KR102018592B1 - Process for preparing anti-reflection film substrate and photovoltaic cell - Google Patents

Abstract

The present invention is to provide a method for producing an antireflection coating part base material having high hardness and suppressing occurrence of cracks, scratches and the like. In the method of manufacturing an antireflection coating part substrate comprising a high refractive index layer formed on an upper substrate and a low refractive index layer formed on the high refractive index layer, (a) containing 1 to 1000 ppm of a basic nitrogen compound and a refractive index of 1.50 Applying a high refractive index metal compound particulate dispersion in the range of ˜2.40; (b) removing the dispersion medium at a temperature below the boiling point of the basic nitrogen compound; (c) applying a low refractive index layer forming component dispersion; (d) removing the dispersion medium; And (e) heat treatment at 120 to 700 ° C., to provide a method of manufacturing an anti-reflective coating part substrate.

Description

Process for preparing anti-reflection film substrate and photovoltaic cell {Process for preparing anti-reflection film substrate and photovoltaic cell}

The present invention relates to a method for producing an antireflection film base substrate which can be suitably used in a photovoltaic cell for converting and providing light energy into electrical energy and a photovoltaic cell (solar cell) using the substrate. More specifically, in the method for producing an antireflection film base material comprising a high refractive index layer formed on a substrate and a low refractive index layer formed on the high refractive index layer to increase the utilization of visible light, the antireflection performance, light transmittance, etc. are excellent, and in particular, A method for producing an antireflection film base substrate having excellent surface hardness and scratch resistance, and a photovoltaic cell using the substrate.

The photoelectric conversion material is a material capable of continuously providing optical energy as electrical energy, and is a material that converts optical energy into electrical energy by using an electrochemical reaction between electrodes. When the photoelectric conversion material is irradiated with light, electrons are generated on one electrode side and move to the counter electrode, and the electrons moved to the counter electrode move in the electrolyte as ions and return to one electrode. This photoelectric energy conversion is caused continuously and is used, for example, in solar cells.

In general, a solar cell is provided with a support on a glass plate in which a separate transparent conductive film is formed as a counter electrode, followed by an electrode formed on a support such as a glass plate on which a transparent conductive film is formed, and an electrolyte between the electrodes. It is comprised by enclosing. When sunlight is irradiated to the photosensitizer adsorbed on the semiconductor for photoelectric conversion materials, the photosensitizer absorbs the light in the visible region and is excited. The electrons generated by this excitation are moved to the semiconductor, and subsequently to the transparent conductive glass electrode, and to the counter electrode through the conductive wire connecting the two electrodes. The electrons moved to the counter electrode reduce the redox system in the electrolyte. The photosensitizer for moving electrons to the semiconductor is in the state of an oxidant, which is reduced by the redox system in the electrolyte and returned to its original state. Such electrons flow continuously and the photoelectric conversion material functions as a photovoltaic cell (solar cell).

As this photoelectric conversion material, what adsorbed the spectrophotochromic dye which adsorb | sucks to visible region in the semiconductor surface is used. For example, Japanese Patent Laid-Open No. 1-220380 (Patent Document 1) describes a solar cell having a spectrophotochromic layer made of transition metal complexes such as ruthenium complexes on the surface of a metal oxide semiconductor layer. In addition, Japanese Patent Application Laid-Open No. 5-504023 (Patent Document 2) describes a solar cell having a spectrophotochromic layer made of transition metal complexes such as ruthenium complexes, etc., on the surface of a titanium oxide semiconductor layer doped with metal ions. have.

As such a solar cell, it is considered to suppress the reflection of sunlight in order to increase the utilization rate and conversion efficiency of sunlight. To this end, it is required to provide an antireflection film having a lower refractive index than the base material on the base material. Moreover, in order to improve antireflection performance, providing a high refractive index layer between a base material and an antireflection film is also performed.

Applicant of the present invention forms a UV blocking film using a coating solution for forming a UV blocking film made of titanium oxide colloid particles and a matrix precursor and the like, and forms a visible light anti-reflection coating using silica gel inorganic oxide fine particles having a cavity therein and a matrix precursor. By forming a visible light antireflection film using a coating liquid for solvents, it is disclosed to obtain an optoelectronic cell having a low bottom reflectance and a low luminous reflectance and excellent durability photoelectric conversion efficiency (Patent Document 3: JP 2002-A). 134178).

Patent Document 1: Japanese Patent Application Laid-Open No. 1-220380 Patent Document 2: Japanese Patent Application Laid-Open No. 5-504023 Patent Document 3: Japanese Unexamined Patent Publication No. 2002-134178

Therefore, the visible light antireflection film obtained by the conventional manufacturing method has low durability (reliability), cracks are generated in the antireflection film due to environmental changes such as temperature and humidity, and deterioration due to long-term use, and the refractive index is changed due to expansion and contraction of the film. There was a case where the antireflection performance was lowered. For this purpose, it is sometimes difficult to maintain high photoelectric conversion efficiency.

Under such circumstances, the present inventors have conducted careful investigations to solve the above problems, and as a result, the present invention has applied and dried a dispersion containing titanium oxide fine particles (high refractive index metal oxide fine particles) and a basic nitrogen compound on a substrate, and also has a low refractive index including a silica precursor. The application of the layer-forming component dispersion and heating it has found that the hardness of the antireflective film obtained is significantly improved and the present invention has been completed.

Specifically, the antireflection film substrate includes 1 to 1000 ppm of a basic nitrogen compound on the substrate, and a metal oxide particle dispersion having a refractive index of 1.50 to 2.40 is applied to remove the dispersion medium at a temperature below the boiling point of the basic nitrogen compound. Step, coating the low refractive index layer-forming component dispersion, removing the dispersion medium of the low refractive index layer-forming component dispersion, and then heating to 120 ~ 700 ℃. The antireflection film base substrate in which a high refractive index layer formed on the substrate produced by this manufacturing method and a low refractive index layer formed on the high refractive index layer is laminated can be used on the entire surface of the photovoltaic cell.

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The present invention provides a method for producing an antireflection film base material having high hardness and suppressing the occurrence of cracks, scratches, and the like, wherein the antireflection film base material and the visible light utilization ratio including the base material are high and stable even for long-term use. It is possible to provide a photovoltaic cell (solar cell) capable of maintaining.

1 shows a schematic cross-sectional view of a photovoltaic cell according to the present invention.

[Method for Producing Antireflection Film Substrate]

The present invention is characterized by the following steps (a) to (e). (a) a step of applying a high refractive metal oxide fine particle dispersion; (b) drying the dispersion; (c) a step of applying the low refractive index layer forming component dispersion; (d) removal of the solvent; And (e) a heating step;

materials

As a base material used for this invention, conventionally well-known glass, a polycarbonate, an acrylic resin, plastic sheets, such as PET and TAC, plastic panels, such as a plastic film, etc. can be used. In addition, the glass substrate is preferable to obtain an antireflection film base substrate having excellent hardness.

On the other hand, the substrate has irregularities on the surface when used in the photovoltaic cell and its surface roughness (Ra _A ) is in the range of 30 nm to 1 μm, preferably in the range of 50 nm to 0.8 μm. Those having irregularities in this range are highly anti-glare and can be suppressed even in sealing. Moreover, when used in the photovoltaic cell, the effect of improving the phototransmission efficiency by improving the light transmittance by suppressing reflection is improved.

As the substrate, it is possible to use a commercially available substrate having irregularities on the surface. On the other hand, unevenness is formed by a conventionally known method such as sandblasting a glass substrate having a flat surface or applying and curing a gel spray liquid on a glass substrate having a flat surface to apply and dry a mixed dispersion of metal oxide fine particles and gel. Can also be used. Moreover, it is preferable that the electrode layer is formed in the surface of a base material.

In the present invention, the surface roughness Ra _A , the surface roughness Ra _B and the surface roughness Ra _C described later are measured by an atomic force microscope (AFM) or a laser microscope. When the surface roughness Ra _A is approximately 100 nm or less, the measurement is performed by AFM. When the surface roughness Ra _A is exceeded, the measurement is performed by a laser microscope.

The substrate used in the present invention preferably has a refractive index in the range of 1.45 to 1.64. It is difficult to obtain a general-purpose glass substrate having an index of refraction less than the lower limit as the optical purpose, and even if the refractive index of the substrate is high, the refractive index difference between the substrate and the high refractive index layer provided on the substrate may be small, so that the effect of improving transmittance may not be sufficiently obtained.

When used in a photovoltaic cell, it is preferable that the visible light transmittance of a board | substrate and an electric layer is high. Specifically, it is preferable that it is 50% or more, More preferably, it is 90% or more. It is preferable that the resistance of an electrode layer is 100 ohms / cm <^2> or less, respectively.

Process (a)

A dispersion containing 1 to 1000 ppm of high refractive index metal oxide particles and a basic nitrogen compound is coated on the substrate.

As the metal oxide particles used in the present invention, it is preferable to use metal oxide particles having a refractive index in the range of 1.50 to 2.40, preferably 1.55 to 2.30. Even if the refractive index of the metal oxide particles is small, even if there is a difference depending on the refractive index of the substrate, the difference in refractive index with the substrate may be small, thereby improving the transmittance. Even when the refractive index of the metal oxide fine particles is high, scattering may be caused by the metal oxide fine particles, so that the effect of improving the transparency may be insufficient.

In the present invention, the refractive index difference between the refractive index of the substrate and the high refractive index layer is approximately 0.1 to 1.0, preferably 0.5 to 1.0 range. Examples of the metal oxide fine particles include metal oxide fine particles such as TiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₅ , In ₂ O ₃ , and Nb ₂ O ₅ , mixture particles thereof, composite oxide particles, and the like. can do.

The metal oxide fine particles can obtain a dispersion of metal oxide fine particles having excellent dispersibility and stability. Particularly, as the average particle size becomes smaller, particles which can be suitably used for scientific purposes with excellent transparency can be easily obtained.

The average particle size of the metal oxide fine particles is in the range of 5 to 100 nm, preferably 7 to 50 nm. As the average particle size of the metal oxide particles becomes smaller, they easily aggregate and the stability of the dispersion is insufficient. The high refractive index layer formed by using the dispersion liquid of such metal oxide particles may be insufficient in precision, resulting in insufficient hardness and scratch resistance of the antireflection film finally obtained. If the average particle size of the metal oxide particles is large, scattering may be caused, resulting in insufficient light transmittance, and in the case of using the photovoltaic cell, the effect of improving the photoelectric conversion efficiency may be insufficient.

As a dispersion medium of a metal oxide fine particle dispersion, For example, Alcohol, such as methanol, ethanol, a propanol, 2-propanol (IPA), butanol, diacetyl alcohol, a furfuryl alcohol, tetrahydro pulfuryl alcohol; Methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol mono Esters such as acetates, glycols such as ethylene glycol and hexylene glycol; Diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Water-soluble solvent containing ethers such as monoethyl ether and propylene glycol monopropyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate and 2-ethylbutyl acetate Esters such as cyclohexyl acetate and ethylene glycol monoacetate; Ketones such as acetate methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone and methyl ketone; Polar solvents such as toluene and the like. These may be used independently, or may mix and use 2 or more types.

The solvent is used as the lower than or equal to the boiling point of the basic nitrogen compound to be used. The concentration of the metal oxide fine particles in the metal oxide fine particle dispersion is in the range of 0.5 to 20% by weight, preferably 1 to 10% by weight as a solid content. When the concentration of the metal oxide particles is not within the above range as the solid content, formation of a high refractive index layer having an average film thickness described later may be difficult.

The basic nitrogen compound contributes to promoting the densification and curing of the low refractive index layer forming component applied on the high refractive index layer. It is preferable that such basic nitrogen compounds are evaporated at the time of drying, and the boiling point is in the range of 40 to 250 ° C, preferably 80 to 150 ° C.

Specifically, n-propylamine (boiling point 48.0 ° C), n-butylamine (boiling point 77.0 ° C), isobutylamine (boiling point 67.5 ° C), sec-butylamine (boiling point 62.5 ° C), tert-butylamine ( Boiling point 43.6 ° C), pentylamine (boiling point 104 ° C), 2-ethylhexylamine (boiling point 169.2 ° C), arylamine (boiling point 53.3 ° C), aniline (boiling point 184.7 ° C), N-methylaniline (boiling point 196.1 ° C), o Toluidine (boiling point 200.7 ° C), n-toluidine (boiling point 202 ° C), p-toluidine (boiling point 200.4 ° C), cyclohexylamine (boiling point 134.5 ° C), pyrrole (boiling point 129 ° C), piperidine (boiling point 105 ° C) , Pyridine (boiling point 115.3 ° C.), alpha-phycoline (boiling point 129.4 ° C.), beta-picolin (boiling point 144.1 ° C.), gamma-picolin (boiling point 145.4 ° C.), quinoline (boiling point 237.1 ° C.), isoquinoline (boiling point 243.2) ° C), formamide (boiling point 210.5 ° C), N-methylformamide (boiling point 182.5 ° C), acetamide (boiling point 221.2 ° C), N-methylacetamide (boiling point 206 ° C), N-methylpropionamide (boiling point 148 ° C) ), Primary grades such as diethylamine (boiling point 55.5 ° C) Min, dipropylamine (boiling point 109.4 ° C), diisopropylamine (boiling point 83.5 ° C), dibutylamine (boiling point 159.6 ° C), diisobutylamine (boiling point 138 ° C), dipentylamine (boiling point 92 ° C), dimethyl Aniline (boiling point 193 ° C), diethylaniline (boiling point 217 ° C), dicyclohexylamine (boiling point 113.5 ° C), 2,4-lutidine (boiling point 157.5 ° C), 2,6-lutidine (boiling point 144 ° C), Ethylenediamine (boiling point 117.3 ° C), propylenediamine (boiling point 119.3 ° C), diethylenetriamine (boiling point 207.1 ° C), N, N-dimethylformamide (boiling point 153.0 ° C), N, N-diethylformamide (boiling point 177.5 Secondary amines such as N, N-dimethylacetamide (boiling point 166.1 ° C), triethylamine (boiling point 89.6 ° C), tributylamine (boiling point 91.5 ° C), and tripentylamine (boiling point 130 ° C) Tertiary ammonium chloride (boiling point: 110 ° C), tetraethyl ammonium chloride (boiling point: 110 ° C), tetrapropyl ammonium chloride (boiling point: 100 ° C), tetrabutylammonium chloride (boiling point) And quaternary ammonium salts such as 100 ° C.).

In addition, when the basic nitrogen compound is dried in the step (d) described later, the densification of the low refractive index layer forming component of the low refractive index layer forming dispersion in which the basic nitrogen compound is applied to the upper layer is promoted, and in the step (e) By heat treatment, it is possible to promote the densification of the low refractive index layer forming component of the low refractive index layer forming dispersion in which the basic nitrogen compound is applied to the upper layer, thereby forming an antireflection film excellent in hardness, scratch resistance and the like.

The concentration of the basic nitrogen compound in the metal oxide particle dispersion is in the range of 1 to 1000 ppm, preferably 5 to 500 ppm. The basic nitrogen compound in the metal oxide particle dispersion becomes less effective at least the compound, the densification of the low refractive index layer is insufficient in the previous step (d), and the effect of improving the hardness and scratch resistance of the finally obtained antireflection film is insufficient. It may become. Even if there are many basic nitrogen compounds in a metal oxide particle dispersion, the dispersion liquid which affects the particle | grains in a metal oxide particle dispersion may become unstable, and the hardness and scratch resistance of the finally obtained antireflection film may become inadequate.

The high refractive index layer-forming metal oxide particle dispersion may contain a matrix forming component as necessary. As a matrix formation component, the thing of the same form as the low refractive index layer formation component mentioned later can be used, Specifically, it is preferable that it is a silica precursor.

The concentration of the matrix forming component in the metal oxide particle dispersion containing the basic nitrogen compound is 4% by weight or less, preferably 3 to 4% by weight as solid content. By including the matrix, a dense high refractive index layer can be formed, thereby improving the adhesion between the low refractive index layer and the substrate.

The total solid solution concentration of the metal oxide particle dispersion for forming the high refractive index layer is in the range of 0.6 to 24% by weight, preferably 1.3 to 14% by weight. When the total solid concentration of the metal oxide fine particle dispersion for forming a high refractive index layer does not fall within the above range, it may be difficult to form a high refractive index layer having an average film thickness in a predetermined range described later.

The method of applying the metal oxide particle dispersion containing the basic nitrogen compound to the substrate is not particularly limited as long as it can be uniformly applied onto the substrate. It is possible to adopt a conventionally known method. For example, the barcode method, the dipping method, the spray method, the spinner method, the roll coating method, the gravure coating method, the slitting coating method, etc. are mentioned.

Process (b)

Here, the dispersion medium is removed at a temperature below the boiling point of the basic nitrogen compound and the coating film is dried. Specifically, it is dried at 50 to 120 ° C, preferably 60 to 100 ° C (above the boiling point of the solvent).

The drying time may vary depending on the drying temperature but is about 20 minutes or less, preferably 30 seconds to 10 minutes. In addition, when used in photovoltaic cells, the surface roughness Ra _B of the high refractive index layer formed on the substrate is in the range of 30 nm to 1 μm, preferably in the range of 50 nm to 0.8 μm. When the surface roughness Ra _B of the high refractive index layer is less than 30 nm, sufficient light transmittance improvement may not be obtained.

On the other hand, in the dispersion coating method recommended in the present invention, the surface roughness Ra _B of the high refractive index layer does not exceed 1 μm. The average roughness of the high refractive index layer is in the range of 50 to 200 nm, preferably 80 to 120 nm.

Even if the average roughness of the high refractive index layer is thin, sufficient light transmittance improvement effect is not obtained so that the reflectance does not decrease. Therefore, when used in photovoltaic cells, the effect of improving photoelectric conversion efficiency is insufficient due to the improvement of light utilization. have. Even if the average refractive index of the high refractive index layer is thick, sufficient light transmittance may not be obtained. Therefore, sufficient photoelectric conversion efficiency improvement effect may not be obtained when used in an optoelectronic cell.

In addition, the average thickness of the high refractive index layer having irregularities on the surface can be obtained by reducing the weight of the substrate from the weight of the high refractive index layer portion, dividing it by the specific gravity of the high refractive index layer, and dividing by the area of the high refractive index layer.

Process (c)

Subsequently, a low refractive index layer forming component dispersion is applied onto the high refractive index layer to form a low refractive index layer.

The low refractive index layer forming component is not particularly limited as long as it can form a low refractive index layer having a lower refractive index than the refractive index of the high refractive index layer and excellent in scratch resistance, and silica precursor or silica precursor and silica sol are preferably used in the present invention. do.

As the silica precursor, polysilazane which is a silazane polymer, polysilane which is a silane polymer, an acidic silicic acid solution and the like are preferably used as the partial hydrolyzate, hydrolyzate and hydrolysis condensation product of the organosilicon compound.

As an organosilicon compound, the organosilicon compound represented by following formula (1) can be used.

R _n -SiX _{4- n} (1)

In the above formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same as or different from each other. X is a C1-C4 alkoxy group, a hydroxyl group, halogen, hydrogen, n is an integer of 0-3.

At this time, a tetrafunctional organosilicon compound having n = 0 is preferable, and specifically, hydrolyzates such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane and hydrolyzed condensation products can be preferably used. have.

In addition, the silazane represented by following formula (2) is used as a silazane.

In which R ₁ and R ₂ And R ₃ are each independently a substituent selected from a hydrogen atom and an alkyl group having 1 to 8 carbon atoms and n is an integer of 1 or more.

In formula (2), R ₁ , R ₂ And inorganic polysilazanes in which all R ₃ are hydrogen atoms and present in an amount such as 55 to 65% by weight of silicon atoms, 20 to 30% by weight of nitrogen atoms and 10 to 15% by weight of hydrogen atoms in one molecule. When such polysilazane is used, impurities such as carbon do not exist in the low refractive index layer, thereby making it possible to form a dense low refractive index layer.

Moreover, it is preferable that ratio (Si / N ratio) of Si atom and N atom in polysilazane is 1.0-1.3. Such inorganic polysilazane is, for example, a method of reacting dihalosilane with a base to form an adduct of dihalosilane and reacting with ammonia (Japanese Patent Publication No. 63-16325), methylphenyldichlorosilane And a method of reacting ammonia with methyldichlorosilane and the like (Japanese Patent Laid-Open No. 62-88327).

The polysilazane having the repeating unit represented by the above formula (2) may be chained or cyclic. Mixtures of chained polysilazanes and cyclic polysilazanes are also preferred. The number average molecular weight converted into polystyrene of such polysilazane is 500-10000, Preferably it is about 1000-4000. When the number average molecular weight is less than 500, when the low dielectric constant silica-based film is formed, low molecular weight polysilazane may be volatilized in the step (b) or step (c) described later, whereby the silica-based film may be greatly shrunk. Moreover, when it exceeds 10000, when the fluidity | liquidity of a coating liquid falls, applicability | paintability may fall and it may not be possible to obtain the low dielectric constant silica type coating film of a flat uniform film.

In addition, the low molecular weight polysilazane having a number average molecular weight of 1000 or less is preferably 10 to 40% by weight, preferably 15 to 40% by weight, based on the total polysilazane. When the low molecular weight polysilazane is in this range for the entire polysilazane, it is possible to smoothly cover the step by wiring and to obtain a film surface having excellent flatness. Even if the amount of the low molecular weight polysilazane having a number average molecular weight of 1000 or less is 40% by weight or more, there is a problem that the membrane shrinkage increases from drying to litigation, resulting in deterioration of flatness and high stress, resulting in cracking.

Moreover, as a silane, the polysilane compound represented by following formula (3)-(5) can be used.

R ⁴ -Si (X ¹ ) ₃ ... (3)

In the formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms and X ¹ represents a halogen atom.

R ⁵ -Si (X ² ) ₃ ... (4)

In the formula, R ⁵ represents an aromatic hydrocarbon group which may have a substituent, and X ² represents a halogen atom.

R ⁶ R ⁷ -Si (X ³ ) ₂ ... (5)

In the formula, R ⁶ represents an alkyl group having 1 to 10 carbon atoms, R ⁷ represents an aromatic hydrocarbon group which may have a substituent, and X ³ represents a halogen atom.

The method for producing polysilane can be prepared according to a method known by condensation polymerization of methylphenyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane and the like in the presence of metal sodium (Japanese Patent Laid-Open No. 2007-145879). .

Specific examples of the silane compound (3) include an alkyltrichlorosilane compound represented by R ¹ SiCl ₃ (wherein R ¹ is the same as described above). As an alkyl trichlorosilane compound, methyl trichlorosilane, ethyl trichlorosilane, n-propyl trichlorosilane, isopropyl trichlorosilane, n-butyl trichlorosilane, t-butyl trichlorosilane, etc. are mentioned. Such compounds may be used alone or in combination of two or more.

Specific examples of the silane compound (4) include phenyltrichlorosilane, 2-chlorophenyltrichlorosilane, 4-methylphenyltrichlorosilane, 2,4,6-trimethylphenyltrichlorosilane, 1-naphthyltrichlorosilane, 2 -Naphthyl trichlorosilane, etc. are mentioned. Such compounds may be used alone or in combination of two or more.

Specific examples of the silane compound (5) include methylphenyldichlorosilane, ethylphenyldichlorosilane, n-propylphenyldichlorosilane, isopropylphenyldichlorosilane, methyl-1-naphthyldichlorosilane, methyl-2-naphthyldichlorosilane, and the like. Preferably, methylphenyldichlorosilane, ethylphenyldichlorosilane, n-propylphenyldichlorosilane, isopropylphenyldichlorosilane are more preferred, and methylphenyldichlorosilane is most preferred.

Polysilanes are known as chain, cyclic and branched. The branching type is preferable because it is required that the change of the refractive index due to the temperature is small and the change of the refractive index due to light irradiation is required to be highly sensitive.

The weight average molecular weight (Mw) of the polysilane compound is 500 to 50000, preferably 1000 to 20,000, in terms of the weight average molecular weight in terms of polystyrene. When the number average molecular weight is low, in the case of forming a silica-based film, low molecular weight polysilane may be volatilized and the silica-based film may shrink significantly. Moreover, even when molecular weight is large, solubility may fall and it may be difficult to melt | dissolve in a solvent.

As the acidic silicic acid solution, an alkali silicate aqueous solution is obtained by de-alkaliating an ion exchange resin or the like. Acidic silicates are used. It is also possible to mix and use a silica particle and a silica precursor. Low silica content of the particles in the high refractive index layer formed in case of using mixed is 0.1 to 40% by weight and preferably from 5 to 30% by weight as SiO _2. When silica particle content exists in this range, the low refractive index layer excellent in more compact hardness, abrasion resistance, etc. can be formed.

This silica sol includes a low refractive index silica-based fine particle dispersion sol disclosed in Japanese Patent Application Laid-Open No. 2001-233611, Japanese Patent Application Laid-open No. 2004-203683, and the like.

In this case, the average particle size of the silica particles is approximately 5 to 100 nm, and preferably 7 to 80 nm. The silica sol having a particle size in this range is stably dispersed, densified with the low refractive index film, and the hardness and scratch resistance of the antireflection film are increased.

Even if the average particle size of the silica particles is small, the particles are easily aggregated, resulting in insufficient stability of the low refractive index layer-forming component dispersion, and the low refractive index film formed using such a dispersion has insufficient densification, resulting in the hardness and scratch resistance of the finally obtained antireflection film. In some cases, the compatibility is insufficient. Even if the average particle size of a silica particle is large, densification may become inadequate with the basic nitrogen compound mentioned above, and the hardness and abrasion resistance of the antireflection film finally obtained may be inadequate. On the contrary, even if densified, scattering may occur, resulting in insufficient light transmittance.

As a dispersion medium of the low refractive index layer forming component dispersion, the same thing as what was used at the time of forming the said high refractive index layer can be mentioned. The concentration of the low refractive index layer forming component dispersion is in the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight as solids.

If the concentration of the low refractive index layer-forming component dispersion is thin, depending on the coating method, the low refractive index layer may not be formed even if the low refractive index layer thickness exceeds 30 nm in one coating. In addition, the surface roughness Ra _C of the low refractive index layer may not be adjusted in a desired range.

Even when the concentration of the low refractive index layer-forming component dispersion is high, the stability of the dispersion is lowered, and the low refractive index layer is not densified even when the low refractive index layer-forming component dispersion is used. In some cases, the compatibility is insufficient.

The method of applying the low refractive index layer forming component dispersion is not particularly limited as long as it is applied uniformly and uniformly on the high refractive index layer. It is also possible to employ a conventionally known method. For example, the same barcode method, dipping method, spray method, spinner method, roll coating method, gravure coating method, slitting coating method and the like as the above-mentioned high refractive index layer may be mentioned.

Process (d) and (e)

Here, (d) the dispersion medium is removed and subsequently heat treated to (e) 120 to 700 ° C, preferably 150 to 500 ° C.

As a method of removing the dispersion medium, the dispersion medium of the dispersion liquid can be substantially removed, and a drying temperature in the range of 50 to 120 ° C., preferably 60 to 100 ° C. is preferable depending on the boiling point of the dispersion medium.

Even when the drying temperature is low, the dispersion medium may be insufficient to remove the dispersion medium. Therefore, when the heat treatment is performed, voids may occur in the low refractive index layer. In this case, the hardness and scratch resistance of the low refractive index layer and the finally obtained antireflection film are insufficient. There is a case to be done.

Even if the drying temperature is high, drying of the surface of the coating film is caused rapidly, resulting in the surface coating. In this case, voids occur in the low refractive index layer, so that the hardness and scratch resistance of the low refractive index layer and the finally obtained antireflection film are insufficient. There is a case. The drying time varies depending on the drying temperature, but in this case, it is also about 20 minutes or less, preferably 30 seconds to 10 minutes.

Even when dried in the above range, the basic nitrogen compound contained in the high refractive index layer densifies the low refractive index layer forming component and promotes hardening of the low refractive index layer. Even if the heat treatment temperature is low, hardening of the high refractive index layer and the low refractive index layer may be insufficient, and the hardness and scratch resistance of the finally obtained antireflection film may be insufficient. Moreover, even if it heats beyond the said range, deformation, alteration, etc. may exist depending on the kind of base material.

The surface roughness Ra _C of the low refractive index layer according to the present invention thus formed can be selected as desired. For example, the surface roughness Ra _C may be 30 nm or less, preferably 10 nm or less. In this range, even if the smoothness is high and the light transmittance is high, only a slight decrease in hardness and scratch resistance occurs.

Meanwhile, the surface roughness Ra _C of the antireflection film is in the range of 30 nm to 1 μm, and preferably in the range of 50 nm to 0.8 μm. It is possible to have high light transmittance and to increase photoelectric conversion rate with the unevenness in this range. Abrasion resistance falls with unevenness | corrugation.

Such surface roughness is also good for the metal oxide particle size, the high refractive index layer thickness, the coating method, and the concentration of each dispersion medium in the surface roughness high refractive index layer of the substrate, but when designing the unevenness, it is preferable to use the uneven substrate and the large particle size. .

The average thickness of the low refractive index layer is in the range of 30 to 200 nm, preferably 50 to 150 nm. Even if the average thickness of the low refractive index layer is thin, the effect of improving the light transmittance is insufficient, and the effect of improving the photoelectric conversion rate may be insufficient when the transparent coating part substrate is used in the photovoltaic cell. Even if the average thickness of the low refractive index layer is thick, the effect of improving the light transmittance is insufficiently obtained, and the effect of improving the photoelectric conversion efficiency may be insufficient when the transparent coating part substrate is used in the photovoltaic cell.

In addition, the average thickness of the low refractive index layer having the surface irregularities is obtained by reducing the weight of the high refractive index layer substrate from the weight of the antireflection film (high refractive index layer and the low refractive index layer) section, dividing it by the specific gravity of the low refractive index layer, and again, the area of the low refractive index layer. It can be obtained by dividing by.

The thickness of the antireflection film of the antireflection film base material thus formed is the sum of only the average thickness of the high refractive index layer and the average thickness of the low refractive index layer, and is in the range of 80 to 400 nm, preferably 130 to 270 nm.

The hardness (pencil hardness) of the antireflection film is 7H or more, preferably 8H or more. When the hardness (pencil hardness) of the antireflection film is 6H or less, it may be damaged during long-term use as an electronic device or a solar cell, resulting in insufficient light transmittance. As a result, when used in a solar cell, the photoelectric conversion rate may decrease.

[Reflective coating part description]

The antireflection film base substrate of the present invention is obtained by the above production method and is a laminate of the base material, the high refractive index layer and the low refractive index layer.

The average thickness of the high refractive index layer is preferably in the range of 50 to 200 nm, preferably 80 to 120 nm. Even if the average thickness of the high refractive index layer is thin, it is difficult to obtain sufficient light transmittance improvement for decreasing the reflectance, and the improvement of photoelectric conversion efficiency may be insufficient due to the improvement of high utilization. Even if the average refractive index of the high refractive index layer is thick, sufficient light transmittance may not be obtained, and sufficient photoelectric conversion efficiency improvement effect may not be obtained.

The average thickness of the low refractive index layer is in the range of 30 to 200 nm, preferably 50 to 150 nm. Even if the average thickness of the low refractive index layer is thin, the effect of improving the light transmittance is insufficient, and the effect of improving the photoelectric conversion efficiency may be insufficient when the transparent coating part substrate is used in the photovoltaic cell. Even if the average thickness of the low refractive index layer is thick, the effect of improving the light transmittance is insufficient, and the effect of improving the photoelectric conversion efficiency is insufficient when the transparent coating part substrate is used in the photovoltaic cell.

The surface roughness Ra _B of the high refractive index layer formed on the substrate is in the range of 30 nm to 1 μm, and preferably in the range of 50 nm to 0.8 μm. Even if the surface roughness Ra _B of the high refractive index layer is small, sufficient light transmission efficiency improvement may not be obtained. The upper limit of surface roughness Ra _B does not exceed 1 micrometer.

The surface roughness Ra _C of the low refractive index layer according to the present invention thus formed may be appropriately selected as desired. Further, the low refractive index layer has a surface roughness Ra _C of 30 nm or less, preferably 10 nm or less. This range is high smoothness, good scratch resistance and slightly low anti-glare.

Meanwhile, the surface roughness Ra _C of the antireflection film is in the range of 30 nm to 1 μm, and preferably in the range of 50 nm to 0.8 μm. It is possible that the anti-glare photoelectric conversion efficiency can be improved because the unevenness in this range can be improved, and the scratch resistance is reduced by the unevenness.

Such surface roughness is good for the surface roughness of the substrate, the metal oxide particle size in the high refractive index layer, the high refractive index layer thickness, the coating method and the concentration of each dispersion, and the uneven substrate and the particle size may be used when designing the unevenness.

When used in the photovoltaic cell, the surface roughness Ra _C of the low refractive index layer is in the range of 30 nm to 1 μm, and preferably in the range of 50 nm to 0.8 μm. It has high scratch resistance and high light transmission efficiency, and therefore can be suitably used for the photovoltaic cell described later, which can enhance the photoelectric conversion efficiency.

When the pencil hardness of such an antireflection film base material is 7H or more, it has very high scratch resistance.

[Photoelectric Cell]

The photovoltaic cell according to the present invention is characterized in that the antireflection film is provided on the front surface of the substrate.

The photovoltaic cell according to the present invention has a substrate (P-) having an electrode layer (1) on its surface and a metal oxide semiconductor film (2) formed by adsorbing a photosensitizer on the surface of the electrode layer (1). 1) having the electrode layer 3 on the surface and the substrate P-2 and the electrode layer 1 and the electrode layer 3 facing each other, the substrate and the electrode layer in at least one direction are transparent and the metal oxide semiconductor In a photovoltaic cell in which an electrolyte layer is provided between the film 2 and the electrode layer 3, the substrate P-1 and / or the substrate P-2 having transparency in at least one direction are the front surface (the inside of the cell and the reflection side). ) Is provided with an antireflection film (subsidiary material) obtained by the above production method.

1 is a schematic cross-sectional view showing one embodiment of a photovoltaic cell according to the present invention. A substrate 5 having a transparent electrode layer 1 on its surface and a porous metal oxide semiconductor film 2 on which a photo-sensitizer is adsorbed on the surface of the transparent electrode layer 1 and an electrode layer 3 having a reducing catalyst on the surface thereof. The substrate 6 with the electrode layers 1 and 3 are disposed to face each other, and the electrolyte 4 is encapsulated between the porous metal oxide semiconductor film 2 and the transparent electrode layer 3. Therefore, the antireflection film is provided on the substrate surface (especially the surface which transmits light).

The photovoltaic cell according to the present invention is provided with an antireflection film base material obtained by the above-described specific manufacturing method, and has a high light transmittance and excellent photoelectric conversion efficiency. In addition, the antireflection film obtained by the above method is also excellent in surface hardness and scratch resistance and is excellent in surface protection performance.

As such a photoelectric cell, For example, Unexamined-Japanese-Patent No. 2010-153232, Unexamined-Japanese-Patent No. 2010-153231, Unexamined-Japanese-Patent No. 2010-108855, Japan Unexamined-Japanese-Patent No. 2010- by the applicant of this invention 073543, Japanese Unexamined Patent Publication No. 2010-040172, Japanese Unexamined Patent Publication No. 2009-289669, Japanese Unexamined Patent Publication No. 2009-218218, Japanese Unexamined Patent Publication No. 2008-277019, Japanese Unexamined Patent Publication 2008- 258099, Unexamined-Japanese-Patent No. 2008-210713, etc. can be enumerated.

As the substrate in one direction, a substrate having transparent and insulating properties, such as a glass substrate and an organic polymer substrate such as PET, may be used. The substrate in the other direction is not particularly limited as long as it has sensitivity necessary for use, but conductive substrates such as metal titanium, metal aluminum, metal copper, and metal nickel may be used in addition to insulating substrates such as organic polymer substrates such as glass substrates and PET substrates. Can be. The substrate is preferably a substrate on which an antireflection film is formed. At least one direction of the substrate is preferably transparent.

As the electrode layer 1 formed on the surface of the substrate 1, conventionally known tin oxide, Sb, F or P doped tin oxide, Sn and / or F doped indium oxide, antimony oxide, zinc oxide, precious metals, and the like An electrode can be used. Such an electrode layer 1 can be formed by conventionally known methods such as pyrolysis and CVD. In addition, the electrode layer 2 formed on the surface of the substrate 2 in the other direction is not particularly limited as long as it has a reducing catalyst, but an electrode material such as platinum, rhodium, ruthenium metal, ruthenium oxide, tin oxide, Sb, F or P A conductive material obtained by plating or depositing the electrode material on the surface of a conductive material such as doped tin oxide, Sn and / or F doped indium oxide, and antimony oxide is conducted by conventionally known methods such as pyrolysis and CDV. After forming a layer, it forms by the conventionally well-known method, such as plating or depositing the said electrode material on the said conductive layer.

In addition, the board | substrate 2 may be a transparent substrate of the same form as the board | substrate 1, and the electrode layer 2 may be a transparent electrode of the same form as the electrode layer 1. The substrate 2 may be the same as the substrate 1, or the electrode layer 2 may be the same as the electrode layer 1.

The visible light transmission efficiency of the transparent substrate 1 and the transparent electrode layer 1 is preferably high, specifically, 50% or more, preferably 90% or more. It is preferable that the resistance values of the electrode layer 1 and the electrode layer 2 are each 100 Ω / cm ² or less.

If necessary, the titanium oxide thin film 1 may be formed on the electrode layer 1, and the film thickness is in the range of 10 to 70 nm, preferably 20 to 40 nm. In addition, the titanium oxide thin film 1 may have a suitable pore.

delete

As a photosensitizer adsorb | sucked to such a semiconductor film, if it can absorb and excite the light of visible region, an ultraviolet region, and an infrared region, it will not restrict but an organic pigment | dye, a metal complex, etc. can be used, for example.

As the organic pigment, conventionally known organic pigments having functional groups such as carboxyl group, hydroxyalkyl group, hydroxyl group, sulfone group and carboxyalkyl group can be used in the molecule. Specifically, methylphthalocyanine, cyanine pigment, metallocyanine pigment, triphenylamine pigment, and xanthine pigments such as uranium, eosin, rosebengal, rhodamine B, dibrofluorescein, and the like are listed. Can be. Such organic dyes have a characteristic that the adsorption rate is increased in the metal oxide semiconductor film. Examples of the metal complexes include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophenyl, hemin, and ruthenium-tris (2,2) described in Japanese Patent Application Laid-Open No. Hei 1-220380 and Japanese Patent Application Laid-open No. Hei 5-504023. '-Bispyridyl-4,4'-dicarboxylate), cis- (SCN ^- )-bis (2,2'-bipyridyl-4,4'-dicarboxylate) ruthenium, ru Luthenium-cis-diaqua-bipyridyl complexes such as tenium-cis-diaqua-bis (2,2'-bipyridyl-4,4'-dicarboxylate), zinc-tetra (4 The complexes, such as ruthenium, osmium, iron, and zinc, may be mentioned, such as polpyrin, such as -carboxyphenyl) polpyrine, and iron-hexacyanide complex. Such a metal complex is excellent in the effect of spectroscopic sensitization and durability. The adsorption amount of the photosensitizer of the porous metal oxide semiconductor film is 100 µg or more, preferably 150 µg or more, per cm ^{2 of the} specific surface area of the porous metal oxide semiconductor film.

As the electrolyte, a mixture of an electrochemically active salt and at least one or more compounds which form a redox system therein is used. As a salt which has electrochemical activity, quaternary ammonium salts, such as tetrapropyl ammonium iodide, are mentioned. Examples of the compound forming the redox quinone, hydroxy hydroquinone, iodine (I ^- / I ^- ₃₎ can be given, such as potassium bromide, potassium iodide, bromine (Br ₃ ^{- -} / Br). In some cases, it may be used by mixing.

The amount of the electrolyte used varies depending on the type of the electrolyte and the type of the solvent described later, but the range of approximately 0.1 to 5 mol / L is preferable. A conventionally well-known solvent can be used for an electrolyte layer. Specifically, sulfur compounds of carbonates such as water, alcohols, oligoethers, propion carbonate, phosphate esters, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane 66 , Ethylene carbonate, acetryl, gamma -butyrolactone, and the like.

EXAMPLE

The present invention will be described in more detail with reference to the following Examples. However, the present invention is not limited by these examples.

(Example 1)

Preparation of Metal Oxide Particle Dispersion (1) for Formation of High Refractive Index Layer

Titanium Chemical Co., Ltd. (Dama Chemical) for 100 g of titanium oxide colloidal methanol dispersion (Ultracatalyst Co., Ltd.): Off-the-lake 1120 Z, average particle size 12 nm, TiO ₂ concentration 20.5 wt%, dispersion medium: methanol, TiO ₂ particle refractive index 2.30 1.88 g of ethyl acetate-A, SiO ₂ concentration 28.8 wt%) was added thereto, and 3.1 g of ultrapure water was added thereto, followed by stirring at 50 ° C. for 6 hours to obtain a surface-treated titanium oxide particle having a solid content concentration of 20.5 wt%. Methanol dispersions were prepared.

80 g of propylene glycol monopropyl ether (PGME) and modified alcohol (Japan Alcohol Sales Co., Ltd.): Soul Mix AP-11: 85.5% by weight of ethanol, isopropyl alcohol 9.8% by weight, 4.7% by weight of methanol) and 2g were added so that triethylamine (boiling point: 90 ° C) was 50 ppm in the coating liquid as a basic nitrogen compound, which was stirred at 25 ° C for 30 minutes to give a solid content of 5% by weight. A metal oxide particle dispersion (1) for forming a refractive index layer was prepared.

Low refractive index layer  Preparation of Forming Component Dispersion (1)

70.0 g of Sodium Mix A-11 (manufactured by Nippon Alcohol Co., Ltd.) was added 10.0 g of water and 0.1 g of nitric acid having a concentration of 61% by weight, and stirred at 25 ° C for 10 minutes, followed by ethyl acetate ( 17.4 g of ethyl acetate-A, SiO ₂ concentration 28.8 wt%) was added thereto, and stirred at 30 ° C. for 30 minutes to prepare 100 g of an ethyl acetate hydrolyzate dispersion having a solid content of 5.0 wt%. The polyethylene equivalent molecular weight of the ethyl acetate hydrolyzate was 1000.

Subsequently, 33 g of propylene glycol monopropyl ether (PGME) and modified alcohol (Japan Alcohol Sales Co., Ltd.): Soul Mix AP-11: 85.5% by weight of ethanol, isopropyl alcohol 9.8% by weight, 4.7% by weight of methanol) was added thereto, followed by stirring at 25 ° C. for 30 minutes to prepare a low refractive index layer-forming component dispersion (1) having a solid concentration of 3.0% by weight.

Anti-reflective coating  Production of the base material 1

The glass substrate (Hamashin Co., Ltd. make: FL porcelain, thickness: 3 mm, refractive index: 1.51) was sandblasted to prepare a glass substrate 1 having a surface roughness Ra _A of 500 nm.

Subsequently, the metal oxide fine particle dispersion 1 for forming a high refractive index layer was applied to the surface having the surface roughness of the glass substrate 1 by a bar coder method (# 5) and dried at 80 ° C. for 120 seconds. At this time, the average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index is measured and the results are shown in the table. Refractive index was measured by the Ellipsomta (EMS-1, made by ULVAC).

Subsequently, the anti-reflective layer-forming component (1) was coated with a barcoder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. Was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. In addition, the surface roughness (Ra _C ) and the refractive index are measured and the results are shown in the table. The refractive index of the low refractive index layer was measured by a reflectometer (Otsuka Electronics Co., Ltd. product: FE-3000).

In the antireflection film part substrate 1, the total light transmittance and the haze were measured by a haze meter (manufactured by Suga Test Equipment Co., Ltd.), and a reflectance was measured by a spectrophotometer (Japanese Spectrophotometer, Ubest-55). The uncoated glass substrate had a total light transmittance of 99.0%, a haze of 0.1%, and a light reflectance of 5.0% at a wavelength of 550 nm.

1) Measurement of pencil hardness

It measured by the pencil hardness tester according to JIS-K-5400.

2) measurement of scratch resistance

The surface of the membrane was visually observed by scratching 10 times under a load of 2 kg / cm ² using # 0000 steel wool, and the results are shown in Table 1 by evaluating the following criteria.

Evaluation standard :

Stripes are not visible: ◎

Stripes look a bit: ○

A lot of stripes are seen: △

The face is entirely erased: ×

Preparation of Photovoltaic Cell (1-1)

The electrode part antireflection film part base material 1-1 formed on the opposite side of the antireflection film part base material 1 using the fluorine-doped tin oxide as an electrode was produced.

Preparation of Metal Oxide Fine Particles for Semiconductor Films

5 g of hydrogen and titanium were suspended in 1 L of pure water, 400 g of 5% hydrogen peroxide solution was added for 30 minutes, and subsequently heated to 80 ° C. to prepare a solution of dissolved peroxysilane. Titanium colloidal particles (A) are produced by adding concentrated ammonia water to pH 9, adjusting the pH to 9, and placing it in an autoclave and performing hydrothermal treatment at 250 ° C for 5 hours under saturated steam pressure. X-ray diffraction revealed high crystallinity of an anitazide titanium oxide. The average particle size was 40 nm.

Semiconductor film  Preparation of Coating Liquid for Formation

Subsequently, the titania colloidal particles (A) obtained by the above method were concentrated to a concentration of 10%, the peroxy titanic acid solution was mixed therein, and the titanium in the mixture was 30% by weight of the weight in terms of TiO ₂ to prepare a film forming aid. Phosphorus hydroxypropyl cellulose was added to prepare a coating liquid for forming a semiconductor film.

Semiconductor film  formation

Subsequently, the coating liquid for forming a semiconductor is applied on the electrode surface of the electrode portion reflective ring membrane substrate 1 and naturally dried, and continuously irradiated with ultraviolet light of 6000 mJ / cm ² using a low pressure mercury lamp to decompose peroxytitanic acid Decomposition, polycondensation) to cure the semiconductor film. Further, heating was carried out at 300 ° C. for 30 minutes to decompose and anneal hydroxypropyl cellulose to form a titanium oxide semiconductor film (A).

The film thickness of the obtained titanium oxide semiconductor film A was 20 µm, the pore volume determined by the nitrogen adsorption method was 0.60 ml / g, and the average pore size was 22 nm.

Adsorption of Spectrosensitizing Pigments

As a spectrophotometer, the concentration of the ruthenium complex represented by cis- (SCN-)-bis (2,2'-bipyridyl-4,4'-dicarboxylate) ruthenium (II) is 3 x 10- ^{. 4} mol / L of ethanol solution was prepared. This spectrophotosensitive dye solution was applied onto a titanium oxide semiconductor film A using an rpm 100 spinner and dried. This application | coating and drying process were performed 5 times. The adsorption amount of the spectral sensitizing dye of the obtained titanium oxide semiconductor film was 150 microgram / cm <^2> . In this case, the amount of adsorption per 1 cm ² of the specific surface area of the titanium oxide film A is expressed. Moreover, the weight increase and decrease of the semiconductor film after coating drying was made into the adsorption amount.

Subsequently, the volume ratio of acetonitrile and ethylene carbonate as a solvent was mixed at a ratio of 1: 4, and the tetrapropylammonium iodide and iodine were dissolved in the solvent so that the concentrations were 0.46 mol / L and 0.06 mol / L, respectively, to prepare an electrolyte solution. It was.

In the above, the electrode antireflective coating part substrate 1 is used as an electrode in one direction, and the electrode in the other direction is formed of fluorine-doped tin oxide as an electrode, and thereafter, platinum is supported thereon so as to face the transparent glass substrate. A photovoltaic cell 1-1 in which a resin was sealed and the electrolyte solution was sealed between the electrodes was connected to each other by a lead wire.

The performance was evaluated in the obtained photovoltaic cell (1-1).

Performance Evaluation (1) (Initial Performance Evaluation)

The photovoltaic cell 1 is irradiated with light of 100 W / m ² intensity with a solar simulator to produce Voc (voltage in a closed circuit), Joc (density of current flowing when the circuit is shorted), FF (curve factor), and η ( The conversion efficiency) is shown in the table.

Performance Evaluation (2) ( Scratch resistance  After the test)

Photoelectrode cells were prepared in the same manner except that the electrode portion antireflection film portion base material 1-2 was formed by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflection film portion 1 of the antireflection film portion 1 having a specified scratch resistance. (1-2) was produced and performance was evaluated in the same manner, and the results are shown in the table.

(Example 2)

Creation of the glass substrate 2

Preparation of Coating Liquid (1) for Surface Roughness Formation

Modified alcohol (Japan Alcohol Sales Co., Ltd. make: Soul Mix AP-11: 85.5% by weight of ethanol, 9.8% by weight of isopropyl alcohol, 4.7% by weight of methanol) 12.5g of water and 0.1g of nitric acid with a concentration of 61% by weight in 72.5g After addition, the mixture was stirred at 25 ° C. for 10 minutes, and 17.4 g of ethyl regular acid (manufactured by Tama Chemical Co., Ltd .: ethyl regular acid-A, SiO ₂ concentration 28.8 wt%) was added thereto, and stirred at 30 ° C. for 30 minutes to give a solid content of 5.0. 100 g of ethyl acetate hydrolyzate dispersion by weight was prepared. The polyethylene equivalent molecular weight of the ethyl acetate hydrolyzate was 1000.

Subsequently, 7.5 g of propylene glycol monopropyl ether (PGME) and 142.5 g of methanol were added to 100 g of a normal ethylene hydrolyzate dispersion having a solid content of 5.0 wt%, followed by stirring at 25 ° C. for 30 minutes to form a surface roughness having a solid concentration of 2.0 wt%. The coating liquid 1 was prepared.

The coating liquid 1 for surface roughness formation was spray-coated to the glass substrate (The Hamasin Co., Ltd. make: FL porcelain, thickness: 3 mm, refractive index: 1.51). Spray application was carried out by heating the glass substrate to 40-42 ° C., and applying a glass nozzle having a diameter of 2 mm at an air flow rate of 25 L / min and an air pressure of 0.4 mPa. Thereafter, the coated substrate was dried at 80 ° C. for 10 minutes, and then fired at 150 ° C. for 30 minutes to prepare a glass substrate 2 having a surface roughness Ra _A of 100 nm.

Anti-reflective coating  Production of the base material 2

Subsequently, a high refractive index layer forming metal oxide particle dispersion (1) prepared in the same manner as in Example 1 was applied to the glass substrate 2 by a bar coder method (# 5) and dried at 80 ° C. for 120 seconds. At this time, the average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index is measured and the results are shown in the table.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film base substrate 2 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part base material 2 were measured and the results are shown in the table.

Of photovoltaic cell (2)  write

The electrode part antireflection film part base material 2 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 2 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion base material 2, and spectrophotochromium was adsorbed to make the electrode portion antireflection film portion base material 2 in one direction and in the other direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 2-1 was manufactured.

On the other hand, the photovoltaic cell 2-2 was manufactured by the same method using the antireflective film part base material 2 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 3)

Creation of the glass substrate 3

Surface roughness  Preparation of Coating Liquid 2 for Formation

Solid content concentration was adjusted to 20% by weight by adding 333 g of pure water to 1000 g of silica fine particle dispersion (Iltracatalyst Co., Ltd. manufacture: CATALOID SS-300; average particle size 300 nm, SiO ₂ concentration 18.00 wt%, dispersion medium: water) Thereafter, 336 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Dion SK1B) was ion-exchanged at 80 ° C. for 3 hours to give a silica fine particle dispersion having a solid concentration of 20% by weight.

This dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a silica fine particles methanol dispersion having a solid content of 20% by weight. 100 g of silica fine particle methanol dispersion was mixed with 1.88 g of ethyl acetate (manufactured by Tama Chemical Co., Ltd.: 28.8 wt% of SiO ₂ , SiO ₂ concentration), 3.1 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 6 hours. A surface-treated silica particulate methanol dispersion having a concentration of 20.5% by weight was prepared.

1 g of NMP and 49 g of PGM were added to 100 g of the surface-treated silica particle methanol dispersion, and stirred at 25 ° C. for 30 minutes to prepare a coating liquid 2 for forming a surface roughness having a solid content concentration of 10.0 wt%.

The coating liquid for surface roughness formation (2) was coated on a glass substrate (Hamashin Co., Ltd .: FL porcelain, thickness: 3mm, refractive index: 1.51) by the barcoder method (# 3), dried at 80 ° C. for 120 seconds, and then 150. It baked at 30 degreeC for 30 minute (s), and produced the glass substrate 3 whose surface roughness Ra _A is 300 nm.

Anti-reflective coating  Preparation of Substrate 3

Subsequently, the high refractive index layer-forming metal oxide particle dispersion 1 prepared in the same manner as in Example 1 was applied to the glass substrate 3 by a bar coder method (# 5) and dried at 80 ° C. for 120 seconds. At this time, the average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index is measured and the results are shown in the table.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film base substrate 3 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness, and the scratch resistance of the antireflection film part substrate 3 were measured and the results are shown in the table.

Of photovoltaic cell (3)  write

The electrode part antireflection film part base material 3 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 3 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion base material 3, and the spectrophotometric dye was adsorbed, so that the electrode portion antireflection film portion base material 3 was an electrode in one direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 3-1 was manufactured.

On the other hand, the photovoltaic cell 3-2 was manufactured using the antireflective film part base material 3 which measured scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 4)

High refractive index layer  Preparation of Metal Oxide Particle Dispersion (2) for Formation

In Example 1, a metal oxide particle dispersion for forming a high refractive index layer having a solid concentration of 5% by weight was prepared in the same manner except that 0.05 g of triethyleneamine was added as 5 ppm in the coating liquid as the basic nitrogen compound. It was.

Anti-reflective coating  Preparation of the substrate 4

Subsequently, a high refractive index layer was formed on the glass substrate 1 in the same manner as in Example 1 except that the metal oxide particle dispersion liquid for forming a high refractive index layer was used. The average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index is measured and the results are shown in the table.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film base substrate 4 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness, and the scratch resistance of the antireflection film part substrate 4 were measured and the results are shown in the table.

Of photovoltaic cell 4-1  write

The electrode part antireflection film part base material 4 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 4 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 4 and the spectrophotometric dye was adsorbed, so that the electrode portion antireflection film portion substrate 4 was used as an electrode in one direction and the other direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 4-1 was manufactured.

On the other hand, the photovoltaic cell 4-2 was manufactured using the antireflection film part base material 4 which measured scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 5)

High refractive index layer  Preparation of Metal Oxide Particle Dispersion (3) for Formation

In Example 1, a metal oxide particle dispersion for forming a high refractive index layer having a solid content concentration of 5% by weight was prepared in the same manner except that 2 g of triethyleneamine was added as a basic nitrogen compound to 200 ppm in the coating solution. It was.

Anti-reflective coating  Production of Substrate 5

Subsequently, a high refractive index layer was formed on the glass substrate 1 in the same manner as in Example 1 except that the metal oxide particle dispersion liquid 3 for forming a high refractive index layer was used. The average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index is measured and the results are shown in the table.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film base substrate 5 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part substrate 5 were measured and the results are shown in the table.

Of photovoltaic cell (5)  write

The electrode part antireflection film part base material 5 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 5 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 5, and the spectrophotosensitive dye was adsorbed, so that the electrode portion antireflection film portion substrate 5 was used as an electrode in one direction and the other direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 5-1 was manufactured.

On the other hand, the photovoltaic cell 5-2 was manufactured using the antireflection film part base material 5 which measured scratch resistance similarly to Example 1. In the obtained photovoltaic cell 5-1 and 5-2, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 6)

High refractive index layer  Preparation of Metal Oxide Particle Dispersion (4) for Formation

In Example 1, high refractive index of 5% by weight of solid content was obtained in the same manner except that 0.5 g of tripropylamine (boiling point: 155 ° C) was added to 50 ppm in the coating liquid as a basic nitrogen compound instead of triethyleneamine. A metal oxide particle dispersion (4) for layer formation was prepared.

Anti-reflective coating  Preparation of the Substrate 6

Subsequently, the high refractive index layer was formed on the glass substrate 1 in the same manner as in Example 1 except that the metal oxide particle dispersion liquid for forming the high refractive index layer was used. The average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index is measured and the results are shown in the table.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film base substrate 6 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part base material 6 were measured and the results are shown in the table.

Of photovoltaic cell (6)  write

The electrode part antireflection film part base material 6 in which the fluorine-doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 6 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion 6, and the spectrophotosensitive dye was adsorbed, so that the electrode portion antireflection film portion 6 was an electrode in one direction, As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 6-1 was manufactured.

On the other hand, the photovoltaic cell 6-2 was manufactured using the antireflective film part base material 6 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 7)

High refractive index layer  Preparation of Metal Oxide Particle Dispersion (5) for Formation

The high refractive index layer having a solid content of 5% by weight in the same manner as in Example 1, except that 0.5 g of triethanolamine (boiling point: 208 ° C) was added to 50 ppm in the coating liquid as a basic nitrogen compound instead of triethyleneamine. Forming metal oxide particle dispersion (5) was prepared.

Anti-reflective coating  Preparation of Substrate 7

Subsequently, a high refractive index layer was formed on the glass substrate 1 in the same manner as in Example 1 except that the metal oxide particle dispersion 5 for forming a high refractive index layer was used. The average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index is measured and the results are shown in the table.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film base substrate 7 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part substrate 7 were measured and the results are shown in the table.

Of photovoltaic cell (7)  write

The electrode part antireflection film part base material 7 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 7 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 7, and the spectrophotochromium was adsorbed to form the electrode portion antireflection film portion substrate 7 as an electrode in one direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photoelectron cell 7-1 was manufactured.

On the other hand, the photovoltaic cell 7-2 was manufactured using the antireflection film part base material 7 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 8)

Anti-reflective coating  Preparation of the Substrate 8

In Example 1, the anti-reflection film part was applied in the same manner except that the low refractive index layer-forming component dispersion 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated and cured at 300 ° C. for 30 minutes. Substrate 8 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness, and the scratch resistance of the antireflection film part substrate 8 were measured and the results are shown in the table.

Of photovoltaic cell (8)  write

The electrode part antireflection film part base material 8 which formed the fluorine doped tin oxide as an electrode on the opposite side of the antireflection film part base material 8 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 8, and spectrophotochromium was adsorbed, so that the electrode portion antireflection film portion substrate 8 was an electrode in one direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 8 was manufactured.

On the other hand, the photovoltaic cell 8-2 was manufactured using the antireflective film part base material 8 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 9)

Anti-reflective coating  Preparation of the Substrate 9

In Example 1, the antireflection film portion was applied in the same manner except that the low refractive index layer-forming component dispersion 1 was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 650 ° C. for 30 minutes to cure. Substrate 9 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part substrate 9 were measured and the results are shown in the table.

Of photovoltaic cell (9)  write

The electrode part antireflection film part base material 9 in which fluorine-doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 9 was prepared.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 9, and spectrophotochromium was adsorbed, so that the electrode portion antireflection film portion substrate 9 was used as an electrode in one direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photoelectron cell 9-1 was manufactured.

On the other hand, the photovoltaic cell 9-2 was manufactured using the antireflection film part base material 9 which measured scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 10)

High refractive index layer  Preparation of Metal Oxide Particle Dispersion Liquid 6 for Formation

Surface Treatment Titanium Oxide Particles Methanol Dispersion 10.24g at 20.5 wt% of Solids Concentration Prepared in the Same Method as Example 1 and Ethyl Hydrolyzate Dispersion (1) 18.0 at 5.0 wt% of Solids Concentration Prepared as in Example 1 g and propylene glycol monopropyl ether (PGME) 20.00 g and methanol, ethanol and isopropyl alcohol modified alcohol (Japan Alcohol Sales Co., Ltd.): Soul Mix AP-11: 85.5% by weight of ethanol, 9.8% by weight of isopropyl alcohol, 4.7 wt% methanol) 51.76 g of methanol and triethylamine (boiling point: 90 ° C.) as a basic nitrogen compound were mixed to 50 ppm in a coating solution, and 2 g were mixed and stirred at 25 ° C. for 30 minutes to form a high refractive index layer having a solid concentration of 5% by weight. A metal oxide fine particle dispersion (6) was prepared.

Anti-reflective coating  Preparation of the Substrate 10

In the same manner as in Example 1, the metal oxide fine particle dispersion 6 for forming the high refractive index layer was applied to the glass substrate 2 by a bar coder method (# 5) and dried at 80 ° C. for 120 seconds. At this time, the average thickness of the high refractive index layer was 100 nm. In addition, the surface roughness (Ra _B ) and the refractive index were measured and the results are shown in the table. In the same manner as in Example 1, the low-refractive-index layer-forming component dispersion (1) was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then cured by heating at 500 ° C. for 30 minutes (10). ) Was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness, and the scratch resistance of the antireflection film part substrate 10 were measured and the results are shown in the table.

Of photovoltaic cell 10  write

The electrode part antireflection film part base material 10 in which the fluorine-doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 10 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 10, and the spectrophotometric dye was adsorbed, so that the electrode portion antireflection film portion substrate 10 was used as an electrode in one direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 10-1 was manufactured.

On the other hand, the photovoltaic cell 10-2 was manufactured using the antireflection film base material 10 which measured scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 11)

Low refractive index layer  Preparation of Forming Component Dispersion (2)

Modified alcohol (Japan Alcohol Sales Co., Ltd. make: Soul Mix AP-11: 85.5% by weight of ethanol, 9.8% by weight of isopropyl alcohol, 4.7% by weight of methanol) 12.5g of water and 0.1g of nitric acid with a concentration of 61% by weight in 72.5g Solid content was added and then stirred at 25 ° C. for 10 minutes, followed by addition of 17.4 g of ethyl regular acid (manufactured by Tama Chemical Co., Ltd .: ethyl regular acid-A, SiO ₂ concentration 28.8 wt%) and stirred at 30 ° C. for 30 minutes. 100 g of 5.0 wt% ethyl acetate hydrolyzate dispersion was prepared. The polyethylene oxide molecular weight of the ethyl acetate hydrolyzate was 1000.

Subsequently, the silica-based hollow particulate dispersion was prepared as silica particles in 40.0 g of ethyl acetate hydrolyzate dispersion having a solid content of 5.0 wt% (Silicon 4320, solid concentration 20.5 wt%, dispersion medium isopropyl alcohol, silica type). Average particle size of hollow fine particles = 60 nm, refractive index = 1.25) 5.85 g, propylene glycol monopropyl ether (PGME) 20.00 g and modified alcohol (Japan Alcohol Co., Ltd. make: Soul Mix AP-11: Ethanol 85.5 wt%, 34.15 g of 9.8% by weight of isopropyl alcohol and 4.7% by weight of methanol) were added thereto, followed by stirring at 25 ° C. for 30 minutes to prepare a low refractive index layer forming component dispersion (2) having a solid content of 3.0% by weight.

Anti-reflective coating  Preparation of the Substrate 11

In the same manner as in Example 1, the metal oxide fine particle dispersion for forming the high refractive index layer 1 was applied to the glass substrate 1 by the barcoder method (# 5) and dried at 80 ° C. for 120 seconds, followed by the dispersion of the low refractive index layer forming component. (2) was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then prepared an antireflection film part base material 11 having a low refractive index layer formed by curing at 500 ° C. for 30 minutes. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part substrate 11 were measured and the results are shown in the table.

Of photovoltaic cell 11  write

The electrode part antireflection film part base material 11 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 11 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 11 and the spectrophotosensitive dye was adsorbed, so that the electrode portion antireflection film portion substrate 11 was used as an electrode in one direction and the other direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 11-1 was manufactured.

On the other hand, the photovoltaic cell 11-2 was manufactured using the antireflection film part base material 11 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Example 12)

Low refractive index layer  Preparation of Forming Component Dispersion (3)

Modified alcohol (Japan Alcohol Sales Co., Ltd. make: Soul Mix AP-11: 85.5% by weight of ethanol, 9.8% by weight of isopropyl alcohol, 4.7% by weight of methanol) 12.5g of water and 0.1g of nitric acid with a concentration of 61% by weight in 72.5g Solid content was added and then stirred at 25 ° C. for 10 minutes, followed by addition of 17.4 g of ethyl regular acid (manufactured by Tama Chemical Co., Ltd .: ethyl regular acid-A, SiO ₂ concentration 28.8 wt%) and stirred at 30 ° C. for 30 minutes. 100 g of 5.0 wt% ethyl acetate hydrolyzate dispersion was prepared. The polyethylene oxide molecular weight of the ethyl acetate hydrolyzate was 1000.

Subsequently, 33 g of propylene glycol monopropyl ether (PGME) and modified alcohol (Japan Alcohol Sales Co., Ltd.): Soul Mix AP-11: 85.5% by weight of ethanol, isopropyl alcohol 16 g of 9.8 wt%, 4.7 wt% of methanol) and 17 g of DAA (boiling point: 168 ° C.) were added thereto, and stirred at 25 ° C. for 30 minutes to prepare a low refractive index layer-forming component dispersion (3) having a solid content of 3.0 wt%.

Anti-reflective coating  Preparation of the Substrate 12

In the same manner as in Example 2, the metal oxide fine particle dispersion for forming the high refractive index layer 1 was applied to the glass substrate 2 by the bar coder method (# 5), dried at 80 ° C. for 120 seconds, and then the low refractive index layer forming component dispersion. (3) was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then prepared an antireflective film portion base material 12 having a low refractive index layer cured by heating at 500 ° C. for 30 minutes. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness, and the scratch resistance of the antireflection film part substrate 12 were measured and the results are shown in the table.

Of photovoltaic cell 12-1  write

The electrode part antireflection film part base material 12 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material 12 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion substrate 12, and spectrophotochromium was adsorbed, so that the electrode portion antireflection film portion substrate 12 was used as an electrode in one direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. The photovoltaic cell 12-1 was manufactured.

On the other hand, the photovoltaic cell 12-2 was manufactured using the antireflective film part base material 12 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell 12-1 and the photovoltaic cell 12-2, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Comparative Example 1)

High refractive index layer  Metal oxide fine particle dispersion for forming ( R1 Manufacturing

A metal oxide fine particle dispersion (R1) for forming a high refractive index layer having a solid content concentration of 5% by weight was prepared in the same manner as in Example 1 except adding triethylamine.

Anti-reflective coating  materials( R1 Manufacturing

A high refractive index layer was formed on the glass substrate 1 in the same manner as in Example 1 except that the metal oxide fine particle dispersion (R1) for forming a high refractive index layer was used. The average thickness of the high refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _B ) and refractive index are measured, and the results are shown in a table.

In the same manner as in Example 1, the low refractive index layer-forming component dispersion (1) was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film part base material R1 was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, haze, pencil hardness and scratch resistance of the antireflection film part base material R1 were measured and the results are shown in the table.

Of photovoltaic cell (R1)  write

An electrode part antireflection film part base material R1 in which fluorine-doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material R1 was prepared.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion R1 and the spectrophotometric dye was adsorbed. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. Photovoltaic cell R1-1 was prepared.

On the other hand, the photovoltaic cell R1-2 was manufactured using the antireflection film part base material R1 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Comparative Example 2)

High refractive index layer  Metal oxide fine particle dispersion for forming ( R2 Manufacturing

In Example 1, a metal oxide fine particle dispersion (R2) for forming a high refractive index layer having a solid content of 5% by weight was added except that 0.5 g of triethylamine was added to 50 ppm in the coating solution as a basic nitrogen compound. Prepared.

Anti-reflective coating  materials( R2 Manufacturing

A high refractive index layer was formed on the glass substrate 1 in the same manner as in Example 1 except that the metal oxide fine particle dispersion (R2) for forming the high refractive index layer was used. The average thickness of the high refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _B ) and refractive index are measured, and the results are shown in a table.

In the same manner as in Example 1, the low refractive index layer-forming component dispersion (1) was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film part base material (R2) was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part base material R2 were measured and the results are shown in the table.

Of photovoltaic cell (R2)  write

The electrode part antireflection film part base material R2 in which the fluorine doped tin oxide was formed as an electrode on the opposite side of the antireflection film part base material R2 was produced.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion anti-reflection film portion R2 and the spectrophotometric adsorbed, so that the electrode portion anti-reflection film portion R2 was an electrode in one direction, As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. Photoelectron cell R2-1 was prepared.

On the other hand, the photovoltaic cell R2-2 was manufactured using the antireflective film part base material R2 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell R2, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in the table.

(Comparative Example 3)

Anti-reflective coating  materials( R3 Manufacturing

In Example 1, the metal oxide fine particle dispersion for forming the high refractive index layer 1 was applied to the surface having the surface roughness of the glass substrate 1 by the bar coder method (# 5) and dried at 45 ° C. for 120 seconds to obtain the high refractive index layer. Formed. At this time, the average thickness of the high refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _B ) and refractive index are measured, and the results are shown in a table.

In the same manner as in Example 1, the low refractive index layer-forming component dispersion (1) was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film part base material (R3) was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part base material R3 were measured and the results are shown in the table.

Of photovoltaic cell (R3)  write

An electrode part antireflection film part base material R3 in which fluorine-doped tin oxide was formed as an electrode on the opposite side to the antireflection film of antireflection film part base material R3 was prepared.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion anti-reflection film portion R3 and the spectrophotochromium was adsorbed, thereby making the electrode portion anti-reflection film portion R3 an electrode in one direction, As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. Photovoltaic cell R3-1 was prepared.

On the other hand, the photovoltaic cell R3-2 was manufactured using the antireflective film part base material R3 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

(Comparative Example 4)

Anti-reflective coating  materials( R4 Manufacturing

In Example 1, the metal oxide fine particle dispersion for forming the high refractive index layer 1 was applied to the surface having the surface roughness of the glass substrate 1 by the bar coder method (# 5) and dried at 130 ° C. for 120 seconds to obtain the high refractive index layer. Formed. At this time, the average thickness of the high refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _B ) and refractive index are measured, and the results are shown in a table.

In the same manner as in Example 1, the low refractive index layer-forming component dispersion (1) was applied by a bar coder method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to form a low refractive index layer. An antireflection film base substrate (R4) was prepared. At this time, the average thickness of the low refractive index layer was 100 nm. Meanwhile, surface roughness (Ra _C ) and refractive index are measured, and the results are shown in a table.

The total light transmittance, the haze, the pencil hardness and the scratch resistance of the antireflection film part substrate (R4) were measured and the results are shown in the table.

Of photovoltaic cell (R4)  write

An electrode part antireflection film part base material R4 in which fluorine-doped tin oxide was formed as an electrode on the opposite side to the antireflection film of antireflection film part base material R4 was prepared.

Subsequently, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the electrode portion antireflection film portion R4, and the spectrophotometric dye was adsorbed to form the electrode portion antireflection film portion R4 as an electrode in one direction and the other direction. As an electrode, fluorine-doped tin oxide was formed as an electrode, and platinum was supported thereon so as to face the transparent glass substrate. The side was sealed with a resin, and the electrolyte solution was sealed between the electrodes to connect the electrodes with lead wires. Photovoltaic cell R4-1 was prepared.

On the other hand, the photovoltaic cell R4 was manufactured using the antireflection film part base material R4 which measured the scratch resistance similarly to Example 1. In the obtained photovoltaic cell, performance evaluation (1) and performance evaluation (2) are performed, and the results are shown in a table.

1. Transparent electrode layer 2. Porous semiconductor film 3. Electrode layer
4. Electrolyte 5. Transparent Substrate 6. Substrate

Claims (19)

In the manufacturing method of the antireflection film part substrate comprising a high refractive index layer formed on the substrate and a low refractive index layer of less than 1.50 refractive index formed on the high refractive index layer,
(a) applying a metal oxide particle dispersion containing 1 to 1000 ppm of a basic nitrogen compound and having a refractive index of 1.50 to 2.40 on the substrate;
(b) removing the dispersion medium of the dispersion at a temperature below the boiling point of the basic nitrogen compound;
(c) applying a low refractive index layer forming component dispersion;
(d) removing the dispersion medium of the low refractive index layer forming component dispersion; And
(e) heating the substrate at 120-700 ° C .;
Method of manufacturing an antireflection film base material having a sequentially.
The method of claim 1, wherein the low refractive index layer forming component is a silica precursor or a silica precursor and a silica sol.
According to claim 2, wherein the silica precursor is at least one selected from a partial hydrolyzate, hydrolyzate, hydrolysis-condensation polymer, polysilazane, polysilane or acidic silicate of the organosilicon compound Manufacturing method.
The method of claim 1, wherein the concentration of the low refractive index layer-forming component dispersion is in the range of 0.5 to 10% by weight as a solid content.
The method of claim 1, wherein the basic nitrogen compound has a boiling point in the range of 40 to 250 ° C.
The method of claim 1, wherein the metal oxide particles are at least one metal oxide selected from TiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₅ , In ₂ O ₃ or Nb ₂ O ₅ , Method for producing a base material of the anti-reflection film, characterized in that the mixture or a composite oxide.
The method of claim 6, wherein the average particle size of the metal oxide particles is in the range of 5 to 100 nm.
The method of claim 1, wherein the concentration of the metal oxide particles in the dispersion of the metal oxide particles including the basic nitrogen compound is in the range of 0.5 to 20 wt% as solid content.
The method of claim 1, wherein the metal oxide particle dispersion containing the basic nitrogen compound further comprises a matrix forming component, the concentration of the matrix forming component is prepared in the range of 0.1 to 4% by weight as a solid content Way.
The method of claim 1, wherein the substrate has irregularities on its surface and the surface roughness (Ra _A ) is in a range of 30 nm to 1 μm.
The method of claim 1, wherein the substrate is a glass substrate.
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