JPH1143556A - Resin material containing surface-modified semiconductor ultrafine particle and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material enabling not only to control the diameters of particles in a production process but also to disperse the particles in a high concentration and useful as an optical material, a sensor material, etc., by reacting surface-modified semiconductor ultrafine particles having functional groups on the surfaces with a resin. SOLUTION: This resin material is obtained by reacting a compound (a thiol compound having an amino group) having two or more functional groups (amino group, etc.), or a compound having two or more functional groups and a compound having one kind of functional group (thiophenol, etc.), with semiconductor ultrafine particles (silicon ultrafine particles, oxide semiconductor ultrafine particles or 12-16 group ultrafine particles having particle diameters of 1-100 nm, etc.), and subsequently reacting the produced surface-modified semiconductor ultrafine particles with a resin having functional groups (e.g. an amino styrenic resin produced by aminating polystyrene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material, a refractive index adjusting material, in particular, a light-to-light conversion element, a light-to-electron conversion element, a nonlinear optical field utilizing a phase conjugate wave generation, an optical bistable phenomenon, and a superlattice element. Semiconductor materials used in electronic fields such as electronic materials, light emitting materials, sensor materials, optical fields such as wavelength cut filters, recording related fields used as materials such as magnetic recording and optical recording, catalyst related fields, surface processing related fields, etc. Regarding fine particles.

[0002]

2. Description of the Related Art In order to enhance the interaction between semiconductor ultrafine particles and light, an exciton state in which electrons and holes are bound to each other and move is created, as in the case of using as a non-linear optical material. In order to utilize it, it is necessary to stabilize the exciton state. For that purpose, the particle diameter of the semiconductor ultrafine particles is made uniform, aggregation between particles,
It is necessary to prevent and stabilize coagulation and to reduce the diameter to about the Bohr radius. However, in this case, since the particle diameter of the semiconductor ultrafine particles is extremely small, coarse particles are likely to be generated due to aggregation of the semiconductor ultrafine particles, and it is difficult to control the particle diameter. From a practical point of view, it is desirable that mass production can be carried out by a simple method and isolation can be performed in a stable state.

As a solution for uniforming and stabilizing the particle diameter of semiconductor ultrafine particles, a technique of coating the surface of semiconductor fine particles with a polymer has been reported. For example, treating the surface of the semiconductor fine particles in advance with hydroxypropylcellulose, adding styrene to a suspension solution of the processed semiconductor fine particles, performing suspension polymerization by high shear stirring, to obtain semiconductor fine particles coated with the polymer. Methods and (Polymer Transactions, Vol. 40, 697-702)
1983), in the presence of metal sulfides such as cadmium sulfide and metal oxides such as zinc oxide, the polymerization of methyl methacrylate is carried out by the addition of sulfite water in an aqueous solution in which methyl methacrylate is dissolved to form polymethyl. Encapsulation with methacrylate (Polymer Transactions, Vol. 34, pp. 413-420, 1977)
Year) are known. These prior arts have the drawback that the number of steps such as pretreatment of particles is increased and they are complicated. In addition, in the case of the latex production method which is usually used, such as the former method, it is difficult to effectively control the particle diameter of about micron or less. According to the latter method, the sulfite radical generated by the redox reaction between the eluted metal ion and the sulfite ion serves as an initiator, and the adhesion of the produced polymer to the particles is due to the electrostatic attraction between the produced polymer terminal group and the particle surface. Although it is known, it has a drawback that the combination of the particle surface charge and the polymer terminal charge needs to meet the conditions.

In order to mass-produce by a simple method and isolate in a stable state, a method of covering the surface of a semiconductor ultrafine particle with a thiol compound and modifying the surface (Japanese Patent Application Laid-Open No. 07-081936).
Has been proposed. The semiconductor ultrafine particles having a modified surface produced by this method can be isolated as a solid powder because the surface of the semiconductor ultrafine particles is covered with pentafluorothiophenol, which is a compound having one functional group. This solves the problem of redispersibility in the solvent after removal.

Furthermore, when used as a device, semiconductor ultrafine particles are often used by dispersing them in a medium such as a resin. In order to disperse semiconductor ultrafine particles in styrene-based resins such as polystyrene and styrene-acrylonitrile copolymer, acrylic-based resins such as polymethylmethacrylic acid and polyacrylic acid, and epoxy resins, these resins are dissolved in a solvent. (U.S. Pat. No. 5,287,082) or a method of evaporating a polymer raw material monomer and a semiconductor ultrafine particle material on a substrate in a vacuum and polymerizing the raw material monomer at the time. Method for dispersing semiconductor ultrafine particles in a film (Japanese Unexamined Patent Application Publication No.
In the former case, depending on the characteristics and amount of the resin used and the semiconductor ultrafine particles to be dispersed, the resin is separated from the semiconductor ultrafine particles during or after drying. The ultrafine particles aggregate or precipitate, and as a result, the entire resin becomes turbid, and it is difficult to obtain a material in which semiconductor ultrafine particles are uniformly dispersed. In the latter case, it is difficult to control the particle diameter of the semiconductor ultrafine particles, the particle diameter distribution, and the control of particle aggregation.

As described above, in the prior art,
Although it is possible to control the particle size of the semiconductor ultrafine particles and take them out, when the semiconductor ultrafine particles are dispersed in the resin, the semiconductor ultrafine particles themselves have reactivity and react with the resin as a medium. There is no report on a method of dispersing by using a chemical method by causing the dispersion.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is directed to a surface-modified semiconductor ultra-fine particle obtained by reacting a surface-modified semiconductor ultra-fine particle having a functional group on the surface with a resin. It is an object to provide a resin material containing fine particles and a method for producing the same.

[0008]

According to the present invention, as a result of intensive studies on the production of a resin material containing surface-modified semiconductor ultrafine particles, a compound having two or more functional groups or two A mixture of the compound having the above functional group and the compound having one kind of functional group is present in the reaction system, and is reacted with the semiconductor ultrafine particles to produce surface-modified semiconductor ultrafine particles. The present invention has been found to be able to produce a resin material containing surface-modified semiconductor ultrafine particles by reacting a resin having a functional group capable of reacting with a functional group which is present on the surface and which has not reacted with the semiconductor ultrafine particles. Completed.

That is, the present invention provides: (1) A resin material containing surface-modified semiconductor ultrafine particles obtained by reacting a resin with surface-modified semiconductor ultrafine particles having a functional group on the surface. (2) a compound having two or more types of functional groups, or 2
A compound having one or more types of functional groups and a compound having one type of functional group are reacted with semiconductor ultrafine particles to produce surface-modified semiconductor ultrafine particles, and then, the surface-modified semiconductor ultrafine particles and having a functional group A method for producing a resin material containing surface-modified semiconductor ultrafine particles, characterized by reacting with a resin. (3) A resin material containing ultrafine surface-modified semiconductor particles produced by the method according to (2). Is provided.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below. Examples of the type of semiconductor ultrafine particles used in the present invention include silicon ultrafine particles, oxide semiconductor ultrafine particles such as TiO ₂ , ZnO, CdO, and PbO, CdS, CdSe, ZnSe, and Cd.
Examples include ultrafine particles of a Group 12-16 semiconductor such as Te, ZnS, HgS, and HgSe, and ultrafine particles of a Group 14-16 semiconductor such as PbS and PbSe.

First, a method of producing ultrafine particles of a surface-modified semiconductor will be described with reference to ultrafine particles of a compound semiconductor of a group 12-16 element semiconductor. The group 12 element compound in the periodic table of the present invention is cadmium perchlorate, zinc nitrate, or the like, and is not particularly limited as long as it is soluble in the solvent used, and may include water of crystallization. The surface-modified semiconductor ultrafine particles obtained according to the present invention may have a particle diameter in the range of 1 to 100 nm.

The functional group in the present invention includes an amino group, a thiol group, a carboxyl group, a carbonyl group, a halogen, a sulfo group, a vinyl group, an epoxy group, and derivatives thereof. The compound having two or more kinds of functional groups in the present invention has a functional group capable of reacting with a resin, and reacts with the semiconductor ultrafine particles in order to make the functional group exist on the surface of the semiconductor ultrafine particles. Any compound having a functional group containing a Group 16 element that can be used may be used.
For example, there are a thiol compound having an amino group, a carboxyl compound having an amino group, a carboxy compound having a thiol group, a thiol compound having a hydroxyl group, and the like.

Examples of thiol compounds having an amino group include 4-aminothiophenol, 2-aminothiophenol, 2-aminoethanethiol, 6-thioguanine-5-amino-1,3,4-thiadiazole-2- There are thiols and the like, each of which may be used alone or in combination.

The thiol compound having a hydroxyl group includes
2-mercaptophenol, 3-mercapto-1,2-
There are propanediol, 1-mercapto-2-propanol, 2-mercaptoethanol and the like, and each of them may be used alone or in combination.

Examples of thiol compounds having a carboxyl group include 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid and 3-mercapto-
There are 1,2,4-triazole, mercaptoacetic acid, sodium mercaptoacetate, etc., and each of them may be used alone or in combination.

The compound having one kind of functional group in the present invention is a compound containing a group 16 element which can be used together with the above-mentioned compound having two or more kinds of functional groups and which can react with semiconductor ultrafine particles. It can be used as needed to adjust the amount of functional groups capable of reacting with the resin present on the surface-modified semiconductor ultrafine particles. For example, there is an aminothiophenol as a compound having two or more types of functional groups, and a combination of thiophenol as a compound having one type of functional group. By changing the addition ratio of the compound having two or more kinds of functional groups and the compound having one kind of functional group, the functional group capable of reacting with the resin introduced by the compound having two or more kinds of functional groups is possible. By controlling the abundance, it becomes possible to control the reaction site between the surface-modified semiconductor ultrafine particles and the resin.

As a solvent for preparing a solution which is a reaction field for producing the surface-modified semiconductor ultrafine particles, a Group 12 element compound, a compound having two or more kinds of functional groups, and a compound having one kind of functional group are used. There is no particular limitation as long as it dissolves, and for example, water, acetone, acetonitrile, dimethylformamide, methanol, ethanol, chloroform, tetrahydrofuran, methyl ethyl ketone, or a mixed solvent thereof can be used.

The group 12 element compound is preferably 1 mol / l or less, preferably 10 ^-6 to 10 ^-1 m in such a liquid phase.
It is desirable that the solution has a concentration of ol / l. If the amount is too large, it becomes difficult to control the particle diameter. As the Group 16 element compound, a hydride gas such as hydrogen sulfide or hydrogen selenide, sodium hydrogen sulfide, or the like can be used, and a solution in which these are dissolved in the above solvent may be used.

The Group 12 element compound, a compound having two or more kinds of functional groups, a compound containing one kind of functional group,
While stirring the solution comprising the solvent, the Group 16 element compound or a solution containing the Group 16 element compound is gradually added. When producing semiconductor ultrafine particles using the former addition method, it is preferable to perform bubbling in order to improve the contact efficiency with the solution in terms of increasing the reaction efficiency and controlling the particle size of the semiconductor ultrafine particles. .

When the Group 16 element compound is a hydride gas, it is an inert gas such as helium or nitrogen, and when it is a solid such as sodium hydrogen sulfide, it is dissolved and diluted in a solvent to produce ultrafine semiconductor particles. Can be further controlled. As the reaction gas concentration,
The concentration is preferably 100% to 0.0001% by volume, and the flow rate may be an amount sufficient to allow the reaction to proceed steadily. The obtained colloid solution containing semiconductor ultrafine particles is concentrated by a method such as evaporation or distillation under reduced pressure, and the resulting semiconductor ultrafine particles are precipitated, taken out, purified, and dried to obtain surface-modified semiconductor ultrafine particles. Is obtained.

Next, a method for producing a resin material containing surface-modified semiconductor ultrafine particles will be described. Examples of the resin that can be used in the present invention include a resin having a functional group present on the surface of the surface-modified semiconductor ultrafine particles and capable of reacting with a functional group that has not reacted with the semiconductor ultrafine particles, such as polystyrene. , Chloromethylated, sulfonated, and styrene-based resins that are derivatives thereof, acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylate, polyethyl acrylate, polybutyl acrylate, and polyacrylamide; vinyl Alcohol-based resins, epoxy-based resins, and the like are included.

In order to produce the desired resin material containing surface-modified semiconductor ultrafine particles, the resin is dissolved in a solvent in which both the surface-modified semiconductor ultrafine particles and the above resin are dissolved, and a catalyst is added as necessary. By heating, the reaction is allowed to proceed, and the desired surface-modified semiconductor ultrafine particle-containing resin material can be produced.

The catalyst to be used includes sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide and the like.
Depending on the combination of a functional group present on the surface of the surface-modified semiconductor ultrafine particles and not reacted with the semiconductor ultrafine particles and a functional group in the resin, it can be used as needed. The reaction temperature may be between the melting point and the boiling point of the solvent.

Next, the oxide semiconductor ultrafine particles will be described in detail. Examples of the oxide semiconductor ultrafine particles include oxide semiconductor ultrafine particles such as TiO ₂ , ZnO, CdO, and PbO. The semiconductor ultrafine particles obtained by the present invention may have any particle diameter in the range of 1 to 100 nm.

The starting compound for the oxide semiconductor is a compound soluble in the solvent used, for example, organic acid salts such as acetates, nitrates, perchlorates, alkoxides, and the like.
Halides and the like are used. Preferably, it is cadmium perchlorate, zinc nitrate, zinc acetate, or the like. There is no particular limitation as long as it is soluble in the solvent used, and it may contain water of crystallization.

The raw material compound of the oxide semiconductor is 1 mol / l or less, preferably 10 ^-6 to 10 ^{-1 in} such a liquid phase.
It is desirable to use a solution having a concentration of mol / l. If the amount is too large, it becomes difficult to control the particle diameter. As the oxygen for oxidation, oxygen in the air may be supplied to the reaction system, but dissolved oxygen in the solvent is sufficient, and if necessary, water is used when water is used as the base or the solvent. If necessary, oxygen generated by the reaction from the hydroxyl group may be used. The base used promotes the reaction from the starting compound of the oxide semiconductor to the oxide semiconductor,
Preferably, it is a strong base. For example, sodium hydroxide, potassium hydroxide and the like are appropriately used.

In the present invention, the compound having two or more kinds of functional groups refers to a compound having a functional group capable of reacting with a resin and causing the functional group to be present on the surface of the semiconductor ultrafine particles. Any compound having a functional group containing it may be used. For example, a carboxyl compound having a thiol group,
Carboxyl compounds having an amino group; hydroxy compounds having an amino group;

Examples of the carboxyl compound containing a thiol group include 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, and mercaptoacetic acid. Examples of the carboxyl compound containing an amino group include aminophenylacetic acid, aminoacetic acid, and aminobenzoic acid. Examples of the hydroxy compound containing an amino group include aminopropanol, aminophenol, aminobutanol,
There are aminoethanol and the like.

The compound having one kind of functional group in the present invention is used in the same manner as described for the ultrafine particles of a compound semiconductor of a group 12-16 element. The solvent for generating the solution is not particularly limited as long as it can dissolve the oxide semiconductor element compound and the compound having two or more kinds of functional groups. For example, water, acetone, acetonitrile, dimethylformamide, methanol, ethanol , Chloroform, tetrahydrofuran, methyl ethyl ketone, etc., or a mixed solvent thereof can be used.

A solution comprising the above-mentioned raw material compound for an oxide semiconductor, a compound having two or more kinds of functional groups, a compound having one kind of functional group, and if necessary, a base and a solvent is prepared. Heating or refluxing oxidizes the raw material compound of the oxide semiconductor. The reaction temperature is between the melting point and the boiling point of the solvent, and the reaction time is several minutes to several days. Thereby, surface-modified semiconductor ultrafine particles are obtained.

The surface-modified ultrafine particles of the semiconductor and the resin thus obtained are dissolved in a solvent, a catalyst is added, if necessary, and the resin is heated to react the resin with the surface-modified ultrafine particles of the resin. A surface-modified semiconductor ultrafine particle-containing resin material can be produced.

[0032]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Acetonitrile methanol (1.0 × 10 ⁻² mol, thiophenol 1.52 × 10 ⁻² mol, aminothiophenol 1.52 × 10 ⁻² mol) dissolved in cadmium perchlorate hexahydrate (1 × 10 ⁻² mol) 1) 400 ml of the mixed solution was placed in a flask, and the solution was replaced with argon gas while stirring the solution with a stirrer chip. A mixed gas of hydrogen sulfide / helium having a composition of 5% by volume was supplied into the solution at a flow rate of 270 ml / min for 2 minutes. This allowed the reaction to proceed. The obtained colloid solution containing semiconductor ultrafine particles was concentrated and mixed with toluene to precipitate semiconductor ultrafine particles. Take out the sediment,
By dissolving again in methanol and mixing with toluene, purification was performed to precipitate ultrafine semiconductor particles and remove unreacted substances. This operation was repeated five times.
Finally, the precipitate was taken out and dried to obtain target surface-modified semiconductor ultrafine particles. The generated surface-modified semiconductor ultrafine particles are soluble in polar solvents such as water, methanol, ethanol, and dimethylformamide,
It was a yellow transparent solution with no apparent scattering. When this solution was taken out and observed with a transmission electron microscope, CdS semiconductor ultrafine particles having a particle diameter of about 3 nm were confirmed.

The obtained surface-modified semiconductor ultrafine particles are
When mixed with Br and made into a tablet, the infrared absorption spectrum of the tablet was measured.
40-1250 cm ^-1 ), and a broad absorption (3000-2800 cm) caused by NH ³⁺ overlapping with aromatic CH stretching
^-1 ), absorption of expansion and contraction of remaining SH groups (2600 to 2550c)
m ^-1 ) was observed, and the presence of an amino group was confirmed on the surface of the ultrafine CdS semiconductor particles (FIG. 1). Subsequently, 0.1 g of the manufactured surface-modified CdS semiconductor ultrafine particles
Was dissolved in 2 ml of dimethylformamide, 0.5 g of polyacrylic acid was added, and the mixture was stirred and dried. As a result, a gel-like yellow transparent reaction product was confirmed. The reaction was no longer soluble in methanol, ethanol, dimethylformamide. Washing the reaction with dimethylformamide,
After removing the unreacted polyacrylic acid, drying was performed, and the measurement of the infrared absorption spectrum indicated that an amide bond was present, indicating that the polyacrylic acid was reacted (FIG. 2).

Example 2 Ultra-fine particles of the surface-modified CdS semiconductor produced in Example 1.
1 g was dissolved in 5 ml of dimethyl sulfoxide, and 0.5 g of polymethyl methacrylate was added. Then 140 ° C
For 3 hours. After the reaction, the reaction product was added to methanol to obtain a yellow precipitate, and the supernatant was colorless and transparent. Further, the reaction product was reprecipitated with methanol and acetonitrile, purified, and dried. This reaction product was soluble in acetonitrile, toluene, benzene, dimethylformamide and the like. When the reaction product was further formed into a film, a yellow transparent film could be obtained. As a result of measuring the infrared absorption spectrum of this film, the presence of an amide bond was suggested, and it was found that the film reacted with polymethyl methacrylate. When this film was observed with a transmission electron microscope, it was confirmed that ultrafine CdS particles having a particle size of about 3 nm were uniformly dispersed (FIG. 3). Also, when the refractive index of this film was measured, it was increased by 0.01 as compared with polymethyl methacrylate in which ultrafine CdS semiconductor particles were not dispersed.

COMPARATIVE EXAMPLE 1 Ultrafine surface-modified CdS semiconductor particles produced in Example 1.
1 g was dissolved in 5 ml of dimethylformamide, and 0.5 g of polymethyl methacrylate was added. This was spread on a petri dish and dried to form a film. However, a yellow transparent film as obtained in Example 2 was not obtained.
A totally opaque yellow film was obtained, and it was presumed that the CdS semiconductor ultrafine particles were aggregated.

Reference Example 1 Cadmium perchlorate hexahydrate 2.5 × 10 ⁻³ mol, p
A mixture of 400 ml of acetonitrile methanol (1: 1) in which 7.6 × 10 ⁻³ mol of -hydroxythiophenol was dissolved was placed in a flask, and the solution was replaced with argon gas while stirring the solution with a stirrer chip. Hydrogen sulfide / helium mixed gas at a flow rate of 270 ml / m
The reaction was allowed to proceed by feeding the solution in for 30 seconds. The obtained colloid solution containing ultrafine semiconductor particles was concentrated and mixed with distilled water to precipitate ultrafine semiconductor particles.
The precipitate was dissolved in methanol again, and then purified water was mixed with distilled water to remove unreacted substances from the semiconductor ultrafine particles. This operation was repeated five times.
Finally, the precipitate was dried to obtain target surface-modified semiconductor ultrafine particles. The produced surface-modified semiconductor ultrafine particles were soluble in dimethylformamide and dimethylsulfoxide, and were a yellow transparent solution having no apparent scattering. Further, the obtained surface-modified semiconductor ultrafine particles are
It was mixed with Br and made into a tablet, and the infrared absorption spectrum was measured. As a result, C—O stretching (around 1260 cm ⁻¹ ), OH
Characteristically, in-plane bending vibration (around 1357 cm ^-1 ) and absorption of di-substituted benzene C-H out-of-plane bending (around 800 cm ^-1 ) are characteristic. The presence of hydroxyl groups was confirmed on the surface (FIG. 4).

Reference Example 2 The procedure of Example 1 was repeated except that 1.0 × 10 ^-2 mol of zinc perchlorate hexahydrate was used instead of cadmium perchlorate hexahydrate. The resulting ultrafine semiconductor particles were soluble in a polar solvent such as dimethylformamide, and were a colorless and transparent solution having no apparent scattering. The solution was taken out and observed with a transmission electron microscope. As a result, ultrafine ZnS semiconductor particles having a particle size of about 3 nm were confirmed. Further, the obtained semiconductor ultrafine particles were mixed with KBr, made into tablets, and the infrared absorption spectrum was measured.
Broad absorption due to NH ³⁺ was observed overlapping with the C—N stretching and aromatic C—H stretching characteristic of the aromatic amine. It is characteristic that absorption of the C-H out-of-plane bending angle of disubstituted benzene is also observed, and the presence of an amino group on the surface of ZnS semiconductor ultrafine particles was confirmed.

Reference Example 3 Methanol-ethanol mixed solvent (volume ratio 5: 7) 40
3.5 × 10 ⁻³ mol of sodium hydroxide,
1.0 × 10 ^-2 mol of mercaptopropionic acid was dissolved. This solution was placed in a flask equipped with a reflux tube, stirred, and refluxed while maintaining the solution temperature at 70 ° C. under a nitrogen stream while heating. Here, zinc nitrate hexahydrate 1.0 × 10 ^-2 mo
was dissolved in 5 ml of ethanol, and the mixture was refluxed for 10 hours under a nitrogen stream. After the reaction, the solvent was removed by an evaporator to obtain a powder. From the result of the X-ray diffraction spectrum of the obtained powder, it was confirmed that the obtained powder was zinc oxide.

Example 3 The procedure of Reference Example 3 was repeated except that titanium tetrachloride was used in place of zinc nitrate and aminobenzoic acid was used in place of 3-mercaptopropionic acid. From the result of the X-ray diffraction spectrum of the obtained powder, it was confirmed that the obtained powder was titanium oxide. In addition, the obtained ultrafine semiconductor particles are K
When mixed with Br and made into a tablet, the infrared absorption spectrum was measured. As a result, a wide range of absorption due to NH ³⁺ was observed overlapping with CN stretching and aromatic CH stretching characteristic of aromatic amines. It is characteristic that the absorption of the C-H out-of-plane bending angle of disubstituted benzene is also observed, and the presence of an amino group on the surface of the TiO ₂ semiconductor ultrafine particles was confirmed. Further, 0.1 g of the obtained powder was dissolved in 2 ml of dimethylformamide,
0.5 g of polyacrylic acid was added, and the mixture was stirred and dried. As a result, a gel-like white reaction product was confirmed. The reaction was no longer soluble in dimethylformamide. The reaction product was washed with dimethylformamide to remove unreacted polyacrylic acid, dried, and measured for infrared absorption spectrum. As a result, the presence of an amide bond was suggested.

[0040]

According to the present invention, not only the particle diameter is controlled in the production process of the semiconductor ultrafine particles but also the semiconductor ultrafine particles and the resin are reacted by the presence of a functional group on the surface of the semiconductor ultrafine particles. This succeeded in achieving high concentration and uniform dispersion. Surface-modified semiconductor ultrafine particle-containing resin material obtained by the present invention,
Refractive index adjusting materials, optical materials, especially light-light conversion elements and light-
Non-linear optical materials used in electronic conversion elements, electronic materials such as superlattice elements, optical fields such as light-emitting materials and sensor materials, recording-related fields used as materials such as magnetic recording and optical recording, and catalyst-related fields The present invention can also contribute to the present invention, and therefore has important significance for industrial use.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of surface-modified cadmium sulfide ultrafine particles obtained from Example 1.

FIG. 2 is an infrared absorption spectrum of a resin material containing surface-modified cadmium sulfide ultrafine particles obtained from Example 1.

FIG. 3 is an electron micrograph of cadmium sulfide particles obtained from Example 2.

FIG. 4 is an infrared absorption spectrum of surface-modified cadmium sulfide obtained from Reference Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/00 C08L 101/00 G02F 1/35 503 G02F 1/35 503

Claims (3)

[Claims] 1. A resin material containing surface-modified semiconductor ultrafine particles obtained by reacting a resin with surface-modified semiconductor ultrafine particles having a functional group on the surface. 2. A compound having two or more kinds of functional groups, or a compound having two or more kinds of functional groups and a compound having one kind of functional group, is reacted with semiconductor ultrafine particles to produce surface-modified semiconductor ultrafine particles. A method for producing a resin material containing surface-modified semiconductor ultrafine particles, which comprises producing, and then reacting the surface-modified semiconductor ultrafine particles with a resin having a functional group. 3. A resin material containing surface-modified semiconductor ultrafine particles produced by the method according to claim 2.