical element.

[0055]

BEST MODE FOR CARRYING OUT THE INVENTION

First Embodiment A hologram according to an embodiment of the present invention will be described with reference to FIGS. In manufacturing the hologram of this example, as shown in FIG. 1, a hologram photosensitive agent having a hexavalent chromium compound, a triphenylmethane dye and a binder was prepared (S21, S22). As triphenylmethane dyes, HSD which is a dye precursor
-9 was used as a plastid obtained by acid treatment. The side chains of this plastid are identical to the side chains of HSD-9. The partition coefficient logP of HSD-9 was 4.9.

Next, this is applied to a transparent member (S2
3) After drying (S24), the amount of water is adjusted to form a photosensitive layer (S25). Next, the photosensitive layer is exposed (S2
6), washing (S27), developing (S28), and sealing (S29). Thereby, the hologram is obtained. The details will be described below.

First, HSD-9 as a dye precursor was synthesized. That is, 4,4'-bis (dimethylamino) benzhydrol (hereinafter referred to as Michler's hydrol) 5
2.0 g and 22.5 g of N-methylaniline in water 10
The mixture was heated to 80 ° C., and 22.1 g of 62% sulfuric acid was added dropwise over 3 hours, followed by stirring for 18 hours. After completion of the reaction, the pH was adjusted to 10 with 48% sodium hydroxide, unreacted N-methylaniline was removed by steam distillation, and extraction was performed with toluene. The toluene layer was separated and separated, and toluene was distilled off under reduced pressure to obtain 76.0 g of a tar-like substance.

76.0 g of the above tar substance was dissolved in 100 ml of methylene chloride, and 54.1 g of chloranil was added over 1 hour, followed by a reaction for 15 hours. After the reaction, add water and
The pH was adjusted to 10 by adding 48% sodium hydroxide, and methylene chloride was distilled off by concentration under reduced pressure. The precipitated blue crystals were separated by filtration and dried at 60 ° C. The yield of the obtained blue crystals was 39.0 g.

The above blue crystals 3 in 50.0 g of acetic anhydride
After 9.0 g was added over 3 hours, the mixture was reacted at 80 ° C. for 32 hours. After completion of the reaction, the acetic anhydride was concentrated under reduced pressure,
It was dissolved in 0 ml, and the insoluble matter was separated by filtration. The filtrate was adjusted to pH 10 by adding 48% sodium hydroxide. Tar-like substances precipitated. Extraction with 100 ml of toluene and separation were performed to separate a toluene layer, and toluene was distilled off by concentration under reduced pressure to obtain a tar-like substance. The obtained tar was brown, and the yield was 11.0 g. This was designated as HSD-9.

Next, a hologram was manufactured using the above dye precursor. First, as shown in FIG. 1, in S21, ammonium bichromate (hereinafter, referred to as DCA) was prepared as a hexavalent chromium compound. This 20g of D
Ion exchange water was added to CA to make 1000 ml. This was used as DCA stock solution.

The above-mentioned dye precursor (HSD-9)
An acidic treatment was performed by dissolving 0.04 g in 3 ml of 2N hydrochloric acid. Next, ion-exchanged water was added to make up to 100 ml. This was used as a pigment stock solution.

4 g of gelatin as a binder was placed in a 200 ml Erlenmeyer flask. Ion-exchanged water is added to the mixture, and the total weight of gelatin and
0 g. This was shaken in a water bath at 40 ° C. for 2 hours to obtain an aqueous gelatin solution. The shaking speed was 125 times / min. As gelatin, p-2406 manufactured by Nitta Gelatin Industries was used.

Next, in S22, 7 ml of DCA stock solution was added to 100 g of the aqueous gelatin solution prepared above,
Stir for 1 minute. Then, the dye stock solution prepared above was added to 7
ml and stirred for 3 minutes. Stirring was performed using a 20 mm long blade stirrer. The rotation speed of the impeller is up to 14
00 rpm. Then, this was filtered with filter paper (No. 4)
Filtration was performed using 1), and the filtrate was used as a photosensitive solution. next,
A 4 inch long, 5 inch wide glass substrate was covered with a transparent film to form a transparent member.

Next, in step S23, the hologram photosensitive agent was applied to the surface of the transparent member and dried. In applying the hologram photosensitive agent, a hot plate and a cold plate were used. Hot plate at 38 ℃
(Temperature accuracy ± 0.5 ° C or less, temperature distribution ± 1 ° C). The temperature of the cold plate was adjusted to 5 ° C (temperature accuracy was ± 0.5 ° C or less, temperature distribution ± 1 ° C). The surface humidity of the cold plate is 50% RH when converted to the humidity at 20 ° C.
The humidity was adjusted as follows.

Next, the transparent member was placed on the hot plate with the glass surface facing upward. Then,
10 ml of the photosensitive solution was applied to the glass surface of the transparent member. Thereafter, the photosensitive solution was quickly spread over the entire glass surface within a short time of 10 seconds or less, and then the transparent member was moved from the hot plate to the cold plate.

Next, in S24, the transparent member was transferred into a constant temperature / humidity bath at 20 ° C. and 50% RH, and dried for 18 hours while keeping the transparent member horizontal. Next, S25
Was adjusted so that the water content in the photosensitive layer was 43% by weight.

In determining the water content in the photosensitive layer,
The following calculation formula was used. M = (W−Wo) / W

In this equation, W is the weight of the photosensitive layer,
Wo is the weight of the photosensitive layer after leaving the transparent member in a thermostat at 120 ° C. for 30 minutes. 3 in this thermostat (120 ° C)
The moisture content in the photosensitive layer after standing for 0 minutes was set to 0% by weight. Since the moisture content in the photosensitive layer was proportional to the humidity in the thermo-hygrostat, it was adjusted by changing it. As a result, a hologram photosensitive material in which the surface of the transparent member was covered with the photosensitive layer was obtained.

Next, in S26, as shown in FIG. 2, the hologram photosensitive material 1 was irradiated with a parallel reference beam 711 and an object beam 721 to expose a desired portion of the photosensitive layer. At this time, the transparent film was peeled off.
That is, first, the hologram photosensitive material 1 was brought into close contact with the mirror 78 using an index matching liquid (silicon oil).

Next, a krypton ion laser 710 is used.
Was reflected by the reflection lens 79. This laser beam 71 is transmitted to an objective lens 73
Then, the light was transmitted through the lens 74 to form the parallel reference light 711. The parallel reference light 711 was applied to the photosensitive layer side of the hologram photosensitive material 1. Further, the parallel reference light 711 transmitted through the hologram photosensitive material 1 was reflected by a mirror 78 to become an object light 721, and the object light 721 was irradiated to the transparent member 12 side of the hologram photosensitive material 1. This gives
The parallel reference light 711 and the object light 721 interfered in the photosensitive layer.

As the laser beam 71, a krypton ion laser (wavelength: 647.1 nm) was used. The exposure amount is preferably 200 mJ / cm ² or more. The parallel reference light 711 was incident at 30 ° to the normal of the hologram photosensitive material. Next, the mirror 78 was peeled off from the hologram photosensitive material 1.

Next, the hologram photosensitive material was washed with ethanol. In this ethanol washing, the hologram photosensitive material was immersed in a 70% by volume ethanol aqueous solution for 1 minute, in a 90% by volume ethanol aqueous solution for 1 minute, and in a 100% by volume ethanol aqueous solution for 1 minute.

Next, in S27, the hologram photosensitive material was immersed in a water bath at 20 ° C. for 5 minutes to remove the hexavalent chromium compound from the photosensitive layer. During the immersion, the hologram photosensitive material was sufficiently shaken. Next, the hologram photosensitive material is
It was immersed in a 50% aqueous solution of Rapid Fixer manufactured by Odak (20 ° C.) for 3 minutes, and then washed with running water for 10 minutes.

Next, in S28, the photosensitive layer was developed. Its highest temperature was 31 ° C. The developing procedure is as follows: a 90% by weight of a 70% by weight aqueous solution of IPA (which means isopropyl alcohol; the same applies hereinafter) in a hot water bath for 1 minute;
1 minute in IPA aqueous solution, 3 minutes in 100% by weight IPA,
The hologram photosensitive material was immersed in order.

Next, in S29, the hologram photosensitive material was dried at 80 ° C. for 10 minutes. Next, the hologram photosensitive material was heated at 120 ° C. for 60 minutes. Next, the hologram photosensitive material was sealed with a glass plate as a cover material using an optical adhesive (Norland NOA61). Thus, the hologram of this example was obtained.

The hologram of this example manufactured by using HSD-9 was free from dyeing due to the triphenylmethane dye on the transparent portion, and was sufficiently decolorized. Further, the diffraction efficiency and the sensitivity were sufficiently high, and the optical element was excellent.

Embodiment 2 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by acid-treating SD-28,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-28 will be described. 14.6 ml of tetrahydrofuran, anisole 10
In a mixed solvent of 0 ml, 2.1 g of lithium and a catalytic amount of iodine were added, and 23.6 g of bromobenzene was added dropwise thereto, and the mixture was heated to 50 ° C. When the reaction started, the heating was stopped and the temperature was maintained at 40 to 50 ° C. in an ice bath. During that time, bromobenzene was added dropwise over 0.5 hour. After that, the reaction was left until the reaction was completed and returned to room temperature.

The above reaction solution was cooled to 10 ° C. in an ice bath,
12.0 g of 4,4'-bis (dimethylamino) benzophenone (hereinafter referred to as Michler's ketone) was added thereto. When the exotherm ceased, the ice bath was removed and stirring continued for 1 hour. The mixture was discharged into 600 ml of ice water and extracted with 200 ml of toluene. The liquid was separated and the toluene layer was separated and concentrated under reduced pressure to obtain a tar-like substance. The obtained tar was loosened with methanol and crystallized. The crystals are filtered off and washed with methanol, 6
Dried at 0 ° C. The obtained crystals were pale yellowish white and had a melting point of 194 to 200 ° C. The yield was 6.0 g. This was designated as HSD-28.

The hologram produced by using HSD-28 did not have any coloring caused by the triphenylmethane-based dye on the transparent portion thereof and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 3 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by acid-treating SD-29,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-29 will be described. At room temperature, 121.0 g of N, N-dimethylaniline and 71.0 g of 2-chlorobenzaldehyde were added to 300 ml of ethyl cellosolve, and 98% sulfuric acid was added dropwise thereto over 2 hours. After the dropwise addition, 48.0 g of urea was added, and the mixture was heated to 60 ° C. and stirred for 22 hours. After the reaction is over,
Discharge to 1000 ml of ice water, add 300 ml of toluene,
48% sodium hydroxide was added dropwise to change the pH of the aqueous layer from 2 to 7, and the layers were separated. The separated toluene layer was separated and concentrated under reduced pressure to obtain a tar-like substance. The obtained tar was loosened with methanol and crystallized. The crystals were separated by filtration, washed with methanol and dried at 60 ° C. The obtained crystals were white and the yield was 30.0 g.

7.3 g of the white crystals obtained above was added to 100 ml of ethanol together with 9.8 g of chloranil.
And stirred for 1.5 hours. After completion of the reaction, the reaction solution was discharged into 300 ml of water, and 50 ml of 48% sodium hydroxide was added. 400 ml of toluene was added and extracted and separated, and the toluene layer was separated and concentrated under reduced pressure to obtain tar. Crystallized by dissolving with methanol. The crystals were separated by filtration, washed with methanol and dried at 60 ° C. The resulting crystals were pale blue-gray and had a melting point of 102-109 ° C. Yield 2.7 g
Met. This was designated as HSD-29.

The hologram produced by using HSD-29 did not have any coloring caused by the triphenylmethane-based dye on the transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 4 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by acid-treating SD-30,
A hologram was produced in the same manner as in the first embodiment.

Next, a method of synthesizing HSD-30 will be described. In a mixed solvent of 14.6 ml of tetrahydrofuran and 100 ml of cyclohexane, 20.0 g of 1,3,5-trimethoxybenzene, 1.0 g of lithium and a catalytic amount of iodine were added, and 23.6 g of bromobenzene was added dropwise thereto. Heated to 50 ° C. When the reaction started, the heating was stopped and the temperature was maintained at 40 to 50 ° C. in an ice bath. During that time, bromobenzene was added dropwise over 0.5 hour. After that, the reaction was left until the reaction was completed and returned to room temperature.

The above reaction solution was cooled to 10 ° C. in an ice bath,
12.0 g of Michler's ketone was added thereto. After the end of the exotherm, the ice bath was removed and stirring was continued for 1 hour. Ice water 60
The mixture was discharged to 0 ml and extracted with 200 ml of toluene. The liquid was separated and the toluene layer was separated and concentrated under reduced pressure to obtain a tar-like substance. The obtained tar was loosened with methanol and crystallized. The crystals were separated by filtration, washed with methanol and dried at 60 ° C. The obtained crystals are white and have a melting point of 194-197.
° C. The yield was 2.2 g. This is HSD-
30.

The hologram produced by using HSD-30 was free from dyeing due to the triphenylmethane dye in the transparent portion and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 5 In this embodiment, as a triphenylmethane dye, H
A hologram was produced in the same manner as in Example 1 except that SD-31 was used.

Next, a method of synthesizing HSD-31 will be described. Michler's Hydrol 1 in 800 ml of toluene
21.0 g and 72.0 g of 2-naphthol were added, and the mixture was stirred under reflux for 2 hours. It was concentrated under reduced pressure to obtain a tar-like substance. The resulting tar was loosened with methanol and crystallized. The crystals were separated by filtration, washed with methanol and dried at 60 ° C. The obtained crystals were white, and the yield was 138.0 g.

15.8 g of the white crystals obtained above were mixed with 1 part of water.
It was put in a mixed solvent of 00 ml and 100 ml of methanol, and then 5.1 g of iodine was added. The mixture was stirred under reflux for 1 hour. After the completion of the reaction, the mixture was allowed to cool, and 20 ml of 40% hydrochloric acid was added to perform an acidic treatment. The precipitated black solid was filtered off, and methanol,
Washed with water and dried at 60 ° C. The resulting crystals were black and had a melting point of 132-139 ° C. The yield is 2.8
g. This was designated as HSD-31.

The hologram produced by using HSD-31 did not have any coloring caused by the triphenylmethane-based dye on the transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 6 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by acid-treating SD-33,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-33 will be described. 58 ml of tetrahydrofuran, 40 of shikilohexane
21.4 g of Michler's ketone is added to 0 ml of the mixed solvent, and 100 ml of phenyllithium (10% tetrahydrofuran / cyclohexane solution of Tokyo Chemicals) is added at 10 ° C. or less.
Was added dropwise over 20 minutes. After the completion of the dropwise addition, the mixture was stirred for 1.5 hours, and 1000 ml of water was added. The organic layer was separated by liquid separation and concentrated under reduced pressure to obtain a tar-like substance. The tar was loosened with methanol and crystallized. Then, the crystals were separated by filtration, washed with methanol and dried at 60 ° C. The obtained crystals were pale greenish white and had a melting point of 104 to 109 ° C. The yield was 6.7 g. This was designated as HSD-33.

The hologram produced by using HSD-33 did not have any coloring caused by the triphenylmethane-based dye on the transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 7 In this embodiment, as a triphenylmethane dye, H
A hologram was produced in the same manner as in Example 1 except that SD-34 was used.

The method for synthesizing HSD-34 will be described. Add 3.0 g of HSD-28 to 160 ml of water and add
The mixture was heated at 85 ° C. for 2 hours after adding 3.5 ml of an aqueous hydrochloric acid solution to perform an acidic treatment. Cool to 30 ° C and add sodium chloride 3
4.4 g was added little by little and adjusted to pH 7 with a 48% aqueous sodium hydroxide solution. After cooling, crystals were precipitated. The crystals were separated by filtration and dried. The resulting crystals were brown and had a melting point of 151-163 ° C. The yield was 4.2 g. This was designated as HSD-34.

The hologram produced by using HSD-34 did not have any coloring caused by the triphenylmethane dye on the transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 8 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by subjecting SD-35 to acid treatment,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-35 will be described. Magnesium 3.6 in 50 ml of tetrahydrofuran
g and a small amount of iodine were added, and the mixture was heated to 50 ° C., and 25 g of 2-bromotoluene was added dropwise thereto over 0.5 hour. After completion of the dropwise addition, the mixture was allowed to cool to room temperature. 26.8 g of Michler's ketone was dispersed in 300 ml of tetrahydrofuran, and the above reaction product was added dropwise thereto over 40 minutes while maintaining the temperature at 10 ° C. or less under ice cooling. After completion of the dropwise addition, the mixture was returned to room temperature and stirred overnight. The reaction product is discharged into 1000 ml of water,
The reaction mixture was changed from H10 to 8, and then the reaction product was extracted with 500 ml of toluene, separated, and the toluene layer was separated. It was concentrated under reduced pressure to obtain a tar-like substance, which was loosened with methanol to crystallize. The crystals were filtered off and dried at 60 ° C. The obtained crystals were pale greenish white and had a melting point of 118 to 123 ° C. The yield was 24.0 g. This was designated as HSD-35.

The hologram produced by using HSD-35 did not have a triphenylmethane dye dyed on its transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 9 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by subjecting SD-36 to acid treatment,
A hologram was produced in the same manner as in the first embodiment.

The method of synthesizing HSD-36 will be described. Magnesium 3.6 in 50 ml of tetrahydrofuran
g and a small amount of iodine were added, and the mixture was heated to 50 ° C., and 25 g of 4-bromotoluene was added dropwise thereto over 0.5 hour. After completion of the dropwise addition, the mixture was allowed to cool to room temperature. 26.8 g of Michler's ketone was dispersed in 300 ml of tetrahydrofuran, and the above reaction product was added dropwise thereto over 40 minutes while maintaining the temperature at 10 ° C. or less under ice cooling. After completion of the dropwise addition, the mixture was returned to room temperature and stirred overnight. The reaction product was drained into 1000 ml of water, and 62% sulfuric acid was added to adjust the pH
The reaction mixture was changed from 10 to 8, and then the reaction product was extracted with 500 ml of toluene, separated, and the toluene layer was separated. It was concentrated under reduced pressure to obtain a tar-like substance. The obtained crystals are tar-like,
The yield was 20.0 g. This was designated as HSD-36.

The hologram produced by using HSD-36 was free from dyeing due to the triphenylmethane dye in the transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 10 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by acid-treating SD-38,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-38 will be described. Magnesium 2.9 in 50 ml of tetrahydrofuran
g and a small amount of iodine were added, and the mixture was heated to 50 ° C and 24.8 g of 1-bromonaphthalene was added dropwise thereto over 0.5 hour. After completion of the dropwise addition, the mixture was allowed to cool to room temperature. Tetrahydrofuran 400
26.8 g of Michler's ketone was dispersed in ml, and the above reaction product was added dropwise thereto over 40 minutes while maintaining the temperature at 10 ° C. or lower under ice cooling. After completion of the dropwise addition, the mixture was returned to room temperature and stirred overnight. The reaction was drained into 1000 ml of water, the pH was changed from 10 to 8 by adding 62% sulfuric acid, and then 500 ml of toluene was added.
The reaction product was extracted with 1 and separated to separate a toluene layer. It was concentrated under reduced pressure to obtain a tar-like substance, which was loosened with methanol, crystallized, filtered and dried at 60 ° C. The obtained crystals were pale yellowish white and had a melting point of 108 to 119 ° C. Yield 2
It was 4.0 g. This was designated as HSD-38.

The hologram produced by using HSD-38 did not have any coloring caused by the triphenylmethane-based dye on the transparent portion thereof, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 11 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by acid-treating SD-39,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-39 will be described. Magnesium 2.9 in 50 ml of tetrahydrofuran
g and a small amount of iodine were added, and the mixture was heated to 50 ° C and 28.0 g of 1-bromoanisole was added dropwise thereto in 0.5 hours. After completion of the dropwise addition, the mixture was allowed to cool to room temperature. Tetrahydrofuran 400
26.8 g of Michler's ketone was dispersed in ml, and the above reaction product was added dropwise thereto over 40 minutes while maintaining the temperature at 10 ° C. or lower under ice cooling. After completion of the dropwise addition, the mixture was returned to room temperature and stirred overnight. The reaction was drained into 1000 ml of water, the pH was changed from 10 to 8 by adding 62% sulfuric acid, and then 500 ml of toluene was added.
The reaction product was extracted with 1 and separated to separate a toluene layer. The crystals obtained by concentration under reduced pressure were filtered off, and the filtrate was further concentrated under reduced pressure to obtain crystals. The mixture was loosened with methanol, filtered and dried at 60 ° C. The obtained crystals are pale bluish white and have a melting point of
128 ° C. The yield was 7.4 g. This is H
SD-39.

The hologram produced by using HSD-39 was free from dyeing due to the triphenylmethane dye in the transparent portion and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 12 In this embodiment, as a triphenylmethane dye, H
Except for using a plastid obtained by acid-treating SD-45,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-45 will be described. 24.2 g of dimethylaniline, 18.5 g of 2-bromobenzaldehyde, and 48.0 g of p-toluenesulfonic acid monohydrate were stirred at 90 ° C. overnight. After the reaction is completed, 300 ml of water is added to the reaction product, and 48% sodium hydroxide pH =
11 was set. The precipitated crystals were separated by filtration, washed with methanol, and dried at 60 ° C. The obtained crystals were white, and the yield was 18.8 g.

To 6.1 g of the crystals obtained above, 3.7 g of chloranil and 100 ml of ethanol were added, and the mixture was stirred under reflux for 2 hours. The solution was discharged into 160 ml of water, and the insoluble matter was removed by filtration. A 48% aqueous sodium hydroxide solution was added to the filtrate to precipitate crystals. After filtration, washing with water and drying at room temperature. The obtained crystals were pale blue tar, and the yield was 4.0 g. This was designated as HSD-45.

The hologram produced by using the HSD-45 did not have any coloring caused by the triphenylmethane-based dye on the transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

Embodiment 13 In this embodiment, as a triphenylmethane dye, H
Except that a plastid obtained by acid-treating SD-46 was used,
A hologram was produced in the same manner as in the first embodiment.

A method for synthesizing HSD-46 will be described. 24.2 g of dimethylaniline, 18.5 g of 4-bromobenzaldehyde, and 48.0 g of p-toluenesulfonic acid monohydrate were stirred at 90 ° C. overnight. After the reaction was completed, 300 ml of water was added to the reaction product, and 48% sodium hydroxide pH = 1.
It was set to 1. The precipitated crystals were separated by filtration and washed with methanol.
Dried at 0 ° C. The obtained crystals are white and the yield is 1
It was 3.0 g.

To 6.1 g of the crystals obtained above, 3.7 g of chloranil and 100 ml of ethanol were added, and the mixture was stirred under reflux for 2 hours. The solution was discharged into 160 ml of water, and the insoluble matter was removed by filtration. A 48% aqueous sodium hydroxide solution was added to the filtrate to precipitate crystals. After filtration, washing with water and drying at 60 ° C. The resulting crystals were pale blue and had a melting point of 144-157 ° C. The yield was 4 g. This was designated as HSD-46.

The hologram produced by using HSD-46 did not have any coloring caused by the triphenylmethane-based dye on the transparent portion, and was sufficiently decolorized. Diffraction efficiency and sensitivity were also good.

(Comparative Example 1) In this example, a hologram was produced in the same manner as in Example 1 except that a pigment obtained by subjecting HSD-11 to an acid treatment was used as a triphenylmethane-based pigment.

The method for synthesizing HSD-11 will be described. 39.0 g of zinc chloride was added to 51.9 g of N, N-dimethylaniline, and at 50 to 60 ° C., paying attention to heat generation.
25.0 g of 2,4-dichlorobenzaldehyde was gradually added. The mixture was further stirred at 95 ° C. for 2 hours. After the reaction is over,
Water was added, neutralized with 48% sodium hydroxide, and unreacted dimethylaniline was removed by steam distillation. Toluene 10
The reaction product was extracted with 0 ml, the insoluble matter was separated by filtration, the toluene layer of the filtrate was separated and separated, and toluene was distilled off by concentration under reduced pressure to obtain 45.0 g of a tar-like substance.

The above-mentioned tar-like substance (20.0 g) was dissolved in methylene chloride (200 ml), chloranil (24.5 g) was added over 1 hour, and the mixture was reacted for 15 hours. After the reaction, add water and
The pH was adjusted to 10 by adding 48% sodium hydroxide, and methylene chloride was distilled off by concentration under reduced pressure. The precipitated blue crystals were separated by filtration and dried at 60 ° C. The resulting crystals were blue and had a melting point of 152-160 ° C. The yield is 8.5 g
Met. This was designated as HSD-11.

In the hologram produced by using HSD-11, dyeing due to the triphenylmethane dye remained on the transparent portion, and it was difficult to remove the color.

(Comparative Example 2) In this example, a hologram was produced in the same manner as in Example 1 except that a dye obtained by subjecting HSD-15 to an acid treatment was used as a triphenylmethane dye.

A method for synthesizing HSD-15 will be described. To 5.4 g of Michler's ketone was added 15.8 g of methylbenzyl toluidine, and 7.4 g of phosphorus oxychloride was added thereto.
Was added over about 10 minutes and slowly heated. After heating to 80 ° C. and stirring for 10 minutes, the reaction was allowed to cool to room temperature.
Water was added dropwise to make the total volume 30 ml. The pH was adjusted to 10 by adding 48% sodium hydroxide. 20m of toluene
The reaction product was extracted by adding 1 and separated to separate the toluene layer, and the excess amine was distilled off by steam distillation.

Next, add 100 ml of perclene and add 60 ml.
The mixture was heated to ℃ to dissolve the reaction product, and made acidic by adding 35% hydrochloric acid. The aqueous layer was separated by liquid separation, and 100 ml of perclene was added to the aqueous layer again, and the pH was adjusted to 10 by adding 48% sodium hydroxide. The parkene layer was separated, concentrated under reduced pressure, and cooled. Crystallized crystals were separated by filtration and dried at 60 ° C. The crystals obtained are pale red-grey, with a melting point of 113.5.
１２120.5 ° C. The yield was 5.4 g. This was designated as HSD-15.

In the hologram produced by using HSD-15, dyeing due to the triphenylmethane dye remained in the transparent portion, and it was difficult to remove the color.

Comparative Example 3 In this example, a hologram was produced in the same manner as in Example 1 except that a dye obtained by subjecting HSD-18 to acid treatment was used as the triphenylmethane dye.

The method for synthesizing HSD-18 will be described. Michler's hydrol 27.0 g, dimethyl-o-
Toluidine 21.3g, add water to make the total volume 180ml
And The mixture was heated to 80 ° C., and 6.7 ml of 62% sulfuric acid was quickly added. Further, 13.9 ml of 62% sulfuric acid was added dropwise over 1 hour, followed by stirring for 16 hours. After completion of the reaction
0 ml, add dilute aqueous sodium hydroxide solution and add
Adjusted to 4.6. The perclene layer was separated by separation, washed with dilute sulfuric acid and warm water, and concentrated under reduced pressure to remove the perchlene. The resulting tar was dissolved in hexane to obtain crystals. The crystals were washed with a mixed solvent of hexane and acetone and dried at room temperature.

8.3 g of the crystals obtained above were dissolved in 20 ml of dichloromethane, and 4.9 g of chloranil was added to give 40 g of chloranil.
The mixture was stirred at reflux for 4 hours. Further heat to 80 ° C,
After the dichloromethane was distilled off, the reaction solution was filtered, and 12.0 ml of 48% sodium hydroxide was added to the filtrate to adjust the pH to pH 1.
After adjusting to 2.6, black crystals were obtained. It was filtered off, washed with hexane and dried at room temperature. The obtained crystals were black, and the yield was 4.6 g. This was designated as HSD-18.

Embodiments 1 to 13 and Comparative Examples 1 to 3
Table 2 summarizes the experimental results.

[0131]

[Table 2]

In the hologram produced by using HSD-18, dyeing due to the triphenylmethane dye remained in the transparent portion, and it was difficult to remove the color.

[Brief description of the drawings]

FIG. 1 is a process chart showing a method for manufacturing a hologram in a first embodiment.

FIG. 2 is an explanatory view showing a method of exposing a hologram photosensitive material according to the first embodiment.

[Explanation of symbols]

 1. . . Hologram photosensitive material, 71. . . Laser light,

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiharu Iinuma 1-1-1, Kamitobakamichocho-cho, Minami-ku, Kyoto Inside Yamada Chemical Industry Co., Ltd. 1 Inside Yamada Chemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A hologram photosensitive agent comprising a hexavalent chromium compound, a triphenylmethane dye and a binder, wherein the triphenylmethane dye has a distribution coefficient of logP ≦ calculated as a dye precursor represented by Chemical Formula 2. 6. A hologram photosensitizer comprising the coloring matter represented by Chemical Formula 1 which is No. 6. Embedded image In “Formula 1”, Y represents a hydrogen atom or an aryl group having a substituent. R1, R2, R3, R4, R5, R
6 represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Z ^- represents an anion. Embedded image In Formula 2, X represents a hydrogen atom or an aryl group having a substituent, and Y represents a hydrogen atom or an aryl group having a substituent. R1, R2, R3, R4, R5, R
6 represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. 2. The following “formula 3” having a distribution coefficient logP ≦ 6.
A method for producing a hologram photosensitizer, comprising subjecting a dye precursor shown in (1) to an acid treatment to prepare a triphenylmethane dye, and then mixing the triphenylmethane dye with a hexavalent chromium compound and a binder. . Embedded image In Chemical Formula 3, X represents a hydrogen atom or an aryl group having a substituent, and Y represents a hydrogen atom or an aryl group having a substituent. R1, R2, R3, R4, R5, R
6 represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. 3. A hologram photosensitive material in which the surface of a transparent member is covered with a photosensitive layer, wherein the photosensitive layer is obtained by applying the hologram photosensitive agent according to claim 1 to the surface of the transparent member and drying it. A hologram photosensitive material, characterized in that: 4. A hologram photosensitive material comprising a transparent member whose surface is covered with a photosensitive layer, wherein the photosensitive layer is formed by applying the hologram photosensitive agent obtained according to claim 2 to the surface of the transparent member and drying the hologram photosensitive material. A hologram photosensitive material, characterized in that: 5. A hologram photosensitive material according to claim 3 or 4, which is irradiated with a laser beam to expose a desired portion of the photosensitive layer.
Next, the hologram photosensitive material is washed to remove a hexavalent chromium compound and a triphenylmethane-based dye from the inside of the photosensitive layer, and then the photosensitive layer is developed. 6. A hologram photosensitive material according to claim 3, which is irradiated with a laser beam to expose a desired portion of said photosensitive layer.
Next, the hologram photosensitive material is washed to remove a hexavalent chromium compound and a triphenylmethane dye from the inside of the photosensitive layer, and then the photosensitive layer is developed.