JP2008280255A - Refractive index-converting material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a refractive index-converting material which provides a large variation of the refractive index and can form a film with ease. <P>SOLUTION: The refractive index-converting material is produced by linking a calixarene trimer compound obtained by reacting resorcinol with 1,5-pentanedial, with a compound represented by formulas (a), (b), (c), (d) or (e) by using chlorovaleric acid chloride as a linker. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a refractive index conversion material.

Norbornadiene (hereinafter also referred to as “NBD”) undergoes photovalence isomerization to a quadricyclane having a low polarizability (hereinafter also referred to as “QC”) by irradiation with ultraviolet rays, A compound having an NBD structure is a light-heat energy conversion storage material that converts light energy into heat energy and accumulates it because it has the property of isomerizing to NBD with heat dissipation by contact and irradiation with light of a short wavelength. (See Non-Patent Document 1 and Non-Patent Document 2).
In addition, a compound having an NBD structure has a different refractive index from that of a compound having an isomerized QC structure, that is, has a characteristic in which the refractive index changes upon irradiation with light. Application to a refractive index conversion material is expected (see Non-Patent Document 3).
On the other hand, anthracene is photodimerized by irradiation with light having a specific wavelength, for example, 365 nm, and the anthracene dimer has a property of being changed to a monomer by irradiation with light having a specific wavelength, for example, 254 nm. Since the monomer has a refractive index different from that of the monomer, the compound having an anthracene skeleton is expected to be applied to a refractive index conversion material used in an optical switch system or the like.

It is important that such a refractive index conversion material can be easily formed into a film. Conventionally, various polymers in which an NBD structure or an anthracene skeleton is introduced have been proposed as compounds capable of forming a film having an NBD structure or an anthracene skeleton (see Non-Patent Document 4 and Patent Document 1). .
However, conventional refractive index conversion materials that can be deposited are not sufficiently large in the amount of change in refractive index due to light irradiation.

T. Nishikubo et al., Macromolecules, 22, 8 (1989) T. Nishikubo et al., Macromolecules, 31, 2789 (1998) K. Kinoshita et al., Appl. Lett., 70, 2940 (1997) C.D.Gutsche (ED), Calixarenes, Royal Soc. Chem. (1989) JP 2006-257322 A

  The present invention has been made based on the above circumstances, and an object of the present invention is to provide a refractive index conversion material that has a large amount of change in refractive index and can be easily formed into a film. is there.

  The refractive index conversion material of the present invention comprises a compound represented by the following general formula (1).

[In General Formula (1), X represents — (CO) (CH ₂ ) ₄ —, and R represents a group represented by any of the following formulas (a) to (e). However, some of the plurality of XRs may be hydrogen atoms. ]

  According to the present invention, it is possible to provide a refractive index conversion material that has a large amount of change in refractive index and that can be easily formed into a film.

The refractive index conversion material of the present invention comprises a compound represented by the above general formula (1) (hereinafter referred to as “specific cyclic compound”).
The specific cyclic compound constituting the refractive index conversion material of the present invention is, for example, a cyclic compound represented by the following formula (2) (hereinafter referred to as “raw material cyclic compound”) and chlorovaleric acid chloride in an appropriate solvent. In the presence of a base to synthesize a cyclic compound represented by the following formula (3) (hereinafter referred to as “intermediate cyclic compound”), and the obtained intermediate compound and 4-phenyl Azophenol, 1-anthracene carboxylic acid, trans-cinnamic acid, 2-anthracene carboxylic acid or 9-anthracene carboxylic acid (hereinafter collectively referred to as “function-imparting compounds”) are removed in an appropriate solvent. It can manufacture by making it react in presence of a hydrogen chloride agent.
Here, the raw material cyclic compound can be obtained by reacting resorcinol and 1,5-pentane dial, and as a specific synthesis method, for example, H. Kudo, R. Hayashi, K. Mitani, T The method described in Yokozawa, NC Kasuga, T. Nishikubo. Angew, Chem, lnt, Ed., 45, 7948-7952 (2006) can be used.

In [formula (3), R ¹ is - _{(CO) (CH 2) 4} Cl. ]

In the synthesis step of the intermediate cyclic compound, tetrahydrofuran, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylacetamide, chloroform, triethylamine, pyridine and the like can be used as the solvent.
As the base, pyridine, N, N-dimethylaminopyridine, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like can be used.
Here, triethylamine and pyridine can be used for both base and solvent.
The reaction temperature is, for example, 0 to 60 ° C., and the reaction time is 2 to 48 hours.
The ratio of the raw material cyclic compound to chlorovaleric acid chloride is, for example, 1.1 to 6.0 equivalents of chlorovaleric acid chloride per 1 equivalent of hydroxyl group in the raw material cyclic compound.
Moreover, the usage-amount of a base is 1.1-10.0 equivalent with respect to 1 equivalent of hydroxyl groups in a raw material cyclic compound, for example.

In the step of synthesizing a specific cyclic compound, 1-methyl-2-pyrrolidone or the like can be used as a solvent.
As the dehydrochlorinating agent, for example, 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter referred to as “DBU”) can be used.
The reaction temperature is, for example, 0 to 60 ° C., and the reaction time is 2 to 48 hours.
The ratio of the intermediate cyclic compound and the function-imparting compound is, for example, 1.0 to 10.0 equivalents of the function-imparting compound with respect to 1 equivalent of the functional group in the raw material cyclic compound.
Moreover, the usage-amount of a dehydrochlorinating agent is 1.1-6.0 equivalent with respect to 1 equivalent of hydroxyl groups in an intermediate | middle cyclic compound, for example.

  Since the refractive index conversion material of the present invention has a group represented by any of the above formulas (a) to (e), all receive light of a specific wavelength, as will be apparent from the examples described later. Thus, the refractive index changes and the amount of change in the refractive index is large, and the film can be easily formed. Therefore, the refractive index conversion material of the present invention is extremely useful as a refractive index conversion material used for an optical storage element, an optical switch system, and the like.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

In the following examples, the following materials and solvents were used.
(1) Commercially available products were used as resorcinol, glutaraldehyde, ethanol and 12N hydrochloric acid (HCl).
(2) Tetrabutylammonium bromide (TBAB) was recrystallized twice using ethyl acetate.
(3) As 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, 4-phenylazophenol and trans-cinnamic acid, commercially available products were used as they were.
(4) As 1-methyl-2-pyrrolidone (NMP), pyridine, and DBU, those that have been pre-dried with calcium hydride and then purified by distillation in the presence of calcium hydride (CaH ₂ ) are used. It was.
(5) As tetrahydrofuran, what was preliminarily dried using sodium wire and then purified by distillation in the presence of sodium wire was used.

Moreover, the following were used as a measuring apparatus.
(1) Infrared spectrophotometer (IR): “FT-IR420 type” manufactured by JASCO Corporation and “Real time-IR FTS 3000 type” manufactured by Nippon Bio-Rad Laboratories Co., Ltd. (detector: Mercury Cadmium Talled)
(2) Nuclear magnetic resonance apparatus ( ¹ H-NMR): “JNM-ECA-500 type” (500 MHz) and “JNM-ECA-600 type” (600 MHz) manufactured by JEOL Ltd.
(3) Elemental analyzer (EA): “PE2400 Series II CHNS / O Analyzer” manufactured by PerkinElman Japan Co., Ltd.
(4) Differential scanning calorimeter (DSC): “Seiko Instruments EXSTAR 6000 / DSC 6200” manufactured by Seiko Instruments Inc. (measurement conditions: heating rate 10 ° C./min under nitrogen stream)
(5) Thermobalance / differential thermal analyzer (TG / DTA): “Seiko Instruments EXSTAR 6000 / TG / DTA6200” manufactured by Seiko Instruments Inc. (measurement conditions: 10 ° C./min heating rate under nitrogen stream, open aluminum Bread)
(6) Light irradiation device: “UV LIGHT SOURCE EX250” manufactured by HOYA-SCHOTT (light source: 250 W super high pressure mercury lamp)
(7) Light meter: UV integrated light meter “UIT-150-A” manufactured by USHIO INC.
(8) Spin coater: “Spin coater 1H-D7” manufactured by Mikasa (setting program: acceleration: Acc = 22, rotation speed: R = 2000-4000, rotation time: T = 25 sec)
(9) Ellipsometer: “DHA-OLX / S4” manufactured by Yokojiri Optical Industry
(10) 500W-xenon lamp: USHIO INC. "UXL-500 D-O"

<Synthesis of Intermediate Cyclic Compound>
In a 50 mL three-necked flask, 0.21 g (0.13 mmol, OH equivalent: 3.0 mmol) of a raw material cyclic compound and 0.710 g (8.98 mmol) of pyridine are suspended, and 3 mL of dehydrated tetrahydrofuran is added and ice-cooled. 1.0 g (8.98 mmol) of valeric chloride was added dropwise under a nitrogen atmosphere and stirred for 24 hours. Then, the reaction solution is diluted with ethyl acetate, washed twice with an aqueous sodium hydrogen carbonate solution and once with tap water, then twice with 1N hydrochloric acid aqueous solution, and further washed once with tap water, so that the organic layer is kept in the middle. And dried with anhydrous magnesium sulfate. The desiccant is filtered off and concentrated, and reprecipitation purification is performed using ethyl acetate as a good solvent and n-hexane as a poor solvent, and then reprecipitation twice using ethyl acetate as a good solvent and methanol as a poor solvent. Purification was performed, and the precipitate was collected and dried under reduced pressure at 60 ° C. to obtain a white powder solid.
From the results of IR analysis and ¹ H-NMR analysis, the obtained product was identified as a cyclic compound represented by the following formula (I). The yield was 0.18 g (32%), and the introduction rate of chlorobutyl residues was 100%. The obtained cyclic compound is referred to as “intermediate cyclic compound (a)”.

〔式（イ）において、Ｒ¹ は、−（ＣＯ）（ＣＨ₂ ）₄ Ｃｌである。〕

[In Formula (A), R ¹ is — (CO) (CH ₂ ) ₄ Cl. ]

Further, the results of IR analysis and ¹ H-NMR analysis of the intermediate cyclic compound (A) are shown below, the IR spectrum diagram is shown in FIG. 1, and the ¹ H-NMR spectrum diagram is shown in FIG.
○ IR (KRS, cm ⁻¹ ): 2943, 2868 (νC—H), 1776 (γC═O ester), 1610, 1494 (νC = C aromatic), 1273, 1123 (γC—O—C ether)
○ ¹ H-NMR (500 MHz, DMSO-d ₆ , TMS); δ (ppm)
^{1.66~1.98 (m, 44.0H, H a} , H b, H g, H h),
2.16 to 2.41 (m, 16.0H, H ⁱ ),
^{3.66~4.02 (m, 20.0H, H c} , H f)
^{7.12 (br, 8.0H, H d} , H e)

<Example 1>
In a 5 mL eggplant flask, 0.20 g (0.04 mmol, functional group equivalent 1.1 mmol) of the intermediate cyclic compound (i), 0.63 g (3.2 mmol) of 4-phenylazophenol, and 1-methyl-2- 1 mL of pyrrolidone was added and completely dissolved. Thereafter, 0.49 ml (3.3 mmol) of DBU was slowly added dropwise while cooling with ice, followed by stirring at 80 ° C. for 48 hours. Thereafter, the reaction solution was diluted with ethyl acetate, extracted twice with 1N hydrochloric acid aqueous solution, twice with saturated aqueous sodium hydrogen carbonate, and once with tap water, and dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated, and isolated by reprecipitation purification using ethyl acetate as a good solvent and ether as a poor solvent. The solid was collected using a membrane and dried under reduced pressure at room temperature for 24 hours to obtain a brown solid.
From the results of IR analysis and ¹ H-NMR analysis, the obtained product was identified as a cyclic compound represented by the following formula (B). The yield was 0.08 g (24%), and the introduction rate of 4-phenylazophenol residue was 79%. Let the obtained cyclic compound be "a specific cyclic compound (b)."

[In (b), X represents — (CO) (CH ₂ ) ₄ —, and R ² represents a group represented by the above formula (a). ]

The results of IR analysis and ¹ H-NMR analysis of the specific cyclic compound (B) are shown below, the IR spectrum diagram is shown in FIG. 3, and the ¹ H-NMR spectrum diagram is shown in FIG.
○ IR (KRS, cm ⁻¹ ): 1753 (γC═O ester), 1599, 1499 (νC = C aromatic), 1250, 1140 (γPh—O—C)
○ ¹ H-NMR (500 MHz, DMSO-d ₆ , TMS); δ (ppm)
^{1.80~2.19 (m, 49.9H, H a} , H b, H f, H g, H h),
^{3.07~4.06 (m, 20.0H, H c} , H i),
^{5.98 (br, 8.0H, H d} , H e)
6.82 to 8.33 (m, 56.8H aromatic H n azobenzenzene)

<Example 2>
In a 5 mL eggplant flask, 0.20 g (0.04 mmol, functional group equivalent 1.1 mmol) of the intermediate cyclic compound (i), 0.70 g (3.2 mmol) of 1-anthracenecarboxylic acid, and 1-methyl-2- 1 mL of pyrrolidone was added and completely dissolved. Thereafter, 0.49 ml (3.3 mmol) of DBU was slowly added dropwise while cooling with ice, followed by stirring at 80 ° C. for 48 hours. Thereafter, the reaction solution was diluted with ethyl acetate, extracted twice with 1N hydrochloric acid aqueous solution, twice with saturated aqueous sodium hydrogen carbonate, and once with tap water, and dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated, and isolated by reprecipitation purification using ethyl acetate as a good solvent and ether as a poor solvent. The solid was collected using a membrane and dried under reduced pressure at room temperature for 24 hours to obtain a milky white solid.
From the results of IR analysis and ¹ H-NMR analysis, the obtained product was identified as a cyclic compound represented by the following formula (C). The yield was 0.22 g (56%), and the introduction rate of 1-anthracene residue was 87%. Let the obtained cyclic compound be a "specific cyclic compound (C)."

[In (c), X represents — (CO) (CH ₂ ) ₄ —, and R ³ represents a group represented by the above formula (b). ]

The results of IR analysis and ¹ H-NMR analysis of the specific cyclic compound (C) are shown below, the IR spectrum diagram is shown in FIG. 5, and the ¹ H-NMR spectrum diagram is shown in FIG.
IR (KRS, cm ⁻¹ ): 1754 (γC═O ester), 1712 (γC═O ester of Anthracene), 1625, 1495 (νC = C aromatic), 1219, 1148 (γPh—O—C)
○ ¹ H-NMR (500 MHz, DMSO-d ₆ , TMS); δ (ppm)
^{1.18~2.36 (m, 53.7H, H a} , H b, H f, H g, H h),
4.36 (m, 20.0 H, H ^c , H ⁱ ),
^{6.53 (br, 8.0H, H d} , H e)
7.41-8.84 (m, 62.6H aromatic H nthracene)

<Example 3>
Into a 5 mL eggplant flask, 0.20 g (0.04 mmol, functional group equivalent 1.1 mmol) of the intermediate cyclic compound (i), 0.70 g (3.2 mmol) of 2-anthracenecarboxylic acid and 1-methyl-2-2 as a solvent were used. 1 mL of pyrrolidone was added and completely dissolved. Thereafter, 0.49 ml (3.3 mmol) of DBU was slowly added dropwise while cooling with ice, followed by stirring at 80 ° C. for 48 hours. Thereafter, the reaction solution was diluted with ethyl acetate, extracted twice with 1N hydrochloric acid aqueous solution, twice with saturated aqueous sodium hydrogen carbonate, and once with tap water, and dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated, and isolated by reprecipitation purification using ethyl acetate as a good solvent and ether as a poor solvent. The solid was recovered using a membrane and dried under reduced pressure at room temperature for 24 hours to obtain a tan solid.
From the results of IR analysis and ¹ H-NMR analysis, the obtained product was identified as a cyclic compound represented by the following formula (d). The yield was 0.25 g (64%), and the introduction rate of 2-anthracene residue was 81%. Let the obtained cyclic compound be "a specific cyclic compound (d)."

[In (d), X represents — (CO) (CH ₂ ) ₄ —, and R ⁴ represents a group represented by the above formula (c). ]

The results of IR analysis and ¹ H-NMR analysis of the specific cyclic compound (d) are shown below, and the ¹ H-NMR spectrum is shown in FIG.
IR (KRS, cm ⁻¹ ): 1756 (γC = O ester of pentyl group), 1709 (γC = O ester of Anthracene), 1615, 1494 (νC = C aromatic), 1221, 1154 (γPh—O—C )
○ ¹ H-NMR (500 MHz, DMSO-d ₆ , TMS); δ (ppm)
^{0.82~2.67 (m, 42.7H, H a} , H b, H f, H g, H h),
4.25 (m, 20.0 H, H ^c , H ⁱ ),
^{6.79 (br, 8.0H, H d} , H e)
7.34-9.27 (m, 46.1H aromatic H nthracene)

<Example 4>
Into a 5 mL eggplant flask, 0.20 g (0.04 mmol, functional group equivalent 1.1 mmol) of the intermediate cyclic compound (i), 0.70 g (3.2 mmol) of 9-anthracenecarboxylic acid and 1-methyl-2-2 as a solvent were used. 1 mL of pyrrolidone was added and completely dissolved. Thereafter, 0.49 ml (3.3 mmol) of DBU was slowly added dropwise while cooling with ice, followed by stirring at 80 ° C. for 48 hours. Thereafter, the reaction solution was diluted with ethyl acetate, extracted twice with 1N hydrochloric acid aqueous solution, twice with saturated aqueous sodium hydrogen carbonate, and once with tap water, and dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated, and isolated by reprecipitation purification using ethyl acetate as a good solvent and ether as a poor solvent. The solid was collected using a membrane and dried under reduced pressure at room temperature for 24 hours to obtain a milky white solid.
From the results of IR analysis and ¹ H-NMR analysis, the obtained product was identified as a cyclic compound represented by the following formula (e). The yield was 0.35 g (87%), and the introduction rate of 9-anthracene residue was 99%. The obtained cyclic compound is referred to as “specific cyclic compound (e)”.

[In (e), X represents — (CO) (CH ₂ ) ₄ —, and R ⁵ represents a group represented by the above formula (d). ]

Further, the results of IR analysis and ¹ H-NMR analysis of the specific cyclic compound (e) are shown below, the IR spectrum diagram is shown in FIG. 8, and the ¹ H-NMR spectrum diagram is shown in FIG.
IR (KRS, cm ⁻¹ ): 1758 (γC═O ester), 1719 (γC = O ester of Anthracene), 1624, 1493 (νC = C aromatic), 1264, 1150 (γPh—O—C)
○ ¹ H-NMR (500 MHz, DMSO-d ₆ , TMS); δ (ppm)
^{1.56~2.67 (m, 59.5H, H a} , H b, H f, H g, H h),
4.30 (m, 20.0 H, H ^c , H ⁱ ),
^{6.75 (br, 8.0H, H d} , H e)
7.33 to 8.54 (m, 71.3H aromatic H nthracene)

<Example 5>
In a 5 mL eggplant flask, 0.20 g (0.04 mmol, functional group equivalent 1.1 mmol) of intermediate cyclic compound (i), 0.47 g (3.2 mmol) of trans-cinnamic acid and 1-methyl-2-pyrrolidone as a solvent 1 mL was added and completely dissolved. Thereafter, 0.49 ml (3.3 mmol) of DBU was slowly added dropwise while cooling with ice, followed by stirring at 80 ° C. for 48 hours. Thereafter, the reaction solution was diluted with ethyl acetate, extracted twice with 1N hydrochloric acid aqueous solution, twice with saturated aqueous sodium hydrogen carbonate, and once with tap water, and dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated, and isolated by reprecipitation purification using ethyl acetate as a good solvent and ether as a poor solvent. The solid was collected using a membrane and dried under reduced pressure at room temperature for 24 hours to obtain a milky white solid.
From the results of IR analysis and ¹ H-NMR analysis, the obtained product was identified as a cyclic compound represented by the following formula (f). The yield was 0.19 g (61%), and the introduction rate of cinnamic acid residues was 99%. The obtained cyclic compound is referred to as “specific cyclic compound (f)”.

[In (f), X represents — (CO) (CH ₂ ) ₄ —, and R ⁶ represents a group represented by the above formula (e). ]

Further, the results of IR analysis and ¹ H-NMR analysis of the specific cyclic compound (f) are shown below, the IR spectrum diagram is shown in FIG. 10, and the ¹ H-NMR spectrum diagram is shown in FIG.
IR (KRS, cm ⁻¹ ): 1758 (γC═O ester), 1711 (γC═O ester of cinnamete), 1636, 1495 (νC = C aromatic), 1203, 1142 (γPh—O—C)
○ ¹ H-NMR (500 MHz, DMSO-d ₆ , TMS); δ (ppm)
^{0.84~2.69 (m, 59.5H, H a} , H b, H f, H g, H h),
4.12 (m, 20.0 H, H ^c , H ⁱ ),
^{6.52 (br, 8.0H, H d} , H e)
7.33 to 7.73 (m, 39.6H aromatic H n cinnamete)

[Characteristics of specific cyclic compounds]
(1) Photoreactive characteristics:
Each of the specific cyclic compound (b) to the specific cyclic compound (e) according to Examples 1 to 4 was dissolved in tetrahydrofuran, and each of the obtained solutions was applied to the inner wall surface of the quartz cell, A thin film was formed by drying under reduced pressure for 2 hours. Here, the density | concentration of each specific cyclic compound was adjusted so that the light absorbency of the maximum absorption wavelength of the obtained thin film might be set to about 0.6. The thin film formed in the quartz cell is irradiated with light using a 500 W xenon lamp under the condition of ² mW / cm ² (313 nm), and the ultraviolet absorption time-lapse of the thin film is measured with an ultraviolet spectrophotometer. Changes were measured. The results are shown in FIGS.

From the result of FIG. 12, in the thin film made of the specific cyclic compound (b) according to Example 1, the absorption of ultraviolet light having a maximum absorption wavelength of 357 nm based on the phenylazophenol residue decreases with the passage of light irradiation time. Confirmed to do.
From the results of FIG. 13, in the thin film made of the specific cyclic compound (c) according to Example 2, the absorption of ultraviolet rays having a maximum absorption wavelength of 383 nm based on the 1-anthracene residue decreases with the passage of light irradiation time. Confirmed to do.
From the results of FIG. 14, in the thin film made of the specific cyclic compound (d) according to Example 3, the absorption of ultraviolet rays having a maximum absorption wavelength of 386 nm based on the 2-anthracene residue decreases with the passage of light irradiation time. Confirmed to do. Further, since the isoabsorption point was not confirmed, from the result of FIG. 15, in the thin film made of the specific cyclic compound (e) according to Example 4, the ultraviolet ray having the maximum absorption wavelength of 365 nm based on the 9-anthracene residue was observed. It was confirmed that absorption decreased with the passage of light irradiation time.

Moreover, the photoisomerization reaction rate or the photodimerization reaction rate in the specific cyclic compound (b) to the specific cyclic compound (e) according to Example 1 to Example 4 is calculated from the rate of decrease in absorbance at the maximum absorption wavelength. FIG. 16 to FIG. 19 show the results of plotting this in the primary velocity equation.
From these results, it is understood that the photoisomerization reaction or the photodimerization reaction in the specific cyclic compound (b) to the specific cyclic compound (e) proceeds in the first order.

  Further, from the rate of decrease in absorbance at the maximum absorption wavelength, the reaction rate constant of the photoisomerization reaction or photodimerization reaction in the specific cyclic compound (b) to the specific cyclic compound (e) according to Example 1 to Example 4 is calculated. Asked. The results are shown in Table 1.

(2) Refractive index change:
Each of the specific cyclic compound (b) to the specific cyclic compound (f) according to Examples 1 to 5 was dissolved in tetrahydrofuran, and the obtained solution was applied to the surface of a silicon wafer by a spin coater. A thin film having a thickness of about 0.1 μm was formed by performing vacuum drying for a period of time. Each of the obtained thin films was irradiated with ultraviolet rays, and the refractive index before and after ultraviolet irradiation was measured with an ellipsometer using a laser beam having a wavelength of 632.8 nm to determine the amount of change in the refractive index. Here, a 500 W-xenon lamp (illuminance: 10.0 mW / cm ² (254 nm)) was used as an ultraviolet light source.
The results are shown in Table 2.

  As is clear from the results in Table 2, the refractive index of each of the specific cyclic compound (b) to the specific cyclic compound (f) according to Examples 1 to 5 changes when irradiated with ultraviolet rays. It has characteristics and has a large amount of change in refractive index, and was confirmed to be useful as a refractive index conversion material.

It is IR spectrum figure of the intermediate cyclic compound synthesize | combined in the Example. ¹ is a ¹ H-NMR spectrum diagram of an intermediate cyclic compound synthesized in an example. FIG. 1 is an IR spectrum diagram of a specific cyclic compound according to Example 1. FIG. 1 is a ¹ H-NMR spectrum of a specific cyclic compound according to Example 1. FIG. 2 is an IR spectrum diagram of a specific cyclic compound according to Example 2. FIG. 2 is a ¹ H-NMR spectrum of a specific cyclic compound according to Example 2. FIG. 2 is a ¹ H-NMR spectrum of a specific cyclic compound according to Example 3. FIG. 4 is an IR spectrum diagram of a specific cyclic compound according to Example 4. FIG. 2 is a ¹ H-NMR spectrum of a specific cyclic compound according to Example 4. FIG. 6 is an IR spectrum diagram of a specific cyclic compound according to Example 5. FIG. 6 is a ¹ H-NMR spectrum of a specific cyclic compound according to Example 5. FIG. It is a figure which shows the change of the light absorbency of the ultraviolet-ray in the thin film of the specific cyclic compound which concerns on Example 1. FIG. It is a figure which shows the change of the light absorbency of the ultraviolet-ray in the thin film of the specific cyclic compound which concerns on Example 2. FIG. It is a figure which shows the change of the light absorbency of the ultraviolet-ray in the thin film of the specific cyclic compound which concerns on Example 3. FIG. It is a figure which shows the change of the light absorbency of the ultraviolet-ray in the thin film of the specific cyclic compound which concerns on Example 4. FIG. FIG. 3 is a diagram in which the isomerization reaction rate of a specific cyclic compound according to Example 1 is plotted in a first-order rate equation. It is the figure which plotted the dimerization reaction rate of the specific cyclic compound which concerns on Example 2 to the primary rate equation. It is the figure which plotted the dimerization reaction rate of the specific cyclic compound which concerns on Example 3 to the primary rate equation. It is the figure which plotted the dimerization reaction rate of the specific cyclic compound which concerns on Example 4 to the primary rate equation.

Claims (1)

A refractive index conversion material comprising a compound represented by the following general formula (1).

[In General Formula (1), X represents — (CO) (CH ₂ ) ₄ —, and R represents a group represented by any of the following formulas (a) to (e). However, some of the plurality of XRs may be hydrogen atoms. ]

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