JP6317874B2 - Method for producing substrate with antireflection film and photoelectric cell - Google Patents

Description

  The present invention relates to a method for producing a substrate with an antireflection film that can be suitably used for a photoelectric cell for converting light energy into electric energy and taking it out, and a photoelectric cell (solar cell) comprising the substrate, About. More specifically, in order to increase the utilization rate of visible light, an antireflection film-coated 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 present invention relates to a method for producing a substrate with an antireflection film excellent in antireflection performance, light transmittance, etc., and having excellent surface hardness and scratch resistance, and a photoelectric cell equipped with the substrate. .

  The photoelectric conversion material is a material that can continuously extract light energy as electric energy, and is a material that converts light energy into electric energy using an electrochemical reaction between electrodes. When such a photoelectric conversion material is irradiated with light, electrons are generated on one electrode side, move to the counter electrode, and the electrons moved to the counter electrode move as ions in the electrolyte and return to the one electrode. Since this photoelectric energy conversion occurs continuously, it is used, for example, in solar cells.

  In general solar cells, a semiconductor film for a photoelectric conversion material is first formed on a support such as a glass plate on which a transparent conductive film is formed, and then another transparent conductive film is used as a counter electrode. A support such as a formed glass plate is provided, and an electrolyte is sealed between these electrodes. When the photosensitizer adsorbed on the semiconductor for photoelectric conversion material is irradiated with sunlight, the photosensitizer absorbs light in the visible region and is excited. The electrons generated by this excitation move to the semiconductor, then move to the transparent conductive glass electrode, move to the counter electrode through the conducting wire connecting the two electrodes, and the electrons transferred to the counter electrode are oxidized in the electrolyte. Reduce the reduction system. On the other hand, the photosensitizer that has moved electrons to the semiconductor is in an oxidant state, but this oxidant is reduced by the redox system in the electrolyte and returns to its original state. In this way, electrons flow continuously, and the photoelectric conversion material functions as a photoelectric cell (solar cell).

  As this photoelectric conversion material, a material obtained by adsorbing a spectral sensitizing dye having absorption in the visible light region on the semiconductor surface is used. For example, Japanese Patent Laid-Open No. 1-220380 (Patent Document 1) describes a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a metal oxide semiconductor layer. Japanese Patent Publication No. 5-504023 (Patent Document 2) discloses a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a titanium oxide semiconductor layer doped with metal ions. Have been described.

  In such a solar cell, it is conceivable to suppress the reflection of sunlight in order to increase the utilization factor and conversion efficiency of sunlight, and for this reason, the antireflection which has a lower refractive index than the substrate on the substrate. A film is provided. Furthermore, in order to improve the antireflection performance, a high refractive index layer is provided between the base material and the antireflection film.

  The applicant of the present application forms an ultraviolet shielding film using a coating liquid for forming an ultraviolet shielding film comprising titanium oxide colloidal particles and the like and a matrix precursor, and silica-based inorganic oxide particles and a matrix having cavities therein. By forming a visible light anti-reflection film using a coating liquid for forming a visible light anti-reflection film composed of a precursor, photoelectricity is excellent in durability and photoelectric conversion efficiency with low bottom reflectance and luminous reflectance. It is disclosed that a cell is obtained. (Patent Document 3: JP 2002-134178 A)

Japanese Unexamined Patent Publication No. 1-220380 Japanese National Patent Publication No. 5-504023 JP 2002-134178 A

  However, the visible light antireflection film obtained by the conventional manufacturing method has low durability (reliability), the antireflection film is cracked due to environmental changes such as temperature and humidity, and deterioration due to long-term use. The refractive index may change due to expansion / contraction, and the antireflection performance may be deteriorated. For this reason, it may be difficult to maintain high photoelectric conversion efficiency.

Under such circumstances , the present inventors have intensively studied to solve the above problems. As a result, titanium oxide fine particles (high refractive index metal oxide fine particles) and a basic nitrogen compound are formed on a substrate. It was found that the hardness of the resulting antireflection film was remarkably improved by applying a dispersion liquid containing, drying, and then applying a low refractive index layer-forming component dispersion liquid containing a silica precursor and then heating. The invention has been completed.
Specifically, this base material with an antireflection film is coated with a dispersion of metal oxide particles having a basic nitrogen compound of 1 to 1000 ppm and a refractive index of 1.50 to 2.40 on the base material. Removing the dispersion medium at a temperature lower than the boiling point of the basic nitrogen compound, applying the low refractive index layer forming component dispersion, removing the dispersion medium of the low refractive index layer forming component dispersion, It is obtained by a production method including a step of heating at 120 to 700 ° C.
The base material with an antireflection film, which is produced by this manufacturing method and is formed by laminating a high refractive index layer formed on a base material and a low refractive index layer formed on the high refractive index layer, It can be used on the front surface of a photovoltaic cell.

The present invention comprises a method for producing a substrate with an antireflection film that has high hardness and suppresses occurrence of cracks, scratches, etc., a substrate with an antireflection film, and the substrate, and has a high utilization rate of visible light. Therefore, it is possible to provide a photoelectric cell (solar cell) that can stably maintain high photoelectric conversion efficiency and the like over a long period of time.

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

[Method for producing base material with antireflection film]
The present invention is characterized by comprising the following steps (a) to (e).
(A) Application process of high refractive metal oxide particle dispersion (b) Drying process of dispersion (c) Application process of low refractive index layer forming component dispersion (d) Removal of solvent, (e) Heating process
Substrate As the substrate used in the present invention, conventionally known glass, polycarbonate, acrylic resin, plastic sheets such as PET and TAC, plastic films and the like, plastic panels, etc. can be used. It is preferable because a base material with an antireflection film is obtained.

Further, the substrate, when used in photovoltaic cell having an uneven surface, the surface roughness (Ra _A) is 30Nm～1myuemu, more preferably in the range of 50Nm～0.8Myuemu.
When it has the unevenness | corrugation of this range, anti-glare property is high and reflection is also suppressed. Furthermore, when used in a photoelectric cell, reflection is suppressed and the light transmittance is improved, and the effect of improving the photoelectric conversion efficiency by improving the light utilization rate is high.

  As the base material, a commercially available substrate having desired irregularities on the surface can be used, a glass substrate with a flat surface is sandblasted, a gel dispersion is applied on a glass substrate with a flat surface, and dried. It can be used by forming irregularities by a conventionally known method such as curing or applying, drying and curing a mixed dispersion of metal oxide particles and gel. An electrode layer may be formed on the substrate surface.

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 (RaA) 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.
It is difficult to obtain a general-purpose glass substrate having a refractive index less than the lower limit of the above range for optical applications. If the refractive index of the substrate is too high, the refractive index of the substrate and the high refractive index layer provided on the substrate There is a case where the difference is small and the effect of improving the transmittance cannot be obtained sufficiently.

When used in a photoelectric cell, the visible light transmittance of the substrate and the electrode layer is preferably high, specifically 50% or more, particularly preferably 90% or more. Each of the resistance values of the electrode layers is preferably 100 Ω / cm ² or less.
・Process (a)
A dispersion containing high refractive index metal oxide particles and 1 to 1,000 ppm of basic nitrogen compound is applied onto the substrate.

As the metal oxide particles used in the present invention, metal oxide particles having a refractive index of 1.50 to 2.40, more preferably 1.55 to 2.30 are preferably used.
If the refractive index of the metal oxide particles is small, the refractive index difference from the substrate is small, and the effect of improving the transmittance may be insufficient, although it depends on the refractive index of the substrate. Even if the refractive index of the metal oxide particles is too high, scattering by the metal oxide particles occurs, and the effect of improving the transmittance may be 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 in the range of about 0.1 to 1.0, more preferably 0.5 to 1.0.
As the metal oxide particles, metal oxide particles such as TiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₅ , In ₂ O ₃ , Nb ₂ O ₅ , a mixture particle thereof, composite oxidation Physical particles.

  These metal oxide particles can obtain a dispersion of metal oxide particles having excellent dispersibility and stability. Particularly, particles having a small average particle diameter and excellent transparency can be suitably used for optical applications. Can be easily obtained.

The average particle diameter of the metal oxide particles is preferably in the range of 5 to 100 nm, more preferably 7 to 50 nm.
When the average particle diameter of the metal oxide particles is small, they easily aggregate and the dispersion stability becomes insufficient, and the highly refractive layer formed using such a dispersion of metal oxide particles is densified. May be insufficient, and the hardness and scratch resistance of the finally obtained antireflection film may be insufficient. If the average particle diameter of the metal oxide particles is too large, Mie scattering will occur, the light transmittance will be insufficient, and the effect of improving the photoelectric conversion efficiency may be insufficient when used in a photoelectric cell. is there.

  Examples of the dispersion medium for the metal oxide particle dispersion include alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; methyl acetate, acetic acid Ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, esters such as ethylene glycol monoacetate, ethylene glycol, hexylene glycol, etc. Glycols: diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, hydrophilic solvents including ethers such as propylene glycol monopropyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, Esters such as pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone And ketones such as diisobutyl ketone; polar solvents such as toluene. These may be used singly or in combination of two or more.

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

  The basic nitrogen compound contributes to promoting densification and curing of the low refractive index layer-forming component applied on the high refractive index layer. Such a basic nitrogen compound is preferably one that does not evaporate during drying, and preferably has a boiling point in the range of 40 to 250 ° C, preferably 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), sec butylamine (boiling point 62.5 ° C), tertbutylamine (Boiling point 43.6 ° C), pentylamine (boiling point 104 ° C), 2-ethylhexylamine (boiling point 169.2 ° C), allylamine (boiling point 53.3 ° C), aniline (boiling point 184.7 ° C), N-methylaniline ( Boiling point 196.1 ° C), o-toluidine (boiling point 200.7 ° C), m-toluidine (boiling point 202 ° C), p-tolyidine (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-picoline (boiling point 129.4 ° C), β-picoline (boiling point 144.1 ° C), γ-picoline (boiling point 145. 4 ° C), quinoline (Boiling point 237.1 ° C), isoquinoline (boiling point 243.2 ° C), formamide (boiling point 210.5 ° C), N-methylformamide (boiling point 182.5 ° C), acetamide (boiling point 221.2 ° C), N-methyl Primary amines such as acetamide (boiling point 206 ° C), N-methylpropionamide (boiling point 148 ° C), diethylamine (boiling point 55.5 ° C), dipropylamine (boiling point 109.4 ° C), diisopropylamine (boiling point 83.5 ° C) ° C), dibutylamine (boiling point 159.6 ° C), diisobutylamine (boiling point 138 ° C), dipentylamine (boiling point 92 ° C), dimethylaniline (boiling point 193 ° C), diethylaniline (boiling point 217 ° C), dicyclohexylamine (boiling point 113). .5 ° C), 2,4-lutidine (boiling point 157.5 ° C), 2,6-lutidine (boiling point 144 ° C), ethylenediamine (boiling point 117.3 ° C), propylene dia (Boiling point 119.3 ° C), diethylenetriamine (boiling point 207.1 ° C), N, N-dimethylformamide (boiling point 153.0 ° C), N, N-diethylformamide (boiling point 177.5 ° C), N, N- Secondary amines such as dimethylacetamide (boiling point 166.1 ° C), tertiary amines such as triethylamine (boiling point 89.6 ° C), tributylamine (boiling point 91.5 ° C), tripentylamine (boiling point 130 ° C), tetramethyl And quaternary ammonium salts such as ammonium hydride (boiling point 110 ° C.), tetraethylammonium hydride (boiling point 110 ° C.), tetrapropylammonium hydride (boiling point 100 ° C.), tetrabutylammonium hydride (boiling point 100 ° C.), and the like. .

Among these, when these basic nitrogen compounds are used, the low refractive index layer formation of the low refractive index layer forming dispersion in which the basic nitrogen compound is applied to the upper layer when drying in the step (d) described later is used. The densification of the components of the low refractive index layer in the dispersion for forming the low refractive index layer applied to the upper layer by the basic nitrogen compound is promoted by promoting densification of the components and then heat treatment in step (e) . And an antireflection film excellent in hardness, scratch resistance and the like can be formed.

The concentration of the basic nitrogen compound in the metal oxide particle dispersion is preferably 1 to 1,000 ppm, more preferably 5 to 500 ppm.
When the basic nitrogen compound in the metal oxide particle dispersion is small, the effect of the compound is low, the densification of the low refractive index layer in the step (d) described above becomes insufficient, and the antireflection film finally obtained The effect of improving the hardness and scratch resistance may not be sufficiently obtained. Even if there is too much basic nitrogen compound in the metal oxide particle dispersion, the dispersion becomes unstable because it affects the particles in the metal oxide particle dispersion, and the hardness of the antireflection film finally obtained, Scratch resistance may be insufficient.

The metal oxide particle dispersion for forming a high refractive index layer may contain a matrix-forming component as necessary.
As the matrix forming component, those similar to the low refractive index layer forming component described later can be used, and specifically, a silica precursor is preferable.

The concentration of the matrix-forming component in the metal oxide particle dispersion containing the basic nitrogen compound is preferably 4% by weight or less, more preferably in the range of 0.3 to 4% by weight as the solid content.
When the matrix is included, a dense high refractive index layer can be formed, and adhesion to the low refractive index layer and the substrate is improved.

  The total solid concentration of the metal oxide particle dispersion for forming a high refractive index layer is preferably in the range of 0.6 to 24% by weight, more preferably 1.3 to 14% by weight. When the total solid content concentration of the metal oxide particle dispersion for forming a high refractive index layer 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 for applying such a metal oxide particle dispersion containing a basic nitrogen compound to a substrate is not particularly limited as long as it can be uniformly applied on the substrate, and a conventionally known method can be employed. Examples thereof include a bar coater method, a dip method, a spray method, a spinner method, a roll coat method, a gravure coat method, and a slit coat method.
・Process (b)
Next, the dispersion medium is removed at a temperature lower than the boiling point of the basic nitrogen compound, and the coating film is dried. Specifically, it is dried at 50 to 120 ° C., preferably 60 to 100 ° C. (however, it is higher than the boiling point of the solvent).

The drying time varies depending on the drying temperature, but is generally about 20 minutes or less, preferably 30 seconds to 10 minutes.
When used in a photoelectric cell, it is desirable that the surface roughness (Ra _B ) of the high refractive index layer formed on the substrate is in the range of 30 nm to 1 μm, more preferably 50 nm to 0.8 μm. When the surface roughness (Ra _B ) of the high refractive index layer is less than 30 nm, sufficient light transmittance may not be improved.

In the dispersion coating method recommended in the present invention, the surface roughness (Ra _B ) of the high refractive index layer does not exceed 1 μm.
The average thickness of the high refractive index layer is preferably 50 to 200 nm, more preferably 80 to 120 nm.

  If the average thickness of the high-refractive index layer is thin, the reflectance does not decrease, so a sufficient light transmittance improvement effect cannot be obtained. When used in a photoelectric cell, the photoelectric conversion efficiency is improved by improving the light utilization rate. In some cases, the above effect cannot be sufficiently obtained. When the average thickness of the high refractive index layer is thick, sufficient light transmittance may not be obtained, and when used in a photoelectric cell, a sufficient photoelectric conversion efficiency improvement effect may not be obtained.

The average thickness of the high refractive index layer having irregularities on the surface can be obtained by subtracting the weight of the substrate from the weight of the substrate with the high refractive index layer and dividing this by the specific gravity of the high refractive index layer.
・Process (c)
Next, a low refractive index layer forming component dispersion is applied on the high refractive index layer to form a low refractive index layer.

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

  As the silica precursor, a partial hydrolyzate of an organosilicon compound, a hydrolyzate, a hydrolytic condensation polymer, a polysilazane that is a polymer of silazane, a polysilane that is a polymer of silane, an acidic silicic acid solution, and the like are suitable. Used for.

As the organosilicon compound, an organosilicon compound represented by the following formula (1) is used.
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted 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, Halogen, hydrogen, n: an integer of 0 to 3)
Of these, tetrafunctional organosilicon compounds with n = 0 are preferable, and specifically, hydrolyzates such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and hydrolysis polycondensates are preferable. Can be used.

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

（式中、Ｒ₁ 、Ｒ₂ およびＲ₃ は、それぞれ独立して水素原子および炭素数１〜８のアルキル基から選ばれる基であり、ｎは１以上の整数である。）
上記式［２］でＲ₁、Ｒ₂およびＲ₃がすべて水素原子であり、１分子中にケイ素原子が５５〜６５重量％、窒素原子が２０〜３０重量％、水素原子が１０〜１５重量％であるような量で存在している無機ポリシラザンが特に好ましい。このようなポリシラザンを用いると、低屈折率層中にカーボンなどの不純分が残存せず、緻密でな低屈折率層を形成することができる。

(In the formula, R ₁ , R ₂ and R ₃ are each independently a group selected from a hydrogen atom and an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 or more.)
In the above formula [2], R ₁ , R ₂ and R ₃ are all hydrogen atoms, 55 to 65% by weight of silicon atom, 20 to 30% by weight of nitrogen atom and 10 to 15% by weight of hydrogen atom in one molecule. Inorganic polysilazane present in an amount such as% is particularly preferred. When such polysilazane is used, an impurity such as carbon does not remain in the low refractive index layer, and a dense low refractive index layer can be formed.

  Moreover, it is preferable that ratio (Si / N ratio) of Si atom and N atom in polysilazane is 1.0-1.3. Examples of such inorganic polysilazanes include a method of reacting dihalosilane with a base to form an adduct of dihalosilane and then reacting with ammonia (Japanese Examined Patent Publication No. 63-16325), methylphenyldichlorosilane, dimethyldichlorosilane, etc. It can be produced according to a known method such as a method of reacting ammonia with ammonia (Japanese Patent Laid-Open No. Sho 62-88327).

The polysilazane having a repeating unit represented by the above formula (2) may be linear or cyclic, or a mixture of linear polysilazane and cyclic polysilazane.
The number average molecular weight of these polysilazanes in terms of polystyrene is 500 to 10,000, preferably 1000 to 4000. When the number average molecular weight is less than 500, when a low dielectric constant silica-based film is formed, polysilazane having a low molecular weight is volatilized or the silica-based film is greatly contracted in the step (b) or step (c) described later. There is. On the other hand, when it exceeds 10,000, the fluidity of the coating solution is lowered, so that the coating property is lowered, and a low-permittivity silica-based film having flatness and uniform film thickness may not be obtained.

  Furthermore, the low molecular weight polysilazane having a number average molecular weight of 1000 or less is 10 to 40% by weight, preferably 15 to 40% by weight, based on the whole polysilazane. If the low molecular weight polysilazane is in such a range with respect to the entire polysilazane, the step due to the wiring can be covered smoothly and a film surface excellent in flatness can be obtained. When the amount of the low molecular weight polysilazane having a number average molecular weight of 1000 or less is 40% by weight or more, problems such as large film shrinkage between drying and firing, poor flatness, high stress, and easy cracking.

Moreover, as a silane, the polysilane compound represented by following formula (3)-(5) is used.
R ⁴ Si (X ¹ ) ₃ (3)
(In 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 group, X ³ represents a halogen atom.)
The polysilane can be produced according to a known method such as a method of polycondensation of methylphenyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, etc. in the presence of metallic sodium (Japanese Patent Laid-Open No. 2007-145879). .

Specific examples of the silane compound (3) include an alkyltrichlorosilane compound represented by R ¹ SiCl ₃ (wherein R ¹ represents the same meaning as described above). Examples of the alkyltrichlorosilane compound include methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, n-butyltrichlorosilane, and t-butyltrichlorosilane. These compounds can be used alone or in combination of two or more.

  Specific examples of the silane compound (4) include phenyltrichlorosilane, 2-chlorophenyltrichlorosilane, 4-methylphenyltrichlorosilane, 2,4,6-trimethylphenyltrichlorosilane, 1-naphthyltrichlorosilane, and 2-naphthyltrichlorosilane. Etc. These compounds can be used alone or in combination of two or more.

  Specific examples of the silane compound (5) include methylphenyldichlorosilane, ethylphenyldichlorosilane, n-propylphenyldichlorosilane, isopropylphenyldichlorosilane, methyl 1-naphthyldichlorosilane, and methyl 2-naphthyldichlorosilane. Phenyldichlorosilane, ethylphenyldichlorosilane, n-propylphenyldichlorosilane, and isopropylphenyldichlorosilane are more preferable, and methylphenyldichlorosilane is particularly preferable.

  As the polysilane, a linear type, a cyclic type, and a branched type are known. The branched type is preferred because the change in refractive index due to temperature is small and the change in refractive index due to irradiation light is highly sensitive.

  As for the weight average molecular weight (Mw) of the polysilane compound, the number average molecular weight converted to polystyrene is 500 to 50,000, preferably 1000 to 20,000. When a silica-based film is formed with a low number average molecular weight, low-molecular weight polysilane may volatilize or the silica-based film may shrink significantly. Moreover, when there is too much molecular weight, solubility will fall and it cannot melt | dissolve in a solvent.

Moreover, as an acidic silicic acid solution, an acidic silicic acid solution obtained by dealkalizing an aqueous alkali silicate solution with an ion exchange resin or the like is used.
The silica particles and the silica precursor can be mixed and used. When mixed and used, the content of silica particles in the low refractive index layer to be formed is preferably in the range of 0.1 to 40% by weight, more preferably 0.5 to 30% by weight as SiO ₂ . When the content of the silica particles is within this range, a denser low refractive index layer having excellent hardness, scratch resistance and the like can be formed.

  This silica sol includes the low-refractive-index silica-based fine particle dispersion sol disclosed in Japanese Patent Application Laid-Open Nos. 2001-233611 and 2004-203683 filed by the present applicant.

  At this time, the average particle size of the silica particles is preferably in the range of about 5 to 100 nm, more preferably 7 to 80 nm. A silica sol having a particle diameter in this range is stably dispersed, the low-refractive-index film is also densified, and the antireflection film has high hardness and scratch resistance.

  When the average particle diameter of the silica particles is small, the particles easily aggregate and the stability of the low refractive index layer forming component dispersion becomes insufficient, and the low refractive index film formed using such a dispersion is dense. In some cases, the hardness and scratch resistance of the antireflection film finally obtained may be insufficient. When the average particle diameter of the silica particles is too large, the above-described densification with the basic nitrogen compound is insufficient, and the hardness and scratch resistance of the finally obtained antireflection film may be insufficient. Moreover, even if it can be densified, Mie scattering occurs and the light transmittance may be insufficient.

Examples of the dispersion medium for the low refractive index layer forming component dispersion include the same ones used in the formation of the high refractive index layer.
The concentration of the low refractive index layer forming component dispersion is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight as the solid content.

If the concentration of the low refractive index layer-forming component dispersion is low, depending on the coating method, a low refractive index layer with a thickness of the low refractive index layer exceeding 30 nm may not be formed by one coating. Further, the surface roughness (Ra _C ) of the low refractive index layer may not be adjusted to a desired range.

  Even if the concentration of the low refractive index layer forming component dispersion is too high, the stability of the coating solution is low, and even if a low refractive index layer is formed using such a low refractive index layer forming component dispersion, it is difficult to densify. For this reason, the hardness and scratch resistance of the finally obtained antireflection film may be insufficient.

The application method of the low refractive index layer forming component dispersion is not particularly limited as long as it can be applied densely and uniformly on the high refractive index layer, and a conventionally known method can be employed. For example, the same bar coater method, dip method, spray method, spinner method, roll coat method, gravure coat method, slit coat method and the like as in the case of forming the high refractive index layer can be mentioned.
-Steps (d) and (e)
Next, (d) the dispersion medium is removed, and then (e) heat treatment is performed at 120 to 700 ° C., preferably 150 to 500 ° C.

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

  If the drying temperature is too low, removal of the dispersion medium may be insufficient, and then voids may be generated in the low refractive index layer during the heat treatment. In this case, the low refractive index layer and the final In some cases, the antireflection film obtained may have insufficient hardness and scratch resistance.

If the drying temperature is high, the surface of the coating will dry rapidly, resulting in a skinning phenomenon. In this case, voids are generated in the low refractive index layer, and the low refractive index layer and finally the antireflection obtained. The film hardness and scratch resistance may be insufficient.
The drying time varies depending on the drying temperature, but in this case as well, it is generally 20 minutes or less, 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 densifies the low refractive index layer forming component and promotes curing of the low refractive index layer.
When the heat treatment temperature is low, the high refractive index layer and the low refractive index layer are not sufficiently cured, and the hardness and scratch resistance of the finally obtained antireflection film may be insufficient. In addition, even if it heats exceeding the said range, depending on the kind of base material, it may deform | transform and degenerate.

The surface roughness (Ra _C ) of the low refractive index layer according to the present invention thus formed can be appropriately selected as desired.
For example, the surface roughness (Ra _C ) may be 30 nm or less, and further 10 nm or less. Within this range, the smoothness is high and the light transmittance is high, but the hardness and scratch resistance may be slightly reduced.

Further, the surface roughness (Ra _C ) of the antireflection film may be 30 nm to 1 μm, and more preferably 50 nm to 0.8 μm. Those having irregularities in this range have high light transmittance and can improve the photoelectric conversion efficiency, but the scratch-resistant body may be deteriorated by the irregularities.

  Such surface roughness depends on the surface roughness of the substrate, the metal oxide particle diameter and the high refractive index layer thickness in the high refractive index layer, the coating method and the concentration of each dispersion, but when unevenness is provided It is desirable to use a concavo-convex base material or one having a large particle size.

  The average thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm. If the average thickness of the low refractive index layer is thin, the effect of improving the light transmittance cannot be sufficiently obtained, and the effect of improving the photoelectric conversion efficiency cannot be obtained sufficiently when the substrate with a transparent coating is used in the photoelectric cell. There is a case. Even if the average thickness of the low refractive index layer is too thick, the effect of improving the light transmittance cannot be obtained sufficiently, and the effect of improving the photoelectric conversion efficiency is sufficiently obtained when a substrate with a transparent coating is used for the photoelectric cell. It may not be possible.

Here, the average thickness of the low refractive index layer having irregularities on the surface is obtained by subtracting the weight of the base material with the high refractive index layer from the weight of the base material with the antireflection film (high refractive index layer and low refractive index layer ). It can be determined by dividing by the specific gravity of the low refractive index layer .

  The thickness of the antireflection film of the base material with the antireflection film thus formed is the sum of the average thickness of the high refractive index layer and the average thickness of the low refractive index layer, and is 80 to 400 nm, more preferably 130 to 270 nm. It is preferable that it exists in the range.

The antireflection film has a hardness (pencil hardness) of preferably 7H or more, more preferably 8H or more.
When the antireflection film has a hardness (pencil hardness) of 6H or less, it may be damaged when used for a long time as an electronic device or a solar battery, and the light transmittance may be insufficient. For this reason, when it uses for a solar cell, photoelectric conversion efficiency may fall gradually.
[Base material with antireflection film]
The base material with an antireflection film of the present invention is obtained by the above production method, and the base material, a high refractive index layer, and a low refractive index layer are laminated.

  The average thickness of the high refractive index layer is 50 to 200 nm, preferably 80 to 120 nm. If the average thickness of the high refractive index layer is thin, the reflectance does not decrease, so that sufficient light transmittance improvement effect cannot be obtained, and the photoelectric conversion efficiency improvement effect due to the improvement of the light utilization rate may not be sufficiently obtained. is there. If the average thickness of the high refractive index layer is thick, sufficient light transmittance may not be obtained, and sufficient photoelectric conversion efficiency improvement effect may not be obtained.

  The average thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm. If the average thickness of the low refractive index layer is thin, the effect of improving the light transmittance cannot be sufficiently obtained, and the effect of improving the photoelectric conversion efficiency cannot be obtained sufficiently when the substrate with a transparent coating is used in the photoelectric cell. There is a case. Even if the average thickness of the low refractive index layer is too thick, the effect of improving the light transmittance is not sufficiently obtained, and the effect of improving the photoelectric conversion efficiency is insufficient when a substrate with a transparent coating is used for a photoelectric cell. It becomes.

The surface roughness (Ra _B ) of the high refractive index layer formed on the substrate is desirably in the range of 30 nm to 1 μm, more preferably 50 nm to 0.8 μm. If the surface roughness (Ra _B ) of the high refractive index layer is small, sufficient light transmittance may not be improved. 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 according to the present invention thus formed can be appropriately selected as desired.
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 antiglare property may be slightly inferior.

Further, the surface roughness (Ra _C ) of the antireflection film may be 30 nm to 1 μm, and more preferably 50 nm to 0.8 μm. Those having irregularities in this range can improve the antiglare property and photoelectric conversion efficiency, but the scratch-resistant body may be deteriorated by the irregularities.

  Such surface roughness depends on the surface roughness of the substrate, the metal oxide particle diameter and the high refractive index layer thickness in the high refractive index layer, the coating method and the concentration of each dispersion, but when unevenness is provided It is desirable to use a concavo-convex base material or one having a large particle size.

When used in a photoelectric cell, the surface roughness (Ra _C ) of the low refractive index layer is preferably 30 nm to 1 μm, more preferably 50 nm to 0.8 μm. Moreover, since the light transmittance is also large, the photoelectric conversion efficiency can be increased, so that it can be suitably used for a photoelectric cell described later.

  Such a substrate with an antireflection film has a pencil hardness of 7H or more, and has very high scratch resistance.

[Photoelectric cell]
The photoelectric cell according to the present invention is characterized in that the antireflection film-coated substrate is provided on the front surface.

  As shown in FIG. 1, the photoelectric cell according to the present invention has a metal oxide semiconductor film having an electrode layer (1) on the surface and adsorbing a photosensitizer on the surface of the electrode layer (1). The substrate (P-1) on which (2) is formed and the substrate (P-2) having the electrode layer (3) on the surface, the electrode layer (1) and the electrode layer (3) face each other. In the photoelectric cell comprising at least one substrate and the electrode layer having transparency, and having an electrolyte layer provided between the metal oxide semiconductor film (2) and the electrode layer (3), at least One transparent substrate (P-1) and / or substrate (P-2) is provided with an antireflection film (base material) obtained by the above production method on the front surface (the side opposite to the inside of the cell). It is characterized by that.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a photoelectric cell according to the present invention, which has a transparent electrode layer 1 on the surface and a porous material in which a photosensitizer is adsorbed on the surface of the transparent electrode layer 1. A substrate 5 on which a metal oxide semiconductor film 2 is formed and a substrate 6 having an electrode layer 3 having a reduction catalytic ability on the surface are arranged so that the electrode layers 1 and 3 face each other, and further a porous metal An electrolyte 4 is sealed between the oxide semiconductor film 2 and the transparent electrode layer 3. The above-described antireflection film is provided on the substrate surface (particularly the surface through which light is transmitted).

  Since the photoelectric cell according to the present invention includes the base material with an antireflection film obtained by the specific manufacturing method described above, the light transmittance is high and the photoelectric conversion efficiency is excellent. Moreover, since the antireflection film obtained by such a method has high surface hardness and scratch resistance, the surface protection performance is excellent.

  As such a photoelectric cell, for example, Japanese Patent Application Laid-Open No. 2010-153232, Japanese Patent Application Laid-Open No. 2010-153231, Japanese Patent Application Laid-Open No. 2010-108855, Japanese Patent Application Laid-Open No. 2010-073543, and Japanese Patent Application Laid-Open No. 2010-073543 by the present applicant. -040172, 2009-289669, 2009-218218, 2008-277019, 2008-258099, 2008-210713, etc. It is done.

  As one substrate, 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 enough strength to withstand use. In addition to insulating substrates such as glass substrates and organic polymer substrates such as PET, metal titanium, metal aluminum, metal copper, metal A conductive substrate such as nickel can be used. The substrate corresponds to a base material on which an antireflection film is formed. Further, it is sufficient that at least one of the substrates is transparent.

  The electrode layer (1) formed on the surface of the substrate (1) includes tin oxide, tin oxide doped with Sb, F or P, indium oxide doped with Sn and / or F, antimony oxide, zinc oxide Conventionally known electrodes such as noble metals can be used. Such an electrode layer (1) can be formed by a conventionally known method such as a thermal decomposition method or a CVD method. In addition, 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 ability, and is composed of platinum, rhodium, ruthenium metal, ruthenium oxide. The electrode material was plated or deposited on the surface of a conductive material such as tin oxide, tin oxide doped with Sb, F or P, indium oxide doped with Sn and / or F, or antimony oxide. Conventionally known electrodes such as electrodes and carbon electrodes can be used. Such an electrode layer (2) was formed by directly coating, plating or vapor-depositing the electrode on the substrate (2), and forming a conductive layer by a conventionally known method such as a thermal decomposition method or a CDV method. Thereafter, the electrode material can be formed on the conductive layer by a conventionally known method such as plating or vapor deposition.

  The substrate (2) may be a transparent substrate similarly to the substrate (1), and the electrode layer (2) may be a transparent electrode similarly to the electrode layer (1). Furthermore, 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 visible light transmittance of the transparent substrate (1) and the transparent electrode layer (1) is preferably higher, specifically 50% or more, particularly preferably 90% or more. The resistance values of the electrode layer (1) and the electrode layer (2) are each preferably 100 Ω / cm ² or less.

  If necessary, a titanium oxide thin film (1) may be formed on the electrode layer (1), and the film thickness may be in the range of 10 to 70 nm, and further 20 to 40 nm. The titanium oxide thin film (1) may have appropriate pores.

A porous metal oxide semiconductor film is formed on the electrode layer (1) or a titanium oxide thin film (1) provided as necessary. The porous metal oxide semiconductor film (1) may have an average pore diameter in the range of 10 to 40 nm and a pore volume in the range of 0.25 to 0.8 ml / g. There are no particular limitations on the porous metal oxide semiconductor, and one or more metal oxides of titanium oxide, lanthanum oxide, zirconium oxide, niobium oxide, tungsten oxide, strontium oxide, zinc oxide, tin oxide, and indium oxide are oxidized. It is preferable to consist of a thing. Among these, crystalline titanium oxides such as anatase type titanium oxide, brookite type titanium oxide, and rutile type titanium oxide can be suitably used. Moreover, it is preferable that the film thickness of a porous metal oxide semiconductor film (1) exists in the range of 0.1-50 micrometers.

  The photosensitizer adsorbed on the semiconductor film is not particularly limited as long as it absorbs and excites light in the visible light region, the ultraviolet light region, and the infrared light region. A metal complex or the like can be used.

As the organic dye, a conventionally known organic dye having a functional group such as a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfone group, or a carboxyalkyl group in the molecule can be used. Specific examples include metal-free phthalocyanines, cyanine dyes, methocyanine dyes, triphenylmethane dyes, and xanthene dyes such as uranin, eosin, rose bengal, rhodamine B, and dibromofluorescein. These organic dyes have a characteristic that the adsorption rate to the metal oxide semiconductor film is fast. Examples of the metal complex include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine described in JP-A-1-220380 and JP-A-5-504023, chlorophyll, hemin, ruthenium-tris (2,2 ′ -Bispyridyl-4,4′-dicarboxylate), cis- (SCN ⁻ ) -bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium, ruthenium-cis-diaqua-bis (2, Ruthenium-cis-diaqua-bipyridyl complexes such as 2'-bipyridyl-4,4'-dicarboxylate), porphyrins such as zinc-tetra (4-carboxyphenyl) porphine, ruthenium such as iron-hexocyanide complexes, osmium, iron And complexes of zinc and the like. These metal complexes are excellent in the effect of spectral sensitization and durability. The adsorption amount of the photosensitizer on the porous metal oxide semiconductor film is preferably 100 μg or more, more preferably 150 μg or more per 1 cm ² of the specific surface area of the porous metal oxide semiconductor film.

As the electrolyte, a mixture with at least one compound that forms a redox system with an electrochemically active salt is used. Examples of the electrochemically active salt include quaternary ammonium salts such as tetrapropylammonium iodide. Examples of the compound forming the redox system, quinone, hydroquinone, iodine _{^{(I - / I - 3)}} , potassium iodide, bromine _{^{(Br - / Br - 3)}} , potassium bromide, and the like. In some cases, these may be used in combination.

The amount of the electrolyte used is preferably approximately in the range of 0.1 to 5 mol / liter, although it varies depending on the type of electrolyte and the type of solvent described later.
A conventionally well-known solvent can be used for an electrolyte layer. Specifically, carbonates such as water, alcohols, oligoethers, propionate carbonate, phosphate esters, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, sulfur compounds of sulfolane 66, ethylene carbonate, acetonitrile , Γ-butyrolactone and the like.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

[Example 1]
Preparation of metal oxide particle dispersion (1) for forming a high refractive index layer Titanium oxide colloid methanol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: OPTRAIQUE 1120Z, average particle diameter 12 nm, TiO ₂ concentration 20.5% by weight, Dispersion medium: methanol, TiO ₂ particle refractive index 2.30) 100 g mixed with normal ethyl silicate (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration 28.8 wt%), Subsequently, 3.1 g of ultrapure water was added and stirred at 50 ° C. for 6 hours to prepare a methanol dispersion of surface-treated titanium oxide particles having a solid content concentration of 20.5% by weight.

  Next, 100 g of a surface-treated titanium oxide particle methanol dispersion having a solid content concentration of 20.5% by weight, 80 g of propylene glycol monopropyl ether (PGME), and denatured alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix AP-11: Ethanol) 25.5 g of 85.5 wt%, isopropyl alcohol 9.8 wt%, methanol 4.7 wt%) and 2 g of triethylamine (boiling point: 90 ° C.) as a basic nitrogen compound were added to the coating solution. Subsequently, the mixture was stirred at 25 ° C. for 30 minutes to prepare a metal oxide particle dispersion (1) for forming a high refractive index layer having a solid concentration of 5% by weight.

Preparation of low refractive index layer forming component dispersion liquid (1 ) To 72.5 g of Solmix A-11 (manufactured by Nippon Alcohol Sales Co., Ltd.) was added 10.0 g of water and 0.1 g of nitric acid having a concentration of 61% by weight. After stirring at 25 ° C. for 10 minutes, 17.4 g of normal ethyl silicate (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration 28.8 wt%) was added and stirred at 30 ° C. for 30 minutes. Thus, 100 g of a normal ethyl silicate hydrolyzate dispersion having a solid content concentration of 5.0% by weight was prepared. The polyethylene-converted molecular weight of the normal ethyl silicate hydrolyzate was 1000.

  Next, 100 g of a normal ethyl silicate hydrolyzate dispersion having a solid content concentration of 5.0% by weight, 33 g of propylene glycol monopropyl ether (PGME) and denatured alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix AP-11: ethanol) 33 g of 85.5 wt%, isopropyl alcohol 9.8 wt%, methanol 4.7 wt%), and then stirred at 25 ° C. for 30 minutes to form a low refractive index layer with a solid content concentration of 3.0 wt% Component dispersion (1) was prepared.

Manufacture of base material with antireflection film (1) Glass substrate ( manufactured by Hamashin Co., Ltd .: FL glass, thickness: 3 mm, refractive index: 1.51) is sandblasted and has a surface roughness (Ra _A ) of 500 nm. A glass substrate (1) was prepared.

Next, the metal oxide particle dispersion liquid (1) for forming a high refractive index layer was applied to the surface having the surface roughness of the glass substrate (1) by the bar coater 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. The refractive index was measured with an ellipsometer (manufactured by ULVAC, EMS-1).

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

For the substrate with antireflection film (1), the total light transmittance and haze are measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the reflectance is measured with a spectrophotometer (JASCO Corporation, Ubest-55). did. The uncoated glass substrate had a total light transmittance of 99.0%, a haze of 0.1%, and a reflectance of light having a wavelength of 550 nm of 5.0%.
1) Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.
2) Measurement of scratch resistance Using # 0000 steel wool, sliding 10 times with a load of 2 kg / cm ² , visually observing the surface of the film and evaluating it according to the following criteria, the results are shown in Table 1.

Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

Preparation of photoelectric cell (1-1) Antireflection film-coated substrate (1-1) formed with fluorine-doped tin oxide as an electrode on the opposite side of the antireflection film substrate (1) It was created.

Preparation of metal oxide particles for semiconductor film 5 g of titanium hydride is suspended in 1 L of pure water, 400 g of 5% hydrogen peroxide solution is added over 30 minutes, then heated to 80 ° C. to dissolve and peroxo A solution of titanic acid was prepared. Concentrated aqueous ammonia was added thereto to adjust the pH to 9, and the mixture was placed in an autoclave and subjected to hydrothermal treatment at 250 ° C. for 5 hours under saturated vapor pressure to prepare titania colloidal particles (A). It was anatase type titanium oxide having high crystallinity by X-ray diffraction. The average particle size was 40 nm.

Preparation of coating solution for forming semiconductor film Next, the titania colloidal particles (A) obtained above are concentrated to a concentration of 10%, and the peroxotitanic acid solution is mixed therewith, and the titanium in the mixture is converted into TiO ₂ . A coating solution for forming a semiconductor film was prepared by adding hydroxypropylcellulose, which is a film forming aid, so as to be 30% by weight of the converted weight.

Formation of semiconductor film Next, a coating solution for forming a semiconductor film is applied on the electrode surface of the substrate with antireflection film with electrode (1), air-dried, and subsequently irradiated with 6000 mJ / cm ² ultraviolet rays using a low-pressure mercury lamp. Irradiation decomposed peroxotitanic acid (hydrolysis and polycondensation) to cure the semiconductor film. Furthermore, the titanium oxide semiconductor film (A) was formed by heating at 300 ° C. for 30 minutes to decompose and anneal hydroxypropylcellulose.
The obtained titanium oxide semiconductor film (A) had a thickness of 20 μm, a pore volume determined by a nitrogen adsorption method of 0.60 ml / g, and an average pore diameter of 22 nm.

Adsorption of spectral sensitizing dye Concentration of ruthenium complex represented by cis- (SCN-)-bis (2,2'-bipyridyl-4,4'-dicarboxylate) ruthenium (II) as a spectral sensitizing dye 3 × A 10 ^-4 mol / liter ethanol solution was prepared. This spectral sensitizing dye solution was applied onto the titanium oxide semiconductor film (A) using an rpm 100 spinner and dried. This coating and drying process was performed five times. The amount of spectral sensitizing dye adsorbed on the obtained titanium oxide semiconductor film was 150 μg / cm ² . At this time, the adsorption amount per 1 cm ² of the specific surface area of the titanium oxide film (A) is shown. In addition, the weight increment of the semiconductor film after application | coating drying was made into adsorption amount.

  Subsequently, tetrapropylammonium iodide and iodine are mixed in a solvent in which acetonitrile and ethylene carbonate are mixed at a volume ratio of 1: 4, and the respective concentrations are 0.46 mol / L and 0.06 mol / L. The electrolyte solution was prepared by dissolving so as to be.

  The base material with an antireflection film with electrode (1) is used as one electrode, and fluorine doped tin oxide is formed as the other electrode as an electrode, and a transparent glass substrate carrying platinum thereon is disposed oppositely. Then, the side surface was sealed with resin, the above electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (1-1).

The performance of the obtained photoelectric cell (1-1) was evaluated.
Performance evaluation (1) (initial performance evaluation)
The photoelectric cell (1) is irradiated with light of 100 W / m ^{2 by} a solar simulator, Voc (voltage in an open circuit state), Joc (density of current that flows when the circuit is short-circuited), FF (curve) Factor) and η (conversion efficiency) were measured and the results are shown in the table.

Performance evaluation (2) (after scratch resistance test)
Create a substrate with antireflection film with electrode (1-2) formed with fluorine-doped tin oxide as an electrode on the opposite side of the antireflection film of antireflection film with measured scratch resistance (1), A photoelectric cell (1-2) was prepared in the same manner except that this was used, the performance was evaluated in the same manner, and the results are shown in the table.

[Example 2]
Creation of glass substrate (2)
Preparation of surface roughness forming coating solution (1) Modified alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix AP-11: ethanol 85.5% by weight, isopropyl alcohol 9.8% by weight, methanol 4.7% by weight ) After adding 10 g of water and 0.1 g of nitric acid having a concentration of 61% by weight to 72.5 g, the mixture was stirred at 25 ° C. for 10 minutes, and then ethyl ethyl silicate (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate- A, SiO ₂ concentration 28.8 wt%) 17.4 g was added and stirred at 30 ° C. for 30 min to prepare 100 g of a normal ethyl silicate hydrolyzate dispersion having a solid content concentration of 5.0 wt%. The polyethylene-converted molecular weight of the normal ethyl silicate hydrolyzate was 1000.

  Next, 7.5 g of propylene glycol monopropyl ether (PGME) and 142.5 g of methanol are added to 100 g of a normal ethyl silicate hydrolyzate dispersion having a solid content concentration of 5.0% by weight, followed by stirring at 25 ° C. for 30 minutes. Thus, a coating solution (1) for forming a surface roughness having a solid content concentration of 2.0% by weight was prepared.

The surface roughness forming coating solution (1) was spray-coated on a glass substrate (Hamashin Co., Ltd .: FL glass, thickness: 3 mm, refractive index: 1.51). For spray coating, the glass substrate was heated to 40 to 42 ° C., and was applied with a glass nozzle having a diameter of 2 mm at an air flow rate of 25 L / min and an air pressure of 0.4 mPa. Thereafter, the coated substrate was dried at 80 ° C. for 10 minutes and baked at 150 ° C. for 30 minutes to prepare a glass substrate (2) having a surface roughness (Ra _A ) of 100 nm.

Production of base material with antireflection film (2) Next, a metal oxide particle dispersion (1) for forming a high refractive index layer prepared in the same manner as in Example 1 was applied to a glass substrate (2) by a bar coater 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.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a substrate (2) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (2), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (2) An antireflection film-coated substrate (2) was formed by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflection film of the substrate (2) with an antireflection film.

  Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (2), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (2) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (2-1).

Further, in the same manner as in Example 1, a photoelectric cell (2-2) was produced in the same manner using the antireflection film-coated substrate (2) whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 3]
Creation of glass substrate (3)
Preparation of surface roughness forming coating liquid (2) Silica fine particle dispersion (1) (manufactured by JGC Catalysts & Chemicals Co., Ltd .: CATALOID SS-300; average particle diameter 300 nm, SiO ₂ concentration 18.00 wt%, dispersion medium: Water) 333 g of pure water was added to 1000 g to adjust the solid content concentration to 20% by weight, and then cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B) 336 g was used at 80 ° C. for 3 hours. The silica fine particle dispersion having a solid concentration of 20% by weight was obtained by exchanging and washing.

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

  To 100 g of the surface-treated silica particle methanol dispersion, 1 g of NMP and 49 g of PGM were added, followed by stirring at 25 ° C. for 30 minutes to prepare a surface roughness forming coating solution (2) having a solid content concentration of 10.0% by weight.

The surface roughness forming coating solution (2) was applied to a glass substrate (Hamashin Co., Ltd .: FL glass, thickness: 3 mm, refractive index: 1.51) by the bar coater method (# 3), 80 The glass substrate (3) having a surface roughness (Ra _A ) of 300 nm was prepared by drying at 150 ° C. for 120 seconds and baking at 150 ° C. for 30 minutes.

Production of substrate with antireflection film (3) A metal oxide particle dispersion (1) for forming a high refractive index layer prepared in the same manner as in Example 1 was applied to a glass substrate (3) by the bar coater 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.

The low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a base material (3) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
With respect to the base material (3) with an antireflection film, the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (3) An antireflective film-coated substrate (3) was formed by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflective film-coated substrate (3).

Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (3), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (3) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (3-1). Further, in the same manner as in Example 1, a photoelectric cell (3-2) was produced using a base material (3) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 4]
Preparation of Metal Oxide Particle Dispersion (2) for Formation of High Refractive Index Layer In Example 1, the solid solid was similarly prepared except that 0.05 g of triethylamine as a basic nitrogen compound was added to the coating solution at 5 ppm. A metal oxide particle dispersion (2) for forming a high refractive index layer having a partial concentration of 5% by weight was prepared.

Production of base material with antireflection film (4) Next, in Example 1, high refractive index was similarly applied to the glass substrate (1) except that the metal oxide particle dispersion (2) for forming a high refractive index layer was used. A rate layer was formed. 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 low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a substrate (4) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (4), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of photoelectric cell (4-1) Production of substrate with antireflection film (4) with electrode made of tin oxide doped with fluorine on the opposite side of antireflection film of substrate with antireflection film (4) did.

Next, in the same manner as in Example 1, a semiconductor film is formed on the electrode surface of the substrate with antireflection film with electrode (4), the spectral sensitizing dye is adsorbed, and the substrate with antireflection film with electrode (4) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (4-1). Moreover, the photoelectric cell (4-2) was produced using the base material (4) with an antireflection film whose abrasion resistance was measured in the same manner as in Example 1.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 5]
Preparation of Metal Oxide Particle Dispersion (3) for Formation of High Refractive Index Layer In Example 1, the solid content concentration was the same except that 2 g of triethylamine was added as a basic nitrogen compound to 200 ppm in the coating solution. A 5% by weight metal oxide particle dispersion (3) for forming a high refractive index layer was prepared.

Production of substrate with antireflection film (5) Next, in Example 1, high refractive index was similarly applied to the glass substrate (1) except that the metal oxide particle dispersion (3) for forming a high refractive index layer was used. A rate layer was formed. 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 low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a substrate (5) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (5), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (5) A substrate with antireflection film with electrode (5) was produced by forming fluorine-doped tin oxide as an electrode on the side opposite to the antireflection film of substrate with antireflection film (5).

Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (5), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (5) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (5-1). Further, in the same manner as in Example 1, a photoelectric cell (5-2) was produced using the antireflection film-coated substrate (5) whose scratch resistance was measured.
Performance evaluation (1) and performance evaluation (2) were performed on the obtained photoelectric cell (5-1) and photoelectric cell (5-2), and the results are shown in the table.

[Example 6]
Preparation of high refractive index layer-forming metal oxide particle dispersion (4) In Example 1, tripropylamine (boiling point: 155 ° C.) as a basic nitrogen compound instead of triethylamine was adjusted to 50 ppm in the coating solution. A metal oxide particle dispersion (4) for forming a high refractive index layer having a solid concentration of 5% by weight was prepared in the same manner except that 0.5 g was added.

Production of base material with antireflection film (6) Next, in Example 1, high refractive index was similarly applied to the glass substrate (1) except that the metal oxide particle dispersion (4) for forming a high refractive index layer was used. A rate layer was formed. 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 low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a substrate (5) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (6), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (6) A substrate with antireflection film with electrode (6) was produced by forming fluorine-doped tin oxide as an electrode on the side opposite to the antireflection film of substrate with antireflection film (6).

Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with an antireflection film with electrode (6), the spectral sensitizing dye was adsorbed, and the substrate with an antireflection film with electrode (6) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (6-1). Further, in the same manner as in Example 1, a photoelectric cell (6-2) was produced using a base material (6) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 7]
Preparation of metal oxide particle dispersion liquid (5) for forming a high refractive index layer In Example 1, triethanolamine (boiling point: 208 ° C.) as a basic nitrogen compound instead of triethylamine was adjusted to 50 ppm in the coating liquid. A metal oxide particle dispersion (5) for forming a high refractive index layer having a solid content concentration of 5% by weight was prepared in the same manner except that 0.5 g was added.

Production of substrate with antireflection film (7) Next, in Example 1, high refractive index was applied to the glass substrate (1) in the same manner except that the metal oxide particle dispersion (5) for forming a high refractive index layer was used. A rate layer was formed. 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 low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a substrate (7) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (7), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (7) An antireflective film-coated substrate (7) was formed by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflective film-coated substrate (7).

Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (7), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (7) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (7-1). Further, in the same manner as in Example 1, a photoelectric cell (7-2) was produced using the antireflection film-coated substrate (7) whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 8]
Production of antireflection film-coated substrate (8) In Example 1, the low refractive index layer forming component dispersion (1) was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then 300 ° C. A substrate with an antireflection film (8) was produced in the same manner except that it was cured by heating for 30 minutes. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
The substrate (8) with an antireflection film was measured for total light transmittance, haze, pencil hardness and scratch resistance, and the results are shown in the table.

Production of Photoelectric Cell (8) A substrate with antireflection film with electrode (8) was prepared by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflection film of substrate with antireflection film (8).

Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (8), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (8) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (8). Further, in the same manner as in Example 1, a photoelectric cell (8-2) was produced using a base material (8) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 9]
Production Example 1 of Substrate with Antireflection Film (9) In Example 1, the low refractive index layer forming component dispersion (1) was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then 650 ° C. A substrate with an antireflection film (9) was produced in the same manner except that it was cured by heating for 30 minutes. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (9), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (9) A substrate with antireflection film with electrode (9) was produced by forming fluorine doped tin oxide as an electrode on the opposite side of the antireflection film of substrate with antireflection film (9).

In the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (9), the spectral sensitizing dye was adsorbed, and the substrate with electrode with antireflection film (9) was The other electrode is made of fluorine-doped tin oxide as an electrode, a transparent glass substrate carrying platinum thereon is placed oppositely, the side surfaces are sealed with a resin, and the above electrolyte is interposed between the electrodes. The solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (9-1). Further, in the same manner as in Example 1, a photoelectric cell (9-2) was produced using a base material (9) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 10]
Preparation of Metal Oxide Particle Dispersion (6) for Formation of High Refractive Index Layer 10.24 g of a surface-treated titanium oxide particle methanol dispersion with a solid content concentration of 20.5% by weight prepared in the same manner as in Example 1, (1) 18.0 g, propylene glycol monopropyl ether (PGME) 20.00 g, methanol, ethanol and isopropyl 51.76 g of a denatured alcohol of alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix AP-11: ethanol 85.5 wt%, isopropyl alcohol 9.8 wt%, methanol 4.7 wt%), and basic nitrogen compound As a mixture, 2 g of triethylamine (boiling point: 90 ° C.) was mixed to make 50 ppm in the coating solution, and then stirred at 25 ° C. for 30 minutes. A solid part concentration of 5% by weight of the high refractive index layer-forming metal oxide particle dispersion liquid (6) was prepared.

Preparation of base material with antireflection film (10) The metal oxide particle dispersion (6) for forming a high refractive index layer was applied to the glass substrate (2) by the bar coater method (# 5) in the same manner as in Example 1. 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. Next, the low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes. And a low refractive index layer was formed by curing to produce a substrate (10) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (10), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (10) A substrate (10) with an antireflective coating with electrodes formed by using fluorine-doped tin oxide as an electrode on the opposite side of the antireflection coating of the substrate (10) with antireflective coating was produced. Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (10), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (10) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (10-1). Further, in the same manner as in Example 1, a photoelectric cell (10-2) was produced using the base material (10) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Example 11]
Preparation of low refractive index layer forming component dispersion liquid (2) Modified alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix AP-11: Ethanol 85.5% by weight, Isopropyl alcohol 9.8% by weight, Methanol 4.7% by weight %) 12.5 g of water and 0.1 g of nitric acid having a concentration of 61% by weight were added to 72.5 g, followed by stirring at 25 ° C. for 10 minutes, and then normal ethyl silicate (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate). -A, SiO ₂ concentration 28.8 wt%) 17.4 g was added and stirred at 30 ° C. for 30 min to prepare 100 g of a normal ethyl silicate hydrolyzate dispersion having a solid content concentration of 5.0 wt%. The polyethylene-converted molecular weight of the normal ethyl silicate hydrolyzate was 1000.

  Subsequently, silica-based hollow fine particle dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Thruria 4320, solid concentration 20 0.5% by weight, dispersion medium isopropyl alcohol, silica-based hollow fine particles average particle size = 60 nm, refractive index = 1.25) 5.85 g, propylene glycol monopropyl ether (PGME) 20.00 g and denatured alcohol (Japan alcohol sales) Co., Ltd .: Solmix AP-11: 34.15 g of ethanol (85.5 wt% ethanol, 9.8 wt% isopropyl alcohol, 4.7 wt% methanol), and then stirred at 25 ° C. for 30 minutes. A low refractive index layer forming component dispersion liquid (2) having a solid content concentration of 3.0% by weight was prepared.

Preparation of base material with antireflection film (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 the bar coater method (# 5). After drying at 80 ° C. for 120 seconds, the low refractive index layer forming component dispersion (2) is applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes. And a low refractive index layer was formed by curing to produce a substrate (11) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (11), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (11) A substrate with antireflection film with electrode (11) was produced by forming fluorine-doped tin oxide as an electrode on the side opposite to the antireflection film of substrate with antireflection film (11). Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (11), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (11) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (11-1). Further, in the same manner as in Example 1, a photoelectric cell (11-2) was produced using the base material (11) with an antireflection film whose scratch resistance was measured.
The obtained photovoltaic cell (11) was subjected to performance evaluation (1) and performance evaluation (2), and the results are shown in the table.

[Example 12]
Preparation of low refractive index layer forming component dispersion liquid (3) Modified alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix AP-11: ethanol 85.5% by weight, isopropyl alcohol 9.8% by weight, methanol 4.7% by weight %) 12.5 g of water and 0.1 g of nitric acid having a concentration of 61% by weight were added to 72.5 g, followed by stirring at 25 ° C. for 10 minutes, and then normal ethyl silicate (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate). -A, SiO ₂ concentration 28.8 wt%) 17.4 g was added and stirred at 30 ° C. for 30 min to prepare 100 g of a normal ethyl silicate hydrolyzate dispersion having a solid content concentration of 5.0 wt%. The polyethylene-converted molecular weight of the normal ethyl silicate hydrolyzate was 1000.

  Next, 100 g of a normal ethyl silicate hydrolyzate dispersion having a solid content concentration of 5.0% by weight, 33 g of propylene glycol monopropyl ether (PGME) and denatured alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix AP-11: ethanol) 85.5 wt%, isopropyl alcohol 9.8 wt%, methanol 4.7 wt%) 16 g and DAA (boiling point: 168 ° C) 17 g were added, and then stirred at 25 ° C for 30 minutes to obtain a solid content concentration of 3 A 0% by weight low refractive index layer forming component dispersion liquid (3) was prepared.

Preparation of substrate with antireflection film (12) In the same manner as in Production Example 2, the metal oxide particle dispersion (1) for forming a high refractive index layer was applied to the glass substrate (2) by the bar coater method (# 5). After drying at 80 ° C. for 120 seconds, the low refractive index layer forming component dispersion (3) is applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes. And a low refractive index layer was formed by curing to produce a substrate with antireflection film (12). At this time, the average thickness of the low refractive index layer was 100 nm.

Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
The substrate with antireflection film (12) was measured for total light transmittance, haze, pencil hardness and scratch resistance, and the results are shown in the table.

Production of photoelectric cell (12-1) Production of substrate with antireflection film (12) with electrode formed by using fluorine-doped tin oxide as an electrode on the opposite side of antireflection film of substrate with antireflection film (12) did.

Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (12), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (12) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (12-1). In addition, a photoelectric cell (12-2) was produced in the same manner as in Example 1 except that the base material with antireflection film (12) whose scratch resistance was measured was used.
Performance evaluation (1) and performance evaluation (2) were performed on the obtained photoelectric cell (12-1) and photoelectric cell (12-2), and the results are shown in the table.

[Comparative Example 1]
Preparation of metal oxide particle dispersion (R1) for forming a high refractive index layer In Example 1, a metal oxide for forming a high refractive index layer having a solid content concentration of 5% by weight was used except that tetraethylamine was not added. A particle dispersion (R1) was prepared.

Production of substrate with antireflection film (R1) Next, in Example 1, high refractive index was applied to the glass substrate (1) in the same manner except that the metal oxide particle dispersion (R1) for forming a high refractive index layer was used. A rate layer was formed. 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 low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a substrate (R1) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (R1), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (R1) An antireflective film-coated substrate (R1) was formed by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflective film-coated substrate (R1).

Next, in the same manner as in Example 1, a semiconductor film is formed on the electrode surface of the substrate with antireflection film with electrode (R1), the spectral sensitizing dye is adsorbed, and the substrate with antireflection film with electrode (R1). Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (R1-1). Further, in the same manner as in Example 1, a photoelectric cell (R1-2) was produced using a base material (R1) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Comparative Example 3]
In Production Example 1 of the base material with antireflection film (R3), the metal oxide particle dispersion (1) for forming the high refractive index layer was applied to the surface having the surface roughness of the glass substrate (1) by the bar coater method ( After coating in # 5), the film was dried at 45 ° C. for 120 seconds to form a high refractive index layer. 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 low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes to cure. Thus, a low refractive index layer was formed to produce a base material (R3) with an antireflection film. At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (R3), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (R3) An antireflective film-coated substrate (R3) was formed by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflective film-coated substrate (R3).

Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (R3), the spectral sensitizing dye was adsorbed, and the substrate with electrode with antireflection film (R3) was prepared. Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, An electrolyte cell (R3-1) was prepared by sealing the electrolyte solution and connecting the electrodes with lead wires. Further, in the same manner as in Example 1, a photoelectric cell (R3-2) was produced using a base material (R3) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

[Comparative Example 4]
In production example 1 of the base material with antireflection film (R4), the metal oxide particle dispersion (1) for forming a high refractive index layer was applied to the surface having the surface roughness of the glass substrate (1) by the bar coater method ( After coating in # 5), the film was dried at 130 ° C. for 120 seconds to form a high refractive index layer. 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.

Next, the low refractive index layer forming component dispersion (1) prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried at 80 ° C. for 2 minutes, and then heated at 500 ° C. for 30 minutes. Then, a low refractive index layer was formed by curing to produce a substrate with antireflection film (R4). At this time, the average thickness of the low refractive index layer was 100 nm. Further, the surface roughness (Ra _C ) and refractive index were measured, and the results are shown in the table.
For the substrate with antireflection film (R4), the total light transmittance, haze, pencil hardness and scratch resistance were measured, and the results are shown in the table.

Production of Photoelectric Cell (R4) An antireflective film-coated substrate (R4) was formed by forming fluorine-doped tin oxide as an electrode on the opposite side of the antireflective film-coated substrate (R4).
Next, in the same manner as in Example 1, a semiconductor film was formed on the electrode surface of the substrate with antireflection film with electrode (R4), the spectral sensitizing dye was adsorbed, and the substrate with antireflection film with electrode (R4) Is used as one electrode, and fluorine-doped tin oxide is formed as the other electrode, and a transparent glass substrate carrying platinum is disposed on the opposite side, and the side surfaces are sealed with resin, The electrolyte solution was sealed, and the electrodes were connected with lead wires to produce a photoelectric cell (R4-1). Further, in the same manner as in Example 1, a photoelectric cell (R4) was produced using a base material (R4) with an antireflection film whose scratch resistance was measured.
About the obtained photoelectric cell, performance evaluation (1) and performance evaluation (2) are performed, and a result is shown to a table | surface.

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

Claims (11)

A method for producing a substrate with an antireflection film comprising a high refractive index layer formed on a substrate and a low refractive index layer formed on the high refractive index layer,
(A) A step of applying a dispersion of metal oxide particles having a refractive index of 1.50 to 2.40 containing 1 to 1000 ppm of a basic nitrogen compound on a substrate;
(B) removing the dispersion medium of the dispersion at a temperature lower than the boiling point of the basic nitrogen compound and at a temperature of 50 to 120 ° C ;
(C) applying a low refractive index layer forming component dispersion;
(D) The manufacturing method of the base material with an antireflection film which comprises the process of removing the dispersion medium of the said low refractive index layer formation component dispersion liquid (e) heating the said base material at 300-650 degreeC in order.   The method for producing a substrate with an antireflection film according to claim 1, wherein the low refractive index layer forming component is a silica precursor or a silica precursor and a silica sol.   The said silica precursor is at least 1 sort (s) selected from the partial hydrolyzate of an organosilicon compound, a hydrolyzate, a hydrolytic polycondensate, polysilazane, polysilane, and acidic silicic acid liquid, The feature of Claim 2 characterized by the above-mentioned. Manufacturing method of base material with antireflection film.   The method for producing a substrate with an antireflection film according to claim 1, wherein the concentration of the low refractive index layer forming component dispersion is in the range of 0.5 to 10 wt% as a solid content.   The method for producing a substrate with an antireflection film according to claim 1, wherein the basic nitrogen compound has a boiling point in the range of 40 to 250 ° C. The metal oxide particles are _{TiO 2, ZrO 2, Al 2} O 3, ZnO, SnO 2, Sb 2 O 5, In 2 O 3, Nb 1 or more metal oxides selected from ₂ O _5, and mixtures thereof The method for producing a substrate with an antireflection film according to claim 1, comprising a composite oxide.   The average particle diameter of the said metal oxide particle exists in the range of 5-100 nm, The manufacturing method of the base material with an antireflection film of Claim 6 characterized by the above-mentioned.   2. The antireflection film according to claim 1, wherein the concentration of the metal oxide particles in the metal oxide particle dispersion containing the basic nitrogen compound is in the range of 0.5 to 20% by weight as a solid content. A method for producing a substrate.   The metal oxide particle dispersion containing the basic nitrogen compound further contains a matrix-forming component, and the concentration of the matrix-forming component is in the range of 0.1 to 4% by weight as a solid content. The manufacturing method of the base material with an antireflection film of description.   The method for producing a substrate with an antireflection film according to claim 1, wherein the substrate has irregularities on the surface and the surface roughness (RaA) is in the range of 30 nm to 1 μm.   The said base material is a glass base material, The manufacturing method of the base material with an antireflection film of Claim 1 characterized by the above-mentioned.

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