TW201418006A - Composite film consisting of antireflective film and diffusion suppression film, and manufacturing method of glass substrate having composite film - Google Patents
Composite film consisting of antireflective film and diffusion suppression film, and manufacturing method of glass substrate having composite film Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 276
- 239000011521 glass Substances 0.000 title claims abstract description 167
- 239000000758 substrate Substances 0.000 title claims abstract description 151
- 238000009792 diffusion process Methods 0.000 title claims abstract description 78
- 230000001629 suppression Effects 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 230000003667 anti-reflective effect Effects 0.000 title abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 31
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- 230000005540 biological transmission Effects 0.000 claims abstract description 17
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- 238000004445 quantitative analysis Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 136
- 239000002245 particle Substances 0.000 claims description 56
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 48
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 29
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 26
- 235000011007 phosphoric acid Nutrition 0.000 claims description 24
- -1 hydrazine alkoxide Chemical class 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 230000002401 inhibitory effect Effects 0.000 claims description 8
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 5
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000005361 soda-lime glass Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 472
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 239000008213 purified water Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
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- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241001460678 Napo <wasp> Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000001506 calcium phosphate Chemical class 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- COQYUAJAXLUAHF-UHFFFAOYSA-N CC(CCCCCCCCCOC)(C)C Chemical compound CC(CCCCCCCCCOC)(C)C COQYUAJAXLUAHF-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HGUBFVKLMFGDJZ-UHFFFAOYSA-N methanol;silicon Chemical compound [Si].OC HGUBFVKLMFGDJZ-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Glass Compositions (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本發明係關於一種由抗反射膜及擴散抑制膜所構成的複合膜、以及具備該複合膜的玻璃基材的製造方法。更詳細而言，係關於一種由高耐久性的抗反射膜及擴散抑制膜所構成的複合膜、以及具備該複合膜的玻璃基材的製造方法。 The present invention relates to a composite film comprising an antireflection film and a diffusion suppression film, and a method of producing a glass substrate comprising the composite film. More specifically, the present invention relates to a composite film comprising a highly durable antireflection film and a diffusion suppression film, and a method for producing a glass substrate comprising the composite film.
已開發出在玻璃或塑料等基材的表面形成薄膜並提供新功能的各種表面處理技術，且公開了由使用矽醇鹽形成於表面的二氧化矽薄膜所構成的抗反射膜(專利文獻1)。 Various surface treatment techniques have been developed for forming a film on the surface of a substrate such as glass or plastic and providing a new function, and an antireflection film composed of a ceria film formed on the surface using a bismuth salt is disclosed (Patent Document 1) ).
在此，作為要求具有抗反射性較高的抗反射膜的基材的用途，可舉出薄膜太陽能電池。圖1中示出使用帶抗反射膜的基材的薄膜太陽能電池的剖面示意圖的一例。圖1為覆板型薄膜太陽能電池的例子。薄膜太陽能電池10依次具備抗反射膜11、玻璃基材12、透明電極層13、光電轉換層14、透明導電膜15及導電性反射膜16， 太陽光從抗反射膜11側入射。在此，若太陽光在玻璃基材12的太陽光的入射面上反射，則到達光電轉換層14的太陽光減少，導致薄膜太陽能電池的轉換效率下降。因此，需要在玻璃基材12的太陽光的入射面上形成抗反射性較高的抗反射膜11，來增加向光電轉換層14入射的太陽光的透射量。 Here, as a use of a base material which is required to have an antireflection film having high antireflection property, a thin film solar cell can be cited. FIG. 1 shows an example of a schematic cross-sectional view of a thin film solar cell using a substrate with an anti-reflection film. 1 is an example of a superstrate type thin film solar cell. The thin film solar cell 10 includes an antireflection film 11 , a glass substrate 12 , a transparent electrode layer 13 , a photoelectric conversion layer 14 , a transparent conductive film 15 , and a conductive reflective film 16 in this order. Sunlight is incident from the side of the anti-reflection film 11 . Here, when sunlight is reflected on the incident surface of the sunlight of the glass substrate 12, the sunlight reaching the photoelectric conversion layer 14 is reduced, and the conversion efficiency of the thin film solar cell is lowered. Therefore, it is necessary to form the antireflection film 11 having high antireflection property on the incident surface of the sunlight of the glass substrate 12 to increase the amount of transmission of sunlight incident on the photoelectric conversion layer 14.
目前，使用最多的鈉鈣玻璃等通用玻璃含有Na、Ca。在此，由於在曝露於外界氣體中的環境下使用薄膜太陽能電池，因此對於用於薄膜太陽能電池的玻璃基材的抗反射膜來說，在由外界氣體的溫度差或氣候引起的高溫且高濕度下的耐久性是必須的。薄膜太陽能電池若長期曝露於這種環境下，則存在Na或Ca從底層的玻璃基材向抗反射膜表面擴散的傾向，導致抗反射膜表面白濁，降低可見光透射率，存在降低薄膜太陽能電池的轉換效率的問題。 Currently, general-purpose glass such as soda lime glass, which is most used, contains Na and Ca. Here, since the thin film solar cell is used in an environment exposed to the outside air, the antireflection film for the glass substrate of the thin film solar cell is high in temperature and high in temperature caused by the temperature difference of the outside air or the weather. Durability under humidity is a must. If the thin film solar cell is exposed to such an environment for a long period of time, there is a tendency for Na or Ca to diffuse from the underlying glass substrate to the surface of the antireflective film, resulting in a white turbidity of the antireflective film surface, a decrease in visible light transmittance, and a reduction in the thin film solar cell. The problem of conversion efficiency.
因此，要求薄膜太陽能電池的玻璃基材具備通過賦予抗反射膜功能來增加入射的太陽光的透射量的同時抑制Na或Ca在高溫高濕下向抗反射膜表面擴散的功能。 Therefore, the glass substrate of the thin film solar cell is required to have a function of increasing the transmission amount of incident sunlight by imparting an antireflection film function, and suppressing the diffusion of Na or Ca to the surface of the antireflection film under high temperature and high humidity.
[專利文獻1]日本專利公開2002-161262號公報 [Patent Document 1] Japanese Patent Publication No. 2002-161262
然而，上述由使用矽醇鹽形成於表面的二氧化矽薄膜所構成的抗反射膜，由於Na或Ca從底層的玻璃基材向抗反射膜表面擴散，導致抗反射膜表面白濁，因此存在不適於薄膜太陽能電池等曝露於外界氣體中的環境下使用之類的問題。 However, the antireflection film composed of the above-described ceria film formed on the surface using a cerium alkoxide has an anti-reflection film surface turbid due to diffusion of Na or Ca from the underlying glass substrate to the surface of the anti-reflection film, and thus there is discomfort. A problem such as use in an environment exposed to external air such as a thin film solar cell.
本發明解决了上述問題。本發明的目的在於提供一種能夠將含有Na、Ca的鈉鈣玻璃等通用玻璃用作高耐久性的抗反射性玻璃基材的製造方法。即，本發明的目的在於提供一種包括能夠抑制玻璃基材中的Na或Ca在高溫高濕下向抗反射膜表面擴散而抑制抗反射膜的白濁、且透射率較高的抗反射膜的複合膜，以及具備該複合膜的玻璃基材的製造方法。 The present invention solves the above problems. An object of the present invention is to provide a method for producing a highly durable antireflective glass substrate by using a general-purpose glass such as soda lime glass containing Na or Ca. In other words, it is an object of the present invention to provide a composite comprising an antireflection film capable of suppressing the diffusion of Na or Ca in a glass substrate to the surface of the antireflection film under high temperature and high humidity to suppress white turbidity of the antireflection film and having high transmittance. A film and a method of producing a glass substrate having the composite film.
本發明人等進行深入研究的結果發現：通過在玻璃基材上形成由以特定範圍含有P的抗反射膜和以特定範圍含有P的擴散抑制膜所構成的複合膜，能夠製造包含可抑制玻璃基材中的Na或Ca在高溫高濕下向抗反射膜表面擴散而抑制抗反射膜的白濁、且透射率較高的抗反射膜的玻璃基材。本發明係關於一種通過以下所示的所構成解决上述課題的由抗反射膜及擴散抑制膜所構成的複合膜、以及具備該複合膜的玻璃基材的製造方法。 As a result of intensive studies, the present inventors have found that it is possible to produce a glass containing a suppressable film by forming a composite film comprising an antireflection film containing P in a specific range and a diffusion suppressing film containing P in a specific range on a glass substrate. A glass substrate in which an antireflection film which diffuses to the surface of the antireflection film under high temperature and high humidity and which suppresses white turbidity of the antireflection film and has high transmittance is formed. The present invention relates to a composite film comprising an antireflection film and a diffusion suppression film which solves the above-described problems, and a method for producing a glass substrate comprising the composite film.
[1]一種複合膜，其特徵為在藉由透射電子顯微鏡附屬的能量分散型X射線光譜分析裝置進行的定量分析中，相對 於Si、P及O的總計100原子%，係由含有1.0~12.0原子%P之擴散抑制膜，及含有0.1~0.7原子%P之抗反射膜所構成，並於含有選自由Na及Ca所構成之群中至少一種的玻璃基材表面，依次形成有擴散抑制膜、抗反射膜。 [1] A composite film characterized by quantitative analysis by an energy dispersive X-ray spectroscopic apparatus attached to a transmission electron microscope The total of 100 atom% of Si, P and O is composed of a diffusion suppression film containing 1.0 to 12.0 atom% of P, and an antireflection film containing 0.1 to 0.7 atom% of P, and contains a material selected from the group consisting of Na and Ca. A surface of the glass substrate of at least one of the constituent groups is formed with a diffusion suppressing film and an antireflection film in this order.
[2]如上述[1]之複合膜，其中，抗反射膜進一步包含膠體二氧化矽粒子。 [2] The composite film according to [1] above, wherein the antireflection film further contains colloidal cerium oxide particles.
[3]一種具備由抗反射膜及擴散抑制膜所構成的複合膜的玻璃基材的製造方法，其特徵為以(1)~(2)之順序包含如下步驟：(1)：在含有選自由Na及Ca所構成之群中至少一種的玻璃基材上，包含(A)矽醇鹽、或者矽醇鹽的水解物或脫水物與(B)選自正磷酸及焦磷酸中至少一種之磷酸，且(B)成分相對於由抗反射膜及擴散抑制膜所構成的複合膜用組成物100質量份，為0.02~0.28質量份，並將由抗反射膜及擴散抑制膜所構成的複合膜用組成物藉由濕式塗佈法進行塗佈之步驟、及(2)：將具有由抗反射膜及擴散抑制膜所構成的複合膜用組成物的塗膜的玻璃基材在100~500℃下燒成30~60分鐘，藉由透射電子顯微鏡附屬的能量分散型X射線光譜分析裝置的定量分析，相對於Si、P及O的總計100原子%，得到含有1.0~12.0原子%P之擴散抑制膜，及含有0.1~0.7原子%P之抗反射膜以此順序形成之複合膜之步驟。 [3] A method for producing a glass substrate comprising a composite film comprising an antireflection film and a diffusion suppression film, comprising the steps of (1) to (2): (1): containing The glass substrate of at least one of the group consisting of free Na and Ca comprises (A) a hydrazine alkoxide or a hydrolyzate or an anhydrate of the decyl salt and (B) at least one selected from the group consisting of orthophosphoric acid and pyrophosphoric acid. The phosphoric acid and the component (B) are 0.02 to 0.28 parts by mass based on 100 parts by mass of the composition for a composite film composed of the antireflection film and the diffusion suppression film, and a composite film composed of an antireflection film and a diffusion suppression film. a step of coating a composition by a wet coating method, and (2) a glass substrate having a coating film of a composition for a composite film composed of an antireflection film and a diffusion suppression film at 100 to 500 After calcination at ° C for 30 to 60 minutes, quantitative analysis by an energy dispersive X-ray spectrometer attached to a transmission electron microscope yields 1.0 to 12.0 atom% of P with respect to a total of 100 atom% of Si, P, and O. a diffusion inhibiting film, and a composite film formed by the antireflection film containing 0.1 to 0.7 atom% of P in this order Sudden.
[4]如上述[3]之具備由抗反射膜及擴散抑制膜所構成的複合膜的玻璃基材的製造方法，其中，在步驟(1)中塗佈的由抗反射膜及擴散抑制膜所構成的複合膜用組成物進一步包含(C)膠體二氧化矽粒子。 [4] The method for producing a glass substrate comprising the composite film comprising an antireflection film and a diffusion suppression film according to the above [3], wherein the antireflection film and the diffusion suppression film are coated in the step (1) The composite film composition further comprises (C) colloidal cerium oxide particles.
根據本發明[1]，能夠將以往在高溫高濕下因玻璃基材中的Na、Ca向抗反射膜表面擴散而導致抗反射膜表面白濁而無法使用的含有Na、Ca的鈉鈣玻璃等通用玻璃用作高耐久性的抗反射性玻璃基材。具體而言，能夠提供一種通過以特定範圍含有P的抗反射膜來增加入射光的透射量，並且通過以特定範圍含有P的擴散抑制膜來抑制玻璃基材中的Na或Ca在高溫高濕下的表面擴散而抑制抗反射膜的白濁的、由抗反射膜及擴散抑制膜所構成的複合膜。根據本發明[2]，能夠提供一種具有硬度較高的抗反射膜的複合膜。 According to the present invention, it is possible to use a soda-lime glass containing Na or Ca which is diffused from the surface of the anti-reflective film by the diffusion of Na and Ca in the glass substrate to the surface of the anti-reflection film under high temperature and high humidity. General purpose glass is used as a highly durable antireflective glass substrate. Specifically, it is possible to provide an antireflection film containing P in a specific range to increase the transmission amount of incident light, and to suppress Na or Ca in the glass substrate at a high temperature and high humidity by a diffusion suppressing film containing P in a specific range. A composite film composed of an antireflection film and a diffusion suppressing film in which the lower surface is diffused to suppress white turbidity of the antireflection film. According to the invention [2], it is possible to provide a composite film having an antireflection film having a high hardness.
根據本發明[3]，能夠簡便地製造具備本發明[1]的複合膜的玻璃基材。在此，複合膜由抗反射膜及擴散抑制膜所構成，認為包含於複合膜用組成物中的磷酸在形成擴散抑制膜時，以磷酸鈉(NaPO3、Na4P2O7、Na3PO4等)、磷酸鈣(Ca(PO3)2、Ca2P2O7、Ca3(PO4)2等)等磷酸鹽化合物的形式將玻璃基材中的Na或Ca帶入來抑制玻璃基材中的Na或Ca向抗反射膜擴散。並且認為當複合膜用組成物中包含磷酸且液態複合膜用組成物塗佈於玻璃基 材上時，與玻璃基材中的Na或Ca反應而瞬間形成磷酸鹽化合物，因此由上述複合膜用組成物形成抗反射膜和擴散抑制膜這兩層膜。根據本發明[4]，能夠提供一種具備由硬度較高且耐久性較高的抗反射膜及擴散抑制膜所構成的複合膜的玻璃基材。 According to the invention [3], the glass substrate provided with the composite film of the invention [1] can be easily produced. Here, the composite film is composed of an antireflection film and a diffusion suppression film, and it is considered that sodium phosphate (NaPO 3 , Na 4 P 2 O 7 , Na 3 ) is formed when the phosphoric acid contained in the composition for the composite film is formed into a diffusion suppression film. In the form of a phosphate compound such as PO 4 or the like, calcium phosphate (Ca(PO 3 ) 2 , Ca 2 P 2 O 7 , Ca 3 (PO 4 ) 2 , etc.), Na or Ca in the glass substrate is brought in to suppress Na or Ca in the glass substrate diffuses toward the antireflection film. In addition, when the composition for a composite film contains phosphoric acid and the composition for a liquid composite film is applied to a glass substrate, it reacts with Na or Ca in the glass substrate to form a phosphate compound instantaneously, so that it is used for the above composite film. The composition forms two films of an antireflection film and a diffusion suppression film. According to the invention [4], it is possible to provide a glass substrate comprising a composite film comprising an antireflection film and a diffusion suppressing film having high hardness and high durability.
1‧‧‧具備複合膜的玻璃基材 1‧‧‧Glass substrate with composite film
2‧‧‧玻璃基材 2‧‧‧glass substrate
3‧‧‧抗反射膜 3‧‧‧Anti-reflective film
4‧‧‧擴散抑制膜 4‧‧‧Diffusion suppression film
5‧‧‧複合膜 5‧‧‧Composite film
10、20‧‧‧薄膜太陽能電池 10, 20‧‧‧ Thin film solar cells
11、21A‧‧‧抗反射膜 11, 21A‧‧‧ anti-reflection film
21B‧‧‧擴散抑制膜 21B‧‧‧Diffusion suppression film
21‧‧‧複合膜 21‧‧‧Composite film
12、22‧‧‧玻璃基材 12, 22‧‧‧ glass substrate
13、23‧‧‧透明電極層 13, 23‧‧‧ transparent electrode layer
14、24‧‧‧光電轉換層 14, 24‧‧‧ photoelectric conversion layer
15、25‧‧‧透明導電膜 15, 25‧‧‧ Transparent conductive film
16、26‧‧‧導電性反射膜 16, 26‧‧‧ Conductive reflective film
圖1是使用帶抗反射膜的基材的薄膜太陽能電池的剖面示意圖的一例。 1 is an example of a schematic cross-sectional view of a thin film solar cell using a substrate with an antireflection film.
圖2是本發明的具備由抗反射膜及擴散抑制膜所構成的複合膜的玻璃基材的剖面的一例。 2 is an example of a cross section of a glass substrate including a composite film composed of an antireflection film and a diffusion suppression film of the present invention.
圖3是本發明的具備由抗反射膜及擴散抑制膜所構成的複合膜的玻璃基材的剖面的透射電子顯微鏡照片的一例。 3 is an example of a transmission electron micrograph of a cross section of a glass substrate having a composite film composed of an antireflection film and a diffusion suppression film of the present invention.
圖4是使用本發明的具備由抗反射膜及擴散抑制膜所構成的複合膜的玻璃基材的薄膜太陽能電池的剖面示意圖的一例。 4 is an example of a schematic cross-sectional view of a thin film solar cell using a glass substrate having a composite film composed of an antireflection film and a diffusion suppression film of the present invention.
以下，根據實施方式對本發明進行具體說明。另外，只要沒有特别示出並且除了數值固有的情況以外，%為質量%。 Hereinafter, the present invention will be specifically described based on the embodiments. In addition, % is % by mass unless otherwise specified and except for the case where the numerical value is inherent.
本發明的複合膜的特徵係在使用透射電子顯微鏡附屬的能量分散型X射線光譜分析裝置進行的定量分析中，相對於Si、P及O的總計100原子%，由含有1.0~12.0原子%P之擴散抑制膜，含有0.1~0.7原子%P之抗反射膜所構成，及含有選自由Na及Ca所構成之群中的至少一種的玻璃基材表面依次形成有擴散抑制膜、抗反射膜。 The composite film of the present invention is characterized in that it is contained in an amount of 1.0 to 12.0 atom% with respect to a total of 100 atom% of Si, P, and O in quantitative analysis using an energy dispersive X-ray spectrum analyzer attached to a transmission electron microscope. The diffusion suppressing film is composed of an antireflection film containing 0.1 to 0.7 at% of P, and a diffusion suppressing film and an antireflection film are sequentially formed on the surface of the glass substrate containing at least one selected from the group consisting of Na and Ca.
首先，圖2中示出本發明的具備由抗反射膜及擴散抑制膜所構成的複合膜(以下稱為複合膜)的玻璃基材的剖面的一例。具備複合膜的玻璃基材1在玻璃基材2的表面上具備依次形成有含有1.0~12.0原子%的P的擴散抑制膜4和含有0.1~0.7原子%的P的抗反射膜3的複合膜5。以下，按擴散抑制膜、抗反射膜的順序進行說明。 First, an example of a cross section of a glass substrate having a composite film (hereinafter referred to as a composite film) composed of an antireflection film and a diffusion suppression film of the present invention is shown in FIG. 2 . The glass substrate 1 having a composite film has a composite film in which a diffusion suppression film 4 containing 1.0 to 12.0 atom% of P and a reflection film 3 containing 0.1 to 0.7 atom% of P are sequentially formed on the surface of the glass substrate 2. 5. Hereinafter, the order of the diffusion suppression film and the antireflection film will be described.
為了在高溫高濕下防止玻璃基材的白濁，擴散抑制膜存在於玻璃基材表面與抗反射膜之間的界面，且在使用透射電子顯微鏡附屬的能量分散型X射線光譜分析裝置進行的定量分析中，相對於Si、P及O的總計100原子%，含有1.0~12.0原子%的P。其低於1.0原子%時，P的添加效果不充分，若超過12.0原子%，則入射光的透射率下降。認為P以磷酸鈉(NaPO3、Na4P2O7、Na3PO4等)、磷酸鈣(Ca(PO3)2、Ca2P2O7、Ca3(PO4)2等)等磷酸鹽化合物的形式將玻璃基材中的Na或Ca帶入來抑制玻璃基材中的Na或Ca向抗反射膜擴散。在此，Si、P及O的定量 分析是使用日本電子(股)製場致發射型透射電子顯微鏡(型號：JEM-2010F)附屬的能量分散型X射線光譜分析裝置(EDS)，以加速電壓：200kV、探針直徑：1nm的測定條件進行，取測定5次的平均值。圖3中示出具備複合膜的玻璃基材的剖面的透射電子顯微鏡照片的一例。圖3中“×”表示進行定量分析的部位，“×”右邊的數字表示部位。部位1~3為抗反射膜的分析部位，部位4為擴散抑制膜的分析部位，部位5~7為玻璃基材的分析部位。接著，表1中示出部位1~7的定量分析結果(單位：原子%)。如從表1可知，相對於Si、P及O的總計100原子%，抗反射膜中的部位1~3中，P為0.1~0.5原子%，在0.1~0.7原子%的範圍內，擴散抑制膜中的部位4中，為5.1原子%，在1.0~12.0原子%的範圍內，玻璃基材中的部位5~7中，P為0原子%。 In order to prevent white turbidity of the glass substrate under high temperature and high humidity, the diffusion suppressing film exists at the interface between the surface of the glass substrate and the antireflection film, and is quantified by using an energy dispersive X-ray spectroscopy apparatus attached to a transmission electron microscope. In the analysis, 1.0 to 12.0 atom% of P was contained with respect to 100 atom% of total of Si, P, and O. When it is less than 1.0 at%, the effect of adding P is insufficient, and when it exceeds 12.0 at%, the transmittance of incident light is lowered. P is considered to be sodium phosphate (NaPO 3 , Na 4 P 2 O 7 , Na 3 PO 4 , etc.), calcium phosphate (Ca(PO 3 ) 2 , Ca 2 P 2 O 7 , Ca 3 (PO 4 ) 2 , etc.), etc. The form of the phosphate compound brings in Na or Ca in the glass substrate to suppress diffusion of Na or Ca into the antireflection film in the glass substrate. Here, the quantitative analysis of Si, P, and O is an energy dispersive X-ray spectroscopy apparatus (EDS) attached to a field emission type transmission electron microscope (Model: JEM-2010F) manufactured by Nippon Denshi Co., Ltd. to accelerate the voltage. : 200 kV, probe diameter: 1 nm measurement conditions were carried out, and the average value of 5 measurements was taken. FIG. 3 shows an example of a transmission electron micrograph of a cross section of a glass substrate including a composite film. In Fig. 3, "x" indicates the portion where the quantitative analysis is performed, and the number on the right side of "x" indicates the portion. The portions 1 to 3 are analysis portions of the antireflection film, the portion 4 is the analysis site of the diffusion suppression film, and the portions 5 to 7 are analysis sites of the glass substrate. Next, Table 1 shows the results of quantitative analysis of the sites 1 to 7 (unit: atomic %). As is clear from Table 1, with respect to 100 atom% of Si, P, and O in total, P is 0.1 to 0.5 atom% in the portions 1 to 3 in the antireflection film, and diffusion suppression is in the range of 0.1 to 0.7 atom%. In the portion 4 of the film, 5.1 atom%, in the range of 1.0 to 12.0 atom%, P is 0 atom% in the portions 5 to 7 in the glass substrate.
另外，擴散抑制膜的厚度優選3~10nm，厚度低於3nm時，無法充分抑制玻璃基材中的Na、Ca在高溫高濕下的表面擴散，因此存在無法防止玻璃基材的白濁的情況，若厚度超過10nm，則產生光干涉，抗反射性易下降。 In addition, when the thickness of the diffusion-suppressing film is preferably 3 to 10 nm and the thickness is less than 3 nm, surface diffusion of Na and Ca in the glass substrate under high temperature and high humidity cannot be sufficiently suppressed, and thus it is impossible to prevent white turbidity of the glass substrate. When the thickness exceeds 10 nm, light interference occurs, and the antireflection property is liable to lower.
抗反射膜含有SiO2及含磷化合物，在使用透射電子顯微鏡附屬的能量分散型X射線光譜分析裝置進行的定量分析中，相對於Si、P及O的總計100原子%，含有0.1~0.7原子%的P。P低於0.1原子%時，抗反射膜的形成不充分，若超過0.7原子%，則抗反射膜的抗反射性下降。並且，從折射率的觀點考慮優選SiO2相對於100質量份的抗反射膜為95.0~99.9質量份。作為含磷化合物可舉出磷酸等。從抗反射性的觀點考慮，抗反射膜的折射率較佳為1.35~1.50，抗反射膜的透射率較佳為90%以上，附複合膜玻璃基材的透射率較佳為92%以上。抗反射膜的優選厚度因玻璃基材的折射率而發生變化，例如玻璃基材的折射率為1.55左右時，為70~130nm。 The antireflection film contains SiO 2 and a phosphorus-containing compound, and is contained in a quantitative analysis by an energy dispersive X-ray spectrometer attached to a transmission electron microscope, and contains 0.1 to 0.7 atom per 100 atomic % of Si, P, and O. % of P. When P is less than 0.1 at%, the formation of the antireflection film is insufficient, and when it exceeds 0.7 at%, the antireflection property of the antireflection film is lowered. Further, from the viewpoint of the refractive index, SiO 2 is preferably 95.0 to 99.9 parts by mass with respect to 100 parts by mass of the antireflection film. Phosphoric acid etc. are mentioned as a phosphorus-containing compound. From the viewpoint of antireflection properties, the refractive index of the antireflection film is preferably 1.35 to 1.50, the transmittance of the antireflection film is preferably 90% or more, and the transmittance of the composite film glass substrate is preferably 92% or more. The preferable thickness of the antireflection film changes depending on the refractive index of the glass substrate. For example, when the refractive index of the glass substrate is about 1.55, it is 70 to 130 nm.
另外，若抗反射膜中含有膠體二氧化矽粒子，則硬度提高，因此優選。對膠體二氧化矽粒子進行後述。 Further, when the anti-reflection film contains colloidal cerium oxide particles, the hardness is improved, which is preferable. The colloidal cerium oxide particles will be described later.
如此，本發明的具備複合膜的玻璃基材通過抗反射膜增加入射光的透射量，並且通過擴散抑制膜抑制玻璃基材中的Na或Ca在高溫高濕下的表面擴散，從而抑制抗反射膜的白濁。 Thus, the glass substrate provided with the composite film of the present invention increases the transmission amount of incident light by the anti-reflection film, and suppresses surface diffusion of Na or Ca in the glass substrate under high temperature and high humidity by the diffusion suppression film, thereby suppressing anti-reflection The film is white and cloudy.
本發明的具備複合膜的玻璃基材的製造方法(以下稱為本發明的製造方法)的特徵在於依次包括如下步驟：(1)：在含有選自由Na及Ca所構成之群中至少一種的玻璃基材上，包含(A)矽醇鹽、或者矽醇鹽的水解物或脫水物與(B)選自正磷酸及焦磷酸中至少一種之磷酸，且(B)成分相對於由抗反射膜及擴散抑制膜所構成的複合膜用組成物100質量份，為0.02~0.28質量份，並將由抗反射膜及擴散抑制膜所構成的複合膜用組成物藉由濕式塗佈法進行塗佈之步驟、及(2)：將具有由抗反射膜及擴散抑制膜所構成的複合膜用組成物的塗膜的玻璃基材在100~500℃下燒成30~60分鐘，於玻璃基材得到藉由透射電子顯微鏡附屬的能量分散型X射線光譜分析裝置的定量分析，相對於Si、P及O的總計100原子%，得到含有1.0~12.0原子%P之擴散抑制膜，及含有0.1~0.7原子%P之抗反射膜以此順序形成之複合膜之步驟。 The method for producing a glass substrate having a composite film according to the present invention (hereinafter referred to as the production method of the present invention) is characterized by comprising the following steps: (1): containing at least one selected from the group consisting of Na and Ca a glass substrate comprising (A) a hydrazine alkoxide or a hydrolyzate or an anhydrate of the decyl salt and (B) a phosphoric acid selected from at least one of orthophosphoric acid and pyrophosphoric acid, and the component (B) is opposite to the antireflection The composition for a composite film comprising a film and a diffusion-suppressing film is 0.02 to 0.28 parts by mass, and the composition for a composite film comprising an antireflection film and a diffusion suppression film is coated by a wet coating method. Step of the cloth, and (2): baking a glass substrate having a coating film of a composition for a composite film composed of an antireflection film and a diffusion suppression film at 100 to 500 ° C for 30 to 60 minutes on a glass base The material was obtained by quantitative analysis of an energy dispersive X-ray spectrometer attached to a transmission electron microscope, and a diffusion suppression film containing 1.0 to 12.0 atom% of P was obtained with respect to 100 atom% of Si, P and O in total, and 0.1 was obtained. Composite film of ~0.7 atom% P antireflection film formed in this order The steps.
認為當該複合膜用組成物中包含磷酸且液體狀的組成物塗佈於玻璃基材上時，與包含於玻璃基材中的Na或Ca反應，且瞬間形成磷酸鹽化合物，因此形成抗反射膜和擴散抑制膜這2層。 When the composite film composition contains phosphoric acid and the liquid composition is applied to a glass substrate, it reacts with Na or Ca contained in the glass substrate, and forms a phosphate compound instantaneously, thereby forming anti-reflection. Two layers of film and diffusion suppression film.
如上述，在本發明的製造方法的(1)步驟中塗佈的複合膜用組成物(以下稱為複合膜用組成物)包含(A)矽醇鹽、或者矽醇鹽的水解物或脫水物和(B)選自正磷酸(H3PO4)及焦磷酸(H4P2O7)的至少一種磷酸，複合膜由抗反射膜及擴散抑制膜所構成。從取得簡易性的觀點考慮，優選正磷酸作為(B)成分的磷酸。從矽醇鹽的水解反應性及擴散抑制膜形成的觀點考慮，(B)成分相對於100質量份的複合膜用組成物為0.02~0.28質量份。若(B)成分低於0.02質量份，則所形成的擴散抑制膜的厚度不充分，因此導致由複合膜用組成物得到的玻璃基材在高溫高濕下白濁，若(B)成分超過0.28質量份，則導致所形成的抗反射膜的抗反射性下降。並且，當使用85%的正磷酸作為(B)成分時，相對於100質量份的複合膜用組成物為0.024~0.329質量份。 As described above, the composition for a composite film (hereinafter referred to as a composition for a composite film) applied in the step (1) of the production method of the present invention contains (A) a hydrazine alkoxide or a hydrolyzate or dehydration of a decyl alkoxide. And (B) at least one phosphoric acid selected from the group consisting of orthophosphoric acid (H 3 PO 4 ) and pyrophosphoric acid (H 4 P 2 O 7 ), and the composite film is composed of an antireflection film and a diffusion inhibiting film. From the viewpoint of obtaining simplicity, phosphoric acid having orthophosphoric acid as the component (B) is preferred. The component (B) is 0.02 to 0.28 parts by mass based on 100 parts by mass of the composition for the composite film, from the viewpoint of the hydrolysis reaction property of the oxime salt and the formation of the diffusion-suppressing film. When the component (B) is less than 0.02 parts by mass, the thickness of the diffusion-suppressing film formed is insufficient. Therefore, the glass substrate obtained from the composition for a composite film is cloudy under high temperature and high humidity, and if the component (B) exceeds 0.28. In the case of a part by mass, the antireflection property of the formed antireflection film is lowered. In addition, when 85% of orthophosphoric acid is used as the component (B), it is 0.024 to 0.329 parts by mass with respect to 100 parts by mass of the composition for a composite film.
作為(A)成分的矽醇鹽可以舉出四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷、三甲基甲氧基矽烷等，從反應控制的簡易性、作為抗反射膜時的膜硬度的觀點考慮優選四乙氧基矽烷。 Examples of the oxime salt of the component (A) include tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetrabutoxy decane, and trimethyl methoxy decane, and the reaction control is simple. From the viewpoint of the film hardness at the time of the antireflection film, tetraethoxy decane is preferable.
關於矽醇鹽的水解物和脫水物，對矽醇鹽為四乙氧基矽烷時的情況進行說明。四乙氧基矽烷的水解物，例如為通過反應式(1)：Si(OC2H5)4+4H2O → Si(OH)4+4C2H5OH (1) The case of the hydrolyzate and the dehydrate of the oxime salt is described when the oxime salt is tetraethoxynonane. A hydrolyzate of tetraethoxy decane, for example, by the reaction formula (1): Si(OC 2 H 5 ) 4 + 4H 2 O → Si(OH) 4 + 4C 2 H 5 OH (1)
生成的Si(OH)4等。並且四乙氧基矽烷的脫水物為以上述水解物的脫水物例如通過反應式(2)：Si(OH)4 → SiO(OH)2+H2O (2) The resulting Si(OH) 4 and the like. And the dehydrate of tetraethoxy decane is an anhydrate of the above hydrolyzate, for example, by the reaction formula (2): Si(OH) 4 → SiO(OH) 2 + H 2 O (2)
生成的SiO(OH)2等，該脫水物在燒成複合膜用組成物之後，例如通過反應式(3)：SiO(OH)2 → SiO2+H2O (3)的反應成為SiO2等。並且，若(A)成分相對於100質量份的複合膜用組成物，以矽醇鹽的形成為5~20質量份，則從抗反射膜的硬度觀點考慮優選。 The produced SiO(OH) 2 or the like, after the composition of the composite film is fired, for example, by the reaction of the reaction formula (3): SiO(OH) 2 → SiO 2 + H 2 O (3), becomes SiO 2 . Wait. In addition, when the component (A) is formed in an amount of 5 to 20 parts by mass based on 100 parts by mass of the composition for a composite film, the formation of the oxime salt is preferred from the viewpoint of the hardness of the antireflection film.
並且，複合膜用組成物包含分散介質，分散介質優選相對於整個分散介質100質量%含有1質量%以上的水和2質量%以上的與水相容的溶劑，例如醇類。例如，分散介質僅由水及醇類構成時，含有2質量%的水時含有98質量%的醇類，含有2質量%的醇類時含有98質量%的水。這是因為水的含量低於1質量%或醇類的含量低於2質量%時，很難在低溫下燒結通過濕式塗佈法塗佈複合膜用組成物而得到的膜，並且在抗反射膜上易產生固化不足的不良情況。作為醇類可以舉出甲醇、乙醇等，也可將這些混合使用。為了得到良好的成膜性，分散介質的含量優選相對於100質量份的複合膜用組成物為63.5~95 質量份。 In addition, the composition for a composite film contains a dispersion medium, and the dispersion medium preferably contains 1% by mass or more of water and 2% by mass or more of a water-compatible solvent such as an alcohol with respect to 100% by mass of the entire dispersion medium. For example, when the dispersion medium is composed only of water and an alcohol, it contains 98% by mass of an alcohol when it contains 2% by mass of water, and 98% by mass of water when it contains 2% by mass of an alcohol. When the content of water is less than 1% by mass or the content of the alcohol is less than 2% by mass, it is difficult to sinter the film obtained by coating the composition for a composite film by a wet coating method at a low temperature, and is resistant. The reflective film is prone to insufficient curing. Examples of the alcohols include methanol and ethanol, and these may be used in combination. In order to obtain good film formability, the content of the dispersion medium is preferably 63.5 to 95 with respect to 100 parts by mass of the composition for the composite film. Parts by mass.
另外，若複合膜用組成物含有膠體二氧化矽粒子作為成分(C)，則抗反射膜的硬度提高，因此優選。作為膠體二氧化矽粒子可舉出球狀膠體二氧化矽粒子、各向異性膠體二氧化矽粒子。 In addition, when the composition for a composite film contains colloidal cerium oxide particles as the component (C), the hardness of the antireflection film is improved, which is preferable. Examples of the colloidal cerium oxide particles include spherical colloidal cerium oxide particles and anisotropic colloidal cerium oxide particles.
球狀膠體二氧化矽粒子平均粒徑較佳為6~40nm，更佳為6~30nm。這是因為，若平均粒徑小於6nm，則粒子易引起二次聚集，很難製造複合膜用組成物，若大於40nm，則阻礙抗反射膜的平坦性。在此，平均粒徑通過使用QUANTACHROME公司製AUTOSORB-1測定比表面積，並假設球狀膠體二氧化矽粒子為真球來進行換算。 The average particle diameter of the spherical colloidal cerium oxide particles is preferably from 6 to 40 nm, more preferably from 6 to 30 nm. This is because if the average particle diameter is less than 6 nm, the particles are liable to cause secondary aggregation, and it is difficult to produce a composition for a composite film. When the average particle diameter is more than 40 nm, the flatness of the antireflection film is inhibited. Here, the average particle diameter was measured by using the AUTOSORB-1 manufactured by QUANTACHROME Co., Ltd., and the spherical colloidal cerium oxide particles were assumed to be true spheres.
各向異性膠體二氧化矽粒子平均粒徑較佳為5~50nm，更佳為12~40nm。這是因為，若平均粒徑小於5nm，則粒子易引起二次聚集，很難製造複合膜用組成物，若大於50nm，則阻礙抗反射膜的平坦性。在此，各向異性膠體二氧化矽粒子的平均粒徑是指利用雷射繞射/散射式粒度分布測定裝置(堀場製造所(股)製/LA-950)進行測定且將粒徑基準作為個數運算的50%平均粒徑(D50)，並成為各向異性膠體二氧化矽粒子的長徑的平均值。各向異性膠體二氧化矽粒子的縱橫比(長徑/短徑)優選在1.5~5的範圍內。另外，關於是各向異性形狀還是球狀則利用以上述掃描型電子顯微鏡觀察的圖像，將所識别的縱橫比(長徑/短徑)為1.5以上的識别為各向異性形狀。 The anisotropic colloidal cerium oxide particles preferably have an average particle diameter of 5 to 50 nm, more preferably 12 to 40 nm. This is because if the average particle diameter is less than 5 nm, the particles are liable to cause secondary aggregation, and it is difficult to produce a composition for a composite film. When the average particle diameter is more than 50 nm, the flatness of the antireflection film is inhibited. Here, the average particle diameter of the anisotropic colloidal cerium oxide particles is measured by a laser diffraction/scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd. / LA-950), and the particle diameter reference is used. The 50% average particle diameter (D 50 ) of the number calculation is the average of the long diameters of the anisotropic colloidal cerium oxide particles. The aspect ratio (long diameter/short diameter) of the anisotropic colloidal cerium oxide particles is preferably in the range of 1.5 to 5. In addition, the anisotropic shape or the spherical shape is recognized as an anisotropic shape by using the image observed by the scanning electron microscope described above, and the identified aspect ratio (long diameter/short diameter) is 1.5 or more.
(C)成分優選相對於100質量份的複合膜用組成物為5~15質量份，更佳為10~15質量份。 The component (C) is preferably 5 to 15 parts by mass, more preferably 10 to 15 parts by mass, per 100 parts by mass of the composition for a composite film.
複合膜用組成物在不損害本發明目的的範圍內，根據需要能夠進一步配合抗氧化劑、整平劑、觸變劑、填充劑、應力緩和劑、導電性聚合物、其他添加劑等。 The composition for a composite film can further contain an antioxidant, a leveling agent, a thixotropic agent, a filler, a stress relieving agent, a conductive polymer, other additives, and the like as needed within a range not impairing the object of the present invention.
複合膜用組成物能夠根據常用方法，通過塗料攪拌器、球磨機、砂磨機、離心式磨機、三輥磨等混合所需成分來製造。當然，也能夠通過一般攪拌操作來製造。 The composition for a composite film can be produced by mixing a desired component by a paint agitator, a ball mill, a sand mill, a centrifugal mill, a three-roll mill or the like according to a usual method. Of course, it can also be manufactured by a general stirring operation.
如此進行所得到的複合膜用組成物能夠使用於本發明的具備複合膜的玻璃基材的製造中。 The composition for a composite film obtained in this manner can be used in the production of the glass substrate having the composite film of the present invention.
作為(1)步驟中的複合膜用組成物的濕式塗佈法優選噴塗法、點膠機塗佈法、旋塗法、刮塗法、狹缝塗佈法、噴墨塗佈法、網版印刷法、膠版印刷法或鑄模塗佈法中的任一種，但並非限定於此，能夠利用所有方法。 The wet coating method as the composition for a composite film in the step (1) is preferably a spray coating method, a dispenser coating method, a spin coating method, a knife coating method, a slit coating method, an inkjet coating method, or a net coating method. Any of the printing method, the offset printing method, and the mold coating method is not limited thereto, and all methods can be utilized.
在(2)步驟中，燒成具有複合膜用組成物塗膜的玻璃基材的燒成條件為在大氣中或者氮或氬等惰性氣體氣氛中以100~500℃燒成30~60分鐘。 In the step (2), the firing conditions of the glass substrate having the composition film for a composite film are fired at 100 to 500 ° C for 30 to 60 minutes in an atmosphere of an inert gas such as nitrogen or argon.
具有塗膜的玻璃基材的燒成溫度設為100~ 500℃範圍，是因為低於100℃時，由於擴散抑制膜中的P濃度變低，因此不僅在高溫高濕下抑制玻璃基材的白濁變得不充分，而且在抗反射膜上產生固化不足的不良情況。並且，若超過500℃，則無法發揮低溫製程這種生產上的優點，即導致製造成本增大，生產率下降。另外，若燒成溫度在550℃以上，則可能導致玻璃基材上產生翹曲。 The baking temperature of the glass substrate having a coating film is set to 100~ In the range of 500 ° C, the P concentration in the diffusion suppressing film is lowered when the temperature is lower than 100 ° C. Therefore, not only the white turbidity of the glass substrate is suppressed to be insufficient under high temperature and high humidity, but also insufficient curing occurs on the antireflection film. Bad situation. Further, when it exceeds 500 ° C, the production advantage of the low-temperature process cannot be exhibited, that is, the manufacturing cost is increased and the productivity is lowered. Further, when the firing temperature is 550 ° C or higher, warpage may occur on the glass substrate.
具有塗膜的玻璃基材的燒成時間設為30~60分鐘範圍，是因為在燒成時間低於30分鐘時，在抗反射膜上產生燒成不充分的不良情況。若燒成時間超過60分鐘，則導致製造成本過度增大，生產率下降。 The firing time of the glass substrate having a coating film is in the range of 30 to 60 minutes because when the firing time is less than 30 minutes, the baking is insufficient in the antireflection film. When the baking time exceeds 60 minutes, the manufacturing cost is excessively increased and the productivity is lowered.
認為形成擴散抑制膜的機制是在燒成複合膜用組成物塗膜時，複合膜用組成物中的磷酸與玻璃基材中的Na或Ca反應，且在玻璃基材與抗反射膜之間形成擴散抑制膜，從而在高溫高濕下防止玻璃基材的白濁。 It is considered that the mechanism for forming the diffusion-inhibiting film is to react the phosphoric acid in the composition for the composite film with Na or Ca in the glass substrate, and between the glass substrate and the anti-reflection film, when the composition for firing the composite film is coated. A diffusion suppressing film is formed to prevent white turbidity of the glass substrate under high temperature and high humidity.
通過以上，能夠製造具備由抗反射膜和在高溫高濕下防止玻璃基材的白濁的擴散抑制膜構成的複合膜的玻璃基材。如此，本發明的製造方法在形成複合膜時使用濕式塗佈法，由此能夠盡可能排除真空蒸鍍法和濺鍍法等真空製程，因此能夠更廉價地製造具備複合膜的玻璃基材。 As described above, it is possible to manufacture a glass substrate including a composite film composed of an antireflection film and a diffusion suppressing film that prevents white turbidity of the glass substrate under high temperature and high humidity. As described above, in the production method of the present invention, a wet coating method is used in forming a composite film, whereby a vacuum process such as a vacuum deposition method or a sputtering method can be eliminated as much as possible, so that a glass substrate having a composite film can be manufactured at a lower cost. .
接著，對本發明的具備複合膜的玻璃基材的應用進行 說明。圖4中示出使用本發明的具備複合膜的玻璃基材的薄膜太陽能電池的剖面示意圖的一例。圖4為覆板型薄膜太陽能電池的例子。薄膜太陽能電池20依次具備由抗反射膜21A及擴散抑制膜21B所構成的複合膜21、玻璃基材22、透明電極層23、光電轉換層24、透明導電膜25及導電性反射膜26，太陽光從抗反射膜21A側入射。由於該薄膜太陽能電池20具備抗反射膜21A，因此入射的太陽光向光電轉換層24的透射量較多，即使在高溫高濕下長時間使用，也通過擴散抑制膜21B抑制玻璃基材22中的Na或Ca向抗反射膜21A表面擴散來抑制抗反射膜21A的白濁，因此能夠提供即使在高溫高濕下光電轉換效率也不會下降的薄膜太陽能電池20。 Next, the application of the glass substrate with the composite film of the present invention is carried out. Description. 4 shows an example of a schematic cross-sectional view of a thin film solar cell using a glass substrate having a composite film of the present invention. 4 is an example of a superstrate type thin film solar cell. The thin film solar cell 20 includes a composite film 21 composed of an antireflection film 21A and a diffusion suppression film 21B in this order, a glass substrate 22, a transparent electrode layer 23, a photoelectric conversion layer 24, a transparent conductive film 25, and a conductive reflection film 26, and the sun. Light is incident from the side of the anti-reflection film 21A. Since the thin film solar cell 20 includes the antireflection film 21A, the amount of incident sunlight transmitted to the photoelectric conversion layer 24 is large, and the glass substrate 22 is suppressed by the diffusion suppressing film 21B even when used for a long time under high temperature and high humidity. Na or Ca diffuses to the surface of the anti-reflection film 21A to suppress white turbidity of the anti-reflection film 21A. Therefore, it is possible to provide the thin film solar cell 20 in which the photoelectric conversion efficiency does not decrease even under high temperature and high humidity.
作為製造該薄膜太陽能電池20的方法，在形成光電轉換層24等之前，預先在玻璃基材22上形成複合膜21的方法更能夠避免在複合膜用組成物塗膜燒成時光電轉換層24劣化，因此優選。然而，也能夠在形成有光電轉換層24~導電性反射膜26的玻璃基板22上形成複合膜21。此時，複合膜用組成物塗膜的燒成溫度較佳為100~400℃，更佳為100~300℃。這是因為非晶矽、微晶矽或使用這些的混合型矽太陽能電池的耐熱性比較弱，轉換效率因燒成步驟而下降。 As a method of manufacturing the thin film solar cell 20, the method of forming the composite film 21 on the glass substrate 22 in advance before forming the photoelectric conversion layer 24 or the like can more avoid the photoelectric conversion layer 24 when the composition film of the composite film is fired. Deterioration is therefore preferred. However, the composite film 21 can also be formed on the glass substrate 22 on which the photoelectric conversion layer 24 to the conductive reflective film 26 are formed. In this case, the baking temperature of the composition film for a composite film is preferably from 100 to 400 ° C, more preferably from 100 to 300 ° C. This is because the amorphous germanium, the microcrystalline germanium or the hybrid type solar cell using these are relatively weak in heat resistance, and the conversion efficiency is lowered by the firing step.
以下，根據實施例對本發明進行詳細說明， 但本發明並不限定於此。 Hereinafter, the present invention will be described in detail based on embodiments. However, the invention is not limited thereto.
以成為表2~4所示的組成(數值表示質量份)的方式，以合計60g放入200cm3的玻璃瓶中，使用100g直徑為0.3mm的氧化鋯珠(MICROHYCA，昭和殼牌石油公司製)，用塗料攪拌器分散6小時，由此製造實施例1~24、比較例2~9中使用的複合膜用組成物。如以下製造複合膜用組成物的製造中使用的複合膜用組成物原料。 In the case of the composition shown in Tables 2 to 4 (the numerical value indicates the mass parts), a total of 60 g was placed in a 200 cm 3 glass bottle, and 100 g of zirconia beads having a diameter of 0.3 mm (MICROHYCA, manufactured by Showa Shell Oil Co., Ltd.) was used. The composition for a composite film used in Examples 1 to 24 and Comparative Examples 2 to 9 was produced by dispersing for 6 hours with a paint shaker. The raw material for a composite film used for the production of the composition for a composite film is produced as follows.
通過使用500cm3的玻璃製四口燒瓶，加入140g四乙氧基矽烷和140g乙醇進行攪拌的同時，一次性加入將1.5g的85%正磷酸(以下稱為磷酸)溶解於120g純水中的溶液，之後使其在50℃下反應3小時來進行製造。 1.5 g of 85% orthophosphoric acid (hereinafter referred to as phosphoric acid) was dissolved in 120 g of pure water by using a 500 cm 3 glass four-necked flask while adding 140 g of tetraethoxysilane and 140 g of ethanol for stirring. The solution was then subjected to a reaction at 50 ° C for 3 hours to carry out production.
通過使用500cm3的玻璃製四口燒瓶，加入115g四乙氧基矽烷和175g乙醇進行攪拌的同時，一次性加入將1.0g的85%磷酸溶解於110g純水中的溶液，之後使其在50℃下反應3小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, tetraethyl orthosilicate was added 115g and 175g of ethanol, was added in one 1.0g of 85% phosphoric acid were dissolved in 110g of purified water, after which it at 50 The reaction was carried out by reacting at ° C for 3 hours.
通過使用500cm3的玻璃製四口燒瓶，加入130g四乙氧基矽烷和145g乙醇進行攪拌的同時，一次性加入將4.5g的85%磷酸溶解於125g純水中的溶液，之後使其在 45℃下反應3小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, tetraethyl orthosilicate was added 130g and 145g of ethanol, was added in one 4.5g of 85% phosphoric acid were dissolved in 125g of purified water, after which it 45 The reaction was carried out by reacting at ° C for 3 hours.
通過使用500cm3的玻璃製四口燒瓶，加入125g四乙氧基矽烷和160g乙醇進行攪拌的同時，一次性加入將2.1g的85%磷酸溶解於115g純水中的溶液，之後使其在60℃下反應2小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, tetraethyl orthosilicate was added 125g and 160g of ethanol, was added in one 2.1g of 85% phosphoric acid were dissolved in 115g of purified water, after which it at 60 The reaction was carried out by reacting at ° C for 2 hours.
通過使用500cm3的玻璃製四口燒瓶，加入145g四乙氧基矽烷和140g乙醇進行攪拌的同時，一次性加入將0.5g的85%磷酸溶解於115g純水中的溶液，之後使其在55℃下反應3小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, tetraethyl orthosilicate was added 145g and 140g of ethanol, was added in one 0.5g of 85% phosphoric acid were dissolved in 115g of purified water, after which it at 55 The reaction was carried out by reacting at ° C for 3 hours.
通過使用500cm3的玻璃製四口燒瓶，加入140g三甲基甲氧基矽烷和140g甲醇進行攪拌的同時，一次性加入將2.0g的85%磷酸溶解於120g純水中的溶液，之後使其在50℃下反應3小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, trimethyl methoxysilane was added 140g and 140g Silane methanol, 85% phosphoric acid was added in one 2.0g were dissolved in 120g of purified water, after which it The reaction was carried out by reacting at 50 ° C for 3 hours.
通過使用500cm3的玻璃製四口燒瓶，加入140g四乙氧基矽烷和140g乙醇進行攪拌的同時，一次性加入將1.5g的60%硝酸溶解於120g純水中的溶液，之後使其在 50℃下反應3小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, tetraethyl orthosilicate was added 140g ethanol and 140g, 60% nitric acid was added in one 1.5g were dissolved in 120g of purified water, after which it at 50 The reaction was carried out by reacting at ° C for 3 hours.
通過使用500cm3的玻璃製四口燒瓶，加入140g四乙氧基矽烷和140g乙醇進行攪拌的同時，一次性加入將1.5g的35%鹽酸溶解於120g純水中的溶液，之後使其在50℃下反應3小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, tetraethyl orthosilicate was added 140g ethanol and 140g, is added in one 1.5g of 35% hydrochloric acid was dissolved in 120g of purified water, after which it at 50 The reaction was carried out by reacting at ° C for 3 hours.
通過使用500cm3的玻璃製四口燒瓶，加入140g四乙氧基矽烷和140g乙醇進行攪拌的同時，一次性加入將1.5g焦磷酸溶解於120g純水中的溶液，之後使其在50℃下反應3小時來進行製造。 A solution in which 1.5 g of pyrophosphoric acid was dissolved in 120 g of pure water was added at once while using a 500 cm 3 glass four-necked flask, 140 g of tetraethoxysilane and 140 g of ethanol were added thereto, followed by making it at 50 ° C. The reaction was carried out for 3 hours.
通過使用500cm3的玻璃製四口燒瓶，加入140g四乙氧基矽烷和140g乙醇進行攪拌的同時，一次性加入將0.2g的85%正磷酸溶解於120g純水中的溶液，之後使其在50℃下反應3小時來進行製造。 While stirring by using a four-necked glass flask of 500cm 3, tetraethyl orthosilicate was added 140g and 140g of ethanol, was added in one 0.2g of 85% orthophosphoric acid was dissolved in 120g of purified water, then allowed to The reaction was carried out by reacting at 50 ° C for 3 hours.
混合溶劑1使用異丙醇、乙醇及N,N-二甲基甲醯胺的混合液(質量比4：2：1)，混合溶劑2使用乙醇與丁醇的混合液(質量比98：2)。 Mixed solvent 1 uses a mixture of isopropanol, ethanol and N,N-dimethylformamide (mass ratio 4:2:1), and mixed solvent 2 uses a mixture of ethanol and butanol (mass ratio 98:2) ).
實施例1中，以作為分散介質的IPA稀釋混合複合膜用組成物原料1來製造複合膜用組成物。(1)通過濕式塗佈法對用作玻璃基材的折射率為1.55的玻璃基板進行複合膜用組成物的成膜之後，(2)在大氣中，在200℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，由此製造附複合膜的玻璃基材。 In Example 1, a composition for a composite film was produced by diluting the composition raw material 1 for a mixed composite film with IPA as a dispersion medium. (1) After forming a film for a composite film using a glass substrate having a refractive index of 1.55 as a glass substrate by a wet coating method, (2) using a composite film at 200 ° C in the atmosphere The glass substrate of the composition coating film was baked for 30 minutes, thereby producing a glass substrate with a composite film.
實施例2中，以作為分散介質的乙醇稀釋混合複合膜用組成物原料2。並且，以相對於複合膜用組成物為10質量%的比例添加並混合平均粒徑為40nm的日產化學工業(股)製各向異性膠體二氧化矽粒子(產品名：ST-OUP)來製造複合膜用組成物。在150℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Example 2, the composition raw material 2 for the mixed composite film was diluted with ethanol as a dispersion medium. Further, an anisotropic colloidal cerium oxide particle (product name: ST-OUP) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 40 nm was added and mixed at a ratio of 10% by mass to the composition for a composite film. A composition for a composite film. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 150 ° C for 30 minutes.
實施例3中，以作為分散介質的IPA稀釋混合複合膜用組成物原料4來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 3, the composition for composite film 4 was prepared by diluting the composite material 4 for composite film for use in IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例4中，以作為分散介質的乙醇稀釋混合複合膜用組成物原料6來製造複合膜用組成物。在120℃下將具有複合膜用組成物塗膜的玻璃基板燒成60分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In the example 4, the composition for composite film 6 was diluted with ethanol as a dispersion medium, and the composition for composite film was manufactured. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 120 ° C for 60 minutes.
實施例5中，以作為分散介質的混合溶劑1 稀釋混合複合膜用組成物原料3。並且，以相對於複合膜用組成物為10質量%的比例添加並混合平均粒徑為12nm的日產化學工業(股)製各向異性膠體二氧化矽粒子(產品名：IPA-ST-UP)來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 5, the mixed solvent 1 as a dispersion medium The raw material 3 for the composition for the mixed composite film was diluted. In addition, anisotropic colloidal cerium oxide particles (product name: IPA-ST-UP) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 12 nm was added and mixed at a ratio of 10% by mass to the composition for the composite film. To manufacture a composition for a composite film. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例6中，以作為分散介質的乙醇稀釋混合複合膜用組成物原料5來製造複合膜用組成物。在150℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In the example 6, the composition for composite film 5 was diluted with the ethanol as a dispersion medium, and the composition for composite film was manufactured. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 150 ° C for 30 minutes.
實施例7中，以作為分散介質的乙醇稀釋混合複合膜用組成物原料6。並且，以相對於複合膜用組成物為15質量%的比例添加並混合平均粒徑為12nm的日產化學工業(股)製各向異性膠體二氧化矽粒子(產品名：IPA-ST-UP)來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 7, the composition raw material 6 for the mixed composite film was diluted with ethanol as a dispersion medium. In addition, anisotropic colloidal cerium oxide particles (product name: IPA-ST-UP) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 12 nm was added and mixed at a ratio of 15% by mass to the composition for the composite film. To manufacture a composition for a composite film. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例8中，以作為分散介質的混合溶劑2稀釋混合複合膜用組成物原料1來製造複合膜用組成物。在120℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In the example 8, the composition for composite film 1 was diluted with the mixed solvent 2 as a dispersion medium, and the composition for composite film was manufactured. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 120 ° C for 30 minutes.
實施例9中，以作為分散介質的混合溶劑1稀釋混合複合膜用組成物原料4。並且，以相對於複合膜用組成物為5質量%的比例混合平均粒徑為30nm的日產 化學工業(股)製各向異性膠體二氧化矽粒子(產品名：ST-OUP)來製造複合膜用組成物。在180℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In the ninth embodiment, the component raw material 4 for the mixed composite film was diluted with the mixed solvent 1 as a dispersion medium. Further, Nissan having an average particle diameter of 30 nm was mixed at a ratio of 5% by mass based on the composition for the composite film. An anisotropic colloidal cerium oxide particle (product name: ST-OUP) manufactured by Chemical Industry Co., Ltd. is used to manufacture a composition for a composite film. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the coating film for a composite film was baked at 180 ° C for 30 minutes.
實施例10中，以作為分散介質的混合溶劑2稀釋混合複合膜用組成物原料5。並且，以相對於複合膜用組成物為10質量%的比例混合平均粒徑為10nm的日產化學工業(股)製球狀膠體二氧化矽粒子(產品名：ST-O)來製造複合膜用組成物。在180℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Example 10, the component raw material 5 for the mixed composite film was diluted with the mixed solvent 2 as a dispersion medium. In addition, a spherical colloidal cerium oxide particle (product name: ST-O) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 10 nm was mixed at a ratio of 10% by mass to the composition for a composite film to produce a composite film. Composition. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the coating film for a composite film was baked at 180 ° C for 30 minutes.
實施例11中，以作為分散介質的混合溶劑2稀釋混合複合膜用組成物原料3來製造複合膜用組成物。在150℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In the example 11, the composition raw material 3 for the mixed composite film was diluted with the mixed solvent 2 as a dispersion medium to produce a composition for a composite film. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 150 ° C for 30 minutes.
實施例12中，以作為分散介質的乙醇稀釋混合複合膜用組成物原料1。並且，以相對於複合膜用組成物為10質量%的比例混合平均粒徑為6nm的日產化學工業(股)製球狀膠體二氧化矽粒子(產品名：ST-OXS)來製造複合膜用組成物。在200℃下將具有複合膜用組成物塗膜的玻璃基板燒成60分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Example 12, the composition raw material 1 for the mixed composite film was diluted with ethanol as a dispersion medium. In addition, a spherical colloidal cerium oxide particle (product name: ST-OXS) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 6 nm was mixed at a ratio of 10% by mass to the composition for a composite film to produce a composite film. Composition. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 200 ° C for 60 minutes.
實施例13中，以作為分散介質的IPA稀釋混 合複合膜用組成物原料2來製造複合膜用組成物。在150℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Example 13, diluted with IPA as a dispersion medium The composite film composition 2 is used to produce a composite film composition. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 150 ° C for 30 minutes.
實施例14中，以作為分散介質的丁醇稀釋混合複合膜用組成物原料6來製造複合膜用組成物。在180℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In the example 14, the composition for composite film 6 was prepared by diluting the mixed raw material composite material 6 with butanol as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the coating film for a composite film was baked at 180 ° C for 30 minutes.
實施例15中，以作為分散介質的IPA稀釋混合複合膜用組成物原料4。並且，以相對於複合膜用組成物為15質量%的比例混合平均粒徑為10nm的日產化學工業(股)製球狀膠體二氧化矽粒子(產品名：IPA-ST)來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 15, the component raw material 4 for the mixed composite film was diluted with IPA as a dispersion medium. In addition, a spherical colloidal cerium oxide particle (product name: IPA-ST) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 10 nm was mixed at a ratio of 15% by mass to the composition for a composite film to produce a composite film. Composition. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例16中，以作為分散介質的混合溶劑2稀釋混合複合膜用組成物原料6。並且，以相對於複合膜用組成物為10質量%的比例混合平均粒徑為10nm的日產化學工業(股)製球狀膠體二氧化矽粒子(產品名：IPA-ST)來製造複合膜用組成物。在100℃下將具有複合膜用組成物塗膜的玻璃基板燒成60分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Example 16, the composition raw material 6 for the mixed composite film was diluted with the mixed solvent 2 as a dispersion medium. In addition, a spherical colloidal cerium oxide particle (product name: IPA-ST) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 10 nm was mixed at a ratio of 10% by mass to the composition for a composite film to produce a composite film. Composition. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 100 ° C for 60 minutes.
實施例17中，以作為分散介質的混合溶劑1稀釋混合複合膜用組成物原料5。並且，以相對於複合膜 用組成物為15質量%的比例混合平均粒徑為40nm的日產化學工業(股)製各向異性膠體二氧化矽粒子(產品名：ST-OUP)來製造複合膜用組成物。在150℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Example 17, the component raw material 5 for a mixed composite film was diluted with a mixed solvent 1 as a dispersion medium. And relative to the composite membrane An anisotropic colloidal cerium oxide particle (product name: ST-OUP) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 40 nm was mixed at a ratio of 15% by mass of the composition to produce a composition for a composite film. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 150 ° C for 30 minutes.
實施例18中，以作為分散介質的IPA稀釋混合複合膜用組成物原料6。並且，以相對於複合膜用組成物為10質量%的比例混合平均粒徑為6nm的日產化學工業(股)製球狀膠體二氧化矽粒子(產品名：ST-OXS)來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 18, the composition raw material 6 for the mixed composite film was diluted with IPA as a dispersion medium. In addition, a spherical colloidal cerium oxide particle (product name: ST-OXS) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 6 nm was mixed at a ratio of 10% by mass to the composition for a composite film to produce a composite film. Composition. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例19中，以作為分散介質的混合溶劑1稀釋混合複合膜用組成物原料3。並且，以相對於複合膜用組成物為10質量%的比例混合平均粒徑為30nm的日產化學工業(股)製各向異性膠體二氧化矽粒子(產品名：ST-OUP)來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 19, the component raw material 3 for the mixed composite film was diluted with the mixed solvent 1 as a dispersion medium. Further, an anisotropic colloidal cerium oxide particle (product name: ST-OUP) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 30 nm was mixed at a ratio of 10% by mass to the composition for a composite film to produce a composite film. Use the composition. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例20中，以作為分散介質的IPA稀釋混合複合膜用組成物原料1。並且，以相對於複合膜用組成物為15質量%的比例混合平均粒徑為45nm的日產化學工業(股)製球狀膠體二氧化矽粒子(產品名：IPA-ST-L)來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 20, the composition raw material 1 for the mixed composite film was diluted with IPA as a dispersion medium. Further, a composite of spherical colloidal cerium oxide particles (product name: IPA-ST-L) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 45 nm was mixed at a ratio of 15% by mass to the composition for a composite film. Membrane composition. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例21中，以作為分散介質的IPA稀釋混 合複合膜用組成物原料1。並且，以相對於複合膜用組成物為40質量%的比例混合平均粒徑為30nm的日產化學工業(股)製各向異性膠體二氧化矽粒子(產品名：ST-OUP)來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 21, diluted with IPA as a dispersion medium The composition raw material 1 for the composite film. Further, an anisotropic colloidal cerium oxide particle (product name: ST-OUP) manufactured by Nissan Chemical Industries Co., Ltd. having an average particle diameter of 30 nm was mixed at a ratio of 40% by mass to the composition for a composite film to produce a composite film. Use the composition. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例22中，以作為分散介質的IPA稀釋混合複合膜用組成物原料9來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Example 22, a composition for a composite film was produced by diluting the composition raw material 9 for a mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1.
實施例23中，以作為分散介質的乙醇稀釋混合複合膜用組成物原料1來製造複合膜用組成物。在120℃下將具有複合膜用組成物塗膜的玻璃基板燒成40分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In the example 23, the composition for composite film 1 was prepared by diluting the raw material 1 for a mixed composite film with ethanol as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 120 ° C for 40 minutes.
實施例24中，以作為分散介質的IPA稀釋混合複合膜用組成物原料1來製造複合膜用組成物。在500℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Example 24, a composition for a composite film was produced by diluting the composition raw material 1 for a mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 500 ° C for 30 minutes.
比較例1中，實施不進行複合膜用組成物的成膜的玻璃單一組分的評估。 In Comparative Example 1, evaluation of a glass single component in which film formation of the composite film composition was not performed was carried out.
比較例2中，以作為分散介質的IPA稀釋混合複合膜用組成物原料7來製造複合膜用組成物。與實施 例1相同地製造附複合膜的玻璃基材。 In Comparative Example 2, a composition for a composite film was prepared by diluting the composition raw material 7 for a mixed composite film with IPA as a dispersion medium. And implementation In the same manner as in Example 1, a glass substrate with a composite film was produced.
比較例3中，以作為分散介質的IPA稀釋混合複合膜用組成物原料8來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Comparative Example 3, a composition for a composite film was produced by diluting the composition raw material 8 for a mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1.
比較例4中，以作為分散介質的IPA稀釋混合複合膜用組成物原料10來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Comparative Example 4, a composition for a composite film was produced by diluting the composition raw material 10 for a mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1.
比較例5中，以作為分散介質的IPA稀釋混合複合膜用組成物原料3來製造複合膜用組成物。與實施例1相同地製造附複合膜的玻璃基材。 In Comparative Example 5, the composition for composite film 3 was prepared by diluting the composition raw material 3 for mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1.
比較例6中，以作為分散介質的IPA稀釋混合複合膜用組成物原料5來製造複合膜用組成物。在100℃下將具有複合膜用組成物塗膜的玻璃基板燒成20分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Comparative Example 6, the composition for composite film 5 was prepared by diluting the composite material 5 for a composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 100 ° C for 20 minutes.
比較例7中，以作為分散介質的IPA稀釋混合複合膜用組成物原料3來製造複合膜用組成物。在200℃下將具有複合膜用組成物塗膜的玻璃基板燒成70分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Comparative Example 7, the composition for composite film 3 was prepared by diluting the composition raw material 3 for mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 200 ° C for 70 minutes.
比較例8中，以作為分散介質的IPA稀釋混合複合膜用組成物原料1來製造複合膜用組成物。在80℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基 材。 In Comparative Example 8, a composition for a composite film was produced by diluting the composition raw material 1 for a mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 80 ° C for 30 minutes. material.
比較例9中，以作為分散介質的IPA稀釋混合複合膜用組成物原料1來製造複合膜用組成物。在550℃下將具有複合膜用組成物塗膜的玻璃基板燒成30分鐘，除此以外，與實施例1相同地製造附複合膜的玻璃基材。 In Comparative Example 9, a composition for a composite film was produced by diluting the composition raw material 1 for a mixed composite film with IPA as a dispersion medium. A glass substrate with a composite film was produced in the same manner as in Example 1 except that the glass substrate having the composition film for a composite film was baked at 550 ° C for 30 minutes.
如下進行Na、Ca的定量分析。首先，利用(股)理學製波長分散型X射線螢光分析裝置(型號：ZSX-Primus II)確認能夠檢測的元素。接著，對檢測出的各元素進行定量分析，Si設為SiO2、Na設為Na2O、Ca設為CaO，K設為K2O、Al設為Al2O3、Fe設為Fe2O3、B設為B2O3、Pb設為PbO、Ti設為TiO2、Zn設為ZnO、Sb設為Sb2O3、Ba設為BaO、Mn設為MnO、Sr設為SrO，對於這些以外的元素設為自然界中存在最多的氧化物來進行計算。在表2~4中示出Na和Ca的相對於玻璃基材的含量。 Quantitative analysis of Na and Ca was carried out as follows. First, the elements that can be detected are confirmed by a wavelength dispersion type X-ray fluorescence analyzer (model: ZSX-Primus II). Next, quantitative analysis was performed on each element detected, Si was SiO 2 , Na was Na 2 O, Ca was CaO, K was K 2 O, Al was Al 2 O 3 , and Fe was Fe 2 . O 3 and B are B 2 O 3 , Pb is PbO, Ti is TiO 2 , Zn is ZnO, Sb is Sb 2 O 3 , Ba is BaO, Mn is MnO, and Sr is SrO. The calculation is performed by setting the elements other than these to be the most abundant oxides in nature. The contents of Na and Ca relative to the glass substrate are shown in Tables 2 to 4.
以觀察用途來加工包括玻璃基材、擴散抑制膜、抗反射膜的界面部分在內的剖面，使用日本電子(股)製場發射型透射電子顯微鏡(型號：JEM-2010F)來觀察擴散抑制膜及抗反射膜。同時，使用日本電子(股)製場發射型透射電子顯微鏡(型號：JEM-2010F)附屬的能量分散型X射線光 譜分析裝置，以加速電壓：200kV、探針直徑：1nm的測定條件進行擴散抑制膜及抗反射膜中的P的定量分析，由測定5次的平均值求得。在表2~4中示出這些結果。 The cross section including the glass substrate, the diffusion suppression film, and the interface portion of the antireflection film was processed for observation purposes, and a diffusion electron microscope (Model: JEM-2010F) was used to observe the diffusion suppression film. And anti-reflective film. At the same time, energy dispersive X-ray light attached to a field emission type transmission electron microscope (model: JEM-2010F) manufactured by JEOL Ltd. In the spectrum analyzer, quantitative analysis of P in the diffusion suppression film and the antireflection film was carried out under the measurement conditions of an acceleration voltage of 200 kV and a probe diameter of 1 nm, and the average value of the measurement was obtained five times. These results are shown in Tables 2 to 4.
通過使用日本電子(股)製場發射型透射電子顯微鏡(型號：JEM-2010F)進行的剖面觀察來測定擴散抑制膜的膜厚。並且，通過使用日立高科技公司製掃描型電子顯微鏡(型號：S-4300、SU-8000)進行的剖面觀察來測定抗反射膜(以下稱為AR膜)的膜厚。在表2~4中示出這些結果。 The film thickness of the diffusion-suppressing film was measured by cross-sectional observation using a field emission type transmission electron microscope (Model: JEM-2010F) manufactured by Nippon Electronics Co., Ltd. In addition, the film thickness of the antireflection film (hereinafter referred to as AR film) was measured by cross-sectional observation using a scanning electron microscope (Model: S-4300, SU-8000) manufactured by Hitachi High-Technologies Corporation. These results are shown in Tables 2 to 4.
作為塑料及透明材料的一般試驗方法即JIS K 7136中規定的霧度獲取方法試驗、及JIS K 7361-1中規定的總透光率試驗，使用Suga Test Instruments Co.,Ltd.製霧度計(型號：HZ-2)測定複合膜的霧度(混濁程度)。霧度(單位：%)是指以以下公式表示的表示透明材料的濁度(混濁程度)的值。 As a general test method for plastics and transparent materials, the haze acquisition method test specified in JIS K 7136 and the total light transmittance test specified in JIS K 7361-1, a haze meter manufactured by Suga Test Instruments Co., Ltd. (Model: HZ-2) The haze (degree of turbidity) of the composite film was measured. The haze (unit: %) is a value indicating the turbidity (degree of turbidity) of the transparent material expressed by the following formula.
霧度=Td/Tt×100(公式中，Td為擴散透射率(單位：%)，Tt為總透光率(單位：%))使用上述霧度計能夠同時測定擴散透射率、總透光率及霧度。用上述霧度計對起始樣品和進行1000小時 上述高溫高濕試驗後的樣品進行測定。在表2~4中示出這些結果。 Haze=Td/Tt×100 (In the formula, Td is the diffuse transmittance (unit: %), and Tt is the total light transmittance (unit: %)). The above-mentioned haze meter can simultaneously measure the diffuse transmittance and the total light transmittance. Rate and haze. The starting sample was subjected to 1000 hours using the above haze meter. The sample after the above high temperature and high humidity test was measured. These results are shown in Tables 2 to 4.
使用分光偏振光分析測定裝置(J.A.Woollam Japan(股)製M-2000)測定複合膜的折射率，並採用分析後的光學常數中的633nm的值。並且，使用日立高科技公司製分光光度計(型號：U-4100)測定附複合膜的玻璃基材的起始透射率，在太陽能電池用途中，透射率變得重要的340~750nm範圍內成為中間值的550nm的透射率(單位：%)的值進行評估。在表2~4中示出這些結果。 The refractive index of the composite film was measured using a spectroscopic polarization analyzer (M-2000 manufactured by J.A. Woollam Japan Co., Ltd.), and a value of 633 nm in the optical constant after the analysis was used. In addition, the initial transmittance of the glass substrate with the composite film was measured using a spectrophotometer (model: U-4100) manufactured by Hitachi High-Tech Co., Ltd., and in the solar cell application, the transmittance became important in the range of 340 to 750 nm. The value of the transmittance (unit: %) of 550 nm of the intermediate value was evaluated. These results are shown in Tables 2 to 4.
並且，將JIS C 8938中規定的高溫高濕試驗作為太陽能電池的壽命評估方法，在85℃且85℃ %RH的溫濕度條件下保持恆定的ESPEC(股)製恆溫恆濕機(型號：PL-1KP)中，將樣品保持1000小時後，用上述的分光光度計測定從恆溫恆濕機取出後恢複室溫的樣品的550nm的透射率，並計算[(高溫高濕試驗後的透射率)/(起始透射率)]。並且，在表2~4中示出這些結果。另外，在表2~4中，將[(高溫高濕試驗後的透射率)/(起始透射率)]記載為高溫高濕試驗後/起始。 In addition, the high-temperature and high-humidity test specified in JIS C 8938 is used as a method for evaluating the life of a solar cell, and a constant temperature and humidity machine (model: PL) is kept at a constant temperature and humidity of 85 ° C and 85 ° C % RH. In -1KP), after the sample was held for 1000 hours, the transmittance at 550 nm of the sample which was returned to the room temperature after being taken out from the constant temperature and humidity machine was measured by the above spectrophotometer, and [[transmittance after high temperature and high humidity test] was calculated. / (initial transmittance)]. Further, these results are shown in Tables 2 to 4. In addition, in Tables 2 to 4, [(transmittance after high temperature and high humidity test) / (initial transmittance)] is described as after/starting after high temperature and high humidity test.
將JIS K 5600中規定的劃痕硬度(鉛筆法)試驗作為塗膜的一般評估法，使用Coating Tester Kougyo,Inc.製手動式鉛筆劃痕試驗儀，以荷載750g、角度45°用三菱鉛筆製劃痕試驗用鉛筆測定AR膜的硬度。在表2~4中示出這些結果。 The scratch hardness (pencil method) test specified in JIS K 5600 was used as a general evaluation method for a coating film, and a manual pencil scratch tester manufactured by Coating Tester Kougyo, Inc. was used, and a Mitsubishi pencil was used for the load of 750 g and an angle of 45°. Trace test The hardness of the AR film was measured with a pencil. These results are shown in Tables 2 to 4.
從表2~4可知，實施例1~24中製造的所有複合膜中形成有含有0.1~0.7原子%的P的抗反射膜和含有1.0~12.0原子%的P的擴散抑制膜，起始霧度為0.01~0.04%，在高溫高濕試驗後抗反射膜也不會產生白濁，高溫高濕試驗後的霧度為0.04~0.14%。並且，實施例1~24中製造的所有複合膜中，起始透射率較高為92.5~94.7%，且由於在高溫高濕試驗後抗反射膜不會產生白濁，因此[(高溫高濕試驗後的透射率)/(起始透射率)]也較高為98.4~99.9%，具有高耐久性。並且，由相對於複合膜用組成物含有10~15質量份的平均粒徑為6~40nm的成分(C)的實施例2、5、7、10、12、15~19的複合膜用組成物製造的AR膜的硬度較高為9H。相對於此，未形成複合膜的比較例1中，在高溫高濕試驗後抗反射膜產生白濁，高溫高濕試驗後的霧度為10%以上，起始透射率較低為91.0%，由於在高溫高濕試驗後抗反射膜產生白濁，因此[(高溫高濕試驗後的透射率)/(起始透射率)]也較低為96.7%。由使用硝酸來代替(B)成分的複合膜用組成物製造的比較例2中未形成擴散抑制膜，因此並不形成複合膜，在高溫高濕試驗後抗反射膜產生白濁，高溫高濕試驗後的霧度為1.47%，[(高溫高濕試驗後的透射率)/(起始透射率)]為96.8%，不具有高耐久性。由使用鹽酸來代替(B)成分的複合膜用組成物製造的比較例3中未形成擴散抑制膜，因此並不形成複合膜，在高溫高濕試驗後抗反射膜產生白濁，高溫高濕試驗後的霧度為1.07%，[(高溫高濕試 驗後的透射率)/(起始透射率)]為97.9%，不具有高耐久性。由(B)成分含量過低的複合膜用組成物製造的比較例4中未形成擴散抑制膜，因此並不形成複合膜，在高溫高濕試驗後抗反射膜產生白濁，高溫高濕試驗後的霧度為0.91%，[(高溫高濕試驗後的透射率)/(起始透射率)]為97.3%，不具有高耐久性。由(B)成分含量過高的複合膜用組成物製造的比較例5的複合膜中，起始透射率較低為90.8%。並且，燒成時間較短、擴散抑制膜的P含量低於1原子%的比較例6的複合膜中，在高溫高濕試驗後抗反射膜稍微產生白濁，高溫高濕試驗後的霧度為0.33%，[(高溫高濕試驗後的透射率)/(起始透射率)]為97.7%，不具有高耐久性。另一方面，擴散抑制膜的P含量多於12原子%的比較例7的複合膜中，起始透射率較低為91.3%。燒成溫度為80℃的比較例8中，擴散抑制膜中的P含量較低，且在高溫高濕試驗後在抗反射膜中可觀察到輕微的白濁，高溫高濕試驗後的霧度為0.20%，[(高溫高濕試驗後的透射率)/(起始透射率)]為98.2%，並且，複合膜的硬度並不充分。燒成溫度為550℃的比較例9中，在玻璃基板上稍微產生翹曲。 As is apparent from Tables 2 to 4, all of the composite films produced in Examples 1 to 24 were formed with an antireflection film containing 0.1 to 0.7 at% of P and a diffusion suppressing film containing 1.0 to 12.0 at% of P, and initial fog. The degree is 0.01 to 0.04%, and the antireflection film does not cause white turbidity after the high temperature and high humidity test, and the haze after the high temperature and high humidity test is 0.04 to 0.14%. Further, in all of the composite films produced in Examples 1 to 24, the initial transmittance was as high as 92.5 to 94.7%, and since the antireflection film did not cause white turbidity after the high temperature and high humidity test, [(high temperature and high humidity test) The subsequent transmittance) / (initial transmittance) is also higher at 98.4 to 99.9%, and has high durability. Further, it is composed of a composite film of Examples 2, 5, 7, 10, 12, and 15 to 19 containing 10 to 15 parts by mass of the component (C) having an average particle diameter of 6 to 40 nm with respect to the composition for a composite film. The hardness of the AR film produced was as high as 9H. On the other hand, in Comparative Example 1 in which the composite film was not formed, the antireflection film was white turbid after the high temperature and high humidity test, and the haze after the high temperature and high humidity test was 10% or more, and the initial transmittance was as low as 91.0% due to The antireflection film produced white turbidity after the high temperature and high humidity test, so [(transmittance after high temperature and high humidity test) / (initial transmittance)] was also as low as 96.7%. In Comparative Example 2 produced by using a composition for a composite film using nitric acid instead of the component (B), a diffusion inhibiting film was not formed, so that a composite film was not formed, and the antireflection film was white turbid after the high temperature and high humidity test, and the high temperature and high humidity test was performed. The latter haze was 1.47%, and [(transmittance after high temperature and high humidity test) / (initial transmittance)] was 96.8%, and it did not have high durability. In Comparative Example 3 produced by using a composition for a composite film using hydrochloric acid instead of the component (B), a diffusion inhibiting film was not formed, so that a composite film was not formed, and the antireflection film was white turbid after the high temperature and high humidity test, and the high temperature and high humidity test was performed. The haze afterwards is 1.07%, [(high temperature and high humidity test) The transmittance after the test) / (initial transmittance) was 97.9%, and did not have high durability. In Comparative Example 4, which was produced from the composition for a composite film having a low content of the component (B), the diffusion inhibiting film was not formed, so that the composite film was not formed, and the antireflection film was white turbid after the high temperature and high humidity test, after the high temperature and high humidity test. The haze was 0.91%, and [(transmittance after high-temperature and high-humidity test) / (initial transmittance)] was 97.3%, and it did not have high durability. In the composite film of Comparative Example 5 produced from the composition for a composite film having an excessively high content of the component (B), the initial transmittance was as low as 90.8%. Further, in the composite film of Comparative Example 6 in which the firing time was short and the P content of the diffusion suppression film was less than 1 atom%, the antireflection film slightly turbid after the high temperature and high humidity test, and the haze after the high temperature and high humidity test was 0.33%, [(transmittance after high-temperature and high-humidity test) / (initial transmittance)] was 97.7%, and did not have high durability. On the other hand, in the composite film of Comparative Example 7 in which the P content of the diffusion-inhibiting film was more than 12 atom%, the initial transmittance was as low as 91.3%. In Comparative Example 8 in which the firing temperature was 80 ° C, the P content in the diffusion suppressing film was low, and slight white turbidity was observed in the antireflection film after the high temperature and high humidity test, and the haze after the high temperature and high humidity test was 0.20%, [(transmittance after high temperature and high humidity test) / (initial transmittance)] was 98.2%, and the hardness of the composite film was not sufficient. In Comparative Example 9 in which the firing temperature was 550 ° C, warpage slightly occurred on the glass substrate.
1‧‧‧具備複合膜的玻璃基材 1‧‧‧Glass substrate with composite film
2‧‧‧玻璃基材 2‧‧‧glass substrate
3‧‧‧抗反射膜 3‧‧‧Anti-reflective film
4‧‧‧擴散抑制膜 4‧‧‧Diffusion suppression film
5‧‧‧複合膜 5‧‧‧Composite film
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| JP2012239662A JP2014088287A (en) | 2012-10-30 | 2012-10-30 | Composite film composed of antireflection film and diffusion suppression film, and method for manufacturing glass substrate comprising composite film |
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| CN100447583C (en) * | 2007-03-30 | 2008-12-31 | 厦门大学 | Double-layer anti-reflection film for ultraviolet detector and its preparation method |
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