JP2002156668A - Nonlinear optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonlinear optical material and a method for manufacturing the material in which attenuation of second harmonic waves is significantly suppressed. SOLUTION: The nonlinear optical material is manufactured by forming a layer containing liquid crystal molecules having both of nonlinear optical responsive groups and a plurality of crosslinkable functional groups as at least a part of the structural component on a substrate or between a pair of substrates. In the nonlinear optical material and the method for manufacturing the material, after the liquid crystal molecules are aligned by applying an external electric field or external magnetic field, the alignment of the nonlinear optical responding groups is fixed by carrying out the crosslinking reaction while applying the external electric field or external magnetic field.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel nonlinear optical material useful in the field of optoelectronics and photonics, and a method of manufacturing the same.

[0002]

2. Description of the Related Art With the development of a highly information-oriented society, many attempts have been made to use optical technology for transmission, processing and recording of information. In such a current situation, a material exhibiting a nonlinear optical effect (nonlinear optical material) has attracted attention in the fields of optoelectronics and photonics. The nonlinear optical effect is a phenomenon in which when a strong electric field (optical electric field) is applied to a substance, a nonlinear response occurs between the generated electric polarization and the applied electric field. Refers to a material that significantly shows Known nonlinear optical materials utilizing the second-order nonlinear response include materials that generate second harmonics and materials that exhibit the Pockels effect (primary electro-optic effect) that causes a change in the refractive index in proportion to the first-order electric field. In particular, the latter is being studied for application to electro-optic (EO) light modulation elements and photorefractive elements.

[0003] Materials search and device preparation of these nonlinear optical materials have hitherto been carried out centering on inorganic nonlinear materials. In recent years, however, 1) they show large nonlinearity, 2) the response speed is high, and 3) the response speed is high. Organic materials have attracted attention because of their high photodamage thresholds, 4) a wide variety of molecular designs are possible, and 5) their excellent manufacturing suitability. However, the appearance of the second-order nonlinear optical effect requires that the polarization induced by the electric field lacks the inversion symmetry center. Therefore, it is necessary to arrange a molecule exhibiting a nonlinear optical effect or a nonlinear optical response group in a structure lacking the inversion symmetry center in the material.

According to the prior art, in order to arrange a molecule exhibiting a nonlinear optical effect or a nonlinear optical response group in a structure lacking the inversion symmetry center, a molecule exhibiting a nonlinear optical effect or a nonlinear optical response group is present in an organic polymer. Introducing and orienting dipoles by, for example, electric fields is widely used. The orientation control by this electric field is polled.
g), and the polled organic polymer is called an electric field alignment polymer (polled polymer). That is, by applying a high voltage at a temperature equal to or higher than the glass transition point of the base polymer to orient the dipoles of molecules or responsive groups exhibiting a second-order nonlinear optical effect, and then cooling the dipoles by the electric field. This is a technique for freezing. For example, SPIE
Magazine, Vol. 1213, pp. 7 (1990) describes an example of an electro-optic (EO) light modulation element manufactured by this method. However, these materials are thermally unstable with time, and the stability of the electro-optical characteristics is degraded.These materials lack stability and cannot be applied to a wide range of applications. A solution was desired (for example, Mol. Cryst. Liq. Crys).
t. Journal, Vol. 189, p. 3 (1990)).

As a technique for suppressing the relaxation of the orientation, for example,
A method has been proposed in which cross-linking is performed by poling using a bifunctional monomer that has an epoxy group and an amino group, but does not exhibit liquid crystallinity, and the alignment is chemically frozen. It has been a problem that it is difficult to remove and a local non-uniform structure is generated.

[0006] For example, Thin Solid F
In ilm, 210, 195 (1992), a polymerizable long-chain alkylamino derivative of 2-amino-5-nitropyridine is synthesized as an amphiphilic compound exhibiting a nonlinear optical effect to form an LB film. There has been reported an example in which orientation is fixed after polymerization by polymerization. However, in the fabrication of devices using the LB method, problems such as defects such as pin poles and lack of suitability for industrial production have been regarded as problems. Furthermore, WO
In the pamphlet of 00/05189, a cross-linkable liquid crystal compound is described.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-linear optical material made of an organic material having no or suppressed orientation relaxation, and a method of manufacturing the same.

[0008]

The above objects of the present invention have been attained by the following (1) to (8).

(1) A non-linear optical response layer on a transparent electrode substrate which may or may not have a single liquid crystal alignment layer, or a transparent electrode which may or may not have a pair of liquid crystal alignment layers The non-linear optical material provided on the substrate has a single liquid crystal alignment layer including at least a layer containing liquid crystal molecules having a non-linear optical response group and a plurality of functional groups capable of cross-linking reaction at least as a component. After being provided on the transparent electrode substrate which may be provided, or between the transparent electrode substrates which may have a pair of liquid crystal alignment layers, by applying an external electric field or an external magnetic field, the liquid crystal molecules are aligned, A nonlinear optical material characterized in that a nonlinear optical response layer is formed by fixing the orientation of the nonlinear optical response group by performing a crosslinking reaction under the application of an external electric field or an external magnetic field. (2) Even if a single liquid crystal alignment layer is formed by coating a layer containing at least a part of liquid crystal molecules having a nonlinear optical response group and a plurality of functional groups capable of cross-linking reaction at least as a component, The nonlinear optical material according to the above (1), which is provided on a good transparent electrode substrate. (3) The liquid crystal molecule according to the above (1), wherein the liquid crystal molecule having a nonlinear optical response group and a plurality of functional groups capable of cross-linking reaction at the same time is a liquid crystal molecule represented by the following general formula (I). Nonlinear optical material. R ¹ -S ¹ -D-M-A-S ² -R ² (I) (wherein, R ¹ and R ² represent a functional group capable of undergoing a crosslinking reaction,
S ¹ and S ^{2 each} represent a divalent linking group, and D represents a single bond, an oxygen atom, a sulfur atom, —NH—, or —NR ³ — (R
³ is an alkyl group having 1 to 6 carbon atoms, or R ¹ -S ¹
-Represents a group represented by-. A represents a carbonyl group,
M represents a sulfonyl group, a carbonyloxy group, or a sulfonyloxy group, and M represents a mesogen group. (4) The nonlinear optical material according to the above (3), wherein the mesogen group (M) contains a biphenylene group, a terphenylene group, a phenyleneethenylene group, a phenyleneethynylene group or a naphthylene group. (5) The nonlinear optical material according to (3), wherein the mesogen group (M) is an organic residue shown below.

[0010]

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(6) The nonlinear optical material according to the above (3), wherein the mesogen group (M) is the following organic residue.

[0012]

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(7) When the nonlinear optical material is electro-optical (E
O) The nonlinear optical material according to the above (1), which is a light modulation material. (8) A layer containing at least a part of liquid crystal molecules having a nonlinear optical response group and a plurality of functional groups capable of cross-linking reaction as a component is provided on one substrate or between a pair of substrates. In the method for producing a nonlinear optical material, after applying an external electric field or an external magnetic field to orient the liquid crystal molecules, a cross-linking reaction is performed under an external electric field or an external magnetic field to change the orientation of the nonlinear optical response group. A method for producing a non-linear optical material, comprising fixing.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a nonlinear optical material of the present invention,
And a method of manufacturing the same will be described in detail. At first,
A layer containing at least a part of a component containing liquid crystal molecules having a nonlinear optical response group and a plurality of functional groups capable of cross-linking reaction at the same time is provided on one substrate or between a pair of substrates. Here, a liquid crystal molecule having a nonlinear optical response group and a plurality of functional groups capable of undergoing a crosslinking reaction at the same time is not particularly limited, but a compound represented by the following general formula (I) is a preferred example. R ¹ -S ¹ -D-M-A-S ² -R ² (I) (wherein, R ¹ and R ² represent a functional group capable of undergoing a crosslinking reaction,
S ¹ and S ^{2 each} represent a divalent linking group, and D represents a single bond, an oxygen atom, a sulfur atom, —NH—, or —NR ³ — (R ³
Represents an alkyl group having 1 to 6 carbon atoms or a group represented by R ¹ -S ^1- . A represents a carbonyl group, a sulfonyl group, a carbonyloxy group or a sulfonyloxy group, and M represents a mesogen group. )

Here, R ¹ and R ² represent functional groups capable of undergoing a cross-linking reaction. Preferred examples thereof include an acryloyloxy group, a methacryloyloxy group, a glycidyl group and a vinyloxy group, and an acryloyloxy group is particularly preferred. S ¹ and S ^{2 each} represent a divalent linking group, and preferred examples thereof include an alkylene group having 2 to 12 carbon atoms, and the linking group may have a substituent. At this time, preferable substituents include a lower alkyl group and a halogen atom. When the carbon atom having a substituent is an asymmetric carbon, the configuration may be any of R, S, and RS. D is a single bond, an oxygen atom, a sulfur atom, -NH-,
Alternatively, —NR ³ — is shown, and an oxygen atom is a preferable example. R ³ represents an alkyl group having 1 to 6 carbon atoms or a group represented by R ¹ -S ^1- , preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group and an ethyl group. A represents a carbonyl group, a sulfonyl group, a carbonyloxy group, or a sulfonyloxy group, and a carbonyloxy group and a sulfonyloxy group are particularly preferable. M represents a mesogen group generally used for a rod-shaped liquid crystal, that is, a main skeleton of a liquid crystal molecule contributing to formation of a rigid liquid crystal. Examples of the mesogen group include, for example, “Flusige Kr
istelle in Tabellen II ", V
EB Deutsche Verlag fur Gr
undstoff Industry, Leipz
ig, (1984), pp. 7-16. Among them, a biphenylene group, a benzoylbiphenylene group, a terphenylene group, a naphthyleneoxycarbonylphenylene group, a phenyleneethenylene group, a phenyleneethynylene group, a naphthylene group, etc. Can be

[0016]

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[0017]

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Specific examples of the compound represented by the general formula (I) include the following compounds.

[0019]

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The layer containing the liquid crystal molecules as at least a part of the constituents contains the liquid crystal molecules in an amount of 80% by weight.
More preferably, it is desirable to contain 90% or more. If necessary, an appropriate polymerization initiator, polymerization inhibitor, photosensitizer, cross-linking agent, liquid crystal alignment aid, and the like may be added. The amount of the additive to be added is not particularly limited, but the upper limit is an amount that does not impair the liquid crystallinity of the layer containing the liquid crystal molecules as at least a part of the constituent components.

The transparent electrode substrate is not particularly limited, but an ITO substrate obtained by depositing ITO on glass, transparent plastic or the like is a particularly preferable example. The transparent electrode substrate may be subjected to processing such as etching as needed. When a pair of transparent electrode substrates that may or may not have a liquid crystal alignment layer are used, a spacer, a sealant, or the like may be used as necessary. Although it is not necessary to have a liquid crystal alignment layer, when it has a liquid crystal alignment layer, a polyimide or polyvinyl alcohol liquid crystal alignment layer is a preferred example. The liquid crystal alignment layer provided on the transparent electrode substrate may be subjected to processing such as rubbing as necessary.

A well-known method for providing a layer containing at least a part of liquid crystal molecules having a non-linear optically responsive group and a plurality of functional groups capable of cross-linking reaction on a single substrate is known. Is adopted. As a method of applying, a known method, for example, a curtain coating method,
Extrusion coating, roll coating, spin coating, dip coating, bar coating, spray coating, slide coating, print coating, and the like are employed. A general method such as a dispenser method or a bell jar method is adopted as a method of injecting the liquid between the substrates.

Next, an external electric field or an external magnetic field is applied to a layer containing at least a part of liquid crystal molecules having a nonlinear optically responsive group and a plurality of functional groups capable of cross-linking reaction at least as a component. The liquid crystal molecules are aligned. As the orientation method, a method using an external electric field is preferable, and a contact poling method (a planar electrode poling method,
It is preferable to employ an electrode sandwich poling method) or a corona poling method. These polling methods are described in "Optical and Electronic Functional Organic Materials Handbook", published by Asakura Shoten (1995). The application of an external electric field or an external magnetic field is preferably performed in a temperature range showing a liquid crystal phase. Further, a method of heating to an isotropic phase under application of an external electric field or an external magnetic field and then cooling to a liquid crystal phase is also preferable. As the intensity of the external electric field or the external magnetic field to be used, an intensity suitable for controlling the alignment of the liquid crystal molecules to be used is adopted. When controlling the tilt angle of the liquid crystal molecules,
It is useful to use an external magnetic field depending on the liquid crystal molecules used.

Finally, in a state where the liquid crystal molecules are oriented under the application of an external electric field or an external magnetic field, the liquid crystal molecules having a nonlinear optical response group and a plurality of functional groups capable of cross-linking reaction are cross-linked to form a non-linear structure. The desired nonlinear optical material can be obtained by fixing the orientation of the optically responsive group. For the crosslinking reaction, various known crosslinking methods using heat or electromagnetic waves can be employed, but radical polymerization using a photopolymerization initiator by ultraviolet light is particularly preferable. In the nonlinear optical material provided on the transparent electrode substrate, which may or may not have a single liquid crystal alignment layer, the nonlinear optical response layer obtained as described above is further provided on the upper layer of the nonlinear optical response layer. An electrode layer may be provided. An example thereof is a gold electrode on which gold is deposited. 1 and 2 show typical examples of the layer structure of the nonlinear optical material of the present invention.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but the scope of the present invention is not limited to the following Examples.

Example 1 4- (4-acryloyloxybutyloxy) was placed between glass substrates having an ITO transparent electrode layer having 4 μm voids.
A constituent material consisting of -4'-biphenylcarboxylic acid 4-4-acryloyloxybutyl ester (100 parts by weight), trimethylolpropane triacrylate (1 part by weight), and Irgacure 651 (3 parts by weight) was sandwiched. Next, the sample obtained was heated to 100 ° C. once while applying a DC voltage of 110 V between the transparent electrodes, and then kept at 60 ° C., and UV irradiation (254 nm, 10 W / cm, 2 minutes) was performed. The sample obtained above was irradiated with YHG laser infrared light (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

Example 2 4- (4-acryloyloxybutyloxy) -4'-biphenylcarboxylic acid 4--4-acryloyloxybutyl ester (100 parts by weight) on a glass substrate having an ITO transparent electrode layer, trimethylolpropane Triacrylate (1 part by weight), Irgacure 651 (3 parts by weight)
Was applied by spin coating (700 rpm, 20 seconds) and dried under reduced pressure for 12 hours. Next, the obtained sample is once heated to 100 ° C., then maintained at 60 ° C., and a voltage is applied (applied voltage: −10 kV, 1 hour) using a corona poling method. 254 nm, 10 W
/ Cm, 2 minutes). For the sample obtained above,
Irradiation of infrared light (1.06 μm) from a YHG laser was performed, and generation of the second harmonic was confirmed. The intensity of the sample second harmonic was retained after 6 months.

Example 3 A glass substrate having an ITO transparent electrode layer coated with a polyimide thin film as an alignment film and subjected to a rubbing treatment was placed in a horizontal alignment cell (manufactured by ET Corporation) having a gap of 4 μm. -Acryloyloxybutyloxy) -4'-
A constituent material composed of biphenylcarboxylic acid 4-4-acryloyloxybutyl ester (100 parts by weight) and hydroquinone monomethyl ether (4 parts by weight) was sandwiched. Next, the sample obtained was heated once to 100 ° C. while applying a DC voltage of 110 V between the transparent electrodes,
° C, UV irradiation (254 nm, 10 W / cm, 2
Min). The sample obtained above was irradiated with YHG laser infrared light (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

Example 4 A 4 μm glass substrate having an ITO transparent electrode layer coated with a polyimide thin film as an alignment film and rubbed was used.
Horizontal alignment cell with voids (made by E.H.I.)
To 4- (4-acryloyloxybutyloxy) -4 '
-Biphenylcarboxylic acid 4-4-acryloyloxybutyl ester (100 parts by weight), trimethylolpropane triacrylate (1 part by weight), Irgacure 65
1 (3 parts by weight), cellulose acetate butyrate (1
(Parts by weight) of a methyl ethyl ketone solution was applied by spin coating (700 rpm, 20 seconds) and dried under reduced pressure for 12 hours. Next, the obtained sample was once heated to 100 ° C.
After heating to 60 ° C., voltage application (applied voltage −10 kV, 1 hour) was performed using a corona poling method, and then UV irradiation (254 n) was performed while applying a voltage.
m, 10 W / cm, 2 minutes). The sample obtained above was irradiated with YHG laser infrared light (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

Example 5 A 4 μm glass substrate having an ITO transparent electrode layer coated with a polyimide thin film as an alignment film and rubbed was used.
Horizontal alignment cell with voids (made by E.H.I.)
4- (4- (8-acryloyloxyoctyloxy) -cinnamoyloxy) -4′-biphenylcarboxylic acid 4-acryloyloxybutyl ester (100
Parts by weight), phenothiazine (1.3 parts by weight), Irgacure 651 (4 parts by weight), and hydroquinone monomethyl ether (4 parts by weight). next,
The obtained sample was once heated to 170 ° C. while applying a DC voltage of 110 V between the transparent electrodes, and then kept at 120 ° C., and UV irradiation (254 nm, 10 W / cm, 3 minutes) was performed. The sample obtained above was irradiated with YHG laser infrared light (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

COMPARATIVE EXAMPLE 1 A glass substrate having an ITO transparent electrode layer and a horizontal alignment cell (manufactured by E.H.I.
(4- (8-acryloyloxyoctyloxy) -cinnamoyloxy) -4′-biphenylcarboxylic acid 4
A constituent material comprising acryloyloxybutyl ester (100 parts by weight), phenothiazine (1.3 parts by weight), Irgacure 651 (4 parts by weight), and hydroquinone monomethyl ether (4 parts by weight) was sandwiched. Next, the sample was heated once to 170 ° C., and then kept at 120 ° C.
V irradiation (254 nm, 10 W / cm, 3 minutes) was performed.
The sample obtained above was irradiated with infrared light (1.06 μm) of a YHG laser, but the generation of the second harmonic could not be confirmed.

[0032]

According to the present invention, a nonlinear optical material made of an organic material, in which the attenuation of the second harmonic with the passage of time is remarkably suppressed, is obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing a layer configuration of a nonlinear optical material of the present invention.

FIG. 2 is a diagram showing a layer configuration of the nonlinear optical material of the present invention.

[Explanation of symbols]

 Reference Signs List 1 nonlinear optical response layer 2 liquid crystal alignment layer 3 transparent electrode substrate

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[Procedure amendment]

[Submission date] March 1, 2001 (2001.3.1)

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The transparent electrode substrate is not particularly limited, but an ITO substrate obtained by depositing ITO on glass, transparent plastic or the like is a particularly preferable example. The transparent electrode substrate may be subjected to processing such as etching as needed. When a pair of transparent electrode substrates that may or may not have a liquid crystal alignment layer are used, a spacer, a sealant, or the like may be used as necessary. May or may not have <br/> have a liquid crystal alignment layer, but if having a liquid crystal alignment layer crystal alignment layer of polyimide, polyvinyl alcohol Preferred examples. The liquid crystal alignment layer provided on the transparent electrode substrate may be subjected to processing such as rubbing as necessary.

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Example 1 4- (4-acryloyloxybutyloxy) was placed between glass substrates having an ITO transparent electrode layer having 4 μm voids.
-4'-biphenylcarboxylic acid 4- acryloyloxybutyl ester (100 parts by weight), trimethylolpropane triacrylate (1 part by weight), Irgacure 6
A constituent material consisting of 51 (3 parts by weight) was sandwiched. next,
After heating the obtained sample to 100 ° C once while applying a DC voltage of 110V between the transparent electrodes, the sample was kept at 60 ° C,
UV irradiation (254 nm, 10 W / cm, 2 minutes) was performed. The sample obtained above was irradiated with YHG laser infrared light (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

[Procedure amendment 4]

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Example 2 On a glass substrate having an ITO transparent electrode layer, 4- (4-acryloyloxybutyloxy) -4'-biphenylcarboxylic acid 4- acryloyloxybutyl ester (1
00 parts by weight), a methyl ethyl ketone solution comprising trimethylolpropane triacrylate (1 part by weight) and Irgacure 651 (3 parts by weight) was applied by spin coating (700 rpm, 20 seconds) and dried under reduced pressure for 12 hours. Next, the obtained sample is once heated to 100 ° C., then maintained at 60 ° C., and a voltage is applied (applied voltage: −10 kV, 1 hour) using a corona poling method. 254 nm, 10 W / c
m, 2 minutes). For the sample obtained above, YH
Irradiation of infrared light (1.06 μm) from a G laser was performed, and generation of a second harmonic was confirmed. The intensity of the sample second harmonic is 6
Retained after months.

[Procedure amendment 5]

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Example 3 A glass substrate having an ITO transparent electrode layer coated with a polyimide thin film as an alignment film and subjected to a rubbing treatment was placed in a horizontal alignment cell (manufactured by ET Corporation) having a gap of 4 μm. -Acryloyloxybutyloxy) -4'-
A constituent material composed of biphenylcarboxylic acid 4- acryloyloxybutyl ester (100 parts by weight) and hydroquinone monomethyl ether (4 parts by weight) was sandwiched. Next, the sample obtained was heated to 100 ° C. once while applying a DC voltage of 110 V between the transparent electrodes, and then kept at 60 ° C., and UV irradiation (254 nm, 10 W / cm, 2 minutes) was performed. The sample obtained above was irradiated with YHG laser infrared light (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

Example 4 A 4 μm glass substrate having an ITO transparent electrode layer coated with a polyimide thin film as an alignment film and rubbed was used.
Horizontal alignment cell with voids (made by E.H.I.)
To 4- (4-acryloyloxybutyloxy) -4 '
-Biphenylcarboxylic acid 4- acryloyloxybutyl ester (100 parts by weight), trimethylolpropane triacrylate (1 part by weight), Irgacure 651
(3 parts by weight) and a methyl ethyl ketone solution composed of cellulose acetate butyrate (1 part by weight) was applied by spin coating (700 rpm, 20 seconds), and then dried under reduced pressure.
Dried for 2 hours. Next, after heating the obtained sample to 100 ° C. once and keeping it at 60 ° C., a voltage was applied (applied voltage −10 kV, 1 hour) using a corona poling method,
Then, UV irradiation (254 nm, 1
0 W / cm, 2 minutes). The sample obtained above was irradiated with YHG laser infrared light (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H088 EA31 EA44 EA56 EA62 2H090 HB08Y MA02 MB09 2K002 AB12 CA14 DA14 FA27 GA10 HA20

Claims (8)

[Claims] 1. A transparent electrode substrate having a non-linear optical response layer which may or may not have a single liquid crystal alignment layer, or a transparent electrode substrate which may or may not have a pair of liquid crystal alignment layers. In the nonlinear optical material provided in the above, a layer containing a liquid crystal molecule having a nonlinear optical response group and a plurality of functional groups capable of cross-linking at the same time as at least a part of the component has a single liquid crystal alignment layer May be provided on the transparent electrode substrate which may be provided, or between the transparent electrode substrates which may have a pair of liquid crystal alignment layers, and after applying an external electric field or an external magnetic field to orient the liquid crystal molecules, A nonlinear optical material characterized in that a nonlinear optical response layer is formed by fixing the orientation of the nonlinear optical response group by performing a crosslinking reaction under application of an electric field or an external magnetic field. 2. A liquid crystal alignment layer is formed by applying a layer containing at least a part of liquid crystal molecules having a nonlinear optical response group and a plurality of functional groups capable of cross-linking reaction at least as a component. 2. The nonlinear optical material according to claim 1, wherein the nonlinear optical material is provided on a transparent electrode substrate. 3. The liquid crystal molecule having a nonlinear optically responsive group and a plurality of functional groups capable of cross-linking reaction at the same time is a liquid crystal molecule represented by the following general formula (I). Nonlinear optical material. R ¹ -S ¹ -D-M-A-S ² -R ² (I) (wherein, R ¹ and R ² represent a functional group capable of undergoing a crosslinking reaction,
S ¹ and S ^{2 each} represent a divalent linking group, and D represents a single bond, an oxygen atom, a sulfur atom, —NH—, or —NR ³ — (R
³ is an alkyl group having 1 to 6 carbon atoms, or R ¹ -S ¹
-Represents a group represented by-. A represents a carbonyl group,
M represents a sulfonyl group, a carbonyloxy group, or a sulfonyloxy group, and M represents a mesogen group. ) 4. The nonlinear optical material according to claim 3, wherein the mesogen group (M) contains a biphenylene group, a terphenylene group, a phenyleneethenylene group, a phenyleneethynylene group or a naphthylene group. 5. The nonlinear optical material according to claim 3, wherein the mesogen group (M) is an organic residue shown below. Embedded image 6. The nonlinear optical material according to claim 3, wherein the mesogen group (M) is an organic residue shown below. Embedded image 7. The nonlinear optical material according to claim 1, wherein said nonlinear optical material is an electro-optic (EO) light modulation material. 8. A layer containing at least a part of liquid crystal molecules having a nonlinear optical response group and a plurality of functional groups capable of cross-linking reaction at least as a constituent component, on a single substrate or between a pair of substrates. In the method for manufacturing a nonlinear optical material provided in the above, after applying an external electric field or an external magnetic field to orient the liquid crystal molecules, a cross-linking reaction is performed under an external electric field or an external magnetic field to form a nonlinear optical response group. A method for producing a nonlinear optical material, comprising fixing an orientation.