TWI572045B - Method for manufacturing substrate with anti-reflection film and photoelectric cell - Google Patents

Description

Method for manufacturing anti-reflection film substrate and photoelectric unit

The present invention relates to a method for producing an antireflection film substrate which can be applied to a photovoltaic cell which converts light energy into electric energy and which is extracted, and a photovoltaic unit (solar cell) including the substrate. More specifically, the present invention relates to an antireflection film substrate comprising a high refractive index layer formed on a substrate and a low refractive index layer formed on the high refractive index layer for improving the utilization of visible light. The production method is a method for producing an antireflection film substrate having excellent surface resistance and scratch resistance, which is excellent in antireflection performance and light transmittance, and a photovoltaic unit including the substrate.

The photoelectric conversion material is a material that continuously extracts light energy into electric energy, and converts light energy into a material of electric energy by using an electrochemical reaction between electrodes. When light is irradiated on the photoelectric conversion material, electrons are generated on one electrode side and moved to the opposite electrode, and electrons that have moved to the opposite electrode move as ions in the electrolyte and return to one of the electrodes. Since the conversion of the photoelectric energy is continuously caused, it can be used, for example, in a solar battery or the like.

General solar cells, first formed with transparency On a support such as a glass plate of a conductive film, a film of a semiconductor for a photoelectric conversion material is formed as an electrode, and then a support such as a glass plate on which another transparent conductive film is formed as a counter electrode is provided, and then an electrolyte is sealed between the electrodes. Composition. When sunlight is applied to the light sensitizing material adsorbed to the semiconductor for photoelectric conversion material, the light sensitizing material absorbs light in the visible light region and is excited. The electrons generated by the excitation move toward the semiconductor, then move toward the transparent conductive glass electrode, move to the opposite electrode by the wires connecting the two electrodes, and move to the electrons of the opposite electrode to reduce the redox system in the electrolyte. On the other hand, the light sensitizing material that moves electrons to the semiconductor is in an oxidized state, but the oxidized body is reduced by the redox system in the electrolyte, and returns to the original state. In this way, the electrons continuously flow, and the photoelectric conversion material functions as a photovoltaic unit (solar cell).

As the photoelectric conversion material, a spectroscopic sensitizing dye having absorption energy in a visible light region adsorbed on a semiconductor surface can be used. For example, JP-A-1-220380 (Patent Document 1) discloses a spectroscopic sensitizing dye layer having a transition metal complex such as a ruthenium complex on the surface of a metal oxide semiconductor layer. Solar battery. Japanese Patent Publication No. 5-504023 (Patent Document 2) discloses a transition metal complex compound such as a ruthenium complex compound on the surface of a titanium oxide semiconductor layer doped with a metal ion. A solar cell constituting a spectrally sensitized pigment layer.

In such a solar cell, in order to improve the utilization rate or conversion efficiency of sunlight, it is considered to suppress the reflection of sunlight, because On the substrate, an antireflection film having a lower refractive index than the substrate is provided. Further, in order to enhance the antireflection performance, a high refractive index layer is provided between the substrate and the antireflection film.

The applicant of the present invention has disclosed that a coating liquid for forming an ultraviolet shielding film composed of a titanium oxide colloidal particle or the like and a matrix precursor is used to form an ultraviolet shielding film, and a ceria-based inorganic oxide having pores therein is used. a coating liquid for forming a visible light anti-reflective film formed of particles and a matrix precursor, and a visible light anti-reflection film formed thereon, thereby obtaining a photovoltaic cell having low underlayer reflectance and visual reflectance, and excellent durability and photoelectric conversion efficiency. Content (Patent Document 3: JP-A-2002-134178).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 1-220380

[Patent Document 2] Japanese Patent Publication No. Hei 5-504023

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-134178

However, the visible light antireflection film obtained by the prior art has low durability (reliability), and may cause cracking of the antireflection film due to environmental changes such as temperature and humidity or deterioration due to long-term use, or The refractive index changes due to expansion or contraction of the film, and the antireflection performance is lowered. Therefore, it is sometimes difficult to maintain high photoelectric conversion efficiency.

In view of the above circumstances, the inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, it has been found that a dispersion containing titanium oxide fine particles (high refractive index metal oxide fine particles) and a basic nitrogen compound is applied onto a substrate. The drying is carried out, and then the dispersion of the low refractive index layer forming component containing the ceria precursor is applied and heated, whereby the hardness of the obtained antireflection film can be remarkably enhanced, and thus the present invention has been completed.

[1] A method for producing an antireflection film substrate comprising an antireflection film substrate comprising a high refractive index layer formed on a substrate and a low refractive index layer formed on the high refractive index layer The manufacturing method is characterized by the following steps (a) to (e): (a) a high refractive index metal oxide particle having a basic nitrogen compound of 1 to 1000 ppm and a refractive index in the range of 1.50 to 2.40. Dispersing liquid, applied to a substrate, (b) removing the dispersion medium at a temperature not reaching the boiling point of the basic nitrogen compound, (c) coating the low refractive index layer forming component dispersion, and (d) removing the dispersion medium, Next, (e) heat treatment is performed at 120 to 700 °C.

[2] The method for producing an antireflection film substrate according to [1], wherein the low refractive index layer forming component is a ceria precursor, or a ceria precursor and a ceria sol.

[3] The method for producing an antireflection film substrate according to [2], wherein the cerium oxide precursor is a partial hydrolyzate selected from the group consisting of an organic hydrazine compound, a hydrolyzate, a hydrolyzed polycondensate, and a polyfluorene nitrogen. Alkane, polydecane, and acid citrate At least one of them.

[4] The method for producing an antireflection film substrate according to [1], wherein the concentration of the low refractive index layer forming component dispersion is in the range of 0.5 to 10% by weight based on the solid content.

[5] The method for producing an antireflection film substrate according to [1], wherein the basic nitrogen compound has a boiling point of from 40 to 250 °C.

[6] The method for producing an antireflection film substrate according to [1], wherein the metal oxide fine particles are selected from the group consisting of TiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, SnO ₂ , and Sb ₂ O. ₅ , a metal oxide of one or more kinds of In ₂ O ₃ and Nb ₂ O ₅ , a mixture of these, and a composite oxide.

[7] The method for producing an antireflection film substrate according to [6], wherein the metal oxide particles have an average particle diameter in a range of 5 to 100 nm.

[8] The method for producing an antireflection film substrate according to [1], wherein a concentration of the metal oxide fine particles in the metal oxide particle dispersion containing the basic nitrogen compound is 0.5 to a solid content. 20% by weight range.

[9] The method for producing an antireflection film substrate according to [1], wherein the metal oxide particle dispersion containing the basic nitrogen compound further contains a matrix-forming component, and a concentration of the matrix-forming component is based on solid content. Located in the range of 0.1 to 4% by weight.

[10] The method for producing an antireflection film substrate according to [1], wherein the substrate has irregularities on the surface, and a surface roughness (Ra _A ) thereof is in a range of 30 nm to 1 μm.

[11] The method for producing an antireflection film substrate according to [1], wherein the substrate is a glass substrate.

[12] An antireflection film substrate comprising the substrate obtained by laminating a substrate and a high refractive index layer.

[13] The antireflection film substrate according to [12], wherein the high refractive index layer has an average thickness in a range of 50 to 200 nm.

[14] The antireflection film substrate according to [12], wherein the average thickness of the aforementioned low refractive index layer is in the range of 30 to 200 nm.

[15] The antireflection film substrate according to [12], wherein the pencil hardness of the antireflection film substrate is 7H or more.

[16] The antireflection film substrate according to [12], wherein the surface roughness (Ra _B ) of the high refractive index layer is in the range of 30 nm to 1 μm.

[17] The antireflection film substrate according to [12], wherein the low refractive index layer has a surface roughness (Ra _C ) of 30 nm or less.

[18] The antireflection film substrate according to [12], wherein the surface roughness (Ra _B ) of the low refractive index layer is in the range of 30 nm to 1 μm.

[19] A photovoltaic unit comprising the above-mentioned anti-reflection film substrate on a front surface thereof.

The present invention can provide a method for producing an anti-reflection film substrate having high hardness and capable of suppressing generation of cracks, scratches, and the like, and an anti-reflection film substrate, and having such a substrate and having high utilization of visible light can be long A photovoltaic cell (solar cell) that maintains high photoelectric conversion efficiency or the like stably during the period.

1‧‧‧Transparent electrode layer

2‧‧‧Porous semiconductor film

3‧‧‧electrode layer

4‧‧‧ Electrolytes

5‧‧‧Transparent substrate

6‧‧‧Substrate

Fig. 1 is a schematic cross-sectional view showing a photovoltaic unit of the present invention.

[Method of Manufacturing Antireflection Film Substrate]

The invention is characterized by the following steps (a) to (e).

(a) Coating step of high refractive index metal oxide particle dispersion

(b) a drying step of the dispersion,

(c) a coating step of forming a dispersion of the low refractive index layer forming component,

(d) solvent removal, (e) heating step

Substrate

As the substrate used in the present invention, a conventionally known glass, polycarbonate, acrylic resin, PET, TA°C, or the like, a plastic film, a plastic plate, or the like can be used. Among them, a glass substrate can be used for anti-reflection with good hardness. The film is preferred.

Further, the aforementioned substrate, when used in a photovoltaic unit, preferably has irregularities on the surface, and the surface roughness (Ra _A ) is in the range of 30 nm to 1 μm, more preferably in the range of 50 nm to 0.8 μm.

When there are irregularities in this range, the anti-glare property is high, and the mapping can also be suppressed. Further, when used in a photovoltaic unit, reflection can be suppressed and light transmittance can be improved, and the effect of improving photoelectric conversion efficiency by the improvement in light utilization efficiency is high.

The substrate may be sandblasted on a flat surface of the glass substrate, or the gel dispersion may be applied to the flat glass substrate and dried and hardened, in addition to a commercially available substrate having a desired unevenness on the surface. The mixed dispersion of the metal oxide particles and the gel is applied, dried and cured, and the like, and the irregularities are formed by a conventionally known method. Yu Ji An electrode layer may also be formed on the surface of the 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, it is measured by AFM, and when it exceeds 100 nm, it is measured 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.

In optical applications, it is difficult to obtain a general-purpose glass substrate having a refractive index which does not reach the lower limit of the above range. When the refractive index of the substrate is too high, the difference in refractive index between the substrate and the high refractive index layer provided on the substrate becomes small. Sometimes the penetration improvement effect cannot be fully obtained.

When used in a photovoltaic unit, the higher the visible light transmittance of the substrate and the electrode layer, the more preferable, specifically 50% or more, particularly preferably 90% or more. The electric resistance value of the electrode layer is preferably 100 Ω/cm ² or less.

. Step (a)

A dispersion containing high refractive index metal oxide particles and 1 to 1,000 ppm of a basic nitrogen compound is applied onto the aforementioned substrate.

The metal oxide particles used in the present invention are preferably metal oxide particles having a refractive index of 1.50 to 2.40, more preferably 1.55 to 2.30.

When the refractive index of the metal oxide particles is small, the refractive index of the base material is different, but the difference in refractive index from the base material is small, and the effect of improving the transmittance may be insufficient. When the refractive index of the metal oxide particles is too high, Metal oxide particles cause scattering, and the effect of improving the transmittance is sometimes insufficient.

In the present invention, the difference between the refractive index of the substrate and the refractive index of the high refractive index layer is preferably from about 0.1 to 1.0, more preferably from 0.5 to 1.0.

Examples of the metal oxide particles include metal oxide 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 , and mixture particles thereof. Composite oxide particles.

These metal oxide particles can obtain a dispersion of metal oxide particles having excellent dispersibility and stability, and in particular, particles having an average particle diameter of small size and excellent transparency can be preferably used for optical applications.

The average particle diameter of the metal oxide particles is preferably from 5 to 100 nm, more preferably from 7 to 50 nm.

When the average particle diameter of the metal oxide particles is small, the aggregation tends to be small and the stability of the dispersion is insufficient. The high refractive index layer formed by using the dispersion of the metal oxide particles is insufficiently compacted, and the final result may be obtained. The anti-reflection film is insufficient in hardness and scratch resistance. When the average particle diameter of the metal oxide particles is too large, Mie scattering is caused, and the light transmittance is insufficient. When used in a photovoltaic unit, the effect of improving the photoelectric conversion efficiency may be insufficient.

Examples of the dispersion medium of the metal oxide particle dispersion liquid include alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, decyl alcohol, and tetrahydrofurfuryl alcohol; methyl acetate and acetic acid; Ethyl ester, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate Esters such as esters and ethylene glycol monoacetates; glycols such as ethylene glycol and hexanediol; Containing 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 An ether-containing hydrophilic solvent such as propylene glycol monoethyl ether or propylene glycol monopropyl ether; propyl acetate, isobutyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-methoxybutyl acetate, acetic acid Esters such as 2-ethylbutyl ester, cyclohexyl acetate, ethylene glycol monoacetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexane Ketones such as ketone, dipropyl ketone, methyl amyl ketone and diisobutyl ketone; polar solvents such as toluene. These may be used alone or in combination of two or more.

The solvent may be used at a lower or equivalent boiling point than the basic nitrogen compound used.

The concentration of the metal oxide particles in the metal oxide particle dispersion is preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, based on the solid content. When the concentration of the metal oxide particles is not within the above range in terms of solid content, it may be difficult to form a high refractive index layer having an average film thickness to be described later.

The basic nitrogen compound is useful for promoting the compaction and hardening of the low refractive index layer forming component coated on the high refractive index layer. The basic nitrogen compound is preferably such that it does not evaporate upon drying, and its boiling point is preferably in the range of 40 to 250 ° C, more preferably in the range of 80 to 150 ° C.

Specifically, for example, n-propylamine (boiling point 48.0 ° C), n-butylamine (boiling point 77.0 ° C), isobutylamine (boiling point 67.5 ° C), secondary butylamine (boiling point 62.5 ° C), tertiary butylamine (boiling point) can be listed. 43.6 ° C), pentylamine (boiling point 104 ° C), 2-ethylhexylamine (boiling point 169.2 ° C), allylamine (boiling point 53.3 ° C), benzene Amine (boiling point 184.7 ° C), N-methylaniline (boiling point 196.1 ° C), o-toluidine (boiling point 200.7 ° C), m-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), α-methylpyridine (boiling point 129.4 ° C), β-methylpyridine (boiling point 144.1 ° C), γ- Methylpyridine (boiling point 145.4 ° C), quinoline (boiling point 237.1 ° C), isoquinoline (boiling point 243.2 ° C), formamidine (boiling point 210.5 ° C), N-methylformamide (boiling point 182.5 ° C), acetamidine Amine (e.g. 221.2 ° C), N-methylacetamide (boiling point 206 ° C), N-methylpropionamide (boiling point 148 ° C), diethylamine (boiling point 55.5 ° C) and other grade 1 amine; dipropylamine (boiling point) 109.4 ° C), diisopropylamine (boiling point 83.5 ° C), dibutylamine (boiling point 159.6 ° C), diisobutylamine (boiling point 138 ° C), diamylamine (boiling point 92 ° C), dimethylaniline (boiling point 193 ° C) , diethyl aniline (boiling point 217 ° C), dicyclohexylamine (boiling point 113.5 ° C), 2,4-dimethylpyridine (boiling point 157.5 ° C), 2,6-lutidine (boiling point 144 ° C), B Diamine (boiling point 117.3 ° C), propylene diamine (boiling point 119.3 ° C), diethylene tripropylamine (boiling point 207.1 ° C), N, N- 2-methylamine (boiling point 153.0 ° C), N,N-diethylformamide (boiling point 177.5 ° C), N,N-dimethylacetamide (boiling point 166.1 ° C) and other grade 2 amine; Grade III amines such as amine (boiling point 89.6 ° C), tributylamine (boiling point 91.5 ° C), and triamylamine (boiling point 130 ° C); tetramethylammonium chloride (boiling point 110 ° C), tetraethylammonium chloride (boiling point 110) °C), a 4-grade ammonium salt such as tetrapropylammonium chloride (boiling point 100 ° C), tetrabutylammonium chloride (boiling point 100 ° C), and the like.

In the case of using the basic nitrogen compound, when the drying is carried out in the step (d) described later, the basic nitrogen compound promotes the formation of the low refractive index layer forming component of the dispersion liquid for forming the low refractive index layer applied to the upper layer. , then proceed in step (e) In the heat treatment, the low-refractive-layer forming component of the dispersion liquid for forming a low-refractive-index layer applied to the upper layer is accelerated by the basic nitrogen compound, and an anti-reflection film having excellent properties such as hardness and scratch resistance can be formed.

The concentration of the basic nitrogen compound in the metal oxide particle dispersion is preferably from 1 to 1,000 ppm, more preferably from 5 to 500 ppm.

When the amount of the basic nitrogen compound in the metal oxide particle dispersion is small, the effect of the compound is low, and the compacting of the low refractive index layer in the above step (d) is insufficient, and the resulting antireflection film may not be sufficient. The effect of improving hardness and scratch resistance is obtained. When the amount of the basic nitrogen compound in the dispersion of the metal oxide particles is too large, the particles in the dispersion of the metal oxide particles may be affected, the dispersion may become unstable, and the hardness and scratch resistance of the antireflection film finally obtained may be obtained. Sometimes it will be insufficient.

The metal oxide particle dispersion liquid for forming a high refractive index layer may contain a matrix forming component as necessary.

The matrix forming component can be the same as the low refractive index layer forming component described later, and specifically, a ceria precursor is preferable.

The concentration of the matrix-forming component in the metal oxide particle dispersion containing a basic nitrogen compound is preferably 4% by weight or less, and more preferably 0.3% to 4% by weight, based on the solid content.

When a matrix is contained, a compact high refractive index layer can be formed while enhancing adhesion to the low refractive index layer or substrate.

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

The method of applying the metal oxide particle dispersion containing a basic nitrogen compound to the substrate is not particularly limited as long as it can be uniformly applied to the substrate, and a conventionally known general method can be employed. For example, a wire bar coating method, a immersion method, a spray method, a spin coating method, a roll coating method, a gravure coating method, a slit coating method, and the like can be given.

. Step (b)

Next, the dispersion medium is removed at a temperature that does not reach the boiling point of the basic nitrogen compound, and the coating film is dried. Specifically, drying is carried out at 50 to 120 ° C, preferably 60 to 100 ° C (except for the boiling point of the solvent).

Although the drying time varies depending on the drying temperature, it is substantially 20 minutes or shorter, preferably 30 seconds to 10 minutes.

When used in a photovoltaic unit, the surface roughness (Ra _B ) of the high refractive index layer formed on the substrate is preferably in the range of 30 nm to 1 μm, more 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, a sufficient light transmittance improving effect may not be obtained.

Further, in the dispersion coating method recommended by the present invention, the surface roughness (Ra _B ) of the high refractive index layer does not exceed 1 μm.

The average thickness of the high refractive index layer is preferably from 50 to 200 nm, more preferably from 80 to 120 nm.

When the average thickness of the high refractive index layer is thin, since the reflectance is not lowered, a sufficient light transmittance improving effect cannot be obtained, and when used in a photovoltaic unit, the light utilization efficiency may not be sufficiently obtained. The effect of the photoelectric conversion efficiency brought by Shengsheng. When the average thickness of the high refractive index layer is thick, sufficient light transmittance may not be obtained, and when used in a photovoltaic unit, a sufficient effect of improving photoelectric conversion efficiency may not be obtained.

The average thickness of the high refractive index layer having irregularities on the surface, the weight of the substrate can be subtracted from the weight of the high refractive index layer substrate, divided by the specific gravity of the high refractive index layer and then divided by the area of the high refractive index layer. Seek.

. Step (c)

Then, a low refractive index layer forming component dispersion liquid is applied onto the above 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 refractive index lower than that of the high refractive index layer and having excellent strength and scratch resistance, and is not particularly limited in the present invention. Preferably, a cerium oxide precursor, or a cerium oxide precursor and a cerium oxide sol, is used.

Further, as the ceria precursor, a partial hydrolyzate, a hydrolyzate, or a hydrolyzed polycondensate of an organic antimony compound can be preferably used, and in addition, a polyazane or a decane of a polymer of decane can be preferably used. Polymer polydecane, acid citric acid solution, and the like.

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

R _n -SiX _4-n (1)

(wherein R is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other; X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, hydrogen, n = 0 to 3 Integer)

Among them, a tetrafunctional organofluorene compound having n = 0 is preferable, and specifically, a hydrolyzate such as tetramethoxynonane, tetraethoxyoxane, tetrapropoxydecane or tetrabutoxydecane or a hydrolyzed polymer can be preferably used. Condensate.

Further, as the decazane, a decazane represented by the following formula (2) can be used.

(wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 or more)

In the above formula (2), it is particularly preferable that all of R ₁ , R ₂ and R ₃ are hydrogen, and in one molecule, the hafnium atom is 55 to 65 wt%, the nitrogen atom is 20 to 30 wt%, and the hydrogen atom is An inorganic polyazane present in an amount of 10 to 15% by weight. When such a polyazide is used, an impurity such as carbon does not remain in the low refractive index layer, and a compact low refractive index layer can be formed.

Further, the ratio of the Si atom to the N atom (Si/N ratio) in the polyazane is preferably from 1.0 to 1.3. The inorganic polyazide can be, for example, a method in which an adduct of dihalothane is reacted with a base to form a dihalodecane, and then reacted with ammonia (Japanese Patent Publication No. 63-16325); It is produced by a generally known method such as a method of reacting methyl phenyldichloromethane or dimethyldichloromethane with ammonia (JP-A-62-88327).

Polyfluorene nitrogen having a repeating unit represented by the above formula (2) The alkane may be linear or cyclic, or a mixture of a linear polyazane and a cyclic polyazane.

The polyazane is converted to polystyrene in a number average molecular weight of from 500 to 10,000, preferably from 1,000 to 4,000. When the number average molecular weight is less than 500, when a low dielectric constant cerium oxide film is formed, in the step (b) or the step (c) described later, the low molecular weight polyazide volatilizes, sometimes two The cerium oxide film is greatly shrunk. In addition, when the fluidity of the coating liquid is lowered, the coating property is lowered, and a cerium oxide-based coating film having a flatness and a uniform film thickness and a low dielectric constant may not be obtained.

Further, the low molecular weight polyazulane having a number average molecular weight of 1,000 or less is from 10 to 40% by weight, preferably from 15 to 40% by weight based on the total of the polyazane. When the low molecular weight polyazane is in this range with respect to the entire polyazide, the step caused by the wiring can be smoothly covered, and a film surface having good flatness can be obtained. When the amount of the low molecular weight polyazide having a number average molecular weight of 1,000 or less is 40% by weight or more, the film shrinkage from drying to sintering becomes large, the flatness is deteriorated, the stress is increased, and cracks and the like are likely to occur.

Further, as the decane, a polydecane compound represented by the following formulas (3) to (5) can be used.

R ⁴ Si(X ¹ ) ₃ (3)

(In the formula (3), 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 (4), 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 (5), 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)

A method for producing polydecane, for example, a method of polycondensing methylphenyldichloromethane, methyltrichlorosilane, phenyltrichloromethane or the like in the presence of sodium metal (JP-A-2007-145879) It is manufactured by a generally known method such as No.

Specific examples of the decane compound (3) include an alkyltrichlorodecane compound represented by R ¹ SiCl ₃ (wherein R ¹ represents the same meaning as defined above). The alkyltrichloromethane compound may, for example, be methyltrichlorodecane, ethyltrichloromethane, n-propyltrichlorodecane, isopropyltrichlorodecane, n-butyltrichloromethane or tert-butyltrichloromethane. Wait. These compounds may be used alone or in combination of two or more.

Specific examples of the decane compound (4) include phenyltrichlorodecane, 2-chlorophenyltrichlorodecane, 4-methylphenyltrichlorodecane, and 2,4,6-trimethylphenyltrichloride. Decane, 1-naphthyltrichlorodecane, 2-naphthyltrichlorodecane, and the like. These compounds may be used alone or in combination of two or more.

Specific examples of the decane compound (5) are preferably methylphenyldichlorodecane, ethylphenyldichlorodecane, n-propylphenyldichlorodecane, isopropylphenyldichlorodecane, and methyl-1- Naphthyldichlorodecane, methyl 2-naphthyldichlorodecane, preferably methylphenyldichlorodecane, ethylphenyldichlorodecane, n-propylphenyldichlorodecane, isopropylphenyl Chlorodecane, especially methyl Phenyldichlorodecane.

Polydecane, which is known to be linear, cyclic, and branched. The branching type is preferred from the viewpoint that the refractive index is less affected by the temperature change and the refractive index change due to the irradiation light is high sensitivity.

The weight average molecular weight (Mw) of the polydecane compound is, in terms of polystyrene, a number average molecular weight of from 500 to 50,000, preferably from 1,000 to 20,000. When the number average molecular weight is low, when a cerium oxide-based coating film is formed, the low molecular weight polydecane volatilizes, and the cerium oxide-based coating film may be largely shrunk. Further, when the molecular weight is too large, the solubility is lowered and it is not dissolved in the solvent.

Further, as the acidic citric acid solution, an acidic citric acid solution obtained by dehydrating an aqueous citric acid solution by an ion exchange resin can be used.

Separate cerium oxide particles and cerium oxide precursors may also be used. When used in combination, the content of the cerium oxide particles in the formed low refractive index layer is preferably from 0.1 to 40% by weight, more preferably from 0.5 to 30% by weight, based on SiO ₂ . When the content of the cerium oxide particles is in this range, a low refractive index layer which is more compact and has better properties such as hardness and scratch resistance can be formed.

The cerium oxide sol is a low refractive index cerium oxide-based fine particle sol disclosed in Japanese Laid-Open Patent Publication No. 2001-233611, and the like.

The average particle diameter of the cerium oxide particles at this time is preferably from about 5 to 100 nm, more preferably from 7 to 80 nm. The cerium oxide sol having a particle diameter in this range can be stably dispersed, and the low refractive index film can be tight Densification, the anti-reflection film is also high in hardness and scratch resistance.

When the average particle diameter of the cerium oxide particles is small, the particles are easily aggregated, and the stability of the dispersion liquid of the low refractive index layer forming component is insufficient. The low refractive index film formed by using the dispersion liquid is insufficient in compaction, and may eventually become final. The obtained antireflection film is insufficient in hardness and scratch resistance. When the average particle diameter of the cerium oxide particles is too large, the formation of the basic nitrogen compound is insufficient, and the hardness and scratch resistance of the finally obtained antireflection film may be insufficient. In addition, even if compaction is formed, Mie scattering is caused, and sometimes the light transmittance is insufficient.

The dispersion medium of the low refractive index layer forming component dispersion liquid is the same as that of the user when the high refractive index layer is formed.

The concentration of the low refractive index layer forming component dispersion liquid is preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, based on the solid content.

When the concentration of the low refractive index layer-forming component dispersion liquid is light, the coating method may differ, but a low refractive index layer having a thickness of the low refractive index layer of more than 30 nm may not be formed in one application. Further, the surface roughness (Ra _C ) of the low refractive index layer may not be adjusted to a desired range.

When the concentration of the dispersion liquid of the low refractive index layer forming component is too rich, the stability of the coating liquid is low, and when the low refractive index layer is formed by using the low refractive index layer forming component dispersion liquid, it is difficult to compact or eventually The hardness and scratch resistance of the obtained antireflection film may be insufficient.

The coating method of the low refractive index layer forming component dispersion liquid is not particularly limited as long as it can be applied to the high refractive index layer in a compact and uniform manner. The conventional method known in the art can be used without limitation. For example, a bar coating method, a dipping method, a spray method, a spin coating method, a roll coating method, a gravure coating method, a slit coating method, and the like, which are the same as those in the case of forming the high refractive index layer, may be mentioned.

. Steps (d) and (e)

Next, (d) the dispersion medium is removed, and then (e) heat treatment is carried out at 120 to 700 ° C, preferably 150 to 500 ° C.

The method of removing the dispersion medium is a dispersion medium capable of substantially removing the dispersion liquid. Specifically, although it varies depending on the boiling point of the dispersion medium, etc., it is preferably in the range of 50 to 120 ° C, more preferably 60 to 100 ° C. Drying temperature.

When the drying temperature is too low, the removal of the dispersion medium may be insufficient, and then, in the heat treatment, voids may be generated in the low refractive index layer, and the hardness and scratch resistance of the low refractive index layer and the finally obtained antireflection film may be caused. Sex is sometimes insufficient.

When the drying temperature is too high, the drying of the surface of the coating film is violently caused, resulting in a surface peeling phenomenon, in which a void is generated in the low refractive index layer, and the hardness of the low refractive index layer and the finally obtained antireflection film, Scratch resistance is sometimes insufficient.

Although the drying time varies depending on the drying temperature, it is preferably 20 minutes or shorter, preferably 30 seconds to 10 minutes.

When the heat treatment is performed in the above range, the basic nitrogen compound contained in the high refractive index layer accelerates the low refractive index layer while compacting the low refractive index layer forming component.

When the heat treatment temperature is low, the high refractive index layer and low The hardening of the refractive index layer is insufficient, and the hardness and scratch resistance of the antireflection film finally obtained may be insufficient. When heating is carried out in excess of the above range, deformation or deterioration may occur depending on the type of the substrate.

The surface roughness (Ra _C ) of the low refractive index layer of the present invention thus formed can be appropriately selected as desired.

For example, the surface roughness (Ra _C ) can be set to 30 nm or less, and further 10 nm or less. In this range, the smoothness is high and the light transmittance is high, but the hardness and scratch resistance are sometimes lowered a little.

Further, the surface roughness (Ra _C ) of the antireflection film may be set to 30 nm to 1 μm, and further 50 nm to 0.8 μm. If the film has irregularities in this range, the light transmittance is high, and the photoelectric conversion efficiency can be improved. However, the scratch resistance is sometimes lowered by the unevenness.

The surface roughness is different depending on the surface roughness of the substrate, the metal oxide particle diameter or the high refractive index layer thickness in the high refractive index layer, the coating method, or the concentration of each dispersion. In the case of irregularities, it is preferred to use a textured substrate or a larger particle size.

The average thickness of the low refractive index layer is preferably from 30 to 200 nm, more preferably from 50 to 150 nm. When the average thickness of the low refractive index layer is thin, the effect of improving the light transmittance cannot be sufficiently obtained, and when the transparent film substrate is used in the photovoltaic unit, the effect of improving the photoelectric conversion efficiency may not be sufficiently obtained. When the average thickness of the low refractive index layer is thick, the effect of improving the light transmittance cannot be sufficiently obtained, and when the transparent film substrate is used in the photovoltaic unit, the effect of improving the photoelectric conversion efficiency may not be sufficiently obtained.

Here, the average thickness of the low refractive index layer having irregularities on the surface can be subtracted from the weight of the substrate with the antireflection film (high refractive index layer and low refractive index layer) to the weight of the substrate with the high refractive index layer, The specific gravity of the low refractive index layer is divided by the area of the low refractive index layer.

The thickness of the antireflection film attached to the antireflection film substrate thus formed is a total of the average thickness of the high refractive index layer and the average thickness of the low refractive index layer, preferably from 80 to 400 nm, more preferably from 130 to 270 nm. range.

The hardness (pencil hardness) of the antireflection film is preferably 7H or more, more preferably 8H or more.

When the hardness (pencil hardness) of the antireflection film is 6H or less, when it is used as an electronic device or a solar cell for a long period of time, damage may occur and the light transmittance may be insufficient. Therefore, when used in a solar cell, the photoelectric conversion efficiency sometimes gradually decreases.

[with anti-reflection film substrate]

The antireflection film substrate of the present invention is obtained by the above-described production method, and the substrate, the high refractive index layer and the low refractive index layer are laminated.

The average thickness of the high refractive index layer is preferably from 50 to 200 nm, more preferably from 80 to 120 nm. When the average thickness of the high refractive index layer is thin, since the reflectance is not lowered, a sufficient light transmittance improvement effect cannot be obtained, and the photoelectric conversion efficiency due to the improvement in light utilization efficiency may not be sufficiently obtained. effect. When the average thickness of the high refractive index layer is thick, sufficient light transmittance may not be obtained, and a sufficient photoelectric conversion efficiency improving effect may not be obtained.

The average thickness of the low refractive index layer is preferably from 30 to 200 nm, more preferably from 50 to 150 nm. When the average thickness of the low refractive index layer is thin, the effect of improving the light transmittance cannot be sufficiently obtained, and when the transparent film substrate is used in the photovoltaic unit, the effect of improving the photoelectric conversion efficiency may not be sufficiently obtained. When the average thickness of the low refractive index layer is too thick, the effect of improving the light transmittance cannot be sufficiently obtained, and when the transparent film substrate is used in the photovoltaic unit, the effect of improving the photoelectric conversion efficiency may not be sufficiently obtained.

The surface roughness (Ra _B ) of the high refractive index layer formed on the substrate is preferably in the range of 30 nm to 1 μm, more preferably in the range of 50 nm to 0.8 μm. When the surface roughness (Ra _B ) of the high refractive index layer is small, a sufficient light transmittance improving effect may not be obtained. The upper limit of the surface roughness (Ra _B ) does not exceed 1 μm.

The surface roughness (Ra _C ) of the low refractive index layer of the present invention thus formed can be appropriately selected as desired.

Further, in the low refractive index layer, the surface roughness (Ra _C ) may be 30 nm or less, and further 10 nm or less. In this range, the smoothness is high and the scratch resistance is good, but the anti-glare property may be slightly inferior.

Further, the surface roughness (Ra _C ) of the antireflection film may be 30 nm to 1 μm, and further 50 nm to 0.8 μm. If it has irregularities in this range, the anti-glare property and the photoelectric conversion efficiency can be improved, but the scratch resistance may be lowered by the unevenness.

Such surface roughness, due to the surface roughness of the substrate, the metal oxide particle size or the high refractive index layer thickness in the high refractive index layer, The coating method or the concentration of each dispersion differs. However, when unevenness is provided, it is preferred to use a textured substrate or a larger particle size.

When used in a photovoltaic unit, the surface roughness (Ra _C ) of the low refractive index layer may be made 30 nm to 1 μm, and further 50 nm to 0.8 μm. When it is in this range, the scratch resistance is high and the light transmittance is also large, and the photoelectric conversion efficiency can be improved, so that the photovoltaic unit described later can be preferably used.

The pencil anti-reflective film substrate has a pencil hardness of 7H or more and has extremely high scratch resistance.

[Photocell]

The photovoltaic unit of the present invention is characterized by comprising the aforementioned anti-reflection film substrate.

The photovoltaic unit of the present invention, as shown in Fig. 1, has an electrode layer (1) on its surface and a metal oxide semiconductor film (2) on which a light sensitizing material is adsorbed on the surface of the electrode layer (1). The substrate (P-1) and the substrate (P-2) having the electrode layer (3) on the surface thereof are disposed such that the electrode layer (1) and the electrode layer (3) face each other, at least one of which A photovoltaic cell in which a substrate and an electrode layer have transparency and an electrolyte layer is provided between the metal oxide semiconductor film (2) and the electrode layer (3), and is characterized in that at least one of the substrates having transparency (P) -1) and/or (P-2), an antireflection film (attached antireflection film substrate) obtained by the above-described production method is provided on the front side (opposite side to the inside of the cell).

1 is a schematic cross-sectional view showing an embodiment of a photovoltaic cell of the present invention, which has a transparent electrode layer 1 on a surface thereof and a porous metal oxide having a light sensitizing material adsorbed thereon on the surface of the electrode layer 1. a substrate 5 made of the semiconductor film 2 and a substrate 6 having an electrode layer 3 having a catalytic reduction energy on the surface thereof, so that the electrode layers 1 and 3 are disposed opposite to each other, and the porous metal oxide semiconductor film is provided. The electrolyte 4 is sealed between the electrode layer 3 and the electrode layer 3. The above anti-reflection film is then disposed on the surface of the substrate (especially the surface through which the light penetrates).

Since the photovoltaic unit of the present invention has the antireflection film substrate obtained by the above specific production method, the light transmittance is high and the photoelectric conversion efficiency is good. Further, since the antireflection film obtained by this method has high surface hardness and scratch resistance, surface protection performance is also good.

For example, Japanese Patent Application Laid-Open No. 2010-153232, JP-A-2010-153231, JP-A-2010-108855, JP-A-2010-073543, and JP-A-2010-073543 Japanese Laid-Open Patent Publication No. 2008- 218 172, Japanese Laid-Open Patent Publication No. 2009-218669, Japanese Laid-Open Patent Publication No. 2009-218218, Japanese Laid-Open Patent Publication No. 2008-277019, No. 2008-258099, and Japanese Patent Laid-Open No. 2008-210713 The person disclosed in the bulletin.

As one of the substrates, a transparent and insulating substrate such as a glass substrate or an organic polymer substrate such as PET can be used. The other substrate is not particularly limited as long as it has a strength to withstand use, and titanium, aluminum, and copper can be used in addition to an insulating substrate such as a glass substrate or an organic polymer substrate such as PET. A conductive substrate such as metallic nickel. The substrate corresponds to a substrate on which an antireflection film is formed. Further, at least one of the substrates may be transparent.

An electrode layer (1) formed on the surface of the substrate (1), oxygen can be used a conventionally known electrode such as tin, doped tin oxide of Sb, F or P, doped with Sn and/or F, such as indium oxide, antimony oxide, zinc oxide or noble metal, and thus the electrode layer (1) can be It is formed by a conventionally known method such as a thermal decomposition method or a CVD method. Further, the electrode layer (2) formed on the surface of the other substrate (2) is not particularly limited as long as it has a reduction catalytic energy, and an electrode material such as platinum, rhodium, ruthenium or iridium oxide can be used. The electrode material is plated or vapor-deposited on the surface of a conductive material such as tin oxide, tin oxide doped with Sb, F or P, tin oxide doped with Sn and/or F, or ruthenium oxide; carbon electrode, etc. A conventionally known electrode. The electrode layer (2) can be directly coated, plated or vapor-deposited on the substrate (2), and the conductive material can be formed by a conventionally known method such as thermal decomposition or CVD. After being formed into a conductive layer, it is formed by a conventionally known method of plating or vapor-depositing the electrode material on the conductive layer.

The substrate (2) may be the same transparent substrate as the substrate (1), and the electrode layer (2) may be the same transparent electrode as the electrode layer (1). Further, the substrate (2) may be the same as the substrate (1), and the electrode layer (2) may be the same as the electrode layer (1).

The higher the visible light transmittance of the transparent substrate (1) and the transparent electrode layer (1), the more preferable, specifically 50% or more, and particularly preferably 90% or more. The electric resistance values of the electrode layer (1) and the electrode layer (2) are preferably 100 Ω/cm ² or less.

It is also possible to form the titanium oxide film (1) on the electrode layer (1) as necessary, and the film thickness is preferably in the range of 10 to 70 nm, more preferably in the range of 20 to 40 nm. Further, the titanium oxide film (1) may have appropriate pores.

A porous metal oxide semiconductor film is formed on the electrode layer (1) or on the titanium oxide film (1) provided as necessary. Porous The average pore diameter of the metal oxide semiconductor film (1) is in the range of 10 to 40 nm, and the pore volume is in the range of 0.25 to 0.8 ml/g. The porous metal oxide semiconductor is not particularly limited, and is preferably one or more metals selected from the group consisting of titanium oxide, cerium oxide, zirconium oxide, cerium oxide, tungsten oxide, cerium oxide, zinc oxide, tin oxide, and indium oxide. Made up of oxides. Among them, crystalline titanium oxide such as anatase type titanium oxide, brookite type titanium oxide, and rutile type titanium oxide can be preferably used. Further, the film thickness of the porous metal oxide semiconductor film (1) is preferably in the range of 0.1 to 50 μm.

The light sensitizing material to which the semiconductor film is adsorbed is not particularly limited as long as it absorbs light in a visible light region, an ultraviolet region, or an infrared region, and for example, an organic dye or a metal complex can be used.

The organic dye can be used as a conventionally known organic dye having a functional group such as a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a thiol group or a carboxyalkyl group in the molecule. Specific examples thereof include metal-free phthalocyanine, anthocyanin-based dye, metal phthalocyanine-based dye, triphenylmethane-based dye, and luciferin, tetrabromofluorescein, bengal rosin, rose bengal B, and dibromofluoride. Oxygen onion such as light yellow. These organic pigments have a property of rapidly adsorbing the metal oxide semiconductor film. In addition, metal phthalocyanine, chlorophyll, and high-iron such as copper phthalocyanine or oxytitanium phthalocyanine described in JP-A-H05-504023, JP-A-H05-504023, and the like. Heme, bismuth-tris(2,2'-bispyridyl-4,4'-dicarboxylate), cis-(SCN ^- )-bis(2,2'-bipyridyl-4,4'-钌-cis-dihydrate-bipyridyl complex of dicarboxylic acid esters, hydrazine, hydrazine-cis-dihydrate-bis(2,2'-bispyridyl-4,4'-dicarboxylate) And a complex of ruthenium, osmium, iron, zinc or the like of porphyrin or iron-hexacyanocyanate complex such as zinc-tetrakis(4-carboxyphenyl) porphin. These metal complexes have excellent spectral sensitization effects and durability. The amount of adsorption of the light sensitizing material of the porous metal oxide semiconductor film is preferably 100 μg or more, and more preferably 150 μg or more per 1 cm ² of the specific surface area of the porous metal oxide semiconductor film.

The electrolyte is a mixture of an electrochemically active salt and at least one compound forming a redox system. The electrochemically active salt may, for example, be a 4-grade ammonium salt such as tetrapropylammonium iodide. Examples of the compound which forms a redox system include hydrazine, hydroquinone, iodine (I ^- /I ^- ₃ ), potassium iodide, bromine (Br ^- /Br ^- ₃ ), potassium bromide and the like. This can be mixed for use depending on the situation.

The amount of the electrolyte used varies depending on the type of the electrolyte and the type of the solvent to be described later, and is preferably in the range of approximately 0.1 to 5 mol/liter.

As the electrolyte layer, a conventionally known solvent can be used. Specific examples thereof include carbonates such as water, alcohols, oligoethers, and propionic acid carbonates, phosphates, dimethylformamide, dimethyl hydrazine, N-methylpyrrolidone, and N- Vinyl pyrrolidone, sulfide of cyclobutane 66, ethylene carbonate, acetonitrile, γ-butyrolactone, and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

[Example 1] Preparation of metal oxide particle dispersion (1) for forming high refractive index layer

1.88 g of n-decanoic acid ethyl ester (manufactured by Tama Chemical Industry Co., Ltd.: ethyl decanoate-A, SiO ₂ concentration: 28.8% by weight) was mixed with a titanium oxide colloidal methanol dispersion (manufactured by Nippon Chemical Co., Ltd.: Optolake 1120Z, average particle diameter 12 nm, TiO ₂ concentration 20.5 wt%, dispersion medium: methanol, TiO ₂ particle refractive index 2.30) 100 g, followed by adding 3.1 g of ultrapure water, stirring at 50 ° C for 6 hours to prepare a solid component A surface-treated titanium oxide particle methanol dispersion having a concentration of 20.5 wt%.

Then, 80 g of propylene glycol monopropyl ether (PGME) and a modified alcohol (Solar AP-11 manufactured by Japan Alcohol Trading Co., Ltd.) were added to 100 g of the surface-treated titanium oxide particle methanol dispersion having a solid concentration of 20.5 wt%. 2 g of ethanol (85.5% by weight, 9.8 wt% of isopropyl alcohol, 4.7 wt% of methanol), and 2 g of triethylamine (boiling point: 90 ° C) as a basic nitrogen compound, and then 50 ppm in a coating liquid, and then The metal oxide particle dispersion liquid (1) for forming a high refractive index layer having a solid content concentration of 5% by weight was prepared by stirring at 25 ° C for 30 minutes.

Preparation of low refractive index layer forming component dispersion (1)

10.0 g of water and 0.1 g of nitric acid having a concentration of 61% by weight were added to 72.5 g of Solmix A-11 (manufactured by Japan Alcohol Trading Co., Ltd.), and then stirred at 25 ° C for 10 minutes, and then ethyl orthosilicate (Tama) was added. Chemical Industry Co., Ltd.: ethyl decanoate-A, SiO ₂ concentration: 28.8% by weight) 17.4 g, and stirred at 30 ° C for 30 minutes to prepare a dispersion of ethyl orthosilicate hydrolyzate having a solid concentration of 5.0% by weight. Liquid 100g. The polyethylene nitrate hydrolyzate dispersion had a molecular weight of 1,000 in terms of polyethylene.

Then, at a solid concentration of 5.0% by weight, n-decanoic acid B In 100 g of the ester hydrolyzate dispersion, 33 g of propylene glycol monopropyl ether (PGME) and a modified alcohol (Solmix AP-11: 85.5 wt% of ethanol, 9.8 wt% of isopropanol, and methanol) were added to Japan Alcohol Trading Co., Ltd. 4.7 wt%) 33 g, and then stirred at 25 ° C for 30 minutes to prepare a low refractive index layer-forming component dispersion liquid (1) having a solid concentration of 3.0% by weight.

Manufacture of anti-reflective film substrate (1)

A glass substrate (manufactured by Fuxin Co., Ltd.: FL glass, thickness: 3 mm, refractive index: 1.51) was subjected to sand blasting to prepare a glass substrate (1) having a surface roughness (Ra _A ) of 500 nm.

Then, the metal oxide particle dispersion liquid (1) for forming a high refractive index layer is applied onto the surface of the glass substrate (1) having surface roughness by a wire bar coating method (#5), and dried at 80 ° C. 120 seconds. At this time, the average thickness of the high refractive index layer was 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table. The refractive index was measured by an elliptical thickness gauge (manufactured by ULVAC, EMS-1).

Then, the low refractive index layer forming component dispersion liquid (1) was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes to be cured to form a low refractive index layer. The antireflection film substrate (1) was produced. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table. The refractive index of the low refractive index layer was measured by a reflectance meter (manufactured by Otsuka Electronics Co., Ltd.: FE-3000).

For the anti-reflection film substrate (1), the total light transmittance and haze were measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.). The reflectance was measured by a spectrophotometer (manufactured by JASCO Corporation, Ubest-55). The uncoated glass substrate had a total light transmittance of 99.0%, a haze of 0.1%, and a reflectance of 5.0% for light having a wavelength of 550 nm.

1) Determination of pencil hardness

It was measured by a pencil hardness tester in accordance with JIS-K-5400.

2) Determination of scratch resistance

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

Evaluation criteria:

No strip damage observed: ◎

Only a few strip damages were observed: ○

Many strip damages were observed: △

The whole face is cut: ×

Production of photovoltaic unit (1-1)

An electrode-attached antireflection film substrate (1-1) formed on the opposite side of the antireflection film attached to the antireflection film substrate (1) with fluorine-doped tin oxide as an electrode was prepared.

Modulation of metal oxide particles for semiconductor films

5 g of titanium hydride was suspended in 1 L of pure water, and 400 g of a 5% hydrogen peroxide solution was added thereto over 30 minutes, followed by heating to 80 ° C to dissolve it, thereby preparing a solution of peroxotitanic acid. Concentrated aqueous ammonia was added thereto and adjusted to pH 9, and placed in a hot press, and subjected to a wet heat treatment at 250 ° C for 5 hours in a saturated vapor pressure to prepare titania colloidal particles (A). An anatase-type titanium oxide having high crystallinity can be known by the X-ray diffraction method. The average particle size is 40nm.

Modulation of coating liquid for forming a semiconductor film

Next, the titania colloidal particles (A) obtained above were concentrated to a concentration of 10%, and the peroxotitanic acid solution was mixed thereto, and the weight in the case where titanium in the mixture was converted into TiO ₂ was 30% by weight. As a film formation aid hydroxypropylcellulose, a coating liquid for forming a semiconductor film is prepared.

Semiconductor film formation

Then, the coating liquid for forming a semiconductor film is applied onto the electrode surface of the antireflection film substrate (1) with an electrode, and is naturally dried, and then irradiated with ultraviolet rays of 6000 mJ/cm ² using a low-pressure mercury lamp to make titanium peroxide. The semiconductor film is hardened by acid decomposition (hydrolysis, polycondensation). Further, the hydroxypropylcellulose was decomposed and annealed by heating at 300 ° C for 30 minutes to form a titanium oxide semiconductor film (A).

The obtained titanium oxide semiconductor film (A) had a film thickness of 20 μm, a pore volume of 0.60 ml/g as determined by a nitrogen adsorption method, and an average pore diameter of 22 nm.

Adsorption of spectrophotogenic pigment

The concentration of the ruthenium complex represented by cis-(SCN)-bis(2,2'-bispyridin-4,4'-dicarboxylate) ruthenium (II) as a spectral sensitizing dye is 3 ×10 ^-4 mol/liter ethanol solution. This spectral sensitizing dye solution was applied onto a titanium oxide semiconductor film (A) and dried using a spin coater of rpm 100. This coating and drying step was carried out 5 times. The amount of adsorption of the spectral sensitizing dye of the obtained titanium oxide semiconductor film was 150 μg/cm ² . In this case, the amount of adsorption of the specific surface area of the titanium oxide semiconductor film (A) per 1 cm ² is shown. The weight-increasing portion of the semiconductor film after coating and drying was used as the adsorption amount.

Then, tetrapropylammonium iodide and iodine were respectively dissolved in a ratio of a ratio of acetonitrile to ethylene carbonate as a solvent of 1:4 in a concentration of 0.46 mol/liter and 0.06 mol/liter, respectively. In the solvent, an electrolyte solution is prepared.

The anti-reflective film substrate (1) with the electrode is used as one electrode, and the electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is disposed opposite to the electrode. The side surface was sealed with a resin, and the electrolyte solution was sealed between the electrodes, and the electrodes were connected by a lead to prepare a photovoltaic unit (1-1).

The obtained photovoltaic unit (1-1) was evaluated for its performance.

Performance Evaluation (1) (Initial Performance Evaluation)

Light of 100 W/m ² was irradiated to the photovoltaic cell (1) by a sunlight simulator, and Vcc (voltage in an open circuit state), Joc (current density in a circuit short circuit), FF (curve factor), and η were measured. (conversion efficiency), the results are shown in the table.

Performance evaluation (2) (after scratch resistance test)

An electrode-attached anti-reflection film substrate (1-2) formed on the opposite side of the anti-reflection film attached to the anti-reflection film substrate (1) after the scratch resistance is prepared by using fluorine-doped tin oxide as an electrode. In addition to this, the photovoltaic unit (1-2) was also produced in the same manner, and the performance was also evaluated. The results are shown in the table.

[Embodiment 2] Production of glass substrate (2) Preparation of coating liquid (1) for surface roughness formation

10.0 g of water and 0.1 g of nitric acid having a concentration of 61% by weight were added to the modified alcohol (made by Japan Alcohol Trading Co., Ltd.: Solmix AP-11: ethanol 85.5 wt%, isopropyl alcohol 9.8 wt%, methanol 4.7 wt%) 72.5 g, and then stirred at 25 ° C for 10 minutes, and then added n-decanoic acid ethyl ester (manufactured by Tama Chemical Industry Co., Ltd.: ethyl decanoate-A, SiO ₂ concentration: 28.8% by weight) 17.4 g at 30 ° C The mixture was stirred for 30 minutes to prepare 100 g of an orthosilicate ethyl ester hydrolyzate dispersion having a solid concentration of 5.0% by weight. The polyethylene nitrate hydrolyzate dispersion had a molecular weight of 1,000 in terms of polyethylene.

Next, propylene glycol monopropyl ether (PGME) 7.5 g and methanol 142.5 g were added to 100 g of a n-decanoic acid ethyl ester hydrolyzate dispersion having a solid concentration of 5.0% by weight, and then stirred at 25 ° C for 30 minutes to prepare a solid concentration of 2.0. The coating liquid (1) for forming a surface roughness of % by weight.

The surface roughness forming coating liquid (1) was spray-coated on a glass substrate (manufactured by Fuxin Co., Ltd.: FL glass, thickness: 3 mm, refractive index: 1.51). In the spray coating, the glass substrate was heated to 40 to 42 ° C, and coated by 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. Then, the coated substrate was dried at 80 ° C for 10 minutes and at 150 ° C for 30 minutes to prepare a glass substrate (2) having a surface roughness (Ra _A ) of 100 nm.

Manufacture of anti-reflective film substrate (2)

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

Then, the low refractive index layer-forming component dispersion liquid (1) prepared in the same manner as in Example 1 was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes. The hardening is performed to form a low refractive index layer to produce an antireflection film substrate (2). At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (2), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (2)

An electrode-attached anti-reflection film substrate (2) formed on the opposite side of the anti-reflection film attached to the anti-reflection film substrate (2) with fluorine-doped tin oxide as an electrode was produced.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (2) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate with the electrode is attached (2). As one of the electrodes, the electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed facing upward, the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire is used to connect the electrodes to form a photovoltaic unit (2-1).

Further, in the same manner as in Example 1, the photovoltaic unit (2-2) was produced in the same manner as the anti-reflection film substrate (2) having the scratch resistance.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Example 3] Production of glass substrate (3) Preparation of coating liquid (2) for surface roughness formation

333 g of pure water was added to a cerium oxide microparticle dispersion (manufactured by Nippon Chemical Co., Ltd.: CATALOID SS-300; average particle diameter: 300 nm, SiO ₂ concentration: 18.00% by weight, dispersion medium: water), 1000 g, and solid content concentration After adjusting to 20% by weight, 336 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B) was used, and ion exchange was performed at 80 ° C for 3 hours, and washing was performed to obtain a dioxide having a solid concentration of 20% by weight.矽Microparticle dispersion.

The dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a cerium oxide microparticle-methanol dispersion having a solid concentration of 20% by weight.

1.88 g of n-decanoic acid ethyl ester (manufactured by Tama Chemical Industry Co., Ltd.: ethyl orthosilicate-A, SiO ₂ concentration: 28.8% by weight) was mixed with 100 g of a cerium oxide microparticle-methanol dispersion, followed by addition of ultrapure water 3.1 g. The mixture was stirred at 50 ° C for 6 hours to obtain a surface-treated cerium oxide microparticle-methanol dispersion having a solid concentration of 20.5 wt%.

NMP1g and PGM49g were added to 100 g of the surface-treated cerium oxide fine particle methanol dispersion, and the mixture was stirred at 25 ° C for 30 minutes to prepare a coating liquid for surface roughness formation (2) having a solid content concentration of 10.0% by weight.

The surface roughness forming coating liquid (2) was applied to a glass substrate (manufactured by Fuxin Co., Ltd.: FL glass, thickness: 3 mm, refractive index: 1.51) by a wire bar coating method (#3), at 80 The film was dried in ° C for 120 seconds and sintered at 150 ° C for 30 minutes to prepare a glass substrate (3) having a surface roughness (Ra _A ) of 300 nm.

Manufacture of anti-reflective film substrate (3)

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

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

For the antireflection film substrate (3), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (3)

An anti-reflection film substrate (3) is formed by using fluorine-doped tin oxide as an electrode on an electrode attached to the opposite side of the anti-reflection film of the anti-reflection film substrate (3).

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (3) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate with the electrode is attached (3). As one of the electrodes, the electrode is formed by doping fluorine-doped tin oxide as the other electrode, and the transparent glass substrate holding the platinum is disposed to face upward, and the side surface is sealed with a resin. The above electrolyte solution was sealed between the electrodes, and the electrodes were connected by a lead to prepare a photovoltaic unit (3-1). Further, in the same manner as in Example 1, the photovoltaic unit (3-2) was produced by using the anti-reflection film substrate (3) to which the scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Example 4] Preparation of metal oxide particle dispersion (2) for forming high refractive index layer

In the first embodiment, a high refractive index layer having a solid content concentration of 5% by weight was prepared by adding 0.05 g of triethylamine as a basic nitrogen compound so as to be 5 ppm in the coating liquid. Metal oxide particle dispersion (2).

Manufacture of anti-reflective film substrate (4)

Next, in the first embodiment, the high refractive index layer was formed on the glass substrate (1) except that the metal oxide particle dispersion liquid (2) for forming a high refractive index layer was used. The high refractive index layer has an average thickness of 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

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

For the anti-reflective film substrate (4), the total light transmittance, haze, pencil Hardness and scratch resistance, the results are shown in the table.

Production of photovoltaic unit (4-1)

An anti-reflection film substrate (4) to which an electrode doped with fluorine-doped tin oxide is formed as an electrode on the opposite side of the anti-reflection film of the anti-reflection film substrate (4) is prepared.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (4) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (4) is attached to the electrode. As one of the electrodes, the electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed facing upward, the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire is used to connect the electrodes to form a photovoltaic unit (4-1). Further, in the same manner as in Example 1, the photovoltaic unit (4-2) was produced by using the anti-reflection film substrate (4) to which the scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Example 5] Preparation of metal oxide particle dispersion (3) for forming high refractive index layer

In the first embodiment, a metal for forming a high refractive index layer having a solid concentration of 5 wt% was prepared in the same manner except that 2 g of triethylamine was added as a basic nitrogen compound so as to be 200 ppm in the coating liquid. Oxide particle dispersion (3).

Manufacture of anti-reflective film substrate (5)

Next, in the first embodiment, the high refractive index layer was formed on the glass substrate (1) except that the metal oxide particle dispersion liquid (3) for forming a high refractive index layer was used. The high refractive index layer has an average thickness of 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

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

For the antireflection film substrate (5), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (5)

An anti-reflection film substrate (5) having fluorine-doped tin oxide as an electrode formed on the opposite side of the anti-reflection film of the anti-reflection film substrate (5) is prepared.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (5) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (5) is attached to the electrode. As one of the electrodes, the electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed facing upward, the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire is used to connect the electrodes to form a photovoltaic unit (5-1). Further, in the same manner as in Example 1, the photovoltaic unit (5-2) was produced by using the anti-reflection film substrate (5) to which the scratch resistance was measured.

The obtained photovoltaic unit (5-1) and the photovoltaic unit (5-2) were evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Embodiment 6] Preparation of metal oxide particle dispersion (4) for forming high refractive index layer

In Example 1, except that 0.5 g of tripropylamine (boiling point: 155 ° C) was added as a basic nitrogen compound in an amount of 50 ppm in the coating liquid, the solid content concentration was adjusted to 5 in the same manner. The metal oxide particle dispersion (4) for forming a high refractive index layer of a weight%.

Manufacture of anti-reflective film substrate (6)

Next, in the first embodiment, the high refractive index layer was formed on the glass substrate (1) except that the metal oxide particle dispersion liquid (4) for forming a high refractive index layer was used. The high refractive index layer has an average thickness of 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

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

For the antireflection film substrate (6), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (6)

An anti-reflection film substrate (6) having fluorine-doped tin oxide as an electrode formed on the opposite side of the anti-reflection film of the anti-reflection film substrate (6) is prepared.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (6) with an electrode to cause spectroscopic sensitizing dye absorption. An electrode is attached with an anti-reflection film substrate (6) as an electrode, and an electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is disposed opposite to each other. On the upper side, the side surface is sealed with a resin, the electrolyte solution is sealed between the electrodes, and the electrodes are connected by wires to form a photovoltaic unit (6-1). Further, in the same manner as in Example 1, the photovoltaic unit (6-2) was produced by using the anti-reflection film substrate (6) to which the scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Embodiment 7] Preparation of Metal Oxide Particle Dispersion (5) for Formation of High Refractive Index Layer

In Example 1, except that 0.5 g of triethanolamine (boiling point: 208 ° C) was added in place of triethylamine as a basic nitrogen compound in a manner of 50 ppm in the coating liquid, the solid content concentration was adjusted to 5 A metal oxide particle dispersion (5) for forming a high refractive index layer of a weight%.

Manufacture of anti-reflective film substrate (7)

Next, in the first embodiment, the high refractive index layer was formed on the glass substrate (1) except that the metal oxide particle dispersion liquid (5) for forming a high refractive index layer was used. The high refractive index layer has an average thickness of 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

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

For the antireflection film substrate (7), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (7)

An anti-reflection film substrate (7) having fluorine-doped tin oxide as an electrode formed on the opposite side of the anti-reflection film of the anti-reflection film substrate (7) is prepared.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (7) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (7) is attached to the electrode. As one of the electrodes, the electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed facing upward, the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire is used to connect the electrodes to form a photovoltaic unit (7-1). Further, in the same manner as in Example 1, the photovoltaic unit (7-2) was produced by using the anti-reflection film substrate (7) to which the scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Embodiment 8] Manufacture of anti-reflective film substrate (8)

In Example 1, except that the low refractive index layer forming component dispersion liquid (1) was applied by a wire bar coating method (#4), and dried at 80 ° C for 2 minutes, it was hardened by heating at 300 ° C for 30 minutes. The antireflection film substrate (8) was produced in the same manner as the other. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (8), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (8)

An anti-reflection film substrate (8) having fluorine-doped tin oxide as an electrode formed on the opposite side of the anti-reflection film of the anti-reflection film substrate (8) is formed.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (8) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (8) is attached to the electrode. As one of the electrodes, the electrode is formed by doping fluorine-doped tin oxide as the other electrode, and the transparent glass substrate holding the platinum is disposed to face upward, the side surface is sealed with a resin, and the electrolyte solution is sealed to the electrode. In the meantime, the electrodes are connected to each other to form a photovoltaic unit (8-1). Further, in the same manner as in Example 1, the photovoltaic unit (8-2) was produced by using the antireflection film substrate (8) having the scratch resistance.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Embodiment 9] Manufacture of anti-reflective film substrate (9)

In Example 1, except that the low refractive index layer forming component dispersion liquid (1) was applied by a wire bar coating method (#4), and dried at 80 ° C for 2 minutes, it was heated at 650 ° C for 30 minutes for hardening. An anti-reflection film substrate (9) was produced in the same manner as the other. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (9), the total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (9)

An anti-reflection film substrate (9) having an electrode doped with fluorine-doped tin oxide as an electrode on the opposite side of the anti-reflection film attached to the anti-reflection film substrate (9) was prepared.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the electrode-attached anti-reflection film substrate (9) to adsorb the spectroscopic sensitizing dye, and the anti-reflection film substrate (9) attached to the electrode is used. One of the electrodes is formed by doping fluorine-doped tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed oppositely, and the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire was used to connect the electrodes to form a photovoltaic unit (9-1). Further, in the same manner as in Example 1, a photovoltaic unit (9-2) was produced by using an anti-reflection film substrate (9) to which scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Embodiment 10] Preparation of metal oxide particle dispersion (6) for forming high refractive index layer

10.24 g of a surface-treated titanium oxide particle methanol dispersion having a solid content concentration of 20.5 wt% prepared in the same manner as in Example 1 and a solid content concentration of 5.0% by weight, which was prepared in the same manner as in Example 1, were dispersed. Liquid (1) 18.0 g, propylene glycol monopropyl ether (PGME) 20.00 g, methanol and ethanol and isopropanol modified alcohol (made by Japan Alcohol Trading Co., Ltd.: Solmix AP-11: ethanol 85.5 wt%, different Propanol 9.8 wt%, Methanol (4.7 wt%) 51.76 g, and 2 g of triethylamine (boiling point: 90 ° C) were added as a basic nitrogen compound so as to be 50 ppm in the coating liquid, and then stirred at 25 ° C for 30 minutes to prepare a solid component. A metal oxide particle dispersion (6) for forming a high refractive index layer having a concentration of 5% by weight.

Manufacture of anti-reflective film substrate (10)

In the same manner as in Example 1, the metal oxide particle dispersion liquid (6) for forming a high refractive index layer was applied onto the glass substrate (2) by a wire bar coating 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. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table. Then, the low refractive index layer-forming component dispersion liquid (1) prepared in the same manner as in Example 1 was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes. The hardening is performed to form a low refractive index layer to produce an antireflection film substrate (10). At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (10), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (10)

An anti-reflection film substrate (10) having fluorine-doped tin oxide as an electrode formed on the opposite side of the anti-reflection film of the anti-reflection film substrate (10) is formed. Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (10) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (10) is attached to the electrode. As one of the electrodes, fluorine-doped tin oxide is used as the other electrode to form an electrode, and the support is held The transparent glass substrate of platinum is disposed opposite to the upper side, and the side surface is sealed with a resin. The electrolyte solution is sealed between the electrodes, and the electrodes are connected by wires to form a photovoltaic unit (10-1). Further, in the same manner as in Example 1, the photovoltaic unit (10-2) was produced by using the anti-reflection film substrate (10) to which the scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Example 11] Preparation of low refractive index layer forming component dispersion (2)

10.0 g of water and 0.1 g of nitric acid having a concentration of 61% by weight were added to the modified alcohol (made by Japan Alcohol Trading Co., Ltd.: Solmix AP-11: ethanol 85.5 wt%, isopropyl alcohol 9.8 wt%, methanol 4.7 wt%) 72.5 g, and then stirred at 25 ° C for 10 minutes, and then added n-decanoic acid ethyl ester (manufactured by Tama Chemical Industry Co., Ltd.: ethyl decanoate-A, SiO ₂ concentration: 28.8% by weight) 17.4 g at 30 ° C The mixture was stirred for 30 minutes to prepare 100 g of an orthosilicate ethyl ester hydrolyzate dispersion having a solid concentration of 5.0% by weight. The methyl ruthenate hydrolyzate has a molecular weight of 1,000 in terms of polyethylene.

Next, a cerium oxide-based hollow fine particle dispersion liquid (Surulia 4320, a solid content concentration of 20.5 wt%) was added to 40.0 g of the n-decanoic acid ethyl ester hydrolyzate dispersion liquid having a solid concentration of 5.0% by weight. , dispersion medium isopropyl alcohol, cerium oxide hollow particles average particle diameter = 60 nm, refractive index = 1.25) 5.85 g, propylene glycol monopropyl ether (PGME) 20.00 g and modified alcohol (Japan Alcohol Trading Co., Ltd. System: Solmix AP-11: ethanol 85.5 wt%, isopropanol 9.8 After the weight% and methanol (4.7% by weight) were 34.15 g, the mixture was stirred at 25 ° C for 30 minutes to prepare a low refractive index layer-forming component dispersion (2) having a solid concentration of 3.0% by weight.

Manufacture of anti-reflective film substrate (11)

In the same manner as in Example 1, the metal oxide particle dispersion (1) for forming a high refractive index layer was applied to the glass substrate (1) by a wire bar coating method (#5), and dried at 80 ° C for 120 seconds. The low refractive index layer forming component dispersion liquid (2) was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then cured by heating at 500 ° C for 30 minutes to form a low refractive index layer. An anti-reflection film substrate (11) was produced. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (11), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (11)

An anti-reflection film substrate (11) having an electrode doped with fluorine-doped tin oxide as an electrode on the opposite side of the anti-reflection film attached to the anti-reflection film substrate (11) was prepared. Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (11) with an electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (11) is attached to the electrode. As one of the electrodes, the electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed facing upward, the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire is used to connect the electrodes to form a photovoltaic unit (11-1). Further, in the same manner as in Example 1, a photovoltaic unit was produced using an anti-reflection film substrate (11) having a scratch resistance. (11-2).

The obtained photovoltaic unit (11) was subjected to performance evaluation (1) and performance evaluation (2), and the results are shown in the table.

[Embodiment 12] Preparation of low refractive index layer forming component dispersion (3)

10.0 g of water and 0.1 g of nitric acid having a concentration of 61% by weight were added to the modified alcohol (Solarix AP-11: 85% by weight of ethanol, 9.8% by weight of isopropyl alcohol, and 4.7% by weight of methanol, manufactured by Japan Alcohol Trading Co., Ltd.) 72.5 g, and then stirred at 25 ° C for 10 minutes, and then added n-decanoic acid ethyl ester (manufactured by Tama Chemical Industry Co., Ltd.: ethyl decanoate-A, SiO ₂ concentration: 28.8% by weight) 17.4 g at 30 ° C The mixture was stirred for 30 minutes to prepare 100 g of an orthosilicate ethyl ester hydrolyzate dispersion having a solid concentration of 5.0% by weight. The methyl ruthenate hydrolyzate has a molecular weight of 1,000 in terms of polyethylene.

Then, 33 g of propylene glycol monopropyl ether (PGME) and a modified alcohol (Solar AP-11 manufactured by Japan Alcohol Trading Co., Ltd.) were added to 100 g of the n-decanoic acid ethyl ester hydrolyzate dispersion having a solid concentration of 5.0% by weight. Ethanol 85.5 wt%, isopropyl alcohol 9.8 wt%, methanol 4.7 wt%) 16 g and DAA (boiling point: 168 ° C) 17 g, and then stirred at 25 ° C for 30 minutes to prepare a low refractive index layer having a solid concentration of 3.0 wt%. A component dispersion (3) is formed.

Manufacture of anti-reflective film substrate (12)

In the same manner as in Example 2, the metal oxide particle dispersion (1) for forming a high refractive index layer was applied to the glass substrate (3) by a bar coating method (#5), and dried at 80 ° C for 120 seconds. , coating low refractive index by wire bar coating method (#4) The layer-forming component dispersion liquid (1) was dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes to be cured to form a low refractive index layer, thereby producing an antireflection film substrate (12). At this time, the average thickness of the low refractive index layer was 100 nm.

Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (12), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (12-1)

An anti-reflection film substrate (12) having fluorine-doped tin oxide as an electrode formed on the opposite side of the anti-reflection film of the anti-reflection film substrate (12) is formed.

Then, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (12) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (12) is attached to the electrode. As one of the electrodes, the electrode is formed by doping fluorine-containing tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed facing upward, the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire is used to connect the electrodes to form a photovoltaic unit (12-1). Further, in Example 1, the photovoltaic unit (12-2) was produced in the same manner except that the anti-reflection film substrate (12) having the scratch resistance was used.

The obtained photovoltaic unit (12-1) and photovoltaic unit (12-2) were evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Comparative Example 1] Preparation of metal oxide particle dispersion (R1) for forming high refractive index layer

In the first embodiment, the metal oxide particle dispersion liquid (R1) for forming a high refractive index layer having a solid content concentration of 5% by weight was prepared in the same manner except that triethylamine was not added.

Manufacture of anti-reflective film substrate (R1)

Next, in the first embodiment, the high refractive index layer was formed on the glass substrate (1) except that the metal oxide particle dispersion liquid (R1) for forming a high refractive index layer was used. The high refractive index layer has an average thickness of 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

Then, the low refractive index layer-forming component dispersion liquid (1) prepared in the same manner as in Example 1 was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes. The film is cured to form a low refractive index layer to produce an antireflection film substrate (R1). At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (R1), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (R1)

An anti-reflection film substrate (R1) having an electrode to which fluorine-doped tin oxide is formed as an electrode on the opposite side of the anti-reflection film attached to the anti-reflection film substrate (R1) is prepared.

Then, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (R1) with the electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (R1) is attached to the electrode. As one of the electrodes, the fluorine-doped tin oxide is used as the other electrode to form the electrode, and The transparent glass substrate holding the platinum was placed on the opposite side, the side surface was sealed with a resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected by a lead to prepare a photovoltaic unit (R1-1). Further, in the same manner as in Example 1, a photovoltaic unit (R1-2) was produced by using an anti-reflection film substrate (R1) to which scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Comparative Example 2] Preparation of metal oxide particle dispersion (R2) for forming high refractive index layer

In the first embodiment, a high refractive index layer having a solid concentration of 5 wt% was prepared by adding 0.5 g of triethylamine as a basic nitrogen compound so as to be 50 ppm in the coating liquid. Metal oxide particle dispersion (R2).

Manufacture of anti-reflective film substrate (R2)

Next, in Example 1, a high refractive index layer was formed on the glass substrate (1) except that the metal oxide particle dispersion liquid (R2) for forming a high refractive index layer was used. The high refractive index layer has an average thickness of 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

Then, the low refractive index layer-forming component dispersion liquid (1) prepared in the same manner as in Example 1 was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes. The film is hardened to form a low refractive index layer to produce an antireflection film substrate (R2). At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (R2), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (R2)

An anti-reflection film substrate (R2) having an electrode doped with fluorine-doped tin oxide as an electrode on the opposite side of the anti-reflection film attached to the anti-reflection film substrate (R2) was prepared.

Next, in the same manner as in the first embodiment, a semiconductor film was formed on the electrode surface of the antireflection film substrate (R2) attached to the electrode, and the spectroscopic sensitizing dye was adsorbed, and the antireflection film substrate (R2) was attached as an electrode. One of the electrodes is formed by doping fluorine-doped tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed oppositely, and the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire was used to connect the electrodes to form a photovoltaic unit (R2-1). Further, in the same manner as in Example 1, a photovoltaic cell (R2-2) was produced by using an antireflection film substrate (R2) to which scratch resistance was measured.

The obtained photovoltaic unit (R2) was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Comparative Example 3] Manufacture of anti-reflective film substrate (R3)

In the first embodiment, the metal oxide particle dispersion liquid (1) for forming a high refractive index layer is applied to the surface having the surface roughness of the glass substrate (1) by a wire bar coating method (#5). The high refractive index layer was formed by drying at 45 ° C for 120 seconds. At this time, the average thickness of the high refractive index layer was 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

Then, the low refractive index layer-forming component dispersion liquid (1) prepared in the same manner as in Example 1 was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes. The film is cured to form a low refractive index layer to produce an antireflection film substrate (R3). At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

For the antireflection film substrate (R3), total light transmittance, haze, pencil hardness, and scratch resistance were measured, and the results are shown in the table.

Production of photovoltaic unit (R3)

An anti-reflection film substrate (R3) having an electrode doped with fluorine-doped tin oxide as an electrode on the opposite side of the anti-reflection film attached to the anti-reflection film substrate (R3) was prepared.

Next, in the same manner as in the first embodiment, a semiconductor film is formed on the electrode surface of the antireflection film substrate (R3) with an electrode, and the spectroscopic sensitizing dye is adsorbed, and the antireflection film substrate (R3) is attached as an electrode. One of the electrodes is formed by doping fluorine-doped tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed oppositely, and the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire was used to connect the electrodes to form a photovoltaic unit (R3-1). Further, in the same manner as in Example 1, a photovoltaic cell (R3-2) was produced by using an antireflection film substrate (R3) to which scratch resistance was measured.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

[Comparative Example 4] Manufacture of anti-reflective film substrate (R4)

In the first embodiment, the metal oxide particle dispersion liquid (1) for forming a high refractive index layer is applied to the surface having the surface roughness of the glass substrate (1) by a wire bar coating method (#5). The high refractive index layer was formed by drying at 130 ° C for 120 seconds. At this time, the average thickness of the high refractive index layer was 100 nm. Further, the surface roughness (Ra _B ) and the refractive index were measured, and the results are shown in the table.

Then, the low refractive index layer-forming component dispersion liquid (1) prepared in the same manner as in Example 1 was applied by a wire bar coating method (#4), dried at 80 ° C for 2 minutes, and then heated at 500 ° C for 30 minutes. The hardening is performed to form a low refractive index layer to produce an antireflection film substrate (R4). At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and the refractive index were measured, and the results are shown in the table.

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

Production of photovoltaic unit (R4)

An anti-reflection film substrate (R4) to which an electrode of fluorine-doped tin oxide is formed as an electrode on the opposite side of the anti-reflection film of the anti-reflection film substrate (R4) is prepared. Next, in the same manner as in the first embodiment, a semiconductor film was formed on the electrode surface of the electrode-attached anti-reflection film substrate (R4) to adsorb the spectroscopic sensitizing dye, and the anti-reflection film substrate (R4) attached to the electrode was used as the substrate. One of the electrodes is formed by doping fluorine-doped tin oxide as the other electrode, and the transparent glass substrate holding the platinum is placed oppositely, and the side surface is sealed with a resin, and the electrolyte solution is sealed between the electrodes. Then, a lead wire was used to connect the electrodes to form a photovoltaic unit (R4-1). In addition, the same as in the first embodiment, the use of the test After the scratch resistance was applied to the antireflection film substrate (R4), a photovoltaic unit (R4) was produced.

The obtained photovoltaic unit was evaluated for performance (1) and performance evaluation (2), and the results are shown in the table.

1‧‧‧Transparent electrode layer

2‧‧‧Porous semiconductor film

3‧‧‧electrode layer

4‧‧‧ Electrolytes

5‧‧‧Transparent substrate

6‧‧‧Substrate

Claims (16)

Method for producing an anti-reflection film substrate comprising a high refractive index layer formed on a substrate and a low refractive index layer formed on the high refractive index layer And sequentially comprising the steps of: (a) applying a dispersion of metal oxide particles having a basic nitrogen compound of 1 to 1000 ppm and having a refractive index of 1.50 to 2.40, on a substrate, and (b) a step of removing the dispersion medium of the dispersion liquid at a temperature not lowering the boiling point of the basic nitrogen compound, (c) a step of applying a low refractive index layer forming component dispersion liquid, and (d) removing the low refractive index layer forming component dispersion a step of dispersing a medium, and (e) a step of heating the aforementioned substrate at 120 to 700 °C. The method for producing an antireflection film substrate according to claim 1, wherein the low refractive index layer forming component is a ceria precursor, or a ceria precursor and a ceria sol. The method for producing an antireflection film substrate according to claim 2, wherein the cerium oxide precursor is a partial hydrolyzate selected from the group consisting of an organic hydrazine compound, a hydrolyzate, a hydrolyzed polycondensate, and a polyfluorene nitrogen. At least one of an alkane, a polydecane, and an acidic tannic acid solution. The method for producing an antireflection film substrate according to the first aspect of the invention, wherein the concentration of the low refractive index layer forming component dispersion liquid is in a range of from 0.5 to 10% by weight based on the solid content. The method for producing an antireflection film substrate according to claim 1, wherein the basic nitrogen compound has a boiling point of from 40 to 250 °C. The method for producing an antireflection film substrate according to claim 1, wherein the metal oxide particles are selected from the group consisting of TiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, SnO ₂ , and Sb ₂ O. ₅ , a metal oxide of one or more kinds of In ₂ O ₃ and Nb ₂ O ₅ , a mixture of these, and a composite oxide. The method for producing an antireflection film substrate according to claim 6, wherein the metal oxide particles have an average particle diameter in the range of 5 to 100 nm. The method for producing an antireflection film substrate according to claim 1, wherein the concentration of the metal oxide particles in the metal oxide particle dispersion containing the basic nitrogen compound is 0.5 in terms of solid content. Up to the range of 20% by weight. The method for producing an antireflection film substrate according to the first aspect of the invention, wherein the metal oxide particle dispersion containing the basic nitrogen compound further comprises a matrix forming component, and a concentration of the matrix forming component is based on solid content. It is in the range of 0.1 to 4% by weight. The method for producing an antireflection film substrate according to claim 1, wherein the substrate has irregularities on the surface, and the surface roughness (Ra _A ) is in the range of 30 nm to 1 μm. The method for producing an antireflection film substrate according to claim 1, wherein the substrate is a glass substrate. An anti-reflective film substrate, which is claimed in the first patent application scope The production method according to any one of the items 11, wherein the substrate, the high refractive index layer, and the low refractive index are laminated. The antireflection film substrate according to claim 12, wherein the high refractive index layer has an average thickness in the range of 50 to 200 nm. The antireflection film substrate according to claim 12, wherein the low refractive index layer has an average thickness in the range of 30 to 200 nm. The anti-reflection film substrate according to claim 12, wherein the anti-reflection film substrate has a pencil hardness of 7H or more. A photovoltaic unit comprising an anti-reflection film substrate as described in any one of claims 12 to 15 on the front surface.