JP2003094546A - Fine polymer particle layer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine polymer particle layer laminate which is capable of making use of a functional group with a functional capability located at the outer peripheral part of a core shell-type microsphere to a maximum degree and can be applied to various use purposes. SOLUTION: In order to achieve the desired purposes, a plurality of fine polymer particle layers including fine polymer particles as core shell-type microspheres are laminated, and the core shell-type microsphere has a functional layer composed of a functional group with a functional capability formed on the outer peripheral part. In addition, the fine polymer particle has an adsorptive layer internally having an electrical charge to such an extent that the adsorption is possible by an electrostatic interaction. This fine polymer particle layer laminate is characterized in that it has the described structure and components.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer fine particle layer laminated body obtained by laminating polymer fine particle layers containing core-shell type microspheres, and is used in various applications such as optical equipment and optical communication equipment. The present invention relates to a polymer fine particle layer laminate that can be used.

[0002]

2. Description of the Related Art In recent years, core-shell type microspheres such as dendrimers and hyperbranched polymers have attracted attention. Since the polymer fine particles having such a structure can add many functional groups to the outer periphery,
By using this functional group as a functional functional group having various functions, various applications are expected to develop.

However, in order to effectively use such core-shell type microspheres, it is necessary to form a layer in which such polymer fine particles are packed at a high density. In the coating method using, the filling amount was limited, and it was not possible to form a polymer fine particle layer that could fully utilize the function of these core-shell type microspheres.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and can maximize the function of the functional functional group located on the outer peripheral portion of the core-shell type microsphere. The main object of the present invention is to provide a polymer fine particle layer laminate which can be applied to various uses.

[0005]

In order to achieve the above object, the present invention provides a plurality of polymer fine particle layers containing polymer fine particles which are core-shell type microspheres as described in claim 1. The core-shell type microspheres, which are laminated, have a functional layer composed of a functional functional group on the outer peripheral portion, and an adsorption layer having an electric charge sufficient to be adsorbed by electrostatic interaction inside thereof. Provided is a polymer particle layer laminated body, which is a polymer particle having the same.

According to the present invention, since the fine polymer particles have an adsorption layer having a charge capable of being adsorbed by electrostatic interaction, an alternate adsorption method using electrostatic interaction is used. By using it, it is possible to form a polymer fine particle layer laminate in which the core-shell type microspheres are densely packed. Therefore, the polymer fine particle layer laminate of the present invention can be effectively used as a functional element that maximizes the function of the functional layer composed of the functional functional groups located on the outer peripheral portion of the polymer fine particles, Various applications can be developed.

In the invention described in claim 1, as described in claim 2, the core-shell type microsphere is preferably a dendrimer or a hyperbranched polymer. With these types of core-shell type microspheres, it is possible to add a functional functional group to the outer peripheral portion at a high density, and the functional layer can be made more effective. This is because the function can be exhibited more effectively when used as an element.

In the invention described in claim 1 or 2, as described in claim 3, plural kinds of polymer particles are used in the polymer particle layer laminate. May be. This is because, depending on the functional element used, a plurality of types of functional functional groups may be required in order to exhibit the required function.

In this case, as described in claim 4, there is provided a polymer fine particle layer laminated body in which a plurality of polymer fine particle layers made of the same type of polymer fine particles are laminated, and the polymer fine particle layer has a high level between the polymer fine particle layers. The types of molecular fine particles may be different. This is because a specific function may be exhibited by combining a plurality of layers having different properties.

In the invention described in claims 1 to 4, as described in claim 5, it is preferable that the diameter of the polymer fine particles is within the range of 10 nm to 300 nm. When the particle size is smaller than the above range,
In order to obtain a sufficient film thickness as a polymer fine particle layer laminate,
It is not preferable because it is necessary to form a large number of layers, and when the particle size is larger than the above range, the effective area of the functional layer formed on the outer periphery of the polymer fine particles becomes small, and the obtained functional element is obtained. This is because there are cases where the functions of can not be fully exerted.

In the invention described in any one of claims 1 to 5, as described in claim 6, the polymer constituting the fine polymer particles has an average polymerization number molecular weight of , Preferably in the range of 100 to 30,000. It is preferably within the above range in consideration of the particle size of the polymer fine particles, the ease of handling, the number of functional functional groups disposed on the outer peripheral portion, and the like.

In the invention described in any one of claims 1 to 6, claim 7
The polymer fine particle layer may be laminated on a support material, as described in 1. This is because the polymer fine particle 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 this case, as described in claim 8, a polymer electrolyte membrane is formed on the support material, and the polymer fine particle layer is laminated on the polymer electrolyte membrane. It is preferable. When laminating the polymer particles by the alternate adsorption method using electrostatic interaction, it is necessary to apply a charge having a polarity different from the polarity of the polymer particles on the support material. At this time, it is possible to impart the charge to the surface of the support at a high charge density by imparting the charge with the polymer electrolyte membrane, and to uniformly attach the polymer fine particles onto the support.

In the invention described in claim 8, as described in claim 9, 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 formed, and thus unnecessary multilayering of polymer particles in the polymer particle layer can be prevented.

In the invention described in claim 8 or claim 9, it is preferable that the polymer electrolyte membrane is a crosslinked polymer electrolyte membrane. 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 10, as described in claim 11, the adhesion between the polymer fine particle layers is caused by the electrostatic interaction. In addition to the above-mentioned adhesion, it is preferable that the adhesion is further performed by a reinforcing adhesion means. Only by electrostatic interaction, the adhesion force of fine particles to the surface of the support,
Adhesive force between the polymer fine particle layers laminated in a plurality of layers may be insufficient, which may cause problems such as insufficient strength. 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 11, as described in claim 12, the reinforcing attachment means includes 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. Such adhesion improves strength and the like, and since the polymer fine particles are fixed in the polymer fine particle 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 11, as described in claim 13, the reinforcing adhering means embeds the layered body while leaving one surface of the layered polymer fine particle layer. It may be a sealing material.
For example, when the strength of the polymer fine particle layer laminate itself is extremely weak, or when it is inconvenient for the polymer fine particle layer laminate to be deformed by moisture or the like, the polymer except for the support side surface is used. By embedding and sealing the fine particle layer laminate, it is possible to secure strength and prevent deformation.

In the invention described in any one of claims 1 to 13, the polymer fine particle layer laminate is formed in a pattern as described in claim 14. It may be one. This is because by forming the polymer fine particle layer laminate in a pattern, it can be used for various applications such as color filters, lens arrays, and optical waveguide circuits.

The present invention also provides, as described in claim 15, a charge imparting step of imparting a charge to the surface of a base material, and dispersion of polymer fine particles having a charge having a sign opposite to that of the charge applied to the surface of the base material. A step of forming a polymer fine particle layer by applying a liquid onto the base material to form a polymer fine particle layer, wherein the polymer fine particles have a functional layer consisting of a functional functional group in the outer peripheral portion, Provided is a method for producing a polymer fine particle layer laminate, which is a core-shell type microsphere having an adsorption layer having an electric charge capable of being adsorbed by electrostatic interaction therein. As described above, the formation of the polymer fine particle layer laminate on the support can be performed by applying the polymer fine particle dispersion liquid on the surface of the support having an electric charge, thus simplifying the manufacturing process. , And efficient. Therefore, it is possible to manufacture a polymer fine particle layer laminate which is cost effective.

In this case, as described in claim 16,
The core-shell microspheres are preferably dendrimers or hyperbranched polymers.
This is because a dendrimer or hyperbranched polymer can collect functional functional groups in the outer peripheral portion, and the resulting polymer fine particle layer laminate can effectively exhibit its function.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The inventor of the present invention arranges a functional functional group on the outer peripheral portion of a core-shell type microsphere, and laminates a polymer fine particle layer filled with this with high density,
Focusing on the fact that it can be applied to functional elements having various functions, and found that such a polymer fine particle layer laminate can be obtained by the alternate adsorption method using electrostatic interaction, The present invention has been completed. Hereinafter, the polymer fine particle layer laminate of the present invention will be described in detail.

The polymer fine particle layer laminate of the present invention comprises a core
A plurality of polymer fine particle layers containing polymer fine particles that are shell type microspheres are laminated, and the core-shell type microsphere has a functional layer composed of a functional functional group in the outer peripheral portion, It is characterized in that it is a polymer fine particle having an adsorption layer having an electric charge capable of being adsorbed by electrostatic interaction.

The polymer fine particle layer laminate of the present invention as described above will be described separately for each element.

(Polymer Fine Particles (Core-Shell Type Microspheres)) The core-shell type microspheres used in the present invention can be alternately adsorbed by forming a core as a central part and a reactive monomer as a starting point. A shell that forms the peripheral field is formed, and it exists as microspheres in the alternate adsorption developing solution.

When the core is in a state of being as close to a molecule as possible, it is in the state of a dendritic monomer. In this regard, the synthesis of dendritic (meth) acrylates has also been reported. (W. Shi et al., J. Appl. Poly.
m. Sci. Part A, 32, 1639 (199
4). ) The core-shell type microspheres used in the present invention are
This may be used as it is, or this derivative may be used. Furthermore, a dendrimer or a hyperbranched polymer may be used. The dendrimer is an ideal single molecular weight polymer having a so-called mesoscopic size with a substantially spherical molecular shape and a diameter of several nm to several tens of nm. On the other hand, the hyperbranched polymer has an advantage that it can be synthesized relatively easily by polymerizing an AB ₂ type monomer. Although it is inferior to dendrimers in terms of molecular morphology and function, it is more advantageous than dendrimers from an industrial viewpoint, and can exhibit excellent properties that linear polymers do not have.

A general method for producing such a core-shell type microsphere of the present invention will be described below.

Generally, the core portion is subjected to dispersion copolymerization using a macromonomer to synthesize microspheres. The macromonomer serves not only as a stabilizer (also referred to as a dispersant) but also as a comonomer. In the present invention, a t-butyl methacrylate macromonomer having a vinylbenzyl group at the terminal may be used, for example, by anionic living polymerization. Microspheres can be formed by copolymerizing the synthesized macromonomer with divinylbenzene using azoisobisbutyronitrile (AIBN) as an initiator in methacrylate.

Further, when the shell chain of microspheres is used, for example, polystyrene chains are chloromethylated and then polymerized with a living radical polymerization initiator to introduce a diethyldithiocarbamate group. By grafting a monomer, a reactive functional group serving as a fixed base point, for example, a double bond of PMMA or the like can be introduced. The size of the core-shell type microsphere varies depending on the macromonomer concentration, divinylbenzene concentration, and the like.

Further, a multi-branched polymer having a minimum core diameter can also be used, but this is also synthesized by radical polymerization (polymer, 11, Vol. 47 (199).
8). B, Yamada, Polym. , 39,371
(1998). ).

Further, the method of synthesizing the dendrimer used in the present invention includes Diver which is synthesized from the center to the outside.
Gent method and Converg from the outside to the center
It is roughly classified into the ent method. Regarding the dendritic polymer, refer to the following review and omit the description here (D.
A. tomalia; Nikkei Science, July issue, 38,
(1995). ). Regarding the hyperbranched polymer as well, refer to the following review article and omit the description here (D.
Holter: Acta. Polym. 48.30 (1
997). ).

When such a core-shell type microsphere is used as an optical functional agent, it is preferably optically transparent, particularly transparent in the visible light region. In the case of a polymer particle layer laminated body using a dendrimer as polymer particles, it can be designed such that various sizes of hydrophobic or hydrophilic pores are formed not only on the surface but also inside.

Such a core-shell type microsphere used in the present invention has a functional layer composed of a functional functional group on the outer peripheral portion, and is internally adsorbed by electrostatic interaction. It is characterized by having an adsorption layer having an electric charge.

The adsorption layer in the present invention is a layer arranged inside the outer peripheral portion of the polymer fine particles, that is, the core-shell type microspheres. As described above, the polymer fine particle layer laminate of the present invention is It is composed of a substance that can have a positive or negative charge required when manufacturing by the alternate adsorption method using electrostatic interaction. The adsorption layer may be the shell portion, the core portion, or both of them in the core-shell structure, but the shell portion is usually the adsorption layer. That is, it is necessary that the compound constituting the shell portion has a charge to such an extent that it can be alternately adsorbed by the electrostatic interaction as described above.

In the present invention, the compounds and structural formulas constituting such an adsorption layer are specifically shown in the following table.
First, examples of the bifunctional or higher functional monomer that can be used in the shell portion include acrylate monomers and methacrylate monomers. Among these, the following may be mentioned as acrylate monomers.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

The following can be mentioned as the methacrylate monomers.

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

[Table 7]

The following compounds can be used as the compound usable in the core part.

[0045]

[Table 8]

[0046]

[Table 9]

The compound usable in the core part can be introduced into the shell part. In the present invention, it is preferable to use the above compound from the viewpoint of effectively imparting electrostatic adsorption force to the adsorption layer.

On the other hand, it is preferable to obtain the adsorption layer by the method shown in FIG. 1 from the viewpoint of easiness of synthesis, and further, easy obtaining of the derivative. The functional monomer in the figure is
The film-forming monomer corresponds to the functional functional group referred to in the present invention, and the film-forming monomer corresponds to the monomer forming the adsorption layer.

Next, the compounds that can be used for the end cap (used for stopping the growth end) are shown below.

[0050]

[Table 10]

[0051]

[Table 11]

On the other hand, the above-mentioned functional layer is composed of functional functional groups added to the outer peripheral portion of the polymer fine particle layer, that is, many terminals existing in the polymer constituting the core-shell type microsphere. It is a thing. This functional layer is
It is the part that determines the properties of the polymer particle layer laminate of the present invention, and the function and application of the polymer particle layer laminate of the present invention are determined by the properties of this functional layer.

Therefore, various kinds of functional functional groups constituting such a functional layer can be used depending on the use (function) of the polymer fine particle layer laminate of the present invention.

Specifically, a polymer fine particle layer laminate having a refractive index much higher than that of a glass substrate and air is formed on a glass substrate, and light incident on this polymer fine particle layer laminate is When the polymer fine particle layer laminate of the present invention is used for an interference film in which only the light that has escaped to outside light exhibits coherence (coloring) by total reflection and refraction on both sides of the polymer fine particle layer laminate, for example, An aromatic chromophore represented by the following chemical formula can be used as a functional functional group.

[0055]

[Chemical 1]

Further, 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 electron transfer, resulting in photocurrent. Observed, when applying the polymer fine particle 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 Is shown in the chemical formula) and the like can be used.

[0057]

[Chemical 2]

The polymer particle layer laminate of the present invention may be formed by using only one kind of such polymer particles, and if necessary, a plurality of kinds of polymer particles may be used. It may be formed.

At this time, a polymer fine particle layer laminated body in which a plurality of kinds of polymer fine particles are filled in each polymer fine particle layer to form a polymer fine particle layer, and the polymer fine particle layer is laminated may be used. Although the polymer fine particle layer is filled with a single type of polymer fine particles, the type of polymer fine particles may be different between the layers.

Specifically, in the case of forming a polymer particle layer laminate having polymer particles A and polymer particles B,
A polymer fine particle layer in which the polymer fine particles A and the polymer fine particles B are mixed may be laminated, and the polymer fine particle layer composed of the polymer fine particle A and the polymer fine particle B may be laminated. It may be a polymer fine particle layer laminated body formed by laminating and. How many kinds of polymer fine particles are used, what kind of layer structure is used, and the like are designed and determined depending on the intended use of the polymer fine particle layer laminate.

In the present invention, the particle size of such fine polymer particles varies greatly depending on the intended use, the required function and the like. In view of having a feature of exerting a function, it is generally 10 nm to 300 nm.
It can be said that the particle size is preferably in the range of, preferably in the range of 15 nm to 100 nm.

The fine polymer particles used in the present invention are preferably dendrimers or hyperbranched polymers. Therefore, it is generally considered that one fine polymer particle is usually composed of one molecule.
From such a viewpoint, the average molecular weight of the polymer constituting the polymer fine particles used in the present invention is 100 to 30.
It is preferably in the range of 000, particularly in the range of 150 to 3000. This is because by setting the range of the molecular weight within this range, the particle size of the polymer fine particles can be set within the preferable range.

(Polymer Fine Particle Layer) The polymer fine particle layer laminated body of the present invention is formed by laminating the polymer fine particle layers in which the above-mentioned polymer fine particles are densely packed.

In the present invention, the density of the polymer fine particles in the polymer fine particle layer is in the range of 40 to 80% in volume percentage, although it varies depending on the use.
In particular, it is preferably in the range of 45 to 80%. As described above, the present invention exerts a function by the functional layer formed on the outer periphery of the polymer fine particles,
If the packing density is smaller than the above range, it may not be possible to exhibit the required function, which is not preferable, and it is not realistic to make the packing density larger than the above range at this time. .

The polymer fine particle layer in the present invention has the polymer fine particles filled with the above density and the gas (usually air) existing between them. However,
For example, when a polymer electrolyte membrane is used for lamination, this polymer electrolyte may be contained in the layer, as described in the section of the method for producing a polymer particle layer laminate described later. Further, as will be described later, in the case of using the reinforcing attachment means, a predetermined resin or the like may be inserted between the polymer particles.

In the present invention, such a polymer fine particle layer is laminated to form a polymer fine particle layer laminated body, and the number of laminated layers can be appropriately selected according to the required function and application. It is possible, and it varies greatly depending on the required film thickness and function. In general,
It may be in the range of 2 to 200 layers, preferably in the range of 3 to 100 layers.

The polymer particles in this polymer particle layer are
As described above, it may be a single type or a mixture of a plurality of polymer fine particles. As described above, the polymer fine particle layers containing different types of polymer fine particles may be laminated.

(Supporting Material) The present invention is a polymer fine particle layer laminate in which polymer fine particle layers filled with polymer fine particles as described above are laminated. Such a laminate is self-supporting. In some cases, a support material may be provided depending on the presence or absence of the product and the application.

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

The material and shape of such a supporting material are largely different depending on the application, and the material is required to be transparent when it is used for optical applications. 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, and a complicated shape.

The application of the polymer fine particle layer laminate of the present invention is
For example, in the case of applications that make full use of optical functions, 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.
In many cases, the size of μm is used.

(Electrostatic Interaction) In the present invention, as described above, the fine polymer particles have an adsorption layer having an electric charge to the extent that they can be adsorbed by electrostatic interaction. Due to the function of the layer, the polymer fine particles are laminated on the base material by electrostatic interaction to form a polymer fine particle layer laminated body. In addition, in the polymer fine particle 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 from this base material and used. Further, it may be used by being transferred to another support, if necessary.

As described above, the adhesion of the polymer fine particles on the base material, in other words, the formation of the polymer fine particle layer on the base material is performed by electrostatic interaction. It is possible to form a polymer fine particle layer laminate capable of arranging fine particles uniformly on the base material and exhibiting various functions on the base material.

When the fine polymer particles are attached to the substrate by such an electrostatic interaction, generally, either positive or negative charges are applied to the substrate, and an adsorption layer having a polarity opposite to this charge is formed. By using the formed polymer fine particles, a method of adhering the polymer fine particles on the substrate by electrostatic interaction is adopted.

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 into 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, in general, the higher the charge density on the surface of the base material, the higher the functional polymer fine particle layer in which the fine polymer particles are uniformly attached 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, a polymer electrolyte membrane is formed on a substrate, and the electrostatic interaction between the polymer electrolyte membrane and the polymer fine particles causes the fine particles to adhere to the substrate, that is, the polymer electrolyte. A fine polymer particle layer in which fine particles are uniformly attached can be formed,
A polymer fine particle layer laminate having high functionality can be obtained.

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 adsorption layer of polymer fine particles is limited to cations. On the other hand, the polyelectrolyte can have anionic property and cationic property, and the density and balance thereof can be arbitrarily selected, so that the charge of the adsorption layer of the polymer particles is not limited to either anion or cation.
From this point as well, as a method of imparting an electric charge to the surface of the substrate,
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 diameter of the polymer fine particles, and the thickness of the polymer electrolyte is further adjusted. It is preferable that the average particle size of the polymer particles is less than 50%. When the film thickness of the polymer electrolyte membrane is equal to or larger than the average particle size of the fine particles, the fine polymer particles cannot be uniformly filled in the fine polymer particle layer, for example, the fine polymer particles are partially laminated in two or more layers. As a result, it may not be possible to obtain a polymer fine particle 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 polymer particles, the polymer particle layer is formed of a single particle film. This is because the polymer electrolyte multilayer film is a polymer complex that is insoluble in the medium (mainly water), hardly diffuses into the medium, and the polymer particles interact only with almost the surface of the polymer electrolyte multilayer film. Because.

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, core-
There are no reports or descriptions focusing on single particle films composed of shell-type microspheres.

Further, in the present invention, the polymer electrolyte forming the polymer electrolyte membrane is preferably a crosslinked polymer electrolyte. By using the crosslinked polymer electrolyte, it is possible to prevent unnecessary and inconvenient multilayering of the polymer particles in the polymer particle 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 as described above, and the polymer particles are attached to the polymer electrolyte layer to form the polymer particle layer. Then, the polymer electrolyte membrane is further formed on the polymer electrolyte layer to form the polymer electrolyte again. When the polymer fine particle layer laminate is formed by repeating the step of attaching the fine particles, the polymer electrolyte is present in each polymer fine particle layer unless the polymer electrolyte is removed thereafter. In addition, after forming the polymer electrolyte membrane on the substrate and attaching the first polymer fine particle layer, the charge of the adsorption layer of the polymer fine particles is changed so that the polymer electrolyte membrane is not interposed. It is also possible to stack a polymer fine particle layer without using it. In this case, the polymer electrolyte does not exist in the second or higher layer of polymer fine particles.

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 others, quaternized polyethyleneimine, 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 cross-linked 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 polymer fine particle layer laminated body of the present invention forms a polymer fine particle layer by adhering polymer fine particles on a substrate by electrostatic interaction, and laminating this. It will be. At this time, if the polymer particles adhere to each polymer particle layer only by electrostatic interaction and between the support material and the polymer particle layer when the base material is used as the support material, the actual use At that time, problems such as scratch resistance may occur. In such a case, a reinforcing adhesion means for improving the adhesion of the polymer fine particle layer laminate may be used.

The reinforcing attachment means is not limited to this, but for example, such a polymer fine particle layer is filled with an actinic radiation-reactive monomer and a polymerization initiator, and these are added. Examples thereof include a curing method and a method of embedding the polymer fine particle layer laminate in a sealing material while leaving one surface thereof.

In addition, as a reinforcing attachment means, a method of dry laminating on a support on which a polymer fine particle layer laminate is formed, a method of extrusion coating the polymer fine particle layer laminate, a film adhesive And a method of applying a pressure-sensitive adhesive to the support material and the polymer fine particle layer laminate, and a method of point-adhesion or line-adhesion.

In the method of filling the above-mentioned polymer fine particle layer with the actinic radiation-reactive monomer and the polymerization initiator and curing it, the polymer fine particles are fixed in the polymer fine particle layer in addition to the reinforcing effect. By doing so, it is possible to obtain an unprecedented optical function, for example, an interference film having a narrow half-wavelength half, which utilizes the effect that the superlattice structure having a fixed function in the film diffracts light of a specific wavelength by Bragg reflection. It will be possible. 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 means 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. The reactive monomer may have the same composition as the shell part of the core-shell structure of the polymer particles.

Specific examples of such reactive monomers 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 for generating radicals by absorbing active radiation to initiate the polymerization of the above reactive monomers.

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 radicals necessary for the above reactive monomers 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 non-volatile components of the composition.

Furthermore, when the above-mentioned polymer fine particle layer laminate of the present invention is irradiated with an active radiation ray, the lamps used also emit the active radiation ray which is most absorbed by each of the contained polymerization initiators. Used. Specifically, it is possible to use a UV irradiation light source (UV lamp). In this case, each polymer fine particle layer is laminated, the reactive monomer and the polymerization initiator are filled in the polymer fine particle layer, and then exposed to UV light and cured to obtain a film. UV exposure is performed by an apparatus such as an aligner, a stepper and a proxy. Further, as the exposure radiation source, it is preferable to use an irradiation wavelength of 230 nm to 480 nm, optimally 320 nm to 420 nm, such as metal halide and short arc Xe.

Further, when UV exposure and curing are carried out under oxygen-blocking conditions, the generated radical deactivation is suppressed, the curing sensitivity is increased, and it is possible to uniformly cure even deep areas. 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 will be described in which the polymer fine particle layer laminated body is embedded with a sealing material leaving one surface thereof. If the sealing material 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 and oxygen depending on the type of polymer fine particles,
This is suitable when it is inconvenient to deform due to moisture or the like.

In the present invention, the polymer fine particle layer laminate is embedded in the encapsulating material while leaving one surface thereof. However, this is based on the assumption that the support is present on this one surface. It was done. Therefore, when the polymer fine particle layer laminate is not formed on the support, it may be one in which the encapsulating material is formed over 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 polymer fine particle layer laminate is utilized. It is preferable.

As a resin component for forming such a transparent sealing material, 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 transparent encapsulant, acrylic resin and epoxy resin are preferable from the viewpoint of adhesion and adhesiveness with the polymer fine particle layer laminate to be encapsulated, and more preferable epoxy As the resin, Epicoat series manufactured by Mitsubishi Yuka Shell Co., 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 glycidyl ester, fatty acid or alicyclic epoxy resin, amino epoxy resin, triphenol methane type epoxy resin, dihydroxybenzene type epoxy resin,
Examples thereof include a copolymerized epoxy compound of glycidyl (meth) acrylate and a monomer capable of radical polymerization.

(Patterning of Polymer Fine Particle Layer Laminate) The polymer fine particle 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 fine polymer particle layer laminate in a pattern as described above, a hydrophilic / hydrophobic pattern or an acid / base pattern is formed on a substrate, and the fine polymer particle layer laminate is formed on this. If necessary, it can be formed by a method of sealing with the above-mentioned sealing material.

(Method for Producing Polymer Fine Particle Layer Laminate) The method for producing a polymer fine particle layer laminate according to the present invention comprises a step of imparting an electric charge to the surface of a base material and a charge imparted to the surface of the base material. And a polymer fine particle layer forming step of forming a polymer fine particle layer by coating a polymer fine particle dispersion liquid having a charge of the opposite sign with the above base material, and the polymer fine particle has a functional property on the outer peripheral portion. The core-shell type microsphere is characterized by having a functional layer composed of a functional group, and having an adsorption layer having an electric charge that allows adsorption by electrostatic interaction inside.

In the present invention, a charge applying step of applying charges 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 polymer fine particle layer laminate has self-supporting property, the polymer fine particle layer laminate is It may be peeled off after formation, and further, after the polymer fine particle layer laminate is formed on the base material, it may be transferred onto a separately-supported support material.

Regarding the method of imparting an electric charge on the substrate,
The description is omitted here because it is the same as the above. As described above, in the alternate adsorption method, since the polymer fine particles are attached to the base material by electrostatic interaction, by applying either positive or negative charge to the substrate, this charge is applied in the subsequent step. By using the polymer fine particles including the adsorption layer having the opposite polarity, the polymer fine particles can be attached to the substrate.

Then, a polymer fine particle layer forming step of forming a polymer fine particle layer by applying a polymer fine particle dispersion liquid having a charge having a sign opposite to that of the charge applied to the surface of the substrate to the polymer fine particle layer is carried out. Be seen.

The polymer fine particles used here are the same as those described above, and thus the description thereof is omitted here. However, the polymer fine particle layer used at this time has an adsorption layer of a base material or the like. An electric charge different from the electric charge applied to the coated surface of is used.

In the present invention, as described above, when the polymer fine particle layer is laminated, the charge of the polymer fine particle to be laminated is changed between positive and negative without interposing the above-mentioned polymer electrolyte membrane. You may make it laminate | stack a layer. In this case, since the polymer particle layer laminated body can be obtained with the polymer particle layer which does not include the polymer electrolyte membrane which is included in the general alternate adsorption method, the polymer particle layer laminated body is It is possible to prevent the inconvenience that the ability of various functions possessed is hindered by the polymer electrolyte, and it is possible to exert a sufficient effect.
Furthermore, in this case, if a charge is applied to the substrate without depending on the polymer electrolyte membrane, a polymer fine particle layer laminated body containing no polymer electrolyte can be obtained.

In the present invention, the concentration of the polymer particles in the polymer particle dispersion is from 1% by volume to 70% by volume, preferably from 1% to 55% by volume, and particularly preferably from 1% by volume to 55% by volume. Preferably 3% to 50% by volume
Within the range of.

When a dendrimer is used as the polymer particles in the polymer particle dispersion used in this step, the relationship between the molecular weight of the dendrimer and the viscosity is examined, and the viscosity can be reduced because the radius of gyration is small. It is highly likely. Therefore, when it is difficult to stack polymer fine particle layers by the alternate adsorption method, a small amount of thickeners such as silica and clathrates, dispersants, stabilizers, and other additives are added for modification. May be.

Further, a viscosity modifier, a fluidity modifier, a rheology control agent and the like may be added to improve the laminated state of the fine polymer particle layer and the film suitability. Specific examples include fine particles of metal oxides such as talc and titanium oxide, silica, silica sol (or gel), polysaccharides such as Shin-Etsu Chemical's cellulose series (MC series, alkali-soluble cellulose), and silicone oil. However, these may be added in an amount of 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 a core-shell type microsphere polymer fine particles, for uniformly laminating when laminated using a polymer fine particle dispersion, or to maintain or improve the homogeneity of the polymer fine particle dispersion, Is used to improve the film quality of the polymer fine particle layer laminate formed. 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 Sols Perth 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 with this, 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%.

Furthermore, when the polymer fine particle layer laminated body places importance on the characteristics of the dye absorbing film and the coloring functional film, the polymer fine particle is added by adding a colorant or a coloring agent to the above polymer fine particle dispersion. These colorants or colorants may be incorporated at the same time when the layer is formed.

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 above polymer fine particle dispersion contains 0.5 to 1
It is also possible to add about 0% by weight of an ultraviolet absorber and also about 0.5 to 10% by weight of a light stabilizer. This is because the weather resistance of the resulting polymer fine particle layer laminate can be further enhanced.

As such an ultraviolet absorber, for example, an organic compound such as benzotriazole, benzophenone, salicylic acid ester or the like, or an inorganic compound such as fine particle zinc oxide or cerium oxide having a particle diameter 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 polymer fine particle layer laminate is provided on the base material, the surface of the base material is subjected to activation or roughening treatment such as corona discharge treatment, or anchor coating is applied on the base material film. It is also possible to form the polymer fine particle layer laminate after taking measures to improve the adhesion to the substrate, such as providing a layer.

(Use) The use and function of the polymer fine particle layer laminate of the present invention include, for example, in the case of using a dendrimer for optical function design, the photocharge trapping ability itself (Aida et al. It has already been reported by Aida et al.

Other than the above-mentioned interference film and photoelectric conversion film, it can be used for various applications such as a photodiode, an EL device, a solar cell, and a photorefractive film (device).

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.

[0135]

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

[Example 1] (Core-shell type microsphere material (fine polymer particles)) A cationic dendrimer having a porphyrin skeleton as a core was synthesized based on the report of Kawakami et al. (J. Che.
m. Soc, 1990, 2713. ).

That is, a cationic bis-fence metal porphyrin complex having a fence structure was obtained from isonicotinic acid, and this dendrimer was used as a multi-cation dendrimer in which isonicotinic acid was bound to the metal porphyrin complex.

Next, as another core-shell type microsphere, a report by Sawamoto et al. By Living Cationic Polymerization (Macromolecules, 23, 2309 (1
What was synthesize | combined based on 991)) was used. That is, a star polymer having an amphiphilic block polymer as a branch by reacting a living polymer with a bifunctional vinyl compound was used.

As reagents and solvents used in each synthesis, commercially available products purified by distillation or recrystallization were used. The reagents used were those of Wako Pure Chemical Industries, Ltd.

Polyacryl methacrylate (PMMA)
The crosslinkable microspheres were synthesized as follows. P
The MMA ultrafine particles were synthesized as follows by emulsion polymerization of AMA. After using potassium persulfate as a polymerization initiator and sodium dodecylsulfate as an emulsifier for a predetermined period of time (to control the molecular weight), the mixture was poured into cold methanol containing an inhibitor to precipitate a polymer. Polymerization of PMMA ultrafine particles and allyl benzoate (ABz) is carried out using a predetermined amount of ABz of P
The MMA ultrafine particles were dissolved and polymerized using BPO as an initiator for a predetermined time and then poured into cold hexane containing an inhibitor to precipitate a polymer. The extraction of ultrafine particles was performed using THF as an extraction solvent.

The particle size of the microspheres varies depending on the polymerization temperature, ranging from 40 nm to 360 nm and 1
A relatively narrow range of 70 nm to 280 nm was obtained.

Polymerization rates of about 15%, 45%, and 70% were obtained, and the molecular weights from 2000 to 50,000 were large according to the light scattering measurement. Ultrafine particle addition amount and UV
The curing due to photocrosslinking by irradiation was measured as a gelation rate, and as a result, it was found to be 25%, 34%, 26.5%, and the crosslinking efficiencies were different. From this, it was confirmed that after alternately adsorbing and laminating the PMMA ultrafine particles in such an amount that the dangling chains of the ultrafine particles overlap with each other, crosslinking and curing can be carried out via the polyfunctional vinyl group.

(Formation of Polymer Electrolyte Membrane) Film formation of the polymer electrolyte membrane was carried out as follows by controlling the adsorption mass. The developing solution was as follows. A cationic polydiallyldimethylammonium chloride (hereinafter abbreviated as PDDA; average molecular weight: 150,000, manufactured by Aldrich) was used to impart a cationic charge. Sodium polystyrene sulfonate (hereinafter abbreviated as PSS; average molecular weight 70,000, manufactured by Aldrich Co.) was used for giving an anionic charge.

0.4 wt% PDDA in water and 0.4
A washed glass substrate (1.
1mm, NA-45, NH Techno Glass)
DDA and PSS are repeatedly adsorbed eight times, and finally P
An alternate adsorption film was prepared by adsorbing SS, 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.

(Formation of Polymer Fine Particle Layer Laminate) Using the charge-imparting base material described above, a laminated film was formed on both surfaces as follows. PSS surface / cationic dendrimer / star polymer / cationic dendrimer / star polymer / P
MMA ultrafine particles / star polymer PMMA ultrafine particles / star polymer were laminated 5 times in this order. The adsorption time of the resin ultrafine particles used for each layer was 1 minute each, and the adsorption time of the PMMA ultrafine particles was 2 minutes. The time for washing with water during the adsorption was 2 minutes. Each layer can be laminated by the alternate adsorption method, and a laminated film can be produced. Furthermore, it was visually confirmed that the laminated film thus formed had optical coherence.

(Evaluation) The particle size and particle size distribution were measured by
The measurement was performed using a laser particle size analyzer manufactured by Nikkiso Co., Ltd. The cross section of the obtained laminated film was observed with a scanning electron microscope H-5000. Since it was difficult to observe the interface and the layers constituting it, dye it with an osmium dye and an azo dye,
I observed. It was confirmed that two different types of core-shell type microsphere layers were laminated.

(Production of Optical Functional Agent) Further, an optical functional material was produced as follows.

On the ITO glass substrate, a cyanine dye / dendrimer having a phthalocyanine skeleton as a core was adsorbed 30 times in this order by the above-mentioned alternate adsorption method to form a laminated film, and then a sandwich cell of a gold counter electrode was prepared. As a result of light irradiation from the ITO side with a 500 W short arc xenon lamp (manufactured by Showa Denko KK), it was confirmed that photoelectromotive force was generated, and a new optical functional film was obtained by combining the dye laminated films in consideration of electron transfer. I was able to make it.

[0149]

EFFECTS OF THE INVENTION According to the present invention, since the fine polymer particles have an adsorption layer having an electric charge capable of being adsorbed by electrostatic interaction, alternate adsorption using electrostatic interaction is performed. By using the method, it is possible to form a polymer fine particle layer laminate in which the core-shell type microspheres are densely packed. Therefore, the polymer fine particle layer laminate of the present invention can be effectively used as a functional element that maximizes the function of the functional layer composed of the functional functional groups located on the outer peripheral portion of the polymer fine particles, The present invention has an effect that various applications can be developed.

[Brief description of drawings]

FIG. 1 is an explanatory diagram illustrating an example of a method of forming an adsorption layer.

Claims (16)

[Claims] 1. A functional layer comprising a plurality of polymer fine particle layers containing polymer fine particles which are core-shell type microspheres, wherein the core-shell type microspheres have a functional functional group on the outer peripheral portion. A polymer fine particle layer laminated body, which is a polymer fine particle layer laminate having a layer and an adsorption layer having an electric charge to an extent capable of being adsorbed by electrostatic interaction. 2. The core-shell type microsphere comprises:
The polymer fine particle layer laminate according to claim 1, which is a dendrimer or a hyperbranched polymer. 3. The polymer particle layer laminate according to claim 1, wherein a plurality of kinds of polymer particles are used. 4. A polymer particle layer laminated body in which a plurality of polymer particle layers made of the same kind of polymer particles are laminated, wherein the kind of polymer particles is different between the polymer particle layers. The polymer fine particle layer laminate according to claim 3. 5. The diameter of the polymer fine particles is 10 nm to 3
It is in the range of 00 nm, The polymeric fine particle layer laminated body in any one of Claim 1 to 4 characterized by the above-mentioned. 6. The polymer according to claim 1, wherein the polymer constituting the polymer fine particles has an average polymerization number molecular weight in the range of 100 to 30,000. Polymer microparticle layer laminate. 7. The polymer fine particle layer laminate according to claim 1, wherein the polymer fine particle layer is laminated on a support material. 8. The polymer according to claim 7, wherein a polymer electrolyte membrane is formed on the support material, and the polymer particle layer is laminated on the polymer electrolyte membrane. Fine particle layer stack. 9. The polymer fine particle layer according to claim 8, wherein the polymer electrolyte membrane is a multi-layer film formed by laminating two or more kinds of polymer electrolyte membranes having different polarities from each other. Laminate. 10. The polymer fine particle layer laminate according to claim 8 or 9, wherein the polymer electrolyte membrane is a crosslinked polymer electrolyte membrane. 11. The adhesion between the polymer fine particle layers is, in addition to the adhesion by the electrostatic interaction, further adhered by a reinforcing adhesion means. The polymer particle layer laminate according to any one of claims. 12. The reinforcing adhesion means comprises means for containing an actinic radiation-reactive monomer and a polymerization initiator in the polymer layer laminate, and curing these by irradiation with actinic radiation. The polymer fine particle layer laminate according to claim 11. 13. The reinforcing attachment means is formed of a sealing material that embeds the polymer fine particle layer laminated body leaving one surface of the laminated body.
The polymer fine particle layer laminate according to item 1. 14. The polymer fine particle layer is formed in a pattern, according to any one of claims 1 to 1.
The polymer fine particle layer laminate according to any one of claims 3 to 3. 15. A charge applying step of applying a charge to the surface of a base material, and a polymer fine particle dispersion 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 polymer. A fine polymer particle layer forming step of forming a fine particle layer, wherein the fine polymer particles have a functional layer composed of a functional functional group on the outer peripheral portion and can be adsorbed by electrostatic interaction inside. A method for producing a polymer fine particle layer laminate, which is a core-shell type microsphere having an adsorption layer having a certain degree of charge. 16. The method for producing a polymer fine particle layer laminate according to claim 15, wherein the core-shell type microsphere is a dendrimer or a hyperbranched polymer.