JPH03154033A - Nonlinear high-polymer material - Google Patents

Abstract

PURPOSE:To increase the amt. of the nonlinear material to be added and to obtain the nonlinear high-polymer material having the refractive index approximate to the refractive index of clad glass by incorporating a siloxane structure into at least one kind of monomer components which form a prescribed high- polymer compd. CONSTITUTION:This nonlinear high-polymer material is formed by chemically bonding a compd. having a nonlinear optical effect to the high-polymer compd. having light tranmittability. At least one kind of the monomers constituting this high-polymer compd. are constituted to contain the siloxane structure. The content of the siloxane part in the entire part is increased in this constitution and since the interaction of the siloxane part and the compd. having the nonlinear optical effect increases, the amt. of the addition is increased, by which the material having the refractive index approximate to the refractive index of the clad glass is formed. The nonlinear high-polymer material made of this constitution exhibits an excellent electrooptical effect and is sufficiently applicable to, for example, a coupler type optical switch.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a nonlinear polymer material that is an element material used in an optical signal processing device.

[Conventional technology]

In recent years, with the development of high-energy-density laser light sources, research on nonlinear optical phenomena, which is the interaction between materials and strong electromagnetic waves, has been actively conducted.

Nonlinear optical phenomena are generally phenomena in which changes in the permittivity of a material due to the incidence of electromagnetic waves on the material are no longer proportional to the electric field amplitude, and are known as higher-order radio frequency generation, mixed wave generation, parametric effects, etc. There is. Such a phenomenon is used in devices such as laser media, optical bistable devices, optical switches, and optical memories.

Various materials such as inorganic materials, organic materials, and semiconductors are used as materials for optical elements exhibiting the above phenomenon.Among these, organic materials include LiNb0. JPKH! It has the advantage of having a larger nonlinear optical constant than inorganic materials such as ferroelectric crystals such as POI, and faster response speed than semiconductor materials such as GaAs. For this reason, para-toluenesulfonate derivatives of polydiacetylene (PTS-PD
A), π-electron conjugated polymer materials such as polyacetylene, and organic small molecules with asymmetrically substituted aminonitrostilbene-based donor-acceptors are being actively researched.

[Problem to be solved by the invention]

As described above, organic materials with nonlinear optical effects have excellent nonlinear optical effects, but they have a problem in that they have a high refractive index because they contain conjugated moieties such as phenyl groups in their molecular skeletons.

When applying an organic material with a nonlinear optical effect to an optical switch such as a coupler-type optical switch or a waveguide-type optical switch or a device such as a wavelength conversion element, the difference in refractive index with the cladding (glass) This is a problem, and materials with little difference are desirable. Therefore, it is necessary to use a light-transmitting polymer compound as a matrix and mix a nonlinear material to create a material that has almost the same refractive index as the cladding (glass).

Although there are thermosetting silicone resins, ultraviolet curable silicone resins, and ladder-type silicone resins as polymer materials that have almost the same refractive index as the cladding (glass), they are not compatible with organic compounds that have nonlinear optical effects. Unfortunately, there was a problem in that the amount added could not be increased very much.

Furthermore, as disclosed in Japanese Patent Application Laid-Open No. 63-1) 3526, there are materials in which a nonlinear material is incorporated in the side chain of a polymer compound having a polysiloxane structure in the main chain.

However, in the case of such a material, the amount added is still low. Therefore, a large nonlinear optical effect cannot be expected.

In view of the current situation, it is an object of the present invention to provide a nonlinear polymer material that has improved nonlinear optical effects compared to conventional materials.

[Means to solve the problem]

The present inventors have conducted intensive studies and studies to solve the above problems, and have found that at least one type of polymer component constituting a light-transmitting polymer compound contains a siloxane structure. When dispersed by chemically bonding the corresponding monomer with a nonlinear material, we have succeeded in achieving a larger nonlinear optical effect than conventional products and making the refractive index almost the same as that of the cladding (glass). I found it.

That is, the present invention provides a nonlinear polymeric material in which a compound having a nonlinear optical effect is chemically bonded to a polymeric compound having optical transparency, wherein at least one monomer constituting the polymeric compound has a siloxane structure. Provided is a nonlinear polymer material characterized by containing.

In the present invention, the polymer component having the siloxane structure has a functional group that reacts with an alcoholic hydroxyl group and a reactive double bond, and the functional group that reacts with the alcoholic hydroxyl group has a compound having the above-mentioned nonlinear optical effect. Chemical bonding is particularly preferred.

Furthermore, in the present invention, it is particularly preferable that the compound having the nonlinear optical effect has an alcoholic hydroxyl group in the molecule.

[Effect]

The nonlinear polymeric material of the present invention is a nonlinear polymeric material in which a compound having a nonlinear optical effect is chemically bonded to a polymeric compound having optical transparency, and the nonlinear polymeric material comprises at least one monomer constituting the polymeric compound. The body contains a siloxane structure.

Since a monomer having a siloxane structure is thus polymerized to form a nonlinear polymer material, the siloxane structure is introduced into the side chain portion. In the case of a polymer material made by polymerizing a siloxane-containing monomer, the content of the siloxane moiety increases relative to the whole, and the interaction between the siloxane moiety and the compound having a nonlinear optical effect becomes stronger, so the amount added increases. It is possible to create a material with a refractive index that is increased and still has a refractive index close to that of the cladding glass.

The monomer having a siloxane structure according to the present invention preferably has a functional group that reacts with an alcoholic hydroxyl group. Here, the alcoholic hydroxyl group refers to a hydroxyl group bonded to an alkyl group. Furthermore, examples of the functional group that reacts with alcoholic hydroxyl groups include functional groups that can cause a dehydration reaction.

Further, the monomer having a siloxane structure of the present invention preferably has a reactive double bond, and examples of the reactive double bond include a vinyl group and an acryloyl group.

Preferred examples of monomers containing a siloxane structure in the present invention include monomers represented by the following general formulas (I) to IV).

General formula CI) In formula (I), R1 represents a hydrogen atom or an alkyl group such as a methyl group or an ethyl group, and R,, R, is a methylene group ÷ Cll
2-) r- or ether group + C1), →70+CI
+2) r-, and 1) m and n represent integers from 0 to 1O. a represents an integer of 1-10000. X is a hydroxyl group or a carboxyl group.

Represents a functional group that reacts with an alcoholic hydroxyl group, such as an epoxy group.

General formula (II) In formula (II), R3 represents a hydrogen atom or an alkyl group such as a methyl group or an ethyl group, and Re and R14 represent a methine group + C
1) 2+- or ether group + C1)! -)-i
−0÷Cl1t)i−, l + m, n is 0
Represents an integer between ~10. R1 to Lffi are methyl groups.

It represents an alkyl group such as an ethyl group or an aryl group such as a phenyl group. b represents an integer from 1 to 1oooo. Y represents a "functional group that reacts with an alcoholic hydroxyl group" such as a hydroxyl group, a carboxyl group, or an epoxy group.

General formula (I[) General formula (IV) RIi Rlm C-R,.

1 llt In the formula (I[), R, s to R1t represent a functional group that reacts with an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, or an alcoholic hydroxyl group such as a hydroxyl group, a carboxyl group, or an epoxy group. represent. Re3 is methylene group+C1h-+r- or ether group+C1)!
→rO+cH, juice, 1. m and n represent integers from θ to lO. R1° represents a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. c and d represent integers from 1 to toooo.

C:0 C-R,.

CII* In formula (IV), 1lte to Lx represent a functional group that reacts with an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, or an alcoholic hydroxyl group such as a hydroxyl group, a carboxyl group or an epoxy group. Lx is methylene group ÷ cH1 or ether group + CI (□→rO+
c1). It is a square, 1. m and n represent integers from 0 to 10. R.I.

represents a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. c and d represent integers from 1 to 10,000.

The polymer material of the present invention has a siloxane structure as shown in the above general formulas (I) to (■), and a monomer having a polymerizable double bond and an alcohol-reactive functional group, and a nonlinear optical effect. It can be obtained by polymerizing a monomer reacted with a compound having a polymerizable double bond, but it is also possible to use a compound having a polymerizable double bond, such as acrylic acid or methacrylic acid, as another monomer.

Compounds having nonlinear optical effects according to the present invention include:
It is desirable to have a chemical bond with a monomer containing a siloxane structure, particularly preferably one having an alcoholic hydroxyl group, such as the following.

4-Hydroxymethyl(methyl)amino-4'-nitrostilbene (referred to as compound ■), 4-hydroxyethyl(methyl)amino-4'-nitrostilbene, 4-hydroxypropyl(methyl)amino-4'-nitrostilbene1. 4-hydroxybutyl(methyl)amino-4'-nitrostilbene, 4-hydroxypentyl(methyl)amino-4'-nitrostilbene, 4-hydroxyhexyl(methyl)amino-4'-nitrostilbene, 4-hydroxymethyl(ethyl) ) Amino-4'-nitrostilbene (referred to as compound ■), 4-hydroxyethyl (ethyl)
Amino-4'-nitrostilbene, 4-hydroxypropyl(ethyl)amino-4'-nitrostilbene, 4-
Hydroxybutyl(ethyl)amino-4'-nitrostilbene, 4-hydroxypentyl(ethyl)amino-4
'-nitrostilbene, 4-hydroxyhexyl(ethyl)amino-4'-nitrostilbene, 4-hydroxymethyl(propyl)amino-4'-nitrostilbene,
4-Hydroxyethyl(propyl)amino-4'-nitrostilbene, 4-hydroxypropyl(propyl)amino-4'-nitrostilbene, 4-hydroxybutyl(propyl)amino-4'-nitrostilbene, 4-hydroxy Pentyl(propyl)amino-4'nitrostilbene, 4-hydroxyhexyl(propyl)amino-
4'-nitrostilbene, 4-hydroxymethyl(butyl)amino-4'nitrostilbene, 4-hydroxyethyl(butyl)amino-4'-nitrostilbene, 4-
Hydroxypropyl(butyl)amino-4'nitrostilbene, 4-hydroxybutyl(butyl)amino-4'
-nitrostilbene, 4-hydroxypentyl(butyl)amino-4'-nitrostilbene, 4-hydroxyhexyl(butyl)amino-4'-nitrostilbene, 4-
Hydroxymethyl(pentyl)amino-4'nitrostilbene, 4-hydroxyethyl(pentyl)amino-4
'-nitrostilbene, 4-hydroxypropyl(pentyl)amino-4'-nitrostilbene, 4-hydroxybutyl(pentyl)amino-4'-nitrostilbene, 4-hydroxypentyl(pentyl)amino-4'-
Nitrostilbene, 4-hydroxyhexyl(pentyl)amino-4'-nitrostilbene, 4-hydroxymethyl(hexyl)amino-4'-nitrostilbene, 4
-Hydroxyethyl(hexyl)amino-4'-nitrostilbene, 4-hydroxypropyl(hexyl)amino-4'-nitrostilbene, 4-hydroxybutyl(
hexyl)amino-4'-nitrostilbene, 4-hydroxypentyl(hexyl)amino-4'-nitrostilbene, 4-hydroxyhexyl(hexyl)amino-
4'nitrostilbene, 2-[ethyl[4-((4-nitrophenyl)azo]phenyl]amino]ethanol)
The compound ■), abbreviated as redl, 2-[methyl[4-
[(4-nitrophenyl)azo]phenyl]amino]ethanol, 2-[[4-[(4-nitrophenyl)aso]phenyl]amino]ethanol (referred to as compound ■),
2-[Propyl[4-C(4-nitrophenyl)azo]
, phenyl]amino]ethanol, 2-[butyl(4-
((4-nitrophenyl)azo]phenyl]amino]ethanol, 2-[pentyl[4-((4-nitrophenyl)azo]phenyl]amino]ethanol), 2-[hexyl(4-[(4-nitrophenyl) ) aso〕phenyl〕
Amino]ethanol, 2-[ethyl[4-[(4-nitrophenyl)azo]phenyl]amino]methanol, 2
-[ethyl[4-[(4nitrophenyl)azo]phenyl]amino]propertool, 2-[ethyl[4-((4
-nitrophenyl)azo]phenyl]amino]butanol, 2-[ethyl[4-((4-nitrophenyl)azo]phenyl]amino]pentanol, 2-[ethyl[4
-[(4-nitrophenyl)azo]phenyl]amino]
Hexanol, 2-[(4-[(4-nitrophenyl)azo]phenyl]amino]methanol, 2-((4-
[(4-nitrophenyl)azo]phenyl]amino]propatol, 2-((4-((4-nitrophenyl)azo]phenyl]amino]butanol, 2-[(4-C
(4-nitrophenyl)azo]phenyl]amino]pentanol, 2((4-((4-nitrophenyl)azo)
phenyl]amino]hexanol, 2-[methyl(4-
[(4-nitrophenyl)azo]phenyl]amino]methanol, 2-[methyl[4-[(4-nitrophenyl)azo]phenyl]amino]propanol, 2-[methyl(4-((4-nitrophenyl) Phenyl)azo]phenyl]amino]butanol, 2-[methyl(4-((4-nitrophenyl)azo]phenyl]amino]pentanol, 2
-[Methyl(4-[(4-nitrophenyl)azo]phenyl]amino]hexanol, 2-[propyl(4-[
(4-nitrophenyl)azo]phenyl]amino]methanol, 2-[propylC4-CC4-nitrophenyl]azo]phenyl]amino]propatur, 2-[propyl[4-[(4-nitrophenyl)azo] Phenyl]
Amino]butanol, 2-[propyl(4-((4-nitrophenyl)azo]phenyl]amino]pentanol, 2-[propyl(4-((4-nitrophenyl)azo]phenyl)amino]hexanol, 2 -[Butyl (4
-((4-nitrophenyl)aso]phenyl]amino)
Methanol, 2-[butyl[4[(4-nitrophenyl)azo]phenyl]amino]propanol, 2-[butyl[4-((4-nitrophenyl)azo]phenyl]amino]butanol, 2-[butyl [4-[(4-nitrophenyl)azo]phenyl]amino]pentanol, 2
-[Butyl[4-[(4-nitrophenyl)azo]phenyl]amino]hexanol, 2-[pentyl[4-[
(4-nitrophenyl)azo]phenyl]amino]methanol, 2-[pentyl(4-((4-nitrophenyl)azo]phenyl]amino)propatur, 2-[pentyl[4-C(4-nitrophenyl) ) azo] phenyl]
Amino]butanol, 2-[pentyl[4-((4-nitrophenyl)azo]phenyl]amino]pentanol, 2-[pentyl[4-[(4-nitrophenyl)azo]phenyl]amino]hexanol, 2 −[hexyl[
4-[(4-nitrophenyl)azo]phenyl]amino]methanol, 2-[hexyl[4-[(4-nitrophenyl)azo]phenyl]amino]propanol, 2-
[Hexyl(4-[(4-nitrophenyl)aso]phenyl]amino]butanol, 2-[hexyl[4[(4
-nitrophenyl)azo]phenyl]amino]pentanol, 2-[hexyl[4-[(4-nitrophenyl)]
Azo]phenyl]amino]hexanol and the like.

In the present invention, a method for chemically bonding a monomer having a siloxane structure and a compound having a nonlinear optical effect is shown in Examples below.

It is desirable that the refractive index of the resin composition chemically bonded with the nonlinear optical material is slightly smaller than the refractive index of the cladding of the optical fiber, and when the cladding is quartz, n = 1.40.
~1.45 is suitable.

〔Example〕

The present invention will be described below with reference to specific examples and comparative examples not based on the structure of the present invention, but the present invention is not limited thereto.

Example 1 A monomeric halogen compound was obtained by reacting a monomer containing a siloxane structure and a hydroxyl group with thionyl chloride and chlorinating the hydroxyl group. A monomer containing a nonlinear material was obtained by reacting this compound with a compound having a nonlinear optical effect and removing Hα. Next, this monomer was polymerized using AIBN (azobisisobutyronitrile) as an initiator to obtain a polymer compound incorporating a nonlinear material. The monomer containing a siloxane structure and the compound having a nonlinear optical effect used at this time are shown in Table 1 below. At this time, the amount of the nonlinear material added was 20% by weight or more when calculated from the monomer having a siloxane structure.

Table 1 All of the obtained materials were optically transparent, and the refractive index was measured to be 1.41 at a wavelength of 1.30.
-1.44. Furthermore, when these materials were applied to a coupler type optical switch shown in FIG. 1 as an example of a device, excellent response characteristics were exhibited. In FIG. 1, l represents a fiber, 2 represents a coupler storage case, 3 represents an optical coupling section, 4 represents a nonlinear polymer material of the present invention, 5 represents an electrode, and 6 represents a conducting wire. Further, FIG. 2 is a sectional view taken along the line AA in FIG. 1.

Example 2 A monomer containing a nonlinear material was prepared by removing H30 by reacting a monomer containing a siloxane structure and a carboxyl group with a compound having a nonlinear optical effect in the presence of a catalytic amount of HaS04. Obtained a mass. The monomer is AI
Polymerization was performed using BN as an initiator to obtain a polymer compound incorporating a nonlinear material. Table 2 below shows the monomers containing a siloxane structure and the compounds having a nonlinear optical effect that were used. At this time, the amount of nonlinear material added is calculated from the monomer having a siloxane structure, and the weight ratio is 2.
It was 0% by weight or more.

Table 2 All of the obtained materials were optically transparent, and when their refractive index was measured, they all had a refractive index of 1 at a wavelength of 1.30/71).
．． It was 41-1.44. Furthermore, when these materials were applied to a coupler type optical switch shown in FIG. 1 as an example of a device, excellent response characteristics were exhibited.

Example 3 A monomer containing a siloxane structure and an epoxy group is reacted with a compound having a nonlinear optical effect in the presence of catalytic amounts of El and Af to perform a ring-opening reaction, thereby producing a nonlinear material. The containing monomer was obtained. This monomer was then polymerized using AIBN as an initiator to obtain a polymer compound incorporating the nonlinear material. The monomer containing a siloxane structure and the compound having a nonlinear optical effect used at this time are shown in Table 3 below. At this time, the amount of the nonlinear material added was 20% by weight or more, calculated from the monomer having a siloxane structure.

Table 3 The materials obtained above. Yo, Izuwa is also completed? The refractive index was measured to be 1.41 to 1.44 at a wavelength of 1.30 ts. Furthermore, when these materials were applied to a coupler type optical switch shown in FIG. 1 as an example of a device, excellent response characteristics were exhibited.

Comparative Example 1 Acrylic acid was used as a monomer having no siloxane structure, the hydroxyl group was chlorinated, and the hydroxyl group was reacted with compounds ■, ■, ■, and ■ as nonlinear optical materials used in Examples 1 to 3, respectively. By removing Hα, a monomer containing a nonlinear material was obtained. Next, the compounds obtained by using this monomer with AIBN as an initiator were all optically transparent, but their refractive index exceeded 1.5, making them suitable for application to coupler-type optical switches. I couldn't do that.

Comparative Example 2 Using methacrylic acid instead of acrylic acid in Comparative Example 1, compounds ① and ② were used as nonlinear materials.

A polymer compound was obtained by reacting with (1) and (2), respectively, and then polymerizing using AIBN as an initiator. All of the obtained compounds were optically transparent, but their refractive index exceeded 1.5, and they could not be applied to coupler-type optical switches.

〔Effect of the invention〕

As explained above, the present invention improves the amount of nonlinear material added by introducing a siloxane structure into the monomer constituting the optically transparent polymer compound and incorporating the nonlinear material through chemical bonding. It is possible to provide a material whose refractive index is almost as low as that of the cladding (glass).

Furthermore, it was found that the nonlinear polymer material of the present invention exhibits an excellent electro-optic effect, and can be applied to a coupler-type optical switch, which was attempted to be made into a device, as an example.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view illustrating the structure of a coupler type optical switch using the nonlinear polymer material of the present invention, and FIG. 2 is a cross-sectional view taken along the line AA in FIG. 1. In the figure, ■ is a fiber, 2 is a coupler storage case, 3 is an optical coupling part, 4 is a nonlinear polymer material of the present invention, 5 is an electrode, and 6
represents a conductor.

Claims (3)

[Claims] (1) A nonlinear polymeric material formed by chemically bonding a compound having a nonlinear optical effect to a polymeric compound having optical transparency, wherein at least one monomer constituting the polymeric compound contains a siloxane structure. A nonlinear polymer material characterized by: (2) the monomer having the siloxane structure has a functional group that reacts with an alcoholic hydroxyl group and a reactive double bond,
2. The nonlinear polymeric material according to claim 1, wherein the functional group portion that reacts with the alcoholic hydroxyl group is chemically bonded to the compound having the nonlinear optical effect. (3) The nonlinear polymer material according to claim (1), wherein the compound having a nonlinear optical effect has an alcoholic hydroxyl group in the molecule.