JP2723200B2 - Manufacturing method of organic microcrystal for nonlinear optics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention, various types of electronics
The present invention relates to a method for producing an organic microcrystal for non-linear optics applicable to a method.

[0002]

2. Description of the Related Art Advances in microelectronics in recent years have sharply increased the demand for conventional nanometer (nm) scale ultrafine particles constituting an intermediate region of a bulk or molecular size. The above microcrystals have a catalytic effect based on a unique surface structure, optical properties due to size effects,
It exhibits various interesting properties such as nonlinear optical properties. Heretofore, methods for producing microcrystals of inorganic semiconductors, metals and ceramics have been studied for the purpose of application to the fields of electronics, catalysts and nonlinear optics.

Microcrystals of inorganic materials have been generally prepared by a gas phase method such as an electric furnace method or a plasma method, or a liquid phase method such as a freeze drying method or a spray drying method. However, only a few examples of the vapor phase method of evaporating in an inert gas have been used for microcrystals of organic materials expected to have higher functions.

For example, Toyotama, Functional Materials, Vol. 7, No. 6, pp. 44-49 (June 1987) discloses low molecular weight organic compounds such as anthracene, pyrene, and phthalocyanine;
A vapor phase growth method of polymer fine particles such as polymethyl methacrylate and polystyrene is described. Also, Yase et al., Surface Science Vol. 8, No. 5, pp. 434-439 (19
1987) describes the preparation of fine particles of calcium stearate by a gas phase method.

[0005] However, the vapor phase growth method has essential restrictions such as (1) high temperature is required, and (2) it is limited to low molecular weight compounds having a molecular weight of about 10,000 or less. In general, organic materials have low heat resistance and are easily deteriorated, so there is a limit to the application of this method.In addition, it is difficult to regulate the crystallinity, molecular weight, and the like in a specific range by a gas phase method, so that it is difficult to apply the method. Prone to problems. Therefore, a more effective manufacturing method has been desired.

On the other hand, as a method for producing fine particles of various materials including organic substances, a chemical condensation method is known.
B. Jagens et al., Translated by Iridescent, "Colloid Chemistry" 2
On pages 0 and 256 (published by Baifukan in 1967), a method of dissolving sulfur in anhydrous alcohol and pouring it into water,
A method is disclosed in which carotene is dissolved in acetone and then poured into water. However, most of the materials except the above are related to inorganic materials, and practically significant functional organic materials, in particular, no crystalline fine particles have been reported.

Further, there is a method called emulsion polymerization obtained by polymerizing polymer fine particles in the presence of a surfactant. However, there is a method called amorphous resin such as acrylic resin and styrene resin which has few features in terms of functionality. It was limited to polymers, and at the same time, a small amount of emulsifier was inevitably mixed into the interior due to restrictions during production, and uniform fine particles of high quality could not be obtained.

[0008] On the other hand, an acid pasting method in which an organic pigment such as a phthalocyanine pigment which is not dissolved in a usual solvent is partially reacted and dissolved in sulfuric acid, and then dispersed and kneaded in water to obtain fine particles is disclosed in, for example, F.I. H. Moser et al., The Phthlocyanines I
Volume I, pp. 35-37 (1983 CRC Press Publishing). This is a special method for obtaining polycrystalline pigment fine particles, which limits the types of materials that can be used to use a strong acid, and generally reduces the purity of most organic materials that are significant in terms of functionality. Could not be used.

[0009]

OBJECTS OF THE INVENTION It is an object of the present invention, molecular <br/> weight, crystallinity, to provide a non-linear optical organic microcrystals <br/> production method of controlling the particle size It is in.

[0010]

Still another object of the present invention is to provide a powder having a particle size of 500
It is an object of the present invention to provide a method for producing an organic microcrystal for nonlinear optics having a diameter of less than nm.

[0012]

The gist of the present invention for solving the above problems is as follows.

(1) An organic material for non-linear optics dissolved in a good solvent is mixed into a poor solvent of the organic material compatible with the solvent, and is mixed with a crystal or an aggregate having a particle size of 500 nm or less. Do
Manufacturing method of organic microcrystals for nonlinear optics .

(2) An organic material for non-linear optics dissolved in a good solvent is mixed into a poor solvent of the organic material compatible with the solvent, and gamma rays, electron beams, X-rays or light rays are emitted. Irradiate
Non-linear light with a crystal or an aggregate having a particle size of 500 nm or less
Production method of organic microcrystals for academic use .

After dispersing the polymerizable or associable organic polymer monomer or its solution in a poor solvent for the organic polymer monomer, it is irradiated with light such as active electron beam, X-ray or ultraviolet light or changes in acidity such as amine. A method of performing required polymerization or association formation by blending the agent is also included.

Further, by adding a charge controlling agent such as a surfactant to the solvent of the organic material and changing the acidity, required polymerization or association formation is carried out, thereby obtaining non-linearity.
A method for obtaining an organic microcrystal for shape optics is also included.

[0017] The organic material may be an organic microcrystal for nonlinear optics comprising a molecule having two or more double bonds or triple bonds in a molecule having a π-electron conjugated system.

Next, examples of the compounds used in the present invention are shown below. These are useful compounds in the field of nonlinear optical science. Note that the present invention is not limited to these materials.

(1) Diacetylene compounds represented by the following formula, and polydiacetylene compounds obtained by polymerizing them

[0020]

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(2) A diene compound represented by the following formula, and a polymer compound obtained by solid-phase polymerization of the diene compound:

[0022]

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(3) Polycyclic aromatic compound represented by the following formula

[0024]

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(4) Long chain compound represented by the following formula

[0026]

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(5) Dye compound represented by the following formula

[0028]

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Various methods can be applied to the production method of the present invention. Typical examples include the following ethanol method and melting method, and the present invention has various modifications that can be easily analogized, such as a change in solvent, and these are all included in the present invention.

In the ethanol method, an ethanol solution of the target sample compound is dropped into stirring water by an injection means such as a syringe or a syringe, and a surfactant is added as necessary to perform the following treatment. For example, when a diacetylene monomer or a derivative thereof is used as a sample compound, polymerization is performed by irradiating ultraviolet light (UV) to obtain microcrystalline particles of a corresponding polydiacetylene or a derivative thereof.

When a cyanine dye molecule is used as a sample compound, the sample is treated with an amine and the corresponding dye J
-Obtaining microcrystalline particles of aggregates. Where the desired properties
In order to obtain microcrystals , processing conditions such as solution concentration, dropping conditions, water temperature, stirring speed, type of surfactant, stability after dropping, ultraviolet intensity and irradiation time, amine processing time, etc. are within the optimal range. It is necessary to select.

The concentration of the organic material is desirably in the range from the saturation concentration to about 1/100 of the saturation concentration. The amount of the ethanol solution with respect to water may be a saturated dissolution amount to 1/1 of this amount.
0 ⁵ about is desirable. The stirring speed at the time of dropping is 50
About 0 to 1000 rpm is desirable. If the speed is lower than the above, microemulsification or aggregation is liable to occur, and if the speed is high, a complicated flow is generated in the liquid, which is not preferable.

Although not particularly limited, in the case of a diacetylene monomer derivative or the like, the solution concentration is 1
In the range of 0 to ¹ to ³ M (molar concentration), the particle size tends to increase as the concentration increases. Polycyclic aromatic compounds such as anthracene, a dye compound and a long chain compounds such as cyanine dye, the optimum concentration tends to exist somewhat lower density side and 10 ~ ² ~10 ~ ⁵ M.

The water temperature is in the range of 0 to 90 ° C., and the optimum temperature that gives the minimum particle size is around room temperature. On the cold side,
The crystal growth rate increases and the grain size increases, and it is easy to control the grain size on the high temperature side.

The ultraviolet light irradiation is in the range of 1 to 90 minutes,
Depending on the material and particle size, a significantly shorter time may be preferred.

The surfactant is preferably SDS (sodium lauryl sulfate), but need not be used.

As a condition for the injection and dropping, there is a method of forming a droplet shape or a jet shape similar to a jet flow, but the particle size is smaller in the case of the jet flow. However, if the flow rate is increased excessively, the effect is reduced due to the viscosity of the water.

Various solvents such as water, alcohols, ketones, esters, aromatic compounds and halogen compounds can be used as the solvent in the present invention. There are a method of dissolving an organic material in an organic solvent and injecting it into water, and a method of injecting a solution of the organic solvent into the organic solvent. The method of injection is preferably simple and preferable using a syringe, but is not particularly limited as long as the injection speed, solubility, temperature, and stirring state are satisfied.
As the treatment after the dispersion, known techniques such as photopolymerization using ultraviolet rays, electron beams, or the like, thermal polymerization, or acidity control using amines or the like can be applied.

On the other hand, in the melting method, the crystal particles of the sample compound are heated in a state where they are stirred in water and dispersed while applying ultrasonic vibration, and then cooled to obtain ultrafine crystal particles. At this time, optimal ranges such as water temperature, holding time, presence / absence of ultrasonic vibration, stirring speed, cooling speed, etc. are selected.

The organic microcrystal of the present invention can be used in various forms, such as dispersion in a liquid or solid, mixing with another material, and coating with another material. A polymer material is used as a matrix for dispersion.

According to the present invention, monodispersed organic microcrystals having a uniform particle size and molecular weight of a π (pi) electron conjugated polymer can be obtained. In addition, by using a polycyclic aromatic molecular crystal having a uniform particle size, exciton (exciton) formation can be analyzed in detail. Further, the particle diameter of the crystallite of the dye molecule and J
-Quantitative examination of the relevance of aggregate formation is possible.

[0042]

By the present invention, although the reason for chromatic sensitive crystal is obtained has not yet been found, it is estimated as outlined below.

The ethanol solution in which the sample compound is dissolved is mixed into water and dispersed as droplets, and gradually evaporates or elutes into the aqueous phase of ethanol, so that the droplets lose solvent and become supersaturated. It is considered that microcrystals are finally deposited. When a surfactant or the like is present in water, the droplets are stabilized in water, and the disappearance of the solvent and the transition to a supersaturated state may be inhibited.

[0044]

The present invention will be described in more detail with reference to the following examples.

Example 1 4 of the structure shown in the following [Chemical Formula 6]
80 mg of -BCMU [5,7- (bis-1,12-n-butylcarboxymethylene-urethane) dodecadine] was dissolved in 5 ml of ethanol to prepare a 3.2 × 10 to ² M solution.

[0046]

## STR6 ## RC—C—C—C—R (where R represents (CH ₂ ) ₄ OCONHCH ₂ COOC ₄ H ₉ ) Then, at room temperature, 10 ml of pure water is vigorously stirred in a beaker. Then, 50 μl of the 4-BCMU solution was added dropwise using a microsyringe. Immediately after the start of the dropwise addition, a white precipitate is formed, and the whole amount is further dropped in a few minutes with stirring to obtain a dispersion. A small amount of the dispersion was transferred to a quartz cell and photopolymerized by irradiation with a high-pressure mercury lamp. The irradiation time is
There are four types: 1, 3, 5, and 20.

FIG. 1 shows the absorption spectrum of the obtained polydiacetylene fine particles. It showed absorption maxima at 627 and 573 nm, confirming that it was a poly-4-BCMU polymer. The maximum at 627 nm increased with the irradiation time, and then decreased from the maximum at the time of 3 minutes. Observation with a scanning electron microscope (SEM) after irradiation for 3 minutes showed that one side was about 100 to 200 nm as shown in FIG.
It was confirmed that fine crystal grains 1 having a cubic or rectangular parallelepiped shape having a good size were formed. Note that FIG.
It is a mimetic diagram of the SEM photograph of.

Observation of the particle shape by SEM when the irradiation time was 20 minutes showed that the shape was slightly unclear as compared with the case where the irradiation time was 3 minutes. It seems that the surface layer of the molecular particles was partially dissociated.

Example 2 A 4-BCMU solution was prepared in the same manner as in Example 1 and rapidly jetted into pure water in the form of a jet stream, and irradiated with ultraviolet light.
m of poly-4-BCMU microcrystalline particles were obtained. Observation of the obtained polymer fine particles with a SEM revealed that the particle size was about 20 nm.
It was confirmed that cubic or rectangular parallelepiped fine crystallites having the above-mentioned size were formed.

Example 3 A merocyanine dye MCSe-C18 [3-carboxymethyl-5 represented by the following chemical formula 7]
[2- (3-Octadecyl-2-benzoselenazolinylidene-ethylidene-rhodanine)]] was dispersed in water from an ethanol solution and treated with an amine to produce a fine particle dispersion of a J-aggregate.

[0051]

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FIG. 4 shows that the treatment times of the amines were 0, 100, 2
It is a graph which shows the change of an absorption spectrum when it changes to 00 and 1000 minutes. By adding amine, clear J-
A sharp absorption maximum of the aggregate appears. However, the properties of the dispersion were almost the same as those of the dye solution, and as a result of observation by SEM, the dispersion was extremely dispersed in ultrafine particles, and favorable microcrystals having a cubic or rectangular parallelepiped shape with a particle size of about 20 nm were formed. It was confirmed.

Example 4 A long-chain compound PNA-C18 (N-octadecyl-4-nitroaniline) represented by the following [Chemical Formula 8] was converted into ultrafine particles in the same manner as in Example 3. Observation of the obtained fine particles by SEM revealed that the fine particles were extremely dispersed in
It was confirmed that good fine crystals having a rectangular parallelepiped shape with a size of nm were formed.

[0054]

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[0055]

According to the present invention, 500 nm following nonlinear optical organic fine applicable to <br/> field of various electronics
Crystals can be obtained.

[Brief description of the drawings]

FIG. 1 is a UV absorption spectrum of the organic microcrystalline particles of Example 1.

FIG. 2 is a SEM photograph of the organic microcrystalline particles of Example 1.

FIG. 3 is a schematic view of an SEM photograph of the organic microcrystalline particles of FIG.

FIG. 4 is a UV absorption spectrum of the organic microcrystalline particles of Example 3.

[Explanation of symbols]

 1: microcrystalline particles, 2: glass substrate

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08F 6/00 C08F 6/00 38/00 38/00 Application for Patent Law Article 30 Paragraph 1 applies. May 26 to 29, 1992 Documented at the 41st (1992) Annual Meeting of the Society of Polymer Science held by the Society of Polymer Science, Japan held at the Pacifico Yokohama Conference Center Article 30 of the Patent Act Article 1 Application for application June 17-18, 1992 Documentary presentation at "Miyazaki International Symposium" hosted by The Institute of Textile Science, held at Kasumigaseki National Education Hall, Tokyo (74) Attorney of the above five agents Akio Takahashi (one outsider) (73) Patentee 000001144 Director of Industrial Technology 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (1) Designated representative of the above-mentioned one Director of the Institute of Materials Technology, National Institute of Industrial Science (2) (72) Inventor Hitoshi Kasai 67, Kawauchiyamayashiki, Aoba-ku, Sendai, Miyagi Prefecture (72) Inventor Hidetoshi Oikawa Sendai, Miyagi Prefecture 3-7-10- 508 Minami Koizumi, Wakabayashi-ku, City (72) Inventor Katsumichi 2-17-14, Inspector General, Izumi Ward, Sendai City, Miyagi Prefecture (72) Inventor Hachiro Nakanishi 2-3-3 Kutake, Miyagino Ward, Sendai City, Miyagi Prefecture 20-404 (72) Inventor Shuji Okada 1-1-4 Higashi, Tsukuba, Ibaraki Pref., Institute of Industrial Science and Technology (72) Inventor Hiroo Matsuda 1-4-1 Higashi, Tsukuba, Ibaraki, Textile In the Polymer Materials Research Laboratory (72) Inventor Shinji Minami 1-1-4 Higashi, Tsukuba City, Ibaraki Industrial Technology Institute In the Textile Polymer Materials Research Laboratory (72) Inventor Hari Sing Narwa 4026 Kuji-cho, Hitachi City, Ibaraki Co., Ltd. Hitachi, Ltd.Hitachi Laboratory (72) Inventor Atsushi Tsunoda 4026 Kuji-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. The laboratory (72) inventor towards the tail Akio Hitachi City, Ibaraki Prefecture Kuji-cho, Hitachi, Ltd. Hitachi Research Laboratory within the examiner Kenichi Mori address 4026 (56) references WO 92/3380 (WO, A)

Claims (2)

(57) [Claims] An organic material for nonlinear optics dissolved in a good solvent is mixed into a poor solvent of the organic material compatible with the solvent to form a crystal or an aggregate having a particle size of 500 nm or less. Manufacturing method of organic microcrystals for nonlinear optics . 2. An organic material for nonlinear optics dissolved in a good solvent is mixed into a poor solvent of the organic material which is compatible with the solvent, and irradiated with a gamma ray, an electron beam, an X-ray or a light beam to obtain a particle size.
Preparation of the nonlinear optical organic microcrystalline you <br/> characterized in that the following crystalline or aggregates 500 nm.