JP2965185B2 - Manufacturing method, usage method and test method of organic optical material resistant to high power density laser light - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic material resistant to high power density laser light and a method for testing the same.

[0002]

2. Description of the Related Art In recent years, optical materials having high functions have been actively developed in the field of optoelectronics. Among them, the organic optical material has (1) a large nonlinear optical constant as compared with an inorganic ferroelectric crystal such as lithium niobate;
(2) Faster response speed compared to inorganic semiconductors such as gallium-arsenic, and (3) Easy processing into thin films and fibers compared to inorganic crystalline materials. It is expected that various properties that have not been met can be satisfied at the same time, and active research and development is being promoted. For example, a second-order nonlinear optical material used for a second harmonic generation element of light, an optical switch or an optical memory using an optical bistable phenomenon, or a high-order 3 used for a real-time holography using an optical phase conjugation phenomenon. The search for a material exhibiting the next nonlinear optical effect is being actively pursued. Nonlinear optical phenomena expected from new and useful organic optical materials are essentially
The higher the order, the higher the dependence on the optical power density. In order to obtain a practical effect, it is necessary to use (A) laser light, and (B) a device for effectively increasing the power density of laser light. (C) It is necessary to develop a material that can withstand high power density laser beam irradiation and has a large nonlinear optical effect. At present, the application of laser light is established as an extremely common technique, and many ideas for effectively increasing the power density of laser light have been proposed.

[0003]

However, there have been few reports on the development of organic optical materials that can withstand high-power-density laser light irradiation, and few organic low-molecular crystals are irradiated with laser light to cause destruction. An example of checking the threshold has been reported [Masao Kato, Hachiro Nakanishi, "Organic Nonlinear Optical Materials", CMC (1985), p. 55]. The present inventors have found that one of the physical processes in which an organic optical material is damaged by high power density laser light irradiation is that volatile components in the material are vaporized and foamed due to heat generated by high power density laser light transmission. Heading to do
As a result of intensive studies, the present invention has been completed. The present invention has several hundred MW /
it is an object to provide an organic light materials and test methods withstand high power density laser beam cm ² to several hundred GW / cm ^2.

[0004]

The present invention comprises the following items. (1) A sample of an organic optical material is placed in a vacuum device whose total volume does not exceed 100,000 times the sample volume, and the pressure in the vacuum device is set to 1 ×
The sample in the vacuum apparatus is heated to a temperature higher than the maximum use temperature of the organic optical material as an optical component by setting the temperature to 10 ⁻⁴ Pa or less, and gas molecules released from the sample are ionized to perform mass spectrometry. When analyzed by the apparatus, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and the number obtained by dividing the mass m of the ions by the charge e. The value obtained by subtracting the counts of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of counts of ions having an m / e value of 29 or more is calculated as carbon monoxide, nitrogen molecule, oxygen molecule and carbon dioxide. The inorganic fine particles or the organic low-molecular compound are dispersed in a matrix composed of an organic high-molecular compound that does not exceed a value obtained by multiplying the total number of the assigned molecular ion counts by 0.1. Ku manufacturing method of an organic light material resistant to high power density laser beam, characterized in that dissolving. (2) The sample of the organic optical material is placed in a vacuum device whose total volume does not exceed 100,000 times the sample volume, and the pressure in the vacuum device is set to 1 ×
The sample in the vacuum apparatus is heated to a temperature higher than the maximum use temperature of the organic optical material as an optical component by setting the temperature to 10 ⁻⁴ Pa or less, and gas molecules released from the sample are ionized to perform mass spectrometry. When analyzed by the apparatus, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and the number obtained by dividing the mass m of the ions by the charge e. The value obtained by subtracting the counts of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of counts of ions having an m / e value of 29 or more is calculated as carbon monoxide, nitrogen molecule, oxygen molecule and carbon dioxide. Dissolving or dispersing, in an inorganic polymer compound, an organic low-molecular compound that does not exceed a value obtained by multiplying the total number of counted molecular ions by 0.1 by 0.1. Method of manufacturing an organic light material resistant to power density laser beam. (3) The method according to item 2, wherein the organic low-molecular compound is a liquid crystal. (4) A sample of the organic optical material is placed in a vacuum device whose total volume does not exceed 100,000 times the sample volume, and the pressure in the vacuum device is set to 1 ×
The sample in the vacuum apparatus is heated to a temperature higher than the maximum use temperature of the organic optical material as an optical component by setting the temperature to 10 ⁻⁴ Pa or less, and gas molecules released from the sample are ionized to perform mass spectrometry. When analyzed by the apparatus, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and the number obtained by dividing the mass m of the ions by the charge e. The value obtained by subtracting the counts of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of counts of ions having an m / e value of 29 or more is calculated as carbon monoxide, nitrogen molecule, oxygen molecule and carbon dioxide. Characterized in that a single crystal of an organic low-molecular compound not exceeding a value obtained by multiplying the total number of counted molecular ions by 0.1 by 0.1 is used as a wavelength conversion element for laser light. Using organic optical materials to withstand high power density laser beam. (5) The sample of the organic optical material is placed in a vacuum device whose total volume does not exceed 100,000 times the sample volume, and the pressure in the vacuum device is set to 1 ×
The sample in the vacuum apparatus is heated to a temperature higher than the maximum use temperature of the organic optical material as an optical component by setting the temperature to 10 ⁻⁴ Pa or less, and gas molecules released from the sample are ionized to perform mass spectrometry. Analyzing with a device and comparing the count number of molecular ions attributed to water molecules with the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and / or
Alternatively, a value obtained by subtracting the count number of molecular ions attributed to oxygen molecules and carbon dioxide from the total count of the count number of ions having a number m / e obtained by dividing the mass m of the ion by the charge e of 29 or more, A method for testing an organic optical material that withstands high power density laser light, wherein the total number of counts of molecular ions assigned to carbon monoxide, nitrogen molecule, oxygen molecule, and carbon dioxide is compared. (6) 1 × 1 using a crusher provided in the vacuum vessel
In a high vacuum state of 0 ⁻⁴ Pa or less, a sample of the material is 1 m in outer diameter.
Item 5. The method for testing an organic optical material that withstands high power density laser light according to Item 5, wherein the test is performed after crushing into small pieces of not more than m. (7) The sample of the organic optical material is placed in a vacuum apparatus in which the total volume of the vacuum system does not exceed 100,000 times the sample volume and the pressure in the vacuum system is 1 × 10 ⁻⁴ Pa or less. Place and gradually heat or cool from room temperature, ionize gas molecules released from the sample and analyze with a mass spectrometer, the number of molecular ions attributed to water molecules attributed to carbon monoxide and nitrogen molecules Measuring the temperature in excess of the number of molecular ions to be performed and / or from the total count of the number of ions having a number m / e equal to or greater than 29 by dividing the mass m of the ion by the charge e, oxygen molecules and The value obtained by subtracting the number of molecular ions attributed to carbon dioxide is 0.1% to the total number of molecular ions attributed to carbon monoxide, nitrogen molecule, oxygen molecule and carbon dioxide.
A method for testing an organic optical material that withstands high power density laser light, characterized by measuring a temperature exceeding a value obtained by multiplying the temperature by a temperature. (8) 1 × 1 using a crusher provided in the vacuum vessel
In a high vacuum state of 0 ⁻⁴ Pa or less, a sample of the material is 1 m in outer diameter.
Item 7. The method for testing an organic optical material that withstands high power density laser light according to Item 7, wherein the test is performed after crushing into small pieces of not more than m.

[0005] The method for testing an organic optical material according to the present invention can be carried out using a test apparatus configured by combining a known vacuum apparatus, a heating apparatus, a cooling apparatus and a mass spectrometer. Hereinafter, the organic optical material of the present invention and the test method thereof will be described in more detail with reference to specific examples. The following specific examples do not limit the present invention. The organic optical material of the present invention is an organic polymer material, an inorganic fine particle / organic polymer composite material, a single crystal of an organic low molecular compound, an organic low molecule / organic polymer compound composite material, an organic low molecular compound /
They can be classified into inorganic glass composite materials, organic low molecular weight / inorganic high molecular compound composite materials, and liquid crystals. Hereinafter, specific examples will be given according to this classification.

[Organic polymer materials] Among organic polymer compounds, those having excellent so-called "optical properties" are widely used as optical materials after being processed into optical components such as optical fibers, lenses, prisms, and optical waveguides. be able to. The organic polymer compound can also be used as a material for dispersing and holding molecules or aggregates of an organic low-molecular compound and fine particles of an inorganic compound, that is, a “matrix material”. Specific examples of such an organic polymer material include polystyrene, poly (α-methylstyrene), polyindene, poly (4-methyl-1-pentene), polyvinylpyridine, polyvinylformal,
Polyvinyl acetal, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl benzyl ether, polyvinyl methyl ketone, poly (N-vinyl carbazole), poly (N-vinyl) Pyrrolidone), polymethyl acrylate, polyethyl acrylate, polyacrylic acid, polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybenzyl methacrylate, polyhexyl methacrylate, polymethacrylic acid, poly Methacrylamide, polymethacrylonitrile, polyacetaldehyde, polychloral, polyethylene oxide, polypropylene oxide,
Polyethylene terephthalate, polybutylene terephthalate, polycarbonates (bisphenols + carbonate), poly (diethylene glycol / bisallyl carbonate), 6-nylon, 6,6-nylon, 12-
Nylon, 6,12-nylon, polyethyl aspartate, polyethylglutamate, polylysine, polyproline, poly (γ-benzyl-L-glutamate), methylcellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, acetylcellulose, Cellulose triacetate, cellulose tributyrate, alkyd resin (phthalic anhydride + glycerin), fatty acid modified alkyd resin (fatty acid + phthalic anhydride + 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 Which resins, organic polysilanes such as poly (phenylmethylsilane), organic polygermanes and their copolymers / copolycondensates, and carbon disulfide, carbon tetrafluoride, ethylbenzene, perfluorobenzene, perfluorocyclohexane, trimethyl Examples thereof include a polymer compound obtained by plasma-polymerizing a compound having no ordinary polymerizability such as chlorosilane.
These organic polymer compounds may contain residues of an organic dye or an organic low-molecular compound exhibiting an optical nonlinear effect as a side chain of a monomer unit, as a crosslinking group, as a copolymerized monomer unit, or as a polymerization initiation terminal. [Reference: Shin Ogawara, Ken Matsuoka, Tsuneaki Hirashima, Teijiro Kitao, "Functional Dyes", Kodansha (1992), pp. 198 to 208
page].

[Inorganic fine particle / organic polymer composite material] As specific examples of the organic optical material of the present invention, selenium, tellurium, germanium, silicon, silicon carbide, Cd _x1 Zn _{x2
Mn x3 Se y1 Te y2 S y3} O y4 (0 ≦ x1, x2, x3,
y1, y2, y3, y4 ≦ x1 + x2 + x3 ≒ 1, y1
+ Y2 + y3 + y4 ≒ 1) and other Group II-IV compounds, G
a _u1 In _u2 Al _u3 As _v1 P _v2 (0 ≦ u1, u2, u3,
v1, v2 ≦ 1, u1 + u2 + u3 {1, v1 + v2}
Examples thereof include inorganic fine particles / organic polymer composite materials in which inorganic semiconductor fine particles such as Group III-V compounds such as 1) and ultra-fine noble metal particles such as gold colloid are dispersed in the above organic polymer compound. [Single Crystal of Organic Low Molecular Weight Compound] As the organic optical material of the present invention, an organic low molecular weight compound forming a single crystal exhibiting a second-order nonlinear optical effect can be exemplified. These single crystals have been expected to be applied as laser light wavelength conversion elements. Specific examples include urea and its derivatives, m-nitroaniline, 2-methyl-4-nitro-aniline,
Benzene derivatives such as (N, N-dimethylamino) -5-nitroacetanilide, N, N'-bis (4-nitrophenyl) methanediamine, biphenyl derivatives such as 4-methoxy-4'-nitrobiphenyl, 4-methoxy −
Stilbene derivatives such as 4′-nitrostilbene, 4-
Nitro-3-picoline = N-oxide, (S)-(-)-
Examples include pyridine derivatives such as N- (5-nitro-2-pyridyl) -prolinol, chalcone derivatives such as 2 ′, 4,4′-trimethoxychalcone, and chenylchalcone derivatives. [Organic low molecular weight / organic high molecular compound composite material] Among the organic optical materials of the present invention, specific examples of those used in the solid state include various organic compounds in addition to the above-mentioned second-order nonlinear optically active organic low molecular compound. Examples thereof include those obtained by dissolving or dispersing an organic low-molecular compound such as a dye or an organic pigment in the organic polymer compound. As described above, the residues of these organic low-molecular compounds and the organic high-molecular compounds may form a chemical bond. [Organic low molecular weight compound / inorganic glass composite material] In addition to the above-described second-order nonlinear optically active organic low molecular weight compound, various organic dyes and organic low molecular weight compounds such as organic pigments can be dissolved or dispersed in the above medium. Instead of the organic polymer compound, an inorganic glass that melts at a temperature not exceeding the thermal decomposition temperature of the organic compound can be used.

[Organic low molecular weight / inorganic high molecular weight compound composite material] As a medium for dissolving or dispersing organic low molecular weight compounds such as various organic dyes and organic pigments in addition to the above-mentioned second-order nonlinear optically active organic low molecular weight compounds. In place of the above inorganic glass, an inorganic polymer compound such as poly (silicon oxide) or poly (silicon oxide-zirconium oxide) formed by a so-called “sol-gel method” can be used. in this case,
Silanol residues may be bonded to an organic low molecular weight compound, or those obtained by modifying the particle surface of an organic pigment with silanol residues may be used. [Liquid Crystal] Among the organic optical materials of the present invention, specific examples of those used in a liquid crystal state include various cholesterol derivatives, 4 ′
-N-butoxybenzylidene-4-cyanoaniline,
4'-alkoxybenzylidene-4-cyanoanilines such as 4'-n-hexylbenzylidene-4-cyanoaniline, 4'-ethoxybenzylidene-4-n-butylaniline, 4'-methoxybenzylideneaminoazobenzene, 4- ( 4'-alkoxybenzylideneanilines such as 4'-methoxybenzylidene) aminobiphenyl and 4- (4'-methoxybenzylidene) aminostilbene, 4'-cyanobenzylidene-4-n-butoxyaniline, 4'-cyanobenzylidene- 4'-cyanobenzylidene-4- such as 4-n-hexyloxyaniline
Carbonic esters such as alkoxyanilines, 4′-n-butoxycarbonyloxybenzylidene-4-methoxyaniline, p-carboxyphenyl n-amylcarbonate, n-heptyl 4- (4′-ethoxyphenoxycarbonyl) phenyl carbonate, 4-alkylbenzoic acid 4'-alkoxy such as -n-butylbenzoic acid 4'-ethoxyphenyl, 4-n-butylbenzoic acid 4'-octyloxyphenyl, 4-n-pentylbenzoic acid 4'-hexyloxyphenyl Phenyl esters, 4,
4'-di-n-amyloxyazoxybenzene, 4,
Azoxybenzene derivatives such as 4'-di-n-nonyloxyazoxybenzene, 4-cyano-4 'such as 4-cyano-4'-n-octylbiphenyl and 4-cyano-4'-n-dodecylbiphenyl Liquid crystals such as -alkylbiphenyls, and 4 ', 4 "-octyloxybiphenyl (2S, 3S) -3-methyl-2-chloropentanoic acid, 4'-(2-methylbutyl) biphenyl-4-
Examples include ferroelectric liquid crystals such as 4-hexyloxyphenyl carboxylate and 4- (2-methylbutyl) phenyl 4 -'- octylbiphenyl-4-carboxylate.

As a specific example of the organic optical material of the present invention, an organic composite optical material in which the above-mentioned liquid crystalline compound is mixed and dispersed in the above-mentioned organic polymer compound, inorganic glass, inorganic polymer compound, or the like is given. be able to. Further, an organic composite optical material using the above liquid crystal compound as a medium for dissolving or dispersing an organic low molecular compound such as the above-described second-order nonlinear optically active organic low molecular compound, various organic dyes, and organic pigments may be mentioned. Can be. These organic composite optical materials using liquid crystals are expected to be used in application fields such as information recording and optical information conversion. Hereinafter, the test apparatus used in the method for testing an organic optical material that can withstand high power density laser light of the present invention will be described in more detail with reference to specific examples. The test apparatus used in the test method of the present invention is, as exemplified in FIGS. 1 and 2, a vacuum pump, a vacuum gauge, a vacuum container, a sample container, a thermometer, a sample heating device, a sample cooling device, a baking device, It consists of a cold trap, a shutter, an ionizer, a mass spectrometer, a sample introduction device, a sample crusher, and their control devices. The total volume of the vacuum system of the test apparatus used in the test method of the present invention shall not exceed 100,000 times the volume of the sample of the organic optical material. Here, the total volume of the vacuum system is to reduce the pressure inside the apparatus to a specific pressure, close the connection to the vacuum pump, measure the pressure rise when introducing a gas with a known number of moles, and measure the temperature of the gas Can be calculated from the equation of state of gas. The volume of the sample is the volume of the organic optical material supplied to the test, and when testing an optical component processed into an optical component, the volume occupied by the organic optical material in the optical component to be sampled. Any vacuum pump can be used as long as it can evacuate the vacuum system of the test apparatus from atmospheric pressure to a degree of vacuum of 1 × 10 ⁻⁴ Pa or less as quickly as possible. Specifically, a combination of a turbo-molecular pump and a rotary pump or a combination of an oil diffusion pump and a rotary pump can be used. As shown in FIG. 2, a vacuum pump of another system may be connected to the vacuum vessel, the ionization device, the mass spectrometer, and the sample introduction device. Any known vacuum gauge can be used as long as it can accurately measure a pressure of 1 × 10 ⁻² Pa or less. Specifically, Bayard-Alp
An ionization vacuum gauge such as an ert type can be used.

The vacuum vessel preferably has a configuration in which the components of the test apparatus are arranged to minimize the volume of the vacuum system. The material is preferably aluminum or stainless steel of high vacuum specification. Any sample container can be used depending on the form of the sample, but the form of the sample container affects the structure of the entire apparatus. For example, a glass tube as shown in Fig. 1 is used to easily test a powdery or pellet-like material before processing, and a stainless steel tray-like material is used to test a plate-like sample without destruction. In order to crush and test the processed optical component, a stainless steel pot-shaped one as shown in FIG. 2 is preferable. The thermometer measures the temperature of the sample,
Any device such as a thermocouple can be used as long as it operates even when the temperature measuring unit is placed under a high vacuum. The sample heating device may be either a type in which a heater portion is placed in a vacuum system or a type in which a sample container forming a vacuum system is heated from outside the vacuum system. When a glass tube is used as the sample container, it is preferable to heat the sample from outside the vacuum system as shown in Fig. 1. When the sample container is dish-shaped or bowl-shaped, the heater is placed in the vacuum system and directly heated. Is preferred. When using a glass tube as the sample container, the sample cooling device is preferably cooled from outside the vacuum system as shown in Fig. 1. When the sample container is dish-shaped or bowl-shaped, the refrigerant is replenished from outside the vacuum system. A method of circulating and cooling is preferable. The sample heating device and the cooling device include a mechanism for controlling the sample temperature to a predetermined value. It is preferable that the baking apparatus can heat-treat all the components constituting the vacuum system. Although a cold trap is not necessary, it is useful for preventing contamination in the vacuum system. Especially when using an oil diffusion pump for the vacuum pump,
Preferably, a cold trap is provided. Various known ionization devices can be used as long as they ionize volatile components existing in the vacuum system. Specifically, an ionization device such as a gas discharge type, an arc discharge type, and an electron impact type can be used. For example, an electron impact type ionizer irradiates thermoelectrons having energy of about 70 eV to generate ions of gas molecules and / or fragment ions generated by decomposition of gas molecules by electron impact.

The mass spectrometer is a number m / e obtained by dividing the mass m of ions generated by the ionizer by the charge e of the ions.
A part (mass separation system) that separates mass according to m / e
As long as it comprises a portion (detection / recording system) for electrically counting the number of ions separated according to the above, various known types can be used. The mass separation system controls a magnetic field and / or an electric field to separate ions according to m / e, and includes a parabolic type, a velocity converging type, a direction converging type, a double converging type, and a time-of-flight type. Either may be used. As the detection / recording system, a system such as a combination of a Faraday box and a high-sensitivity DC amplifier, or a combination of a secondary electron multiplier and a high-sensitivity DC amplifier can be used. The shutter is used to properly shield between the ionization device and mass spectrometer and the vacuum vessel, and it is not necessary to provide the shutter.However, volatile components and ions generated in the vacuum system due to heating of the sample fly unnecessarily and cause mass This is useful for preventing the analyzer from being contaminated. When a shutter is provided, it is preferable to connect a vacuum pump of another system to the vacuum vessel and the mass spectrometer. As the shutter, a gate valve or the like of a high vacuum specification can be used. The sample introduction device is not necessarily provided, but is effective in shortening the evacuation time when installing the sample in the vacuum system. The sample introduction device is a vacuum container, a lid or gate valve for introducing a sample from outside, a magnetic coupling type or bellows type linear introduction device, a gate valve between the vacuum container of the measurement device, a vacuum pump, and a vacuum gauge. Consists of The sample crusher is useful for testing an optical material after processing into an optical component. Especially,
Organic components such as an optical component in which a thin film of an organic optical material is sandwiched between two inorganic glass plates and an optical component in which an organic optical material is sealed in a tubular or box-shaped sealed container made of inorganic glass. This is an indispensable device when testing an optical component in which a system optical material is sealed with a material having low gas permeability. The sample crushing device may be of any form and type as long as it can crush the sample into small pieces having an outer diameter of 1 mm or less under high vacuum. For example, as shown in FIG. 2, a method in which a sample placed in a bowl-shaped sample container is crushed by a stainless steel mallet attached to the tip of a linear introduction device can be used. Hereinafter, the method for testing an organic optical material that can withstand high power density laser light according to the present invention will be described in more detail by describing a specific operation procedure and a method for determining a test result.

Procedure 1. Sample container and test equipment in vacuum system
Cleaning the wall Since the test method of the present invention heats a sample of the organic optical material and analyzes the components volatilized from the sample, every time the test is carried out, the sample container and the vacuum system of the test apparatus are used. The inner wall is contaminated with the volatile components. In order to perform an accurate test, it is preferable to clean the sample container and the inner wall of the test apparatus by a known method every time the test is performed. Specifically, it may be washed with an organic solvent such as alcohol or acetone, or may be wiped off with a lint-free wiper moistened with these solvents. When a glass tube as shown in FIG. 1 is used as a sample container, a new tube may be used for each test.

Procedure 2. Equipment baking and backing
After cleaning the round measuring device, do not put the sample in the sample container.
It is preferable to perform an operation in which the inside of the apparatus is evacuated and volatile components adsorbed on the vacuum system wall of the apparatus are removed from the vacuum system by so-called baking. The baking temperature depends on the heat resistance of the components that make up the apparatus.
It is preferable to heat to a temperature of at least 150 ° C. if possible. During baking, the sample container may be heated by a sample heating device. In the final stage of baking, the ionizer and the mass spectrometer are operated, and the atmospheric components remaining or leaking into the vacuum system and the volatile components released from the surface and the inside of the vacuum system inner wall (hereinafter referred to as “back (Called ground) to confirm the end of baking. When the inner wall of the vacuum system of the test apparatus is mainly made of stainless steel, the background having a mass larger than the molecular ion attributed to the water molecule of m / e = 18 is m / e = 28. Molecular ions belonging to carbon and nitrogen molecules, oxygen molecules at m / e = 32, and carbon dioxide at m / e = 44 are detected.
Here, when the resolution of the mass spectrometer can measure the value of m / e to four decimal places, the molecular weight is 27.994.
9 of carbon monoxide ⁽¹² C ¹⁶ O) and can distinguish between the nitrogen molecules of molecular weight 28.0061 ⁽¹⁴ N _2). Also,
When the sensitivity of the mass spectrometer is high, argon can be detected at m / e = 40 as a background.
When the baking no longer detects signals other than the above background at m / e = 18 or more, it can be determined that cleaning and baking have been completed. In the following description, in describing the mass spectrometry results,
m / e = n (n is a positive integer) the count number of ions
(N), a value obtained by subtracting the counts of ions belonging to oxygen molecules and carbon dioxide from the total count of ions having m / e of 29 or more is denoted by Σ (S), and carbon monoxide , (N) the value obtained by multiplying the total number of the molecular ions assigned to each of nitrogen, nitrogen, oxygen and carbon dioxide by 0.1. In the test method of the present invention, it is not necessary to distinguish between carbon monoxide and molecular ions of nitrogen molecules. That is, N (28) represents the total value of the count number of molecular ions attributed to carbon monoxide and nitrogen molecules.

Procedure 3. Sample introduction and volatilization below room temperature
The amount of the sample to be analyzed for the emission component to be introduced is such that the volume of the organic optical material in the sample exceeds one hundred thousandth of the volume of the vacuum system of the test apparatus when performing mass analysis of volatile components. If a sample introduction device is not provided, after the above procedure 2 is completed, nitrogen gas is introduced through a precision filter having a trapped particle diameter of about 0.1 μm, and the vacuum system of the test device is returned to atmospheric pressure. It is introduced into a container, and the inside of the apparatus is evacuated to 1 × 10 ⁻⁴ Pa or less at room temperature. When the sample introduction device is provided, after the above procedure 2 is completed, the gate valve between the sample introduction device and the vacuum vessel is closed,
Nitrogen gas was introduced through a precision filter having a trapped particle diameter of about 0.1 μm to return the vacuum system of the sample introduction device to atmospheric pressure, and then the sample was introduced. At room temperature, the inside of the device was 1 × 10 ⁻⁴ Pa.
Exhaust to below. Next, the gate valve between the sample introduction device and the vacuum container is opened, the sample is introduced into the sample container using the linear introduction device, and then the gate valve between the sample introduction device and the vacuum container is closed. The sample is introduced into the sample container and the inside of the device is 1 ×
At the time of evacuation to 10 ⁻⁴ Pa or less, if a shutter is provided, the shutter is opened, the ionization device and the mass spectrometer are operated, and mass analysis of the gas in the vacuum system at room temperature after sample introduction is performed. When testing an optical component in which an organic optical material is sealed with a material having low gas permeability, a sample is introduced in a non-destructive state, and the inside of the apparatus is set to 1 × 10 ⁻⁴ P.
After evacuating to a or less, the sample is crushed into small pieces having an outer diameter of 1 mm or less by a sample crusher, and mass analysis of gas in a vacuum system at room temperature is performed. At this time, N (18) was changed to N (2
8) and / or Σ (S) is Σ
When the value exceeds (B), the sample contains a large amount of volatile components, so that it is determined that the sample does not have durability against a high power density laser beam in a room temperature range. For such samples,
The temperature of the sample was gradually lowered using a sample cooling device, and N (1
8) does not exceed N (28), and Σ (S) is Σ (B)
Can be determined. If the properties of the optical material, such as transparency and nonlinear optical properties, are not lost even when the material is cooled to such a temperature, this temperature is regarded as the upper limit temperature of use of the material for high power density laser light. Can be.

Procedure 4. In the mass spectrometry at room temperature in the mass spectrometry of the volatile components at room temperature or higher in the third step, when N (18) does not exceed N (28) and Σ (S) does not exceed Σ (B), Is gradually heated to perform mass spectrometry of the gas in the vacuum system. The upper limit of the heating temperature is: (1) a temperature exceeding the maximum temperature that can be reached when the sample is used as an optical component (this is called T1), (2) N (18)
Temperature exceeds N (28) (this is called T2), or (3) temperature where 温度 (S) exceeds Σ (B) (this is called T2).
3). Here, as a precaution to prevent the mass spectrometer from being unnecessarily contaminated, N (18) is replaced by N (2).
If a temperature exceeding 8) is reached, and / or
When the temperature of Σ (S) exceeds the temperature of Σ (B), it is recommended that the heating be stopped immediately and, if a shutter is provided, it be closed. The maximum temperature (T1) that can be reached when the sample is used as an optical component is estimated by measuring the temperature rise of the portion irradiated with the high power density laser beam using an infrared surface thermometer or the like. be able to. If heating to a temperature above T1 does not reach T2 or T3, ie if N (18) does not exceed N (18) and Σ (S) does not exceed Σ (B), the sample is It is determined that the optical material is suitable for the application. on the other hand,
T2 and T3 define the upper limit of the working temperature from the material side when the sample is used as an optical component. In order to develop an excellent organic optical material that can withstand high power density laser light, it is only necessary to improve T2 and T3 by increasing the selection of raw materials, the purification method, and the processing method. When it is necessary to use a specific organic optical material, the maximum temperature that can be reached when the material is used as an optical component does not exceed T2 and T3.
The optical component may be cooled.

[0016]

The present invention will be described in more detail with reference to the following examples. The following examples do not limit the present invention. Example 1 Commercially available polymethyl methacrylate (weight average molecular weight 120
00; hereinafter abbreviated as PMMA) in acetone,
After re-precipitation with water to give a fine powder, the powder was dried at room temperature under a reduced pressure of 1.33 Pa for 5 days. This powder is referred to below as PMMA
Called powder sample J. After introducing 0.2 g of the PMMA powder sample J into a sealed end of a glass tube having an inner diameter of 10 mm and a length of 80 cm, which is sealed at one end, using a foot-length funnel, 2 μm from the open end of the glass tube.
0cm place is heated and melted with a burner, bent at 90 degrees and attached to the device of Fig. 1, and the pressure inside the system is gradually reduced.
The gas in the vacuum system was analyzed with a quadrupole mass spectrometer (AQA-200 manufactured by Nidec Anelva) at a sample temperature of 27 ° C. under a vacuum of 7.3 × 10 ⁻⁶ Pa. Incidentally, the volume of the vacuum system of the vacuum device used for mass spectrometry is 256 cm ^3, it was 1524 times the volume 0.168Cm ³ samples used for the test. The analysis results are as shown in Table 1.

[0017]

[Table 1]

That is, the PMMA powder sample J was 7.3 ×
In mass spectrometry at a sample temperature of 27 ° C. under a vacuum of 10 ⁻⁶ Pa, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and The number [Σ (S) obtained by subtracting the number of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of the number of ions having a number m / e equal to or greater than 29 obtained by dividing the mass m of the ions by the charge e. )] Is 0.1 for the total number of molecular ions assigned to carbon monoxide, nitrogen molecules, oxygen molecules, and carbon dioxide, respectively.
Does not exceed the value [Σ (B)]. Next, when the sample was heated to 80 ° C., the pressure of the vacuum system temporarily increased to 2.0 × 10 ⁻⁴ Pa and then gradually decreased.
Table 2 shows the results of mass spectrometry of volatile components at a sample temperature of 80 ° C. under a vacuum of 1 × 10 ⁻⁴ Pa.

[0019]

[Table 2]

That is, the PMMA powder sample J was 1.0 ×
In mass spectrometry at a sample temperature of 80 ° C. under a vacuum of 10 ⁻⁴ Pa, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, The mass m of the ion is the charge e
The value [Σ (S)] obtained by subtracting the count number of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of the count number of ions having a number m / e of 29 or more divided by carbon monoxide, It was found that the value was much more than the value [Σ (B)] obtained by multiplying the total number of the molecular ions assigned to nitrogen molecule, oxygen molecule and carbon dioxide by 0.1, respectively. For the above sample, under high vacuum, continue the heating process, and gradually increase the sample temperature,
The volatile components gradually decreased, and reached a pressure of 7.5 × 10 ⁻⁶ Pa in the vacuum system at the time of treatment at 110 ° C. for 48 hours. The sample subjected to the above high vacuum heat treatment is hereinafter referred to as PMM
It is called A powder sample G. 7.5x1 PMMA powder sample G
Table 3 shows the results of mass spectrometry of volatile components at a sample temperature of 110 ° C. under a vacuum of 0 ⁻⁶ Pa.

[0021]

[Table 3]

That is, the PMMA powder sample G is 7.5 ×
In mass spectrometry at a sample temperature of 110 ° C. under a vacuum of 10 ⁻⁶ Pa, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and The mass m of the ion is the charge e
The value [Σ (S)] obtained by subtracting the counts of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of the counts of ions having a number m / e of 29 or more divided by [(S)] is carbon monoxide. It does not exceed the value [た (B)] obtained by multiplying the total number of the counted molecular ions to nitrogen molecule, oxygen molecule, and carbon dioxide by 0.1. As described above, two types of PMMA powder samples having different mass spectrometry results of volatile components during heating under high vacuum were respectively subjected to the method described in Japanese Patent Application No. 2-79481 (vacuum hot pressing method).
According to the above, the sample was sandwiched between two cover glasses, and compression molded at a pressure of 50 kgf / cm ² while heating to 150 ° C. under a vacuum of 0.1 Pa to obtain a PMMA thin film sample J. Similarly, PMM
A PMMA thin film sample G was obtained from the A powder sample G. Nd: Y
The output of the laser light obtained by converting the harmonics of the wavelength 532 nm of the AG laser to 625 nm by the dye laser is adjusted, and the pulse light oscillation cycle is 10 Hz, the pulse width is 10 ns, and the average power is 20
A pulse light of mW is oscillated, and this light is condensed by a convex lens having a focal length of 50 cm to a beam cross-sectional area of 1.8 × 10 ^-4 cm ² at the irradiation point, and a peak power density of 1.13 GW / cm ² Irradiation was performed on the above cover glass sandwich PMMA thin film sample G, but no optical damage occurred. In addition, when the surface temperature change of the glass of the laser beam transmission part was measured by the infrared surface thermometer, it was confirmed that the temperature rose to about 80 ° C. when the above-mentioned pulsed light irradiation was continued.
It is estimated that the temperature of the PMMA thin film portion has reached 80 ° C. or higher. On the other hand, a peak power density of 1.13 GW / cm ² was applied to the PMMA thin film sample J in the same manner as in the case of the thin film sample G.
When the pulsed light was irradiated, bubbles were instantaneously generated in the PMMA thin film portion, and when the irradiation was continued, significant damage occurred. Rhodamine R excited by argon ion laser
Collision pulse mode using a 6G and 3,3'-diethyl oxadicarbocyanine iodide dye jet (Co
Liding pulse mode synchronous laser (hereinafter, referred to as CPM laser) has an oscillation wavelength of 625 nm,
Oscillation is performed at a pulse light oscillation period of 84.9 MHz, a pulse width of 50 fs, and an average power of 500 mW, and this pulse light is placed in a ring resonator in two concave mirrors (radius of curvature 5 cm).
7.85 × 10 ^-7 c beam cross section at confocal using
converged m ^2, as the peak power density 150GW / cm ^2,
The PMMA thin film sample G placed at the confocal point was irradiated,
No light damage occurred for more than one hour. On the other hand, PMMA
When a portion of the thin film sample J which was not damaged by the light in the above test was inserted into the optical path of the CPM laser in the same manner as in the case of the thin film sample G, the laser oscillation rapidly attenuated and stopped. Observation of the portion of the PMMA thin film sample J where the laser beam was transmitted just before the oscillation was stopped was observed with an optical microscope, and it was found that fine bubbles were generated. To summarize the above examples, to the peak power density 1.13GW / cm ² no PMMA film withstood the high power density laser beam irradiation 150GW / cm ² is in powder form before being processed into thin film,
In mass spectrometry at a test temperature of 110 ° C. under a vacuum of 7.5 × 10 ⁻⁶ Pa, the count of molecular ions attributed to water molecules exceeds the count of molecular ions attributed to carbon monoxide and nitrogen molecules. And the mass of the ion m
Is divided by the electric charge e. The value obtained by subtracting the counts of the molecular ions attributed to oxygen molecules and carbon dioxide from the total count of the counts of the ions having a number m / e of 29 or more is obtained by dividing carbon monoxide, nitrogen molecules, It does not exceed the value obtained by multiplying the total number of the molecular ions, which are respectively assigned to oxygen molecules and carbon dioxide, by 0.1. On the other hand, the PMMA powder sample J had a sample temperature of 80 ° C. under a vacuum of 2.0 × 10 ⁻⁴ Pa.
In the mass spectrometry, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to nitrogen molecules and carbon monoxide, but the number m obtained by dividing the mass m of ions by the charge e The value obtained by subtracting the count number of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of the count number of ions having a value of / e of 29 or more is converted into carbon monoxide, nitrogen molecule, oxygen molecule, and carbon dioxide, It far exceeds the value obtained by multiplying the total number of the counted molecular ions by 0.1 by 0.1, and such volatile components remain in the transparent thin film formed by the vacuum hot pressing method. It is presumed that light damage was caused by vaporization and foaming due to the temperature rise accompanying the irradiation of the high power density laser beam. Example 2 The PMMA thin film sample J used in the photodamage test in Example 1 was put into a vacuum apparatus equipped with a sample crushing device shown in FIG. 2, evacuated to 1 × 10 ⁻⁵ Pa at room temperature, and then crushed. The mass of the vaporized component was analyzed while increasing the temperature. The dimensions of the transparent thin film-like PMMA portion in the sample were 1.8 cm × 1.8 cm × 20 μm.
m, the volume of the vacuum system is 0.00648 cm ³ , and the volume of the vacuum system of the vacuum device is 570 cm ³ with the gate valve between the sample introduction device and the vacuum vessel closed and the shutter of the mass spectrometer opened. It was 8.80 × 10 ⁴ times the volume of the PMMA portion. The analysis results at 80 ° C. under a vacuum of 6.9 × 10 ⁻⁶ Pa are as shown in Table 4.

[0023]

[Table 4]

That is, the PMMA thin film sample J which caused optical damage in the laser irradiation test of Example 1 was 6.9 × 10 ^-6.
In mass spectrometry at 80 ° C. under a vacuum of Pa, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules. Number m / divided by charge e
The value [Σ (S)] obtained by subtracting the count number of molecular ions attributed to oxygen molecules and carbon dioxide from the total count of the count number of ions having an e value of 29 or more is carbon monoxide,
It was confirmed that the value exceeded the value [Σ (B)] obtained by multiplying the total number of the molecular ions attributed to the nitrogen molecule, oxygen molecule, and carbon dioxide by 0.1, respectively. Example 3 In the same manner as in Example 1, 0.2 g of PMMA powder treated at 110 ° C. under a vacuum of 7.5 × 10 ⁻⁶ Pa or less.
And a vacuum of 1.12 × 10 ⁻⁵ Pa and a temperature of 150.
The treatment was performed at 180 ° C. and 2.53 × 10 ⁻⁴ Pa and the mass spectrometry of volatile components was performed. The results were as shown in Table 5.

[0025]

[Table 5]

From this result, it can be seen that decomposition occurs at 180 ° C. Looking at the analysis results in detail, 15
It can be interpreted that decomposition occurs slightly even at 0 ° C., and it can be determined that the upper limit of use temperature when processing and using the above-mentioned PMMA as a material for optical components is 150 ° C. In addition, the behavior of thermal decomposition of an organic polymer material often depends on the raw material, synthetic recipe, purification method, and heat history of the material, and the above test results are examples. Example 4 Two cover glass sandwich thin films were prepared by vacuum hot pressing using the PMMA powder sample G prepared by performing the high vacuum heat treatment in Example 1, and one (hereinafter, referred to as sample 4A) was formed in a peripheral portion. An aluminum foil was adhered and sealed with an epoxy resin, and the other end (hereinafter, referred to as sample 4B) was left open. The dimensions of the transparent thin film-shaped PMMA portion were both 1.8 cm × 1.8 cm × 20 μm, and the volume was 0.0
It was 0648 cm ³ . These two samples were sealed in a desiccator together with a beaker containing water under light shielding,
The sample 4A was left at room temperature for 5 months and irradiated with pulsed light having a wavelength of 625 nm using a Nd: YAG laser as a light source in the same manner as in Example 1. As a result, Sample 4A withstood a peak power density of 1.7 GW / cm ² , but Sample 4B In the peak power density 170MW / cm ²
The formation of air bubbles was observed in the portion irradiated with. Sample 4B
Into a vacuum device equipped with a sample crushing device shown in FIG.
After reducing the pressure to 1 × 10 ⁻⁵ Pa at room temperature, the mixture was crushed, and the mass of the vaporized component was analyzed while increasing the temperature. As a result, the number of ions (m / e = 18) attributed to water at 50 ° C. or more was counted. Ions assigned to nitrogen and carbon monoxide (m / e = 2
It was found that the count number exceeded 8). When the sample 4A was tested in the same manner, the count of m / e = 18 did not exceed the count of m / e = 28 even when the temperature was raised to a temperature exceeding 110 ° C. Note that the volume of the vacuum system of the vacuum device was 570 when the gate valve between the sample introduction device and the vacuum vessel was closed and the shutter of the mass spectrometer was opened.
cm ^3, and the volume of 8.8 × 10 of PMMA portion of Sample
⁴ times. From the above test results, it is presumed that in sample 4B, the water vapor that entered from the end face diffused into the resin thin film, and was vaporized and foamed by the heat generated by high power density laser beam irradiation. Example 5 2-methyl-4-nitroaniline (hereinafter abbreviated as MNA) 2 sublimated and purified at 70 ° C. under a vacuum of 1 × 10 ⁻⁵ Pa
0 parts by weight and 80 parts by weight of a PMMA powder heat-treated in a high vacuum in the same manner as in Example 1 were sufficiently mixed with the powder, and a glass sandwich thin film was formed by a vacuum hot press method. MN
A / The dimensions of the PMMA thin film part are 1.8 cm x 1.8 cm x 20
μm. Hereinafter, this is referred to as sample 5A. On the other hand, 20 parts by weight of MNA recrystallized from ethanol and dried under reduced pressure at 0.13 Pa, and 80 parts by weight of PMMA powder subjected to high-vacuum heat treatment in the same manner as in Example 1 were sufficiently mixed with the powder, and were subjected to a vacuum hot press method. A glass sandwich thin film having the same dimensions as Sample 5A was used. This is called Sample 4B. Using a Nd: YAG laser as a light source, a wavelength of 625 nm, an oscillation frequency of 10 Hz and a pulse width of 10 ns in the same manner as in Example 1.
As a result of the irradiation test, the sample 5A was not damaged even at a peak power density of 143 MW / cm ² . On the other hand, sample 5B
Laser pulse with a peak power density of 90 MW / cm ²
When irradiation was performed for 0 seconds, that is, 100 pulses, bubbles were generated in the irradiated portion. Samples 5A and 5B were each
Put into a vacuum device equipped with a sample crushing device as shown in the figure,
After reducing the pressure to 1 × 10 ⁻⁵ Pa at room temperature, the mixture was crushed, and the mass of the vaporized component was analyzed while increasing the temperature. The volume of the vacuum system during mass spectrometry was 570 cm ³ , and the MNA / P
8.8 × of the volume (0.00648 cm ³ ) of the MMA thin film part
It was 10 ⁴ times. Under vacuum of 1 × 10 ⁻⁵ Pa or less, 50
Table 6 shows the results of mass spectrometry at ° C.

[0027]

[Table 6]

That is, the sample 5A is 5.3 × 10 ⁻⁶ P
In the mass spectrometry at a sample temperature of 50 ° C. under the vacuum of a, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and the mass of ions The number m / e obtained by dividing m by the charge e
The value [Σ (S)] obtained by subtracting the counts of molecular ions belonging to oxygen molecules and carbon dioxide from the total count of the counts of ions having a value of 29 or more is [炭素 (S)]. It does not exceed the value [Σ (B)] obtained by multiplying the total number of the counts of molecular ions assigned to carbon dioxide by 0.1. -, Sample 5B is 5.
In mass spectrometry at a sample temperature of 50 ° C. under a vacuum of 7 × 10 ⁻⁶ Pa, the count number of molecular ions attributed to water molecules does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules. Gives the mass m of the ion to the charge e
The value obtained by subtracting the number of molecular ions attributed to oxygen molecules and carbon dioxide from the total count of the number of ions having a number m / e of 29 or more divided by [除 (S)]
Exceeds the value [Σ (B)] obtained by multiplying the total number of the molecular ions assigned to carbon monoxide, nitrogen molecule, oxygen molecule, and carbon dioxide by 0.1, respectively. . Note that m / e = 4 detected in the case of sample 5B.
Ion 6 is assigned to the molecular ion of ethanol used for recrystallization of MNA. In sample 5B, ethanol as a recrystallization solvent remains, which is presumed to be caused by vaporization and foaming due to temperature rise due to irradiation with high power density laser light, resulting in photodamage. Example 6 Tetrakis (tert-butyl) oxyvanadium phthalocyanine synthesized from 4-tert-butylphthalonitrile and vanadium trichloride (composition formula C ₄₈ H ₄₈ N ₈ O)
V: Elemental analysis value C = 72.0%, H = 6.02%, N =
(13.9%) 10 parts by weight of PMMA and 90 parts by weight of PMMA were dissolved in chloroform and coated on a 1 mm thick quartz glass substrate by spin coating to form a thin film having a thickness of 20 μm. This coating film is heated at 150 ° C. under a vacuum of 1 × 10 ⁻⁵ Pa for 120 hours.
After high-vacuum heat treatment for one hour, another one is applied to the coated surface under reduced pressure.
Two 1 mm thick quartz glass plates were pressed. After the sample was taken out into the atmosphere, the end face was sealed with an epoxy resin and aluminum foil. Hereinafter, this is referred to as Sample 6A. Sample 6B was prepared in the same manner as Sample 6A, except that the coating film was subjected to high vacuum treatment at room temperature. For these samples, N
d: A laser pulse having a wavelength of 1.89 μm, an energy of 5 mJ / pulse, a pulse width of 2.5 ns and a focal length of 50 cm generated by light mixing of a YAG laser (basic oscillation wavelength 1.06 μm) and a dye laser (wavelength about 700 nm). Condensed by a convex lens, peak power density 100 GW / cm
^When the irradiation test of No. ² was performed, Sample 6A withstood irradiation for 1 hour, but Sample 6B caused damage due to the generation of bubbles. For samples 6A and 6B, Example 5
As in the above case, the mixture was crushed and heated under a high vacuum, and the volatile components were analyzed. The size of the coating film portion of the sample is the same as that of sample 6A.
3.0cm × 3.0cm × 20μm for both and 6B,
A volume 0.018 cm ^3, exceeds 100,000 parts per volume 570 cm ³ of a vacuum system during mass spectrometry. As a result of mass spectrometry of the volatile component, the same result as in Example 1 was obtained for Sample 6A. On the other hand, in the case of sample 6B, 7.3 × 10
^By mass spectrometry at a sample temperature of 50 ° C. under a vacuum of ⁻⁶ Pa, a large number of ions attributed to chloroform as a coating solvent were detected, and the value of several m / e obtained by dividing the mass m of the ion by the charge e was 29 or more. The value obtained by subtracting the number of molecular ions attributed to oxygen molecules and carbon dioxide from the total count of the number of ions of-is the value of the molecular ions assigned to carbon oxide, nitrogen molecule, oxygen molecule, and carbon dioxide, respectively. It exceeded the value obtained by multiplying the total number of counts by 0.1.

[0029]

The organic optical material according to the present invention has a density of several hundred MW / cm ^2.
In addition, light damage due to vaporization and foaming of volatile components in the material due to heat generated by transmission of high power density laser light of several hundred GW / cm ² can be avoided. In addition, the test method of the present invention can prevent light damage caused by vaporization and foaming of volatile components in a material due to heat generated by transmission of a high power density laser beam of several hundred MW / cm ^{2 to} several hundred GW / cm ^2. It is extremely useful for developing and improving organic optical materials that can be avoided. The method for testing an organic optical material of the present invention can be applied to each stage before processing the material, during the processing, and after processing the optical component. For example, in the case of manufacturing an optical component by heating and melting a powder or a pellet of an organic polymer based optical material, the durability to a high power density laser beam is predicted in advance at the stage of the powder or the pellet before the processing. be able to. When the heat melting process is performed in a high vacuum, the appropriateness of the pretreatment of the raw material and the appropriateness of the processing conditions can be determined by sequentially analyzing the volatile components released in the process. In addition, the light part after processing is crushed under high vacuum, then heated and analyzed for volatile components to test the storage stability of optical components and the absorption of volatile components (mainly water). it can. By applying the test method of the present invention at the stage before processing and predicting the durability against high power density laser in advance, it is possible to extremely efficiently conduct new searches for organic optical materials and study pretreatment methods for raw materials. It is possible to do. Applying the test method of the present invention in the middle of processing can be performed when an organic optical material is processed using a volatile solvent such as a coating method or an LB film method, or when a volatile compound such as a sol-gel method or a polycondensation method is used. When processing using the chemical reaction produced by
It is particularly effective, and the degree of removal of volatile components, which is one of the causes of damage due to irradiation with high power density laser light, can be known very accurately. It is also possible to prevent the material from being thermally decomposed due to overheating. When an organic optical material is processed into an optical component in a high vacuum by a processing method utilizing a vacuum technique such as a vacuum deposition method, a CVD method, an organic molecular beam deposition method, or a vacuum hot press method, the optical component is required to have a high quality. Except in special cases such as when used in a vacuum system, the optical material is exposed directly to the atmosphere or indirectly via a gas barrier material, so that it can be stored or used in actual use. May absorb permeable volatile components (primarily moisture). In addition, in newly developed organic optical materials, in the storage state after processing or the actual use state,
Unexpected side reactions can also produce volatile organic compounds. Among the test methods of the present invention, a method of crushing an optical component after processing under a high vacuum and then testing it is extremely useful in verifying these possibilities and taking countermeasures.

[Brief description of the drawings]

FIG. 1 is a schematic view illustrating a test apparatus used in a method for testing an organic optical material that withstands high power density laser light according to the present invention.

FIG. 2 is a schematic view illustrating a test apparatus used in the method for testing an organic optical material that withstands high power density laser light according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Turbo molecular vacuum pump 12 Rotary pump 13 Vacuum gauge 21 Vacuum container 22 Glass tube type sample container 23 Stainless steel pot type sample container 31 Thermocouple thermometer 32 Sample heating device 33 Sample cooling device 41 Gate valve 51 Shutter 52 Ionization device and Mass spectrometer 61 Vacuum container of sample introduction device 62 Magnetic coupling type linear introduction device 71 Hammer of sample crushing device

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Norio Tanaka 2-14-22, Chuohonmachi, Adachi-ku, Tokyo (72) Inventor Shigeru Takarada 2-17-12, Jobandaira, Matsudo-shi, Chiba (72) Inventor Yuichi Yamazaki 2-19-13 Machiya, Arakawa-ku, Tokyo (72) Inventor Michie Nakamura 475-6 Kinmeicho, Soka-shi, Saitama Examiner Hiroko Sato (58) Field surveyed (Int.Cl. ⁶ , DB name) G02F 1 / 35 504 G01N 27/62 JICST file (JOIS)

Claims (8)

(57) [Claims] 1. A total volume A sample was placed on the organic light material to a vacuum apparatus which does not exceed ten thousand times the sample volume, and set the pressure in the vacuum apparatus below 1 × 10 -4 ^Pa, the organic When the sample in the vacuum apparatus is heated to a temperature exceeding the maximum use temperature of the optical material as an optical component, and gas molecules released from the sample are ionized and analyzed by a mass spectrometer, the sample is attributed to water molecules. The count number of molecular ions does not exceed the count number of molecular ions attributed to carbon monoxide and nitrogen molecules, and the value of the number m / e obtained by dividing the mass m of the ions by the charge e is 2
The value obtained by subtracting the count number of the molecular ion attributed to oxygen molecule and carbon dioxide from the total count of the count number of 9 or more ions is the molecule attributed to carbon monoxide, nitrogen molecule, oxygen molecule and carbon dioxide, respectively. Organic fraction not exceeding the total number of ions multiplied by 0.1
Inorganic fine particles or organic
Manufacture of organic optical materials resistant to high power density laser light characterized by dispersing or dissolving low molecular compounds
Method. 2. An organic optical material sample is placed in a vacuum device having a total volume not exceeding 100,000 times the sample volume, and the pressure in the vacuum device is set to 1 × 10 ⁻⁴ Pa or less. when the sample in the vacuum device to a temperature above the maximum use temperature as an optical component of the optical material was heated, and analyzed by mass spectrometer gas molecules released from the sample are ionized, it is attributed to water molecules that counts molecular ions does not exceed the count number of molecular ions attributed to carbon monoxide and molecular nitrogen, or
The value of the number m / e obtained by dividing the ion mass m by the charge e is 2
The value obtained by subtracting the count number of the molecular ion attributed to oxygen molecule and carbon dioxide from the total count of the count number of 9 or more ions is the molecule attributed to carbon monoxide, nitrogen molecule, oxygen molecule and carbon dioxide, respectively. Organic fraction not exceeding the total number of ion counts multiplied by 0.1
The compound is dissolved or dispersed in the inorganic polymer compound.
A method for producing an organic optical material that withstands high power density laser light . 3. The method according to claim 1, wherein the organic low-molecular compound is a liquid crystal.
3. Withstands high power density laser light according to claim 2.
A method for producing an organic optical material. 4. A vacuum having a total volume not exceeding 100,000 times the sample volume.
A sample of an organic optical material is placed in the device, and the pressure in the vacuum device is
Is set to 1 × 10 ⁻⁴ Pa or less, and the light of the organic optical material is
Vacuum equipment up to a temperature exceeding the maximum operating temperature of parts
The sample inside the sample is heated and gas molecules released from the sample are
When turned on and analyzed with a mass spectrometer, it is assigned to water molecules
Counted molecular ions are carbon monoxide and nitrogen
Does not exceed the number of molecular ions assigned to the molecule
The value of the number m / e obtained by dividing the ion mass m by the charge e is 2
From the total count of 9 or more ions,
And the number of molecular ions attributed to carbon dioxide
The subtracted values are the values of carbon monoxide, molecular nitrogen, molecular oxygen and
Of molecular ions assigned to
Organic fraction not exceeding the value obtained by multiplying the total number of components by 0.1
Single crystal of the compound is used as a wavelength conversion element for laser light.
Withstands high power density laser light
How to use organic optical materials. 5. A vacuum having a total volume not exceeding 100,000 times the sample volume.
A sample of an organic optical material is placed in the device, and the pressure in the vacuum device is
Is set to 1 × 10 ⁻⁴ Pa or less, and the light of the organic optical material is
Vacuum equipment up to a temperature exceeding the maximum operating temperature of parts
The sample inside the sample is heated and gas molecules released from the sample are
Turn on and analyze with mass spectrometer, attributed to water molecule
Molecular ion counts and carbon monoxide and nitrogen molecules
Comparing the counts of the assigned molecular ions,
And / or the number m obtained by dividing the mass m of the ion by the charge e
Is the total count of the count number of ions with an / e value of 29 or more?
Of molecular ions belonging to oxygen molecules and carbon dioxide
The value after subtracting the count number, carbon monoxide, nitrogen molecule,
Molecules assigned to oxygen molecule and carbon dioxide, respectively
It is characterized by comparing the total number of ion counts.
Of organic optical materials that can withstand high power density laser light
Method. 6. Using a crushing device provided in the vacuum vessel.
Remove the sample of the material under a high vacuum of 1 × 10 ⁻⁴ Pa or less.
Characterized by crushing into small pieces with a diameter of 1 mm or less before testing
Withstand high power density laser beam according to claim 5 shall be the
Test method for organic optical materials. 7. The method according to claim 7, wherein the sample of the organic optical material has a total volume of the vacuum system.
With a size not exceeding 100,000 times the sample volume,
^Room temperature at a pressure of 1 × 10 ⁻⁴ Pa or less in a vacuum device
Gradually heat or cool from the
Ionize body molecules and analyze them with a mass spectrometer to form water molecules
The assigned molecular ion counts are carbon monoxide and
Exceeds the count of molecular ions attributed to nitrogen molecules
Measuring temperature and / or mass of ions
The value of the number m / e obtained by dividing m by the charge e is 29 or more.
From total counting to oxygen molecule and carbon dioxide
The value obtained by subtracting the count number of the assigned molecular ion is
To carbon monoxide, nitrogen molecules, oxygen molecules and carbon dioxide,
To the total number of molecular ion counts assigned to each
It is characterized by measuring the temperature exceeding the value multiplied by 0.1
Of Organic Optical Materials That Can Withstand High Power Density Laser Light
Test method. 8. Using a crusher provided in the vacuum vessel,
Remove the sample of the material under a high vacuum of 1 × 10 ⁻⁴ Pa or less.
Characterized by crushing into small pieces with a diameter of 1 mm or less before testing
8. Withstands the high power density laser light according to claim 7.
Test method for organic optical materials.