JP2012208169A - Hard coat film, heat ray shielding film and organic element device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film which can maintain excellent antibacterial properties, transparency, and scratch resistance even when being stored under a variety of indoor and outdoor environments (for instance, high temperature, high humidity, ultraviolet radiation or the like) for a long period, and a heat ray shielding film and an organic element device using the same.SOLUTION: In a hard coat film, on at least one face of a plastic base material, a hard coat layer is provided that contains a polymer having polyfunctional pentaerythritol (meta) acrylate monomer components and antibacterial monomer components.

Description

  The present invention relates to a hard coat film excellent in antibacterial properties, transparency and scratch resistance, a heat ray blocking film using the same, and an organic element device.

  In recent years, interest in energy conservation measures has increased, and from the viewpoint of reducing the load on cooling equipment, there has been an increasing demand for heat ray blocking films that can be attached to building and vehicle window glass to block the penetration of solar heat rays into the room. It is coming. Similarly, from the viewpoint of energy saving, flexible type organic materials using films such as solar cell systems that can generate power directly from natural energy and organic electroluminescence displays and lighting that emit light efficiently and with high brightness. Element devices have been proposed and put into practical use.

  In addition to heat ray blocking films, flexible organic element devices can be installed on glass windows, walls, doors, etc. that have not been used before, both indoors and outdoors. Therefore, it is desired to ensure safety in terms of hygiene such as antibacterial properties.

  In conventional antibacterial agents, particles containing silver or molybdenum oxide are known as inorganic antibacterial agents, and amino acid-containing compounds or nitrogen-containing sulfur compounds are known as organic antibacterial agents. Yes. These compounds imparted antibacterial properties to the object by a method of kneading into a resin or a method of coating a coating solution mixed with a resin. However, the inorganic antibacterial agent has the disadvantages that the transparency and strength of the coating film are impaired, and the visibility and scratch resistance are not sufficient. On the other hand, organic antibacterial agents are poorly soluble and bleed out on the coating surface at high temperature and high humidity, or decompose by irradiation with light such as ultraviolet rays, resulting in poor visibility, resulting in loss of antibacterial properties. There was a problem such as alive.

  Based on the above problems, a method for improving the transparency by setting the particle size of the inorganic particles to 10 to 500 nm and a method for improving the scratch resistance by using a slipping agent, an antifouling agent and the like have been proposed ( For example, see Patent Documents 1 and 2.) However, none of the proposed methods are sufficient in terms of durability, and when used in various indoor and outdoor environments (for example, high temperature, high humidity, ultraviolet irradiation, etc.), sufficient antibacterial properties and Since the scratch resistance is not exhibited and the deterioration of transparency is caused, the current situation is that the efficiency and life of the heat ray blocking film and the organic element device are lowered.

JP-A-9-316369 JP 2009-216750 A

  The present invention has been made in view of the above problems, and its purpose is to provide excellent antibacterial properties even when stored for a long period of time in various indoor and outdoor environments (for example, high temperature, high humidity, ultraviolet irradiation, etc.). It is providing the hard coat film which can maintain property, transparency, and scratch resistance, a heat ray blocking film using the same, and an organic element device.

  The above object of the present invention is achieved by the following configurations.

  1. A hard coat film comprising a hard coat layer containing a polymer having a polyfunctional pentaerythritol (meth) acrylate monomer component and an antibacterial monomer component on at least one surface of a plastic substrate.

  2. 2. The hard coat film as described in 1 above, wherein the hard coat layer is cured by irradiation with ultraviolet rays.

  3. 3. The hard coat film as described in 1 or 2 above, wherein the antibacterial monomer component has at least one salt selected from a quaternary ammonium salt, a quaternary phosphonium salt and a quaternary sulfonium salt.

  4). 3. The hard coat film as described in 1 or 2 above, wherein the antibacterial monomer component has at least one salt selected from a pyridium salt and a piperidinium salt.

5. The surface roughness Ra of the hard coat layer is 1 nm or more and 50 nm or less, and the number of protrusions of 20 nm or more per 125 μm ² is 10 or more and 10,000 or less, The hard coat film of any one.

  6). 6. A heat ray shielding film comprising the hard coat film according to any one of 1 to 5 above.

  7). 6. An organic element device comprising the hard coat film according to any one of 1 to 5 above.

  According to the present invention, a hard coat film capable of maintaining excellent antibacterial properties, transparency and scratch resistance even when stored for a long period of time in various indoor and outdoor environments (for example, high temperature, high humidity, ultraviolet irradiation, etc.) A heat ray shielding film and an organic element device using the same can be provided.

It is sectional drawing which shows the solar cell which consists of a bulk hetero junction type organic photoelectric conversion element. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor has found that a hard containing a polymer having a polyfunctional pentaerythritol (meth) acrylate monomer component and an antibacterial monomer component on at least one surface on a plastic substrate. Excellent antibacterial properties and transparency even when stored for a long time in various indoor and outdoor environments (for example, high temperature, high humidity, UV irradiation, etc.) As a result, it has been found that a hard coat film capable of maintaining the property and scratch resistance can be realized, and the present invention has been completed.

  That is, in the configuration defined in the present invention, transparency, antibacterial property, and scratch resistance are imparted by reacting a specific photopolymerizable monomer with an antibacterial monomer, and the antibacterial component remains in the coating film by a curing reaction. Therefore, it is estimated that deterioration of performance due to bleed-out or photolysis under various environments (heat, humidity, ultraviolet rays, etc.) is suppressed, and sufficient durability can be obtained. Further, it is presumed that by forming a fine uneven shape on the film surface, dirt and the like are efficiently decomposed by the antibacterial component, and effective in terms of durability.

  Hereinafter, the details of the hard coat film of the present invention will be described.

《Hard coat film》
The hard coat film of the present invention has a hard coat layer containing a polymer having a polyfunctional pentaerythritol (meth) acrylate monomer component and an antibacterial monomer component on at least one surface on a plastic substrate. To do.

[Plastic substrate]
The plastic substrate (hereinafter also referred to as a support) according to the present invention is not particularly limited as long as it is formed with a transparent plastic resin as a main component.

  Examples of the plastic substrate applicable to the present invention include methacrylate ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, and polyether. Examples include resin films such as ether ketone, polysulfone, polyether sulfone, polyimide, and polyetherimide, and a laminated resin film formed by laminating two or more layers of the resin. From the viewpoint of cost and availability, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used.

  The thickness of the plastic substrate is preferably about 5 to 200 μm, more preferably 15 to 150 μm.

  Further, the plastic substrate according to the present invention preferably has a visible light region transmittance of 85% or more as shown in JIS R3106-1998, and particularly preferably 90% or more. The plastic substrate having the above transmittance or more is advantageous in that the transmittance in the visible light region conforming to JIS R3106-1998 is 70% or more when applied to a heat ray shielding film or an organic element device. ,preferable.

  Moreover, the unstretched film may be sufficient as the plastic base material using the said resin etc., and a stretched film may be sufficient as it. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.

  The plastic substrate used in the present invention can be produced by a conventionally known general method. For example, an unstretched plastic substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched plastic base material is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, and other known methods such as plastic base material flow (vertical axis) direction. Alternatively, the stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis). Although the draw ratio in this case can be suitably selected according to the resin used as the raw material for the plastic substrate, it is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  In addition, the plastic substrate used in the present invention may be subjected to relaxation treatment or off-line heat treatment in terms of dimensional stability. The relaxation treatment is preferably performed, for example, in a process from heat setting in a stretch film forming process of a polyester film to a winding process after exiting the tenter. The relaxation treatment is preferably performed at a treatment temperature of 80 to 200 ° C, more preferably a treatment temperature of 100 to 180 ° C. Moreover, it is preferable that the relaxation rate is in the range of 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably, the relaxation rate is 2 to 6%. The relaxation-treated plastic base material is improved in heat resistance by the following off-line heat treatment, and further has good dimensional stability.

In the plastic substrate according to the present invention, it is preferable to apply the undercoat layer coating solution on one side or both sides in-line during the film forming process. In the present invention, the application of the undercoat layer coating solution during the film forming process is referred to as inline subbing. Examples of resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used. A conventionally well-known additive can also be added to these undercoat layers. The undercoat layer can be coated by a known coating method such as roll coating, gravure coating, knife coating, dip coating, spray coating or the like. The coating amount of the undercoat layer is preferably about 0.01 to ² g / m ² (dry state).

[Hard coat layer]
The hard coat layer according to the present invention is characterized by being composed of a polymer having a polyfunctional pentaerythritol (meth) acrylate monomer component and an antibacterial monomer component. By combining the above two types of monomers, a hard coat film having excellent durability and excellent antibacterial properties, transparency, and scratch resistance can be formed.

  Although the mechanism of function expression by the combination of the two types of monomer components defined in the present invention is unknown, the compatibility of the salt component or polar group component of the antibacterial monomer with the hydroxyl group or ether group of pentaerythritol is good, and the membrane By being mixed uniformly and cured inside, it was difficult to bleed out and decompose even in high temperature, high humidity, ultraviolet irradiation, etc., so it was possible to form a hard coat layer with excellent durability I guess.

(Polyfunctional pentaerythritol (meth) acrylate monomer)
The polyfunctional pentaerythritol (meth) acrylate monomer component according to the present invention is not particularly limited as long as it has a pentaerythritol skeleton and the (meth) acrylate component has two or more functional groups. . In the present invention, (meth) acrylate means methacrylate or acrylate.

  Examples of the polyfunctional pentaerythritol (meth) acrylate monomer component according to the present invention include pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). Examples include acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol di (meth) acrylate. In addition, a monomer obtained by further modifying propionic acid, propylene oxide, ethylene oxide, caprolactone or the like can be used. These polyfunctional pentaerythritol (meth) acrylates may be used alone or in combination of two or more.

  Among the polyfunctional pentaerythritol (meth) acrylate monomers, dipentaerythritol-based monomers are preferred because they have a large number of functional groups in terms of durability and can react with a large amount of antibacterial monomers.

  The amount of the polyfunctional pentaerythritol (meth) acrylate monomer used depends on the amount of the antibacterial monomer, but is 3 to 90 parts by mass when the total solid content of the hard coat layer forming composition is 100 parts by mass. It is preferably 5 to 70 parts by mass, particularly preferably 10 to 50 parts by mass. If the amount of the polyfunctional pentaerythritol (meth) acrylate is 3 parts by mass or more, the desired film hardness can be obtained, and sufficient scratch resistance and antibacterial monomer bleeding out and decomposition can be prevented. it can. Moreover, if it is 90 mass parts or less, a flexible film | membrane can be formed and generation | occurrence | production of a crack etc. can be prevented.

(Antimicrobial monomer)
The antibacterial monomer component according to the present invention is not particularly limited as long as it has a substituent having antibacterial properties and has a polymerizable group in the molecule. In addition, the antimicrobial property in this invention acts on the bacteria which contact, and makes bacteria kill or inactivate.

  Examples of the antibacterial substituent in the antibacterial monomer component include, for example, primary to tertiary amino groups, primary to quaternary ammonium bases, primary to quaternary phosphonium bases, primary to quaternary sulfonium bases, biguanidine groups, and antimicrobial peptides. , Phenol radicals, polyphenol radicals and the like. Among the above, preferred substituents from the viewpoint of antibacterial properties are a quaternary ammonium base, a quaternary phosphonium base, and a quaternary sulfonium base. More preferably, the quaternary ammonium base pyridium base and piperidium base are preferable from the viewpoint of compatibility with the polyfunctional pentaerythritol (meth) acrylate monomer according to the present invention.

  On the other hand, the polymerizable group in the molecule is not limited as long as it is a radical polymerizable group, but a (meth) acrylate group is preferable from the viewpoint of reactivity with the polyfunctional pentaerythritol (meth) acrylate monomer. The polymerizable group in the molecule may be monofunctional or polyfunctional. When antibacterial properties that are stronger than durability are required, select a monofunctional type that can place more antibacterial groups, and when higher durability than antibacterial properties is required, increase the crosslinking density. It is preferable to select a multifunctional type that can be used.

  The antibacterial monomer according to the present invention is particularly preferably a compound represented by the following general formula (1).

In the general formula (1), R ₁ represents a hydrogen atom or a methyl group. A is absent or represents —COO—, —CONH—, or —OCO—, and B is absent, — (CH ₂ ) _m —, —O— (CH ₂ ) _m —, —S— (CH ₂ ) _m −, — (OCH ₂ ) _m —, or — (C ₆ H ₄ ) — may be used, and A and B may be combined. m represents an integer of 0 to 6, and p represents an integer of 1 to 3.

X represents an antibacterial group and is composed of a cationic group represented by Y ⁺ and an anionic group represented by Z ⁻ . Z ⁻ represents Cl ⁻ , Br ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , NO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₃ ) ₂ N ⁻ , ArSO ₃ ⁻ , CF ₃ CO _2. ^-, and _CH 3 CO ₂ ^- represents at least one member selected from.

Y ⁺ represents at least one selected from the following a) to g).

In the above formula, R ¹¹ is represented by — (D) —W, D is not present, or — (CH ₂ ) _n —, —O— (CH ₂ ) _n —, —S— (CH ₂ ) _n -, - _{(OCH 2) n} -, or - _(C 6 _{H 4)} - it represents, W is, -H, -CH ₃ or - represents a _(C 6 _{H 5).} n represents an integer of 0 to 6.

  Although an example of the exemplary compound of the antibacterial monomer represented by the general formula (1) is shown below, the present invention is not limited to these exemplified compounds.

  The content of the antibacterial monomer is 1 to 70 parts by weight, preferably 3 to 50 parts by weight, more preferably 5 to 35 parts by weight, when the total solid content of the hard coat layer forming composition is 100 parts by weight. is there. When the amount of the antibacterial monomer is 1 part by mass or more, an antibacterial effect can be exhibited. Moreover, if it is 70 mass parts or less, the film | membrane provided with sufficient film | membrane intensity | strength and excellent in scratch resistance or transparency can be formed.

  The ratio of the polyfunctional pentaerythritol (meth) acrylate monomer (A) and the antibacterial monomer (B) in the composition for forming a hard coat layer according to the present invention depends on the film thickness of the hard coat layer. = 1/1 to 50/1 is preferable, and A / B = 2/1 to 20/1 is more preferable. If A / B is 1/1 or more (the ratio of the antibacterial monomer is high), sufficient retention ability in the compatibility of the antibacterial monomer of the polyfunctional pentaerythritol (meth) acrylate monomer is obtained, and the antibacterial monomer Bleed out can be suppressed. On the other hand, if A / B is 50/1 or less (the ratio of the polyfunctional pentaerythritol (meth) acrylate monomer is high), the antibacterial monomer is not buried in the polyfunctional pentaerythritol (meth) acrylate monomer and sufficient antibacterial properties are obtained. Sex can be expressed.

As a method for producing the antibacterial monomer according to the present invention, it can be synthesized by a known method. For example, as shown in the following reaction formula, it can be produced by reacting an acrylate or methacrylate component having a halogen atom such as bromine or chlorine at the terminal with an antibacterial group. In the following reaction formula, Z is a chlorine atom or a bromine atom, and can be replaced with Z ⁻ by a subsequent reaction of the reaction shown in the following reaction formula. In the following reaction formula, Y is a cationic group and has the same meaning as Y in the general formula (1).

  In the present invention, a known inorganic antibacterial agent or organic antibacterial agent can be used in combination with the antibacterial monomer, if necessary.

(Hard coat layer additives)
In addition to the above-described polyfunctional pentaerythritol (meth) acrylate monomer and antibacterial monomer, various additives can be used as necessary in the hard coat layer according to the present invention.

<Other curable resins (monomers) and thermoplastic resins>
In the hard coat layer according to the present invention, in addition to the polyfunctional pentaerythritol (meth) acrylate monomer and the antibacterial monomer according to the present invention, various curable resins (monomers) and heat can be used without impairing the effects of the present invention. A plastic resin can be used.

  The curable resin applicable to the present invention can be used without particular limitation as long as it forms a transparent resin composition by curing, such as silicon resin, epoxy resin, vinyl ester resin, acrylic resin, allyl. Examples include ester resins. Particularly preferably, an acrylic resin can be used from the viewpoints of hardness, smoothness, and transparency.

  Examples of the acrylic resin composition include acrylate compounds having a radical reactive unsaturated compound, mercapto compounds having an acrylate compound and a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate and the like. The thing etc. which dissolved the monofunctional and polyfunctional acrylate monomer are mentioned. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, bisphenol A- and the like, such as ethylene oxide-modified diacrylate. In the resin composition as described above, any mixture can be used, particularly if it contains a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. There is no limit.

  As the acrylic resin, from the viewpoint of hardness, smoothness, and transparency, reactivity in which a photosensitive group having photopolymerization reactivity is introduced on the surface as described in International Publication No. 2008/035669 is disclosed. Silica particles (hereinafter also simply referred to as “reactive silica particles”) may be included. Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin also contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be a thing. In addition, the polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to the silica particles by generating a silyloxy group by a hydrolysis reaction of the hydrolyzable silyl group. It can be used as reactive silica particles. Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle diameter in such a range, transparency, smoothness, and hardness can be satisfied in a well-balanced manner.

  Moreover, as an acrylic resin, a fluorine-containing vinyl monomer can also be used at the point which can adjust a refractive index. Examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), partial (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM). (Trade name, manufactured by Osaka Organic Chemical Co., Ltd.) and R-2020 (trade name, manufactured by Daikin) and the like, and complete or partially fluorinated vinyl ethers.

  In addition, examples of the thermoplastic resin include a polyester resin, an acrylic-modified polyester resin, a polyurethane resin, an acrylic resin, and a vinyl resin.

  As a photoinitiator, a well-known thing can be used and it can be used by 1 type, or 2 or more types of combination.

<Infrared absorber>
When the hard coat film of the present invention is applied to a heat ray blocking film or an organic element device, it is preferable to add an infrared absorber to the hard coat layer according to the present invention. By adding an infrared absorber, the value of the heat ray-shielding film can be increased by improving the heat ray-shielding property, and also suppresses the influence of heat on the organic element device when used in an organic element device. Can do.

  As the infrared absorber applicable to the present invention, known ones can be used, for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tungsten oxide-based compound, diimonium-based compound, aluminum-based compound, Examples include phthalocyanine compounds, organometallic complexes, cyanine compounds, azo compounds, polymethine compounds, quinone compounds, diphenylmethane compounds, and triphenylmethane compounds. Among these, ITO or ATO is preferably used from the viewpoints of transparency, infrared absorptivity, dispersibility in the resin, and the like.

  As an average particle diameter of ITO and ATO, 5-100 nm is preferable, and 10-50 nm is especially preferable. When the average particle size is 5 nm or more, stable dispersibility in the resin and infrared absorption can be obtained. On the other hand, if it is 100 nm or less, the fall of visible light transmittance can be prevented.

  The measurement of the average particle diameter in the present invention is obtained by taking an image with a transmission electron microscope, randomly extracting, for example, 50 ITO or ATO particles, measuring the particle diameter, and averaging these. Moreover, when the shape of particle | grains is not spherical, it defines as what was calculated by measuring a major axis.

  The content of the ITO and ATO particles in the hard coat layer is preferably 1.0 to 80% by mass and more preferably 5 to 50% by mass when the total solid content is 100% by mass. If the content of the infrared absorber is 1.0% by mass or more, a sufficient infrared absorption effect is exhibited, and if it is 80% by mass or less, a sufficient amount of visible light can be transmitted.

<Ultraviolet absorber (UV absorber)>
When the hard coat film of the present invention is applied to a heat ray shielding film or an organic element device, the hard coat layer according to the present invention preferably contains a UV absorber. By adding a UV absorber to the hard coat layer according to the present invention, when a heat ray blocking film or an organic element device is used, the influence of ultraviolet rays on the plastic substrate or the organic element device of the heat ray blocking film, for example, Photolysis, yellowing, influence on device performance, etc. can be suppressed.

  As the UV absorber applicable to the present invention, known ones can be used. For example, as inorganic particles, titanium dioxide, zinc oxide, cerium oxide, and hybrid inorganic obtained by complexing titanium dioxide fine particles with iron oxide. Examples thereof include powder and hybrid inorganic powder in which the surface of cerium oxide fine particles is coated with amorphous silica. On the other hand, examples of the organic UV absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based UV absorbers, and the like. Among these, inorganic particles are preferable from the viewpoints of transparency, UV absorption, dispersibility in the resin, and the like. Particularly preferred are titanium oxide and zinc oxide. The particle size of these inorganic particles is preferably 0.1 μm or less from the viewpoint of transparency and smoothness.

  UV absorbers are useful because they improve weather resistance when used in combination with light stabilizers. Examples of light stabilizers that can be used in combination include materials such as hindered amines.

  Although there is no restriction | limiting in particular as content of UV absorber in a hard-coat layer, From the point of transparency and smoothness, 0.1-50 mass% of hard-coat layer total solids, Preferably it is 1-20 mass%. It is a range.

<Other additives>
In addition to the above-described compounds, the hard coat layer according to the present invention includes an antioxidant, a plasticizer, a matting agent, a polymerization inhibitor, a fluorescent agent, a colorant, an activator, and an antifouling agent as necessary. Additives such as can be added. Moreover, as a solvent used when forming a hard-coat layer using the coating liquid which melt | dissolved or disperse | distributed resin in the solvent, a well-known thing can be used.

<Method for forming hard coat layer>
The method for forming the hard coat layer according to the present invention is not particularly limited, but may be formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as an evaporation method. preferable.

  As a method for curing the hard coat layer according to the present invention, heat treatment is used when a thermosetting resin is used, or ultraviolet rays or electron beams are irradiated when an actinic ray curable resin is used. Although there is a method, the method of irradiating with ultraviolet rays is preferred in the present invention. Ultraviolet rays are preferable in that the curing reaction can proceed in a short time, so that bleeding out of the antibacterial monomer in the reaction and insufficient reaction can be suppressed.

  As a method of irradiating the formed hard coat layer with ultraviolet rays, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, etc. are irradiated. It can be performed by a known method.

(Surface roughness)
In the hard coat layer according to the present invention, the surface roughness Ra (arithmetic average surface roughness Ra) is preferably 1 nm or more and 50 nm or less, more preferably Ra is 3 nm or more and 40 nm or less, and particularly preferably. Is 5 nm or more and 30 nm or less. The number of protrusions of 20 nm or more per 125 μm ² is preferably 10 or more and 10,000 or less, more preferably 30 or more and 5000 or less, and particularly preferably 100 or more and 3000. It is as follows.

  By setting the surface roughness Ra and the number of protrusions of 20 nm or more to the ranges specified above, the surface area is increased, the antibacterial efficiency is increased, and the antibacterial durability can be improved. That is, if the surface roughness Ra or the number of protrusions of 20 nm or more is equal to or more than the lower limit range specified above, the surface of the hard coat layer has sufficient roughness, and antibacterial maintainability can be obtained. On the other hand, if it is below the upper limit range specified above, the surface roughness does not become excessively large, and as a result, sufficient transparency can be obtained, and when used in a heat ray blocking film or an organic element device The visible light transmittance does not decrease and a good appearance can be obtained.

  The means for setting the surface roughness of the hard coat layer according to the present invention and the number of protrusions of 20 nm or more within the range specified in the present invention is not particularly limited, but for example, a monomer composition and additives used for forming the hard coat layer It can be controlled by the composition, particularly the type and amount of the organic solvent and surfactant, the addition of fillers such as a matting agent, the drying conditions after forming the hard coat layer, and the UV irradiation conditions.

  The surface roughness (Ra) and the number of protrusions of 20 nm or more of the hard coat layer according to the present invention can be measured based on images obtained by an atomic force microscope according to the methods and conditions described below. Shows an example of a specific measurement method.

  First, after cutting a sample having a hard coat layer to be measured into a 1.0 cm square size, setting it on a horizontal sample stage on a piezo scanner, approaching the cantilever to the sample surface, and a region where atomic force works When the value reaches the XY direction, scanning is performed in the XY directions, and in this case, the unevenness of the sample is captured by the displacement of the piezoelectric element in the Z direction.

  With respect to the concavo-convex image obtained by the atomic force microscope, two straight lines are arbitrarily drawn in a direction perpendicular to the direction in which the concave portions and / or convex portions are connected, and a contour curve (cross-sectional curve) is drawn on the portion on the straight line. Ask for each.

  Next, the surface roughness is obtained from the contour curve (cross-sectional curve) on these straight lines. 20 places are measured at different places, and the arithmetic average is Ra. In addition, a slice line is selected at 20 nm on the measurement visual field, and the number of protrusions of 20 nm or more is measured. In addition, the specific measurement conditions used by the measurement by the said method are as follows.

Surface roughness measuring device: Nanoscope IIIa AFM (manufactured by Digital Instruments)
Cantilever: Silicon single crystal Scanning mode: Tapping mode Scanning speed: 0.5Hz
Measurement field: 125 μm ²
Z range: 7 to 15 times Ra obtained from the cross section curve Flatten filter Mode: Flatten auto Order: 3
《Heat ray blocking film》
The heat ray blocking film of the present invention is a heat ray reflective unit comprising a structure in which the hard coat layer film of the present invention is provided on one surface on a substrate and two or more layers having different refractive indexes are alternately laminated on the other surface. It is preferable to have at least two or more.

  Hereinafter, in a configuration in which two or more layers having different refractive indexes are alternately stacked, a layer having a relatively high refractive index is referred to as a “high refractive index layer”, and a layer having a relatively low refractive index is referred to as “low refractive index”. It will be referred to as “rate layer”.

  In the reflection type of the heat ray blocking film of the present invention, the larger the difference in the refractive index between the high refractive index layer and the low refractive index layer, the more preferable in view of increasing the heat ray (infrared) reflectance with a small number of layers. However, in the present invention, at least two or more units composed of a high refractive index layer and a low refractive index layer, and the refractive index difference between the adjacent high refractive index layer and low refractive index layer is 0.1 or more. Preferably there is. Especially preferably, it is 0.3 or more, More preferably, it is 0.4 or more.

  The number of units depends on the refractive index difference between the high refractive index layer and the low refractive index layer, but when the high refractive index layer and the low refractive index layer are one unit, it is preferably 40 units or less, more preferably 20 units or less. More preferably, it is 10 units or less.

  Incidentally, in the present invention, the refractive indexes of the high refractive index layer and the low refractive index layer can be determined according to the following method.

  A sample in which each refractive index layer whose refractive index is to be measured is coated as a single layer on a substrate is prepared, and the sample is cut into 10 cm × 10 cm, and then the refractive index is obtained according to the following method.

  Using a U-4000 type (manufactured by Hitachi, Ltd.) as a spectrophotometer, the back side on the measurement side of each sample is roughened, and then light absorption is performed with a black spray to reflect light on the back side. In this case, the reflectance of the visible light region (400 to 700 nm) is measured at 25 points under the condition of regular reflection at 5 degrees to obtain an average value, and the average refractive index is obtained from the measurement result.

  In the present invention, the preferable refractive index of the high refractive index layer is 1.80 to 2.50, more preferably 1.90 to 2.20. Moreover, as a preferable refractive index of a low-refractive-index layer, it is 1.10-1.60, More preferably, it is 1.30-1.50.

  In the heat ray blocking film of the present invention, a layer structure in which the layer adjacent to the substrate is a low refractive index layer containing silicon oxide and the outermost layer is also a low refractive index layer containing silicon oxide is preferable.

  In a preferred embodiment, the high refractive layer and the low refractive index layer in the present invention each contain metal oxide particles and a water-soluble resin.

[Metal oxide]
Examples of the metal oxide according to the present invention include titanium dioxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide. And ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide.

  The content of the metal oxide is preferably 50% by mass or more and 95% by mass or less, and more preferably 60% by mass or more and 90% by mass or less. By setting the content of the metal oxide to 50% by mass or more, it becomes easy to increase the refractive index difference between the high refractive index layer and the low refractive index layer, and the content of the metal oxide is set to 95% by mass or less. By this, the film | membrane flexibility is obtained and it becomes easy to form a heat ray blocking film.

  In each refractive index layer, the mass ratio (F / B) between the metal oxide particles (F) and the water-soluble polymer (B) that is a binder constituting each layer is in the range of 0.5 to 20. It is preferable that there is, and more preferably 1.0 to 10.

As the metal oxide used in the high refractive index layer according to the present invention, TiO ₂ , ZnO and ZrO ₂ are preferable, and from the viewpoint of the stability of the metal oxide particle-containing composition described later for forming the high refractive index layer. TiO ₂ (titanium dioxide sol) is more preferable. Of TiO _2, the rutile type is preferable because the catalyst activity is low and the weather resistance of the high refractive index layer and the adjacent layer is high, and the refractive index is high.

  Examples of the method for preparing the titanium dioxide sol that can be used in the present invention include JP-A 63-17221, JP-A 7-819, JP-A 9-165218, and JP-A 11-43327. Can be a reference.

  As other methods for preparing titanium dioxide sol, refer to, for example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, and the like. be able to.

  The preferable primary particle diameter of the titanium dioxide fine particles is 4 to 50 nm, and more preferably 4 to 30 nm.

  In the low refractive index layer according to the present invention, as the metal oxide particles, silicon dioxide particles are preferably used, and acidic colloidal silica sol is particularly preferably used.

  The silicon dioxide particles according to the present invention preferably have an average particle size of 100 nm or less. The average particle diameter of silicon dioxide dispersed in the primary particle state (particle diameter in the dispersion state before coating) is preferably 20 nm or less, more preferably 10 nm or less. Moreover, as an average particle diameter of secondary particle | grains, it is preferable from a viewpoint with few hazes and excellent visible light transmittance | permeability that it is 30 nm or less.

The volume average particle diameter of the titanium oxide particles or silicon dioxide particles according to the present invention refers to a method of observing the particles themselves using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, and a cross section of the refractive index layer. the method of observing the particle image appearing on or surface with an electron microscope, 1,000 the particle size of any particles is measured, the particle diameter of _{d 1, d 2 ··· d i} ··· d k respectively In a group of titanium oxide particles and silicon dioxide particles in which n ₁ , n ₂ ... N _i ... _K exist, respectively, the volume average is obtained when the volume per particle is v _i. Particle size m _v = average particle size weighted by the volume represented by {Σ (v _i · d _i )} / {Σ (v _i )}.

(Water-soluble polymer)
In the present invention, it is preferable that at least one of two or more layers having different refractive indexes contains a water-soluble polymer together with metal oxide particles.

  The water-soluble polymer that can be used in the present invention is preferably at least one selected from polymers obtained by vinyl polymerization, inorganic polymers, thickening polysaccharides, and gelatin.

  The “water-soluble” as used in the water-soluble polymer according to the present invention is a polymer compound that dissolves in an aqueous medium by 30% by mass or more, and preferably 40% by mass or more.

  The concentration of the water-soluble polymer in the coating solution for forming a high refractive layer and the coating solution for forming a low refractive index layer according to the present invention is preferably 0.3 to 3.0% by mass, and 0.35 to 2%. More preferably, it is in the range of 0.0 mass%.

<Polymers obtained by vinyl polymerization>
Examples of the water-soluble polymer applicable to the present invention include polymers obtained by vinyl polymerization, such as polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate. -Acrylic resins such as acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, or acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene -Styrene acrylic acid resin such as methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, or styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene- Sodium styrenesulfonate copolymer, Examples thereof include styrene-2-hydroxyethyl acrylate copolymers, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymers, styrene-maleic acid copolymers, and salts thereof. Among these, particularly preferable examples include polyvinyl alcohol, polyvinyl pyrrolidones, and copolymers containing the same.

  The weight average molecular weight of the water-soluble polymer is preferably 1,000 or more and 200,000 or less. Furthermore, 3,000 or more and 40,000 or less are more preferable.

  The polyvinyl alcohol preferably used in the present invention includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a cation-modified terminal and anion-modified polyvinyl alcohol having an anionic group. Alcohol is also included.

<Inorganic polymer>
Examples of the inorganic polymer include an inorganic polymer composed of a metal oxide formed by hydrolytic polycondensation of a metal salt compound capable of hydrolysis polycondensation by a so-called sol-gel method. An inorganic polymer formed by hydrolytic polycondensation of a compound containing a zirconium atom or a compound containing an aluminum atom is preferable.

  These inorganic polymers also have an effect of containing water in the containing layer itself, as in the case of polyvinyl alcohol, because OH groups generated in the hydrolysis process remain after the polycondensation reaction. Moreover, it is considered that the flexibility is improved because the inorganic polymer forms a network of hydrogen bonds of OH.

  Specific examples of the compound containing a zirconium atom as a precursor of these inorganic polymers include zirconium difluoride, zirconium trifluoride, zirconium tetrafluoride, hexafluorozirconium salt (for example, potassium salt), heptafluorozirconium. Acid salts (for example, sodium salts, potassium salts and ammonium salts), octafluorozirconium salts (for example, lithium salts), zirconium fluoride oxide, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, hexachlorozirconium salts (for example, , Sodium salt and potassium salt), zirconium oxychloride (zirconyl chloride), zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium bromide oxide, zirconium triiodide, zirconium tetraiodide, zirconium peroxide Zirconium hydroxide, zirconium sulfide, zirconium sulfate, zirconium p-toluenesulfonate, zirconyl sulfate, sodium zirconyl sulfate, acidic zirconyl sulfate trihydrate, potassium zirconium sulfate, zirconium selenate, zirconium nitrate, zirconyl nitrate, phosphoric acid Zirconium, zirconyl carbonate, zirconyl ammonium carbonate, zirconium acetate, zirconyl acetate, zirconyl ammonium acetate, zirconyl lactate, zirconyl citrate, zirconyl stearate, zirconyl phosphate, zirconium oxalate, zirconium isopropylate, zirconium butyrate, zirconium acetylacetonate , Acetylacetone zirconium butyrate, zirconium stearate butyrate, zirconium acetate, vinyl (Acetylacetonato) dichloro zirconium and tris (acetylacetonato) chloro zirconium, and the like.

  Specific examples of the compound containing an aluminum atom that can be used in the present invention include aluminum fluoride, hexafluoroaluminic acid (for example, potassium salt), aluminum chloride, basic aluminum chloride (for example, polyaluminum chloride), and tetrachloro. Aluminates (eg, sodium salts), aluminum bromides, tetrabromoaluminates (eg, potassium salts), aluminum iodide, aluminates (eg, sodium, potassium, calcium salts), aluminum chlorate, Aluminum perchlorate, aluminum thiocyanate, aluminum sulfate, basic aluminum sulfate, potassium aluminum sulfate (alum), ammonium aluminum sulfate (ammonium alum), sodium aluminum sulfate, aluminum phosphate, Aluminum phosphate, Aluminum hydrogen phosphate, Aluminum carbonate, Aluminum polysulfate silicate, Aluminum formate, Aluminum acetate, Aluminum lactate, Aluminum oxalate, Aluminum isopropylate, Aluminum butyrate, Ethyl acetate aluminum diisopropylate, Aluminum tris (acetylacetonate), Aluminum tris (ethyl acetoacetate), aluminum monoacetylacetonate bis (ethyl acetoacetonate), etc. can be mentioned.

<Thickening polysaccharide>
The thickening polysaccharide that can be used in the present invention is not particularly limited, and examples thereof include generally known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. The details of these polysaccharides can be referred to “Biochemical Encyclopedia (2nd edition), Tokyo Chemical Doujinshi”, “Food Industry”, Vol. 31 (1988), p.

  The thickening polysaccharide referred to in the present invention is a polymer of saccharides and has many hydrogen bonding groups in the molecule, and the viscosity at low temperature and the viscosity at high temperature due to the difference in hydrogen bonding force between molecules depending on the temperature. It is a polysaccharide with a large difference in characteristics, and when adding metal oxide fine particles, it causes a viscosity increase that seems to be due to hydrogen bonding with the metal oxide fine particles at a low temperature. When added, it is a polysaccharide that increases its viscosity at 15 ° C. by 1.0 mPa · s or more, preferably 5.0 mPa · s or more, more preferably 10.0 mPa · s or more. Polysaccharides.

  Examples of the thickening polysaccharide applicable to the present invention include galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, etc.), Glucomannoglycan (eg, salmon mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (eg, softwood-derived glycan), arabinogalactoglycan (eg, soybean-derived glycan, microorganism-derived glycan, etc.), Red algae such as glucuronoglycan (for example, gellan gum), glycosaminoglycan (for example, hyaluronic acid, keratan sulfate, etc.), alginic acid and alginates, agar, κ-carrageenan, λ-carrageenan, ι-carrageenan Derived from Natural polymeric polysaccharides and the like, from the viewpoint of not lowering the dispersion stability of the metal oxide fine particles coexisting in the coating solution, preferably, those whose structural unit has no carboxyl group or sulfonic acid group. Such polysaccharides include, for example, pentoses such as L-arabitose, D-ribose, 2-deoxyribose and D-xylose, and hexoses such as D-glucose, D-fructose, D-mannose and D-galactose only. It is preferable that it is a polysaccharide. Specifically, tamarind seed gum known as xyloglucan whose main chain is glucose and side chain is glucose, guar gum known as galactomannan whose main chain is mannose and side chain is glucose, cationized guar gum, Hydroxypropyl guar gum, locust bean gum, tara gum, and arabinogalactan whose main chain is galactose and whose side chain is arabinose can be preferably used. In the present invention, tamarind, guar gum, cationized guar gum, and hydroxypropyl guar gum are particularly preferable.

  In the present invention, it is further preferable to use two or more thickening polysaccharides in combination.

<gelatin>
In the high refractive index layer according to the present invention, gelatin can be used as the water-soluble polymer.

  As the gelatin applicable to the present invention, various gelatins that have been widely used in the field of silver halide photographic light-sensitive materials can be applied. For example, in addition to acid-processed gelatin and alkali-processed gelatin, production of gelatin is possible. Enzyme-treated gelatin and gelatin derivatives that undergo enzyme treatment in the process, that is, modified by treatment with a reagent that has an amino group, imino group, hydroxyl group, carboxyl group as a functional group in the molecule and a group obtained by reaction with it. You may have done. The general method for producing gelatin is well known and is described, for example, in T.W. H. James: The Theory of Photographic Process 4th. ed. Reference can be made to descriptions such as 1977 (Machillan) 55, Science Photo Handbook (above) 72-75 (Maruzen), Fundamentals of Photographic Engineering-Silver Salt Photographs 119-124 (Corona). Also, Research Disclosure Magazine Vol. 176, No. And gelatin described in Section IX of 17643 (December, 1978).

<Curing agent>
In the present invention, it is preferable to use a curing agent in order to cure the water-soluble polymer as a binder.

  The curing agent applicable to the present invention is not particularly limited as long as it causes a curing reaction with a water-soluble polymer. However, when the water-soluble polymer is polyvinyl alcohol, boric acid and its salt are preferable. However, other known compounds can be used and are generally compounds having groups capable of reacting with water-soluble polymers or compounds that promote the reaction between different groups of water-soluble polymers. The polymer is appropriately selected according to the type of the conductive polymer. Specific examples of the curing agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3,5) -S-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum and the like.

  Boric acid or a salt thereof refers to an oxygen acid having a boron atom as a central atom and a salt thereof, specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaboron. Examples include acids and their salts.

  Boric acid having a boron atom and a salt thereof as a curing agent may be used as a single aqueous solution or as a mixture of two or more. Particularly preferred is a mixed aqueous solution of boric acid and borax.

  The aqueous solutions of boric acid and borax can be added only in relatively dilute aqueous solutions, respectively, but by mixing both, a concentrated aqueous solution can be obtained and the coating solution can be concentrated. Further, there is an advantage that the pH of the aqueous solution to be added can be controlled relatively freely.

  The total amount of the curing agent used is preferably 1 to 600 mg per 1 g of the water-soluble polymer.

[Surfactant]
In the unit in which two or more layers having different refractive indexes constituting the heat ray reflective unit according to the present invention are alternately laminated, at least one layer may contain a surfactant. As the surfactant species, any of anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In particular, acetylene glycol-based nonionic surfactants, quaternary ammonium salt-based cationic surfactants and fluorine-based cationic surfactants are preferred.

  Specific examples of the surfactant include acetylene glycol-based nonionic surfactants such as Olphine E1004 and Olefi E1010 manufactured by Nissin Chemical Industry, and examples of the fluorine-based cationic surfactant include AGC Seimi. Examples include Surflon S221 manufactured by Chemical Corporation.

  In the present invention, the addition amount of the surfactant is preferably 0.005 to 0.30% by mass as the solid content when the respective coating liquids are 100% by mass, and more preferably 0.01%. It is preferable that it is -0.10 mass%.

[Other additives]
Next, other additives applicable to the layers having different refractive indexes constituting the heat ray reflective unit according to the present invention include amino acids, lithium compounds, emulsion resins (oil-soluble monomers, emulsions in aqueous solutions containing dispersants) Examples thereof include resin fine particles which are emulsion-polymerized using a polymerization initiator while maintaining the state, and compounds described in the following patent publications. For example, the ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988 and JP-A-62-261476, JP-A-57-74192, JP-A-57-87989, JP-A-60- No. 72785, 61-146591, JP-A-1-95091 and 3-13376, etc., JP-A-59-42993, 59-52689 , 62-280069, 61-242871, and JP 4-219266, etc., optical brighteners, sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide Contains various known additives such as pH adjusters such as potassium carbonate, antifoaming agents, lubricants such as diethylene glycol, preservatives, antistatic agents, and matting agents. Rukoto can also.

[Method for producing heat ray blocking film]
Various known production methods can be applied as the production method of the heat ray blocking film of the present invention. In this invention, it is preferable that it is a manufacturing method of the aspect which has the process of forming the layer which comprises the heat ray blocking film of this invention especially using a water-system coating liquid. That is, the heat ray blocking film of the present invention is composed of a high refractive index layer and a low refractive index layer on a base material and is formed by laminating units. It is preferable to form a laminate by wet coating alternately with the refractive index layer coating solution, or by simultaneously coating all the constituent layers simultaneously and drying.

  Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791. The slide bead coating method using the described hopper, the extrusion coating method and the like are preferably used.

  When the slide bead coating method is used, the viscosity of the high refractive index layer coating solution and the low refractive index layer coating solution in simultaneous multilayer coating is preferably in the range of 5 to 100 mPa · s, more preferably 10 to 10 mPa · s. The range is 50 mPa · s. Moreover, when using a curtain application | coating system, the range of 5-1200 mPa * s is preferable, More preferably, it is the range of 25-500 mPa * s.

  Further, the viscosity at 15 ° C. of the coating solution is preferably 100 mPa · s or more, more preferably 100 to 30,000 mPa · s, further preferably 3,000 to 30,000 mPa · s, and most preferably 10 , 30,000 to 30,000 mPa · s.

  As a drying method after coating, the coating temperature of the formed coating film is set to 1 to 15 ° C. after heating and applying the aqueous high refractive index layer coating solution and the low refractive index layer coating solution to 30 ° C. or higher. It is preferable that the temperature is once cooled and dried at 10 ° C. or higher. More preferably, the drying conditions are a wet bulb temperature of 5 to 50 ° C. and a film surface temperature of 10 to 50 ° C. Moreover, as a cooling method immediately after application | coating, it is preferable to carry out by a horizontal set system from a viewpoint of the formed coating-film uniformity.

[Application of heat ray blocking film]
The heat ray shielding film of the present invention can be applied to a wide range of fields. For example, film for window pasting such as heat ray reflecting film that gives heat ray reflecting effect, film for agricultural greenhouse etc. As, it is mainly used for the purpose of improving the weather resistance.

  In particular, the heat ray shielding film according to the present invention is suitable for a member bonded to glass or a glass substitute resin base material directly or via an adhesive.

  The adhesive is placed so that the heat ray blocking film is on the sunlight (heat ray) incident surface side when bonded to a window glass or the like. Further, when the heat ray blocking film is sandwiched between the window glass and the base material, it can be sealed from ambient gas such as moisture, which is preferable for durability. Even if the heat ray blocking film of the present invention is installed outdoors or on the outside of a vehicle (for external application), it is preferable because of environmental durability.

  As an adhesive applicable to the present invention, an adhesive mainly composed of a photocurable or thermosetting resin can be used.

  The adhesive preferably has durability against ultraviolet rays. For example, an acrylic adhesive or a silicon adhesive is preferable. Furthermore, an acrylic adhesive is preferable from the viewpoint of adhesive properties and cost. In particular, since the peel strength can be easily controlled, a solvent system is preferable among the solvent system and the emulsion system in the acrylic adhesive. When a solution polymerization polymer is used as the acrylic solvent-based pressure-sensitive adhesive, known monomers can be used as the monomer.

  Moreover, you may use the polyvinyl butyral resin used as an intermediate | middle layer of a laminated glass, or ethylene-vinyl acetate copolymer type resin. Specifically, plastic polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.), ethylene-vinyl acetate copolymer (manufactured by DuPont, Takeda Pharmaceutical Co., Ltd., duramin), modified ethylene-vinyl acetate copolymer (Mersen G, manufactured by Tosoh Corporation). In addition, you may add and mix | blend an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, coloring, an adhesion regulator etc. suitably in an adhesion layer.

《Organic element device》
One feature of the hard coat film of the present invention is that it is used as a film for an organic element device. Examples of the organic element device of the present invention include an organic electroluminescence element (hereinafter abbreviated as an organic EL element), an organic photoelectric conversion element, and the like. Below, the detail at the time of applying the hard coat film of this invention to an organic EL element and an organic photoelectric conversion element as an organic element device is demonstrated.

[Organic electroluminescence device]
(Configuration of organic electroluminescence element)
Although the details of the embodiment of the organic EL element which is an example of the organic element device of the present invention will be described, the contents described below are representative examples of the embodiment of the present invention, and the present invention does not exceed the gist thereof. However, it is not limited to these contents.

  Preferred specific examples of the layer structure of the organic EL element are shown below.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode Here, in order for the light generated in the light emitting layer to be emitted to the outside, it is necessary that at least one of the anode and the cathode is transparent. In the method, it is preferable to use the transparent conductive layer mainly as an anode.

  The light emitting layer preferably contains at least two kinds of light emitting materials having different emission colors, and a single layer or a light emitting layer unit composed of a plurality of light emitting layers may be formed. The hole transport layer also includes a hole injection layer and an electron blocking layer.

(Constituent elements of organic electroluminescence elements)
<Transparent conductive layer>
As the transparent conductive layer in the organic EL device according to the present invention, a material having a work function (4 eV or more) of a metal, an alloy, an electrically conductive compound and a mixture thereof as an electrode material for forming the transparent conductive layer is preferably used. It is done. Specific examples of such an electrode material include metals such as Au, and conductive light transmissive materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, a material such as IDIXO (In ₂ O ₃ —ZnO) that can form an amorphous light-transmitting conductive film may be used. In the present invention, the transparent conductive layer is preferably used as an anode. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method. ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film forming methods, such as a printing system and a coating system, can also be used. The sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 50 to 200 nm.

  In the transparent conductive layer, metal nanowires can also be used. In the case of using metal nanowires, in order to form a long conductive path with one metal nanowire, and from the viewpoint of expressing appropriate light scattering properties, the average length is preferably 3 μm or more, and more preferably 3 to 500 μm. In particular, the thickness is preferably 3 to 300 μm. In addition, the relative standard deviation of the length is preferably 40% or less. In addition, the average diameter is preferably small from the viewpoint of transparency, and conversely, it is preferably large from the viewpoint of conductivity. However, in the present invention, the average diameter of the metal nanowire should be in the range of 10 to 300 nm. Is preferable, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  The metal composition of the metal nanowire is not particularly limited, and may be composed of one or more metals such as a noble metal element and a base metal element, but noble metals (for example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium) , Osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper and tin, and more preferably at least silver from the viewpoint of conductivity.

  In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire contains two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire may have the same metal composition.

  As a manufacturing method of Ag nanowire, for example, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. 2002, 14, 4736-4745, etc. As a method for producing Au nanowires, for example, JP 2006-233252A, etc. As a method for producing Cu nanowires, for example, JP 2002-266007 A, etc., Co nanowires For example, Japanese Patent Application Laid-Open No. 2004-149871 can be referred to as a manufacturing method of the above. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can easily produce Ag nanowires in water, and since silver has the highest conductivity in metals, it can be preferably applied as a method for producing metal nanowires. it can.

<Light emitting layer>
The light-emitting layer is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light-emitting portion is the light-emitting layer even in the light-emitting layer. It may be an interface with an adjacent layer.

  As a light emitting layer, if the light emitting material contained satisfies the said requirements, there will be no restriction | limiting in particular in the structure. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. Moreover, it is preferable to have a non-light emitting intermediate | middle layer between each light emitting layer.

  The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably 1 nm or more and 30 nm or less because a lower driving voltage can be obtained. Note that the total film thickness of the light emitting layer is a film thickness including the intermediate layer when a non-light emitting intermediate layer exists between the light emitting layers.

  The thickness of each light emitting layer is preferably adjusted to a range of 1 to 50 nm, more preferably adjusted to a range of 1 to 20 nm. There is no particular limitation on the relationship between the film thicknesses of the blue, green and red light emitting layers.

  For the formation of the light emitting layer, a light emitting material or a host compound, which will be described later, is formed by forming a film by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. it can.

  A plurality of light emitting materials may be mixed in each light emitting layer, and a phosphorescent light emitting material and a fluorescent light emitting material may be mixed and used in the same light emitting layer.

  As a structure of the light emitting layer, it is preferable to contain a host compound and a light emitting material (also referred to as a light emitting dopant compound) and emit light from the light emitting material.

  As the host compound contained in the light emitting layer of the organic EL device, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

  As the known host compound, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable. Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

  Specific examples of known host compounds include compounds described in the following documents. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. , 2002-302516, 2002-305083, 2002-305084, 2002-308837 and the like.

  Next, the light emitting material will be described.

  In the organic EL device according to the present invention, a fluorescent compound or a phosphorescent material (also referred to as a phosphorescent compound or a phosphorescent compound) can be used as the light emitting material.

  A phosphorescent material is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0.01 or more at 25 ° C. However, the preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. The phosphorescence quantum yield in a solution can be measured using various solvents. However, when a phosphorescent material is used in the present invention, the phosphorescence quantum yield (0.01 or more) is achieved in any solvent. Just do it.

  There are two types of light-emitting principles of phosphorescent materials. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent material. This is an energy transfer type that obtains light emission from the phosphorescent light emitting material, and the other is that the phosphorescent light emitting material becomes a carrier trap, and recombination of carriers occurs on the phosphorescent light emitting material, and light emission from the phosphorescent light emitting material is obtained. Although it is a carrier trap type, in any case, it is a condition that the excited state energy of the phosphorescent material is lower than the excited state energy of the host compound.

  The phosphorescent light-emitting material can be appropriately selected from known compounds used in the light-emitting layer of the organic EL element, but is preferably a complex system containing a group 8-10 metal in the periodic table of elements. A compound, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex, and most preferably an iridium compound.

  In the organic EL element, a fluorescent light emitter can also be used. Typical examples of fluorescent emitters (fluorescent dopants) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, and pyrylium dyes. Examples thereof include dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Conventionally known dopants can also be used in the present invention. For example, WO 00/70655, JP-A 2002-280178, 2001-181616, 2002-280179, 2001-181617, 2002-280180, 2001-247859, 2002-299060, 2001-313178, 2002-302671, 2001-345183, 2002 No. 324679, International Publication No. 02/15645, JP 2002-332291 A, 2002-50484, 2002-332292, 2002-83684, JP 2002-540572 A JP, 2002-11 No. 978, No. 2002-338588, No. 2002-170684, No. 2002-352960, WO 01/93642, JP-A No. 2002-50483, No. 2002-1000047. JP 2002-173674, 2002-359082, 2002-17584, 2002-363552, 2002-184582, 2003-7469, JP 2002-525808, JP 2003-7471 A, JP 2002-525833 A, JP 2003-31366 A, 2002-226495 A, 2002-234894 A, 2002-23076 A, 2002-241751 Gazette, 200 -319779, 2001-319780, 2002-62824, 2002-1000047, 2002-203679, 2002-343572, 2002-203678, and the like. .

  In the present invention, at least one light emitting layer may contain two or more kinds of light emitting materials, and the concentration ratio of the light emitting materials in the light emitting layer may vary in the thickness direction of the light emitting layer.

<Intermediate layer>
Next, a case where a non-light emitting intermediate layer (also referred to as an undoped region) is provided between the light emitting layers will be described.

  In the present invention, the non-light-emitting intermediate layer is a layer provided between the light-emitting layers when having a plurality of light-emitting layers. The film thickness of the non-light emitting intermediate layer is preferably in the range of 1 to 20 nm, and further in the range of 3 to 10 nm suppresses interaction such as energy transfer between adjacent light emitting layers, and the current of the device This is preferable because a large load is not applied to the voltage characteristics.

  The material used for the non-light emitting intermediate layer may be the same as or different from the host compound of the light emitting layer, but may be the same as the host material of at least one of the adjacent light emitting layers. preferable.

  The non-light-emitting intermediate layer may contain a non-light-emitting layer, a compound common to each light-emitting layer (for example, a host compound), and each common host material (where a common host material is used) , Phosphorescent emission energy, glass transition point and other physicochemical properties, and the case where the host compound has the same molecular structure, etc.). The injection barrier is reduced, and it is possible to obtain an effect that the injection balance of holes and electrons can be easily maintained even when the voltage (current) is changed. Furthermore, by using a host material having the same physical characteristics or the same molecular structure as the host compound contained in each light-emitting layer in the undoped light-emitting layer, device fabrication, which is a major problem in conventional organic EL device fabrication, is achieved. Complexity can also be eliminated.

  Since the host material is responsible for carrier transportation, a material having carrier transportation ability is preferable. Although carrier mobility is used as a characteristic value representing carrier transport ability, the carrier mobility of organic materials generally depends on the electric field strength. Since a material having a high electric field strength dependency easily breaks the balance of hole and electron injection / transport, it is preferable to use a material having a low mobility electric field strength dependency for the intermediate layer material and the host material.

  On the other hand, in order to optimally adjust the injection balance of holes and electrons, it is also preferable that the non-light emitting intermediate layer functions as a blocking layer described later, that is, a hole blocking layer and an electron blocking layer. As mentioned.

<Injection layer: electron injection layer, hole injection layer>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  In a broad sense, the hole blocking layer has a function of an electron transport layer and is composed of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes, and transports electrons. However, the probability of recombination of electrons and holes can be improved by blocking holes. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer.

  On the other hand, the electron blocking layer, in a broad sense, has the function of a hole transport layer and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports holes. However, the recombination probability of electrons and holes can be improved by blocking electrons. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thicknesses of the hole blocking layer and the electron transport layer are preferably 3 to 100 nm, and more preferably 5 to 30 nm.

<Hole transport layer>
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  As the hole transport material, the above-mentioned materials can be used, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds are preferably used, and aromatic tertiary amine compounds are particularly used. preferable.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Containing a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPD), JP-A-4-3 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8688 are linked in a starburst type ( (Abbreviation: MTDATA).

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  For the hole transport layer, the hole transport material is a known material such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, a Langmuir-Blodgett method (hereinafter abbreviated as LB method), and the like. The thin film can be formed by the method. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  It is preferable to use such a hole transport layer having a high p property because an organic EL element with lower power consumption can be produced.

<Electron transport layer>
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc., and the central metal of these metal complexes A metal complex in which In, Mg, Cu, Ca, Sn, Ga, or Pb is replaced can also be used as an electron transporting material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Further, the distyrylpyrazine derivatives exemplified as the material of the light emitting layer can also be used as the electron transport material, and inorganic semiconductors such as n-type-Si and n-type-SiC can be used as well as the hole injection layer and the hole transport layer. It can be used as an electron transport material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use an electron transport layer having such a high n property because an element with lower power consumption can be manufactured.

<Counter electrode>
The counter electrode is an electrode facing the transparent conductive layer described above. In the present invention, since the transparent conductive layer is mainly used as an anode, the following cathode can be used as the counter electrode. As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after forming the said metal with a film thickness of 1 nm-20 nm as a cathode, a transparent or semi-transparent cathode can be produced by forming a conductive transparent material on it, and applying this Thus, an organic EL element in which both the anode and the cathode are transmissive can be manufactured.

[Method for manufacturing organic electroluminescence element]
The organic EL of the present invention can be produced by sequentially forming a light extraction layer, a transparent conductive layer, an organic electroluminescence layer, and a counter electrode on a transparent substrate.

(Method for forming transparent conductive layer)
A transparent conductive layer can be formed on a transparent substrate using a desired electrode material. For example, when ITO (indium oxide added with tin) is used as the electrode material, the transparent conductive layer can be formed by a method such as vapor deposition or sputtering. In addition, a transparent conductive layer can be formed from a material containing metal nanowires, a conductive polymer, or a transparent conductive metal oxide by a liquid phase film forming method such as a coating method or a printing method.

  From the viewpoint of improving productivity, improving electrode quality such as smoothness and thin film uniformity of the obtained transparent conductive layer, and reducing environmental impact, the transparent conductive layer containing metal nanowires can be applied in a liquid phase such as coating or printing. It is preferable to form by a film forming method. As coating methods, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method Etc. can be used. As the printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used. In addition, as necessary, physical surface treatment such as corona discharge treatment or plasma discharge treatment can be applied to the surface of the releasable base material as a preliminary treatment for improving adhesion and coating properties.

(Formation of organic electroluminescence layer)
In the present invention, an anode buffer layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, a layer formed between all or part of the cathode buffer layer, formed between the transparent conductive layer and the cathode, It is called an organic electroluminescence layer (hereinafter also referred to as an organic EL layer). As an example of a method for producing this organic electroluminescence layer, a method for producing an organic electroluminescence layer comprising a hole injection layer / a hole transport layer / a light emitting layer / a hole blocking layer / an electron transport layer will be described below.

  On the transparent substrate on which the transparent conductive layer is formed according to the above method, the organic compound thin film of the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron transport layer, which are constituent materials of the organic EL layer, is formed. Let it form.

As a method for thinning the organic compound thin film, there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but it is easy to obtain a uniform film and a pinhole. From the point of being difficult to form, a vacuum deposition method, a spin coating method, an ink jet method, and a printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When employing a vapor deposition method for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is 50 to 450 ° C., the degree of vacuum is 10 ⁻⁶ to 10 ⁻² Pa, and the vapor deposition rate is 0. It is desirable to select from 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., a film thickness of 0.1 nm to 5 μm, preferably 5 to 200 nm.

(Formation of cathode)
After forming the organic electroluminescence layer, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 50 to 200 nm, A cathode is provided.

  Through the above steps, an organic electroluminescence layer is obtained. The organic electroluminescence layer is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor liquid crystal display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

[Organic light conversion element]
Although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated, it is not limited to this. There is no restriction | limiting in particular as an organic photoelectric conversion element, At least 1 layer of the electric power generation layer (The layer in which p type semiconductor and n type semiconductor were mixed, a bulk heterojunction layer, i layer) was sandwiched between the anode and the cathode. It may be any element that has a current and generates a current when irradiated with light.

  The preferable specific example of the layer structure of an organic photoelectric conversion element is shown below.

(I) Anode / power generation layer / cathode (ii) Anode / hole transport layer / power generation layer / cathode (iii) Anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first light-emitting layer / electron transport layer / intermediate electrode / hole transport layer / second light-emitting layer Here, the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons, which are substantially two layers and heterojunction. Alternatively, a bulk heterojunction in a mixed state in one layer may be formed, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

  Like an organic EL element, in an organic light conversion element, a power generation layer is sandwiched between a hole transport layer and an electron transport layer, so that the efficiency of extracting holes and electrons to the anode and cathode can be increased. (Items (ii) and (iii) above) are preferred. In addition, in order to enhance the rectification of holes and electrons (selection of carrier extraction), the power generation layer itself is composed of a layer composed of a p-type semiconductor material and a single n-type semiconductor material as described in the above item (iv). A structure (also referred to as a pin structure) may be employed. Moreover, in order to improve the utilization efficiency of sunlight, a tandem configuration (configuration described in the above (v)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

  For the purpose of improving the sunlight utilization rate (photoelectric conversion efficiency), instead of the sandwich structure in the organic photoelectric conversion element 10 shown in FIG. 1 described below, a hole transport layer 14 is respectively formed on a pair of comb-like electrodes, A back contact type organic photoelectric conversion element in which the electron transport layer 16 is formed and the photoelectric conversion portion 15 is disposed thereon may be configured.

  Furthermore, the preferable aspect of the organic photoelectric conversion element which concerns on detailed this invention is demonstrated below.

  FIG. 1 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element.

  In FIG. 1, a bulk heterojunction organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a bulk heterojunction power generation layer 14, an electron transport layer 18, and a cathode 13 in this order on one surface of a substrate 11. Are stacked.

  The substrate 11 is a member that holds the anode 12, the power generation layer 14, and the cathode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member with high permeability. As the substrate 11, for example, a glass substrate or a resin substrate is used. The substrate 11 is not essential, and for example, the bulk heterojunction type organic photoelectric conversion element 10 may be formed by forming the anode 12 and the cathode 13 on both surfaces of the power generation layer 14.

  The power generation layer 14 is a layer that converts light energy into electric energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor).

  In FIG. 1, light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the power generation layer 14, and electrons move from the electron donor to the electron acceptor. A pair of holes and electrons (charge separation state) is formed. In the case where the generated electric charges have different internal electric fields, for example, when the work functions of the anode 12 and the cathode 13 are different, due to the potential difference between the anode 12 and the cathode 13, electrons pass between the electron acceptors and holes pass between the electron donors. And is carried to different electrodes, and photocurrent is detected. For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13. If the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

  Although not shown in FIG. 1, other layers such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.

  As a more preferable configuration, the power generation layer 14 has a so-called p-i-n three-layer configuration, and an example of the configuration is shown in FIG. A normal bulk heterojunction layer is a single i layer in which a p-type semiconductor material and an n-type semiconductor layer are mixed, but is sandwiched between a p-layer made of a single p-type semiconductor material and an n-layer made of a single n-type semiconductor material. As a result, the rectification of holes and electrons becomes higher, loss due to recombination of charge-separated holes and electrons is reduced, and higher photoelectric conversion efficiency can be obtained.

  Furthermore, it is good also as a tandem-type structure which laminated | stacked such a photoelectric conversion element for the purpose of the improvement of sunlight utilization factor (photoelectric conversion efficiency).

  FIG. 3 is a cross-sectional view illustrating an example of a solar cell including an organic photoelectric conversion element including a tandem bulk heterojunction layer.

  In the case of the tandem configuration as shown in FIG. 3, the transparent electrode 12 and the first power generation layer 14 ′ are sequentially stacked on the substrate 11, and then the charge recombination layer 15 is stacked, and then the second power generation layer. 16 and the counter electrode 13 are stacked to form a tandem configuration. The second power generation layer 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first power generation layer 14 ′ or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. The first power generation layer 14 ′ and the second power generation layer 16 may both have the above-described three-layer configuration of pin.

  Below, the material which forms each layer which comprises these organic light conversion elements is demonstrated.

(Organic photoelectric conversion element material)
<P-type semiconductor material>
Examples of the p-type semiconductor material used for the power generation layer (bulk heterojunction layer) include various condensed polycyclic aromatic low-molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zesulene, Compounds such as heptazesulene, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (abbreviation: TTF) -tetracyanoquinodimethane (abbreviation: TCNQ) complex, bis (ethylene And dithio) tetrathiafulvalene (abbreviation: BEDT-TTF) -perchloric acid complex, and derivatives and precursors thereof.

  Examples of the derivative having the above condensed polycycle include International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004. Pentacene derivatives having substituents described in JP-A-107216 and the like, pentacene precursors described in US Patent Application Publication No. 2003/136964, and the like; Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  As the conjugated polymer, for example, a polythiophene such as poly-3-hexylthiophene (abbreviation: P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene as described in Nature Material, (2006) vol. 5, a polythiophene-thienothiophene copolymer described in p328, a polythiophene-diketopyrrolopyrrole copolymer described in WO2008 / 000664, and a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160. Combined, Nature Mat. vol. 6 (2007), p497, polythiophene copolymer such as poly (cyclopentadithiophene-benzothiadiazole) copolymer (abbreviation: PCPDTBT), polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene And oligomer materials thereof, polythienylene vinylene and oligomers thereof, polymer materials such as σ-conjugated polymers such as polyacetylene, polydiacetylene, polysilane, and polygermane.

  In addition, oligomeric materials instead of polymer materials include thiophene hexamer α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene can be preferably used.

  Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable.

  In addition, when the electron transport layer is formed on the power generation layer by a coating method, there is a problem that the electron transport layer solution dissolves the power generation layer. Therefore, a material that can be insolubilized after being applied by a solution process may be used. good. As such a material, for example, polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225 is used to insolubilize a coating film after coating. Material or a soluble substituent reacts and insolubilizes by applying energy such as heat as described in US Patent Application Publication No. 2003/136964 and JP 2008-16834 A Materials (to be pigmented) can be mentioned.

<N-type semiconductor material>
The n-type semiconductor material used for the bulk heterojunction layer is not particularly limited. For example, perfluoro compounds in which hydrogen atoms of a p-type semiconductor such as fullerene and octaazaporphyrin are substituted with fluorine atoms (for example, perfluoropentacene or perfluoropentacene). Fluorophthalocyanine, etc.), naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, etc. Can be mentioned.

  However, fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed (˜50 fs) and efficiently are preferable. Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Some are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Examples thereof include substituted fullerene derivatives.

  Among them, [6,6] -phenyl C61-butyric acid methyl ester (abbreviation: PCBM), [6,6] -phenyl C61-butyric acid-nbutyl ester (abbreviation: PCBnB), [6,6] -phenyl C61-butyric acid-isobutyl ester (abbreviation: PCBiB), [6,6] -phenyl C61-butyric acid-n-hexyl ester (abbreviation: PCBH), Adv. Mater. , Vol. 20 (2008), p2116, etc., aminated fullerenes described in JP-A 2006-199674, etc., metallocene fullerenes described in JP-A 2008-130889, etc., US Pat. No. 7,329,709 It is preferable to use a fullerene derivative having a substituent and having improved solubility, such as a fullerene having a cyclic ether group described in a book.

<Hole transport layer and electron block layer>
In the organic photoelectric conversion element 10 according to the present invention, since the hole transport layer 17 can be more efficiently taken out between the bulk heterojunction layer and the anode, the charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable to have a layer.

  As a material constituting these layers, for example, as the hole transport layer 17, poly-3,4-ethylenedioxythiophene (abbreviation: PEDOT) such as Stark Vuitec Co., Ltd., trade name BaytronP, polyaniline, and the like A doping material, a cyanide compound described in International Publication No. 2006/019270, or the like can be used. Note that the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer has a rectifying effect that prevents electrons generated in the bulk heterojunction layer from flowing to the anode side. It has an electronic block function. Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used. A layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

<Electron transport layer / hole blocking layer>
In the organic photoelectric conversion element 10 according to the present invention, the electron transport layer 18 is formed between the bulk heterojunction layer and the cathode, so that charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable to have these layers.

  Further, as the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro product (for example, perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, the p-type used for the bulk heterojunction layer is used. The electron transport layer having a HOMO level deeper than the HOMO level of the semiconductor material is provided with a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side. . Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function. Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and oxidation. N-type inorganic oxides such as titanium, zinc oxide, and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

<Other layers>
For the purpose of improving energy conversion efficiency and improving the lifetime of the element, a structure having various intermediate layers in the element may be employed. Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.

<Transparent electrode (first electrode)>
The transparent electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration. Preferably, the transparent electrode is used as an anode. For example, when a transparent electrode is used as the anode, it is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires, and carbon nanotubes can be used.

  Also selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

<Counter electrode (second electrode)>
The counter electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The counter electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The (average) film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  If a metal material is used as the conductive material of the counter electrode, the light coming to the counter electrode side is reflected and reflected to the first electrode side, and this light can be reused and is absorbed again by the photoelectric conversion layer, and more photoelectric conversion efficiency Is preferable.

  In addition, the counter electrode may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. If it is a thing, it can form a transparent and highly conductive counter electrode by the apply | coating method, and is preferable.

  In addition, when the counter electrode side is made light-transmitting, for example, a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound is made thin with an average film thickness of about 1 to 20 nm. Thereafter, a light-transmitting counter electrode can be obtained by providing a film of the conductive light-transmitting material mentioned in the description of the transparent electrode.

<Intermediate electrode>
In addition, the intermediate electrode material required in the case of the tandem configuration as shown in the section (v) (configuration shown in FIG. 3) is a layer using a compound having both transparency and conductivity. Preferably, the material used in the transparent electrode (for example, a transparent metal oxide such as ITO, AZO, FTO, and titanium oxide, a very thin metal layer such as Ag, Al, or Au, or a nanoparticle / nanowire) Layer, PEDOT: PSS, conductive polymer material such as polyaniline, etc.) can be used.

  In addition, in the hole transport layer and the electron transport layer described above, there is a combination that works as an intermediate electrode (charge recombination layer) by stacking them in an appropriate combination. This is preferable because the process can be omitted.

<Optical function layer>
The organic photoelectric conversion element according to the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight. As the optical functional layer, for example, a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .

  Various known antireflection layers can be provided as the antireflection layer. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved. As a method for adjusting the refractive index, for example, it can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

  As the condensing layer, for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.

  As an example of the microlens array, square pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it is smaller than this, the effect of diffraction is generated and colored, and if it is too large, the thickness becomes thick, which is not preferable.

  Examples of the light scattering layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

<Method for forming various layers>
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, a transport layer, an electrode, and the like include a vapor deposition method and a coating method (including a casting method and a spin coating method). . Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. The coating method is also excellent in production speed.

  Although there is no restriction | limiting in the coating method applied above, For example, a spin coat method, the cast method from a solution, a dip coat method, a blade coat method, a wire bar coat method, a gravure coat method, a spray coat method etc. are mentioned. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.

  After the application, it is preferable to perform heating in order to cause removal of residual solvent, moisture and gas, and improvement of mobility and absorption of long wave by crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, aggregation or crystallization is partially promoted microscopically, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.

  The power generation layer (bulk heterojunction layer) 14 may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise. In this case, it can be formed by using a material that can be insolubilized after coating as described above.

<Patterning>
There is no particular limitation on the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like, and known methods can be applied as appropriate.

  If it is a soluble material such as a bulk heterojunction layer and a transport layer, only unnecessary portions may be wiped after the entire surface of die coating, dip coating, etc., or direct patterning at the time of coating using a method such as an ink jet method or screen printing. May be.

  In the case of an insoluble material such as an electrode material, the electrode can be patterned by a known method such as mask evaporation at the time of vacuum deposition or etching or lift-off. Alternatively, the pattern may be formed by transferring a pattern formed on another substrate.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<Preparation of support>
[Preparation of support 1]
A 125 μm-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films, KDL86W-125 μm) having both surfaces subjected to easy adhesion processing was used as the support 1.

[Preparation of support 2]
A polyethylene naphthalate film having a thickness of 125 μm (Q65FWA-125 μm, manufactured by Teijin DuPont Films Ltd.) subjected to off-line annealing treatment on both surfaces was used as the support 2.

<< Production of hard coat film >>
[Preparation of hard coat film 1]
While transporting the coating agent coating solution 1 below on one side of the prepared support 1 at a speed of 30 m / min under the condition that the thickness of the hard coat layer after drying is 4.0 μm, the wire It was applied with a bar. Next, after drying at 80 ° C. for 3 minutes, the hard coating layer 1 is formed by curing using a high-pressure mercury lamp having an irradiation intensity of 0.5 J / cm ² under atmospheric pressure as a curing condition. Coat film 1 was produced.

(Preparation of coating agent coating solution 1)
Pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., M-306) 50 parts by mass Urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., U-6HA) 30 parts by mass Initiator (BASF Japan, Irgacure 184) 2 parts by mass Silver Inorganic antibacterial agent (Shinagawa Fuel Co., Ltd., silver-supported zeolite, average particle size 2.0 μm) 18 parts by mass Methyl ethyl ketone 100 parts by mass [Preparation of hard coat films 2 to 15]
In the production of the hard coat film 1, the type of support, the type and amount of monomer of the coating agent coating solution, and the type and amount of addition of the antibacterial agent were changed in the same manner except that the conditions shown in Table 1 were changed. Hard coat films 2 to 15 were produced.

  In addition, the detail of each additive described in Table 1 is as follows.

(monomer)
Pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd., M-306)
Dipenta: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., M-405)
Urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., U-6HA)
Trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., M-309)
(Antimicrobial agent)
Inorganic: Silver-based inorganic antibacterial agent (manufactured by Shinagawa Fuel, silver-supported zeolite, average particle size 2.0 μm)
Organic: Aromatic compound antibacterial agent (Awaden EC, manufactured by Daiwa Chemical Industries)
<< Evaluation of hard coat film >>
About each produced said hard coat film, the following characteristic value was measured and evaluated.

[Measurement of characteristic values]
(Measurement of surface roughness Ra of hard coat layer, measurement of number of protrusions)
The surface roughness Ra of each hard coat layer surface was measured based on an image obtained by an atomic force microscope according to the following method and conditions.

  After cutting each hard coat film to a size of 1 cm square, set it on a horizontal sample stage on a piezo scanner, approach the sample surface to the cantilever, and when it reaches the region where the atomic force works, it scans in the XY direction At that time, the unevenness of the sample was captured by the displacement of the piezo in the Z direction. Draw two straight lines in the direction perpendicular to the direction in which the concave and convex portions are connected to the concavo-convex image obtained by the atomic force microscope, and draw contour curves (cross-section curves) for the portions on this straight line. Asked. Next, the roughness was obtained from the contour curve (cross-sectional curve) on these straight lines. The measurement position was changed and 20 points were measured, and the arithmetic average was obtained as the surface roughness Ra.

In addition, a slice line was selected at 20 nm on the measurement field, and the number of protrusions of 20 nm or more in the 125 μm ² field was measured.

  The measurement conditions used in the present invention are as follows.

Measuring apparatus: Nanoscope IIIa AFM (manufactured by Digital Instruments)
Cantilever: Silicon single crystal Scanning mode: Tapping mode Scanning speed: 0.5Hz
Measurement field: 125 μm ²
Z range: 7 to 15 times Ra obtained from the cross section curve Flatten filter Mode: Flatten auto Order: 3
[Performance evaluation]
(Evaluation of untreated samples)
<Evaluation of transparency: measurement of haze value>
A haze value (%) was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and this was used as a measure of transparency.

<Scratch resistance evaluation>
The surface of the hard coat layer was rubbed 10 times under a load of 200 g using steel wool # 0000, and then the surface of the hard coat layer was visually observed, and scratch resistance was evaluated according to the following criteria. If it was in the range of ○ to Δ as the evaluation rank, it was determined to be practical.

○: No scratches are observed. Δ: One or two extremely weak scratches are observed. Δ: One or two slight scratches are observed. Δ ×: Three or more and nine or less scratches. X: occurrence of 10 or more wounds <Evaluation of antibacterial activity 1: E. coli evaluation>
Based on the standard of JIS Z 2801, antibacterial property 1 was evaluated using Escherichia coli as a test bacterium.

  For the determination, the antibacterial activity value for the sample (unprocessed product) only for the support was obtained, and the antibacterial property 1 was evaluated according to the following criteria. If it was in the range of ○ to Δ as the evaluation rank, it was determined to be practical.

○: Antibacterial activity value is 2.0 or more ○ △: Antibacterial activity value is 1.5 or more and less than 2.0 Δ: Antibacterial activity value is 1.0 or more and less than 1.5 Δ: Antibacterial activity value is 0.5 or more and less than 1.0 ×: Antibacterial activity value is less than 0.5 <Evaluation of antibacterial property 2: Staphylococcal evaluation>
In the evaluation of antibacterial property 1, the antibacterial property 2 was evaluated in the same manner except that staphylococci were used instead of Escherichia coli as test bacteria.

(Durability evaluation)
<Forced deterioration treatment of hard coat film>
For each hard coat film, using a metal halide lamp type weather resistance tester (manufactured by Daipura Wintes Co., Ltd.), the sample surface radiation intensity is 2.16 MJ / m ² or less, the black panel temperature is 63 ° C., the relative humidity is 50%, A durability test was performed under the condition of an irradiation time of 500 hours, and thereafter, as a high temperature and high humidity condition, the sample was stored for 3000 hours in an environment of a temperature of 85 ° C. and a humidity of 85% RH, and subjected to a forced deterioration treatment.

<Evaluation of forced deterioration samples>
About each hard coat film which performed the said forced deterioration process, each evaluation of transparency, scratch resistance, antibacterial 1, and antibacterial 2 was performed by the method similar to the above.

  The results obtained as described above are shown in Table 1.

  As is clear from the results shown in Table 1, the hard coat film of the present invention containing a polyfunctional pentaerythritol (meth) acrylate monomer component and an antibacterial monomer component in the hard coat layer is more transparent than the comparative example. It can be seen that it is excellent in scratch resistance and antibacterial properties, and has excellent transparency, scratch resistance and antibacterial properties even after being stored in various environments (heat, humidity, ultraviolet rays, etc.).

Example 2
<< Production of hard coat film >>
[Preparation of hard coat film 21]
The following coating agent coating solution 21 is conveyed at a speed of 30 m / min on one surface side of the support 1 described in Example 1 under the condition that the film thickness of the hard coat layer after drying is 4.0 μm. While applying with a wire bar. Next, after drying at 80 ° C. for 3 minutes, the hard coat layer 21 is formed by curing using a high pressure mercury lamp having an irradiation intensity of 0.5 J / cm ² under atmospheric pressure as a curing condition. Coat film 21 was produced.

(Preparation of coating agent coating solution 21)
Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., M-405) 40 parts by mass Urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., U-6HA) 20 parts by mass Initiator (BASF Japan, Irgacure 184) 2 parts by mass Silver series Inorganic antibacterial agent (manufactured by Shinagawa Fuel Co., Ltd., silver-supported zeolite, average particle size 2 μm) 18 parts by mass UV absorbent 1: zinc oxide (manufactured by Teika, ZD019, solid content 40%, average particle size 20 nm, (Abbreviated as “zinc”)
Ultraviolet absorber 2: Organic UV agent (manufactured by BASF Japan, Tinuvin 400, abbreviated as “organic UV” in Table 2) 2 parts by mass Methyl ethyl ketone 100 parts by mass [Production of hard coat films 22 to 28]
In the production of the hard coat film 21, hard coat films 22 to 28 were produced in the same manner except that the monomer type and antibacterial agent type of the coating agent coating solution were changed to the conditions shown in Table 2, respectively.

<< Production of gas barrier film >>
[Preparation of gas barrier film 21]
(Formation of gas barrier layer)
A gas barrier layer was formed on the hard coat layer of the hard coat film 21 produced as described above using a gas barrier layer coating solution under the following conditions.

  As a gas barrier layer coating solution, a 20% by mass dibutyl ether solution of perhydropolysilazane (PHPS, manufactured by AZ Electronic Materials, Aquamica NN320) is used to dry on the hard coat layer of the hard coat film 21 with a wireless bar. Coating was performed so that the subsequent (average) film thickness was 0.30 μm, and a coated sample 21 was obtained.

(First step; drying treatment)
The obtained coated sample 21 was treated in an atmosphere of a temperature of 85 ° C. and a humidity of 55% RH for 1 minute to obtain a dried sample.

(Second step; dehumidification treatment)
The dried sample was further dehumidified by being held for 10 minutes in an atmosphere at a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.).

(Modification A)
The sample 21 subjected to the dehumidification treatment was subjected to a modification treatment under the following conditions to form a gas barrier layer. The dew point temperature during the reforming treatment was -8 ° C.

<Modification processing equipment>
Excimer irradiation device MODEL: MECL-M-1-200 manufactured by M.D.Com Co., Ltd., wavelength: 172 nm, lamp gas: Xe
The sample fixed on the operation stage was subjected to a modification treatment under the following conditions.

<Reforming treatment conditions>
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0% by volume
Excimer irradiation time: 3 seconds The above gas barrier layer formation was repeated twice to produce a gas barrier film 21 having a gas barrier layer having a two-layer structure.

[Production of gas barrier films 22 to 28]
In producing the gas barrier film 21, gas barrier films 22 to 28 were produced in the same manner except that the hard coat films 22 to 28 were used instead of the hard coat film 21, respectively.

<< Production of organic photoelectric conversion element >>
The gas barrier films 21 to 28 produced as described above are each deposited with a 150 nm indium tin oxide (ITO) transparent conductive film (sheet resistance 10 Ω / □) on the gas barrier layer side, using a normal photolithography technique and wet etching. And patterning to a width of 2 mm to form a first electrode. The patterned first electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

  On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, is applied and dried so that the (average) film thickness is 30 nm, and then heat treated at 150 ° C. for 30 minutes to form a hole transport layer. A film was formed.

  Thereafter, the substrate was brought into a nitrogen chamber, and each constituent layer was formed under a nitrogen atmosphere.

  First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, 3.0% by mass of P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon: 6,6-phenyl-C61-butyric acid methyl ester) in chlorobenzene. Then, a liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm and the film was filtered (filtered), and allowed to dry at room temperature. Subsequently, a heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

Next, the substrate on which the series of functional layers is formed is moved into a vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then fluorinated at a deposition rate of 0.01 nm / second. Laminate 0.6 nm of lithium, and then continue to deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec through a shadow mask with a width of 2 mm (vaporization is performed so that the light receiving part is 2 × 2 mm). A second electrode was formed. The obtained organic photoelectric conversion element was moved to a nitrogen chamber, and sealed using a sealing cap and a UV curable resin, to produce an organic photoelectric conversion element having a light receiving portion of 2 × 2 mm size.

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), an epoxy-based photocurable adhesive was applied as a sealant to the surface provided with the gas barrier layer using the gas barrier films 21 to 28. The organic photoelectric conversion element obtained by the above-described method was sandwiched between the adhesive-coated surfaces of the gas barrier films 21 to 28 coated with the adhesive, and then irradiated with UV light from one substrate side. Then, the organic photoelectric conversion elements 21 to 28 were produced.

<< Evaluation of organic photoelectric conversion element >>
[Forced degradation treatment of organic photoelectric conversion elements]
For each organic photoelectric conversion element, using a metal halide lamp type weather resistance tester (manufactured by Daipura Wintes Co., Ltd.), the sample surface radiation intensity is 2.16 MJ / m ² or less, the black panel temperature is 63 ° C., and the relative humidity is 50%. Then, the treatment was carried out under the condition of irradiation time of 500 hours, and thereafter, as a high temperature and high humidity condition, it was stored in an environment of a temperature of 85 ° C. and a humidity of 85% RH for 3000 hours and subjected to a forced deterioration treatment.

[Evaluation of forced deterioration samples]
For each of the organic photoelectric conversion elements subjected to the above-mentioned forced deterioration treatment, in the same manner as the method described in Example 1, evaluation of transparency, scratch resistance, antibacterial property 1, antibacterial property 2 after the forced deterioration treatment, the following method The durability of energy conversion efficiency was evaluated according to the above.

(Evaluation of durability of energy conversion efficiency)
About the produced organic photoelectric conversion element with or without forced deterioration treatment, a solar simulator (AM1.5G filter) was used to irradiate light having an intensity of 100 mW / cm ² and an effective area of 4.0 mm ² as a light receiving portion. The four light receiving parts formed on the same element with the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V) and the fill factor FF (%) are evaluated by evaluating the IV characteristics. The four-point average value of energy conversion efficiency PCE (%) determined according to the following formula 1 was estimated.

(Formula 1)
PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
Next, PCE fluctuation resistance was determined by the following (Equation 2), and the durability of the energy conversion efficiency was evaluated according to the following criteria.

(Formula 2)
PCE fluctuation tolerance (%) = (PCE value of sample subjected to forced deterioration treatment / PCE value of non-forced deterioration processing sample) × 100
5: PCE fluctuation resistance is 90% or more 4: PCE fluctuation resistance is 70% or more and less than 90% 3: PCE fluctuation resistance is 40% or more and less than 70% 2: PCE fluctuation resistance is 20% or more and less than 40% 1: PCE fluctuation resistance is less than 20% Table 2 shows the results obtained as described above.

  As is clear from the results shown in Table 2, the organic photoelectric conversion device produced using the hard coat film of the present invention has a performance degradation even after being stored for a long time in a harsh environment with respect to the comparative example. It turns out that it is hard to generate.

Example 3
<< Production of organic EL element >>
[Production of Organic EL Element 31]
(Formation of ITO conductive layer)
Using the gas barrier film 21 produced in Example 2, ITO (indium tin oxide) is formed on the gas barrier layer forming surface side under the condition of a thickness of 100 nm and patterned to form an ITO conductive layer. It was. Next, the substrate provided with the ITO conductive layer was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

(Formation of hole injection layer)
On this substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water was used at 3000 rpm for 30 seconds. After forming the film by spin coating, the substrate was dried at a substrate surface temperature of 200 ° C. for 1 hour to provide a hole injection layer having a thickness of 30 nm.

(Formation of hole transport layer)
This substrate was transferred to a glove box having a cleanliness of class 100, a dew point temperature of −80 ° C. or less, and an oxygen concentration of 0.8 ppm measured by a measurement method according to JIS B 9920 in a nitrogen atmosphere. A coating solution for a hole transport layer was prepared as follows in a glove box, and applied with a spin coater under conditions of 1500 rpm and 30 seconds. This substrate was dried by heating at a substrate surface temperature of 150 ° C. for 30 minutes to provide a hole transport layer. The film thickness was 20 nm when it apply | coated and measured on the conditions with the board | substrate prepared separately.

<Hole transport layer coating solution>
Monochlorobenzene 100g
Poly-N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl) benzidine (ADS254BE: manufactured by American Die Source) 0.5 g
(Formation of light emitting layer)
Subsequently, the light emitting layer coating liquid was prepared as follows, and it apply | coated on 2000 rpm and the conditions for 30 seconds with the spin coater. Furthermore, it heated at the substrate surface temperature of 120 degreeC for 30 minutes, and provided the light emitting layer. When the coating was performed under the same conditions on a separately prepared substrate and measured, the film thickness was 40 nm. In addition, among the following light emitting layer composition, it was HA which showed the lowest Tg, and it was 132 degreeC.

<Coating solution for light emitting layer>
Butyl acetate 100g
H-A 1.0g
DA 0.11g
DB 0.002g
D-C 0.002g
(Formation of electron transport layer)
Subsequently, the coating liquid for electron carrying layers was prepared as follows, and it apply | coated on the conditions of 1500 rpm and 30 seconds with a spin coater. Furthermore, it heated for 30 minutes at the substrate surface temperature of 120 degreeC, and provided the electron carrying layer. The film thickness was 30 nm when it applied and measured on the conditions prepared with the board | substrate prepared separately.

<Coating liquid for electron transport layer>
2,2,3,3-tetrafluoro-1-propanol 100 g
ET-A 0.75g

(Formation of electron injection layer)
Next, the substrate provided up to the electron transport layer was moved to a vapor deposition unit without being exposed to the atmosphere, and the pressure was reduced to 4 × 10 ⁻⁴ Pa. In addition, potassium fluoride and aluminum were each put in a resistance heating boat made of tantalum and attached to a vapor deposition device.

  First, a resistance heating boat containing potassium fluoride was energized and heated to provide 3 nm of an electron injection layer made of potassium fluoride on the substrate.

(Formation of cathode)
Subsequently, a resistance heating boat containing aluminum was energized and heated, a cathode having a film thickness of 100 nm made of aluminum was provided at a deposition rate of 1 to 2 nm / second, and an organic EL element 31 was produced.

[Preparation of organic EL elements 32-38]
In the production of the organic EL element 31, the organic EL element 32 was similarly obtained except that the gas barrier films 22 to 28 similarly produced in Example 2 were used in place of the gas barrier film 21 produced in Example 2. -38 were made.

<< Evaluation of organic EL elements >>
[Forced deterioration treatment of organic EL elements]
For each organic EL element, using a metal halide lamp type weather resistance tester (manufactured by Daipura Wintes Co., Ltd.), the sample surface radiation intensity is 2.16 MJ / m ² or less, the black panel temperature is 63 ° C., the relative humidity is 50%, The treatment was performed under the condition of an irradiation time of 500 hours, and thereafter, as a high-temperature and high-humidity condition, it was stored for 3000 hours in an environment of a temperature of 85 ° C. and a humidity of 85% RH, and subjected to a forced deterioration treatment.

[Evaluation of forced deterioration samples]
For each of the organic EL elements subjected to the above-mentioned forced deterioration treatment, in the same manner as the method described in Example 1, evaluation of transparency, scratch resistance, antibacterial property 1, antibacterial property 2 after the forced deterioration treatment, and the following method The device life was evaluated according to the above.

(Evaluation of device life)
For the organic EL element subjected to the forced deterioration treatment and the unprocessed organic EL element, the light emission luminance when driven at a constant current of ^2.5 mA / cm ² is used as a driving power source. Measuring and measuring instrument R6243, using Konica Minolta Sensing Co., Ltd., spectral radiance meter CS-2000 as a luminance measuring instrument, measuring the luminance durability according to the following (formula 3), element life according to the following criteria Evaluated.

(Formula 3)
Luminance durability rate (%) = (emission luminance of sample after forced deterioration treatment / emission luminance of untreated sample) × 100
5: The luminance durability is 70% or more 4: The luminance durability is 50% or more and less than 70% 3: The luminance durability is 30% or more and less than 50% 2: The luminance durability is 10% or more, 30 1 is less than 10%. The results obtained as described above are shown in Table 3.

  As is apparent from the results shown in Table 3, the organic EL device produced using the hard coat film of the present invention deteriorated in performance even after being stored for a long time in a harsh environment with respect to the comparative example. It is difficult to see and has a long life.

Example 4
<< Production of hard coat film >>
[Preparation of hard coat film 41]
The following coating agent coating solution 41 is conveyed at a speed of 30 m / min on one surface side of the support 1 described in Example 1 under the condition that the film thickness of the hard coat layer after drying is 4.0 μm. While applying with a wire bar. Next, after drying at 80 ° C. for 3 minutes, the hard coat layer 41 is formed by curing using a high-pressure mercury lamp having an irradiation intensity of 0.5 J / cm ² under atmospheric pressure as a curing condition. A coat film 41 was produced.

(Preparation of coating agent coating solution 41)
Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., M-405) 40 parts by mass Urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., U-6HA) 20 parts by mass Initiator (BASF Japan, Irgacure 184) 2 parts by mass Silver series Inorganic antibacterial agent (Shinagawa Fuel Co., Ltd., silver-supported zeolite, average particle size 2 μm) 18 parts by mass ITO powder (manufactured by Sumitomo Metal Mining Co., Ltd., ultrafine particle ITO) 20 parts by mass Methyl ethyl ketone 100 parts by mass [Preparation of hard coat films 42 to 48 ]
In the production of the hard coat film 41, hard coat films 42 to 48 were produced in the same manner except that the monomer type and antibacterial agent type of the coating agent coating solution were changed to the conditions shown in Table 4, respectively.

<Production of heat ray blocking film>
[Preparation of heat ray blocking film 1]
(Preparation of coating solution 1 for high refractive index layer)
140.3 parts, 14.8% by weight of 1.03% acid-treated gelatin (isoelectric point: 9.5, weight average molecular weight: 20,000) as thickening polysaccharide in 10.3 parts of pure water 17.3 parts of an aqueous picolinic acid solution and 2.58 parts of a 5.5% by weight aqueous solution of boric acid were added and mixed, respectively, and then 38.2 parts of the following titanium oxide dispersion 1 was added and mixed. Further, 0.067 part of Surflon S221 (manufactured by AGC Seimi Chemical Co., Ltd.) is added as a fluorine-based cationic surfactant, and finally finished to 223 parts with pure water. Was prepared. In addition, content of Surflon S221 which is surfactant in the coating liquid 1 for high refractive index layers is 0.03 mass%.

<Preparation of titanium oxide dispersion 1>
28.9 parts of a 20.0% by mass titanium oxide sol containing rutile-type titanium oxide fine particles having a volume average particle diameter of 35 nm, 5.41 parts of a 14.8% by mass picolinic acid aqueous solution, and 2.1% of lithium hydroxide. A titanium oxide dispersion was prepared by mixing and dispersing 3.92 parts of a 1 mass% aqueous solution.

(Preparation of coating solution 1 for low refractive index layer)
9.18 parts of a 23.5% by weight aqueous solution of polyaluminum chloride (Taki Chemical Co., Takibine # 1500), 510 parts of a 10% by weight aqueous solution of colloidal silica (Nissan Chemical Co., Snowtex OS), 103.4 parts of a 5.5% by weight aqueous solution of acid and 4.75 parts of a 2.1% by weight aqueous solution of lithium hydroxide are mixed and dispersed, finished to 1000 parts with pure water, and dispersed in silicon oxide. Liquid 1 was prepared.

  Next, in 17.6 parts of pure water, 26.2 parts of a 1.0% by weight tamarind seed gum aqueous solution and 3.43 parts of a 5.0% by weight solution of polyvinyl alcohol (PVA217, manufactured by Kuraray Co., Ltd.) Then, 0.06 part of 2.1 mass% picolinic acid aqueous solution is added and mixed, and then 96.5 parts of the silicon oxide dispersion 1 is added and mixed, and further, as a fluorine-based cationic surfactant. 0.045 part of Surflon S221 (manufactured by AGC Seimi Chemical Co., Ltd.) was added, and finally it was finished to 150 parts with pure water to prepare a coating solution 1 for low refractive index layer. In addition, content of Surflon S221 which is surfactant in the coating liquid 1 for low refractive index layers is 0.03 mass%.

(Preparation of outermost coating solution)
In the preparation of the coating solution 1 for the low refractive index layer, the addition amount of Olfine E1004 (manufactured by Nissin Chemical Co., Ltd.), which is an acetylene glycol-based nonionic surfactant, with respect to the total coating solution mass is 0.03% by mass to 0.03% by mass. A coating solution for the outermost layer was prepared in the same manner except that the content was changed to 06% by mass.

(Method for forming heat ray blocking film)
Using a slide hopper coating apparatus capable of simultaneous coating of 15 layers, a total of 14 layers of the above-prepared coating solution 1 for the low refractive index layer and coating solution 1 for the high refractive index layer were alternately laminated, On the surface opposite to the hard coat layer-forming surface of the hard coat film 41 heated to 45 ° C. while keeping the temperature at 45 ° C., a total of 15 layers with the outermost layer coating solution laminated thereon are simultaneously laminated. Application was performed. Next, after setting the film surface by blowing cold air for 1 minute under the condition that the film surface was 15 ° C. or lower, the hot air was blown and dried by blowing 80 ° C. to prepare a heat ray blocking film 41 consisting of 15 layers.

[Production of heat ray blocking films 42 to 48]
In preparation of the said heat ray blocking film 41, it replaced with the hard coat film 41 and produced the heat ray blocking films 42-48 similarly except having used the produced said hard coat films 42-48, respectively.

<Evaluation of heat ray blocking film>
(Forced deterioration treatment of heat ray blocking film)
For each heat ray blocking film, using a metal halide lamp type weather resistance tester (manufactured by Daipura Wintes Co., Ltd.), the sample surface radiation intensity is 2.16 MJ / m ² or less, the black panel temperature is 63 ° C., the relative humidity is 50%, The treatment was performed under the condition of an irradiation time of 500 hours, and thereafter, as a high-temperature and high-humidity condition, it was stored for 3000 hours in an environment of a temperature of 85 ° C. and a humidity of 85% RH, and subjected to a forced deterioration treatment.

[Evaluation of forced deterioration samples]
For each heat ray blocking film subjected to the above-mentioned forced deterioration treatment, in the same manner as in the method described in Example 1, evaluation of transparency, scratch resistance, antibacterial property 1, antibacterial property 2 after the forced deterioration treatment, and the following method According to the evaluation, the retention of the infrared ray shielding effect after the forced deterioration treatment was evaluated.

(Retainability of infrared shielding effect)
Using a spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type) for the heat ray shielding film subjected to the forced deterioration treatment and the untreated heat ray shielding film, transmittance in a region of 300 nm to 2000 nm is obtained. The transmittance value at 1200 nm was measured as the near infrared transmittance, the infrared transmittance retention was measured according to the following (formula 4), and the retention of the infrared blocking effect was evaluated according to the following criteria.

(Formula 4)
Infrared transmittance retention = (Near infrared transmittance of untreated heat ray shielding film / Near infrared transmittance of heat ray shielding film after forced deterioration treatment) × 100 (%)
5: Infrared transparent retention is 70% or more 4: Infrared transparent retention is 50% or more and less than 70% 3: Infrared transparent retention is 30% or more, 50% 2. The infrared transmittance holding ratio is 10% or more and less than 30%. 1: The infrared transmittance holding ratio is less than 10%. Table 4 shows the results obtained as described above.

  As is clear from the results shown in Table 4, the heat ray shielding film produced using the hard coat film of the present invention causes a deterioration in performance even after being stored for a long time in a harsh environment compared to the comparative example. It is difficult to see that the infrared shielding effect is maintained for a long time.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Transparent electrode 13 Counter electrode 14 Photoelectric conversion part (bulk hetero junction layer)
14p p layer 14i i layer 14n n layer 14 'first photoelectric conversion unit 15 charge recombination layer 16 second photoelectric conversion unit 17 hole transport layer 18 electron transport layer

Claims (7)

  A hard coat film comprising a hard coat layer containing a polymer having a polyfunctional pentaerythritol (meth) acrylate monomer component and an antibacterial monomer component on at least one surface of a plastic substrate.   The hard coat film according to claim 1, wherein the hard coat layer is cured by irradiation with ultraviolet rays.   The hard coat film according to claim 1 or 2, wherein the antibacterial monomer component has at least one salt selected from a quaternary ammonium salt, a quaternary phosphonium salt, and a quaternary sulfonium salt.   The hard coat film according to claim 1 or 2, wherein the antibacterial monomer component has at least one salt selected from a pyridium salt and a piperidinium salt. The surface roughness Ra of the hard coat layer is 1 nm or more and 50 nm or less, and the number of protrusions of 20 nm or more per 125 μm ² is 10 or more and 10,000 or less. The hard coat film of any one of these.   A heat ray blocking film comprising the hard coat film according to claim 1.   An organic element device comprising the hard coat film according to any one of claims 1 to 5.

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