JP2003205568A - Nanoparticle layer laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nanoparticle layer laminate which can be applied to a variety of functional elements by packing a nanoparticle with a functional polymer having a variety of functions formed on the surface to the high density without flocculating the nanoparticle. <P>SOLUTION: This nanoparticle layer laminate comprises an inorganic nanoparticle which has adsorptive groups on the surface and also an electric charge of such a level that the attraction can occur due to an electrostatic interaction and a functional polymer which contains an anchor part with a plurality of adsorptive groups which cause an adsorption action between these groups and those existing on the surface of the described inorganic nanoparticle and also a functional part with a functional group. In addition, a plurality of the nanoparticle layers containing the functional nanoparticle comprising the anchor part of the functional polymer sticking to the adsorptive group on the surface of the inorganic nanoparticle, are laminated. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nanoparticle layer formed by laminating nanoparticle layers containing functional nanoparticles composed of inorganic nanoparticles such as semiconductor nanoparticles and functional polymers attached to the surface thereof. The present invention relates to a laminate, which relates to a nanoparticle layer laminate that can be used in various applications such as optical devices and optical communication devices.

[0002]

2. Description of the Related Art Semiconductor nanoparticles having a particle diameter of 10 nm or less are located in a transition region between a bulk semiconductor crystal and a molecule, and therefore exhibit unique photophysicochemical properties. In such a region, the energy band structure as seen in the bulk semiconductor changes due to the expression of the quantum size effect, and the energy gap increases. If such characteristics can be effectively brought out by precisely controlling a one-dimensional or two-dimensional array such as a film, it is possible to create a novel optical element as a semiconductor nanoparticle array.

Further, since such semiconductor nanoparticles or other inorganic nanoparticles have a sufficiently small average particle diameter, there is almost no scattering of light by the particles. Therefore, there is an advantage that the refractive index can be controlled without impairing the transparency.

By disposing a functional polymer on the surface of such semiconductor nanoparticles or other inorganic nanoparticles, it can be used for various further highly useful applications.

However, since such a semiconductor nanoparticle has a very large surface area to volume ratio, it is very likely to aggregate, which causes a problem in film forming characteristics and stabilizes the semiconductor nanoparticle. In order to make them exist, it was necessary to take measures to prevent collision and fusion of particles.

As such a measure, the following method is used. 1) Physical isolation of semiconductor nanoparticles from each other by incorporation into a solid matrix and a polymer matrix. 2) Deactivation of the particle surface by chemically modifying the metal ion site on the particle surface with a low molecular weight organic compound having a high complex forming ability.

Furthermore, in order to form an array of semiconductor nanoparticles, the self-assembly of the nanoparticles is mainly performed by solvent evaporation, lan.
The gmuir-Blodgett method, chemical bonding between nanoparticles, and the like are used.

However, with such a method, it is difficult to immobilize nanoparticles having a small particle size in a thin film by high density packing, and as a result, the function of effectively using the nanoparticles as described above is obtained. There is a problem that it is difficult to develop a sex element.

On the other hand, in recent years, a method for producing an optical functional material has been proposed which applies the alternate adsorption method using an organic polymer or the surface sol-gel method using a metal alkoxide. (Swan, Applied Physics, Volume 69, pages 553-557, 2000
Year). This method is different from the conventional method in that the optical functional material is produced by a wet process, and it uses adsorption and surface reaction in the liquid layer. It is a solution to the conventional problems that it is unnecessary and that it is easy to increase the area. Further, according to this method, there is an advantage that a film can be evenly formed on a curved surface or an uneven surface.

However, the disadvantages of such a method are that it takes time to form a film because of repeated stacking in the molecular order, and that the film is fixed to the substrate or the strength of the film is insufficient.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is possible to achieve high density of functional nanoparticles having functional polymers having various functions on the surface without agglomeration. The main purpose of the present invention is to provide a nanoparticle layer laminate that can be applied to various functional devices by filling with.

[0012]

In order to achieve the above-mentioned object, the present invention, as described in claim 1, has an adsorption group on the surface and is capable of adsorption by electrostatic interaction. Inorganic nanoparticles capable of having a charge of, an anchor part having a plurality of adsorbing groups that adsorb with an adsorbing group present on the surface of the inorganic nanoparticle, and a functional high-functional group having a functional functional group A nanoparticle layer comprising a functional nanoparticle having a molecule and an anchor portion of the functional polymer attached to an adsorption group on the surface of the inorganic nanoparticle, and comprising a plurality of laminated layers. A nanoparticle layer stack is provided.

According to the present invention, since the functional nanoparticles have an electric charge such that they can be adsorbed by electrostatic interaction, by using the alternate adsorption method using electrostatic interaction, It is possible to form a nanoparticle layer laminate in which the functional nanoparticles are packed at a high density. Therefore, the nanoparticle layer laminate of the present invention can be effectively used as a functional element that makes the best use of the function of the functional part of the functional polymer adsorbed around the inorganic nanoparticles, and can be used in various applications. Can be developed.

In the invention described in claim 1, as described in claim 2, the inorganic nanoparticles are
Inorganic nanoparticles composed of a metal oxide or a metal sulfide are preferable. Inorganic nanoparticles composed of metal oxides or metal sulfides have an adsorbing group on the surface thereof, so that the functional polymer can be attached to the surface without pretreatment or the like. Because.

In the invention described in claim 2, as described in claim 3, the inorganic nanoparticles are
More preferably, it is a functional semiconductor. As described above, if the inorganic nanoparticles themselves have a function, it is possible to further develop applications as various functional elements by cooperating with the function of the functional polymer attached to the outer peripheral portion. Is.

In the invention described in any one of claims 1 to 3, the average particle diameter of the inorganic nanoparticles is 1 nm to 1 as described in claim 4.
It is preferably within the range of 50 nm. When the diameter of the inorganic nanoparticles is smaller than the above range, it is not preferable because it is necessary to form a large number of layers in order to obtain a sufficient film thickness as the nanoparticle layer laminate, and when the particle size is larger than the above range. The reason is that the volume ratio of the inorganic nanoparticles in the nanoparticle layer laminated body becomes too large, so that the function of the functional part of the functional polymer may not be sufficiently exhibited.

In the invention described in any one of claims 1 to 4, the functional polymer has a function as a dispersant, as described in claim 5. Is preferred. As described above, since the functional polymer has a function as a dispersant, when the functional polymer is attached to the surface of the inorganic nanoparticles to form the functional nanoparticles, the functional polymer serves as a dispersant. It is possible to use, and also when laminating a nanoparticle layer filled with functional nanoparticles by the alternating adsorption method, the functional polymer on the surface of the inorganic nanoparticles exhibits the function as a dispersant. In some cases, it can be produced without using another dispersant or the like.

In the invention described in any one of claims 1 to 5, as described in claim 6, the anchor portion of the functional polymer is 1 to 1
It is preferable to have a comb structure having 0 adsorbing group. As long as the anchor portion has a comb structure and has an adsorbing group within the above range, the functional polymer should be easily attached to the inorganic nanoparticles and should be strong. Because you can

In the invention according to any one of claims 1 to 6, as described in claim 7, the functional polymer has an average polymerization number molecular weight of 10
It is preferably in the range of 0 to 30,000. Considering that the functional polymer requires an anchor part and a functional part, and considering the particle size of the inorganic nanoparticles to which the functional polymer is attached, it is considered to be preferably within the above range. Is.

In the invention described in any one of claims 1 to 7, as described in claim 8, even if plural kinds of the functional nanoparticles are used, Further, as described in claim 9, a single type of the functional nanoparticles may be used. This is because, depending on the functional element used, a single functional functional group or a plurality of functional functional groups may be required in order to exhibit the required function.

In the invention described in any one of claims 1 to 9, the nanoparticle layer is laminated on a support material as described in claim 10. Is preferred. This is because the nanoparticle layer laminate of the present invention may have a self-supporting property, but since it is a thin film, it may be preferable that it is formed on a supporting material in terms of strength. Further, it is because the function may be exhibited by being formed on the support material.

In the invention described in claim 10, as described in claim 11, a polymer electrolyte membrane is formed on the support material, and the nanoparticle layer is formed on the polymer electrolyte membrane. Are preferably laminated. When laminating the functional nanoparticles by the alternate adsorption method using electrostatic interaction, it is necessary to apply a charge having a polarity different from that of the functional nanoparticles on the support material. At this time, by applying an electric charge by the polymer electrolyte membrane,
This is because charges can be imparted to the surface of the support with a high charge density, and the functional nanoparticles can be uniformly attached to the support.

In the invention described in claim 11, as described in claim 12, the polymer electrolyte membrane is formed by laminating two or more kinds of polymer electrolyte membranes having polarities different from each other. It is preferably a multilayer film. This is because a polymer electrolyte membrane having a uniform and high charge density can be obtained, and thus unnecessary multilayering of the functional nanoparticles in the nanoparticle layer can be prevented.

In the invention described in claim 11 or 12, the polymer electrolyte membrane is preferably a crosslinked polymer electrolyte membrane as described in claim 13. This is because a polymer electrolyte membrane that is also uniform and has a high charge density can be obtained.

In the invention described in any one of claims 1 to 13, as described in claim 14, the adhesion between the nanoparticle layers is caused by the electrostatic interaction. In addition to the attachment, it is preferable that they are attached by a reinforcing attachment means. The electrostatic interaction alone may cause insufficient adhesion of the functional nanoparticles to the surface of the support or mutual adhesion of the multiple nanoparticle layers, which may cause problems such as insufficient strength. is there. Therefore, it is preferable to improve the adhesive force by using an auxiliary adhesion means in addition to the electrostatic interaction.

In the invention described in claim 14, as described in claim 15, the reinforcing attachment means comprises an actinic radiation-reactive monomer and a polymerization initiator in the polymer layer laminate. It is preferable that it is contained and cured by irradiation with actinic radiation. By attaching in this way, the strength and the like are improved, and since the functional nanoparticles are fixed in the nanoparticle layer, it has various functions such as diffracting light of a specific wavelength by Bragg reflection. Because there is a possibility.

In the invention described in claim 14, as described in claim 16, the reinforcing attachment means embeds the nanoparticle layer laminated body leaving one surface thereof. It may be based on a sealing material. For example, when the strength of the nanoparticle layer laminate itself is extremely weak,
In the case where it is inconvenient for the nanoparticle layer laminated body to be deformed due to moisture, etc., the strength can be secured by embedding and sealing the nanoparticle layer laminated body except for the surface on the support side in this way. This is because deformation can be prevented.

In the invention described in any one of claims 1 to 16, the nanoparticle layer laminate is formed in a pattern as described in claim 17. May be By forming the nanoparticle layer laminate in a pattern in this manner, it may be used for various applications such as color filters, lens arrays, and optical waveguide circuits.

In the present invention, as described in claim 18, a charge applying step of applying an electric charge to the surface of the base material, and a functionality having a charge having a sign opposite to that of the electric charge applied to the surface of the base material. And a nanoparticle layer forming step of forming a nanoparticle layer by coating a functional nanoparticle dispersion liquid containing nanoparticles on the base material, and the functional nanoparticle has an adsorption group on the surface. And an inorganic nanoparticle capable of having an electric charge capable of being adsorbed by electrostatic interaction, an anchor part having a plurality of adsorbing groups that adsorb with an adsorbing group present on the surface of the inorganic nanoparticle, and functionality A functional nanoparticle comprising a functional polymer having a functional group having a functional group, wherein the anchor portion of the functional polymer is a functional nanoparticle adhered to an adsorption group on the surface of the inorganic nanoparticle, Of nanoparticle layer stack To provide a method.

As described above, the formation of the nanoparticle layer laminated body on the support can be performed by applying the functional nanoparticle dispersion liquid on the surface of the support having an electric charge, so that the manufacturing process is It is simple and efficient. Therefore, it is possible to manufacture a nanoparticle layer laminated body which is advantageous in terms of cost. Further, since the interaction due to the electrostatic interaction is used, it is possible to pack the functional nanoparticles at a high density, so that it is possible to manufacture a functional element having good quality.

In the invention described in claim 18, as described in claim 19, it is preferable that the inorganic nanoparticles are metal oxides or metal sulfides. As described above, inorganic nanoparticles composed of metal oxides or metal sulfides have adsorbing groups on the surface thereof, and therefore the adhesion of the functional polymer to the surface without pretreatment or the like. Because it can do.

In the invention described in claim 18 or claim 19, as described in claim 20, the charge application step is a step of forming a polymer electrolyte membrane on a substrate. preferable. As described above, by imparting charges by the polymer electrolyte membrane, it is possible to impart charges to the surface of the support at a high charge density in the charge imparting step. Therefore, in the subsequent nanoparticle layer forming step, the functional nanoparticles can be uniformly attached to the support.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventor has made a functional nanoparticle by adsorbing a functional polymer having a functional functional group on the surface of an inorganic nanoparticle, and forming a nanoparticle layer in which the functional nanoparticle is densely packed. It is possible to obtain such a nanoparticle layer laminated body by the alternate adsorption method using electrostatic interaction, paying attention to the fact that it can be applied to functional elements having various functions by stacking. The inventors discovered the points and completed the present invention. Hereinafter, the nanoparticle layer laminate of the present invention will be described, and then the method for producing the nanoparticle layer laminate will be described.

A. Nanoparticle Layer Laminated Body The nanoparticle layer laminated body of the present invention comprises an inorganic nanoparticle that has an adsorption group on the surface and can have an electric charge capable of being adsorbed by electrostatic interaction, and the above-mentioned inorganic nanoparticle. An anchor part having a plurality of adsorptive groups that are adsorbed on the particle surface and an adsorbing group that adsorbs, and a functional polymer containing a functional part having a functional functional group, wherein the anchor part of the functional polymer is It is characterized in that a plurality of nanoparticle layers containing functional nanoparticles attached to the adsorption groups on the surface of the inorganic nanoparticles are laminated.

The nanoparticle layer laminate of the present invention as described above is
Each element will be described separately.

(Inorganic Nanoparticles) The inorganic nanoparticles used in the present invention have an adsorbing group capable of attaching an anchor portion of a functional polymer on the surface as described above, and the inorganic nanoparticles themselves. Is not particularly limited as long as it has an electric charge such that it can be adsorbed by electrostatic interaction.

The adsorptive group referred to here may be any functional group as long as it is a group capable of adsorbing to the adsorptive group of the anchor portion of the functional polymer described later, but specifically, a hydrogen bond is present. It is preferable that the functional group is a functional group capable of being adsorbed to the adsorptive group that the anchor portion of the functional polymer has.

Examples of such an adsorptive group include --OH, epoxy group, aldehyde group, active ester group, or substituent capable of reacting with amino group, --SH and the like.

The inorganic nanoparticles of the present invention may have the above-mentioned functional groups themselves, or the surface of the inorganic nanoparticles may be treated to form the above-mentioned functional groups on the surface. It may be one. Moreover,
The functional group as described above may be present on the surface by coating the surface of the inorganic nanoparticle with an inorganic or organic material having the functional group as described above.

However, in consideration of the size of the inorganic nanoparticles themselves, it is preferable that the inorganic nanoparticles themselves have the above-mentioned functional group, and specifically,
Mention may be made of metal oxides and metal sulfides.

In the present invention, further, among these metal oxides and metal sulfides, when they are formed into a nanoparticle layer laminate, they exhibit a function in cooperation with the function of the surrounding functional polymer. Inorganic nanoparticles formed of a functional semiconductor material capable of producing This is because the inorganic nanoparticles themselves have a function as described above, and by using them together with the function of the functional polymer as described above, it is possible to further develop various applications.

As such a functional semiconductor material, Z
_{nS, CdS, ZnO 2, WO} 3, etc. TiO ₂ and the like. Among them, a functional semiconductor material exhibiting transparency even in a nano size is preferable because it exhibits unique optical properties when used as an optical functional material.

The inorganic nanoparticles composed of the functional semiconductor as described above are prepared by the size selective photoetching method of Torimoto et al. (T. Torimoto et al., J. Electroche).
m. Soc. , 145, (1998) 1964. ) And the like. That is, the energy gap of semiconductor nanoparticles (inorganic nanoparticles formed of a functional semiconductor material) increases as the particle size decreases due to the quantum size effect, and the metal chalcogenide semiconductor is oxidized and dissolved by light irradiation under dissolved oxygen. By irradiating semiconductor particles having a wide particle size distribution with monochromatic light having a wavelength shorter than the absorption edge wavelength, only semiconductor nanoparticles having a large particle size are selectively photoexcited and dissolved. This is a method of adjusting the particle size to smaller semiconductors. By using this method, inorganic nanoparticles composed of a functional semiconductor can be prepared by converting CdS and ZnS into monodisperse particles.

In the present invention, the average particle size of the above-mentioned inorganic nanoparticles is in the range of 1 nm to 150 nm, and particularly 3 n.
It is preferably in the range of m to 30 nm. This is because it is difficult at present to obtain inorganic nanoparticles having an average particle size smaller than the above range, and the inorganic nanoparticles having an average particle size larger than the above range are densely packed in the nanoparticle layer. This is because even if it does, the function cannot be exerted effectively.

(Functional Polymer) The functional polymer used in the present invention has an anchor portion having a plurality of adsorbing groups that adsorb the adsorbing groups present on the surface of the above-mentioned inorganic nanoparticles, and a functional functional group. It is characterized by containing a functional part.

In the present invention, it is preferable that such a functional polymer also has a function as a dispersant. This is because, as will be described later, in the process of manufacturing the functional nanoparticle by adhering this functional polymer onto the inorganic nanoparticle, the inorganic nanoparticle is prevented from agglomerating and the surface of the inorganic nanoparticle is uniformly highly functionalized. In order to adsorb molecules, it is necessary to add a dispersant to the dispersion liquid of inorganic nanoparticles. At this time, it is not necessary to use another dispersant as long as the functional polymer has a dispersibility.

Further, the obtained functional nanoparticles are formed into a nanoparticle layer by an alternate adsorption method using electrostatic interaction, and in order to stack the layers, the functional nanoparticles are aggregated or the like. This is because it is necessary to prepare a dispersed liquid (developing liquid) without dispersion, and it is preferable that the functional polymer also has a function as a dispersant at this time.

Generally, a dispersant is used when the inorganic particles or pigments are made into a coating material, and their surface modification improves the dispersion. Most of these general dispersants are surfactants and have a dispersion component that is an anchor part adsorbed on the particle surface and a surfactant part. The functional polymer having a function as a dispersant in the present invention does not indicate these general surface active dispersants, and has excellent electrostatic adsorption ability and surface adsorption ability, and a functional functional group. It is characterized by having a functional part consisting of.

The functional polymer used in the present invention has a multi-polar group-containing high amount which forms an anchor structure of a "comb-shaped" polymer having multi-point adsorption ability with respect to a weak polar portion existing on the surface of the inorganic nanoparticles. The molecule is designed so that it interacts with the interaction between the cross-linked chain that shows the molecule and the dispersion component or the resin, and shows the role of the steric hindrance effect on the Van der Waals force that is the basis of the cohesive force. It is preferably a polymer.

As described above, the functional polymer used in the present invention preferably has a function as a dispersant, and the function as the dispersant is preferably as follows. That is, 30 parts by weight of a dispersant is dispersed in a solvent (stirring, with respect to 100 parts by weight of dispersed particles).
Mix). After the dispersion, the mixture is allowed to stand at room temperature for complete color separation (dispersed particles are separated in a solvent), and the time (settling speed) until sedimentation is 3 hours to 3 months, preferably half a day to
It is preferable to use one that can be held for one month.

The molecular weight of the above-mentioned functional polymer is an average polymerization number molecular weight in the range of 100 to 30,000, and particularly 1
It is preferably in the range of 50 to 900. The functional polymer having a molecular weight smaller than the above range is structurally difficult, and when the molecular weight is larger than the above range, in relation to the size of the inorganic nanoparticles, it has a large number of functions on its surface. This is because it may be difficult to adsorb the functional polymer.

As the structure of such a functional polymer,
Although not particularly limited, it is usually composed of a main chain and an anchor part and a functional part connected to the main chain. Hereinafter, the functional polymer used in the present invention will be described separately for the anchor portion, the functional portion, and the main chain portion.

1. Anchor Part The functional polymer in the present invention has an anchor part having a plurality of adsorbing groups for adsorbing on the surface of the inorganic nanoparticles, as described above.

The adsorptive group possessed by this anchor part is not particularly limited as long as it can adsorb with the adsorptive group present on the surface of the above-mentioned inorganic nanoparticles, but above all, the surface of the above-mentioned inorganic nanoparticles due to hydrogen bonding It is preferable that it is an adsorption group that adsorbs with the adsorption group present in.

Examples of such adsorbing groups include --OH and --N.
H _2, can be mentioned -SH, aldehyde group, cationic ammonium group, an active ester group. Examples of the polymerizable monomer having such an adsorptive group include those listed in Table 1, and the anchor portion can be formed by polymerizing these.

[0056]

[Table 1]

The portion surrounded by the broken line in the table shows the adsorbed portion. In the example shown in the table, the vinyl group is polymerized to form an anchor portion having a plurality of adsorbed groups. .

In the present invention, it is preferable that one functional polymer anchor portion has 1 to 100, preferably 1 to 10 adsorption groups. This is because when the number of adsorbing groups is less than the above range, the adsorbing ability is low and the functional polymer cannot be effectively adsorbed on the inorganic nanoparticles. Further, when the number of adsorbing groups is more than the above range, the adsorbing groups may influence each other in the anchor portion, and as a result, the adsorbing ability with the inorganic nanoparticles may decrease, and the functional polymer itself This is because the molecular weight becomes too large and the number of functional polymers attached to the inorganic nanoparticles is limited.

The anchor portion is not particularly limited, but preferably has a "comb structure". Generally, this comb-shaped portion is synthesized by dispersion copolymerization using a macromonomer. The macromonomer serves not only as a stabilizer (also referred to as a dispersant) but also as a comonomer. In the present invention, t having a vinylbenzyl group at a terminal is obtained by, for example, anionic living polymerization.
-Butyl methacrylate macromonomer can be used. When the synthesized macromonomer is copolymerized with divinylbenzene in methacrylate using AIBN (azoisobisbutyronitrile) as an initiator, microspheres are formed. Furthermore, when using the shell chain of microspheres, for example, polystyrene chains are chloromethylated and then polymerized with a living radical polymerization initiator to introduce a diethyldithiocarbamate group, and a monomer is grafted from the surface of the microspheres into the monomer as described above. Reactive functional group, such as PMMA
Can be introduced. Further, a multi-branched polymer can be used, but it is also synthesized by radical polymerization (polymer, 11, Vol. 47 (199).
8). B, Yamada, Polym. , 39,371
(1998). ).

In such a "comb-type" structure, the distance from the main chain to the end adsorption group is related to the thickness of the adsorption layer, and in the dispersion of nanoparticles, it should be in the range of 5 nm to 300 Å. Is preferred. If the distance from the main chain is too short, it is not preferable because the adsorbing group cannot effectively adsorb to the inorganic nanoparticles, and if it is too long, there is a possibility that a large number of adsorbing groups are entangled with each other. .

2. Functional part The functional part of the functional polymer used in the present invention is a part that exerts a function when the nanoparticle layer laminate of the present invention is used as a functional element, and from the functional functional group It is a part that becomes. This functional part is a part which determines the property of the nanoparticle layer laminated body of this invention, and the function and use of the nanoparticle layer laminated product of this invention are determined by the property of this functional part.

Therefore, various kinds of functional functional groups constituting such a functional part can be mentioned depending on the use (function) of the nanoparticle layer laminate of the present invention.

Specifically, a nanoparticle layer laminated body having a refractive index much higher than that of a glass substrate and air is formed on a glass substrate, and the light incident on the nanoparticle layer laminated body is made up of nanoparticles. When the nanoparticle layer laminate of the present invention is used for an interference film in which only the light that escapes to the outside light exhibits coherence (coloring) by total reflection and refraction on both sides of the layer laminate, for example, the following chemical formula The aromatic chromophores shown can be used as functional functional groups

[0064]

[Chemical 1]

Also, by absorbing and exciting light energy corresponding to the chromophore, an electron of Ip (ionization potential) is knocked out, which becomes a source of photoelectrons, resulting in photocurrent as a result of electron transfer. Observed, when applying the nanoparticle layer laminate of the present invention to the photoelectric conversion film, as the functional functional group, in addition to the aromatic chromophore, ruthenium bipyridine, europium complex, viologens (redox group, the following Chemical formula) and the like can be used.

[0066]

[Chemical 2]

The functional polymer of the present invention may simply function as a dispersant. In this case, the functional part serves as a part that functions as a dispersant together with the anchor part. The main function of the functional nanoparticle layer laminate in this case is due to the above-mentioned inorganic nanoparticles.

3. Main chain The functional polymer used in the present invention preferably has a structure in which the anchor portion and the functional portion are pendantly added to the main chain. Further, it may have a structure capable of having surface activity, and as such an example, a chain alkyl compound can be mentioned.

The compounds used for such a main chain include polyalkyl groups, polyamide groups, urethane bonding groups,
An active ester group, and

[0070]

[Chemical 3]

And the like.

(Functional Nanoparticles) In the present invention, functional nanoparticles can be formed by adsorbing a functional polymer on the surface of the inorganic nanoparticles.

Such functional nanoparticles are adsorbed by an alternate adsorption method using electrostatic interaction to form a nanoparticle layer, and by stacking these layers, the nanoparticle layer laminate of the present invention is obtained. However, the properties and uses of this nanoparticle layer laminate are basically due to the function of the functional part of the functional polymer attached to the surface of the inorganic nanoparticles.
Therefore, it is preferable that the functional polymer is densely attached to the surface of the inorganic nanoparticles.

In this case, the number and density of the functional polymer deposited on the inorganic nanoparticles vary greatly depending on the molecular weight of the functional polymer used and the particle size of the inorganic nanoparticles. It is preferable that 1 to 50 functional polymers are attached to one inorganic nanoparticle.

Further, the functional polymer attached to the above-mentioned inorganic nanoparticles is not limited to one type, and a plurality of types may be attached. In this case, one kind may have only a dispersing function, and the other kind may have a specific functional group.

The nanoparticle layer laminate of the present invention may be formed by using only one kind of such functional nanoparticles, and if necessary, plural kinds of functional nanoparticles may be used. It may be formed by

In this case, each nanoparticle layer may be filled with a plurality of types of functional nanoparticles to form a nanoparticle layer, and the nanoparticle layer may be a laminated body of nanoparticle layers. Although a single type of functional nanoparticles is filled in each layer, the type of functional nanoparticles may be different between layers.

(Nanoparticle Layer) The nanoparticle layer laminate of the present invention is formed by laminating the nanoparticle layers in which the above-mentioned functional nanoparticles are packed at a high density.

In the present invention, the density of the functional nanoparticles in the nanoparticle layer is within the range of 40 to 80% by volume, particularly 45 to 80%, although it depends on the use. It is preferably within the range. As described above, since the present invention exerts its function by the functional part of the functional polymer existing on the outer periphery of the functional nanoparticle, when the packing density is smaller than the above range, it is required. It is not preferable because the function may not be exerted, and it is not realistic to make the packing density larger than the above range at this time.

The nanoparticle layer in the present invention has the functional nanoparticles filled with the above density and the gas (usually air) existing between them. However, as will be described later in the section of the method for producing a nanoparticle layer laminate, for example, when a polymer electrolyte membrane is used for lamination,
This polyelectrolyte may be included in the layer. Also,
As will be described later, when a reinforcing attachment means is used, a predetermined resin or the like may be inserted between the functional nanoparticles.

In the present invention, such nanoparticle layers are laminated to form a nanoparticle layer laminate, and the number of layers can be appropriately selected according to the required function and application. Therefore, it depends on the required film thickness and function. Generally, it can be in the range of 2 to 200 layers, preferably in the range of 3 to 100 layers.

The functional nanoparticles in the nanoparticle layer may be of a single type or a mixture of a plurality of functional nanoparticles as described above. As described above, the nanoparticle layers containing different types of functional nanoparticles may be laminated.

(Supporting Material) The present invention is a nanoparticle layer laminated body obtained by laminating nanoparticle layers filled with functional nanoparticles as described above. Such a laminated body has a self-supporting property. There may be a supporting material depending on the presence or absence, the application, etc.

Further, such a nanoparticle layer laminated body is formed by laminating it on a base material, which will be described later in the section of its manufacturing method, and this base material is used as a support material. You may

The material and shape of such a support material are largely different depending on the application. As a material, transparency is required when used for optical applications, but a support material that is not transparent is used depending on the application. It may be preferably used. Further, the shape may be any shape such as a film shape, a sheet shape, a plate shape, a shape having a curved surface, a tubular structure, or a complicated shape.

When the use of the nanoparticle layer laminate of the present invention is, for example, to make use of its optical function, a transparent support material is required. As such a transparent support material, plate-like glass or film-like plastic is usually used, and it can be said that the display glass is excellent in surface smoothness and transparency. Further, the thickness thereof is generally 0.4 mm to 10 mm in consideration of price. In this case, the support material is usually a single layer, but it may be a multi-layer. The thickness of the film-shaped support material is not particularly limited, but is usually 10 to 300 μm.
Often, the size of m is used.

(Electrostatic Interaction) In the present invention, as described above, the functional nanoparticles have inorganic nanoparticles capable of having an electric charge such that they can be adsorbed by electrostatic interaction. By the function of the inorganic nanoparticles, functional nanoparticles are laminated on a base material by electrostatic interaction to form a nanoparticle layer laminate. In addition, in the nanoparticle layer laminate of the present invention, this base material may be used as a support material, or when it has self-supporting property, it may be peeled off from this base material and used. Further, it may be used by being transferred to another support, if necessary.

As described above, since the adhesion of the functional nanoparticles on the base material, in other words, the formation of the nanoparticle layer on the base material, is performed by electrostatic interaction, the functionality of the present invention is improved. It is possible to form a nanoparticle layer laminated body in which nanoparticles are uniformly arranged on the base material and which can exhibit various functions, on the base material.

When the functional nanoparticles are attached to the base material by such electrostatic interaction, generally, an electric charge of positive or negative is applied to the base material, and the adsorption layer having a polarity opposite to this charge. By using the functional nanoparticles in which the functional nanoparticles are formed, a method is adopted in which the functional nanoparticles are attached to the substrate by electrostatic interaction.

As a method for applying an electric charge to the surface of the substrate,
In some cases, the surface of the substrate is simply charged physically, and in some cases, the surface of the substrate is physically or chemically imparted with an ionic functional group. In the present invention, the former is poor in charge stability, and therefore the latter method of imparting an ionic functional group to the surface of the substrate is preferable.

As a method for introducing an ionic functional group on the surface of the base material, corona discharge treatment, glow discharge treatment, plasma treatment, hydrolysis treatment, silane coupling treatment, coating of polymer electrolyte, polymer electrolyte multilayer film In the present invention, it is preferable to form a polymer electrolyte membrane obtained by applying a polymer electrolyte or the like. This is for the following reason.

First, when the charge density on the surface of the base material is higher, a highly functional nanoparticle layer in which the functional nanoparticles are uniformly attached can be formed on the base material. On the other hand, by forming the polymer electrolyte membrane on the base material, the charge density can be increased as compared with other methods. Therefore, it is necessary to form a polymer electrolyte membrane on a substrate and to attach the functional nanoparticles on the substrate, that is, on the polymer electrolyte by electrostatic interaction between the polymer electrolyte membrane and the functional nanoparticles. Due to
It is possible to obtain a nanoparticle layer in which functional nanoparticles are evenly attached, and it is possible to obtain a highly functional nanoparticle layer laminate.

Corona discharge treatment, glow discharge treatment,
In the plasma treatment and the hydrolysis treatment, the ionic functional group generally introduced is often an anionic group.
Therefore, the charge of the inorganic nanoparticles of the functional nanoparticles is limited to cations. On the other hand, the polyelectrolyte can be arbitrarily selected from anionic, cationic, and their density and balance, so that the charge of the inorganic nanoparticles in the functional nanoparticles is limited to either anion or cation. Absent. From this point as well, as a method for imparting an electric charge to the surface of the base material, it is preferable to form a polymer electrolyte membrane made of a polymer electrolyte.

When a polymer electrolyte membrane is formed to give an electric charge to the surface of the substrate, the thickness of the polymer electrolyte membrane is preferably smaller than the average particle size of the functional nanoparticles, and the thickness of the polymer electrolyte is further reduced. Is preferably less than 50% of the average particle size of the functional nanoparticles. When the thickness of the polymer electrolyte membrane is equal to or larger than the average particle size of the functional nanoparticles, the functional nanoparticles are partially stacked in two or more layers, and the functional nanoparticles are uniformly filled in the nanoparticle layer. This is because it may not be possible, and as a result, it may not be possible to obtain a nanoparticle layer laminate that exhibits high-quality functions.

In the present invention, such a polymer electrolyte membrane is preferably a multilayer film formed by laminating two or more kinds of polymer electrolytes having different polarities. As a method for forming such a polyelectrolyte multilayer film, there is known a so-called alternate adsorption film manufacturing method (Layer-by-Layer).
Assembly method) can be preferably used. This method, by alternately immersing the substrate in a cationic polyelectrolyte aqueous solution and an anionic polyelectrolyte aqueous solution,
This is a method of forming a polyelectrolyte multilayer film on a substrate by controlling the film thickness on the order of nanometers (for example, Gero Decher et al., Scienc
e, Vol. 277, p. 1232, 1997; Y. Shiratori et al., IEICE Tech., OME98-106, 1998; Joseph B. Schlenoff et al., Macr.
omolecules, 32, 8153, 1999). According to this method, even if the polymer electrolyte multilayer film is a thick film having a particle size equal to or larger than the particle size of the functional nanoparticles, the nanoparticle layer is formed of a single particle film. Because the polyelectrolyte multilayer is a polymer complex that is insoluble in the medium (mainly water), it hardly diffuses into the medium, and the functional nanoparticles interact only with almost the surface of the polyelectrolyte multilayer. Because it does.

Many examples of producing an alternating multilayer film using a polymer electrolyte and fine particles or an example of producing a single particle film have already been reported (for example, alternating multilayer film: Kunitake
Chemistry Letters, 125 pages, 1997; Single particle film: Akashi et al., Langmuir, 14, 4088 pages, 1998.
Year). However, in the prior art including these, there is no report or description focusing on a single particle film composed of functional nanoparticles in which a functional polymer is attached to inorganic nanoparticles.

Further, in the present invention, the polymer electrolyte forming the polymer electrolyte membrane is preferably a crosslinked polymer electrolyte. This is because the use of a crosslinked polyelectrolyte can prevent unnecessary and inconvenient multilayering of functional nanoparticles in the nanoparticle layer. This crosslinked polyelectrolyte is preferably used both when the polyelectrolyte is formed as a single layer and when the polyelectrolyte multilayer film is formed. When the polyelectrolyte multilayer film is formed, only the uppermost layer thereof is used. A crosslinked polyelectrolyte may be used, or all layers may be formed of a crosslinked polyelectrolyte.

In the present invention, the polymer electrolyte membrane is formed in this manner, and the functional nanoparticles are attached to the polymer electrolyte membrane to form a nanoparticle layer. Then, the polymer electrolyte membrane is further formed on the polymer electrolyte membrane to form the functional layer again. When the nanoparticle layer laminate is formed by the method of repeating the step of attaching nanoparticles, the polyelectrolyte is present in each nanoparticle layer unless the polyelectrolyte is subsequently removed. In addition, after forming the polymer electrolyte membrane on the substrate and attaching the first nanoparticle layer, by changing the charge of the inorganic nanoparticles in the functional nanoparticles, the polymer electrolyte membrane is changed. It is also possible to stack a nanoparticle layer without interposing. In this case, the polymer electrolyte does not exist in the second or higher layer of nanoparticles.

As the polymer electrolyte used in the present invention, polyethyleneimine and its quaternary compound, polydiallyldimethylammonium chloride, poly (N, N ') are used.
-Dimethyl-3,5-dimethylene-piperidinium chloride), polyallylamine and quaternary compounds thereof, polydimethylaminoethyl (meth) acrylate and quaternary compounds thereof, polydimethylaminopropyl (meth) acrylamide and quaternary compounds thereof , Polydimethyl (meth) acrylamide and its quaternized products, poly (meth) acrylic acid and its ionized products, sodium polystyrene sulfonate, poly (2-acrylamido-2-methyl-1)
-Propane sulfonic acid), polyamic acid, potassium polyvinyl sulfonate, and further monomers (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-isopropyl (meth) constituting the above-mentioned polymer.
For example, a copolymer with a nonionic aqueous solution monomer such as acrylamide can be used.

In the present invention, among them, polyethyleneimine quaternized product, polydiallyldimethylammonium chloride, poly (N, N′-dimethyl-3,5-dimethylene-piperidinium chloride), polyallylamine 4
Quaternized product, polydimethylaminoethyl (meth) acrylate quaternized product, polydimethylaminopropyl (meth) acrylamide quaternized product, polydimethyl (meth) acrylamide quaternized product, sodium poly (meth) acrylate, sodium polystyrene sulfonate, Poly (2-acrylamido-2-methyl-1-propane sulfonic acid), potassium polyvinyl sulfonate, and further monomers constituting the polymer and (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-isopropyl (meth) ) It is preferable to use a copolymer with a nonionic aqueous solution monomer such as acrylamide.

Further, as the crosslinked polymer electrolyte,
Cross-linked product of a monomer constituting the above-mentioned polymer electrolyte and a polyfunctional monomer such as methylenebisacrylamide, a cross-linked product by the reaction between the above-mentioned polymer electrolyte and aldehydes, an electron beam to the above-mentioned polymer electrolyte, and a cross-linked product by gamma ray irradiation. And so on.

(Reinforcing Adhesion Means) The nanoparticle layer laminate of the present invention is formed by laminating functional nanoparticles on a base material by electrostatic interaction to form a nanoparticle layer. It is a thing. At this time, when the functional nanoparticles are adhered to each other only by electrostatic interaction between the respective nanoparticle layers, and when the support material and the nanoparticle layer when the base material is used as the support material are attached, At that time, problems such as scratch resistance may occur. In such a case, a reinforcing adhesion means for improving the adhesion of the nanoparticle layer laminate may be used.

Such a reinforcing attachment means is not limited to this, but for example, such a nanoparticle layer is filled with an actinic radiation-reactive monomer and a polymerization initiator and cured. And a method of embedding the above-mentioned nanoparticle layer laminated body in the encapsulating material while leaving one surface thereof.

In addition, as a reinforcing attachment means, a method of dry-laminating the support on which the nanoparticle layer laminate is formed, a method of extrusion coating the nanoparticle layer laminate, or a film adhesive is used. And a method of applying a pressure-sensitive adhesive or the like to bond the support material to the nanoparticle layer laminate, or a method of spot bonding or line bonding.

In the method of filling the above-mentioned nanoparticle layer with the actinic radiation-reactive monomer and the polymerization initiator and curing the same, the functional nanoparticles are fixed in the nanoparticle layer in addition to the reinforcing action. As a result, a superlattice structure having a fixed function in the film utilizes an effect of diffracting light of a specific wavelength by Bragg reflection, which is an unprecedented optical function.
For example, it is possible to obtain an interference film having a narrow half wavelength.
Further, it becomes possible to form an optical waveguide easily because it can be cured by actinic radiation and can be patterned using a crosslinking reaction, and it can be used as a hologram or a selective reflection film utilizing a change in refractive index.

The reactive monomer used herein refers to a monomer whose polymerization is induced by radicals generated by absorption of actinic radiation by a polymerization initiator described later. In the present invention, this property is Any monomer can be used as long as it has a monomer, and a compound having at least one polymerizable carbon-carbon unsaturated bond can be used.

Specific examples of the reactive monomer include allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate. , 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate,
Phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol acrylate,
1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane acrylate, glycerol diacrylate, triprylene glycol diacrylate, glycerol triacrylate, tri Methylol propane triacrylate, polyoxyethylated trimethylol propane triacrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyl trimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate, 2,2,4-trimethyl-1,3-pentanediol Diacrylate, diallyl fumarate,
1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, and those obtained by substituting the above acrylate group with a methacrylate group, γ-methacryloxypropyltrimethoxysilane,
1-vinyl-2-pyrrolidone, 2-hydroxyethylacryloyl phosphate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxy acrylate, 3-butanediol acrylate, neopentyl glycol diacrylate,
Polyethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, phenol-ethylene oxide modified acrylate, phenol-propylene oxide modified acrylate, N-vinyl-2-pyrrolidone, bisphenol A-
Acrylate monomers such as ethylene oxide-modified diacrylate, and those in which these acrylate groups are substituted with methacrylate groups, polyurethane acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyurethane structure, and acrylate groups in an oligomer having a polyester structure It is possible to use a polyester acrylate oligomer in which is bonded, an epoxy acrylate oligomer in which an acrylate group is bonded to an oligomer having an epoxy group, or an epoxy methacrylate resin having a methacrylate group.

These are examples of reactive monomers that can be used, and the present invention is not limited to these. The content of such a reactive monomer is 10 to 90% by weight, preferably 20 to 8% by weight of the non-volatile components of the resin composition.
A range of 0% by weight is desirable.

The above reactive monomers may be used alone or in combination of two or more. Among them, a trifunctional or higher polyfunctional acrylate monomer can be used particularly preferably.

The polymerization initiator used in the present invention is one for generating radicals by absorbing actinic radiation to initiate the polymerization of the above reactive monomer.

For example, aromatic ketones, benzoin ethers, benzoins, imidazole dimers, halomethylthiazole compounds, halomethyl-S-triazine compounds, benzophenone, [4- (methylphenylthio) phenyl] phenylmeta Non-, ethylanthraquinone, p-dimethylaminobenzoic acid isoamyl ester,
p-Dimethylaminobenzoic acid ethyl ester, 2,2-
Dimethoxy-1,2-diphenylethan-1-one, 1
-Hydroxy-cyclohexyl-phenyl-ketone, 2
-Hydroxy-2-methyl-1-phenyl-propane-
1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, methylbenzoinformate, benzoinisobutylether, benzyldimethylketal, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, (2-
Hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl)) propanone, 2-[(2-dimethylaminoethyl) amino] -4,6-bis (trichloromethyl) -S-triazine-dimethyl Sulfate, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, Octel
Chemicals made QUANTACURE ITX,
ABQ, CPTX, BMS, EPD, DMB, MCA,
EHA, TAZ-100, 101, 10 manufactured by Midori Kagaku
2, 104, 106, 107, 108, etc. can be used.

Further, 2,4-diethylthioxanthone,
2-chlorothioxanthone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- [2- (furan-2-yl) ethenyl]-
4,6-bis (trichloromethyl) -S-triazine,
2- [2- (5-methylfuran-2-yl) ethenyl]
-4,6-bis (trichloromethyl) -S-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, bis (2,6) -Dimethoxybenzoyl) -2,
Acylphosphine oxides such as 4,4-trimethyl-pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, QUANT manufactured by Octel Chemicals
ACURE QTX, Midori Kagaku TAZ-110, 1
13, 118, 120, 121, 122, 123, La
It is possible to use ESACURE KTO46 etc. made from Mberti.

Furthermore, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-)
3- (1H-pyrrol-1-yl) -phenyl) titanium or η ⁵ -cyclopentadienyl-η ⁶ -cumenyl-
Iron (1 +)-Hexafluorophosphate (1
-) And the like metallocene, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, TA manufactured by Midori Kagaku
Z-114 or the like can be used.

The polymerization initiator that can be used in the present invention is particularly limited as long as it has a light absorption region described below and generates a radical necessary for the above reactive monomer to be polymerized. is not. Also,
In the present invention, these polymerization initiators may be used alone or in combination of 2
A mixture of two or more species can be used.

The addition amount of such a polymerization initiator can be set in the range of 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, relative to 100 parts by weight of the nonvolatile components of the composition.

Furthermore, when the nanoparticle layer laminate of the present invention is irradiated with an actinic radiation, the lamp used should be one that emits the actinic radiation most absorbed by each of the contained polymerization initiators. To be Specifically, it is possible to use a UV irradiation light source (UV lamp). In this case, each nanoparticle layer is laminated, the reactive monomer and the polymerization initiator are filled in the nanoparticle layer, and then the film is obtained by exposing to UV light and curing. UV exposure is an aligner,
It is performed by a device such as a stepper or a proxy. further,
The exposure radiation source is metal halide, short arc Xe, etc.
Irradiation wavelength is 230nm-480nm, optimally 320n
It is preferable to use m to 420 nm.

Further, when UV exposure and curing are carried out under oxygen-shielding conditions, the generated radical deactivation is suppressed, the curing sensitivity is enhanced, and even deep curing is possible. Furthermore, for example, Irgacure 369 (manufactured by Ciba Specialty Chemicals), which is one of the above-mentioned photopolymerization initiators,
Since a light having a wavelength of about 290 nm to 365 nm is most absorbed, it is preferable to use a lamp (for example, a mercury lamp) that emits light in the range, and one of the photopolymerization initiators is used.
Since IRGACURE 907 (manufactured by Ciba Specialty Chemicals), which is one of the two, most absorbs light having a wavelength of about 260 nm to 330 nm, it is preferable to use a lamp that emits light in the range using a quartz lens as the optical system. .

Next, as another example of the auxiliary attaching means, a case where the nanoparticle layer laminated body is embedded with a sealing material leaving one surface thereof will be described. When the sealant is used as an auxiliary attachment means in this way, it is necessary not only to reinforce the adhesive force but also to prevent the ingress of water or oxygen depending on the type of the functional nanoparticles, or This is suitable when it is inconvenient to be deformed due to such reasons.

In the present invention, one surface of the nanoparticle layer laminated body is left to be embedded in the encapsulating material, but it is premised that the support is present on this one surface. It is a thing. Therefore, when the nanoparticle layer laminated body is not formed on the support, the encapsulating material may be formed on the entire surface and sealed if necessary.

In the present invention, such a sealing material is not particularly limited, but a transparent sealing material is used when the optical function of the nanoparticle layer laminate is utilized. Is preferred.

As the resin component for forming such a transparent encapsulant, a conductive resin such as polyvinyl butyral resin, polyaniline resin, polyvinylidene fluoride, etc., particularly polyaniline resin, polyphenyl ether resin, polyphenylene vinylene resin, etc. are preferable. Is. Further, alkyd resin, mixed resin of fluorine resin and acrylic resin, various rubbers such as epoxy-modified urethane rubber, and various synthetic resins such as silicone can be used. Furthermore, for example, polyethylene resin, polypropylene resin, polymethylpentene resin, polybutene resin, ethylene-propylene copolymer resin, olefin resin such as olefin thermoplastic elastomer, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, chloride Vinyl
Vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl resin such as ethylene-vinyl alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate, ethylene-terephthalate-isophthalate copolymer resin,
Polyester resin such as polyester thermoplastic elastomer, poly (meth) acrylic acid methyl resin, poly (meth) acrylic acid ethyl resin, poly (meth) acrylic acid butyl resin, (meth) acrylic acid methyl- (meth) acrylic acid Acrylic resin such as butyl copolymer resin, polyamide resin represented by nylon 6 or nylon 66, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, epoxy phenol resin, epoxy resin, epoxy Urethane-modified resin, phenolic resin, copolymers or mixtures thereof, and the like can also be used. It is desirable that these are selected in consideration of the dielectric constant.

Among the above, cellulose type, polyether sulfone type, polyacrylic type, polyurethane type, polyester type, polycarbonate type, polysulfone type, polyether ketone type, (meth) acrylonitrile type resin, polyvinyl butyral resin, polyaniline resin , Alkyd resin, mixed resin of fluorine resin and acrylic resin, epoxy modified urethane rubber, silicone, epoxy phenol resin, epoxy urethane modified resin, phenol resin, acrylic resin, or copolymers or mixtures of these. Is particularly preferable.

As a special case, thermoplastic elastomer, biaxially oriented polyester film (PET), biaxially oriented nylon film (ONY), biaxially oriented polypropylene film (OPP), non-oriented polypropylene film (CPP), non-oriented Nylon film (CNY) is preferably used. In addition, various transparent films such as polycarbonate film, polyvinyl chloride film, polyvinylidene chloride film, polyethylene film, ethylene copolymer film, ethylene-vinyl alcohol copolymer film, polysulfone film, and cellulose-based film are also available. Can be used.

Among the resins of the above-mentioned transparent encapsulant, acrylic resin and epoxy resin are preferable and more preferable epoxy resin from the viewpoint of adhesion and adhesiveness with the nanoparticle layer laminate to be encapsulated. As Mitsubishi Yuka Shell Co., Ltd.
Epicoat series manufactured by Daicel Corporation, Celoxide series manufactured by Daicel Co., Ltd., Epolide series, bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol-S type epoxy resin, bisphenol-F type epoxy resin, polycarboxylic acid glycidyl ester, polyol Examples thereof include glycidyl ester, fatty acid or alicyclic epoxy resin, aminoepoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, and copolymerized epoxy compound of glycidyl (meth) acrylate and radically polymerizable monomer. .

(Patterning of Nanoparticle Layer Laminate) The nanoparticle layer laminate of the present invention may be formed in a pattern on a support. This is because by forming it in a pattern, it can be used for various purposes such as being used as an optical filter or the like.

As a method for forming the nanoparticle layer laminated body in a pattern like this, a hydrophilic / hydrophobic pattern or an acid / base pattern is formed on a substrate, and the nanoparticle layer laminated body is formed on this. If necessary, it can be formed by a method of sealing with the above sealing material.

B. Method for producing nanoparticle layer laminate The method for producing a nanoparticle layer laminate of the present invention has a charge applying step of applying an electric charge to the surface of a base material, and a charge having a sign opposite to the electric charge applied to the surface of the base material. A functional nanoparticle dispersion containing functional nanoparticles is applied onto the base material, and a nanoparticle layer forming step of forming a nanoparticle layer is included, and the functional nanoparticle has an adsorption group on the surface. And an inorganic nanoparticle capable of having an electric charge capable of being adsorbed by electrostatic interaction, an anchor portion having a plurality of adsorption groups that adsorb with an adsorption group present on the surface of the inorganic nanoparticle, and It is composed of a functional polymer containing a functional part having a functional functional group, and the anchor part of the functional polymer is a functional nanoparticle formed by adhering to an adsorption group on the surface of the inorganic nanoparticle. It is a feature.

(Method for Producing Functional Nanoparticles) Before explaining the method for producing the nanoparticle layer laminate of the present invention, the method for producing the functional nanoparticles used in the present invention will be described.
In the present invention, a dispersion liquid in which the above-mentioned inorganic nanoparticles and the above-mentioned functional polymer are dispersed is prepared. At this time, when the functional polymer has a function as a dispersant, no other dispersant is necessary, but if the dispersibility is insufficient or not, a dispersant as described below is added. Thus, the above dispersion is prepared.

Then, by stirring this dispersion for a predetermined time, the anchor portion of the functional polymer is attached to the surface of the inorganic nanoparticles in the dispersion to form the functional nanoparticles.

(Charge Applying Step) In the present invention, a charge applying step of applying an electric charge to the surface of the substrate is first carried out.
Here, this base material may be used as it is as a support material as described above, and when the nanoparticle layer laminate has self-supporting property, after forming the nanoparticle layer laminate. It may be peeled off, and further, after the nanoparticle layer laminated body is formed on the base material, it may be transferred onto a separately-supported support material.

Regarding the method for imparting an electric charge onto the substrate,
The description is omitted here because it is the same as the above. As described above, in the alternate adsorption method, the above-mentioned functional nanoparticles are attached to the substrate by electrostatic interaction, and therefore, by applying either positive or negative charge to the substrate, the subsequent steps are performed. By using a functional nanoparticle containing an inorganic nanoparticle having a polarity opposite to this charge, the functional nanoparticle can be attached to the substrate.

(Nanoparticle Layer Forming Step) Then, a functional nanoparticle dispersion liquid having a charge having a sign opposite to that of the charge applied to the surface of the base material is applied onto the base material to form a nanoparticle layer. A particle layer forming step is performed. As the functional nanoparticle dispersion liquid, the dispersion liquid prepared at the time of producing the functional nanoparticles may be used as it is.

Since the functional nanoparticles used here are the same as those described above, the description thereof is omitted here. However, the functional nanoparticles used in this case are the same as the charges of the inorganic nanoparticles. However, an electric charge different from the electric charge applied to the coated surface of the substrate or the like is used.

In the present invention, as described above, when laminating the nanoparticle layer, the electric charge of the functional nanoparticles to be laminated is changed between positive and negative without interposing the above-mentioned polymer electrolyte membrane. May be laminated. In this case, the nanoparticle layer laminated body can be obtained with the nanoparticle layer that does not include the polymer electrolyte membrane that is included in the general alternate adsorption method. It is possible to prevent the inconvenience that the above-mentioned ability is hindered by the polymer electrolyte, and it is possible to exert a sufficient effect. Furthermore, in this case,
If an electric charge is applied to the base material without depending on the polymer electrolyte membrane,
It becomes possible to obtain a nanoparticle layer laminated body containing no polymer electrolyte at all.

In the present invention, the concentration of the functional nanoparticles in the functional nanoparticle dispersion liquid is 1% by volume to 70% by volume, preferably 1% by volume with respect to the functional nanoparticle dispersion liquid.
Volume to 55 volume%, particularly preferably 3 volume% to 50 volume
It is within the range of% by volume.

The functional nanoparticle dispersion liquid used in this step has a small radius of gyration when the relationship between the particle size of the inorganic nanoparticles contained therein and the molecular weight of the functional polymer attached to the surroundings and the adjusted dispersion viscosity is examined. Therefore, the viscosity is likely to be small. Therefore, if it is difficult to stack the nanoparticle layers by the alternate adsorption method, a small amount of additives such as thickeners and dispersants such as silica and clathrates, and stabilizers should be added for modification. Good.

Further, a viscosity modifier, a fluidity modifier, a rheology control agent and the like may be added to improve the layered state of the nanoparticle layer and the film suitability. As a concrete example,
Talc, metal oxide fine particles such as titanium oxide, silica,
Silica sol (or gel), polysaccharides such as cellulose series (MC type, alkali-soluble cellulose) manufactured by Shin-Etsu Chemical Co., Ltd., silicone oil and the like can be mentioned, and these may be added by several% or less.

In the present invention, the clathrate is particularly preferable, and as such clathrate, calixarene, zeolite, montmorillonite, smectite, crown ether and other cage compounds can be used. The clathrate itself may be modified with various substituents. Here, montmorillonite and smectite having particularly high transparency are preferable in terms of dispersibility and inclusion-stabilizing action.

As the dispersant, a polymeric wetting / dispersing agent can be used. The dispersant is used because the functional nanoparticles having the functional polymer adsorbed on the surface of the inorganic nanoparticles are uniformly laminated when the functional nanoparticle dispersion is used for the lamination, or the functional nanoparticle dispersion is homogeneous. It is used for maintaining and improving the property, and further for improving the film quality of the formed nanoparticle layer laminate. It should be noted that such a dispersant must be carefully selected so as not to impair the adhesion of the substrate.

Examples of the material of this dispersant include Disparon series manufactured by Kusumoto Kasei Co., Ltd. and Solspers series manufactured by Avicia Co., Ltd. Among these, it is preferable to use a polymeric wetting / dispersing agent having an acid value of 8 to 20 and an amine value of 20 to 32. Specifically, Disparlon product number DA-703-50,
DA-705, DA-725, DA-234, DA-3
25, DA-375, Sols Perth 24000, 120
00, 5000, etc. can be mentioned.

Further, as a dispersant which can be used in combination therewith, for example, polyoxyethylene alkylphenyl ether type, polyethylene glycol diester type,
Examples thereof include sorbitan fatty acid ester type, fatty acid modified polyester type, and tertiary amine modified polyurethane type. Further, a conventionally known dispersant can also be used.

Such a dispersant is contained in an amount of 0.01 wt% to 3%.
In the range of 0 wt%, preferably 0.1 wt% to 10 wt
Used in the range of%.

Further, in the case where the nanoparticle layer laminated body places importance on the characteristics of the dye absorbing film and the colored functional film, the colorant or the coloring agent is added to the above-mentioned functional nanoparticle dispersion liquid to form the nanoparticle layer. At the time of formation, these coloring agents or coloring agents may be incorporated at the same time.

As the colorant, a dye or a pigment may be combined, or an organic dye derivative or the like may be used. Examples of such organic dye derivatives include photochromic dyes, and pigments include phthalocyanine-based, azo-based, anthraquinone-based, and quinacridone-based organic dyes (pigments, dyes, etc.) having a skeleton of a carboxyl group and a sulfone group. Examples thereof include those to which an acid group, amino group, carbonyl group, sulfonyl group and the like have been added, and salts thereof.

Further, known dyes and / or pigments can be used. That is, as the chemical structure, anthraquinone series, isoindoline series, isoindolinone series, azo series, pyrrolopyrrole series, quinophthalone series,
Phthalocyanine type, slene type, triphenylmethane type,
Examples thereof include triallylmethane-based, quinacridone-based, dioxazine-based, perylene-based, perinone-based and metal complexes thereof. In the case of these organic dyes, the pigment form is preferable from the viewpoint of heat resistance and light resistance.

The functional nanoparticle dispersion liquid contains 0.5 to
About 10% by weight of UV absorber and 0.5-10%
It is also possible to add a light stabilizer in an amount of about% by weight. This is because the weather resistance of the obtained nanoparticle layer laminate can be further enhanced.

As such an ultraviolet absorber, for example, an organic compound such as benzotriazole, benzophenone or salicylate, or an inorganic compound such as fine particle zinc oxide or cerium oxide having a particle size of 0.2 μm or less is used. You can As the light stabilizer, for example, a hindered amine-based radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, or a radical scavenger such as piperidine-based radical scavenger should be used. You can

When the nanoparticle layer laminate is provided on the substrate, the surface of the substrate is subjected to activation or roughening treatment such as corona discharge treatment, or the anchor coating layer is provided on the substrate film. The nanoparticle layer laminated body may be formed after taking measures to improve the adhesiveness with the base material, such as providing.

(Use) The use and function of the nanoparticle layer laminate of the present invention include, for example, light transmission control, photorefraction, photoconductor, film resistor, condenser, etc. It can be applied to electrical wiring by surface modification patterning, especially as a nanowire, and also as a substrate or element for nanodevices using nanotechnology.

The present invention is not limited to the above embodiment. The above-described embodiments are merely examples, and the present invention has substantially the same configuration as the technical idea described in the scope of claims of the present invention, and has any similar effects to the present invention. It is included in the technical scope of.

[0151]

EXAMPLES The present invention will be further described with reference to the following examples.

(Preparation of Functional Nanoparticles) As reagents and solvents used in each synthesis, commercially available products purified by distillation or recrystallization were used. Each reagent is Wako Pure Chemical Industries, Ltd.
I used the one.

The inorganic nanoparticles are prepared by the size-selective photo-etching method of Torimoto et al. (T. Torimoto et al., J. El.
microchem. Soc. , 145, (1998)
1964. ).

That is, by irradiating inorganic nanoparticles having a wide particle size distribution with monochromatic light having a wavelength shorter than the wavelength at the absorption edge, only the inorganic nanoparticles having a large particle size are selectively photoexcited and dissolved. Then, the particle diameter was adjusted to smaller inorganic nanoparticles, and the inorganic nanoparticles were adjusted by monodisperse particles of CdS.

Hexametaphosphoric acid is used as a stabilizer,
CdS particles (average particle diameter 8 nm) were irradiated with an argon laser beam of 478 nm in an aqueous solution. The obtained CdS particles could be adjusted to have an average particle diameter of 3.5 nm and a narrow distribution width (about 7% of the average particle diameter).

Then, functional polymer having a polyoxyethyleneimine chain, which is a comb-shaped polymer, was adsorbed on the surface with 3.2 g of Solsperse 24000 to obtain functional nanoparticles having CdS nanoparticles as inorganic nanoparticles. . (Charge application step) In order to make the functional nanoparticles into a solid-state device for a light-to-electric energy conversion element, immobilization on a substrate is essential.

The alternate adsorption was carried out as follows by controlling the adsorption mass. The functional nanoparticle dispersion liquid was prepared as follows. That is, cationic polydiallyldimethylammonium chloride (hereinafter P
Abbreviated as DDA. (Average molecular weight 150,000, manufactured by Aldrich)
Was used. For imparting an anionic charge, sodium polystyrene sulfonate (hereinafter abbreviated as PSS. Average molecular weight 7
Manufactured by Aldrich) was used.

Using a 4 wt% PDDA aqueous solution and a 0.4 wt% PSS aqueous solution, a cleaned glass substrate (1.1 m
m, NA-45, manufactured by NH Techno Glass Co., Ltd.)
DA and PSS are repeatedly adsorbed eight times, and finally PS
An alternate adsorption film was produced by adsorbing S, and a positive charge was applied to the surface of the base material. The adsorption conditions were 2 minutes for each charge-providing developing solution and 1.5 minutes for each cleaning between adsorption.

(Nanoparticle Layer Forming Step) N, N′-divinyl-γ-glycidylpropylmethoxysilane (manufactured by Toshiba Silicone Co., Ltd.) was added to the functional nanoparticle dispersion liquid as a polyfunctional alkylsilane coupling agent. 0.1%
Alternating adsorption was performed using the aqueous solution under the above-mentioned film forming conditions. It was confirmed that the nanoparticle layer laminate was obtained by the alternate adsorption method. (Evaluation) Xe short arc 500W as light source
Was used. A copper sulfate solution was used as a solution filter for heat ray cutting. Further, a sharp cut filter (manufactured by HOYA) was used in order to select the wavelength.

Cd fixed on a glass substrate by the alternate adsorption method
A nanoparticle layer stack comprising S nanoparticles as inorganic nanoparticles;
Triethanolamine 0.02mol as a hole trap
0.1 mol / l KCl aqueous solution containing 1 / l was immersed in an electrochemical measurement cell having a quartz window, and light irradiation was performed. As a result, a photocurrent having photoresponsiveness similar to that of the n-type semiconductor electrode was confirmed.

[0161]

EFFECTS OF THE INVENTION According to the present invention, since the functional nanoparticles have a charge to the extent that they can be adsorbed by electrostatic interaction, the alternate adsorption method using electrostatic interaction is used. Thereby, it is possible to form a nanoparticle layer laminated body in which the functional nanoparticles are densely packed. Therefore, the nanoparticle layer laminate of the present invention can be effectively used as a functional element that makes the best use of the function of the functional part of the functional polymer adsorbed around the inorganic nanoparticles, and can be used in various applications. The effect that it can be deployed is achieved.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F100 AA01B AA01C AA09B AA09C                       AA17B AA17C AK01A AK01B                       BA02 BA03 BA04 DE01B                       DE01C EH462 EH902 EJ05A                       EJ05D EJ511 EJ82B GB41                       GB90 HB08B HB08C JA07A                       JB14B JB20A JB20D JM02A                       JM02D                 5F088 AA11 AB09 CB20

Claims (20)

[Claims] 1. Inorganic nanoparticles having an adsorbing group on the surface and having a charge capable of being adsorbed by electrostatic interaction; and adsorbing with an adsorbing group present on the surface of the inorganic nanoparticles. An anchor part having a plurality of adsorption groups, and a functional polymer containing a functional part having a functional functional group, the anchor part of the functional polymer to the adsorption group of the inorganic nanoparticle surface A nanoparticle layer laminated body comprising a plurality of nanoparticle layers including functional nanoparticles attached to each other. 2. The nanoparticle layer laminate according to claim 1, wherein the inorganic nanoparticles are inorganic nanoparticles made of a metal oxide or a metal sulfide. 3. The nanoparticle layer laminated body according to claim 2, wherein the inorganic nanoparticles are a functional semiconductor. 4. The average particle size of the inorganic nanoparticles is from 1 nm to
It is in the range of 150 nm, The nanoparticle layer laminated body in any one of Claim 1 to Claim 3 characterized by the above-mentioned. 5. The nanoparticle layer laminate according to any one of claims 1 to 4, wherein the functional polymer has a function as a dispersant. 6. The anchor portion of the functional polymer is 1 to
The nanoparticle layer laminate according to any one of claims 1 to 5, which has a comb structure having 10 adsorbing groups. 7. The nanoparticle layer laminate according to any one of claims 1 to 6, wherein the functional polymer has an average polymerization number molecular weight of 100 to 30,000. 8. The nanoparticle layer laminate according to claim 1, wherein a plurality of types of the functional nanoparticles are used. 9. The nanoparticle layer laminate according to claim 1, wherein a single type of the functional nanoparticles is used. 10. The nanoparticle layer laminate according to any one of claims 1 to 9, wherein the nanoparticle layer is laminated on a support material. 11. The nanoparticle layer according to claim 10, wherein a polymer electrolyte membrane is formed on the support material, and the nanoparticle layer is laminated on the polymer electrolyte membrane. Laminate. 12. The nanoparticle layer stack according to claim 11, wherein the polymer electrolyte membrane is a multilayer film formed by stacking two or more kinds of polymer electrolyte membranes having different polarities. body. 13. The nanoparticle layer laminate according to claim 11 or 12, wherein the polymer electrolyte membrane is a crosslinked polymer electrolyte membrane. 14. The adhesion between the nano-particle layers is, in addition to the adhesion due to the electrostatic interaction, further adhered by a reinforcing adhesion means, according to any one of claims 1 to 13. Nanoparticle layer laminate according to any one of the claims. 15. The reinforcing adhesion means comprises means for containing an actinic radiation-reactive monomer and a polymerization initiator in the nanoparticle layer laminate, and curing these by irradiation with actinic radiation. The nanoparticle layer laminate according to claim 14. 16. The nano according to claim 14, wherein the reinforcing attachment means is a sealing material that embeds the nanoparticle layer laminated body leaving one surface thereof buried. Particle layer stack. 17. The nanoparticle layer laminate according to any one of claims 1 to 16, wherein the nanoparticle layer is formed in a pattern. 18. A functional nanoparticle dispersion liquid containing a functional nanoparticle dispersion having a charge imparting step of imparting an electric charge to the surface of a base material, and functional nanoparticles having a charge having a sign opposite to that of the electric charge applied to the surface of the base material. And a nanoparticle layer forming step of forming a nanoparticle layer on the material, wherein the functional nanoparticle has an adsorption group on the surface and is capable of being adsorbed by electrostatic interaction. Inorganic nanoparticles capable of having an electric charge, an anchor portion having a plurality of adsorption groups that adsorb with an adsorption group existing on the surface of the inorganic nanoparticles, and a functional polymer having a functional portion having a functional functional group A method for producing a nanoparticle layer laminate, comprising: a functional nanoparticle having an anchor part of the functional polymer attached to an adsorption group on the surface of the inorganic nanoparticle. 19. The method for producing a nanoparticle layer laminate according to claim 18, wherein the inorganic nanoparticles are metal oxides or metal sulfides. 20. The method for producing a nanoparticle layer according to claim 18, wherein the charge applying step is a step of forming a polymer electrolyte membrane on a base material.