JPH08217982A - Resin composition, production of resin composite material having fine metallic particle dispersed therein and optical recording device - Google Patents

Abstract

PURPOSE: To obtain a resin composition having a high content of fine metallic particles with controlled particle diameter distribution and improved in heat resistance and electrical characteristics by using a curable or polymerizable resin, an inorganic or organic salt of a metal, and a reducing agent as the constituents. CONSTITUTION: A curable or polymerizable liquid resin is mixed with a metal salt serving as a precursor for fine metallic particles, a reducing agent that reacts with the metal salt to deposit fine metallic particles and, if necessary, a curing or polymerization catalyst, and the mixture is heat treated at a temperature higher than the temperature at which fine metallic particles are formed and also than the curing or polymerization temperature of the resin to cure or polymerize the resin and deposit the inorganic or organic salt of the metal, thus a resin composition containing 1-60vol.% inorganic or organic salt of the metal with a particle diameter of 1-100mn is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition, a method for producing a metal fine particle dispersed resin composite material from the resin composition,
And an optical recording device having a fine particle dispersed resin composite material as a constituent element.

[0002]

2. Description of the Related Art Recently, a composite material in which ultrafine particles of metal or semiconductor are dispersed in glass or the like has attracted attention as a third-order nonlinear optical material. Among them, a composite material in which fine particles are dispersed in a polymer has a good moldability for a thin film and the like, and therefore its importance has increased in recent years. Such a polymer-based composite material is disclosed, for example, in JP-A-5-22400.
No. 6, for example, many of these are sol-
It is prepared by the gel method. However, in the sol-gel method, not only a large amount of solvent is required for the preparation, but also the restrictions on the molecular structure of the polymer that can be used are large, and the content ratio of fine particles to the dispersion medium (polymer) should be made so high. I can't. Further, in methods other than the sol-gel method, the preparation conditions of the composite material are very special,
Molding of the prepared composite materials is often difficult.

As a method for preparing a composite material of ultrafine metal particles, which solves the above problems, Japanese Patent Laid-Open No. 11346/1989 has been proposed.
No. 4 discloses that a soluble salt of a noble metal is dissolved in a liquid monomer such as an epoxy resin and then this is polymerized to be solidified, and then this resin cured product is heated to a temperature (colloid formation temperature) or higher at which noble metal fine particles are generated. A method of obtaining a resin composite material in which fine metal particles are dispersed by heat treatment is disclosed. However, this method has drawbacks in that it requires heat treatment at a relatively high temperature in order to generate fine metal particles, and cannot be applied to a resin having a too high glass transition temperature. Further, since the metal fine particles are generated after the resin is cured, the conversion rate of the metal salt to the metal fine particles is low, and as a result, it is difficult to increase the content ratio of the metal fine particles, and it is difficult to adjust the particle size distribution of the metal fine particles. In addition, it is difficult to form different parts such as particle size distribution, particle shape, and agglomeration state in one metal fine particle dispersed resin composite material.

[0004]

As described above, the conventional metal fine particle-dispersed resin composite material requires a large amount of solvent and high temperature heat treatment at the time of preparation, and it is difficult to increase the content rate of fine particles. Also, there was a problem in formability such as film forming property. Even if these problems could be solved, the particle size distribution of the metal fine particles could not be adjusted arbitrarily.

The present invention solves these problems and improves the content of fine particles and the particle size distribution of the fine particles as a raw material of a metal fine particle dispersed resin composite material having excellent heat resistance and electrical characteristics. It is an object of the present invention to provide a resin composition capable of adjusting the composition, a method for producing a metal fine particle-dispersed resin composite material from the resin composition, and an optical recording device using such a fine particle-dispersed resin composite material. .

[0006]

The resin composition of the present invention comprises (a) a curable resin or a polymerizable resin, (b) an inorganic or organic salt of a metal, and (c) a component (b). It is characterized by containing a reducing agent.

The method for producing a metal fine particle-dispersed resin composite material of the present invention is characterized in that the resin composition is treated at a temperature higher than the temperature for forming the metal fine particles and the curing or polymerization initiation temperature of the resin. It is what In the present invention, during this treatment, the resin composition may be irradiated with light having a wavelength corresponding to the surface plasmon absorption wavelength of the metal fine particles having a predetermined particle diameter.

The optical recording medium of the present invention is an optical recording medium made of a fine particle-dispersed resin composite material containing conductive fine particles in a resin-based dispersion medium, a light source for irradiating the optical recording medium with light, and light detection. Means and means are provided. In this optical recording medium, writing is performed by changing the dispersion state of the conductive fine particles in the optical recording medium by irradiation of light from a light source.

The present invention will be described in more detail below. In the resin composition of the present invention, the curable resin or the polymerizable resin which is the component (a) has a two-dimensional structure which causes a rise in viscosity and curing from a liquid state due to a polymerization reaction or a crosslinking reaction by heating or light. Alternatively, it is not particularly limited as long as it produces a resin polymer or a resin cured product having a three-dimensional network structure. Specifically, unsaturated polyester resin, epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin or polyimide resin, vinyl chloride resin, acrylic resin, polyurethane resin, styrene resin or polycarbonate resin, etc. One obtained by adding a crosslinking agent such as isocyanate to the above thermoplastic resin.

However, considering the heat resistance and mechanical strength of the resin as the dispersion medium, it is preferable to use a curable resin which produces a resin cured product having a three-dimensional network structure. Further, of the curable resins, an epoxy resin is particularly preferable, and such an epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule. Here, examples of the epoxy group include those represented by the following structural formula.

[0011]

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The epoxy resin may be an acrylic modified epoxy resin having an unsaturated double bond in the molecule. Here, examples of the unsaturated double bond include those represented by the following structural formulas.

[0013]

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In the above structural formula, the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom such as chlorine or fluorine, an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like. .

Such an acrylic modified epoxy resin is
The molecule can be designed according to the purpose and synthesized by any method. However, a method of synthesizing by reacting an ordinary epoxy resin with acrylic acid, methacrylic acid, cinnamic acid, maleic acid or the like is easy. Examples of the epoxy resin used in this method include bisphenol A type epoxy resin, bisphenol F type epoxy resin; phenol novolac type epoxy resin; alicyclic epoxy resin; triglycidyl isocyanate, nitrogen-containing epoxy resin such as hydantoin epoxy; Hydrogenated bisphenol A type epoxy resin, propylene glycol-diglycidyl ether,
Aliphatic epoxy resin such as pentaerythritol polyglycidyl ether; Epoxy resin obtained by reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin; Spiro ring-containing epoxy resin; o-allylphenol novolac compound and epichlorohydrin And a glycidyl ether type epoxy resin which is a reaction product of bisphenol A; a glycidyl ether type epoxy resin which is a reaction product of a diallyl bisphenol compound having an allyl group at the ortho position of each hydroxyl group of bisphenol A and epichlorohydrin. As the epoxy resin, at least one selected from the group consisting of these is used.

In the resin composition of the present invention, the metal salt of component (b) includes gold chloride, gold bromide, silver chloride, silver bromide,
Halides such as silver iodide and palladium chloride, and inorganic metal salts such as chloroplatinic acid, sodium chloroaurate and silver nitrate,
Alternatively, an acetylacetonate such as platinum acetylacetonate or palladium acetylacetonate or an organic metal salt such as a noble metal organic ammonium salt is used.

In the resin composition of the present invention, as the reducing agent of the component (c), alcohols such as benzyl alcohol and dextrin, formalin, benzaldehyde,
Aldehydes such as terephthalaldehyde, sodium borohydride, lithium aluminum hydride, hydrogen gas, phosphorus, hydrazine, tannin, and pyrogallol are used.

In order to obtain a metal fine particle dispersed resin composite material from the resin composition of the present invention, a curable resin or a polymerizable resin such as a liquid epoxy resin monomer is added to a metal salt which is a precursor substance of fine particles and this metal. After mixing with a reducing agent that reacts with a salt to precipitate fine metal particles, and if necessary a predetermined curing or polymerization catalyst is added thereto, the temperature is higher than the temperature for forming the fine metal particles and the curing or polymerization initiation temperature of the resin. A method of curing or polymerizing the resin and reducing the metal salt to deposit desired fine particles in the resin by heat treatment at a high temperature can be used. In this method, the content of the fine particles in the cured product or the polymer changes depending on the addition amount of the metal salt, and the particle size or the aggregation state of the fine particles changes depending on the curing or polymerization rate of the resin. When the resin is photocurable or photopolymerizable, light irradiation for curing or polymerizing the resin may be appropriately used in combination with the heat treatment as described above.

Here, the particle size and the state of aggregation of the fine particles are affected by the viscosity of the surrounding field where the fine particles are deposited. In general, when the viscosity of the surroundings is large, the particle size is small and the particles tend to be difficult to aggregate. On the contrary, when the viscosity of the surroundings is small, the particle size is large and the particles are likely to be aggregated. Therefore, it is considered that if the resin is sufficiently cured or polymerized to increase the viscosity and then the particles are precipitated, a composite material having a small particle size and good dispersibility, which is not much aggregated, can be obtained. However, if the viscosity of the resin is too high, the process in which the metal salt reacts and grows into fine particles is hindered, and as a result, the amount of fine particles to be deposited is smaller than the addition amount of the metal salt, resulting in poor efficiency. Therefore,
In the initial stage of the reaction, the viscosity of the resin is small and the reaction of the metal salt proceeds rapidly, but in the latter stage of the reaction, the viscosity of the resin is so high that the particle size of the particles does not become coarser than necessary or aggregated. Ideal.

In the present invention, since the reaction between the metal salt capable of forming the metal fine particles under a relatively mild temperature condition and the reducing agent is utilized, the resin has a very low viscosity in parallel with the formation of the metal fine particles. It continuously changes from a monomer state to a resin cured product or resin polymerized product having a very high viscosity.
Therefore, by appropriately setting the reaction rate of the metal salt and the curing rate or the polymerization rate of the resin, the viscosity of the surrounding resin can be controlled to the ideal state as described above in accordance with the progress of the reaction of the metal salt. Specifically, if the reactivity of the metal salt is high, select a curable resin with a high curing rate,
On the contrary, when the reactivity of the metal salt is low, a curable resin having a low curing rate is selected, so that the dispersed state of the particles can be controlled by the combination of the metal salt and the curable resin or the polymerizable resin. Here, the curing rate of the curable resin can be easily adjusted, for example, according to the curing agent component of the curable resin.

Further, in the present invention, it is desired that the formation temperature of the fine metal particles is higher than the curing or polymerization initiation temperature of the resin, and the temperature difference is within 100 ° C, more preferably within 20 ° C. . This is because when the curing or polymerization initiation temperature of the resin is higher than the formation temperature of the metal fine particles, the precipitation of fine particles is started before the curing or polymerization of the resin, and therefore the particle size of the fine particles is large while the viscosity of the resin is small. This is because there is a risk that the dispersibility will decrease and the dispersibility will decrease, and this tendency becomes more pronounced as the temperature rising rate during the heat treatment becomes slower. On the other hand, if the forming temperature of the metal fine particles is too high, curing or polymerization of the resin will proceed too much during the temperature rise during the heat treatment, and the amount of fine particles to be precipitated will be small, resulting in poor efficiency. However, the forming temperature of the metal fine particles and the curing or polymerization initiation temperature of the resin here mean that the reaction rate of the reduction reaction of the metal salt or the curing or polymerization reaction of the resin is 3 at that temperature.
It is defined as the temperature which reaches 50% within a week, preferably within a week.

Further, the fine particles generated in the above reaction process exhibit surface plasmon absorption when the particle size is sufficiently small, and absorb the light of a specific wavelength in the visible region mainly from the ultraviolet and release it as heat to the surroundings. Have. At this time, the surface plasmon absorption wavelength of fine particles of a certain material mainly depends on the particle diameter of the fine particles, and the maximum absorption wavelength of fine particles having a specific particle diameter is almost uniquely determined. Therefore, in the process of curing or polymerizing the resin, when a laser beam having a wavelength corresponding to a desired particle size is irradiated, surface plasmon absorption occurs at the time when the precipitated fine particles reach the desired particle size, and the absorbed light is absorbed. It is released to the environment as heat. As a result, only the resin around the fine particles having a desired particle size is heated to accelerate curing or polymerization, and it is possible to prevent the fine particles from growing or aggregating beyond the particle size. That is, individual particles grow rapidly until they reach a desired particle size, and stop growing at a particle size corresponding to the wavelength of irradiation light, so that the particles have a desired particle size, no agglomeration, and metal particles It is possible to prepare a fine particle-dispersed resin composite material having a high conversion rate to, and it is very effective and useful. At this time, it is possible to freely change the particle size distribution, particle shape, and aggregation state in a very fine region by narrowing down the laser optical axis for irradiation, especially for forming a nonlinear optical element or hologram recording medium. It is very effective when doing. In this case,
Before irradiation with laser light or the like, even if the temperature of the resin composition is equal to or higher than the formation temperature of the metal fine particles and lower than the curing or polymerization initiation temperature of the resin, the surface plasmon absorption of the metal fine particles as described above after irradiation with laser light or the like When the temperature of the resin composition rises above the curing or polymerization initiation temperature of the resin due to heat generation, it becomes possible to obtain a metal fine particle-dispersed resin composite material.

Next, the fine particle-dispersed resin composite material prepared from the resin composition of the present invention will be described by taking the case where the resin composition contains a curable resin as an example. The fine particle-dispersed resin composite material is obtained by dispersing fine particles in a dispersion medium made of a cured resin. The fine particles dispersed in the dispersion medium here become metal fine particles when prepared using the resin composition of the present invention as described above, but in general, if it is a conductor, metal, alloy, compound, etc. It is not limited and may be a mixture or complex of these. The conductor fine particles may have any shape, and the dispersion form thereof is not particularly limited, but the particle diameter is preferably in the range of 1 to 100 nm. The reason for this is that it is difficult to manufacture conductive fine particles having a particle size of less than 1 nm, whereas when the particle size exceeds 100 nm, the size effect such as the effect of increasing the surface area per unit weight, and the characteristic properties of ultrafine particles such as the quantum effect are observed. This is because the expression becomes small. Further, the conductor fine particles have a particle size of 1 to 2
It is more preferable that the particle diameter is 0 nm and the particle diameters are sufficiently uniform.

In such a composite material, by dispersing the above-mentioned conductive fine particles in a resin cured product,
At the interface between the resin cured product and the fine particles, various interactions such as electron transfer and chemical bond formation work. As a result, the fine particles act equivalently to the resin crosslinking agent and filler (filler),
Moreover, since the particle size of the fine particles is very small and the surface area of the fine particles per unit total volume is large, the above-mentioned function is remarkably large as compared with ordinary fillers. Therefore, the obtained fine particle-dispersed resin composite material is greatly improved in heat resistance, light resistance, elastic modulus, etc. as compared with ordinary resin cured products, and can be suitably used as a structural material. In particular, when used as an optoelectronic material such as a third-order nonlinear optical material, the fine particles exhibit a function such as a nonlinear optical effect, and at the same time, have a durability against laser irradiation due to the characteristic improving effect as described above. Therefore, it is not necessary to separately add an ordinary crosslinking agent or filler that hinders the expression of functions. Furthermore, conventionally, when a filler is added to improve the properties, it is necessary to add the filler to the resin before curing in advance and then perform molding by casting, etc., and the viscosity of the resin increases and work such as casting However, when preparing a fine particle-dispersed resin composite material using the resin composition of the present invention, fine particles corresponding to the filler are precipitated during casting before curing. Therefore, the above-mentioned increase in viscosity does not occur and workability is very excellent.

In the present invention, the compounding amount of the above-mentioned conductor fine particles with respect to the resin-based dispersion medium is not particularly limited. However, when used as an optoelectronic functional material such as a third-order nonlinear optical material or an optical recording medium of an optical recording device,
It is preferably set to 0.1 to 60% by volume, more preferably 5 to 40% by volume. The reason for this is that if the amount of the conductive fine particles blended is too small, the interaction between the fine particles and the resin cured product is small, so that the expression of functions such as a nonlinear optical effect is small,
On the other hand, if the amount of the conductive fine particles is too large, the dispersibility of the fine particles is lowered, and a good quantum size effect cannot be obtained, and in turn, a function such as a large nonlinear optical effect may not be exhibited. When it is used as a structural material, it is preferably set to 0.01 to 50% by weight, more preferably 0.1 to 20% by weight. The reason for this is that if the amount of the conductive fine particles is too small, the interaction between the fine particles and the resin cured product is small, so that the characteristic improvement such as the elastic modulus is small. On the contrary, if the amount of the conductive fine particles is too large, This is because the dispersibility is reduced and aggregation or the like is likely to occur, resulting in non-uniform expression of properties or a small improvement in properties. Therefore, in the resin composition of the present invention, it is preferable to determine the blending amount of each component according to the application so that the blending amount of the generated fine particles is within the above range.

Specifically, the addition amount of the metal salt is set to 1 to 2 equivalents of the preferable mixing amount of the fine particles with respect to the resin-based dispersion medium as described above, and the reducing agent is 1 to the metal salt.
It is desired to be blended in an amount of -20 equivalents, more preferably 1-5 equivalents. That is, when the addition amount of the metal salt is out of the range of 1 to 2 equivalents, it becomes difficult to control the compounding amount of the fine particles to the resin dispersion medium to a preferable value according to the application of the composite material. If the amount of the reducing agent is too small, the reduction of the metal salt may be difficult to proceed and the precipitation of fine particles may be insufficient. On the contrary, if the amount of the reducing agent is too large, excess reducing agent causes the fine particle dispersion resin to be dispersed. It remains in the composite material and its mechanical strength and the like tend to decrease. However, from the viewpoint of specifically increasing or decreasing the reaction rate of the metal salt in relation to the curing rate or the polymerization rate of the resin, the amount of the reducing agent to be added is set outside the range of 1 to 5 equivalents, if necessary. It doesn't matter.

Next, an example of a non-linear optical element having the above-mentioned fine particle dispersed resin composite material as a constituent element will be described with reference to FIG. In FIG. 1, a clad layer 8 is provided on a substrate 1 made of, for example, quartz or glass. In the clad layer 8, a nonlinear optical material 2 made of a fine particle dispersed resin composite material is provided in the center portion, and around the periphery thereof, the optical waveguides 3 and 4 on the incident side and the optical waveguides 5, 6 and 7 on the outgoing side.
Are formed, and the cladding layer 8 and each optical waveguide have different refractive indexes. An optical fiber 9 is provided outside each optical waveguide. In the non-linear optical element of the present invention, the optical waveguide portion may be entirely formed of the fine particle dispersed resin composite material, and it is not always necessary to provide the clad layer.

The principle of operation of the nonlinear optical element shown in FIG. 1 will be described. Now, laser light from a not-shown modulatable laser light source is passed through the optical fiber 9 to the optical waveguide 3 or 4.
When the laser beam is incident on the optical waveguide 5 or 6 alone,
Is emitted as is. On the other hand, the laser light is passed through the optical waveguide 3
When the two laser beams are simultaneously incident on and 4, the optical axes of the two laser beams intersect in the nonlinear optical material 2, so that an electronic lattice is formed at the intersection of the optical axes of the two laser beams. Therefore, for example, the laser light incident on the optical waveguide 3 is diffracted by this electronic grating when passing through the nonlinear optical material 2, and the diffracted light is emitted from the optical waveguide 7. Therefore, if a photodetector is attached to the optical fiber 9 outside the optical waveguide 7, the diffracted light emitted from the optical waveguide 7 can be detected.

Therefore, the nonlinear optical element shown in FIG. 1 is used in the optical waveguide 4 with the light always entering the optical waveguide 3.
It can be preferably applied as an optical switching element capable of controlling the on / off of the light emitted from the optical waveguide 7 by turning on / off the light incident on the optical waveguide 7. Further, as described above, light is emitted from the optical waveguide 7 only when light is simultaneously incident on the optical waveguides 3 and 4, and even if light is incident on only one of the optical waveguides 3 and 4, the optical waveguide 7 Since no light is emitted from the above, it also functions well as an and circuit in which light is incident on the optical waveguides 3 and 4 under two conditions. Furthermore, such nonlinear optical elements can be expected to be applied to phase conjugate mirrors, ultrafast spectroscopy, real-time holograms, cryptographic conversion elements, and the like.

An example of an optical recording apparatus according to the present invention, which has the same fine particle-dispersed resin composite material as a constituent element, will be described with reference to FIG. As shown in FIG. 2, this optical recording apparatus has an optical recording medium 13 made of a fine particle dispersed resin composite material mounted on a movable stage 14, two sets of laser light sources 11 and 12, and a light detecting means. Photodetector 1
5 and 5. The operating principle of this optical recording device is as follows. Now, when the optical recording medium 13 is simultaneously irradiated with laser light from the light sources 11 and 12, interference occurs in the irradiation part. At this time, in the bright part of the interference fringes, the fine particles cause surface plasmon absorption and heat is generated, and the irregularly aggregated fine particles are sintered and deformed into a spherical shape, so that the surface plasmon absorption wavelength, refractive index, etc. The optical characteristics of. As a result, an irreversible diffraction grating corresponding to the interference fringes is formed in the irradiation portion, and writing is performed by this. In this state, for example, when sufficiently weak light that does not cause the above-described change is incident from the light source 11, the incident light is diffracted at the portion where the diffraction grating is formed, and the diffracted light is detected by the photodetector 15. To be done. On the other hand, in the portion where the diffraction grating is not formed, the light from the light source 11 is not diffracted, so the diffracted light is not detected by the photodetector 15. In this way, the written record can be read. The method of writing to and reading from the optical recording medium 13 is not limited to this. For example, light irradiation from a single light source may simply change the optical characteristics of the irradiation section in the same manner to identify the change in the optical characteristics. It may be optically detected using a reading light or a light detection means.

As described above, the optical recording apparatus of the present invention records by utilizing the change of the dispersion state of fine particles and does not require any other chemical change, so that stable recording with very little change with time is made. Is possible. In addition, since the resolution of recording and reading thereof mainly depends on the particle size of the fine particles, it is possible to record with extremely high density by reducing the particle size. Moreover, not only as a planar two-dimensional optical recording medium, but also as a volume type three-dimensional recording is possible, it is very useful as a recording medium for holograms, for example.
In the above, the fine particle-dispersed resin composite material using the resin cured product as the dispersion medium and its application have been described, but the same applies to the case where the resin polymer is used as the dispersion medium instead of the resin cured product.

[0032]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 Sodium chloroaurate dihydrate as an inorganic metal salt 13.
4 mg, terephthalaldehyde 11.5 as reducing agent
mg, aluminum acetylacetonate 6.5 mg,
Then, 0.5 ml of an acetone solution containing 200 mg of triphenylsilanol was added to 1 g of an epoxy resin (trade name CEL2021 manufactured by Daicel Co., Ltd.) as a curable resin, and well mixed with stirring. After mixing, the mixture was vacuum dried at room temperature to remove the solvent, and sandwiched between two glass plates having a 25 μm spacer. After leaving it at room temperature for 15 hours, it was further heated at 60 ° C. for 15 hours to obtain a pink epoxy resin cured product.

By X-ray scattering measurement, it was confirmed that this epoxy resin cured product contained metallic gold. In addition, as a result of measurement of a visible ultraviolet absorption spectrum,
Absorption that was thought to be due to surface plasmon absorption of gold was confirmed in the vicinity of nm. According to a transmission electron microscope (TEM) observation, the average particle size of the gold fine particles was 7 nm.

Example 2 Sodium chloroaurate dihydrate 6.4 mg, terephthalaldehyde 40.2 mg, aluminum acetylacetonate 67 mg, and triphenylsilanol 0.9 m
5 ml of acetone solution of epoxy resin (CEL202
1) Added to 20 g and mixed well with stirring. After mixing, vacuum drying was performed at room temperature to remove the solvent, and the mixture was cast into a plate-shaped mold having a thickness of 5 mm. Leave at room temperature for 15 hours, then at 40 ° C for 2 hours.
After heating for an hour, a blue-violet cured epoxy resin product was obtained.

From the X-ray scattering measurement, it was confirmed that the cured product contained metallic gold. In addition, as a result of measurement of visible-ultraviolet absorption spectrum, absorption that was thought to be due to surface plasmon absorption of gold was confirmed at around 573 nm. According to transmission electron microscope (TEM) observation, the average particle size of the gold fine particles was 15 nm.

Using a dye laser (wavelength 560 nm) of Nd ³⁺ YAG second harmonic excitation, this cured product was used.
When the third-order nonlinear optical constant χ ⁽³⁾ was measured by the degenerate four-wave mixing method, it was found that χ ⁽³⁾ = 1.1 × 10 ^{-10, which} is a good value.

Example 3 17 mg of palladium chloride and 0.1 of terephthalaldehyde
2 g, aluminum acetylacetonate 0.15 g,
And 0.9 g of triphenylsilanol in methanol and dimethylformaldehyde were mixed with epoxy resin (C
EL2021) 20 g and well mixed with stirring. After mixing, vacuum drying was performed to remove the solvent, and the mixture was cast in a predetermined mold. Leave at room temperature for 5 hours, then at 80 ℃ for 4 hours, 120
It heated at 1 degreeC for 1 hour, and obtained the yellow epoxy resin hardened | cured material.

On the other hand, for comparison, an epoxy resin cured product was obtained under the same curing conditions as above, without adding a metal salt. When an elastic modulus test was performed on these cured products at room temperature, the cured product of the comparative example had a flexural modulus of 261 MPa, whereas the cured product of the present invention had a flexural modulus of 430 MP.
It was found to have excellent characteristics as a.

Example 4 6.4 mg of sodium chloroaurate dihydrate, 40.2 mg of terephthalaldehyde, 67 mg of aluminum acetylacetonate, and 0.9 g of triphenylsilanol.
5 ml of acetone solution of epoxy resin (CEL202
1) Added to 20 g and mixed well with stirring. After mixing, the mixture was water-cooled and vacuum-dried to distill off the solvent, and the mixture was cast into a mold with a 5 mm-thick quartz glass window. This mold was kept warm at 30 ° C., and a dye laser (wavelength: 520 nm) of Nd ³⁺ YAG second harmonic excitation was irradiated through the window for 5 hours.

As a result, the non-irradiated portion was blue, while the laser-irradiated portion was colored reddish purple. When the visible-ultraviolet absorption spectrum was measured, the unirradiated part was 571n.
In the irradiated part, absorption considered to be caused by surface plasmon absorption of gold could be observed in the vicinity of 532 nm. According to a transmission electron microscope (TEM) observation, the average particle size and the particle size distribution of the gold particles are about 15 ± 10 nm in the unirradiated part and about 7 ± 10 nm in the irradiated part.
It was 5 nm. From this, it was found that the particle size of the fine particles can be controlled by laser irradiation, and a fine particle-dispersed resin composite material having a narrow particle size distribution can be prepared.

Example 5 The epoxy resin composition prepared in Example 4 was applied on a quartz substrate by a doctor blade method to a thickness of about 20 μm,
This was irradiated with a laser beam (wavelength 520 nm) similar to that of Example 4, which was focused on the substrate with water and having a diameter of 30 μm while scanning, and the same particle size distribution as in Example 4 was obtained according to the scanned shape. The region was formed with a width of about 50 μm.

Example 6 The epoxy resin cured product having the fine gold particles dispersed therein obtained in Example 2 was molded into a piece of 5 × 5 × 2 mm, which was used as a non-linear optical material with optical fibers arranged around it. The optical switching element shown in 1 was obtained. When an operation test was performed on this optical switching element using a dye laser beam having a wavelength of 560 nm, it was confirmed that the optical switching element functions well as an and circuit.

Example 7 The epoxy resin cured product having the gold fine particles dispersed therein obtained in Example 2 was used as the optical recording medium 13 in FIG. 2, and the intensity of the dye laser light (wavelength 560 nm) was 3 mW in average power.
When the laser light sources 11 and 12 simultaneously entered with a peak power of 30 kW, irreversible interference fringes were formed on the irradiation part. Next, when laser light having an average power of 0.3 mW and a peak power of 3 kW was incident only from the laser light source 11, emitted light which was not observed before forming the interference fringes was observed by the photodetector 15. From this, it was found that the cured epoxy resin in which the fine gold particles were dispersed worked as an optical recording device using the optical recording medium 13.

Example 8 The epoxy resin cured product having the fine gold particles dispersed therein obtained in Example 2 was irradiated with a laser beam having an average power of 3 mW and a peak power of 30 kW from a dye laser having a wavelength of 560 nm. Discolored. When the visible absorption spectrum of the discolored part was measured, the absorption wavelength was 573 nm.
From 550 nm to 551 nm, and the tailing of absorption on the long wavelength side, which is considered to be caused by aggregation of gold fine particles, was reduced. As a result of TEM observation of the irradiated part, the aggregation sites of the gold fine particles observed before the irradiation disappeared, and the shape of each fine particle also changed to a spherical shape, and the gold fine particles were changed by laser irradiation. It was found that writing can be performed by changing the dispersion state of fine particles in the epoxy resin cured product in which is dispersed.

[0045]

As described above in detail, according to the present invention, a fine particle-dispersed resin composite material having a high content rate of fine particles and having a controlled particle size distribution of fine particles and having excellent heat resistance and electrical characteristics. Can be obtained. Further, such a fine particle dispersed resin composite material is a non-linear optical material used for an optical switch, an optical recording medium of an optical recording device, an optical filter such as a color filter, a conductive material, an infrared light receiving element,
It can be suitably used as various functional elements such as detection elements, chemical sensors such as gas detectors, thick film materials for forming metal wiring, and various structural materials having high strength.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration of a non-linear optical element including a fine particle dispersed resin composite material as a component.

FIG. 2 is a diagram showing a configuration of an optical recording medium according to the present invention.

[Explanation of symbols]

1 ... Substrate, 2 ... Non-linear optical material, 3, 4, 5, 6, 7 ...
Optical waveguide, 8 ... Clad layer, 9 ... Optical fiber, 11,
12 ... Laser light source, 13 ... Optical recording medium, 14 ... Stage, 15 ... Photodetector.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G11B 7/00 7416-2H B41M 5/26 W

Claims (5)

[Claims] 1. (a) a curable resin or a polymerizable resin,
(B) an inorganic or organic salt of a metal, and (c) (b)
A resin composition comprising a reducing agent as a component. 2. (a) a curable resin or a polymerizable resin,
(B) an inorganic or organic salt of a metal, and (c) (b)
A resin composition containing a reducing agent as a component is treated at a temperature higher than the formation temperature of the metal fine particles and the curing or polymerization initiation temperature of the resin. . 3. The resin composition containing dispersed metal fine particles according to claim 2, wherein the resin composition is irradiated with light having a wavelength corresponding to a surface plasmon absorption wavelength of the metal fine particles having a predetermined particle diameter. Material manufacturing method. 4. An optical recording medium comprising a fine particle-dispersed resin composite material containing conductor fine particles in a resin-based dispersion medium, a light source for irradiating the optical recording medium with light, and a light detection means. An optical recording device characterized by: 5. The optical recording apparatus according to claim 4, wherein the light irradiation from the light source changes the dispersed state of the conductive fine particles in the optical recording medium to perform writing.