WO2016151933A1 - Composition and optical functional film including same - Google Patents

Abstract

[Problem] To provide: a composition which can be either water-soluble or oil-soluble, is excellent in terms of various properties including luminescent efficiency, durability, and stability of an emission wavelength peak, has excellent heat resistance, and is highly inhibited from suffering binder resin deterioration; and an optical functional film. [Solution] A composition which comprises inorganic nanoparticles and a ligand adsorbed on the inorganic nanoparticles and having at least one adsorbable group, wherein the ligand is a nonionic organic compound or an oxide compound and the adsorbable group is either an oxoacid residue which contains a sulfur or phosphorus atom as a central atom or an N-oxide group.

Description

Composition and optical functional film containing the same

The present invention relates to a composition and an optical functional film containing the composition.

When the size of metals and semiconductors is in the nano-range, physical and chemical properties that are different from those of bulk, such as drastic reduction in melting and firing temperatures, fluorescence emission, higher catalyst efficiency, and new reactions It is known to show such as. These are thought to be due to an increase in the movement, diffusion, and solubility of atoms due to the high surface area, the quantum size effect, or the influence of the surface and interface. For example, when light hits the surface of titanium oxide, which is a semiconductor, electrons are generated in the conduction band and holes are generated in the valence band in titanium oxide. In particular, since holes have strong oxidizing power, attempts are being made to remove contaminants (NOx, formaldehyde, etc.), electrochemical solar cells, and electrophotography. Increasing the specific surface area as a photocatalyst leads to an improvement in activity, so it is effective to use ultrafine particles or nanoparticles having a small particle size.

In the quantum dot (QD), excitons of a substance such as a semiconductor are confined in all directions in a three-dimensional space. As a result, such materials have intermediate electronic properties between bulk semiconductors and discrete molecular systems. The quantum dots can control the emission wavelength according to the size of the dots, that is, can perform color conversion according to the emission wavelength. When excitation light emitted from a blue LED or the like is applied to a quantum dot having a specific particle diameter, green light emission or red light emission is emitted, and white light having a narrow spectrum peak of three primary colors can be obtained. The white light is obtained by concentrating a large amount of visible energy in the narrow wavelength region of the three primary colors of red, green, and blue, that is, it generates little light outside the narrow wavelength region. Therefore, clear colors and high efficiency can be obtained.

In this way, quantum dots (QD) have the characteristic of concentrating a large amount of visible energy in the narrow wavelength region of the three primary colors red, green, and blue, so that quantum dots with green and red emission spectra diffuse into the polymer. In addition to the color gamut expansion film thus formed, its application is expected for various optical functional films such as a color filter and a color tone conversion filter.

In particular, the above-described color gamut expansion film is expected to improve the color tone (spectrum) of the backlight by applying it to a liquid crystal display, and greatly improve the colors that can be displayed on the liquid crystal display.

The conventional general liquid crystal display can express only about 20% to 30% of colors that can be identified by humans, but it can be reduced to about 60% by applying a color gamut expansion film as an optical functional film. It can be raised.

As described above, optical functional films to which quantum dots are applied are highly expected from the viewpoints of light emission efficiency and the like for the various uses described above. However, quantum dots deteriorate due to oxygen, light, and heat, and emit light. There is a problem that the intensity (luminous efficiency) decreases. One of the causes is considered that the quantum dots have surface atoms that serve as ligand sites, and thus have high reactivity and are likely to cause aggregation of particles.

In order to solve such a problem, there exists a technique for capping surface atoms with a protecting group (ligand) to immobilize them (Patent Document 1: US Patent Application Publication No. 2014/275431).

However, at present, it is not sufficiently stabilized, and deterioration due to oxygen, light, and heat cannot be suppressed, and conventional optical functional films have various properties such as light emission efficiency, durability, and stability of light emission wavelength peak. The characteristics were not sufficient. In addition, the quantum dots have extremely high luminance and are less likely to be discolored by excitation light compared to organic fluorescent dyes and fluorescent proteins. Therefore, high-sensitivity fluorescence observation over a long time is possible. In addition, it is easy to observe with multi-color fluorescence after excitation at one wavelength, and it is possible to develop multi-color fluorescent probes in cells or living bodies by modifying the quantum dots with antibodies and ligands for receptors. . In order to work for biological labeling, it is necessary to be soluble in water, but the quantum dot itself is not soluble in water and is synthesized using a hydrophobic capping agent in a nonpolar solvent, It does not have a functional group that is covalently bonded to a biomolecule. The water solubilization method includes a method of exchanging the hydrophobic capping agent with an amphiphilic thiol compound (ligand exchange method) and a method of coating with an amphiphilic polymer while leaving the hydrophobic capping agent (encapsulation). Law). However, in the former case, emission characteristics such as a decrease in quantum yield and agglomeration occur, and in the latter case, the particle size of the generated water-soluble quantum dots increases because of surface modification with an amphiphilic polymer having a large molecular weight. However, it was not sufficient (Patent Document 2: Japanese Translation of PCT International Publication No. 2010-523557).

In addition, Patent Document 3: Japanese Translation of PCT International Publication No. 2014-523634 describes a light-emitting device incorporated in a transparent poly (meth) acrylate encapsulating medium, but does not describe a ligand of inorganic nanoparticles.

Therefore, the present invention is intended to solve the problem by combining the inorganic ligand with the specific ligand of the present invention, so that both water-soluble and oil-soluble compositions are possible. An object of the present invention is to provide a composition and an optical functional film that are excellent in various characteristics of wavelength peak stability and further excellent in suppressing deterioration of the binder resin.

The present inventors have conducted intensive research to solve the above problems. As a result, it contains an inorganic nanoparticle and a ligand having at least one adsorbing group that adsorbs to the inorganic nanoparticle, the ligand is a nonionic organic compound or an oxide compound, and the adsorbing group is a central atom Has been found to be able to be solved by a composition comprising an oxo acid residue in which sulfur atom or phosphorus atom or an N oxide group is included, and an optical functional film, and the present invention has been completed.

The present invention includes inorganic nanoparticles; and a ligand having at least one adsorbing group adsorbed on the inorganic nanoparticles, wherein the ligand is a nonionic organic compound or an oxide compound, and the adsorption A composition and an optically functional film containing a compound in which the group is a residue of an oxo acid whose central atom is a sulfur atom or a phosphorus atom or an N-oxide group.

According to the present invention, both water-soluble and oil-soluble are possible, excellent luminous properties, durability, and various characteristics such as stability of emission wavelength peak, and excellent heat resistance and binder resin deterioration suppression. A functional membrane can be provided.

As described above, when the above-described color gamut expansion film is applied to a liquid crystal display as an optical functional film, the color tone (spectrum) of the backlight is improved, and the displayable color of the liquid crystal display is remarkably improved. It is expected that. Therefore, hereinafter, a color gamut expansion film which is an embodiment of the present invention will be described. Of course, since the present invention is characterized in that a specific ligand is used, the optical functional film is not limited to the color gamut expansion film of the following embodiment, and the color filter as described above. It can be used in various applications such as a color tone conversion filter as an optical functional film.

The color gamut expanding film of the present embodiment includes inorganic nanoparticles; and a ligand having at least one adsorbing group that is adsorbed on the inorganic nanoparticles, and the ligand is a nonionic organic compound or It is an oxide compound, and the adsorbing group has an optical functional film formed by using a composition containing a compound having an oxo acid residue or N-oxide group whose central atom is a sulfur atom or a phosphorus atom. By having such a configuration, the color gamut expansion film of the present embodiment has improved luminous efficiency, heat resistance, and oxidation resistance.

As described above, the present inventors diligently studied the cause of the conventional optical functional film not being excellent in various properties. In the process, we focused on ligand coordination elements. In the conventionally proposed ligand, when oxygen is present in the vicinity, the ligand coordination element is oxidized by oxygen, resulting in a decrease in the electron density of the coordination element and coordination with the inorganic nanoparticles. I thought that my position would be weak. When the coordinating power is weakened, in some cases, the ligand is desorbed from the inorganic nanoparticles, and defective portions of the inorganic nanoparticles exposed by the desorption are damaged by oxidation or the like. I guessed it might have led to deterioration.

As described above, the fact that the ligand is oxidized by oxygen means that electrons are attracted to the assigned oxygen atom, and the δ-characteristic of the coordination element is lowered. Enthalpy is reduced. Or, the energy level of the changed structure is changed due to oxygen oxidation, and the relationship of the good energy level with the quantum dot is broken, and the LUMO of the ligand deepens, acting as an electron trapping agent, or coordination It is considered that the HOMO of the child becomes shallow, and an adverse effect of acting as a hole trapping agent occurs.

Therefore, the structure is changed by oxygen oxidation, and it is no longer susceptible to oxygen oxidation in order to avoid desorption due to weak coordination force and change in energy level balance (that is, structural change). It is the present invention that has been solved by adopting the ligand of inorganic nanoparticles as a difficult) and further increasing the complex stability constant by the entropy effect.

However, the mechanism is based on speculation, and the present invention is not limited to the mechanism.

Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, this invention is not limited only to the following embodiment.

In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, operations and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

<< Composition >>
In the present invention, the composition is a combination of inorganic nanoparticles and a ligand having at least one adsorbing group that adsorbs to the inorganic nanoparticles.

<Inorganic nanoparticles>
In the present specification, the inorganic nanoparticles are inorganic fine particles having a particle size of about several nm to several hundred nm. The average particle diameter is preferably 1 to 200 nm, more preferably 1 to 100 nm, and still more preferably 1 to 50 nm. The following explanation of the average particle diameter of the semiconductor nanoparticles is applied to the description of the method for measuring the average particle diameter of the inorganic nanoparticles.

Examples of the inorganic nanoparticles include semiconductor nanoparticles, metal oxide nanoparticles, and metal nanoparticles.

[Semiconductor nanoparticles]
In this specification, the semiconductor nanoparticle is a particle having a predetermined size that is composed of a crystal of a semiconductor material and has a quantum confinement effect, and is a fine particle having a particle size of about several nanometers to several tens of nanometers. The quantum dot effect shown in FIG. In the present specification, “semiconductor nanoparticles” capable of obtaining the quantum dot effect may be simply referred to as “quantum dots”.

The shape of the semiconductor nanoparticles is not particularly limited, such as dots, rods, wires, squares, tetrapots, and stars.

The energy level E of such semiconductor nanoparticles is generally expressed by the following formula (1) when the Planck constant is “h”, the effective mass of electrons is “m”, and the radius of the semiconductor nanoparticles is “R”. ).

As shown by the formula (1), the band gap of the semiconductor nanoparticles increases in proportion to “R ⁻² ”, and a so-called quantum dot effect is obtained. Thus, the band gap value of the semiconductor nanoparticles can be controlled by controlling and defining the particle diameter of the semiconductor nanoparticles. That is, by controlling and defining the particle size of the fine particles, it is possible to provide diversity not found in ordinary atoms. Therefore, it can be excited by light, or converted into light having a desired wavelength and emitted. In this specification, such a light-emitting semiconductor nanoparticle material is defined as a semiconductor nanoparticle.

As described above, the average particle size of the semiconductor nanoparticles is about several nm to several tens of nm, and is set to an average particle size corresponding to the target emission color. For example, when it is desired to obtain red light emission, the average particle size of the semiconductor nanoparticles is preferably set within a range of 3.0 to 20 nm. The particle size is preferably set in the range of 1.5 to 10 nm, and when blue light emission is desired, the average particle size of the semiconductor nanoparticles may be set in the range of 1.0 to 3.0 nm. preferable. The average particle diameter of the semiconductor nanoparticles can be controlled by a known method.

A known method can be used as a method for measuring the average particle diameter. For example, a method of observing semiconductor nanoparticles using a transmission electron microscope (TEM) and determining the number average particle size of the particle size distribution therefrom, or a method of determining an average particle size using an electron force microscope (AFM) The particle size can be measured using a particle size measuring apparatus using a dynamic light scattering method, for example, “ZETASIZER Nano Series Nano-ZS” manufactured by Malvern. In addition, there is a method of deriving the particle size distribution from the spectrum obtained by the X-ray small angle scattering method using the particle size distribution simulation calculation of the semiconductor nanoparticles. In the present invention, a transmission electron microscope ( A method of obtaining an average particle diameter using TEM) is preferable.

As a constituent material of the semiconductor nanoparticle, for example, a simple substance of a long-period periodic table group 14 element such as carbon, silicon, germanium, or tin; a simple substance of a long-period periodic table group 15 element such as phosphorus (black phosphorus) , Selenium, tellurium and other long-period periodic table group 16 element simple substance; silicon carbide (SiC) and other long-period periodic table group 14 element compounds; tin (IV) (SnO ₂ ), Tin sulfide (II, IV) (Sn (II) Sn (IV) S ₃ ), tin sulfide (IV) (SnS ₂ ), tin sulfide (II) (SnS), tin selenide (II) (SnSe), tellurium Long-period periodic table group 14 elements such as tin (II) fluoride (SnTe), lead sulfide (II) (PbS), lead selenide (II) (PbSe), lead telluride (II) (PbTe) Compound with periodic group 16 element; nitriding Boron (BN), boron phosphide (BP), boron arsenide (BAs), aluminum nitride (AlN), aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum antimonide (AlSb), gallium nitride ( GaN, gallium phosphide (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb) Compounds of Group 13 elements and Group 15 elements of the periodic table (or Group III-V compound semiconductor) such as aluminum sulfide (Al ₂ S ₃ ), aluminum selenide (Al ₂ Se ₃ ), gallium sulfide _{(Ga 2 S} 3), gallium selenide _(Ga 2 _Se 3), telluride gallium _(Ga 2 _Te 3), indium oxide _{(In 2 O} 3), indium sulfide _{(In 2 S} 3), indium selenide _(In 2 _Se 3), the long-form periodic such telluride, indium _(In 2 Te ₃₎ Compounds of Group 13 elements and Group 16 elements of the Long Periodic Periodic Table; lengths of thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), thallium iodide (I) (TlI), etc. Compound of periodic group 13 element and long periodic group 17 element; zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide (CdO), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (H gTe) and other long-period periodic table group 12 elements and long-period periodic table group 16 elements (or II-VI compound semiconductors), arsenic sulfide (III) (As ₂ S ₃ ), selenization Arsenic (III) (As ₂ Se ₃ ), Arsenic telluride (III) (As ₂ Te ₃ ), Antimony (III) sulfide (Sb ₂ S ₃ ), Antimony selenide (III) (Sb ₂ Se ₃ ), Tellurium Antimony (III) iodide (Sb ₂ Te ₃ ), bismuth sulfide (III) (Bi ₂ S ₃ ), bismuth selenide (III) (Bi ₂ Se ₃ ), bismuth telluride (III) (Bi ₂ Te ₃ ), etc. Long period type periodic table group 15 element and long period type periodic table group 16 element compound; copper (I) (Cu ₂ O), copper selenide (I) (Cu ₂ Se), etc. long period Periodic Table Group 11 elements And a compound of Group 16 element of the long-period type periodic table; copper chloride (I) (CuCl), copper bromide (I) (CuBr), copper iodide (I) (CuI), silver chloride (AgCl), odor A compound of a long-period periodic table group 11 element such as silver halide (AgBr) and a long-period periodic table group 17 element; a long-period periodic table group 10 element such as nickel oxide (II) (NiO); Long Periodic Periodic Table Group 16 Element; Long Periodic Periodic Group 9 Element such as Cobalt (II) Oxide (CoO), Cobalt Sulfide (CoS) and Long Periodic Periodic Group 16 A compound with an element, a compound of a Group 8 element of a long-period periodic table and a Group 16 element of a long-period periodic table, such as triiron tetroxide (Fe ₃ O ₄ ), iron (II) sulfide (FeS); A long-period periodic table group 7 element such as manganese (II) (MnO) and a long-period periodic table group 16 element Compound: Compound of long-period periodic table group 6 element such as molybdenum sulfide (IV) (MoS ₂ ), tungsten oxide (IV) (WO ₂ ), etc .; long-period periodic table group 16 element; vanadium oxide (II) ) (VO), vanadium oxide (IV) (VO ₂ ), long period periodic table group 5 element such as tantalum oxide (V) (Ta ₂ O ₅ ), etc. and long period periodic table group 16 element A compound of a long-period periodic table group 4 element and a long-period periodic table group 16 element such as titanium oxide (TiO ₂ , Ti ₂ O ₅ , Ti ₂ O ₃ , Ti ₅ O _9, etc.); magnesium sulfide (MgS), magnesium selenide (MgSe) long period type periodic table group 2 elements and long period type periodic table group 16 elements; cadmium (II) chromium (III) (CdCr ₂ O ₄ ) , Cadmium selenide (I ) Chromium _{(III) (CdCr 2 Se 4} ), copper sulfide (II) chromium _{(III) (CuCr 2 S 4} ), chalcogen spinels such as mercury selenide (II) chromium _{(III) (HgCr 2 Se 4} ), Examples include barium titanate (BaTiO ₃ ).

Among these, compounds of group 14 elements of the long periodic table such as SnS ₂ , SnS, SnSe, SnTe, PbS, PbSe, PbTe, and group 16 elements of the long period periodic table, GaN, GaP, GaAs, GaSb III-V compound semiconductors such as InN, InP, InAs, InSb, Ga ₂ O ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , In ₂ O ₃ , In ₂ S ₃ , In ₂ Se ₃ , a compound of a group 13 element of a long periodic table such as In ₂ Te ₃ and a group 16 element of a long periodic table; ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS II-VI compound semiconductors such as HgSe, HgTe, As ₂ O ₃ , As ₂ S ₃ , As ₂ Se ₃ , As ₂ Te ₃ , Sb ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂ O ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , Bi ₂ Te _3, etc. Compounds with group elements; compounds with long-period periodic table group 2 elements such as MgS and MgSe and long-period periodic table group 16 elements are preferred, among which Si, Ge, GaN, GaP, InN, InP, Ga ₂ O ₃ , Ga ₂ S ₃ , In ₂ O ₃ , In ₂ S ₃ , ZnO, ZnS, ZnSe, CdO, CdS, and CdSe are more preferable. Since these substances do not contain highly toxic negative elements, they are excellent in environmental pollution resistance and safety to living organisms, and because a pure spectrum can be stably obtained in the visible light region, light emitting devices Is advantageous for the formation of Of these materials, InP, CdSe, ZnSe, and CdS are preferable in terms of light emission stability. From the viewpoints of luminous efficiency, high refractive index, safety and economy, ZnO and ZnS semiconductor nanoparticles are preferred. Moreover, said material may be used by 1 type and may be used in combination of 2 or more type.

The semiconductor nanoparticles described above can be doped with trace amounts of various elements as impurities as necessary. By adding such a doping substance, the emission characteristics can be greatly improved.

The semiconductor nanoparticles used in this embodiment preferably have a core / shell structure. By having the core / shell structure, a quantum well is formed and the luminance is improved by the quantum confinement effect.

The core / shell structure is preferably formed of at least two kinds of compounds, and a gradient structure (gradient structure) may be formed of two or more kinds of compounds.

As the material of the core part, the materials mentioned above can be mentioned.

As the shell part, any material can be used as long as it functions as a protective film for the core part. The shell part preferably includes a semiconductor having a band gap (forbidden band width) larger than that of the core part. By using such a semiconductor for the shell portion, an energy barrier is formed in the semiconductor nanoparticles, and good light emission performance can be obtained.

The semiconductor material preferably used for the shell depends on the band gap of the core used, but for example, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaAs One or more semiconductors selected from the group consisting of GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, and AlSb, or alloys or mixed crystals thereof are preferable. Used. Among these materials for the shell portion, ZnS, ZnSe, ZnTe, and CdSe are preferable from the viewpoint of improving luminance.

In the present specification, the semiconductor nanoparticles having a core / shell structure are also simply referred to as “core-shell semiconductor nanoparticles”. Further, in this specification, as a notation method of the semiconductor nanoparticles having a core / shell structure, for example, when the core portion is CdSe and the shell portion is ZnS, it may be expressed as “CdSe / ZnS”. The core-shell semiconductor nanoparticles may be referred to as “CdSe / ZnS core-shell semiconductor nanoparticles”.

In general, the emission color can be controlled by the average particle diameter of the semiconductor nanoparticles, and if the thickness of the coating is within the above range, the thickness of the coating can be reduced from the thickness corresponding to several atoms. The thickness is less than one particle, the semiconductor nanoparticles can be filled with high density, and a sufficient amount of light emission can be obtained. In addition, the presence of the coating can suppress non-luminous electron energy transfer due to defects existing on the particle surfaces of the core particles and electron traps on the dangling bonds, thereby suppressing a decrease in quantum efficiency.

As a method for measuring the average particle size of the core-shell semiconductor nanoparticles, a known method, for example, a method for obtaining an average particle size using an electron force microscope (AFM), a particle size measuring device by a dynamic light scattering method (for example, Use a method of measurement using ZETASIZER Nanos Nano-ZS manufactured by Malvern, a method of deriving a particle size distribution from a spectrum obtained by a small-angle X-ray scattering method using a particle size distribution simulation calculation of semiconductor nanoparticles, and the like. Can do. In the present specification, semiconductor nanoparticles are observed with a transmission electron microscope (TEM), and the number average particle size (hereinafter referred to as particle size) of the particle size distribution is expressed therefrom. Specifically, the average volume particle size of the core-shell semiconductor nanoparticles used in the present embodiment is preferably in the range of 1 to 20 nm, and more preferably in the range of 1 to 10 nm. The particle size of the core part is preferably 1 to 8 nm, and more preferably 2 to 5 nm.

The constituent material of the semiconductor nanoparticles described above can be doped with a small amount of various elements as impurities as necessary. By adding such a doping substance, the light emission characteristics can be further improved.

[Method for producing semiconductor nanoparticles]
As a method for producing semiconductor nanoparticles, any conventionally known method such as a liquid phase method and a gas phase method can be used.

The liquid phase method includes a precipitation method such as a coprecipitation method, a sol-gel method, a uniform precipitation method, and a reduction method. In addition, reverse micelle method, supercritical hydrothermal synthesis method, hot soap method and the like are also excellent methods for producing nanoparticles (for example, JP 2002-322468 A, JP 2005-239775 A, (See JP-A-10-310770, JP-A-2000-104058, etc.).

As a manufacturing method of the gas phase method, a raw material semiconductor facing each other is evaporated by the first high temperature plasma generated between the electrodes, and is passed through the second high temperature plasma generated by electrodeless discharge in a reduced pressure atmosphere. (See, for example, JP-A-6-279015), a method of separating and removing nanoparticles from an anode made of a raw material semiconductor by electrochemical etching (for example, see JP-A-2003-515458), a laser ablation method (for example, JP No. 2004-356163) is used. In addition, a method of synthesizing a powder containing particles by reacting a raw material gas in a gas phase in a low pressure state is also preferably used.

As a method for producing semiconductor nanoparticles, a production method by a liquid phase method is preferred.

Further, the semiconductor nanoparticles used in the present embodiment may contain other components such as a stabilizer, a surfactant, a solvent and the like that can be used in the synthesis process as long as the function as a phosphor is not impaired.

[Metal oxide nanoparticles]
The metal oxide nanoparticles are not particularly limited, and examples thereof include oxides containing a desired metal in the finally formed metal oxide-containing layer. The type of metal is not particularly limited, and examples thereof include Group 1 to Group 12 elements, Group 13 aluminum, gallium, indium, thallium, Group 14 tin, lead, and Group 15 bismuth. The metal oxide in the metal oxide nanoparticles may contain only one kind of these metals or may be a composite oxide containing two or more kinds in any combination and ratio. For example, scandium oxide, titanium oxide, zirconium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, indium oxide, gallium oxide, aluminum oxide, tin oxide or lead oxide Is mentioned.

[Metal nanoparticles]
It has been confirmed that metal nanoparticles have a high binding property resulting from a fine particle size, and bonding between particles occurs at a temperature much lower than the melting point of the metal constituting the metal nanoparticles. In addition, the structural strength of the resulting conjugate is expected to be maintained up to near the melting point of the metal. Examples of the metal constituting the metal nanoparticle include those containing at least one transition metal such as Au, Ag, Cu, Pt, Pd, Ni, Rh, Co, Ru, Fe, and Mo.

The metal nanoparticles are generally used as organic-metal composite nanoparticles having a structure in which the metal nanoparticles are coated with an organic shell (in the present invention, a ligand). At room temperature, the organic shell (ligand) can prevent the nanoparticles from self-aggregating and maintain an independently dispersed form.

From the viewpoint of strength of interaction with the ligand of the present invention, semiconductor nanoparticles and metal oxide nanoparticles are preferable, and semiconductor nanoparticles are more preferable.

Note that semiconductor nanoparticles are names from physical properties, and metal oxide nanoparticles and metal nanoparticles are names from structural formulas, so these specific examples may overlap each other.

[Ligand]
In the color gamut expansion film of this embodiment, a ligand having at least one kind of adsorption group is adsorbed on the inorganic nanoparticles. The ligand has a function of protecting the inorganic nanoparticles from the external environment and suppressing the deterioration of the inorganic nanoparticles due to oxygen or the like. Therefore, the color gamut expansion film having inorganic nanoparticles adsorbed with the ligand has improved durability and stability of emission wavelength.

The ligand is an oxoacid residue-containing nonionic organic compound or N-oxide compound whose central atom is a sulfur atom or a phosphorus atom. Since these compounds are less susceptible to oxygen oxidation and the structure is less likely to change, it is thought that these compounds are stably adsorbed on inorganic nanoparticles. In the present invention, “nonionic” is defined as follows. That is, in this specification, a molecule having no positively charged cation moiety and negatively charged anion moiety in the molecule is defined as “nonionic”.

In addition, the ligand has an oxo acid residue having a central atom which is a sulfur atom or a phosphorus atom, or an N-oxide group as an adsorbing group. Therefore, it is difficult to undergo structural changes due to oxygen oxidation as described above, and inorganic nanoparticles can be stably protected.

According to a preferred embodiment of the present invention, the ligand is preferably a ligand having at least two adsorbing groups, a so-called multidentate ligand. That is, the ligand is preferably a multidentate ligand having at least two adsorbing groups. If it is a multidentate ligand, it can be strongly adsorbed by inorganic nanoparticles, and the durability of the color gamut expanding film and the stability of the emission wavelength are further improved.

The ligand according to the present invention specifically has the following structure as an adsorptive group adsorbed on the inorganic nanoparticles:

(In the above structure, each R is independently a hydrogen atom or a monovalent organic group, and * is a bonding point), and preferably has at least one selected from the group consisting of:

Further, according to one embodiment of the present invention, the bonding points form a single ring or a condensed ring with each other. Moreover, the single ring and the condensed ring may have a substituent described below. When forming a single ring or a condensed ring with each other, at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom may be interposed.

According to one embodiment of the present invention, the monovalent organic group is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

The alkyl group may be linear or cyclic. The alkyl group preferably has 1 to 24 carbon atoms, and preferably has a long-chain alkyl group in the molecule from the viewpoints of dispersion stability and aggregation suppression. The long-chain alkyl group preferably has 3 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

Specific examples of the alkyl group are not particularly limited, but are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, tert-pentyl group. Group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group A group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 2-hexyldecyl group and the like are preferable.

The number of carbon atoms of the aryl group is preferably 6-20, and more preferably 6-10.

Specific examples of the aryl group are not particularly limited, but a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, a benzhydryl group, a trityl group, a pyrenyl group, and the like are preferable.

The heteroaryl group refers to a group in which part of the carbon atoms in the aryl group is substituted with a heteroatom (oxygen atom, nitrogen atom or sulfur atom), for example, a pyridine group, a pyrrole group, a furan group, or a pyran group. Imidazole group, pyrazole group, oxazole group, pyridazine group, pyrimidine group, purine group, triazine, triazole and the like are preferable.

According to a preferred embodiment of the present invention, the ligand is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylthio group, substituted or unsubstituted. Or at least one group selected from the group consisting of a substituted or unsubstituted heteroaryl group, or a structure in which the at least one group is bonded to each other.

The alkyl group, aryl group and heteroaryl group are as described above.

The alkoxy group has a structure of “—O—X”, and “X” is the alkyl group.

The alkylthio group has a structure of “—S—X”, and “X” is the above alkyl group.

The alkoxycarbonyl group has a structure of “—COO—X”, and “X” is the alkyl group.

Here, the “structure in which the at least one group is bonded to each other” will be described with an example. For example, the structure in which an alkoxy group and an alkoxy group are bonded to each other is as follows:

n is, for example, 1 to 24.
It has the following structure.

In addition, the above substituents are each independently an alkyl group, aryl group, heteroaryl group, alkoxy group, acid amide group, alkylthio group, carboxyl group, hydroxyl group, alkoxycarbonyl group, and ethylenic group. Examples thereof include at least one selected from the group consisting of saturated bonding groups.

Here, the acid amide group has a structure of “—NHCO—X”, and “X” is the alkyl group.

The ethylenically unsaturated bond group is a group in which a part of the alkyl group has at least one of a double bond and a triple bond.

Further, in a preferred embodiment of the present invention, the ligand is a polymer having at least one structural unit containing the adsorbing group. The adsorbing group may be in the main chain or in the side chain.

From the above, the following can be cited as ligands.

The compound L-48 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The L-50 compound is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-51 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-54 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-56 is a copolymer containing structural units of m = 5 to 85, structural units of n = 5 to 85, and structural units of o = 5 to 85. Note that m + n + o = 100.

The compound of L-57 is a copolymer containing a structural unit of m = 5 to 85, a structural unit of n = 5 to 85, and a structural unit of o = 5 to 85. Note that m + n + o = 100.

The compound of L-58 is a copolymer containing a structural unit of m = 5 to 85, a structural unit of n = 5 to 85, and a structural unit of o = 5 to 85. Note that m + n + o = 100.

The compound of L-59 is a copolymer containing a structural unit of m = 5 to 85, a structural unit of n = 5 to 85, and a structural unit of o = 5 to 85. Note that m + n + o = 100.

The L-68 compound is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

In the above compound L-69, n is 100.

In the above compound L-74, n is 100.

In the above L-75 compound, n is 100.

In the above L-77 compound, n is 100.

Since L-69, 74, 75 and 77 are homopolymers, the mass% is 100.

The compound L-78 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-79 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-80 is a copolymer containing structural units of m = 5 to 95 and structural units of n = 5 to 95. Note that m + n = 100.

The L-82 compound is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-83 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-84 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

The compound of L-85 is a copolymer containing m = 5 to 95 structural units and n = 5 to 95 structural units. Note that m + n = 100.

Those skilled in the art can synthesize the above ligands using commercially available raw materials without undue trial and error. The synthetic formulation of L-68 is described below as a representative compound.

<Synthesis Example of L-68>
Weigh 1.5 g of 2- (dimethylamino) ethyl methacrylate and 1.95 g of dodecyl methacrylate in 100 ml of three-headed Kolben substituted with nitrogen, dissolve it by adding 15 ml of deoxygenated toluene, and then add 1.17 g of AIBN. The polymerization reaction was carried out by stirring at 90 ° C. for 7 hours under a nitrogen atmosphere. Then, it heated up to recirculation | reflux and stirred for further 1 hour. After allowing to cool, the reaction solution was dropped into 300 ml of methanol that was vigorously stirred. After stirring for a while, the oil-out component was separated by decantation.

The obtained oil component was dissolved in 30 ml of dichloromethane, 1.32 g of hydrogen peroxide urea was added, and the mixture was stirred while cooling to 0 ° C. Next, 2.81 g of trifluoroacetic anhydride was slowly added dropwise while maintaining the temperature at 0 ° C. After stirring for 2 hours as it was, the temperature was raised to room temperature and the reaction was continued for another 24 hours. After completion of the reaction, an aqueous solution in which 1.7 g of sodium sulfite was dissolved in 10 ml of water was added, and the mixture was vigorously stirred at 40 ° C. to quench the excess oxidizing agent. Thereafter, dichloromethane was distilled off under reduced pressure, and THF was added for extraction, followed by washing with aqueous sodium hydrogen carbonate to neutralize the pH. The extracted THF was once distilled off under reduced pressure, dissolved again in THF, and insolubles were removed by filtration. Thereafter, the THF solution was added dropwise into vigorously stirred methanol and stirred for a while. The oil-out component was separated by decantation to obtain 1.1 g of L-68. The structure could be confirmed by NMR.

Other ligands can also be synthesized by appropriately referring to the above synthesis examples or by combining conventionally known knowledge.

Note that m, n, and o represent mass%.

The ligands may be used alone or in combination of two or more.

The content of the inorganic nanoparticles in the inorganic nanoparticle dispersion is preferably 1 mg / ml to 100 mg / ml, more preferably 3 mg / ml to 40 mg / ml.

The content of the ligand in the dispersion when the compound of the present invention is coordinated to the inorganic nanoparticles is preferably 10 mmol / l to 5000 mmol / l with respect to the total volume of the inorganic nanoparticle dispersion.

[Binder resin]
The binder resin that can be used in combination with the composition according to the present invention is not particularly limited, and may be a water-soluble binder resin or a hydrophobic binder resin. For example, polyester, thermoplastic polyester elastomer (TPEE), Acetylcellulose (TAC), diacetylcellulose (DAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyethersulfone, poly Sulphone, polypropylene (PP), polystyrene, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate petrate, cellulose Cetate propionate butyrate, cellulose benzoate, polyvinyl chloride, acrylic resin (eg, polyacrylic acid), polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), poly-N-vinylacetamide, polymethyl methacrylate (PMMA) (Polymethacrylic acid), polycarbonate (PC), epoxy resin, urea resin, urethane resin, melamine resin, cycloaliphatic polyolefin, phenol resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer (COC) and the like. These binder resins can be used alone or in combination of two or more.

Among these, from the viewpoint of solubility, polyester, triacetyl cellulose (TAC), diacetyl cellulose (DAC), polystyrene, cellulose acetate propionate, polymethyl methacrylate (PMMA), polycarbonate (PC), alicyclic polyolefin, PVA and polyvinyl pyrrolidone are preferred.

The content of the binder resin is preferably 30 to 99% by mass, more preferably 50 to 98% by mass based on the total mass of the optical functional film (for example, color gamut expansion film).

[Antioxidant]
It is preferable that the color gamut expansion film of this embodiment contains an antioxidant. By including an antioxidant, durability and stability of the emission wavelength are further improved.

The “antioxidant” in the present invention uses a singlet oxygen quencher or a secondary antioxidant in addition to a compound having an ultraviolet absorption function, a radical scavenging function (radical quencher), or a peroxide decomposition function. Specifically, the following known antioxidants and the like can be used.

These antioxidants can be used alone or in admixture of two or more.

The content of the antioxidant is preferably 0.1 to 50% by mass, more preferably 1 to 35% by mass, based on the total mass of the optical functional film (eg, color gamut expanding film). preferable. In this example, it was 10 to 30% by mass.

[Fine particles]
The color gamut expanding film of the present embodiment preferably contains fine particles in order to improve slipperiness.

As fine particles used in the present invention, examples of inorganic compounds include, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydration Mention may be made of calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Further, fine particles of an organic compound can also be preferably used. Examples of organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine Examples thereof include pulverized and classified products of organic polymer compounds such as resins, polyolefin-based powders, polyester-based resins, polyamide-based resins, polyimide-based resins, polyfluorinated ethylene-based resins, and starches. Alternatively, a high molecular compound synthesized by a suspension polymerization method, a high molecular compound made spherical by a spray drying method or a dispersion method, or an inorganic compound can be used.

Fine particles containing silicon are preferable from the viewpoint of low turbidity, and silicon dioxide is particularly preferable.

The average primary particle size of the fine particles is preferably 5 to 400 nm, more preferably 10 to 300 nm.

These may be mainly contained as secondary aggregates having a particle size of 0.05 to 0.3 μm, and may be contained as primary particles without being aggregated if the particles have an average particle size of 100 to 400 nm. preferable.

The content of these fine particles in the optical functional film (for example, color gamut expansion film) is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass. In this example, it was 0.3% by mass.

Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil (registered trademark) R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). can do.

Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil (registered trademark) R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.).

Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) Are commercially available and can be used.

Among these, Aerosil 200V and Aerosil R972V are particularly preferred because they have a large effect of reducing the friction coefficient while keeping the turbidity of the optical film low.

Various additives may be batch-added to the main dope (dope solution) for forming the optical functional film, or an additive solution may be separately prepared and added in-line. In particular, it is preferable to add a part or all of the fine particles in-line in order to reduce the load on the filter medium.

[Other ingredients]
In addition to the above, the optical functional film (for example, color gamut expansion film) of the present invention may contain other components such as a plasticizer, a hydrolysis inhibitor, and an ultraviolet absorber in addition to the above effects. Good.

The thickness of the optical functional film (for example, color gamut expanding film) of the present invention is preferably 20 to 500 μm, more preferably 50 to 300 μm, and still more preferably 70 to 150 μm.

[Method for producing optical functional film (for example, color gamut expansion film)]
The production method of the optical functional film (for example, color gamut expansion film) of the present invention is not particularly limited, and a known method such as a melt-flow method or a solution-flow method can be used. A manufacturing method including mixing other components in a solvent as necessary to prepare a dope solution and then casting (casting) the dope solution on a support such as glass and drying is preferable.

Examples of the solvent (or dispersion medium) that can be used for mixing each component include hydrocarbon solvents such as water, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons; Examples include ether solvents such as aliphatic ethers and alicyclic ethers; alcohol solvents; ketone solvents; ester solvents; polar solvents and the like. More specifically, hydrocarbon solvents such as pentane, hexane, octadecene, cyclohexane, toluene, xylene, solvesso, terpene, methylene chloride and trichloroethane; ether solvents such as dibutyl ether, 1,4-dioxane and tetrahydrofuran (THF) Methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2- Propanol, 2,2,3,3,3-pentafluoro-1-propyl Alcohol solvents such as panol; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, amyl acetate, ethyl formate; N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) , Polar solvents such as nitroethane, and the like. These solvents can be used alone or in admixture of two or more. The ligand of Example 5 is water soluble.

The dope solution may be prepared by a method of adding each component to a solvent and mixing, or by preparing a solution or dispersion of each component and mixing the solution or dispersion. .

As a casting method, an air doctor coater, blade coater, knife coater, rod coater, squeeze coater, impregnation coater, gravure coater, kiss roll coater, die coater, reverse roll coater, transfer roll coater, spray coater, etc. were used. The method can be used.

The conditions during drying are not particularly limited, and the amount of residual solvent after drying can be set as appropriate. The residual solvent amount is defined by the following equation as the residual solvent amount of the film.

Residual solvent amount (%) = (mass before heat treatment of film−mass after heat treatment of film) / (mass after heat treatment of film) × 100
Note that the heat treatment for measuring the residual solvent amount means a heat treatment at 115 ° C. for 1 hour.

The method for drying the film may be a method of drying with hot air, infrared rays, a heating roller, microwave, or the like, and a method of drying with hot air is preferable because it is simple.

[Usage]
As described above, the optical functional film of the present invention can be suitably used for, for example, a color gamut expansion film, a color tone conversion filter, and a color filter that are preferably used in a display backlight unit or the like.

Hereinafter, specific examples and comparative examples will be described. However, the technical scope of the present invention is not limited only to the following examples. Further, in the following operations, unless otherwise specified, operations and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

Example 1-1
(Synthesis of Semiconductor Nanoparticle A: Synthesis of InP / ZnS Semiconductor Nanoparticle A)
While adding 1.5 mmol of indium myristate, 1.5 mmol of myristic acid, 1.5 mmol of trimethylsilylphosphine, 1.5 mmol of dodecanethiol, and 1.5 mmol of zinc undecylenate together with 120 ml of octadecene, while refluxing in a nitrogen atmosphere It heated at 300 degreeC for 1 hour, and the octadecene solution containing InP / ZnS (semiconductor nanoparticle A) was obtained. Next, it was dried under vacuum to obtain a powder of InP / ZnS semiconductor nanoparticles A. Note that in this specification, as a notation method of semiconductor nanoparticles having a core-shell structure, for example, when the core is InP and the shell is ZnS, it is expressed as InP / ZnS.

By directly observing the obtained semiconductor nanoparticles A with a transmission electron microscope, it was possible to confirm that the surface of the InP core part was a core-shell structure covered with a ZnS shell. Further, according to this observation, the InP / ZnS semiconductor nanoparticles A synthesized by this synthesis method had a core part particle size of 2.1 to 3.8 nm and a core part particle size distribution of 6 to 40%. Here, a JEM-2100 transmission electron microscope manufactured by JEOL Ltd. was used for the observation.

Note that the core-shell particle diameter of the InP / ZnS semiconductor nanoparticles A is 3.0 to 8.3 nm.

Also, the optical properties of InP / ZnS semiconductor nanoparticles A were measured using the octadecene solution containing the semiconductor nanoparticles A obtained above. It was confirmed that the emission peak wavelength was 430 to 720 nm and the emission half width was 35 to 90 nm. The luminous efficiency reached a maximum of 70.9%. In the present invention, a fluorescence spectrophotometer FluoroMax-4 manufactured by JOBIN YVON is used to measure the emission characteristics of InP / ZnS semiconductor nanoparticles A, and the stock spectrum is used to measure the absorption spectrum of InP / ZnS semiconductor fine particle phosphor. A spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation was used.

The semiconductor nanoparticles A obtained above were separated by adjusting the particle size according to the centrifugal separation method.

Semiconductor nanoparticles A are surface modified with myristic acid.

(Synthesis of Semiconductor Nanoparticle B: Synthesis of InP / ZnS Semiconductor Nanoparticle B Coordinated with the Ligand According to the Present Invention)
The semiconductor nanoparticles A obtained above were subjected to centrifugal separation to separate the nanoparticle components exhibiting green light emission, and the particle size was adjusted.

The synthesis of the semiconductor nanoparticles B was performed using the semiconductor nanoparticles A from which the green light-emitting particle components were separated in advance by a centrifugal separation method.

A toluene solution (concentration: 40 mM) of the compound (L-4) of the present invention and an octadecene solution (concentration: 5 mg / ml) of semiconductor nanoparticles A were mixed at a mass ratio of 1: 1, and the mixture was mixed in a glove box in a dark place. The mixture was stirred overnight, then centrifuged (6000 rpm, about 1 minute), and the supernatant was drained. Repeated washing with methanol, and then redispersed in toluene (15 mL) to obtain a dispersion 1-1 of InP / ZnS semiconductor nanoparticles having a core-shell structure surface-modified with the compound (L-4) of the present invention. . The surface modification state was measured by FTIR and NMR, and it was confirmed that the surface of InP / ZnS semiconductor nanoparticles was modified with the compound (L-4) of the present invention.

The core-shell particle size of the semiconductor nanoparticles B obtained by centrifuging the semiconductor nanoparticles A was 3.0 to 5.0 nm.

<Preparation of fine particle dispersion>
Fine particles (average primary particle size: 16 nm) (Aerosil (registered trademark) R972V, manufactured by Nippon Aerosil Co., Ltd.) 9 parts by mass Ethanol 89 parts by mass Fine particles and ethanol were mixed at the above ratio using a dissolver for 50 minutes, and then Menton A fine particle dispersion was prepared by dispersing with gorin.

<Preparation of fine particle additive solution>
Methylene chloride 89 parts by mass Fine particle dispersion 98 parts by mass (total amount of the fine particle dispersion)
Methylene chloride was put into a container, and the fine particle dispersion prepared above was slowly added at the above addition amount with sufficient stirring. Subsequently, after being dispersed with an attritor so that the particle size of the secondary particles of the fine particles becomes a predetermined size, the fine particles are filtered through Finemet (registered trademark) NF (manufactured by Nippon Seisen Co., Ltd.) Got.

<Preparation of dope solution>
Methylene chloride: 15ml
Cellulose acetate propionate CAP482 as binder resin
-20 (weight average molecular weight 215000, manufactured by Eastman Chemical Co.):
3g
Semiconductor nanoparticle dispersion 1-1: 15 ml
Fine particle additive solution: 0.18 g
The methylene chloride and the semiconductor nanoparticle dispersion 1-1 were mixed. Next, the cellulose acetate propionate as a binder resin and the fine particle additive solution prepared above were added while stirring, and were stirred and completely dissolved in a dark place to prepare a dope solution.

<Preparation of color gamut expansion film 101>
The obtained dope solution was flowed on a glass stage, and a blade coater that was movable relative to the stage at a predetermined interval was pulled and cast (cast). The solvent in the cast film is evaporated until the residual solvent amount reaches 75% by mass, and the obtained film is peeled off from the glass stage and dried to obtain a color gamut expanding film 101 (hereinafter simply referred to as “film 101”). Also referred to as). The film thickness of the film 101 was 100 μm.

(Examples 1-2 to 1-10: Production of color gamut expansion films 102 to 110)
Color gamut expanding films 102 to 110 (films 102 to 110) were produced in the same manner as in Example 1 except that the compound (L-4) of the present invention was changed to those shown in Table 1.

(Comparative Examples 1-1 to 1-2 (films 111 to 112))
In the same manner as in Example 1-1 except that Comparative Compound 1 (tridecanoic acid) and Comparative Compound 2 were used instead of the compound (L-4) of the present invention, the color gamut expanding film 111 (film 111) and A color gamut expansion film 112 (film 112) was produced.

(Example 1-11: Production of color gamut expansion film 113)
A color gamut expansion film 113 (film 113) was produced in the same manner as in Example 1 except that the compound (L-4) of the present invention was changed to that shown in Table 1.

Example 2-1
Methylene chloride: 15ml
Cellulose acetate propionate CAP482 as binder resin
-20 (weight average molecular weight 215,000, Eastman Chemical Co.):
3g
Semiconductor nanoparticle dispersion 2-1: 15 ml
Antioxidant (AO-1): 0.3g
Fine particle additive solution: 0.18 g
The above methylene chloride and antioxidant (AO-1) were dissolved, and then the semiconductor nanoparticle dispersion 2-1 was mixed. Thereafter, the cellulose acetate propionate and the fine particle addition liquid prepared above were added while stirring, and the mixture was stirred and completely dissolved in the dark to prepare a dope solution.

The semiconductor nanoparticle dispersion 2-1 was prepared in the same manner as the semiconductor nanoparticle dispersion 1-1 except that the compound (L-4) of the present invention was changed to the compound (L-48) of the present invention. did.

<Preparation of color gamut expansion film 201>
The obtained dope solution was allowed to flow on a glass stage, and a blade coater that was able to move relatively horizontally with a predetermined interval with respect to this stage was drawn and cast to obtain a film. The solvent in the cast film is evaporated until the residual solvent amount reaches 75% by mass, and the obtained film is peeled off from the glass stage and dried to obtain a color gamut expanding film 201 (hereinafter simply referred to as “film 201”). Obtained). The film thickness was 100 μm.

(Examples 2-2 to 2-12)
Except that the compound of the present invention (L-48) and the antioxidant (AO-1) were changed to the compounds shown in Table 2 below, in the same manner as in Example 2-1, the color gamut expansion films 202 to 212 (films 202 to 212) were produced.

(Comparative Examples 2-1 and 2-2)
In the same manner as in Example 2-1, except that the compound of the present invention (L-48) and the antioxidant (AO-1) were changed to the compounds shown in Table 2 below, the color gamut expanding films 213 to 214 was produced.

(Examples 2-13 to 2-15)
Except that the compound of the present invention (L-48) and the antioxidant (AO-1) were changed to the compounds shown in Table 2 below, in the same manner as in Example 2-1, the color gamut expansion films 215 to 217 (films 215 to 217) were produced.

Example 3-1
Methylene chloride: 15ml
CAP482-20: 3g
Semiconductor nanoparticle dispersion 3-1: 15 ml
Antioxidant (AO-1): 0.3g
Antioxidant (AO-6): 0.3 g
Antioxidant (AO-11): 0.3 g
Fine particle additive solution: 0.18 g
The methylene chloride and the antioxidant were mixed and dissolved, and then the semiconductor nanoparticle dispersion 3-1 was mixed. Thereafter, the above-mentioned CAP482-20 as a binder resin and the fine particle addition liquid prepared above were added with stirring, and were stirred and completely dissolved in a dark place to prepare a dope solution. The semiconductor nanoparticle dispersion 3-1 was prepared in the same manner as the semiconductor nanoparticle dispersion 1-1 except that the compound (L-4) of the present invention was changed to the compound (L-44) of the present invention. did.

<Preparation of color gamut expansion film 301>
The obtained dope solution was flowed on a glass stage, and a blade coater that was movable relative to the stage at a predetermined interval was pulled and cast (cast). The solvent in the cast dope solution film is evaporated until the residual solvent amount reaches 75% by mass, and the obtained film is peeled off from the glass stage and dried to obtain a color gamut expanding film 301 (hereinafter simply referred to as “film 301”. Is also called). The film thickness was 100 μm.

(Examples 3-2 to 3-12)
Except that the compound of the present invention (L-44), binder resin (CAP482-20), and antioxidant (AO-1, AO-6, AO-11) were changed to the compounds shown in Table 3 below, In the same manner as in Example 3-1, color gamut expansion films 302 to 312 (films 302 to 312) were produced.

(Comparative Examples 3-1 and 3-2)
Except that the compound of the present invention (L-44), binder resin (CAP482-20), and antioxidant (AO-1, AO-6, AO-11) were changed to the compounds shown in Table 3 below, In the same manner as in Example 3-1, color gamut expansion films 313 to 314 (films 313 to 314) were produced.

(Examples 3-13 to 3-15)
Except that the compound of the present invention (L-44), binder resin (CAP482-20), and antioxidant (AO-1, AO-6, AO-11) were changed to the compounds shown in Table 3 below, In the same manner as in Example 3-1, color gamut expansion films 315 to 317 (films 315 to 317) were produced.

<Evaluation method>
The following evaluation was performed about the color gamut expansion film produced as mentioned above.

(Luminescence efficiency)
When the color gamut expansion film was excited with 405 nm blue-violet light, the respective light emission efficiency of white light emission with a color temperature of 7000 K was measured.

For the measurement, a light emission measurement system MCPD-7000 manufactured by Otsuka Electronics Co., Ltd. was used.

Further, relative luminous efficiency when the luminous efficiency measured by the above method of the comparative films (Comparative 1-1, Comparative 2-1 and Comparative 3-1) is set to 100 for the obtained luminous efficiency results. And the relative luminous efficiency as the luminous characteristics was evaluated according to the following criteria.

◎: Relative luminous efficiency is 125 or more ○: Relative luminous efficiency is 115 or more and less than 125 ○ △: Relative luminous efficiency is 105 or more and less than 115 Δ: Relative luminous efficiency is 95 or more and less than 105 Δ ×: Relative luminous efficiency is 85 or more and less than 95 x: Relative luminous efficiency is less than 85.

(durability)
The color gamut expansion film produced above was subjected to an accelerated deterioration treatment for 1000 hours in an environment of 85 ° C. and 85% RH. Thereafter, the respective light emission efficiencies are measured by the same method as the evaluation of the light emission characteristics, and the ratio of the light emission efficiency after the accelerated deterioration process to the light emission efficiency before the accelerated deterioration process (light emission efficiency after the accelerated deterioration process / before the accelerated deterioration process). The light emission efficiency) was determined, and the durability was evaluated according to the following criteria.

◎: Ratio value is 0.95 or more ○: Ratio value is 0.85 or more and less than 0.95 △: Ratio value is 0.75 or more and less than 0.85 △: Ratio value Is 0.50 or more and less than 0.75 x: The value of the ratio is less than 0.50.

(Emission wavelength stability)
The emission wavelength peak was measured when the color gamut expanding film was excited with 405 nm blue-violet light. Thereafter, the same color gamut expansion film was subjected to an accelerated deterioration treatment for 1000 hours in an environment of 85 ° C. and 85% RH, and then measured in the same manner as the measurement of the emission wavelength peak. The value of the shift of the wavelength peak after accelerated deterioration treatment relative to (the emission wavelength peak after accelerated deterioration treatment−the emission wavelength peak before accelerated deterioration treatment) was determined, and the stability of the emission wavelength peak was evaluated according to the following criteria.

A: The deviation value is less than 5 nm. B: The deviation value is 5 nm or more and less than 10 nm. Δ: The deviation value is 10 nm or more and less than 15 nm. X: The deviation value is 15 nm or more.

The configurations and evaluation results of the examples and comparative examples are shown in Tables 1 to 3 below.

Note that “CAP” and “CAP482-20” are the same.

As is clear from the above table, the color gamut expansion films of the examples are excellent in luminous efficiency, heat resistance, and oxidation resistance.

Example 4-1
An aqueous solution (concentration 40 mM) of the compound (L-69) of the present invention and an octadecene solution (concentration: 5 mg / ml) containing the semiconductor nanoparticles A were mixed at a mass ratio of 1: 1 and stirred at room temperature for 3 hours. . Thereafter, the octadecene layer was removed, tetrahydrofuran was added to the remaining aqueous layer, and the oil-out component was collected by decantation. When the FT-IR of the composition 401 (oil component) collected by decantation was measured, a peak not observed in L-69 and the semiconductor nanoparticle A was observed, and the interaction between the semiconductor nanoparticle and the compound of the present invention was observed. It was confirmed that was expressed. Next, the oil component was redispersed in water, and the luminous efficiency was measured.

For the measurement, a light emission measurement system MCPD-7000 manufactured by Otsuka Electronics Co., Ltd. was used.

The relative luminous efficiency when the octadecene solution containing the semiconductor nanoparticles A (concentration: 5 mg / ml) was measured as 100 was determined, and the relative luminous efficiency as the luminous characteristics was evaluated according to the following criteria.

A: Relative luminous efficiency is 90 or more B: Relative luminous efficiency is 75 or more and less than 90 Δ: Relative luminous efficiency is 60 or more and less than 75 ×: Relative luminous efficiency is less than 60

(Examples 4-2 to 4-3)
Compositions 402 to 403 were prepared in the same manner as in Example 4-1, except that the compound of the present invention (L-69) was changed to a compound as shown in Table 4 below. Then, FT-IR and luminous efficiency were measured.

(Comparative Examples 4-1 to 4-2)
Compositions 404 to 405 were prepared in the same manner as in Example 4-1, except that Comparative Compound 3 and Comparative Compound 4 were used instead of the compound (L-69) of the present invention. Example 4-1 FT-IR and luminous efficiency were measured in the same manner as described above.

Comparative compound 3: mercaptopropionic acid Comparative compound 4: polyethyleneimine (branched, MW 1,800, manufactured by Wako Pure Chemical Industries, Ltd.)

Example 5-1
An aqueous solution (concentration 40 mM) of the compound (L-62) of the present invention and a titanium oxide aqueous dispersion (X-ray particle size 20 nm, STS-21 manufactured by Ishihara Sangyo Co., Ltd.) were mixed at a mass ratio of 1: 1 for 3 hours. Stir at room temperature. Thereafter, a part of the mixed solution was extracted, the water was dried, and the FT-IR of the remaining solid was measured. A peak not observed in L-62 and titanium oxide was observed, and the metal oxide nanoparticles and It was confirmed that interaction with the compound of the present invention was expressed.

Next, the mixed solution and a PVA (Wako Pure Chemical Industries, Ltd. (CH (OH) CH ₂ ) _n n = 2000) dispersion aqueous solution (concentration: 10 wt%) were added at a mass ratio of 1:50, and 45 ° C. The mixture was sufficiently defoamed and then defoamed, poured onto a glass plate so that the thickness after drying was 70 μm, and dried at 80 ° C. to produce an optical functional film 501.

The color of the produced film was visually observed and evaluated according to the following 4 levels.

Film coloring (appearance)
A: White or colorless, no coloration is observed. B: Light yellow, almost no coloration. Δ: Yellow to yellowish brown, slightly colored. ×: Brown to reddish brown, clearly colored.

(Examples 5-2 to 5-3)
Optical functional films 502 to 503 were produced in the same manner as in Example 5-1, except that the compound of the present invention (L-62) was changed to the compounds shown in Table 5 below.

(Comparative Examples 5-1 and 5-2)
Optical functional films 504 to 505 were produced in the same manner as in Example 5-1, except that the comparative compound 5 was used instead of the compound (L-62) of the present invention or a blank was used.

Comparative compound 5: Triethylamine

From the above results, in the structure of titanium oxide + ligand + PVA, the ligand has a strong interaction with titanium oxide (using the strong interaction between the nanoparticles and the ligand), which has an adverse effect on PVA. It is suggested that can be suppressed.

Note that this application is based on Japanese Patent Application No. 2015-059048 filed on Mar. 23, 2015, the disclosure of which is incorporated by reference in its entirety.

Claims (8)

1. With inorganic nanoparticles;
   A ligand having at least one adsorbing group adsorbed on the inorganic nanoparticles,
   The ligand is a nonionic organic compound or an oxide compound;
   A composition comprising a compound in which the adsorptive group is a residue of an oxo acid whose central atom is a sulfur atom or a phosphorus atom or an N-oxide group.
2. The composition according to claim 1, wherein the ligand has at least two adsorbing groups.
3. The adsorbing group has the following structure:
   

   

   
   In the above structure,
   Each R is independently a hydrogen atom or a monovalent organic group;
   * Is the point of attachment,
   The composition of Claim 1 or 2 which has at least 1 type selected from the group which consists of.
4. The composition according to claim 3, wherein the monovalent organic group is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
5. The ligand is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted alkoxycarbonyl group, and a substituted The composition according to any one of claims 1 to 4, wherein the composition has at least one group selected from the group consisting of unsubstituted heteroaryl groups, or a structure in which the at least one group is bonded to each other. object.
6. The composition according to any one of claims 1 to 5, wherein the ligand is a polymer having at least one structural unit containing the adsorptive group.
7. An optical functional film comprising the composition according to any one of claims 1 to 6 and a binder resin.
8. The optical functional film according to claim 7, comprising an antioxidant.