JPH06263885A - Process for molding organic optical material - Google Patents

Abstract

PURPOSE:To produce a high-quality optical material by molding even from a difficultly vaporizable material, an easily heat-decomsable material or the like. CONSTITUTION:This molding process comprises mixing a solution prepared by dissolving a plurality of organic optical materials in a good solvent common to them with a poor solvent compatible to the good solvent and common to the materials to form a precipitate, filtering off the obtained precipitate, vacuum-drying the cake, grinding the dried product, heat-treating the powder in a vacuum and melt-molding the powder in a vacuum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for molding and manufacturing an organic optical material. More specifically, the present invention provides a new organic optical material that can be molded as a high-quality and highly-functional optical material regardless of whether it is an optical material that hardly vaporizes or an optical material that easily decomposes thermally. The present invention relates to a molding manufacturing method.

[0002]

2. Description of the Related Art Conventionally, the development and application of optical materials have expanded rapidly, and with the recent development of optoelectronics, expectations for higher-performance optical materials have increased, and the development for that purpose is also vigorous. Is being promoted. Among these optical materials, the organic optical materials are (1)
Compared with inorganic ferroelectric crystals such as lithium niobate, the nonlinear optical constant is large, (2) Response speed is faster than inorganic semiconductors such as gallium-arsenic, (3) Compared with inorganic crystalline materials, Active research and development is being promoted because it is expected that it will be possible to simultaneously satisfy various properties that conventional inorganic materials cannot simultaneously satisfy, such as easy processing into thin films and fibers. For example,
Specifically, it is used for second-order nonlinear optical materials used for the second harmonic generation device of light, optical switches and optical memories that use the optical bistable phenomenon, or real-time holography that uses the optical phase conjugation phenomenon. The search for materials that exhibit a high third-order nonlinear optical effect is being actively pursued.

The methods for producing these organic optical materials are as follows: 1) cutting and polishing of single crystals 2) coating method (spin coating, dipping, etc.) 3) vacuum deposition method 4) CVD method 5) organic molecular beam The vapor deposition method is used. However, in reality, these conventional methods have various drawbacks in order to realize a high degree of material fine structure control and obtain a more highly functional optical material.

That is, in the case of the above-mentioned single crystal cutting / polishing process, most of the organic compound single crystals are fragile, and there is a drawback that fine cracks are likely to occur during the cutting / polishing process. In addition, it is difficult to obtain a "single crystal" of a material that is a composite of two or more kinds of organic compounds. In the case of the following coating method, there is a problem that the coating solvent is likely to remain inside the coating film, and due to the heat generated by laser irradiation with high energy density, this vaporizes and foams to cause optical damage.

Particularly, when the thickness of the coating film is several tens of μm or more, the solvent is likely to remain and it is not easy to remove it.
The vacuum vapor deposition method, the CVD method, and the organic molecular beam vapor deposition method commonly have an organic compound that is difficult to vaporize,
It has the drawback that it cannot be applied to organic compounds that decompose simultaneously with vaporization. In particular, it is difficult to vaporize polymer compounds and salts of organic ions.

Moreover, it is extremely difficult to process an optical component in a form in which the fine structure of an optical material in which two or more kinds of organic compounds are mixed is controlled. So this invention
By eliminating the drawbacks of the prior art as described above, even if it is an optical material that is easily decomposed by heat or an optical material that is difficult to vaporize, it is possible to use a highly functional organic optical material that enables high-quality fine structure control. It is intended to provide a new manufacturing method that can be manufactured.

[0007]

In order to solve the above-mentioned problems, the present invention provides a solution in which a plurality of kinds of organic optical materials are dissolved in a common good solvent, which is compatible with the good solvent. It is mixed with a poor solvent that is common to organic optical materials to cause precipitation. A method for forming and manufacturing an organic optical material is provided.

The method for producing the optical material of the present invention will be described in more detail below. That is, first, any substance that can be used in the organic optical material of the present invention can be used as long as it can be dissolved in a suitable solvent. Specifically, a solution of a plurality of organic polymer materials, a liquid in which inorganic fine particles are further dispersed, a liquid in which an organic low-molecular compound and an organic polymer material are dissolved in a common solvent, and fine particles of an organic compound are used as an organic polymer material. It is possible to use a liquid dispersed in the above solution, a liquid crystal in which a liquid crystal and an organic polymer material are dissolved in a common solvent, or the like.

A specific example is as follows. [Organic Polymer Material] Among the organic polymer compounds, those having “optical properties and functions” can be used as the optical material of the present invention. In addition, these organic polymer compounds can also be used as a material that disperses and holds molecules or aggregates of organic low molecular weight compounds and fine particles of inorganic compounds, that is, as a “matrix material”.

Specific examples of such organic polymer materials include polystyrene, poly (α-methylstyrene), polyindene, poly (4-methyl-1-pentene), polyvinylpyridine, polyvinylforchol, polyvinylacetal, polyvinyl. Butyral, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl benzyl ether, polyvinyl methyl ketone, poly (N-vinylcarbazole), poly (N-
Vinylpyrrolidone), polymethyl acrylate, polyethyl acrylate, polyacrylic acid, polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, benzyl polymethacrylate, cyclohexyl methacrylate, polymethacrylic acid, Polymethacrylic acid amide, polymethacrylonitrile, polyacetaldehyde, polychloral, polyethylene oxide, polypropylene oxide, polyethylene terephthalate, polybutylene terephthalate, polycarbonates (bisphenols + carbonic acid), poly (diethylene glycol / bisallyl carbonate), 6-
Nylon, 6,6-nylon, 12-nylon, 6,1
2-nylon, ethyl polyaspartate, ethyl polyglutamate, polylysine, polyproline, poly (γ-
Benzyl-L-glutamate), methyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, acetyl cellulose, cellulose triacetate, cellulose tributyrate, alkyd resin (phthalic anhydride + glycerin), fatty acid modified alkyd resin (fatty acid + anhydrous) Phthalic acid + glycerin), unsaturated polyester resin (maleic anhydride + phthalic anhydride + propylene glycol), epoxy resin (bisphenols + epichlorohydrin),
Polyurethane resin, phenol resin, urea resin, melamine resin, xylene resin, toluene resin, guanamine resin and other resins, poly (phenylmethylsilane) and other organic polysilanes, organic polygermanes and their copolymerization
Copolycondensates and polymer compounds obtained by plasma polymerization of normally non-polymerizable compounds such as carbon disulfide, carbon tetrafluoride, ethylbenzene, perfluorobenzene, perfluorocyclohexane, and trimethylchlorosilane. Can be mentioned.

These organic polymer compounds contain an organic dye or a residue of an organic low molecular weight compound exhibiting an optical nonlinear effect as a side chain of a monomer unit, as a cross-linking group, as a copolymerization monomer unit, or as a polymerization initiation terminal. Good. Also,
These organic polymer compounds may be used as a mixture of several kinds, or a combination of "microphase separation" may be used. [Inorganic fine particles / organic polymer material] Specific examples of the inorganic fine particles that can be used as the optical material of the present invention in combination with the above organic polymer materials include selenium, tellurium, germanium, silicon, silicon carbide, and Cd-Zn-. Mn
-Se-Te-S-Ox, Ga-In-Al-As-P
Examples thereof include semiconductor particles such as, and ultrafine particles of precious metal such as Au colloid. [Organic low molecular weight / organic polymeric material] Specific examples of the organic low molecular weight compound used in the optical material of the present invention in combination with the above organic polymeric materials include urea and its derivatives, m-nitroaniline, 2- Benzene derivatives such as methyl-4-nitro-aniline, 2- (N, N-dimethylamino) -5-nitroacetanilide, N, N'-bis (4-nitrophenyl) methanediamine, 4-methoxy-4'- Biphenyl derivatives such as nitrobiphenyl,
A stilbene derivative such as 4-methoxy-4′-nitrostilbene, 4-nitro-3-picoline = N-oxide,
(S)-(-)-N- (5-nitro-2-pyridyl)-
Pyridine derivatives such as prolinol, 2 ', 4,4'-
In addition to chalcone derivatives such as trimethoxychalcone and secondary non-linear optically active substances such as thienylchalcone derivatives, various organic dyes and organic pigments can be mentioned.

As described above, the residue of these organic low molecular weight compounds and the organic polymer compound may form a chemical bond. [Liquid Crystal] Specific examples of the liquid crystal used in the optical material of the present invention in combination with the above organic polymer materials include various cholesterol derivatives, 4′-n-butoxybenzylidene-4-cyanoaniline and 4′-n. 4′-alkoxybenzylidene-4-cyanoanilines such as hexylbenzylidene-4-cyanoaniline, 4′-ethoxybenzylidene-4-n-butylaniline, 4′-methoxybenzylideneaminoazobenzene, 4- (4′-methoxy) 4'-alkoxybenzylideneanilines such as benzylidene) aminobiphenyl and 4- (4'-methoxybenzylidene) aminostilbene, 4'-cyanobenzylidene-4-n-butoxyaniline, 4'-cyanobenzylidene-4-n- 4'such as hexyloxyaniline
-Cyanobenzylidene-4-alkoxyanilines,
4'-n-butoxycarbonyloxybenzylidene-4
Carbonic acid esters such as -methoxyaniline, p-carboxyphenyl n-amyl carbonate, n-heptyl 4- (4'-ethoxyphenoxycarbonyl) phenyl carbonate, 4-n-butylbenzoic acid 4'-ethoxyphenyl, 4-n -Butylbenzoic acid 4'-octyloxyphenyl, 4-n-pentylbenzoic acid 4'-hexylyloxyphenyl and other 4-alkyllbenzoic acid 4'-alkoxyphenyl esters, 4,4'-di-n-amyl Azoxybenzene derivatives such as oxyazoxybenzene, 4,4'-di-n-nonyloxyazoxybenzene, 4-cyano-4'-n-octylbiphenyl, 4-
Liquid crystals such as 4-cyano-4'-acyl rubiphenyls such as cyano-4'-n-dodecyl biphenyl, and (2S, 3S) -3-methyl-2-chloropentanoic acid 4 ', 4 "- Octyloxybiphenyl, 4'-
(2-Methylbutyl) biphenyl-4-carboxylic acid 4-
Hexyloxyphenyl, 4'-octylbiphenyl-
Ferroelectric liquid crystals such as 4- (2-methylbutyl) phenyl 4-carboxylate may be mentioned.

For example, in order to mold and manufacture the above-mentioned organic optical material into a desired shape, in the present invention, plural kinds of these materials are dissolved in a common good solvent, and then the obtained solution is prepared. , This good solvent is compatible, and
The optical material is mixed with a solvent which is a poor solvent in common, and reprecipitated to obtain a precipitate. Such a good solvent or a poor solvent can be selected, for example, from the following depending on the type of optical material.

Specifically, alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, amyl alcohol, cyclohexanol and benzyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol and glycerin, ethyl acetate,
Esters such as n-butyl acetate, amyl acetate and isopropyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, diethyl ether, dibutyl ether, methoxyethanol, ethoxyethanol, butoxyethanol, carbitol and other ethers , Tetrahydrofuran, 1,4
-Cyclic ethers such as dioxane, dichloromethane,
Chloroform, carbon tetrachloride, 1,2-dichloroethane,
Halogenated hydrocarbons such as 1,1,2-trichloroethane and trichlene, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene, anisole, α-chloronaphthalene and other aromatic hydrocarbons, n-pentane, Aliphatic hydrocarbons such as n-hexane, n-heptane and cyclohexane, N, N-
Amides such as dimethylformamide, N, N-dimethylacetamide and hexamethylphosphoric triamide, cyclic amides such as N-methylpyrrolidone, urea derivatives such as tetramethylurea and 1,3-dimethyl-2-imidazolidinone , Sulfoxides such as dimethyl sulfoxide, carbonates such as ethylene carbonate and propylene carbonate, nitriles such as acetonitrile, propionitrile and benzonitrile, nitrogen-containing heterocyclic compounds such as pyridine and quinoline, triethylamine, triethanolamine In addition to amines such as diethylamino alcohol and aniline, solvents such as water, nitromethane, carbon disulfide and sulfolane can be used.

These solvents may be used as a mixture of plural kinds. Note that the categories of "good solvent" and "poor solvent" are relative, and when an organic optical material to be a solute is specified, the solubility of the solute (generally,
In a permutation based on a constant weight, or defined as the soluble mass that can dissolve a volume of solvent), solvents with high solubility are “good solvents” and solvents with low solubility are “poor solvents”. It is.

Next, in the method of the present invention, the obtained precipitate is filtered, dried under reduced pressure of, for example, 1 pa or less, and pulverized into a small piece having an outer diameter of less than 1 mm to obtain a powder. Then, more preferably, the heat treatment is performed under a vacuum of 1 × 10 ⁻⁴ Pa or less. Needless to say, conventionally known means can be appropriately adopted for the reduced-pressure drying and pulverization. Further, the depressurization condition and the particle size at that time are not particularly critical.

However, it has been confirmed that the outer diameter is preferably less than 1 mm in order to effectively carry out the subsequent vacuum heat treatment. Of course, even if it is 1 mm or more, it can be dealt with by changing the vacuum heat treatment conditions. The vacuum heat treatment is intended to completely remove the residual solvent. To confirm the presence of volatile components such as solvent and adsorbed water remaining in the powder and to completely remove the volatile components, ionize the gas molecules released when the powder is placed in an ultrahigh vacuum and heated. A method of analyzing with a mass spectrometer can be used. The details of this method are also described in the specification of Japanese Patent Application No. 4-360252.

For this reason, the vacuum heat treatment is carried out by an ionizer,
It is preferably carried out in a vacuum vessel equipped with a mass spectrometer. Next, the vacuum heat-treated powder is heated and melt-molded under vacuum. This molding is performed by applying a hydrostatic pressure of 50 kg / cm ² for about 10 minutes at a temperature of, for example, about 150 ° C., as already proposed (JP-A-4-99609). At this time, it is also preferable to apply pressure while applying shear stress in one direction. By this pressure treatment, an optical thin film or the like can be obtained.

Since the molding production is carried out at a lower temperature,
There is no concern about thermal decomposition, and it is possible to mold a high quality optical material even in a mixed system of an organic ionic salt and a polymer compound, which are difficult to vaporize. Hereinafter, the present invention will be described in more detail with reference to examples.

[0020]

EXAMPLES Organic optical materials such as 3,3'-Di of the following formula
ethyloxadicarbocyanine Iodide

[0021]

[Chemical 1]

When (DODCI) is dispersed in a polymer, such as polymethylmethacrylate (PMMA), the DODCI is dissolved in a suitable solvent that dissolves both DODCI and PMMA, such as 1 liter of acetone.
^-3 mol (486.35 mg) and PMMA (10 ^-2 mol (1001.2 mg)) were dissolved and sufficiently stirred and mixed, and then 10 liters of poor solvent was stirred by a stirrer or an ultrasonic vibration device. (For example, n-hexane) is added dropwise little by little to obtain a coprecipitate of DODCI.PMMA.

The resulting precipitate was filtered off, dried under reduced pressure of 1 Pa or less by a vacuum dryer, and then pulverized into small pieces having an outer diameter of less than 1 mm and pulverized. × 10 ^-4 Pa until below the thermal decomposition temperature (150
C.) below 140.degree. C. and heat treated. The dried PMMA powder containing DODCI was heated at a temperature of 150 ° C. by the hot pressing method (Japanese Patent Laid-Open No. 4-99609) to give 5
A heating / pressurizing treatment was performed in a vacuum for about 10 minutes with a hydrostatic pressure of 0 kg / cm ² . An optically transparent thin film was obtained.

This thin film is a dispersion of DODCI in PMMA, which decomposes without melting when heated, and was realized for the first time by the present invention as an optically transparent thin film. Figure 1 shows the DO of this thin film material.
It is an absorption / emission spectrum of DCI.

[0025]

According to the present invention, as described in detail above, like a mixed system of a salt of an organic ion and a polymer compound,
It is possible to process and manufacture an organic optical material that hardly vaporizes. Further, it becomes easy to manufacture a material which is easily decomposed by heat. Further, there is an advantage that, for example, a film having durability against a high power laser can be processed rather than a coating method.

[Brief description of drawings]

FIG. 1 is an absorption / emission spectrum diagram of DODCI of a thin film as an example.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Hiraga 1-101-308 Kasuga, Tsukuba City, Ibaraki Prefecture (72) Inventor Tetsuro Moriya 1-1-4 Umezono, Tsukuba City, Ibaraki Prefecture Industrial Technology Institute Electronic Technology General (72) Inventor Norio Tanaka 1-9-4 Horinouchi, Adachi-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. Tokyo Manufacturing Office

Claims (1)

[Claims] 1. A solution prepared by dissolving a plurality of types of organic optical materials in a common good solvent thereof is mixed with a poor solvent which is compatible with the good solvent and is common to the organic optical materials to cause precipitation. A method for forming and manufacturing an organic optical material, which comprises filtering the obtained precipitate, drying under reduced pressure, then pulverizing, and subjecting the obtained powder to vacuum heat treatment, and further heat-melt forming under vacuum.