JP2003082033A - Photosensitive material for relief formation on surface by light irradiation, photosensitive thin film and method for relief formation using the photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material for light surface relief formation which has high sensitivity for more improving relief formation efficiency, forms a relief having thermal stability and stability with time and has chemical stability to various organic solvents and a photosensitive thin film and to provide a method for pattern formation using the photosensitive material. SOLUTION: This azobenzene derivative is represented by general formula (1) (R1 is one kind selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group; R2 and R3 are each H or an alkyl group; n is an integer of >=1; x is a number satisfying 0<x<1). This method for relief formation comprises forming a photosensitive thin film by spin coating method or LB method, irradiating the thin film with light rays including light ray at 365 nm wavelength to form a chemical structure of cis form and irradiating the thin film with fixed light rays.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azobenzene derivative, and in particular, it is suitable as a photosensitive material for forming a light surface relief for forming a relief of a predetermined pattern on the surface only by light irradiation without going through a developing step. Related to namono. Further, the present invention is a thin film material composed of such a photosensitive material for forming a light surface relief, which is a rewritable type for repeatedly writing and erasing information by light irradiation,
Also, the present invention relates to a one-time write type hologram recording that stably holds the recording of information written by light irradiation for a long period of time.

[0002]

2. Description of the Related Art Conventionally, a predetermined pattern is exposed as a photosensitive material (hereinafter, simply referred to as "photosensitive material") for forming a predetermined pattern on a surface only by light irradiation without a developing process. As a result, there is a technique of inducing lateral movement of a film substance in a portion irradiated with light to form a relief on the surface. For example, Na at Queen's University, Canada
Tanshn and Tripathy et al. of the University of Massachusetts in the United States formed a film using a polymer substance having a side chain of azobenzene which is sensitive to light, and irradiating the film with an interference light of an argon ion laser, It is reported that a relief grating (diffraction grating) corresponding to the interference pattern of interference light is formed on the surface. This content is published in the academic journal Appl. Phys. Lett. , 66, 136 (19
95), and Appl. Phys. Lett. , 6
6, 1166 (1995). here,
The “lateral movement” means that a substance moves a distance of several micrometers to several tens of micrometers by energy such as light.

According to this technique, it is possible to form a relief having a regular pattern on the surface of the material only by light irradiation, without going through a developing process. Since the disclosure of this technique, researches for elucidating the mechanism of forming such reliefs and researches for methods for efficiently forming such reliefs have become active. As the photosensitive material capable of forming the relief, poly (4 ′-{[2-
(Acryloyloxy) ethyl] ethylamino} -4-nitroazobenzene, poly (4 '{[2- (acryloyloxy) ethyl] ethylamino-4-nitroazobenzene-co-methylmethacrylate, etc. are known, but these are known. The photosensitive material of is relatively insensitive, and in order to form a relief on the surface of such a photosensitive material,
A large exposure amount of tens of thousands of mJ / cm ² (exposure time: about several tens of minutes) is required, which causes a problem that the relief forming efficiency is low.

In order to solve such a problem, the present inventors have disclosed a photosensitive composition and a thin film having dramatically high sensitivity by mixing a liquid crystal with a polymer substance having an azobenzene skeleton. ing. This content is based on the academic journal Adv. Mater. 12, 1675 (20
00) and Japanese Patent Application No. 2000-297382. According to the photosensitive composition and the thin film,
It becomes possible to form a relief on the surface even by irradiation with light having a relatively low energy level of 100 mJ / cm ² , and a higher relief forming ability can be obtained.

That is, a photosensitive composition and a thin film formed by mixing a liquid crystal with a polymer having an azobenzene skeleton can form a clear relief on the surface even when irradiated with light at a relatively low energy level. As a result, the present invention realizes a photosensitive material having a significantly improved relief forming efficiency. However, since the photosensitive composition and the thin film contain a liquid crystal substance, they are likely to undergo plasticization, and as a result, the relief prepared by irradiation with light can be stably maintained at a relatively high temperature for a long period of time. There was a problem that it was difficult.

As described above, in the conventional photosensitive materials, in general, in order to improve the efficiency of forming relief by light irradiation, in order to promote the lateral movement of the photosensitive material,
Although a polymer material with appropriate flexibility was selected,
As a result, there has been a problem that the long-term stability and thermal stability of the relief are reduced.

On the other hand, in the conventional photosensitive material as described above, in order to sufficiently secure the long-term stability and thermal stability of the relief, the glass transition temperature of the photosensitive material is set relatively high. Therefore, it is necessary to form it to a certain degree of hardness, but it is necessary to be appropriately flexible in order to improve the efficiency of forming relief by light irradiation on the photosensitive material. As described above, the conditions necessary for improving the efficiency of forming a relief upon light irradiation to the photosensitive material and the conditions necessary for sufficiently ensuring the long-term stability and thermal stability of this relief are mutually There was a trade-off relationship.

[0008]

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a high sensitivity for further improving the relief forming efficiency when forming a relief on a photosensitive material by light irradiation. And a photosensitive material and a photosensitive thin film having a relief formed therein which is thermally and temporally stable and chemically stable against various organic solvents, and a pattern forming method using the photosensitive material. To provide.

[0009]

In order to solve the above-mentioned problems, the inventors of the present invention have found that when a photosensitive material is irradiated with light, lateral movement is promoted in the light-irradiated portion to form a relief. The present invention was found by discovering a photosensitive material having a characteristic that efficiency is improved and lateral movement is less likely to occur due to the occurrence of appropriate curing in the light-irradiated portion, and the invention is created. Came to.

The inventors of the present invention firstly describe the following photosensitive materials which are softened promptly when the photosensitive material is irradiated with light and are appropriately cured at the stage when the light irradiation is completed. I thought that it was necessary to prepare for such conditions. (Α) It has an azobenzene structure for providing photosensitivity. (Β) It has characteristics as an elastomer at around room temperature so that the photosensitive thin film formed from the photosensitive material is provided with appropriate flexibility so that lateral movement can be promoted with high efficiency by light irradiation. thing. (Γ) Having a functional group capable of forming a physical or chemical crosslinked structure after the photosensitive thin film is irradiated with light to form a relief having a predetermined pattern.

As a result of intensive investigations by the present inventors,
As the photosensitive material satisfying the above conditions (α) to (γ),
A polymer substance composed of a random copolymer of a (meth) acrylic monomer having an azobenzene skeleton and a (meth) acrylic monomer having an oligoethylene oxide is considered, and the present inventors have proposed such a novel polymer substance. I succeeded in synthesizing.

That is, the invention according to claim 1 of the present invention provides an azobenzene derivative represented by the general formula (1).

[0013]

[Chemical 3]

In the formula (1), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, preferably a straight chain or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . Further, n is a number of 1 or more, and x is a number satisfying 0 <x <1.

The invention according to claim 2 of the present invention provides an azobenzene derivative represented by the general formula (2).

[Chemical 4]

In the formula (2), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, and preferably a linear or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . x is a number that satisfies 0 <x <1.

In the present invention, R ₁ in the formulas (1) and (2) does not hinder the photosensitivity of the polymer substance represented by the formula (1) or (2) due to its steric hindrance. There is no particular limitation as long as it is one, and one selected from various alkyl groups, alkoxyl groups, halogenated alkyl groups and halogenated alkoxyl groups can be used. Furthermore, in the present invention, the formula (1)
R ₂ and R ₃ in formula (2) are not particularly limited as long as they do not inhibit the photosensitivity of the polymer represented by formula (1) or (2) due to steric hindrance. , H or various alkyl groups can be used.
The azobenzene derivative represented by the formula (1) or the formula (2) is a novel polymer substance, and includes the photosensitive material for forming a light surface according to the present invention, and lateral movement by various kinds of light irradiation. It is possible to apply to the material using.

Further, the invention according to claim 3 of the present invention provides a photosensitive material for forming a light surface relief, which is composed of the azobenzene derivative according to claim 1 or 2.

According to this structure, the above (α) to
A photosensitive material for forming a light surface relief satisfying the condition (γ) is embodied. That is, this photosensitive material has flexibility near room temperature, and lateral movement is efficiently promoted in the portion irradiated with light, so that the relief forming efficiency is relatively high.

In the formula (1), the site of oligoethylene oxide gives the photosensitive thin film formed from this photosensitive material the property as an elastomer at room temperature, and forms a formalin bridge at the terminal hydroxyl group to form a predetermined pattern. The photosensitive thin film on which the relief having the structure is formed can be fixed. Therefore, the relief thus formed becomes stable with respect to heat, aging and various organic solvents.

Further, the light-surface-relief-forming photosensitive material composed of the azobenzene derivative represented by the formula (2) has a relatively low relief forming efficiency as compared with the azobenzene derivative represented by the formula (1). Therefore, it is possible to increase the dimensional accuracy and further improve the pattern shape accuracy by appropriately lowering the relief formation sensitivity and appropriately lengthening the exposure time. That is, when the light irradiation intensity is the same, the azobenzene derivative represented by the formula (2) has a slower lateral movement speed when the light irradiation intensity is the same, so that the relief with higher dimensional accuracy is obtained. It becomes possible to perform formation. In the present invention, it is also possible to appropriately blend the azobenzene derivative represented by the formula (1) and the azobenzene derivative represented by the formula (2) to appropriately adjust the relief forming sensitivity.

As described above, according to the present invention, a photosensitive thin film formed from this photosensitive material has properties as an elastomer at room temperature by containing an oligoethylene oxide site and appropriately adjusting the length thereof, if necessary. In addition to immobilizing a photosensitive thin film on which a relief having a predetermined pattern structure is formed by forming a formalin crosslink with a hydroxyl group at the terminal, or not containing the site of oligoethylene oxide, the relief formation efficiency is moderate. By reducing the height, relief formation can be performed with higher dimensional accuracy.
The polymer substances represented by the formulas (1) and (2) are completely newly synthesized.

The invention according to claim 4 of the present invention provides a photosensitive thin film formed by using the photosensitive material for forming a light surface relief according to claim 3. With this photosensitive thin film, a relief having stability against the above-mentioned thermal, aging and various organic solvents can be efficiently formed.

Further, the invention according to claim 4 of the present invention is a pattern forming method using the photosensitive material for forming an optical surface relief according to claim 3, wherein (A1) the photosensitive material for forming an optical surface relief. Dissolve the conductive material in a predetermined organic solvent,
A step of preparing a solution of a photosensitive material, applying the solution of the photosensitive material onto a predetermined substrate by a spin coating method to form a coating film of the photosensitive material, and (A2) forming the coating film. A step of irradiating the substrate with light of a predetermined wavelength to perform a pretreatment for interference exposure; and a step (A3) of performing the interference exposure on the pretreated substrate through a mask having a predetermined pattern. It is characterized by including.

Further, the invention according to claim 5 of the present invention is a pattern forming method using the photosensitive material for forming an optical surface relief according to claim 3, wherein (B1) the predetermined liquid surface is formed on the surface of the liquid. By forming a floating monolayer of a photosensitive material for forming a light surface relief, and transferring the floating monolayer to a predetermined substrate to form a highly ordered monolayer on this substrate by the Langmuir-Blodgett film forming method, A step of forming a monomolecular film of a photosensitive material; (B2) a step of irradiating the substrate having the coating film formed thereon with light of a predetermined wavelength to perform a pretreatment for interference exposure; and (B3) the pretreatment And a step of performing interference exposure on the substrate subjected to the treatment through a mask having a predetermined pattern.

When a pattern is formed on the light surface relief forming material according to the present invention by using such a pattern forming method, a relief having stability to the above-mentioned thermal, aging and various organic solvents is formed. Since the photosensitive thin film that can be formed is formed to have a desired film thickness and film quality, it becomes possible to optimize the relief forming conditions of the material for forming a light surface relief, thereby improving the relief forming efficiency. It can be improved as much as possible.

The invention according to claim 6 of the present invention is
An elastomer composed of the azobenzene derivative according to claim 1 or 2 is provided. According to this structure, it is possible to realize a novel elastomer which is composed of the azobenzene derivative and has the above-mentioned effects.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described in detail. The photosensitive material for forming a light surface relief (azobenzene derivative) according to the present invention is a novel polymer containing an azobenzene skeleton represented by the general formula (1) or (2) and oligoethylene oxide. It is a substance. Incidentally, these photosensitive materials for forming a light surface relief are those in which the structure represented by the formula (1) or the formula (2) is identified by ¹ H-NMR measurement described later.

[0029]

[Chemical 5]

In the formula (1), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, and preferably a linear or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . Further, n is a number of 1 or more, and x is a number satisfying 0 <x <1.

[0031]

[Chemical 6]

In the formula (2), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, and preferably a linear or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . x is a number that satisfies 0 <x <1.

(Mass Average Molecular Weight Mw) The mass average molecular weight Mw of the photosensitive material (azobenzene derivative) for forming a light surface relief according to the present invention is not particularly limited as long as the effects of the present invention can be obtained. , Practically, 5.
It is preferably in the range of 0 × 10 ^{3 to} 1.0 × 10 ⁵ . That is, when the mass average molecular weight Mw is less than 5.0 × 10 ³ , it tends to be plasticized and it becomes difficult to stably maintain the relief structure. Moreover, Mw is 1.0 × 10 ^5.
Since the efficiency of the lateral movement due to the irradiation of light exceeding the above is significantly reduced, it becomes difficult to form the relief.

(Number Average Molecular Weight Mn) The mass average molecular weight Mn of the photosensitive material (azobenzene derivative) for forming a light surface relief according to the present invention is not particularly limited as long as the effects of the present invention can be obtained. , Practically 3.0
It is preferably in the range of × 10 ^{3 to} 7.0 × 10 ⁴ . That is, the mass average molecular weight Mn is 3.0 × 10
^If it is less than ³ , it tends to be plasticized and it becomes difficult to stably maintain the relief structure. Moreover, Mn is 7.0 × 10.
^When it exceeds ⁴ , the efficiency of lateral movement due to light irradiation is significantly reduced.

(Structural Formula of Substituent) In the photosensitive material (azobenzene derivative) for forming a light surface relief according to the present invention, the substituent R contained in the general formula (1) or the general formula (2), respectively. _1, R ₂ is still more preferably selected from the following substituent R ₁ shown in Table 1, the R ₂ various combinations. The reason is that the photosensitive material for forming a light surface relief (azobenzene derivative) according to the present invention exhibits appropriate phase transition behavior depending on the various substituents R ₁ and R ₂ shown in Table 1. This is because it is expressed. Therefore, depending on the phase transition behavior as shown in Table 1, the substituent R ₁ ,
The combination of R ₂ can be appropriately selected. In addition,
In the present invention, the substituent R ₃ is the above-mentioned substituents R ₁ , R ₂
It is appropriately determined as necessary regardless of the combination of.

[0036]

[Chemical 7]

In the formula (1), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, and preferably a linear or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . Further, n is a number of 1 or more, and x is a number satisfying 0 <x <1.

[0038]

[Chemical 8]

In the formula (2), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, preferably a straight chain or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . x is a number that satisfies 0 <x <1.

[0040]

[Table 1]

(Synthesis Method of Photosensitive Material for Forming Optical Surface Relief (Azobenzene Derivative)) The method for synthesizing the photosensitive material for forming optical surface relief according to the present invention is not particularly limited, and the effects of the present invention can be obtained. Various synthesis methods can be applied as long as they can be reproduced. That is, the photosensitive material for forming an optical surface relief according to the present invention, which is represented by the general formula (1) in FIG. 1, can be synthesized as follows according to the flow of the example shown in FIG.

First, in the example flow shown in FIG.
A method for synthesizing (4′-R ₁ -phenylazo) -phenol (Compound 1) will be described (the substituent R ₁ is an alkyl group or an alkoxy group). As a starting material, a predetermined amount of p-R ₁ aniline is weighed, hydrochloric acid is added to this, and the mixture is stirred with moderate heating to prepare a p-R ₁ aniline hydrochloride solution. After that, the solution is cooled, and an aqueous solution of sodium nitrite having a predetermined concentration is added dropwise to the p-
The diazonium salt of R ₁ aniline is synthesized.

Separately from this, a mixed solution is prepared by adding sodium carbonate as a buffer solution to a mixed solution of sodium hydroxide and phenol. While stirring this mixed solution, the diazonium salt of p-R ₁ aniline was added at 0 ° C., and this was thoroughly stirred. Then, this solution is neutralized with hydrochloric acid, and then this solution is filtered to collect a precipitate. Subsequently, the precipitate was dissolved in ethyl acetate, washed with water, an aqueous solution of sodium hydrogen carbonate, a saturated sodium chloride solution, concentrated, and recrystallized using a low-polarity organic solvent such as hexane. The compound 1 shown in FIG. 1 with the required purity is obtained.

Next, the 4- (4'-R ₁ -phenylazo) -phenoxy compound (Compound 2) shown in FIG. 1 is synthesized (the substituent R ₁ is an alkyl group or an alkoxy group). A predetermined amount of the compound 1 is weighed, and dehydrated acetone is added thereto. Subsequently, a predetermined amount of potassium carbonate is added to this solution, and subsequently a catalytic amount of potassium iodide is added. This is heated to 60 ° C. for 24 hours while stirring. Then, chloroform was added to this, and this was washed with water, an aqueous solution of sodium hydrogencarbonate and a saturated sodium chloride solution, concentrated, and recrystallized with hexane.
The compound 2 shown in FIG. 1 with the required purity is obtained.

Next, the acrylate-based azobenzene monomer (compound 3) shown in FIG. 1 is synthesized. A predetermined amount of the compound 2 is weighed, and dehydrated tetrahydrofuran is added thereto. Separately from this, a predetermined acrylate-based acid chloride (containing a substituent R ₃ ) was weighed in an equimolar number with the compound 2, and triethylamine or the like as an acid trap was added to the acrylate-based acid chloride. 1.5
About 2 times the amount is added, and the tetrahydrofuran solution of the compound 2 is added dropwise thereto at ice temperature. Then, after sufficiently stirring under ice temperature, the temperature is returned to room temperature, and further stirred sufficiently. Then, this was washed with water, an aqueous solution of sodium hydrogencarbonate and a saturated solution of sodium chloride, concentrated, and recrystallized with methanol to give compound 2 shown in FIG.
Is obtained in high purity.

Next, the copolymer shown in FIG. 1: [4, (4 '
R ₁ -Phenylazo) -phenoxy] -decyl R ₃ acrylate / ω-alkoxy (including the substituent R ₂ ) oligo (ethylene oxide) methacrylate is synthesized. A predetermined amount of the compound 3 was weighed and charged into a polymerization tube, and a mixed solvent of tetrahydrofuran (THF) and benzene (mass ratio 1:
4) is added to the polymerization tube and stirred sufficiently. The mixed solvent may be a mixed solvent of benzene and dioxane. Further, a predetermined methacrylate monomer having an oligoethylene oxide site in this solution (containing a substituent R ₂ , for example, trade name of NOF CORPORATION; Blemmer PE200, Blemmer AE20)
0) and stir.

Further, a predetermined amount of 2,2-azobisisobutyronitrile (AIBN) is added as a polymerization initiator. The mixed solution thus prepared is deaerated by appropriately repeating freezing and evacuation, the polymerization tube is sealed, and the polymerization tube is vibrated at 70 ° C. for about 30 hours to polymerize the compound 3. Let Then, the polymerization tube is released to the atmosphere,
The polymerized product thus obtained is reprecipitated a predetermined number of times using ethanol to obtain a polymer substance represented by the general formula (1) which is an elastomeric product. Although the method of synthesizing the polymer represented by the general formula (1) shown in FIG. 1 has been described here, the present invention is not limited to this synthesizing method.

The photosensitive material for forming a light surface relief according to the present invention represented by the general formula (2) is, for example,
In the method of synthesizing the photosensitive material for forming a light surface relief according to the present invention represented by the general formula (1) (see FIG. 1), a methacrylate-based compound having an oligoethylene oxide moiety to be reacted with an acrylate-based azobenzene monomer (compound 3). Instead of the monomer, the methacrylic acid monomer which is a monomer not containing the oligoethylene oxide can be used for the synthesis.

(Method of Forming Relief Having Predetermined Pattern) A method of forming a relief having a predetermined pattern using the photosensitive material for forming a light surface relief according to the present invention will be described. In the following, the optical surface relief is referred to as “SRG (Sur
face relief grating: surface relief grating) ”. First, the SR according to the present invention
A predetermined polymer thin film is formed on a glass substrate using the G-forming photosensitive material. The following two methods can be used as a method for producing this polymer thin film.

(C1) An azobenzene polymer / cyclohexanone solution in which a predetermined concentration of azobenzene polymer is dissolved in a cyclohexanone solvent is prepared, and a polymer thin film is formed on a glass substrate by a conventionally known spin coating method. (C2) Conventionally known Langmuir Blodgett (L
B: Langmuir-Blodgett) method,
A multilayer LB film is formed on a glass substrate. The LB film can be formed as follows. First, add azobenzene polymer to 1.0 × 10 per azobenzene unit.
^An azobenzene polymer solution is prepared by dissolving it in chloroform at a concentration of ³ M, and this solution is spread on the water surface filled in a conventionally known LB film forming apparatus. The monomolecular film of azobenzene polymer on the water surface formed by this operation is compressed to a predetermined area, and the glass substrate is reciprocated so as to cross the water surface. At this time, when the glass substrate is reciprocated once on the water surface, two layers of the monomolecular film are formed on the surface of the glass substrate. By repeating this operation, the LB film of the azobenzene polymer can be laminated in a desired number of layers on the surface of the glass substrate. The normal LB film is made by reciprocating the glass substrate about 5 to 100 times on the water surface to obtain about 10
Up to 200 layers.

The SRG-forming thin film according to the present invention formed on the glass substrate as described above is irradiated with ultraviolet rays (light rays including light having a wavelength of 365 nm) irradiated from a mercury lamp or the like.
By irradiating with, the molecular structure of the SRG forming thin film is in a state in which there are many cis types. The reason why the molecular structure of the SRG-forming thin film has a large cis type structure is that the absorption intensity in the photosensitive region of the argon ion laser increases and that the film is plasticized and mass transfer is easily induced. is there.

After that, the interference light of the ultraviolet rays is generated by an optical device of an example as shown in FIG. 3, and the thin film for SRG formation is subjected to interference exposure processing. FIG. 3 shows an optical device that uses an Ar ion laser (wavelength: 458 nm) as a light source to irradiate light on a thin film for SRG formation formed on the glass substrate to perform exposure processing. Interference exposure processing or exposure processing through a photomask having a predetermined pattern. In the photosensitive material according to the present invention, the wavelength range capable of inducing mass transfer is 400 to 520n.
m.

When the SRG-forming thin film formed on the glass substrate is exposed by using the optical device as shown in FIG. 3, the SRG-forming thin film according to the present invention formed on the glass substrate is exposed. On the surface, where the light irradiation intensity is relatively high, the formation of a cross-linking structure due to a photochemical reaction is further promoted and volume contraction occurs, which causes the light irradiation intensity to be changed from the site where the light irradiation intensity is relatively weak. Lateral movement of the SRG forming thin film is caused toward a relatively strong portion, and a relief structure having a pattern corresponding to the intensity distribution of the interference light of the irradiated ultraviolet rays is formed.

Further, in the optical device as shown in FIG. 3, the SRG forming thin film formed on the glass substrate is exposed to ultraviolet rays through a photomask having a predetermined pattern without generating the interference light of the ultraviolet rays. When the pattern exposure treatment is performed by the method described above, the formation of the cross-linking structure by the photochemical reaction is further promoted at the site where the light is irradiated on the SRG forming thin film through the pattern of the photomask to cause volume contraction, and the light is irradiated by the light. Lateral movement of the SRG-forming thin film occurs from the unexposed portion to the portion irradiated with light. As a result, a relief structure having a pattern corresponding to the intensity distribution of the irradiated interference light of the ultraviolet rays is formed.

[0055]

EXAMPLES The photosensitive material and the photosensitive thin film for forming a light surface relief according to the present invention, and the relief forming method using the photosensitive material will be described in more detail with reference to the following examples.

(Synthesis Method of Sample) According to the flow shown in FIG. 1, R ₁ of the formula (1) is —C ₆ as a photosensitive material (azobenzene derivative) for forming a light surface relief according to the present invention.
_{H 13, -C 8 H 17,} CH 3, R 2 is _{H, CH 3, C 2 H} 5, R
Samples in which ₃ is H, CH ₃ , C ₂ H ₅ and R in formula (2)
₁ is _{-C 6 H 13, -C 8 H} 17, CH 3, R 2 is H, CH _3, C
Samples of ₂ H ₅ , R ₃ of H, CH ₃ , and C ₂ H ₅ were synthesized. Of these samples, here, 6Az10 shown in FIG.
The specific synthesis of the azobenzene derivative of -PEn will be described.

In the example flow shown in FIG. 2, first, 4- (4
′ -Hexyl-phenylazo) -phenol (Compound 1
1) was synthesized. 25 g (0.14 mol) of p-hexylaniline as a starting material was weighed and put in a 200 ml eggplant-shaped flask, hydrochloric acid was added thereto, and the mixture was stirred with gentle heating to give a mixed solution of p-hexylaniline hydrochloride. Prepared. Then, this mixed solution of p-hexylaniline hydrochloride was cooled to 4 ° C. or lower in an ice bath. On the other hand, separately from this, sodium nitrite 20.7g (0.3mo
1) was weighed and an aqueous sodium nitrite solution was prepared using an Erlenmeyer flask. This aqueous sodium nitrite solution was added dropwise to the cooled mixed solution to synthesize a diazonium salt of p-hexylaniline.

Separately from this, an aqueous solution of sodium hydroxide (containing 0.5 mol of sodium hydroxide in total) and 28.2 g (0.3 mol) of phenol were placed in a three-necked flask, stirred and buffered. A mixed solution was prepared by adding an aqueous solution of sodium carbonate as a solution. At this time,
A thermometer and a mechanical stirrer were attached to the three-necked flask, and the mixture was stirred in an ice bath. Then, while stirring this mixed solution, ice was added as necessary to maintain the temperature at 4 ° C., the diazonium salt of p-hexylaniline was gradually added dropwise, and after completion of the addition, a further 2 minutes in an ice bath. Stir for hours.

Then, at room temperature, TLC (Thin
The mixture was stirred for 3 hours while following the progress of the reaction by Layer Chromatography (thin layer chromatography). After completion of the reaction, this solution was gradually neutralized with 2 N hydrochloric acid while suppressing the heat generation, and then the solution was filtered to remove the filtrate. Subsequently, the solid obtained by this filtration was dissolved in ethyl acetate, washed successively with water, an aqueous sodium hydrogen carbonate solution and a saturated sodium chloride solution, and the solid obtained by concentrating it with a rotary evaporator was reconstituted with hexane. Crystallization gave the compound 11 shown in FIG.

Compound 11 thus synthesized
The yield was 87% and the melting point was 70-71 ° C.
Further, when ¹ H-NMR of this compound 1 was measured,
The following peaks were measured and the chemical formula was determined.
0.89 (3H, t, J = 6Hz, -CH 3), 1.3
_{2~1.68 (8H, m, -CH 2} -), 5.31 (1
H, m, Ar-OH), 2.67 (2H, t, J = 8H
_{z, Ar-CH 2 -)} , 6.93 (2H, d, J = 9H
z, ArH), 7.30 (2H, d, J = 9Hz, Ar
H), 7.79 (2H, d, J = 8Hz, ArH),
7.86 (2H, d, J = 9Hz, ArH) (δ: pp
m, 200 MHz, CDCl ₃ solvent)

Next, 4- (4'-hexyl-phenylazo) -phenoxy (Compound 12) shown in FIG. 2 was synthesized. 4.03 g (14.3 mmol) of the compound 11
Compound 1 was weighed and added with dehydrated acetone.
An acetone solution of 1 was prepared. Subsequently, 6.0 g (43.4 mmol) of potassium carbonate was added to this acetone solution, and then a small amount of potassium iodide was added as a catalyst.
Then, this solution was transferred to a three-necked flask equipped with a reflux condenser and heated at 60 ° C. for 24 hours while stirring. Then add chloroform to this solution,
Further, the solid obtained by successively washing with water, an aqueous solution of sodium hydrogencarbonate and a saturated sodium chloride solution and concentrating with a rotary evaporator was recrystallized with hexane to obtain the compound 12 shown in FIG.

Compound 12 thus synthesized
The yield was 96% and the melting point was 77-78 ° C.
Moreover, when ¹ H-NMR of this compound 2 was measured,
The following peaks were measured and the chemical formula was determined.
_{0.887 (3H, t, -CH 3} ), 1.23~1.8
_{5 (27H, m, -CH 2} -), 2.67 (2H, t,
_{-CH 2 -Ph), 3.64 (2H} , t, -CH 2 -O
-), 4.04 (2H, t , -O-CH 2 -), 6.9
9 (2H, d, J = 9.0 Hz, ArH), 7.29
(2H, d, J = 8.8Hz, ArH), 7.79-
7.91 (4H, q, J = 8.2, 9.0Hz, Ar
H) (δ: ppm, 200 MHz, CDCl ₃ solvent)

Next, the acrylate-based azobenzene monomer (compound 13) shown in FIG. 2 was synthesized. Compound 2
Was weighed and 8.06 g (18.4 mmol) was weighed, and dehydrated tetrahydrofuran (THF) was added thereto to prepare a THF solution of compound 3. Separately from this, 1.67 g (18.4 mmol) of acrylic acid chloride was weighed, and 5.58 g (55.2 m) of triethylamine was weighed.
mol), and a THF solution of the compound 12 was added dropwise in an ice bath over 1 hour. After completion of the dropwise addition, the mixture was sufficiently stirred in an ice bath for 2 hours, and further stirred at room temperature for 3 hours while tracking the progress of the reaction by TLC (thin layer chromatography). After completion of the reaction, this was washed successively with water, an aqueous sodium hydrogen carbonate solution and a saturated sodium chloride solution, and subsequently, the solid obtained by concentrating with a rotary evaporator was recrystallized with methanol to give compound 13 shown in FIG.
was gotten.

Compound 13 thus synthesized
The yield was 86.6% and the melting point was 77-79 ° C. When ¹ H-NMR of this compound 3 was measured, the following peaks were measured and the chemical formula was determined. _{0.886 (3H, t, -CH 3} ), 1.34~
_{1.95 (24H, m, -CH 2} -), 2.68 (2
_{H, t, -CH 2 -Ph)} , 4.02 (2H, t, -C
_{H 2 -O -), 4.15 (} 2H, t, -O-CH 2 -),
5.78 (1H, dd, J = 12, 1.6Hz, Vin
yl-H), 5.83 to 6.10 (1H, dd, J = 1)
8, 8.8 Hz, ArH), 6.99 (2H, d, J =
9 Hz, ArH), 7.29 (2H, d, J = 9 Hz,
ArH), 8.84 (4H, q, J = 9Hz) (δ: p
pm, 200MHz, CDCl ₃ solvent)

Next, the copoly [4, (4'hexyl-phenylazo) -phenoxy] -decyl acrylate / ω-hydroxy oligo (ethylene oxide) methacrylate (6Az10-PEn) shown in FIG. 2 was synthesized. 15.00 g (3.0 mmol) of the compound 13 was weighed and charged into a polymerization tube, and a mixed solvent of tetrahydrofuran (THF) and benzene (mass ratio 1: mass ratio 1:20) so that the mass concentration of the compound 13 was 20%. 4) was added to the polymerization tube and stirred sufficiently.

Further, as the methacrylate type monomer having an oligoethylene oxide site in the polymerization tube, one in which n in the formula (1) is 8 (trade name: Blemmer PE
200, manufactured by NOF CORPORATION, 0.64 g (3.0 mm)
ol) and stirred. Then, as a polymerization initiator,
2,2-azobisisobutyronitrile (AIBN) 2
1 mg was added to prepare a mixed solution. The mixed solution was degassed by repeating freezing and evacuation, and then the polymerization tube was sealed. Then, keep the polymerization tube at 70 ° C. for 3
The polymerization reaction of the compound 3 was carried out while shaking for 0 hour. Then, the polymerization product obtained by exposing the polymerization tube to the atmosphere was reprecipitated 3 times with ethanol to give a yellow rubber-like product 6Az10-PEn (see FIG. 2).
was gotten.

The above 6Az synthesized in this manner is used.
10-PEn ([4, (4 'hexyl-phenylazo)
The yield of -phenoxy] -decyl acrylate / ω-hydroxy oligo (ethylene oxide) methacrylate was 73%, the mass average molecular weight Mw was 13000, and the number average molecular weight Mn was 10,000. Further, when ¹ H-NMR of 6Az10-PEn was measured, the following peaks were measured and the chemical formula was determined. 0.858-0.983 (3H, bro
_{ad, -CH 3), 0.117~0.147 (} 24H,
_{broad, -CH 2 -), 1.68} (3H, broa
_{d, -CH 3), 2.66 (} 2H, t, -CH 2 -P
h), 3.66 (4H, broad , -CH 2 -CH 2 -
O -), 4.11 (2H, broad, -CH 2 -O
-), 6.99 (2H, d, J = 9Hz, ArH),
7.28 (2H, d, J = 9Hz, ArH), 8.84
(4H, q, J = 9Hz, ArH) (δ: ppm, 20
0MHz, CDCl ₃ solvent)

(Method for Forming Photosensitive Thin Film for Forming Optical Surface Relief) Next, a method for forming the photosensitive thin film for forming optical surface relief according to the present invention will be described. In the method of forming the photosensitive thin film for forming a light surface relief according to the present invention, a conventionally known spin coating method can be used when the uniformity of the film thickness and the economical efficiency are harmonized. That is, an azobenzene derivative represented by the general formula (1) or the general formula (2) is dissolved in a predetermined solvent to prepare a solution having a predetermined concentration and viscosity, and this solution is supplied in a predetermined amount at a predetermined rotation speed. By dropping on a rotating substrate, it is possible to relatively easily form the photosensitive thin film for forming a light surface relief according to the present invention having a predetermined film thickness. The predetermined solvent can be used as long as it is a solvent other than alcohols and saturated hydrocarbons (hexane and the like), but solvents such as cyclohexanone, cyclopentanone, benzene, toluene, chloroform, tetrahydrofuran and dioxane, or these It is preferable to use a mixed solvent. Of these, a particularly preferred solvent is cyclohexanone.

[0069]

[Chemical 9]

In the formula (1), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, and preferably a linear or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . Further, n is a number of 1 or more, and x is a number satisfying 0 <x <1.

[0071]

[Chemical 10]

In the formula (2), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, and preferably a linear or branched chain. C ₁ is a ~C _12. R ₂ and R ₃ are each independently H or an alkyl group, and preferably linear or branched C _{1 to} C ₄ . x is a number that satisfies 0 <x <1.

Further, in the method for forming a photosensitive thin film for forming a light surface relief according to the present invention, when it is desired to further enhance the uniformity of the film thickness and the uniformity of the film quality, a conventionally known Langmuir Blodgett ( The LB) method can be applied.
Here, the LB film was formed by using the following method. First, an azobenzene polymer is dissolved in chloroform at a concentration of 1.0 × 10 ³ M per azobenzene unit to prepare an azobenzene polymer solution, and this solution is spread on a water surface filled in a conventionally known LB film forming apparatus. It was The azobenzene polymer monomolecular film on the water surface formed by this operation was compressed to a predetermined area, and the glass substrate was reciprocated 50 times across the water surface to form about 100 layers of LB film. When the film thickness distribution of the LB film formed in this way was measured, the variation in film thickness was ± 1%.
It was found to be below, and the film thickness uniformity was good.

(Pretreatment of Interference Exposure) In the present invention,
In order to increase the photosensitivity and improve the relief formation efficiency, it is preferable to perform a pretreatment before the interference exposure treatment on the thin film formed of the photosensitive material for forming the optical surface relief. That is, this pretreatment is performed on the thin film of the photosensitive material for forming the optical surface relief formed as described above with a wavelength of 36.
By irradiating with light containing 5 nm ultraviolet light, the thin film contains a larger amount of one having a cis structure, and the photosensitivity of the thin film is further enhanced.

Next, a predetermined relief structure was formed using the SRG forming thin film according to the present invention, and the relief structure was evaluated. First, a SRG forming thin film was formed on a glass substrate by a conventionally known spin coating method. Next, the entire surface of the SRG thin film-forming thin film is irradiated with ultraviolet rays (including light having a wavelength of 365 nm) emitted from a mercury lamp or the like so that the structure of the SRG thin film-forming thin film includes a large amount of cis type. Formed. After that, an interference light (wavelength: 458 nm, output: 40) of an argon ion laser is applied to the SRG forming thin film by using an optical device as shown in FIG.
mW / cm ² ) at an incident angle of 7 ° (period: 2 μm),
Interference exposure processing was performed by irradiating at 3.5 ° (cycle; 4 μm) for 5 seconds. As a result, a relief structure having a pattern corresponding to the intensity distribution of the irradiated interference light of the ultraviolet rays was obtained.

(Evaluation of Light Surface Relief Forming Ability) The relief forming ability of the photosensitive material for light surface relief forming according to the present invention formed as described above was evaluated as follows. That is, using the optical device as shown in FIG. 4, the relief structure of the photosensitive material for forming the optical surface relief formed as described above is irradiated with He—Ne laser light (wavelength: 632.8 nm). The intensity of the first-order diffracted light of this relief structure was measured. Then, the diffraction efficiency of the intensity of this first-order diffracted light was calculated using the following formula (I). The exposure conditions at this time were an exposure time of 5 seconds and an exposure light intensity of about 200 mJ / cm ² .

Η = I _t / I ₀ (I) In the formula (I), I _t is the intensity of the first-order diffracted light of the relief structure, and I ₀ is the intensity of light incident on the SRG-forming thin film. is there. The results are shown in Table 1. Further, FIG. 5 shows an AFM (Atomic Force Mi) of the relief structure of the SRG forming thin film thus formed.
It is a figure which shows the uneven | corrugated pattern of the relief structure in the photosensitive material for optical surface relief formation measured using croscope: atomic force microscope. In FIG. 5, the horizontal axis represents the distance in the horizontal direction, and the vertical axis represents the distance in the depth direction. As is clear from the results shown in FIG. 5, the photosensitive material for forming an optical surface relief according to the present invention has a sharp cross-sectional shape.

[0078]

[Table 2]

As shown in Table 2, the SRG-forming thin film according to the present invention has a thickness of ^{2 to 8 even with} a very small exposure amount of about 200 mJ / cm ^{2 in} a relatively short time of 5 seconds. It can be seen that it has a first-order diffracted light efficiency of%. Further, as shown in FIG. 5, the SR according to the present invention
It can be seen that the relief structure formed on the G forming thin film has a clear sine curve pattern. Figure 5
Then, although only the result of 6Az10-PEn shown in FIG. 2 has been described, R _{1 of the} formula (1), which is another photosensitive material (azobenzene derivative) for forming a light surface relief according to the present invention, is CH ₃ , Each sample in which R ₂ is H, CH ₃ , C ₂ H ₅ , R ₃ is H, CH ₃ , C ₂ H ₅ , and R _{1 in the} formula (2) is —C ₆ H ₁₃ , R ₂ is H, CH ₃ , C ₂ H ₅ , R ₃ is H, C
Similar results were obtained with each of the H ₃ and C ₂ H ₅ samples.

Further, the SRG-forming thin film according to the present invention having the relief structure thus produced was left in a dark room, and the stability of the relief structure was investigated. As a result, it was confirmed that the relief structure formed by such an exposure process was retained as it was for one month or more in a dark room.

On the other hand, when the SRG-forming thin film according to the present invention having the above-mentioned relief structure thus produced is irradiated with ultraviolet rays or heated to a temperature higher than the phase transition temperature to the isotropic phase, the surface is The relief structure disappears and therefore the efficiency of the first order diffracted light is also reduced to 0%. That is, as described above, the thin film for SRG formation having the relief structure according to the present invention is irradiated with ultraviolet rays, or
By heating above the phase transition temperature to the isotropic phase, the relief structure can be completely extinguished, and the original plane can be regenerated.

As described above, in the SRG-forming thin film according to the present invention, the relief structure is formed on the surface by irradiating the ultraviolet rays to expose the predetermined pattern, and the SRG-forming thin film is formed in this way. The relief structure is
Since it can be completely erased by irradiation with ultraviolet rays or heating at a temperature higher than the phase transition temperature to the isotropic phase, writing and erasing of a relief structure having a predetermined pattern can be repeated.

Finally, the S according to the present invention is thus obtained.
A method of immobilizing the relief structure having a predetermined pattern formed on the RG forming thin film in order to stably hold the relief structure for a relatively long period of time will be described. S according to the present invention
As one of the methods for fixing the relief structure having a predetermined pattern formed on the RG forming thin film, the SRG according to the present invention
A method of forming a crosslinked structure by acetalization in steam using the OH group of the terminal structure of oligooxyethylene contained in the forming material can be mentioned. This method is specifically performed as follows.

First, 6 N hydrochloric acid aqueous solution and formalin (30%, formaldehyde aqueous solution) are filled in predetermined containers. Meanwhile, the glass substrate on which the SRG-forming thin film according to the present invention is formed is placed on a predetermined table.
The predetermined container and the glass substrate are set in, for example, a reaction tank as shown in FIG. 6, and the reaction tank is closed. Then, the inside of the reaction vessel is maintained at a predetermined temperature, and the 6N hydrochloric acid aqueous solution and formalin (30
%, Formaldehyde aqueous solution) and the acetalization reaction of the SRG forming thin film is performed for a predetermined time. The reaction formula of this acetalization reaction is shown in the following reaction formula (3).

[0085]

[Chemical 11]

After that, the SRG-forming thin film thus treated with acetal is washed with water. By doing so, the relief structure formed on the SRG-forming thin film according to the present invention is fixed, and the structure is stably maintained for a long period of time. By cross-linking the SRG-forming thin film according to the present invention having the relief structure formed in this manner, the relief structure can be stably maintained even at a high temperature of 250 ° C.

Although 6Az10-PEn shown in FIG. 2 has been described as an example, the present invention is not limited to this example, and the general formula (1) and the general formula ( Applies to all polymeric substances represented by 2).

[0088]

According to the present invention constituted as described above, a photo-surface composed of a novel polymer material containing an azobenzene structure having photosensitivity and an oligoethylene oxide moiety which gives elastomeric properties at room temperature is obtained. Provided are a photosensitive material for forming a relief, a photosensitive thin film using the photosensitive material, and a relief forming method using the photosensitive material.

In the light-sensitive material for forming a light surface relief according to the present invention as described above, since the lateral movement is efficiently promoted by the light irradiation, the desired material can be obtained only by the light irradiation without the development treatment. It is possible to efficiently form the pattern. Furthermore, the relief thus formed has stability over time.

The photosensitive material for forming a light surface relief according to the present invention comprises a photosensitive material formed from this photosensitive material, if necessary, containing an oligoethylene oxide site and appropriately adjusting the length thereof. It imparts the properties of an elastic thin film at room temperature as an elastomer and immobilizes a photosensitive thin film on which a relief having a predetermined pattern structure is formed by forming a formalin bridge with a hydroxyl group at the terminal, or containing a site of oligoethylene oxide. Instead, the relief forming efficiency can be appropriately lowered, and the relief can be formed with higher dimensional accuracy.

Furthermore, in the above-mentioned photosensitive material for forming a light surface relief according to the present invention, the structure of the relief having a predetermined pattern structure is fixed by forming a formalin bridge with a hydroxyl group provided at the end of the chemical structure. You can
The relief thus formed is stable with respect to heat, aging and various organic solvents.

A photosensitive thin film using the photosensitive material for forming a light surface relief according to the present invention can be repeatedly written and erased by a photochemical reaction by the relief forming method according to the present invention. Rewritable holograms (before the crosslinking treatment) or single write-in type holograms (after the crosslinking treatment) that can stably retain a predetermined relief structure for a long period of time by immobilizing the reliefs. A recording material can be provided.

The photosensitive material for forming a light surface relief according to the present invention is a holographic image, a phase mask for modulating the light intensity, a polarization orientation identification element, a liquid crystal alignment film, an alignment polymer. The present invention can be applied to various types of light-using components such as a film and a waveguide coupler (light introducing portion, light outputting portion).

[Brief description of drawings]

FIG. 1 is an example flow for synthesizing a photosensitive material for forming a light surface relief according to the present invention.

FIG. 2 is a flow of synthesizing a photosensitive material (6Az10-PEn) for forming a light surface relief that is an example of the present invention.

FIG. 3 is a schematic view of an example of an optical device used for irradiating a thin film of a photosensitive material for forming a light surface relief according to the present invention with light to perform an exposure process.

FIG. 4 is a schematic view of an optical device used for evaluating the efficiency of first-order diffracted light of a relief structure formed on a thin film of a light-sensitive material for forming an optical surface relief according to the present invention.

FIG. 5 shows an AFM (A) for a relief structure formed on a thin film of a photosensitive material for forming an optical surface relief according to the present invention.
It is a graph which shows the measurement result of the uneven | corrugated pattern of the relief structure obtained by the atomic force microscope (atomic force microscope).

FIG. 6 is a schematic view of an example of a reaction tank used for applying an acetalization treatment to the light surface type positive photosensitive material according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/004 521 G03F 7/004 521 G03H 1/02 G03H 1/02 (72) Inventor Kozu Nobuyuki Kanagawa 4259 Nagatsuta-cho, Midori-ku, Yokohama-shi, Tokyo (72) Inventor Shun Satoshi Ikata 47-11 Matsufudai, Aoba-ku, Yokohama-shi, Kanagawa F-term (reference) 2H025 AA01 AB20 AC01 BH05 FA03 2K008 AA04 BB01 BB04 DD12 DD14 FF13 HH06 HH18 HH25 4J027 AC03 AJ02 BA13 CB09 CD10 4J100 AL08P AL08Q BA02Q BA03P BA08P BA45Q BC43Q DA61 JA38

Claims (7)

[Claims] 1. A compound represented by the general formula (1): (In the formula (1), R ₁ is _one selected from an alkyl group, an alkoxy group, a halogenated alkyl group and a halogenated alkoxy group, and R ₂ and R ₃ are independently H or an alkyl group. Where n is a number greater than or equal to 1 and x is 0
It is a number that satisfies <x <1. ) An azobenzene derivative represented by. 2. A general formula (2): (In the formula (2), R ₁ is one kind selected from an alkyl group, an alkoxy group, a halogenated alkyl group, and a halogenated alkoxy group, and R ₂ and R ₃ are independently H.
Alternatively, it is an alkyl group, and x is a number satisfying 0 <x <1. ) An azobenzene derivative represented by. 3. A photosensitive material for forming a light surface relief, which is composed of the azobenzene derivative according to claim 1 or 2. 4. A photosensitive thin film formed using the photosensitive material for forming a light surface relief according to claim 3. 5. A method of forming a relief having a predetermined pattern by using the photosensitive material for forming a light surface relief according to claim 3, wherein (A1) the photosensitive material for forming a light surface relief is formed into a predetermined shape. A step of preparing a solution of a photosensitive material by dissolving it in an organic solvent, applying the solution of the photosensitive material onto a predetermined substrate by a spin coating method to form a coating film of the photosensitive material, (A2) Irradiating the substrate on which the coating film is formed with light of a predetermined wavelength to perform a pretreatment of interference exposure; and (A3) the pretreated substrate,
A step of performing interference exposure through a mask having a predetermined pattern, and a relief forming method using a photosensitive material for forming a light surface relief. 6. A method for forming a relief having a predetermined pattern by using the photosensitive material for forming a light surface relief according to claim 3, wherein (B1) the photosensitive material for forming a light surface relief is formed on a predetermined liquid surface. Of a photosensitive material by a Langmuir-Blodgett film formation method in which a floating monolayer of a photosensitive material is formed, and the floating monolayer is transferred to a predetermined substrate to form a highly ordered monolayer on the substrate. A step of forming a film, and (B2) a step of irradiating the substrate on which the coating film is formed with light of a predetermined wavelength to perform pretreatment of interference exposure,
(B3) a step of subjecting the pretreated substrate to interference exposure through a mask having a predetermined pattern, and a relief forming method using a photosensitive material for forming an optical surface relief. . 7. An elastomer composed of the azobenzene derivative according to claim 1 or 2.