JP6826363B2 - Manufacturing method of antireflection film - Google Patents
Manufacturing method of antireflection film Download PDFInfo
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- JP6826363B2 JP6826363B2 JP2015181388A JP2015181388A JP6826363B2 JP 6826363 B2 JP6826363 B2 JP 6826363B2 JP 2015181388 A JP2015181388 A JP 2015181388A JP 2015181388 A JP2015181388 A JP 2015181388A JP 6826363 B2 JP6826363 B2 JP 6826363B2
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- JP
- Japan
- Prior art keywords
- film
- sol
- acidic
- treatment
- antireflection film
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 173
- 230000002378 acidificating effect Effects 0.000 claims description 76
- 239000000377 silicon dioxide Substances 0.000 claims description 71
- 239000003054 catalyst Substances 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- 230000003301 hydrolyzing effect Effects 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000004965 Silica aerogel Substances 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 230000003449 preventive effect Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 description 152
- 239000010410 layer Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 38
- 239000000463 material Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000002585 base Substances 0.000 description 16
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- 230000000694 effects Effects 0.000 description 15
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- 230000007062 hydrolysis Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
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- 239000002245 particle Substances 0.000 description 11
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- 125000004432 carbon atom Chemical group C* 0.000 description 5
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- 229910052814 silicon oxide Inorganic materials 0.000 description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- 229910001635 magnesium fluoride Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-UHFFFAOYSA-N 0.000 description 2
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- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
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- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
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- FHSWXOCOMAVQKE-UHFFFAOYSA-N phenylazanium;acetate Chemical compound CC([O-])=O.[NH3+]C1=CC=CC=C1 FHSWXOCOMAVQKE-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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- 239000005297 pyrex Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 125000005372 silanol group Chemical group 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
本発明は、ナノサイズの微細孔を有し、低屈折率及び優れた耐擦傷性を有するシリカエアロゲル膜を有する反射防止膜の製造方法に関する。 The present invention relates to a method for producing an antireflection film having a silica airgel film having nano-sized micropores, a low refractive index and excellent scratch resistance.
反射防止膜は真空蒸着、スパッタリング、イオンプレーティング等の物理蒸着法や、ゾルゲル法等の液相法により成膜される。反射防止膜は基材より小さな屈折率を有する必要があり、例えばガラスやプラスチック（屈折率：約1.5〜1.9）を基材として用いた場合、反射防止膜にとって理想の屈折率は1.2〜1.25である。物理蒸着法で反射防止膜を形成する場合、最も小さな屈折率を有する材料（MgF2）を用いても屈折率は1.38と比較的大きく、可視光領域（波長：400〜700 nm）における反射率は1％以上となってしまう。 The antireflection film is formed by a physical vapor deposition method such as vacuum deposition, sputtering, or ion plating, or a liquid phase method such as a sol-gel method. The antireflection film must have a lower refractive index than the base material. For example, when glass or plastic (refractive index: about 1.5 to 1.9) is used as the base material, the ideal refractive index for the antireflection film is 1.2 to 1.25. is there. When the antireflection film is formed by the physical vapor deposition method, the refractive index is relatively large at 1.38 even if the material having the smallest refractive index (MgF 2 ) is used, and the reflectance in the visible light region (wavelength: 400 to 700 nm). Will be over 1%.
ゾルゲル法により得られるシリカエアロゲル膜は、物理蒸着法で得られるMgF2より小さな屈折率を有する。反射防止膜に使用できるエアロゲルを製造する方法として、米国特許5,948,482号（特許文献１）は、SiO2を含むゾルを熟成してゲルにした後、表面を有機基で修飾して得られる反応物を用いてシリカエアロゲル膜を製造する方法を記載している。この製造方法によって形成されるシリカエアロゲル膜は、99％以上の気孔率を有し低い屈折率を示す。しかしながら、このシリカエアロゲル膜は機械的強度が著しく低く、耐擦傷性に欠けるという問題がある。 The silica airgel film obtained by the sol-gel method has a refractive index smaller than that of MgF 2 obtained by the physical vapor deposition method. As a method for producing an airgel that can be used as an antireflection film, US Pat. No. 5,948,482 (Patent Document 1) is a reaction product obtained by aging a sol containing SiO 2 to form a gel and then modifying the surface with an organic group. Describes a method for producing a silica airgel film using the above. The silica airgel film formed by this production method has a porosity of 99% or more and a low refractive index. However, this silica airgel film has a problem that its mechanical strength is extremely low and it lacks scratch resistance.
「ジャーナル・オブ・ゾルゲル・サイエンス・アンド・テクノロジー（Journal of Sol-Gel Science and Technology）」，2000年，第18巻，219〜224頁（非特許文献１）は、耐擦傷性に優れたナノポーラスシリカ膜を作製する方法を提案している。このナノポーラスシリカ膜は、テトラエトキシシランをエタノール／水混合溶媒中でアンモニアにより80℃で2〜20時間加水分解及び縮重合してアルカリ性ゾルを調製し、これにテトラエトキシシラン、水及び塩酸を加えて60℃で15日間熟成し、得られたゾルを基板上に塗布し、80℃で30分間乾燥した後、アンモニア・水蒸気混合ガス中又は大気中で熱処理（400℃で30分間）することにより形成する。しかしながら、この方法は熟成に15日間もの時間を要するため生産効率が低いのみならず、得られるナノポーラスシリカ膜は特にカメラのレンズ等の光学素子用の反射防止膜として使用するには耐擦傷性が不十分である。さらに、このような多孔質膜は製造後の時間の経過により屈折率が変動し、所望の反射防止性能が得られなくなるといった問題がある。 "Journal of Sol-Gel Science and Technology", 2000, Vol. 18, pp. 219-224 (Non-Patent Document 1) is a nanoporous with excellent scratch resistance. We are proposing a method for producing a silica film. This nanoporous silica film is prepared by hydrolyzing and shrink-polymerizing tetraethoxysilane with ammonia in an ethanol / water mixed solvent at 80 ° C. for 2 to 20 hours to prepare an alkaline sol, to which tetraethoxysilane, water and hydrochloric acid are added. Aged at 60 ° C for 15 days, the obtained sol is applied onto a substrate, dried at 80 ° C for 30 minutes, and then heat-treated in an ammonia / steam mixed gas or in the air (400 ° C for 30 minutes). Form. However, this method requires as long as 15 days for aging, so not only is the production efficiency low, but the obtained nanoporous silica film is scratch resistant, especially when used as an antireflection film for optical elements such as camera lenses. Insufficient. Further, such a porous film has a problem that the refractive index fluctuates with the passage of time after production, and a desired antireflection performance cannot be obtained.
特開平9-1064号（特許文献２）は、テトラアルコキシシランの塩基性縮合組成物と酸性縮合組成物とを混合して得られる縮合組成物に、さらにアルキルアルコキシシランの縮合組成物を混合して得られる縮合組成物を基材上に塗布してなる塗布物を相対湿度70％以上の環境下に置くこと（湿度処理）により、反射防止効果の経時変化の少ない被膜が得られると記載している。しかしながら特許文献２に記載の方法は、湿度処理に時間がかかるため非常に生産性が低い。さらに特許文献２には、前記処理時間が短い場合、経時変化の変動を防止する効果が不十分であるため、さらに光照射する必要があると記載しており、生産性を向上させるためには新たな製造工程を追加する必要があり現行の設備のままでは対応が困難である。 Japanese Patent Application Laid-Open No. 9-1064 (Patent Document 2) further mixes a condensation composition of alkylalkoxysilane with a condensation composition obtained by mixing a basic condensation composition of tetraalkoxysilane and an acidic condensation composition. It is stated that by applying the condensation composition obtained above on a substrate and placing the coating in an environment with a relative humidity of 70% or more (humidity treatment), a film having a small antireflection effect with time can be obtained. ing. However, the method described in Patent Document 2 is very low in productivity because the humidity treatment takes time. Further, Patent Document 2 describes that when the processing time is short, the effect of preventing fluctuations in changes over time is insufficient, and therefore it is necessary to further irradiate with light, in order to improve productivity. It is necessary to add a new manufacturing process, and it is difficult to deal with it with the current equipment.
特開2009-75583号（特許文献３）は、順次塩基性触媒及び酸性触媒の存在下でアルコキシシランを加水分解・重合してなる第一の酸性ゾルと、酸性触媒の存在下でアルコキシシランを加水分解・重合してなる第二の酸性ゾルとを混合することにより、低屈折率及び優れた耐擦傷性を有するシリカエアロゲル膜を効率良く製造することができると記載している。 Japanese Patent Application Laid-Open No. 2009-75583 (Patent Document 3) describes a first acidic sol obtained by hydrolyzing and polymerizing an alkoxysilane in the presence of a basic catalyst and an acidic catalyst, and an alkoxysilane in the presence of an acidic catalyst. It is described that a silica airgel film having a low refractive index and excellent scratch resistance can be efficiently produced by mixing with a second acidic sol obtained by hydrolysis and polymerization.
特開2009-258711号（特許文献４）は、順次塩基性触媒及び酸性触媒の存在下でアルコキシシランを加水分解・重合した第一の酸性ゾルと、酸性触媒の存在下でアルコキシシランを加水分解・重合した第二の酸性ゾルとを混合し、得られた混合ゾルを基材に塗布し、得られたシリカエアロゲル膜をアルカリで処理すると、比較的短い時間で、低屈折率及び優れた耐擦傷性を有するシリカエアロゲル膜を形成することができると記載している。 Japanese Patent Application Laid-Open No. 2009-258711 (Patent Document 4) describes a first acidic sol obtained by hydrolyzing and polymerizing an alkoxysilane in the presence of a basic catalyst and an acidic catalyst, and an alkoxysilane hydrolyzed in the presence of an acidic catalyst. -Mixing with the polymerized second acidic sol, applying the obtained mixed sol to the base material, and treating the obtained silica airgel film with alkali, it has a low refractive index and excellent resistance in a relatively short time. It is stated that a scratchable silica airgel film can be formed.
特開2010-204394号（特許文献５）は、アルコキシシランを塩基性触媒下で加水分解及び縮重合して調製したアルカリ性ゾルに、さらに酸性溶液を添加して得られた第一の酸性ゾル、及びアルコキシシランを酸性触媒下で加水分解及び縮重合して得られた第二の酸性ゾルを混合してなる混合ゾルを、基板上に塗布及び乾燥した後、高湿度条件に保存することにより、機械的強度が向上し、さらに屈折率の時間変動が小さいシリカエアロゲル膜が得られると記載している。 Japanese Patent Application Laid-Open No. 2010-204394 (Patent Document 5) describes a first acidic sol obtained by further adding an acidic solution to an alkaline sol prepared by hydrolyzing and decomposing alkoxysilane under a basic catalyst. And a mixed sol formed by mixing a second acidic sol obtained by hydrolyzing and shrink-polymerizing alkoxysilane under an acidic catalyst is applied on a substrate, dried, and then stored under high humidity conditions. It is stated that a silica airgel film with improved mechanical strength and less time variation in refractive index can be obtained.
しかしながら、引用文献３〜５の実施例に記載の方法で製造した場合、シリカエアロゲル膜表面に、数10〜数100 nmのクラックが発生することが分かった。これらのマイクロクラックは、可視光の散乱を起こさない程度の大きさであるが、機械的強度を低下させるとともに、湿度変化による反射防止効果の変動の原因となるため、このようなマイクロクラックが発生しない製造法の開発が望まれている。 However, it was found that cracks of several tens to several hundreds nm occur on the surface of the silica airgel film when produced by the method described in Examples of References 3 to 5. Although these microcracks are large enough not to cause scattering of visible light, such microcracks occur because they reduce the mechanical strength and cause fluctuations in the antireflection effect due to changes in humidity. It is desired to develop a manufacturing method that does not.
従って、本発明の目的は、優れた耐擦傷性を有し屈折率の変動が少ない低屈折率シリカエアロゲル膜を有する反射防止膜を、前記シリカエアロゲル膜の表面にマクロクラックが発生しないように製造する方法、並びにこの方法により形成された反射防止膜、及びこの反射防止膜を有する光学素子を提供することである。 Therefore, an object of the present invention is to manufacture an antireflection film having a low refractive index silica airgel film having excellent scratch resistance and little fluctuation in the refractive index so that macrocracks do not occur on the surface of the silica airgel film. It is an object of the present invention to provide an antireflection film formed by this method, and an optical element having the antireflection film.
上記目的に鑑み鋭意研究の結果、本発明者等は、アルコキシシランを塩基性触媒下で加水分解及び縮重合して調製したアルカリ性ゾルに、さらに酸性溶液を添加して得られた第一の酸性ゾル、及びアルコキシシランを酸性触媒下で加水分解及び縮重合して得られた第二の酸性ゾルを混合してなる混合ゾルを、基材上に塗布した後、前記混合ゾルの塗布物が乾燥する前に高湿度条件に保存することにより、形成されるシリカエアロゲル膜の機械的強度が向上し、さらに屈折率の時間変動が小さくなることを見出し、本発明に想到した。 As a result of diligent research in view of the above objectives, the present inventors have obtained the first acidity obtained by further adding an acidic solution to an alkaline sol prepared by hydrolyzing and polycondensing alkoxysilane under a basic catalyst. A mixed sol obtained by mixing a sol and a second acidic sol obtained by hydrolyzing and polycondensing an alkoxysilane under an acidic catalyst is applied onto a substrate, and then the coated material of the mixed sol is dried. We have found that the mechanical strength of the formed silica airgel film is improved and the time variation of the refractive index is reduced by storing the sol in a high humidity condition, and the present invention has been conceived.
すなわち、シリカエアロゲル膜を少なくとも一層有する反射防止膜を製造する本発明の方法は、前記シリカエアロゲル膜を、アルコキシシランを塩基性触媒下で加水分解及び縮重合して調製したアルカリ性ゾルに、さらに酸性溶液を添加して得られたメジアン径100 nm以下の第一の酸性ゾル、及びアルコキシシランを酸性触媒下で加水分解及び縮重合して得られたメジアン径10 nm以下の第二の酸性ゾルを混合してなる混合ゾルを、基材上に塗布し、前記混合ゾルが乾燥する前に、温度35℃以上、相対湿度70％以上の環境に載置し、30分以上保存する湿度処理を施して形成することを特徴とする。 That is, the method of the present invention for producing an antireflection film having at least one silica aerogel film is further acidic to an alkaline sol prepared by hydrolyzing and polycondensing the silica airgel film under a basic catalyst. A first acidic sol with a median diameter of 100 nm or less obtained by adding a solution, and a second acidic sol with a median diameter of 10 nm or less obtained by hydrolyzing and polycondensing alkoxysilane under an acidic catalyst. The mixed sol to be mixed is applied onto a substrate, and before the mixed sol dries, it is placed in an environment with a temperature of 35 ° C. or higher and a relative humidity of 70% or higher, and subjected to humidity treatment for storage for 30 minutes or longer. It is characterized by forming.
前記湿度処理を施した後に、100℃以上の加熱処理及びアルカリ処理を行うのが好ましい。 After the humidity treatment, it is preferable to perform a heat treatment at 100 ° C. or higher and an alkali treatment.
前記アルカリ処理は、アルカリ溶液を塗布、又はアンモニア雰囲気中に載置することにより行うのが好ましい。 The alkaline treatment is preferably carried out by applying an alkaline solution or placing it in an ammonia atmosphere.
前記湿度処理の時間は５〜48時間であるのが好ましい。 The time of the humidity treatment is preferably 5 to 48 hours.
本発明の方法により形成されるシリカエアロゲル膜は、低屈折率及び優れた耐擦傷性を有するとともに、マイクロクラックの発生が少なく、屈折率の時間変動が少ないため、得られる反射防止膜は高い反射防止効果及び高い保存安定性を有する。このためこの反射防止膜は広い分野の光学素子に好適である。 The silica airgel film formed by the method of the present invention has a low refractive index and excellent scratch resistance, less microcracks occur, and the refractive index does not fluctuate with time. Therefore, the obtained antireflection film has high reflection. Has a preventive effect and high storage stability. Therefore, this antireflection film is suitable for optical elements in a wide range of fields.
[1] 反射防止膜の製造方法
本発明は、シリカエアロゲル膜を少なくとも一層有する反射防止膜を製造する方法であり、(1)アルコキシシランを塩基性触媒下で加水分解及び縮重合して調製したアルカリ性ゾルに、さらに酸性溶液を添加してメジアン径100 nm以下の第一の酸性ゾルを得る工程、(2)アルコキシシランを酸性触媒下で加水分解及び縮重合してメジアン径10 nm以下の第二の酸性ゾルを得る工程、(3)前記第一及び第二の酸性ゾルを混合する工程、(4)得られた混合ゾルを基材上に塗布する工程、及び(5)前記塗布した混合ゾルが乾燥する前に湿度処理する工程を含む。前記シリカエアロゲル膜は、前記(1)〜(5)の工程によって形成されるが、さらに必要に応じて(6)加熱処理工程、(7)アルカリ処理工程、及び(8)洗浄工程を追加するのが好ましい。
[1] Method for Producing Antireflection Film The present invention is a method for producing an antireflection film having at least one layer of silica airgel film, and (1) was prepared by hydrolyzing and shrink-polymerizing alkoxysilane under a basic catalyst. A step of further adding an acidic solution to an alkaline sol to obtain a first acidic sol having a median diameter of 100 nm or less. (2) Hydrolyzing and shrink-polymerizing an alkoxysilane under an acidic catalyst to obtain a first acidic sol having a median diameter of 10 nm or less. The step of obtaining the second acidic sol, (3) the step of mixing the first and second acidic sol, (4) the step of applying the obtained mixed sol on the substrate, and (5) the step of applying the coated mixture. Includes a step of humidity treatment before the sol dries. The silica airgel film is formed by the steps (1) to (5), and if necessary, (6) heat treatment step, (7) alkali treatment step, and (8) cleaning step are added. Is preferable.
反射防止膜は、基材上に前記シリカエアロゲル膜のみを有する構成でも良いが、前記基材と前記シリカエアロゲル膜との間に、少なくとも一層の緻密膜を有する多層反射防止膜としても良い。多層反射防止膜とすることにより、より広い波長範囲において高い反射防止効果を得ることができる。 The antireflection film may have a structure in which only the silica airgel film is provided on the base material, or may be a multilayer antireflection film having at least one more dense film between the base material and the silica airgel film. By using the multi-layer antireflection film, a high antireflection effect can be obtained in a wider wavelength range.
(A) シリカエアロゲル膜の形成
(1) 第一の酸性ゾルを調製する工程
(a) アルコキシシラン
第一の酸性ゾル用のアルコキシシランはテトラアルコキシシランのモノマー又はオリゴマー（縮重合物）が好ましい。4官能のアルコキシシランを用いた場合、比較的大きな粒径を有するコロイド状シリカ粒子のゾルを得るのにことができる。テトラアルコキシシランは、Si(OR)4［Rは炭素数1〜5のアルキル基（メチル、エチル、プロピル、ブチル等）、又は炭素数1〜4のアシル基（アセチル等）］により表されるものが好ましい。テトラアルコキシシランの具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、ジエトキシジメトキシシラン等が挙げられる。中でもテトラメトキシシラン及びテトラエトキシシランが好ましい。本発明の効果を阻害しない範囲で、テトラアルコキシシランに少量の3官能以下のアルコキシシランを配合しても良い。
(A) Formation of silica airgel film
(1) Step of preparing the first acidic sol
(a) Alkoxysilane As the alkoxysilane for the first acidic sol, a monomer or oligomer (condensation polymer) of tetraalkoxysilane is preferable. When a tetrafunctional alkoxysilane is used, a sol of colloidal silica particles having a relatively large particle size can be obtained. Tetraalkoxysilane is represented by Si (OR) 4 [R is an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, butyl, etc.) or an acyl group having 1 to 4 carbon atoms (acetyl, etc.)]. Is preferable. Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like. Of these, tetramethoxysilane and tetraethoxysilane are preferable. A small amount of trifunctional or less-functional alkoxysilane may be added to tetraalkoxysilane as long as the effects of the present invention are not impaired.
(b) 塩基性触媒の存在下での加水分解及び縮重合
アルコキシシランに有機溶媒、塩基性触媒及び水を添加することにより、加水分解及び縮重合が進行する。有機溶媒としては、メタノール、エタノール、n-プロパノール、i-プロパノール、ブタノール等のアルコールが好ましく、メタノール又はエタノールがより好ましい。塩基性触媒としては、アンモニア、アミン、NaOH又はKOHが好ましい。好ましいアミンは、アルコールアミン又はアルキルアミン（メチルアミン、ジメチルアミン、トリメチルアミン、n-ブチルアミン、n-プロピルアミン等）である。
(b) Hydrolysis and polycondensation in the presence of a basic catalyst Hydrolysis and polycondensation proceed by adding an organic solvent, a basic catalyst and water to alkoxysilane. As the organic solvent, alcohols such as methanol, ethanol, n-propanol, i-propanol and butanol are preferable, and methanol or ethanol is more preferable. As the basic catalyst, ammonia, amine, NaOH or KOH is preferable. Preferred amines are alcohol amines or alkyl amines (methylamine, dimethylamine, trimethylamine, n-butylamine, n-propylamine, etc.).
有機溶媒とアルコキシシランとの量比は、アルコキシシランの濃度がSiO2換算で0.1〜10質量％（シリカ濃度）となるように設定するのが好ましい。シリカ濃度が10質量％超であると、得られるゾル中のシリカ粒子の粒径は大きくなり過ぎる。一方シリカ濃度が0.1未満であると、得られるゾル中のシリカ粒子の粒径は小さくなり過ぎる。なお有機溶媒／アルコキシシランのモル比としては5×102〜5×104の範囲が好ましい。 The amount ratio of the organic solvent to the alkoxysilane is preferably set so that the concentration of the alkoxysilane is 0.1 to 10% by mass (silica concentration) in terms of SiO 2 . If the silica concentration is more than 10% by mass, the particle size of the silica particles in the obtained sol becomes too large. On the other hand, if the silica concentration is less than 0.1, the particle size of the silica particles in the obtained sol becomes too small. The molar ratio of organic solvent / alkoxysilane is preferably in the range of 5 × 10 2 to 5 × 10 4 .
塩基性触媒／アルコキシシランのモル比は１×10-4〜１にするのが好ましく、１×10-4〜0.8にするのがより好ましく、３×10-4〜0.5にするのが特に好ましい。塩基性触媒／アルコキシシランのモル比が1×10-4未満であると、アルコキシシランの加水分解反応が十分に起こらない。一方モル比が1を超えて塩基を添加しても触媒効果は飽和する。 The molar ratio of basic catalyst / alkoxysilane is preferably 1 × 10 -4 to 1, more preferably 1 × 10 -4 to 0.8, and particularly preferably 3 × 10 -4 to 0.5. .. If the molar ratio of basic catalyst / alkoxysilane is less than 1 × 10 -4 , the hydrolysis reaction of alkoxysilane does not occur sufficiently. On the other hand, even if the molar ratio exceeds 1 and a base is added, the catalytic effect is saturated.
水／アルコキシシランのモル比は1〜30が好ましい。水／アルコキシシランのモル比が30超であると、加水分解反応が速く進行し過ぎるため反応の制御が難しく、均一なシリカエアロゲル膜が得られにくくなる。一方1未満であると、アルコキシシランの加水分解が十分に起こらない。 The molar ratio of water / alkoxysilane is preferably 1 to 30. If the molar ratio of water / alkoxysilane is more than 30, the hydrolysis reaction proceeds too quickly, making it difficult to control the reaction and making it difficult to obtain a uniform silica airgel film. On the other hand, if it is less than 1, hydrolysis of the alkoxysilane does not occur sufficiently.
塩基性触媒及び水を含有するアルコキシシランの溶液は、10〜90℃で約10〜60時間静置又はゆっくり撹拌することにより熟成するのが好ましい。熟成により加水分解及び縮重合が進行し、シリカゾルが生成する。シリカゾルは、コロイド状シリカ粒子の分散液の他、コロイド状シリカ粒子がクラスター状に凝集した分散液も含む。 The solution of alkoxysilane containing a basic catalyst and water is preferably aged by allowing it to stand at 10 to 90 ° C. for about 10 to 60 hours or by stirring slowly. Hydrolysis and polycondensation proceed by aging to produce silica sol. The silica sol includes not only a dispersion liquid of colloidal silica particles but also a dispersion liquid in which colloidal silica particles are aggregated in a cluster shape.
(c) 酸性触媒の存在下での加水分解及び縮重合
得られたアルカリ性ゾルに酸性触媒、並びに必要に応じて水及び有機溶媒を添加し、酸性状態で加水分解及び縮重合をさらに進行させる。酸性触媒としては、塩酸、硝酸、硫酸、燐酸、酢酸等が挙げられる。有機溶媒は上記と同じものを使用できる。第一の酸性ゾルにおいて酸性触媒／塩基性触媒のモル比は1.1〜10が好ましく、1.5〜5がより好ましく、2〜4が最も好ましい。酸性触媒／塩基性触媒のモル比が1.1未満であると、酸性触媒による重合が十分に進行しない。一方10を超えると触媒効果は飽和する。有機溶媒／アルコキシシランのモル比及び水／アルコキシシランのモル比は上記と同じで良い。酸性触媒を含有するゾルは10〜90℃で約15分〜24時間静置又はゆっくり撹拌して熟成するのが好ましい。熟成により加水分解及び縮重合が進行し、第一の酸性ゾルが生成する。
(c) Hydrolysis and polycondensation in the presence of an acidic catalyst An acidic catalyst and, if necessary, water and an organic solvent are added to the obtained alkaline sol to further promote hydrolysis and polycondensation in an acidic state. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid and the like. The same organic solvent as above can be used. In the first acidic sol, the molar ratio of the acidic catalyst / basic catalyst is preferably 1.1 to 10, more preferably 1.5 to 5, and most preferably 2 to 4. If the molar ratio of the acidic catalyst / basic catalyst is less than 1.1, the polymerization by the acidic catalyst does not proceed sufficiently. On the other hand, if it exceeds 10, the catalytic effect is saturated. The molar ratio of organic solvent / alkoxysilane and the molar ratio of water / alkoxysilane may be the same as above. The sol containing the acidic catalyst is preferably aged at 10 to 90 ° C. for about 15 minutes to 24 hours by allowing it to stand or stirring slowly. Hydrolysis and polycondensation proceed by aging to produce a first acidic sol.
第一の酸性ゾル中のシリカ粒子のメジアン径は100 nm以下であり、好ましくは10〜50 nmである。メジアン径は動的光散乱法により測定する。 The median diameter of the silica particles in the first acidic sol is 100 nm or less, preferably 10 to 50 nm. The median diameter is measured by the dynamic light scattering method.
(2) 第二の酸性ゾルを調製する工程
(a) アルコキシシラン
第二の酸性ゾル用のアルコキシシランはSi(OR1)x(R2)4-x［xは2〜4の整数である。］により表される2〜4官能のものでよい。R1は炭素数1〜5のアルキル基（メチル、エチル、プロピル、ブチル等）、又は炭素数1〜4のアシル基（アセチル等）が好ましい。R2は炭素数1〜10の有機基が好ましく、例えばメチル、エチル、プロピル、ブチル、ヘキシル、シクロヘキシル、オクチル、デシル、フェニル、ビニル、アリル等の炭化水素基、及びγ-クロロプロピル、CF3CH2-、CF3CH2CH2-、C2F5CH2CH2-、C3F7CH2CH2CH2-、CF3OCH2CH2CH2-、C2F5OCH2CH2CH2-、C3F7OCH2CH2CH2-、(CF3)2CHOCH2CH2CH2-、C4F9CH2OCH2CH2CH2-、3-(パーフルオロシクロヘキシルオキシ)プロピル、H(CF2)4CH2OCH2CH2CH2-、H(CF2)4CH2CH2CH2-、γ-グリシドキシプロピル、γ-メルカプトプロピル、3,4-エポキシシクロヘキシルエチル、γ-メタクリロイルオキシプロピル等の置換炭化水素基が挙げられる。
(2) Step to prepare the second acidic sol
(a) Alkoxysilane The alkoxysilane for the second acidic sol is Si (OR 1 ) x (R 2 ) 4-x [x is an integer of 2-4. ] Can be 2 to 4 functional. R 1 is preferably an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, butyl, etc.) or an acyl group having 1 to 4 carbon atoms (acetyl, etc.). R 2 is preferably an organic group having 1 to 10 carbon atoms, for example, a hydrocarbon group such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl, phenyl, vinyl, allyl, and γ-chloropropyl, CF 3 CH 2- , CF 3 CH 2 CH 2- , C 2 F 5 CH 2 CH 2- , C 3 F 7 CH 2 CH 2 CH 2- , CF 3 OCH 2 CH 2 CH 2- , C 2 F 5 OCH 2 CH 2 CH 2- , C 3 F 7 OCH 2 CH 2 CH 2- , (CF 3 ) 2 CHOCH 2 CH 2 CH 2- , C 4 F 9 CH 2 OCH 2 CH 2 CH 2- , 3- (Perfluoro Cyclohexyloxy) propyl, H (CF 2 ) 4 CH 2 OCH 2 CH 2 CH 2- , H (CF 2 ) 4 CH 2 CH 2 CH 2- , γ-glycidoxypropyl, γ-mercaptopropyl, 3,4 -Substituted hydrocarbon groups such as epoxycyclohexylethyl and γ-methacryloyloxypropyl can be mentioned.
2官能のアルコキシシランの具体例としては、ジメチルジメトキシシラン、ジメチルジエトキシシラン等のジメチルジアルコキシシランが挙げられる。3官能のアルコキシシランの具体例としては、メチルトリメトキシシラン、メチルトリエトキシシラン等のメチルトリアルコキシシラン、及びフェニルトリエトキシシラン等のフェニルトリアルコキシシランが挙げられる。4官能のアルコキシシランとしては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、ジエトキシジメトキシシラン等が挙げられる。アルコキシシランは3官能以上が好ましく、メチルトリアルコキシシラン及びテトラアルコキシシランがより好ましい。 Specific examples of the bifunctional alkoxysilane include dimethyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane. Specific examples of the trifunctional alkoxysilane include methyltrialkoxysilane such as methyltrimethoxysilane and methyltriethoxysilane, and phenyltrialkoxysilane such as phenyltriethoxysilane. Examples of the tetrafunctional alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and diethoxydimethoxysilane. The alkoxysilane is preferably trifunctional or higher, and more preferably methyltrialkoxysilane and tetraalkoxysilane.
(b) 酸性触媒の存在下での加水分解及び縮重合
アルコキシシランのモノマー又はオリゴマー（縮重合物）に有機溶媒、酸性触媒及び水を添加することにより、加水分解及び縮重合が進行する。有機溶媒及び酸性触媒は第一の酸性ゾルを調製する工程で説明したものと同じものを使用できる。酸性触媒／アルコキシシランのモル比は、1×10-4〜1が好ましく、1×10-4〜3×10-2がより好ましく、3×10-4〜1×10-2が最も好ましい。有機溶媒／アルコキシシランのモル比及び水／アルコキシシランのモル比は、第一の酸性ゾルを調製する工程で説明した比と同じで良い。
(b) Hydrolysis and polycondensation in the presence of an acidic catalyst Hydrolysis and polycondensation proceed by adding an organic solvent, an acidic catalyst and water to a monomer or oligomer (condensation polymer) of alkoxysilane. The organic solvent and the acidic catalyst can be the same as those described in the step of preparing the first acidic sol. The molar ratio of acidic catalyst / alkoxysilane is preferably 1 × 10 -4 to 1, more preferably 1 × 10 -4 to 3 × 10 −2, and most preferably 3 × 10 -4 to 1 × 10 −2 . The molar ratio of organic solvent / alkoxysilane and the molar ratio of water / alkoxysilane may be the same as those described in the step of preparing the first acidic sol.
酸性触媒及び水を含有するアルコキシシランの溶液は、10〜90℃で約30分〜60時間静置又はゆっくり撹拌することにより熟成するのが好ましい。熟成により加水分解及び縮重合が進行し、第二の酸性ゾルが生成する。熟成時間が60時間を超えると、ゾル中のシリカ粒子のメジアン径が大きくなり過ぎる。 The solution of alkoxysilane containing an acidic catalyst and water is preferably aged by allowing it to stand at 10 to 90 ° C. for about 30 minutes to 60 hours or by stirring slowly. Hydrolysis and polycondensation proceed by aging to produce a second acidic sol. If the aging time exceeds 60 hours, the median diameter of the silica particles in the sol becomes too large.
得られる第二の酸性ゾル中のコロイド状シリカ粒子は、第一の酸性ゾルに比べて小さなメジアン径を有する。第二の酸性ゾル中のコロイド状シリカ粒子のメジアン径は10 nm以下であり、好ましくは1〜5 nmである。第一の酸性ゾル中のシリカ粒子と第二の酸性ゾル中のシリカ粒子とのメジアン径比は5〜50であるのが好ましく、5〜35であるのがより好ましい。メジアン径比が5未満又は50超であると、シリカエアロゲル膜の耐擦傷性が低い。 The colloidal silica particles in the obtained second acidic sol have a smaller median diameter than the first acidic sol. The median diameter of the colloidal silica particles in the second acidic sol is 10 nm or less, preferably 1 to 5 nm. The median diameter ratio of the silica particles in the first acidic sol to the silica particles in the second acidic sol is preferably 5 to 50, more preferably 5 to 35. When the median diameter ratio is less than 5 or more than 50, the scratch resistance of the silica airgel film is low.
(3) 混合ゾルを調製する工程
第一の酸性ゾル及び第二の酸性ゾルを混合し、1〜30℃で約1分〜6時間ゆっくり撹拌するのが好ましい。必要に応じて混合物を80℃以下で加熱しても良い。第一の酸性ゾルと第二の酸性ゾルとの固形分質量比は5〜90であるのが好ましく、5〜80であるのがより好ましい。固形分質量比が5未満又は90超であると、シリカエアロゲル膜の耐擦傷性が低い。
(3) Step of preparing a mixed sol It is preferable to mix the first acidic sol and the second acidic sol and slowly stir at 1 to 30 ° C. for about 1 minute to 6 hours. If desired, the mixture may be heated below 80 ° C. The solid content mass ratio of the first acidic sol to the second acidic sol is preferably 5 to 90, more preferably 5 to 80. When the solid content mass ratio is less than 5 or more than 90, the scratch resistance of the silica airgel film is low.
(4) 塗布工程
混合ゾルを基材の表面に塗布する方法としては、ディップコート法、スプレーコート法、スピンコート法、印刷法等が挙げられる。レンズのような三次元構造物に塗布する場合、ディッピング法が好ましい。ディッピング法における引き上げ速度は約0.1〜3.0 mm／秒であるのが好ましい。
(4) Coating process Examples of the method of applying the mixed sol to the surface of the base material include a dip coating method, a spray coating method, a spin coating method, and a printing method. When applied to three-dimensional structures such as lenses, the dipping method is preferred. The pulling speed in the dipping method is preferably about 0.1 to 3.0 mm / sec.
混合ゾルの濃度及び流動性を調整し塗布適性を高めるため、分散媒として前記有機溶媒を加えても良い。塗布時の混合ゾル中のシリカの濃度は0.1〜20質量％が好ましい。必要に応じて、混合ゾルを超音波処理しても良い。超音波処理によってコロイド粒子の凝集を防止できる。超音波の周波数は10〜30 kHzが好ましく、出力は300〜900 Wが好ましく、処理時間は5〜120分間が好ましい。 The organic solvent may be added as a dispersion medium in order to adjust the concentration and fluidity of the mixed sol and improve the coating suitability. The concentration of silica in the mixed sol at the time of coating is preferably 0.1 to 20% by mass. If desired, the mixed sol may be sonicated. Agglomeration of colloidal particles can be prevented by ultrasonic treatment. The frequency of the ultrasonic wave is preferably 10 to 30 kHz, the output is preferably 300 to 900 W, and the processing time is preferably 5 to 120 minutes.
(5)湿度処理工程
混合ゾルの塗布後、高湿度条件下で湿度処理を施す。湿度処理により、未反応のアルコキシシランの加水分解、及びシラノール基の縮重合反応が進行すると考えられ、シリカエアロゲル膜の機械的強度が向上するとともに、成膜後の時間経過による屈折率の変動が抑制される。前記塗布した混合ゾルを乾燥させた後で湿度処理を施しても、機械的強度の向上効果及び屈折率の経時変動の抑制効果が得られるが、前記塗布した混合ゾルを乾燥させた後で湿度処理を施した場合、マイクロクラックが発生する場合がある。特に90℃を越える高温で乾燥させた場合、マイクロクラックの発生が顕著となるので、塗布後、90℃以下で乾燥した後に湿度処理を施すのが好ましく、前記塗布した混合ゾルが乾燥する前に湿度処理を施すのがより好ましい。このように、塗布した混合ゾルが乾燥する前に湿度処理を施すことにより、シリカエアロゲル膜は、その表面にマイクロクラックがほとんど発生しなくなり、得られる反射防止膜は、機械的強度が向上し、さらに屈折率の時間変動が小さくなる。
(5) Humidity treatment process After applying the mixed sol, humidity treatment is performed under high humidity conditions. It is considered that the hydrolysis of unreacted alkoxysilane and the polycondensation reaction of silanol groups proceed by the humidity treatment, and the mechanical strength of the silica airgel film is improved and the refractive index fluctuates with the passage of time after the film formation. It is suppressed. Even if the applied mixed sol is dried and then subjected to humidity treatment, the effect of improving the mechanical strength and the effect of suppressing the time-dependent fluctuation of the refractive index can be obtained, but the humidity after the applied mixed sol is dried. When treated, microcracks may occur. In particular, when dried at a high temperature exceeding 90 ° C., microcracks are prominently generated. Therefore, it is preferable to perform humidity treatment after coating and drying at 90 ° C. or lower, and before the applied mixed sol is dried. It is more preferable to apply humidity treatment. By subjecting the applied mixed sol to humidity treatment before it dries in this way, the silica airgel film has almost no microcracks on its surface, and the obtained antireflection film has improved mechanical strength. Further, the time variation of the refractive index becomes small.
湿度処理は、温度35℃以上、相対湿度70％以上の環境に30分以上保存することにより行う。処理の湿度が70％RH未満では前記の効果が十分に得られない。湿度は75％RH以上であるのが好ましく、80％RH以上であるのがさらに好ましく、90％RH以上であるのが最も好ましい。処理温度は、35〜90℃であるのが好ましく、40〜80℃であるのがさらに好ましく、50〜80℃であるのが最も好ましい。処理温度が35℃未満の場合、前記の効果が十分に得られず、90℃超にしても効果は飽和してしまう。処理時間は、温度条件及び湿度条件にもよるが、30分以上行うことにより前記効果が得られる。処理時間は、長いほど機械的強度が向上するため好ましいが、コストや生産性を考慮すると、好ましくは５〜120時間であり、さらに好ましくは５〜48時間である。処理時間が120時間超では効果は飽和する。 Humidity treatment is performed by storing in an environment with a temperature of 35 ° C or higher and a relative humidity of 70% or higher for 30 minutes or longer. If the treatment humidity is less than 70% RH, the above effect cannot be sufficiently obtained. Humidity is preferably 75% RH or higher, more preferably 80% RH or higher, and most preferably 90% RH or higher. The treatment temperature is preferably 35 to 90 ° C, more preferably 40 to 80 ° C, and most preferably 50 to 80 ° C. If the treatment temperature is less than 35 ° C, the above effect cannot be sufficiently obtained, and even if it exceeds 90 ° C, the effect is saturated. The treatment time depends on the temperature condition and the humidity condition, but the above effect can be obtained by carrying out the treatment for 30 minutes or more. The longer the treatment time is, the higher the mechanical strength is, so that it is preferable, but in consideration of cost and productivity, it is preferably 5 to 120 hours, and more preferably 5 to 48 hours. If the processing time exceeds 120 hours, the effect will be saturated.
(6)加熱処理工程
湿度処理後の塗布膜は、必要に応じて加熱処理する。加熱は、縮重合反応を促進するために、例えば、水の沸点未満の温度で15分〜24時間熱処理した後、100〜200℃の温度で15分〜24時間熱処理する。加熱処理の条件は基材の耐熱性に応じて適宜選択するのが好ましい。熱処理することによりシリカエアロゲル膜は高い耐擦傷性を発揮する。
(6) Heat treatment process The coating film after humidity treatment is heat-treated as necessary. In order to promote the polycondensation reaction, for example, the heating is heat-treated at a temperature below the boiling point of water for 15 minutes to 24 hours, and then heat-treated at a temperature of 100 to 200 ° C. for 15 minutes to 24 hours. The heat treatment conditions are preferably selected as appropriate according to the heat resistance of the base material. By heat treatment, the silica airgel film exhibits high scratch resistance.
(7)アルカリ処理工程
加熱処理後のシリカエアロゲル膜をアルカリで処理することにより耐擦傷性がいっそう向上する。アルカリ処理は、アルカリ溶液を塗布、又はアンモニア雰囲気中に載置することにより行うのが好ましい。アルカリ溶液の溶媒はアルカリに応じて適宜選択でき、水、アルコール等が好ましい。アルカリ溶液の濃度は、１×10-4〜20Ｎが好ましく、１×10-3〜15Ｎがより好ましい。なおアルカリ処理は、前述の加熱処理の前に行っても良い。
(7) Alkali treatment step By treating the silica airgel film after heat treatment with alkali, the scratch resistance is further improved. The alkaline treatment is preferably carried out by applying an alkaline solution or placing it in an ammonia atmosphere. The solvent of the alkaline solution can be appropriately selected depending on the alkali, and water, alcohol and the like are preferable. The concentration of the alkaline solution is preferably 1 × 10 -4 to 20 N, more preferably 1 × 10 -3 to 15 N. The alkali treatment may be performed before the above-mentioned heat treatment.
前記アルカリとして、水酸化ナトリウム、水酸化カリウム、アンモニア等の無機アルカリ；炭酸ナトリウム、炭酸水素ナトリウム、炭酸アンモニウム、炭酸水素アンモニウム等の無機アルカリ塩；モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、n-プロピルアミン、ジ-n-プロピルアミン、n-ブチルアミン、ジ-n-ブチルアミン、n-アミルアミン、n-ヘキシルアミン、ラウリルアミン、エチレンジアミン、ヘキサメチレンジアミン、アニリン、メチルアニリン、エチルアニリン、シクロヘキシルアミン、ジシクロヘキシルアミン、ピロリジン、ピリジン、イミダゾール、グアニジン、テトラメチルアンモニウムハイドロオキサイド、テトラエチルアンモニウムハイドロオキサイド、テトラブチルアンモニウムハイドロオキサイド、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、コリン等の有機アルカリ；蟻酸アンモニウム、酢酸アンモニウム、蟻酸モノメチルアミン、酢酸ジメチルアミン、酢酸アニリン、乳酸ピリジン、グアニジノ酢酸等の有機酸アルカリ塩等を用いることができる。 As the alkali, inorganic alkalis such as sodium hydroxide, potassium hydroxide and ammonia; inorganic alkali salts such as sodium carbonate, sodium hydrogencarbonate, ammonium carbonate and ammonium hydrogencarbonate; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, Triethylamine, n-propylamine, di-n-propylamine, n-butylamine, di-n-butylamine, n-amylamine, n-hexylamine, laurylamine, ethylenediamine, hexamethylenediamine, aniline, methylaniline, ethylaniline, Organic alkalis such as cyclohexylamine, dicyclohexylamine, pyrrolidine, pyridine, imidazole, guanidine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, choline; ammonium formate, Organic acid alkali salts such as ammonium acetate, monomethylamine formicate, dimethylamine acetate, aniline acetate, pyridine lactate, and guanidinoacetic acid can be used.
アルカリ溶液の塗布によりアルカリ処理する場合、シリカエアロゲル膜１cm2当たり10〜200 mL塗布するのが好ましい。塗布はシリカエアロゲル膜を塗布する場合と同様の方法ででき、スピンコート法が好ましい。スピンコート法における基材回転速度は、1,000〜15,000 rpm程度にするのが好ましい。アルカリ溶液を塗布後の膜は、好ましくは１〜40℃、より好ましくは10〜30℃で保存する。保存時間は、0.1〜10時間が好ましく、0.2〜１時間がより好ましい。 In the case of alkaline treatment by applying an alkaline solution, it is preferable to apply 10 to 200 mL per 1 cm 2 of the silica airgel film. The coating can be performed by the same method as in the case of coating the silica airgel film, and the spin coating method is preferable. The base rotation speed in the spin coating method is preferably about 1,000 to 15,000 rpm. The membrane after applying the alkaline solution is preferably stored at 1 to 40 ° C, more preferably 10 to 30 ° C. The storage time is preferably 0.1 to 10 hours, more preferably 0.2 to 1 hour.
アンモニア雰囲気中に載置してアルカリ処理する場合、１×10-1〜１×105 Paのアンモニアガス分圧中で処理するのが好ましい。処理温度は、１〜40℃が好ましく、10〜30℃がより好ましい。処理時間は、1〜170時間が好ましく、５〜80時間がより好ましい。 When placed in an ammonia atmosphere for alkaline treatment, it is preferable to perform treatment in an ammonia gas partial pressure of 1 × 10 -1 to 1 × 10 5 Pa. The treatment temperature is preferably 1 to 40 ° C, more preferably 10 to 30 ° C. The treatment time is preferably 1 to 170 hours, more preferably 5 to 80 hours.
必要に応じて、アルカリ処理したシリカエアロゲル膜は乾燥する。乾燥は、100〜200℃の温度で15分〜24時間行うのが好ましい。 If necessary, the alkali-treated silica airgel membrane is dried. Drying is preferably carried out at a temperature of 100 to 200 ° C. for 15 minutes to 24 hours.
(8) 洗浄工程
アルカリ処理後のシリカエアロゲル膜は、必要に応じて洗浄してもよい。洗浄は、水及び／又はアルコールに浸漬する方法、シャワーする方法、又はこれらの組合せにより行うのが好ましい。浸漬しながら超音波処理してもよい。洗浄の温度は１〜40℃が好ましく、時間は0.2〜15分が好ましい。シリカエアロゲル膜１ cm2当たり0.01〜1,000 mLの水及び／又はアルコールで洗浄するのが好ましい。洗浄後のシリカエアロゲル膜は、100〜200℃の温度で15分〜24時間乾燥するのが好ましい。アルコールとしてはメタノール、エタノール、イソプロピルアルコールが好ましい。
(8) Cleaning step The silica airgel film after the alkali treatment may be washed if necessary. The washing is preferably carried out by a method of immersing in water and / or alcohol, a method of showering, or a combination thereof. You may sonicate while immersing. The washing temperature is preferably 1 to 40 ° C., and the time is preferably 0.2 to 15 minutes. It is preferred to wash with 0.01-1,000 mL of water and / or alcohol per cm 2 of the silica airgel membrane. The washed silica airgel film is preferably dried at a temperature of 100 to 200 ° C. for 15 minutes to 24 hours. As the alcohol, methanol, ethanol and isopropyl alcohol are preferable.
(B) 緻密膜の形成
基材上にシリカエアロゲル膜のみを塗布して単層の反射防止膜を形成しても良いが、予め形成した少なくとも一層の緻密膜の上にシリカエアロゲル膜を塗布し多層反射防止膜を形成しても良い。多層反射防止膜を形成することにより、より広い波長範囲において高い反射防止効果を得ることができる。緻密膜は、金属酸化物等の無機材料からなる層（「無機層」と言う）、無機微粒子とバインダからなる複合層（「無機微粒子−バインダ複合層」又は単に「複合層」と言う）、樹脂からなる層等で形成する。緻密膜の屈折率は、基材の屈折率より小さく、シリカエアロゲル膜の屈折率より大きな値に設定する。
(B) Formation of dense film Although only the silica airgel film may be applied on the substrate to form a single-layer antireflection film, the silica airgel film may be applied on at least one layer of the dense film formed in advance. A multilayer antireflection film may be formed. By forming the multilayer antireflection film, a high antireflection effect can be obtained in a wider wavelength range. The dense film is a layer made of an inorganic material such as a metal oxide (referred to as an "inorganic layer"), a composite layer composed of inorganic fine particles and a binder (referred to as an "inorganic fine particle-binder composite layer" or simply a "composite layer"), It is formed of a layer made of resin or the like. The refractive index of the dense film is set to be smaller than the refractive index of the base material and larger than the refractive index of the silica airgel film.
前記無機層に使用可能な無機材料の例としては、フッ化マグネシウム、フッ化カルシウム、フッ化アルミニウム、フッ化リチウム、フッ化ナトリウム、フッ化セリウム、酸化珪素、酸化アルミニウム、酸化ジルコニウム、クライオライト、チオライト、酸化チタン、酸化セリウム、窒化珪素及びこれらの混合物が挙げられる。 Examples of inorganic materials that can be used for the inorganic layer include magnesium fluoride, calcium fluoride, aluminum fluoride, lithium fluoride, sodium fluoride, cerium fluoride, silicon oxide, aluminum oxide, zirconium oxide, cryolite, and the like. Examples thereof include thiolite, titanium oxide, cerium oxide, silicon fluoride and mixtures thereof.
前記複合層に使用可能な無機微粒子の例としては、フッ化カルシウム、フッ化マグネシウム、フッ化アルミニウム、フッ化ナトリウム、フッ化リチウム、フッ化セリウム、酸化珪素、酸化アルミニウム、酸化ジルコニウム、クライオライト、チオライト、酸化チタン、酸化インジウム、酸化スズ、酸化アンチモン、酸化セリウム、酸化ハフニウム及び酸化亜鉛からなる群から選ばれた少なくとも一種の無機物の微粒子が挙げられる。酸化珪素は好ましくはコロイダルシリカであり、コロイダルシリカはシランカップリング剤等により表面処理しても良い。無機微粒子−バインダ複合層の屈折率は、無機微粒子の組成や含有率の他、バインダの組成に依存する。 Examples of the inorganic fine particles that can be used in the composite layer include calcium fluoride, magnesium fluoride, aluminum fluoride, sodium fluoride, lithium fluoride, cerium fluoride, silicon oxide, aluminum oxide, zinc oxide, cryolite, and the like. Examples thereof include at least one inorganic fine particle selected from the group consisting of thiolite, titanium oxide, indium oxide, tin oxide, antimony oxide, cerium oxide, hafnium oxide and zinc oxide. Silicon oxide is preferably colloidal silica, and colloidal silica may be surface-treated with a silane coupling agent or the like. The refractive index of the inorganic fine particle-binder composite layer depends on the composition and content of the inorganic fine particles as well as the composition of the binder.
前記樹脂層の例としては、フッ素樹脂層、エポキシ樹脂層、アクリル樹脂層、シリコーン樹脂層及びウレタン樹脂層が挙げられる。フッ素樹脂には、ポリテトラフルオロエチレン樹脂、パーフルオロエチレンプロピレン共重合体、パーフルオロアルコキシ樹脂、ポリビニリデンフルオライド、エチレン−テトラフルオロエチレン共重合体、ポリクロロトリフルオロエチレン等の結晶性フッ素樹脂と、非結晶性フッ素樹脂とがあるが、非結晶性フッ素樹脂の方が優れた透明度を有するので好ましい。非結晶性のフッ素樹脂の具体例としては、フルオロオレフィン系の共重合体、含フッ素脂肪族環構造を有する重合体、フッ素化アクリレート系の共重合体が挙げられる。フルオロオレフィン系の共重合体の例としては、37〜48質量％のテトラフルオロエチレンと、15〜35質量％のビニリデンフルオライドと、26〜44質量％のヘキサフルオロプロピレンとが共重合したものが挙げられる。含フッ素脂肪族環構造を有する重合体には、含フッ素脂肪族環構造を有するモノマーが重合したものや、少なくとも二つの重合性二重結合を有する含フッ素モノマーを環化重合したものがある。 Examples of the resin layer include a fluororesin layer, an epoxy resin layer, an acrylic resin layer, a silicone resin layer, and a urethane resin layer. Fluororesin includes crystalline fluororesins such as polytetrafluoroethylene resin, perfluoroethylene propylene copolymer, perfluoroalkoxy resin, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, and polychlorotrifluoroethylene. , Non-crystalline fluororesin, but non-crystalline fluororesin is preferable because it has excellent transparency. Specific examples of the non-crystalline fluororesin include a fluoroolefin-based copolymer, a polymer having a fluorine-containing aliphatic ring structure, and a fluorinated acrylate-based copolymer. Examples of fluoroolefin-based copolymers are those obtained by copolymerizing 37 to 48% by mass of tetrafluoroethylene, 15 to 35% by mass of vinylidene fluoride, and 26 to 44% by mass of hexafluoropropylene. Can be mentioned. Examples of the polymer having a fluorine-containing aliphatic ring structure include those obtained by polymerizing a monomer having a fluorine-containing aliphatic ring structure and those obtained by cyclizing and polymerizing a fluorine-containing monomer having at least two polymerizable double bonds.
緻密膜は複数の層を積層したものであってもよい。複数の緻密膜は、上記無機層、複合層及び樹脂層のいずれかにより形成することができる。無機層を積層することにより複数の緻密膜を形成する場合、例えばフッ化マグネシウム、酸化珪素、酸化アルミニウム、酸化ジルコニウム、酸化チタン、酸化セリウム、窒化珪素等を材料として用いることができる。 The dense film may be a stack of a plurality of layers. The plurality of dense films can be formed by any of the above-mentioned inorganic layer, composite layer and resin layer. When a plurality of dense films are formed by laminating inorganic layers, for example, magnesium fluoride, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, silicon nitride and the like can be used as materials.
無機材料のみからなる層は真空蒸着法、スパッタリング法、イオンプレーティング法等の物理蒸着法、熱CVD、プラズマCVD、光CVD等の化学蒸着法等により形成することができるが、真空蒸着法が好ましい。無機微粒子−バインダ複合層はディップコート法、スピンコート法、スプレー法、ロールコティング法、スクリーン印刷法等の湿式の方法で形成することができるが、ディップコート法が好ましい。樹脂層は化学蒸着法や湿式法で形成可能である。これらの方法のうち、蒸着法により無機層を作製する方法、及びディップコート法により無機微粒子−バインダ複合層及びフッ素樹脂層を作製する方法が、例えば特開2006-215542号に記載されている。 A layer made of only an inorganic material can be formed by a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method or an ion plating method, or a chemical vapor deposition method such as thermal CVD, plasma CVD or optical CVD. preferable. The inorganic fine particle-binder composite layer can be formed by a wet method such as a dip coating method, a spin coating method, a spray method, a roll coating method, or a screen printing method, but the dip coating method is preferable. The resin layer can be formed by a chemical vapor deposition method or a wet method. Among these methods, a method for producing an inorganic layer by a vapor deposition method and a method for producing an inorganic fine particle-binder composite layer and a fluororesin layer by a dip coating method are described in, for example, Japanese Patent Application Laid-Open No. 2006-215542.
[2] 反射防止膜
反射防止膜は、シリカエアロゲル膜のみからなるか、シリカエアロゲル膜と一層又は複数の緻密膜との多層膜からなる。シリカエアロゲル膜の物理膜厚は15〜500 nmが好ましく、70〜170 nmがより好ましい。シリカエアロゲル膜の物理膜厚は混合ゾルの濃度や、塗布の回数等によって適宜調製できる。シリカエアロゲル膜は、前述の本発明の方法によって製造されるのが好ましい。
[2] Antireflection film The antireflection film is composed of only a silica airgel film or a multilayer film of a silica airgel film and one or more dense films. The physical film thickness of the silica airgel film is preferably 15 to 500 nm, more preferably 70 to 170 nm. The physical film thickness of the silica airgel film can be appropriately adjusted depending on the concentration of the mixed sol, the number of times of application, and the like. The silica airgel film is preferably produced by the method of the present invention described above.
シリカエアロゲル膜はSi-O結合を有する骨格からなり、ナノサイズの均一な微細孔を有し、高い透明性を有する多孔質膜である。シリカエアロゲル膜の屈折率は空隙率が大きくなるにつれて小さくなる。シリカエアロゲル膜の空隙率は30〜90％であるのが好ましい。30〜90％の空隙率を有するシリカエアロゲル膜は1.05〜1.35の屈折率を有する。シリカエアロゲル膜の屈折率は1.15〜1.27であるのがより好ましい。例えば空隙率78％のシリカエアロゲル膜の屈折率は約1.1である。空隙率が90％超であるとシリカエアロゲル膜の耐擦傷性が低下する。空隙率が30％未満であると、屈折率が大きすぎる。 The silica airgel membrane is a porous membrane composed of a skeleton having a Si-O bond, having nano-sized uniform micropores, and having high transparency. The refractive index of the silica airgel film decreases as the porosity increases. The porosity of the silica airgel film is preferably 30 to 90%. Silica airgel membranes with a porosity of 30-90% have a refractive index of 1.05-1.35. The refractive index of the silica airgel film is more preferably 1.15 to 1.27. For example, the refractive index of a silica airgel film having a porosity of 78% is about 1.1. If the porosity is more than 90%, the scratch resistance of the silica airgel film is lowered. If the porosity is less than 30%, the refractive index is too high.
本発明の方法により形成されるシリカエアロゲル膜は、その表面にマイクロクラックがほとんど発生しないため、機械的強度に優れ、さらに屈折率の時間変動が小さい。さらに第一の酸性ゾルから生成する比較的大きなシリカ粒子の隙間に、第二の酸性ゾルから生成する比較的小さなシリカ粒子が入り込んだ構造を有するので、低屈折率でありながら優れた耐擦傷性を有するとともに、湿度処理により屈折率の時間変動が小さくなる。 Since the silica airgel film formed by the method of the present invention hardly generates microcracks on its surface, it is excellent in mechanical strength and has a small time variation of the refractive index. Further, since it has a structure in which relatively small silica particles generated from the second acidic sol are inserted in the gaps between the relatively large silica particles generated from the first acidic sol, it has a low refractive index and excellent scratch resistance. And the time variation of the refractive index is reduced by the humidity treatment.
反射防止膜が、シリカエアロゲル膜と一層の緻密膜との二層膜からなる場合、基材側から緻密膜、シリカエアロゲル膜及び入射媒質の順に屈折率が小さくなっているのが好ましい。緻密膜及びシリカエアロゲル膜の光学膜厚d1及びd2は設計波長λdに対してλd/5〜λd/3の範囲であるのが好ましい。光学膜厚は膜の屈折率と物理膜厚との積である。また薄膜の構成を決定する際に用いる設計波長λdは、光学素子に使用する波長に応じて適宜設定し得るが、例えば可視域［CIE（国際照明委員会）の定義による380〜780 nmの波長域］のほぼ中心波長であるのが好ましい。 When the antireflection film is composed of a two-layer film consisting of a silica airgel film and a one-layer dense film, it is preferable that the refractive index decreases in the order of the dense film, the silica airgel film, and the incident medium from the substrate side. The optical film thicknesses d 1 and d 2 of the dense film and the silica airgel film are preferably in the range of λd / 5 to λd / 3 with respect to the design wavelength λd. The optical film thickness is the product of the refractive index of the film and the physical film thickness. The design wavelength λd used when determining the composition of the thin film can be appropriately set according to the wavelength used for the optical element. For example, the wavelength of 380 to 780 nm as defined by the visible region [CIE (International Commission on Illumination)]. It is preferable that the wavelength is approximately the center wavelength of the region.
前記二層膜からなる反射防止膜において、緻密膜及びシリカエアロゲル膜の光学膜厚を設計波長λdに対してλd/5〜λd/3の範囲にすると、反射防止膜の光学膜厚（光学膜厚d1及びd2の合計）は2λd/5〜2λd/3の範囲となり、基材から入射媒質にかけての光学膜厚に対する屈折率の変化は、滑らかな階段状となる。反射防止膜の光学膜厚が2λd/5〜2λd/3の範囲であると、反射防止膜表面での反射光と、反射防止膜と基材の境界での反射光との光路差が設計波長λdのほぼ1/2となるので、これらの光線が干渉により打ち消し合う。基材から入射媒質にかけての光学膜厚に対する屈折率の変化を滑らかな階段状にすると、各層の境界において起こる入射光の反射を広い波長域で低減できる。さらに各層の界面で生じる反射光は、各層に入射する光線と干渉することによって相殺し合う。従って、反射防止膜は広い波長域及び広い入射角範囲の光線に対して優れた反射防止効果を示す。緻密膜及びシリカエアロゲル膜の光学膜厚がλd/5〜λd/3の範囲でないと、基材から入射媒質にかけての光学膜厚に対する屈折率の変化が滑らかでなくなるため、各膜の界面における反射率が大きくなってしまう。前記光学膜厚d1及びd2は設計波長λdに対して各々λd/4.5〜λd/3.5であるのがより好ましい。 In the antireflection film composed of the two-layer film, when the optical film thickness of the dense film and the silica aerogel film is set in the range of λd / 5 to λd / 3 with respect to the design wavelength λd, the optical film thickness of the antireflection film (optical film). The thickness (the sum of the thicknesses d 1 and d 2 ) is in the range of 2λ d / 5 to 2 λ d / 3, and the change in the refractive index with respect to the optical film thickness from the base material to the incident medium is smooth and stepped. When the optical film thickness of the antireflection film is in the range of 2λd / 5 to 2λd / 3, the optical path difference between the reflected light on the surface of the antireflection film and the reflected light at the boundary between the antireflection film and the base material is the design wavelength. Since it is almost half of λd, these rays cancel each other out due to interference. If the change in the refractive index with respect to the optical film thickness from the base material to the incident medium is made into a smooth step shape, the reflection of the incident light occurring at the boundary of each layer can be reduced in a wide wavelength range. Further, the reflected light generated at the interface of each layer cancels each other by interfering with the light rays incident on each layer. Therefore, the antireflection film exhibits an excellent antireflection effect for light rays in a wide wavelength range and a wide angle of incidence range. Unless the optical film thickness of the dense film and the silica aerogel film is in the range of λd / 5 to λd / 3, the change in the refractive index with respect to the optical film thickness from the base material to the incident medium is not smooth, so that the reflectance at the interface of each film is not smooth. The rate will increase. It is more preferable that the optical film thicknesses d 1 and d 2 are λ d / 4.5 to λ d / 3.5, respectively, with respect to the design wavelength λ d.
基材と緻密膜との間、緻密膜とシリカエアロゲル膜との間、及びシリカエアロゲル膜と入射媒質との間の屈折率差R1，R2及びR3はそれぞれ0.02〜0.4であるのが好ましい。これにより光学膜厚に対する屈折率の変化を直線に近似できる程度に滑らにでき、反射防止効果がいっそう向上する。 The refractive index differences R 1 , R 2 and R 3 between the substrate and the dense film, between the dense film and the silica airgel film, and between the silica airgel film and the incident medium are 0.02 to 0.4, respectively. preferable. As a result, the change in the refractive index with respect to the optical film thickness can be made smooth to the extent that it can be approximated to a straight line, and the antireflection effect is further improved.
反射防止膜が、シリカエアロゲル膜と複数の緻密膜との多層膜からなる場合、複数の緻密膜は、各層の界面で生じた反射光と、各層に入射する光線とが干渉によって相殺し合うように、屈折率の異なる複数の膜を適宜組合せて設計するのが好ましい。このような設計により、反射防止効率をより高めることができる。 When the antireflection film is composed of a multilayer film of a silica aerogel film and a plurality of dense films, the plurality of dense films are such that the reflected light generated at the interface of each layer and the light rays incident on each layer cancel each other out by interference. In addition, it is preferable to design by appropriately combining a plurality of films having different refractive indexes. With such a design, the antireflection efficiency can be further improved.
[3] 光学素子
光学素子は、光学基材の表面に上記反射防止膜を有する。光学基材の材料は、ガラス、結晶性材料及びプラスチックのいずれでも良い。光学基材の材料の具体例として、BK7、LASF01、LASF016、LaFK55、LAK14、SF5等の光学ガラス、パイレックス（登録商標）ガラス、石英、青板ガラス、白板ガラス、PMMA樹脂、PC樹脂、鎖状又は環状のオレフィンを主成分とするポリオレフィン系樹脂等が挙げられる。これらの基材の屈折率は1.35〜2.00の範囲内であるのが好ましい。光学基材の形状としては、平板状、レンズ状、プリズム状、ライトガイド状、フィルム状、回折素子状等が挙げられる。
[3] Optical element The optical element has the antireflection film on the surface of the optical base material. The material of the optical base material may be glass, crystalline material or plastic. Specific examples of the material of the optical base material include optical glass such as BK7, LASF01, LASF016, LaFK55, LAK14, SF5, Pyrex (registered trademark) glass, quartz, blue plate glass, white plate glass, PMMA resin, PC resin, chain or chain. Examples thereof include polyolefin-based resins containing cyclic olefins as a main component. The refractive index of these substrates is preferably in the range of 1.35 to 2.00. Examples of the shape of the optical substrate include a flat plate shape, a lens shape, a prism shape, a light guide shape, a film shape, a diffraction element shape, and the like.
本発明を以下の実施例によりさらに詳細に説明するが、本発明はこれらに限定されない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
実施例1
(1) 混合ゾルの調製
テトラエトキシシラン17.05 gとメタノール69.13 gとを混合した後、アンモニア水溶液（3 N）3.88 gを加えて室温で15時間撹拌し、アルカリ性ゾルを調製した。このアルカリ性ゾル40.01 gに、メタノール2.50 gと塩酸（12 N）1.71 gとを添加して室温で30分間撹拌し、第一の酸性ゾル（固形分：4.94質量％）を44.22 g調製した。
Example 1
(1) Preparation of mixed sol After mixing 17.05 g of tetraethoxysilane and 69.13 g of methanol, 3.88 g of aqueous ammonia (3 N) was added and stirred at room temperature for 15 hours to prepare an alkaline sol. To 40.01 g of this alkaline sol, 2.50 g of methanol and 1.71 g of hydrochloric acid (12 N) were added and stirred at room temperature for 30 minutes to prepare 44.22 g of the first acidic sol (solid content: 4.94% by mass).
室温でテトラエトキシシラン30 mlと、エタノール30 mlと、水2.4 mlとを混合した後、塩酸（1 N）0.1 mlを加え、60℃で90分間撹拌し、第二の酸性ゾル（固形分：14.8質量％）を調製した。 After mixing 30 ml of tetraethoxysilane, 30 ml of ethanol, and 2.4 ml of water at room temperature, 0.1 ml of hydrochloric acid (1 N) was added, and the mixture was stirred at 60 ° C. for 90 minutes, and the second acidic sol (solid content: solid content:: 14.8% by mass) was prepared.
第一の酸性ゾルの全量（44.22 g）に、第二の酸性ゾル0.22 gを添加（第一の酸性ゾル／第二の酸性ゾルの固形分質量比：67.1）し、室温で5分間攪拌して混合ゾルを調製した。 To the total amount of the first acidic sol (44.22 g), add 0.22 g of the second acidic sol (mass ratio of solid content of the first acidic sol / second acidic sol: 67.1), and stir at room temperature for 5 minutes. To prepare a mixed sol.
メジアン径の測定
第一の酸性ゾル及び第二の酸性ゾルのシリカ粒子のメジアン径は、それぞれ16.0 nm、1.8 nmであり、第一の酸性ゾルのシリカ粒子と第二の酸性ゾルのシリカ粒子とのメジアン径比は8.9であった。なお、メジアン径は動的光散乱式粒径分布測定装置LB-550（株式会社堀場製作所製）を使用して測定した。
Measurement of median diameter The median diameters of the silica particles of the first acidic sol and the second acidic sol are 16.0 nm and 1.8 nm, respectively, and the silica particles of the first acidic sol and the silica particles of the second acidic sol The median particle ratio was 8.9. The median diameter was measured using a dynamic light scattering type particle size distribution measuring device LB-550 (manufactured by HORIBA, Ltd.).
第一の酸性ゾル、第二の酸性ゾル及び混合ゾルの調製条件及びメジアン径を表１にまとめた。 Table 1 summarizes the preparation conditions and median diameter of the first acidic sol, the second acidic sol and the mixed sol.
(2) 第一の酸性ゾルと第二の酸性ゾルとの固形分質量比。
(3) 第一の酸性ゾル中のシリカ粒子と第二の酸性ゾル中のシリカ粒子とのメジアン径比。
(2) Solid content mass ratio of the first acidic sol and the second acidic sol.
(3) Median diameter ratio of silica particles in the first acidic sol to silica particles in the second acidic sol.
(2)反射防止膜の形成
(a)６層緻密膜の形成
LF5ガラス平板（直径30 mmの円板状、屈折率nD=1.585）に、表２に示す構成になるように、電子ビーム式の蒸着源を有する装置を用いて真空蒸着法により、基材側から順に第１層〜第６層の緻密膜を形成した。なお物理膜厚及び屈折率の測定には、レンズ反射率測定機（型番：USPM-RU、オリンパス株式会社製）を使用した。
(2) Formation of antireflection film
(a) Formation of 6-layer dense film
On the LF5 glass flat plate (disk-shaped with a diameter of 30 mm, refractive index nD = 1.585), the substrate side is subjected to a vacuum vapor deposition method using an apparatus having an electron beam type vapor deposition source as shown in Table 2. The dense films of the first layer to the sixth layer were formed in order from the beginning. A lens reflectance measuring machine (model number: USPM-RU, manufactured by Olympus Corporation) was used to measure the physical film thickness and the refractive index.
(b) シリカエアロゲル膜の形成
真空蒸着法により形成した６層緻密膜の上に、得られた混合ゾルをスピンコート法により塗布し、その直後、前記混合ゾルが乾燥する前に60℃90%RHの恒温恒湿下に48時間静置（湿度処理）し、さらに160℃で30分間加熱処理した。熱処理後の試料を一旦冷却した後、0.03 Nの水酸化ナトリウム水溶液をスピンコート法で塗布（アルカリ処理）し、120℃で30分間乾燥後、水及びイソプロピルアルコールで順次洗浄し、80℃で30分間乾燥し、前記６層緻密膜の上にシリカエアロゲル膜が形成された反射防止膜を得た。
(b) Formation of silica airgel film The obtained mixed sol is applied by spin coating on a 6-layer dense film formed by vacuum deposition method, and immediately after that, before the mixed sol dries, 60 ° C. 90%. It was allowed to stand under constant temperature and humidity of RH for 48 hours (humidity treatment), and further heat-treated at 160 ° C. for 30 minutes. After cooling the sample after heat treatment, 0.03 N aqueous sodium hydroxide solution is applied by spin coating (alkali treatment), dried at 120 ° C for 30 minutes, washed sequentially with water and isopropyl alcohol, and 30 at 80 ° C. After drying for a minute, an antireflection film having a silica aerogel film formed on the 6-layer dense film was obtained.
(3）評価
得られた反射防止膜のシリカエアロゲル膜（第７層）の屈折率の測定、及び耐擦傷性の評価を行った。なおシリカエアロゾル膜の屈折率は、反射防止膜の反射率を測定しシミュレーションにより求めた。屈折率及び物理膜厚（前述）の測定には、レンズ反射率測定機（型番：USPM-RU、オリンパス株式会社製）を使用した。結果を表５に示す。
(3) Evaluation The refractive index of the obtained silica airgel film (7th layer) of the antireflection film was measured, and the scratch resistance was evaluated. The refractive index of the silica aerosol film was determined by measuring the reflectance of the antireflection film and simulating it. A lens reflectance measuring machine (model number: USPM-RU, manufactured by Olympus Corporation) was used for measuring the refractive index and the physical film thickness (described above). The results are shown in Table 5.
耐傷性評価方法
反射防止膜の最表面のシリカエアロゲル膜を、１ Kg/cm2の圧力をかけながら3600 mm/分の速度で20 mm×20 mmの不織布（商品名「スピックレンズワイパー」、小津産業株式会社製）で30回擦り、表面の傷を目視で確認し以下の基準で評価した。
＜判定基準＞
シリカエアロ膜に全く傷が付かなかった・・・○
シリカエアロ膜に傷は付いたが剥離しなかった・・・△
シリカエアロ膜が剥離した・・・×
Scratch resistance evaluation method The silica airgel film on the outermost surface of the antireflection film is a 20 mm x 20 mm non-woven fabric (trade name "Spic Lens Wiper", Ozu) at a speed of 3600 mm / min while applying a pressure of 1 Kg / cm 2. It was rubbed 30 times with (manufactured by Sangyo Co., Ltd.), and the scratches on the surface were visually confirmed and evaluated according to the following criteria.
<Criteria>
The silica aero film was not scratched at all ... ○
The silica aero film was scratched but did not peel off ... △
The silica aero film peeled off ... ×
比較例１
層構成を表３に示すように変更し、さらに混合ゾルをスピンコート法により塗布した後に、60℃90％RHの恒温恒湿下に48時間静置（湿度処理）する代わりに、80℃で30分間静置した以外は実施例１と同様にして反射防止膜を作製し、実施例１と同様の評価を行った。結果を表５に示す。
Comparative Example 1
The layer structure was changed as shown in Table 3, and the mixed sol was further applied by the spin coating method, and then allowed to stand at 60 ° C. and 90% RH under constant temperature and humidity for 48 hours (humidity treatment) at 80 ° C. An antireflection film was prepared in the same manner as in Example 1 except that it was allowed to stand for 30 minutes, and the same evaluation as in Example 1 was performed. The results are shown in Table 5.
比較例２
層構成を表４に示すように変更し、アルカリ処理及び洗浄・乾燥後の試料を60℃90％RHの条件で72時間湿度処理した以外は比較例１と同様にして反射防止膜を作製し、実施例１と同様の評価を行った。結果を表５に示す。
Comparative Example 2
The layer structure was changed as shown in Table 4, and an antireflection film was prepared in the same manner as in Comparative Example 1 except that the sample after alkali treatment and washing / drying was subjected to humidity treatment at 60 ° C. and 90% RH for 72 hours. , The same evaluation as in Example 1 was performed. The results are shown in Table 5.
表５（続き）
Table 5 (continued)
表５から明らかなように、混合ゾルを塗布直後に湿度処理を行った実施例１のシリカエアロゲル膜は、低屈折率であり耐擦傷性に優れていた。さらに実施例１、比較例１及び２の反射防止膜の表面の様子をFE-SEMで観察した結果（それぞれ図１〜３に示す画像）から分かるように、比較例１及び２の反射防止膜は多数のマイクロクラックが観察されるが、本発明の方法により作製した実施例１の反射防止膜は、その表面のシリカエアロゲル膜にマイクロクラックがほとんど観察されなかった。 As is clear from Table 5, the silica airgel film of Example 1 which was subjected to humidity treatment immediately after the application of the mixed sol had a low refractive index and was excellent in scratch resistance. Further, as can be seen from the results of FE-SEM observation of the surface appearance of the antireflection films of Examples 1 and Comparative Examples 1 and 2 (images shown in FIGS. 1 to 3 respectively), the antireflection films of Comparative Examples 1 and 2 Although a large number of microcracks were observed in the antireflection film of Example 1 produced by the method of the present invention, almost no microcracks were observed in the silica airgel film on the surface thereof.
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