JP2018060137A - lens - Google Patents
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- JP2018060137A JP2018060137A JP2016199269A JP2016199269A JP2018060137A JP 2018060137 A JP2018060137 A JP 2018060137A JP 2016199269 A JP2016199269 A JP 2016199269A JP 2016199269 A JP2016199269 A JP 2016199269A JP 2018060137 A JP2018060137 A JP 2018060137A
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- 230000003287 optical effect Effects 0.000 claims abstract description 129
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011737 fluorine Substances 0.000 claims abstract description 42
- 239000005871 repellent Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000002940 repellent Effects 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims description 55
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 abstract description 8
- 230000000903 blocking effect Effects 0.000 abstract 2
- 239000010408 film Substances 0.000 description 90
- 239000000463 material Substances 0.000 description 26
- 238000011156 evaluation Methods 0.000 description 23
- 239000011521 glass Substances 0.000 description 22
- 239000010409 thin film Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000000758 substrate Substances 0.000 description 14
- 230000002093 peripheral effect Effects 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 9
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- LMYSNFBROWBKMB-UHFFFAOYSA-N 4-[2-(dipropylamino)ethyl]benzene-1,2-diol Chemical compound CCCN(CCC)CCC1=CC=C(O)C(O)=C1 LMYSNFBROWBKMB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- -1 for example Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
本発明は、レンズに関する。 The present invention relates to a lens.
フレアやゴーストを抑制するため、遮光膜によって覆われた遮光部がレンズの光学面の外側の周縁部や外周面（以下、これらをまとめて外周部という）に設けられる場合がある（例えば、特許文献１参照）。 In order to suppress flare and ghost, the light shielding part covered with the light shielding film may be provided on the outer peripheral part or outer peripheral surface (hereinafter collectively referred to as the outer peripheral part) of the optical surface of the lens (for example, patent) Reference 1).
特許文献１に記載されたレンズでは、光学面の有効領域の外側の外周領域及び光学面の外側のコバ面に遮光膜が設けられている。遮光膜は、エポキシ樹脂等のバインダ樹脂、酸化チタン等の無機微粒子、及び染料を含有する遮光塗料が光学面の外周領域及びコバ面に塗布されることによって形成されている。 In the lens described in Patent Document 1, a light shielding film is provided on the outer peripheral area outside the effective area of the optical surface and on the outer surface outside the optical surface. The light shielding film is formed by applying a light shielding paint containing a binder resin such as an epoxy resin, inorganic fine particles such as titanium oxide, and a dye to the outer peripheral region and the edge surface of the optical surface.
また、特許文献１に記載されたレンズでは、フッ化マグネシウムを含有する反射防止膜が光学面の有効領域に形成されており、光学面の外周領域と遮光膜との間には、フッ化マグネシウムと酸発生型の光カチオン重合開始剤から発生した酸とが反応した生成物を含有する中間膜が形成されている。中間膜は遮光膜との密着力を高めるものであり、この中間膜によって遮光膜が光学面の外周領域側から剥離することが抑制されている。 Moreover, in the lens described in Patent Document 1, an antireflection film containing magnesium fluoride is formed in the effective area of the optical surface, and magnesium fluoride is provided between the outer peripheral area of the optical surface and the light shielding film. An intermediate film containing a product obtained by reacting an acid generated from an acid-generating photocationic polymerization initiator and an acid is formed. The intermediate film increases the adhesion with the light shielding film, and the intermediate film suppresses the light shielding film from being peeled off from the outer peripheral region side of the optical surface.
遮光膜は、特許文献１にも記載されるように、遮光部とされるレンズの外周部の表面に遮光塗料が塗布されるが、塗布された遮光塗料が光学面にはみ出る虞がある。 As described in Patent Document 1, the light-shielding film is coated with a light-shielding paint on the outer peripheral surface of a lens serving as a light-shielding part. However, the applied light-shielding paint may protrude from the optical surface.
特許文献１に記載されたレンズでは、フッ化マグネシウムを含有する反射防止膜が光学面の有効領域に形成されているが、フッ化マグネシウムの膜の水に対する接触角は概ね７０°であり、この程度の疎水性では、光学面の有効領域に形成された反射防止膜によって遮光塗料の有効領域へのはみ出しを抑制するには不十分である。 In the lens described in Patent Document 1, an antireflection film containing magnesium fluoride is formed in the effective area of the optical surface, but the contact angle of the magnesium fluoride film with respect to water is approximately 70 °. The degree of hydrophobicity is insufficient to prevent the antireflection film formed in the effective area of the optical surface from suppressing the light shielding paint from protruding into the effective area.
本発明は、上述した事情に鑑みなされたものであり、遮光膜が光学面にかかることなく光学面の外側に形成されたレンズを、低コストにて提供することを目的とする。 The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a lens formed on the outside of an optical surface without a light shielding film on the optical surface at a low cost.
本発明の一態様のレンズは、光学面の外側に、遮光膜によって覆われている遮光部を備え、フッ素含有有機ケイ素化合物からなる撥水膜が、上記光学面を含み且つ上記遮光部を除く領域の表面に形成されている。 The lens of one embodiment of the present invention includes a light-shielding portion covered with a light-shielding film outside the optical surface, and the water-repellent film made of a fluorine-containing organosilicon compound includes the optical surface and excludes the light-shielding portion. It is formed on the surface of the region.
本発明によれば、遮光膜が光学面にかかることなく光学面の外側に形成されたレンズを、低コストにて提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the lens formed in the outer side of the optical surface can be provided at low cost, without a light shielding film covering an optical surface.
図１は、本発明の実施形態を説明するための、レンズの一例を示す。 FIG. 1 shows an example of a lens for explaining an embodiment of the present invention.
図１に示すレンズ１は、光学面２と、光学面２の外側に設けられたフランジ面３とを有する。図示の例では、光学面２は凸曲面に形成されているが、平坦面であってもよいし、凹曲面であってもよい。レンズ１の材料としては、特に限定されないが、例えばシクロオレフィンポリマー（Cyclo Olefin Polymer：ＣＯＰ）、ポリメチルメタクリレート（Polymethyl methacrylate：ＰＭＭＡ）、ポリカーボネート（Polycarbonate：ＰＣ）等の樹脂材料、及び石英ガラス等のガラス材料を用いることができる。 A lens 1 shown in FIG. 1 has an optical surface 2 and a flange surface 3 provided outside the optical surface 2. In the illustrated example, the optical surface 2 is formed as a convex curved surface, but may be a flat surface or a concave curved surface. The material of the lens 1 is not particularly limited, but for example, a resin material such as cycloolefin polymer (COP), polymethyl methacrylate (PMMA), polycarbonate (Polycarbonate: PC), and quartz glass. Glass materials can be used.
そして、レンズ１は遮光膜６によって覆われている遮光部５を光学面２の外側に備え、レンズ１の光学面２を含み且つ遮光部５を除く領域の表面には、撥水膜７が形成されている。図示の例では、遮光膜６はフランジ面３の全体及びレンズ１の外周面４に形成されており、撥水膜７は光学面２にのみ形成されている。 The lens 1 includes a light shielding part 5 covered with a light shielding film 6 outside the optical surface 2, and a water repellent film 7 is formed on the surface of the region including the optical surface 2 of the lens 1 and excluding the light shielding part 5. Is formed. In the illustrated example, the light shielding film 6 is formed on the entire flange surface 3 and the outer peripheral surface 4 of the lens 1, and the water repellent film 7 is formed only on the optical surface 2.
なお、撥水膜７と光学面２との間に反射防止膜が設けられていてもよい。反射防止膜としては、特に限定されないが、例えば高屈折率層及び低屈折率層が交互に積層された多層構造の反射防止膜を用いることができる。高屈折率層の材料としては、酸化チタン（ＴｉＯ２）、酸化アルミニウム（Ａｌ２Ｏ３）、二酸化ケイ素（ＳｉＯ２）等を例示でき、低屈折率層の材料としては、フッ化マグネシウム（ＭｇＦ２）、フッ化バリウム（ＢａＦ２）、フッ化リチウム（ＬｉＦ）等を例示できる。 An antireflection film may be provided between the water repellent film 7 and the optical surface 2. The antireflection film is not particularly limited. For example, an antireflection film having a multilayer structure in which high refractive index layers and low refractive index layers are alternately stacked can be used. Examples of the material for the high refractive index layer include titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), and silicon dioxide (SiO 2 ). Examples of the material for the low refractive index layer include magnesium fluoride (MgF 2 ), barium fluoride (BaF 2 ), lithium fluoride (LiF) and the like.
＜撥水膜＞
撥水膜７はフッ素含有有機ケイ素化合物からなり、フッ素含有有機ケイ素化合物は撥水性及び撥油性に優れる。なお、フッ素含有有機ケイ素化合物は、撥水性及び撥油性を利用し、典型的には液晶ディスプレイのカバーガラス、眼鏡レンズ等の透明基体の表面に形成される防汚膜の材料として用いられる（例えば、国際公開２０１４／１１９４５３号、特開２０１４−１４５９５５号公報参照）。
<Water repellent film>
The water repellent film 7 is made of a fluorine-containing organic silicon compound, and the fluorine-containing organic silicon compound is excellent in water repellency and oil repellency. The fluorine-containing organosilicon compound utilizes water repellency and oil repellency, and is typically used as a material for an antifouling film formed on the surface of a transparent substrate such as a cover glass of a liquid crystal display or a spectacle lens (for example, International Publication 2014/119453, JP-A-2014-145955).
また、フッ素含有有機ケイ素化合物は、ケイ素化合物との親和性に優れ、レンズ１がガラス材料からなる場合に比較的高い撥水膜７の密着力を得ることができる。また、撥水膜７と光学面２との間に反射防止膜が設けられる場合に、撥水膜７に接する反射防止膜の最表層がケイ素化合物によって構成されていれば、レンズ１が樹脂材料からなる場合であっても、反射防止膜を介して撥水膜７の密着力を高めることができる。 Further, the fluorine-containing organosilicon compound is excellent in affinity with the silicon compound, and can obtain a relatively high adhesion of the water-repellent film 7 when the lens 1 is made of a glass material. Further, when an antireflection film is provided between the water repellent film 7 and the optical surface 2, the lens 1 is made of a resin material if the outermost layer of the antireflection film in contact with the water repellent film 7 is made of a silicon compound. Even in this case, the adhesion of the water repellent film 7 can be enhanced through the antireflection film.
フッ素含有有機ケイ素化合物としては、ポリフルオロポリエーテル基、ポリフルオロアルキレン基、及びポリフルオロアルキル基からなる群から選ばれる１つ以上の基を有するフッ素含有有機ケイ素化合物を例示できる。なお、ポリフルオロポリエーテル基とは、ポリフルオロアルキレン基とエーテル性酸素原子とが交互に結合した構造を有する２価の基のことである。 Examples of the fluorine-containing organosilicon compound include a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group. The polyfluoropolyether group is a divalent group having a structure in which polyfluoroalkylene groups and etheric oxygen atoms are alternately bonded.
ポリフルオロポリエーテル基、ポリフルオロアルキレン基、及びポリフルオロアルキル基からなる群から選ばれる１つ以上の基を有するフッ素含有有機ケイ素化合物の具体例としては、下記一般式（Ｉ）〜（Ｖ）で表される化合物等を例示できる。 Specific examples of the fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group include the following general formulas (I) to (V): The compound etc. which are represented by these can be illustrated.
ここで、Ｒｆは炭素数１〜１６の直鎖状のポリフルオロアルキル基（アルキル基として、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）、Ｘは水素原子又は炭素数１〜５の低級アルキル基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）、Ｒ１は加水分解可能な基（例えば、アミノ基、アルコキシ基等）又はハロゲン原子（例えば、フッ素、塩素、臭素、ヨウ素等）、ｍは１〜５０、好ましくは１〜３０の整数、ｎは０〜２、好ましくは１〜２の整数、ｐは１〜１０、好ましくは１〜８の整数である。
Here, Rf is a linear polyfluoroalkyl group having 1 to 16 carbon atoms (as an alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), and X is hydrogen. An atom or a lower alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), R1 is a hydrolyzable group (for example, amino group, alkoxy group) Etc.) or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), m is an integer of 1 to 50, preferably 1 to 30, n is an integer of 0 to 2, preferably 1 to 2, and p is 1 to 2. It is an integer of 10, preferably 1-8.
ＣｑＦ２ｑ＋１ＣＨ２ＣＨ２Ｓｉ(ＮＨ２)３ （ＩＩ）
ここで、ｑは１以上、好ましくは２〜２０の整数である。
C q F 2q + 1 CH 2 CH 2 Si (NH 2) 3 (II)
Here, q is 1 or more, preferably an integer of 2 to 20.
一般式（ＩＩ）で表される化合物としては、ｎ−トリフロロ（１，１，２，２−テトラヒドロ）プロピルシラザン（ｎ−ＣＦ３ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３）、ｎ−ヘプタフロロ（１，１，２，２−テトラヒドロ）ペンチルシラザン（ｎ−Ｃ３Ｆ７ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３）等を例示できる。 Examples of the compound represented by the general formula (II) include n-trifluoro (1,1,2,2-tetrahydro) propylsilazane (n-CF 3 CH 2 CH 2 Si (NH 2 ) 3 ), n-heptafluoro ( 1,1,2,2-tetrahydro) Penchirushirazan (n-C 3 F 7 CH 2 CH 2 Si (NH 2) 3) or the like can be mentioned.
Ｃｑ’Ｆ２ｑ’＋１ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３ (ＩＩＩ)
ここで、ｑ'は１以上、好ましくは１〜２０の整数である。
C q ′ F 2q ′ + 1 CH 2 CH 2 Si (OCH 3 ) 3 (III)
Here, q ′ is 1 or more, preferably an integer of 1-20.
一般式(ＩＩＩ)で表される化合物としては、２−（パーフルオロオクチル）エチルトリメトキシシラン（ｎ−Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３）等が例示される。 Examples of the compound represented by the general formula (III), 2- (perfluorooctyl) ethyltrimethoxysilane (n-C 8 F 17 CH 2 CH 2 Si (OCH 3) 3) , and the like.
ここで、Ｒｆ２は、−（ＯＣ３Ｆ６）ｓ−（ＯＣ２Ｆ４）ｔ−（ＯＣＦ２）ｕ−（ｓ、ｔ、ｕはそれぞれ独立に０〜２００の整数）で表わされる２価の直鎖状ポリフルオロポリエーテル基であり、Ｒ２、Ｒ３は、それぞれ独立に炭素原子数１〜８の一価炭化水素基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基等）である。Ｘ２、Ｘ３は独立に加水分解可能な基（例えば、アミノ基、アルコキシ基、アシロキシ基、アルケニルオキシ基、イソシアネート基等）またはハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等）であり、ｄ、ｅは独立に１〜２の整数であり、ｃ、ｆは独立に１〜５（好ましくは１〜２）の整数であり、ａおよびｂは独立に２または３である。
Here, R f2 is, - (OC 3 F 6) s - (OC 2 F 4) t - (OCF 2) u - (s, t, u are each independently an integer of 0 to 200) represented by 2 R 2 and R 3 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group). Group, n-butyl group, etc.). X 2 and X 3 are independently hydrolyzable groups (for example, amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom) D and e are independently integers of 1 to 2, c and f are independently integers of 1 to 5 (preferably 1 to 2), and a and b are independently 2 or 3. is there.
化合物(ＩＶ)が有するＲｆ２においてｓ＋ｔ＋ｕは、２０〜３００であることが好ましく、２５〜１００であることがより好ましい。また、Ｒ２、Ｒ３としては、メチル基、エチル基、ブチル基がより好ましい。Ｘ２、Ｘ３で示される加水分解性基としては、炭素数１〜６のアルコキシ基がより好ましく、メトキシ基、エトキシ基が特に好ましい。また、ａおよびｂはそれぞれ３が好ましい。 In R f2 of the compound (IV), s + t + u is preferably 20 to 300, more preferably 25 to 100. R 2 and R 3 are more preferably a methyl group, an ethyl group, or a butyl group. As a hydrolysable group shown by X < 2 >, X < 3 >, a C1-C6 alkoxy group is more preferable, and a methoxy group and an ethoxy group are especially preferable. Further, a and b are each preferably 3.
式（Ｖ）中、ｖは１〜３の整数であり、ｗ、ｙ、ｚはそれぞれ独立に０〜２００の整数であり、ｈは１または２であり、ｉは２〜２０の整数であり、Ｘ４は加水分解性基であり、Ｒ４は炭素数１〜２２の直鎖または分岐の炭化水素基であり、ｋは０〜２の整数である。ｗ＋ｙ＋ｚは、２０〜３００であることが好ましく、２５〜１００であることがより好ましい。また、ｉは２〜１０であることがより好ましい。Ｘ４は、炭素数１〜６のアルコキシ基が好ましく、メトキシ基、エトキシ基がより好ましい。Ｒ４としては、炭素数１〜１０のアルキル基がより好ましい。
In the formula (V), v is an integer of 1 to 3, w, y and z are each independently an integer of 0 to 200, h is 1 or 2, and i is an integer of 2 to 20. , X 4 is a hydrolyzable group, R 4 is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and k is an integer of 0 to 2. w + y + z is preferably 20 to 300, and more preferably 25 to 100. Further, i is more preferably 2 to 10. X 4 is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group or an ethoxy group. R 4 is more preferably an alkyl group having 1 to 10 carbon atoms.
また、ポリフルオロポリエーテル基、ポリフルオロアルキレン基、及びポリフルオロアルキル基からなる群から選ばれる１つ以上の基を有するフッ素含有有機ケイ素化合物として、市販されているものでは、ＫＰ−８０１（商品名、信越化学社製）、ＫＹ１７８（商品名、信越化学社製）、ＫＹ−１３０（商品名、信越化学社製）、ＫＹ−１８５（商品名、信越化学社製）、オプツ−ル（登録商標）ＤＳＸおよびオプツールＡＥＳ（いずれも商品名、ダイキン社製）等を例示できる。 In addition, as a commercially available fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group, KP-801 (commodity) Name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-130 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Opt Tool (registered) Trademarks) DSX and OPTOOL AES (both trade names, manufactured by Daikin) can be exemplified.
また、特開２００９−１７３７８７号公報、及び特開２０１４−１９１１８６号公報に記載されたフッ素含有有機ケイ素化合物を含む混合物も、撥水膜７の材料として用いることができる。 Further, a mixture containing a fluorine-containing organosilicon compound described in JP2009-173787A and JP2014-191186A can also be used as the material of the water repellent film 7.
高分子は、一般に分子量が大きくなるほど溶解しにくくなり、フッ素含有有機ケイ素化合物の撥水性を高める観点から、フッ素含有有機ケイ素化合物の分子量は２０００以上であることが好ましい。 In general, the higher the molecular weight of a polymer, the more difficult it is to dissolve, and the molecular weight of the fluorine-containing organosilicon compound is preferably 2000 or more from the viewpoint of increasing the water repellency of the fluorine-containing organosilicon compound.
撥水膜７の形成方法は、特に限定されるものではないが、蒸着法が好ましく、蒸着源としては、例えば溶液若しくは原液のフッ素含有有機ケイ素化合物、又はポーラスな金属若しくは繊維状金属にフッ素含有有機ケイ素化合物を一定量含侵させた、いわゆる蒸着用ペレットを用いることができる。 The method for forming the water-repellent film 7 is not particularly limited, but a vapor deposition method is preferable. As a vapor deposition source, for example, a fluorine-containing organosilicon compound in a solution or a stock solution, or a fluorine-containing metal or a fibrous metal contains fluorine. So-called deposition pellets impregnated with a certain amount of an organosilicon compound can be used.
＜遮光膜＞
遮光膜６は、レンズ１の表面に塗布可能な流動性を有する遮光材料によって形成され、例えば有機又は無機の黒色粒子を含有する樹脂（以下、遮光性インクという）を用いることができる。
<Light shielding film>
The light shielding film 6 is formed of a fluid light shielding material that can be applied to the surface of the lens 1. For example, a resin containing organic or inorganic black particles (hereinafter referred to as a light shielding ink) can be used.
遮光性インクに用いられる樹脂としては、後述する遮光膜６の形成方法との関係において、重合反応の開始をコントロールすることが可能な熱硬化性樹脂及び光硬化性樹脂等のエネルギー硬化性樹脂が好適であり、なかでも光硬化性樹脂が特に好適である。光硬化性樹脂は、熱硬化性樹脂に比べて短時間に効率よく重合反応が進行する。光硬化性樹脂としては、特に限定されないが、例えばアクリル樹脂、エポキシ樹脂等を用いることができる。 Examples of the resin used for the light-shielding ink include energy curable resins such as a thermosetting resin and a photocurable resin that can control the start of the polymerization reaction in relation to the method of forming the light-shielding film 6 described later. Among them, a photocurable resin is particularly preferable. The photocurable resin efficiently proceeds in a shorter time than the thermosetting resin. Although it does not specifically limit as photocurable resin, For example, an acrylic resin, an epoxy resin, etc. can be used.
黒色粒子は、光硬化性樹脂の硬化用の光によっても退色が生じにくいものとして、カーボン粒子、チタン化合物粒子、酸化鉄粒子、酸化銅粒子、酸化クロム粒子、及びシリコンカーバイド粒子が好適であり、これら列挙した粒子の群から選ばれる一つ以上の粒子を用いることができる。 As the black particles, carbon particles, titanium compound particles, iron oxide particles, copper oxide particles, chromium oxide particles, and silicon carbide particles are suitable as those that are not easily faded by light for curing the photocurable resin. One or more particles selected from these listed particle groups can be used.
遮光性インクの塗布方法としては、刷毛塗、スクリーン印刷法、パッド印刷法、及びインクジェット法を例示できるが、これら列挙した塗布方法のなかでも高い塗布精度が得られるインクジェット法が好ましい。 Examples of the method for applying the light-shielding ink include brush coating, screen printing, pad printing, and inkjet. Among these listed, the inkjet method that can provide high coating accuracy is preferable.
図２Ａ〜図２Ｃは、インクジェット法を用いた遮光膜６の形成方法の一例を示す。なお、遮光性インクに用いられる樹脂は光硬化性樹脂であるものとする。 2A to 2C show an example of a method for forming the light shielding film 6 using an ink jet method. Note that the resin used for the light-shielding ink is a photocurable resin.
まず、図２Ａに示すように、レンズ１の光学面２に撥水膜７が形成される。撥水膜７は、上記のとおり、蒸着法によって形成することができ、レンズ１の光学面２を除く他の面がマスクされた状態で、蒸発したフッ素含有有機ケイ素化合物が露呈した光学面２に付着することによって、光学面２に撥水膜７が形成される。なお、必要に応じて光学面２を含むレンズ１の表面に反射防止膜が形成されてもよく、撥水膜７は、光学面２に形成された反射防止膜上に形成されてもよい。 First, as shown in FIG. 2A, a water repellent film 7 is formed on the optical surface 2 of the lens 1. As described above, the water repellent film 7 can be formed by a vapor deposition method, and the optical surface 2 in which the evaporated fluorine-containing organosilicon compound is exposed in a state where the other surfaces except the optical surface 2 of the lens 1 are masked. As a result, the water repellent film 7 is formed on the optical surface 2. If necessary, an antireflection film may be formed on the surface of the lens 1 including the optical surface 2, and the water repellent film 7 may be formed on the antireflection film formed on the optical surface 2.
次に、図２Ｂに示すように、レンズ１のフランジ面３の全体及び外周面４（以下、塗布面という）に遮光性インクＩがインクジェット法によって塗布される。万一、インクジェットヘッドＨから吐出された遮光性インクが光学面２に着弾した場合にも、光学面２は撥水膜７によって覆われていることから、光学面２に付着した遮光性インクを余すことなく除去可能である。さらに、遮光性インクに用いられる樹脂が光硬化性樹脂であれば、遮光性インクの硬化が自然に進行せず、光学面２に付着した遮光性インクの除去が一層容易となる。 Next, as shown in FIG. 2B, the light-shielding ink I is applied to the entire flange surface 3 and the outer peripheral surface 4 (hereinafter referred to as a coating surface) of the lens 1 by an ink jet method. Should the light-shielding ink ejected from the inkjet head H land on the optical surface 2, the optical surface 2 is covered with the water-repellent film 7, so that the light-shielding ink attached to the optical surface 2 is removed. It can be removed without leaving. Furthermore, if the resin used for the light-shielding ink is a photo-curable resin, the light-shielding ink does not naturally cure and the light-shielding ink attached to the optical surface 2 can be removed more easily.
光学面２に付着した遮光性インクを除去する観点から、レンズ１の上記塗布面に遮光性インクが塗布される際に、レンズ１が光軸ｘ周りに回転されることが好ましい。撥水膜７によって覆われている光学面２に付着した遮光性インクは、比較的小さな力が作用しただけでも撥水膜７上において移動される。そして、レンズ１が光軸ｘ周りに回転されることにより遮光性インクには遠心力が作用し、光学面２に付着した遮光性インクは、この遠心力によって、光学面２の外側の上記塗布面に移動される。これにより、光学面２に付着した遮光性インクの除去が一層容易となる。 From the viewpoint of removing the light-shielding ink attached to the optical surface 2, it is preferable that the lens 1 is rotated around the optical axis x when the light-shielding ink is applied to the application surface of the lens 1. The light shielding ink attached to the optical surface 2 covered with the water repellent film 7 is moved on the water repellent film 7 even when a relatively small force is applied. Then, when the lens 1 is rotated around the optical axis x, a centrifugal force acts on the light-shielding ink, and the light-shielding ink attached to the optical surface 2 is applied to the outside of the optical surface 2 by the centrifugal force. Moved to the surface. Thereby, the removal of the light-shielding ink attached to the optical surface 2 is further facilitated.
次に、図２Ｃに示すように、レンズ１の上記塗布面に塗布された遮光性インクに硬化用の光Ｌが照射され、遮光性インクが硬化されることによって遮光膜６が形成される。 Next, as shown in FIG. 2C, the light-shielding ink applied to the application surface of the lens 1 is irradiated with the curing light L, and the light-shielding ink is cured, whereby the light-shielding film 6 is formed.
遮光性インクの表面張力は２０ｍＮ／ｍ以上４０ｍＮ／ｍが好ましく、２５ｍＮ／ｍ以上３５ｍＮ／ｍがより好ましい。また、遮光性インクの粘度は３ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下が好ましく、６ｍＰａ・ｓ以上１５ｍＰａ・ｓがより好ましい。遮光性インクの表面張力及び粘度が上記範囲にあることにより、一般的なインクジェットヘッドを用いて遮光性インクを吐出することが可能である。また、遮光性インクの表面張力及び粘度が上記範囲にあることにより、光学面２に付着した遮光性インクを、レンズ１の回転に伴う遠心力によって、光学面２の外側の上記塗布面により確実に移動させることが可能である。 The surface tension of the light-shielding ink is preferably 20 mN / m or more and 40 mN / m, and more preferably 25 mN / m or more and 35 mN / m. Further, the viscosity of the light-shielding ink is preferably 3 mPa · s or more and 20 mPa · s or less, and more preferably 6 mPa · s or more and 15 mPa · s. When the surface tension and viscosity of the light-shielding ink are in the above ranges, the light-shielding ink can be ejected using a general inkjet head. In addition, since the surface tension and viscosity of the light-shielding ink are within the above ranges, the light-shielding ink attached to the optical surface 2 is more reliably secured to the coating surface outside the optical surface 2 by the centrifugal force accompanying the rotation of the lens 1. It is possible to move to.
また、遮光性インク及び遮光性インクが硬化してなる遮光膜６における黒色粒子の平均粒径は３００ｎｍ以下が好ましく、２５０ｎｍ以下がより好ましい。なお、黒色粒子の平均粒径は、二次粒子の体積平均径であり、光散乱法によって測定される値とする。黒色粒子の平均粒径が上記範囲にあることにより、一般的なインクジェットヘッドを用いて遮光性インクを吐出する際にノズルに詰りが発生することを抑制することができる。また、黒色粒子の平均粒径が上記範囲にあることにより、撥水膜７の撥水効果を高めることができ、光学面２に付着した遮光性インクの除去が一層容易となる。 The average particle diameter of the black particles in the light-shielding ink and the light-shielding film 6 formed by curing the light-shielding ink is preferably 300 nm or less, and more preferably 250 nm or less. The average particle diameter of the black particles is the volume average diameter of the secondary particles and is a value measured by a light scattering method. When the average particle diameter of the black particles is in the above range, it is possible to suppress clogging of the nozzles when ejecting the light-shielding ink using a general inkjet head. Moreover, when the average particle diameter of the black particles is in the above range, the water repellent effect of the water repellent film 7 can be enhanced, and the light-shielding ink attached to the optical surface 2 can be more easily removed.
＜光学面形状＞
図３から図５は、上述した遮光膜６の形成方法との関係において光学面２の好ましい形状を示す。
<Optical surface shape>
3 to 5 show preferred shapes of the optical surface 2 in relation to the method for forming the light shielding film 6 described above.
光学面２に付着した遮光性インクIを、レンズ１の回転に伴う遠心力によって、光学面２の外側の上記塗布面に移動させる場合に、上記塗布面の内縁Ｅ（遮光部５の内縁）から光軸ｘに向けて距離０．５ｍｍまでの領域において、光軸ｘを含む断面内の光学面２各部の接線ｔと光軸ｘとの交差角度θが４５°以上１８０°未満であることが好ましい。図３は、光学面２が凹曲面である場合の交差角度θを、図４は、光学面２が平坦面である場合の交差角度θを、図５は、光学面２が凸曲面である場合の交差角度θを示している。 When the light-shielding ink I attached to the optical surface 2 is moved to the application surface outside the optical surface 2 by centrifugal force accompanying the rotation of the lens 1, the inner edge E of the application surface (the inner edge of the light-shielding portion 5). The crossing angle θ between the tangent t of each part of the optical surface 2 in the cross section including the optical axis x and the optical axis x is in the range from 45 ° to less than 180 ° in the region from the optical axis x to the distance 0.5 mm. Is preferred. 3 shows the intersection angle θ when the optical surface 2 is a concave curved surface, FIG. 4 shows the intersection angle θ when the optical surface 2 is a flat surface, and FIG. 5 shows the optical surface 2 is a convex curved surface. The crossing angle θ in the case is shown.
光学面２に付着した遮光性インクIが遠心力によって上記塗布面に向けて移動される際に、交差角度θが４５°以上１８０°未満であることにより、遮光性インクIの移動に対して光学面２の形状が障壁とならず、遮光性インクIが円滑に上記塗布面に移動される。これにより、光学面２に付着した遮光性インクを、レンズ１の回転によって、より確実に除去することができる。 When the light-shielding ink I attached to the optical surface 2 is moved toward the application surface by centrifugal force, the crossing angle θ is 45 ° or more and less than 180 °. The shape of the optical surface 2 does not become a barrier, and the light-shielding ink I is smoothly moved to the application surface. Thereby, the light-shielding ink attached to the optical surface 2 can be more reliably removed by the rotation of the lens 1.
このように、レンズ１の光学面２を含み且つ遮光部５を除く領域の表面に、フッ素含有有機ケイ素化合物からなる撥水膜７を形成することにより、遮光部５を覆う遮光膜６を形成する遮光性インクが光学面２に付着したとしても、光学面２に付着した遮光性インクを容易に且つ確実に除去することができる。これにより、遮光膜６が光学面２にかかることなく光学面２の外側に形成されたレンズを、低コストにて提供できる。なお、レンズ１では、遮光性インクが塗布されることによって遮光膜６が形成されるレンズ１の表面（塗布面）は、光学面２と同様の平滑面であるが、フレアやゴーストの発生を抑制するため、研削等の処理が施されるによって粗面とされていてもよい。塗布面が粗面とされる場合にも撥水膜７は同様の効果を奏する。 As described above, the water-repellent film 7 made of a fluorine-containing organosilicon compound is formed on the surface of the region including the optical surface 2 of the lens 1 and excluding the light-shielding part 5, thereby forming the light-shielding film 6 that covers the light-shielding part 5. Even if the light-shielding ink that adheres to the optical surface 2, the light-shielding ink attached to the optical surface 2 can be easily and reliably removed. Thereby, the lens formed in the outer side of the optical surface 2 without the light shielding film 6 covering the optical surface 2 can be provided at low cost. In the lens 1, the surface (application surface) of the lens 1 on which the light shielding film 6 is formed by applying light shielding ink is a smooth surface similar to the optical surface 2, but flare and ghosting are generated. In order to suppress it, the surface may be roughened by a process such as grinding. Even when the coated surface is a rough surface, the water repellent film 7 has the same effect.
＜変形例＞
上述したレンズ１の構成は一例であり、図６に示すように、レンズ１は下地層８を遮光部５に有し、遮光膜６は下地層８の上に形成されていてもよい。例えばレンズ１がガラス材料からなる場合に、一般に、無機材料のガラスと遮光膜６に含まれる有機材料の樹脂とは密着力が比較的低いとされるが、下地層８を介して遮光膜６とレンズ１との密着力を高めることができる。
<Modification>
The configuration of the lens 1 described above is an example, and as shown in FIG. 6, the lens 1 may have a base layer 8 in the light shielding portion 5, and the light shielding film 6 may be formed on the base layer 8. For example, in the case where the lens 1 is made of a glass material, it is generally considered that the adhesion between the inorganic material glass and the organic material resin contained in the light shielding film 6 is relatively low, but the light shielding film 6 is interposed via the base layer 8. The adhesion between the lens 1 and the lens 1 can be increased.
下地層８は、レンズ１の表面に塗布可能な流動性を有し、且つレンズ１に対する密着力が遮光膜６を形成する遮光性インクよりも高い材料によって形成され、例えばレンズ１がガラス材料からなる場合に、下地層８の材料としてはシランカップリング剤を例示できる。そして、下地層８の材料としては、重合反応の開始をコントロールすることが可能な光硬化性のものが好ましい。これにより、遮光性インクと同様に、光学面２に付着した下地層８の材料を容易に且つ確実に除去することができる。光硬化性のシランカップリング剤としては、アクリル基を有機官能基として含有するシランカップリング剤を例示できる。さらに、一般的なシランカップリング剤では膜の形成に乾燥工程が必要となるが、光硬化性のシランカップリング剤であれば乾燥工程を省略することができ、工程の簡素化によってコストの増加を抑制することができる。 The underlayer 8 is formed of a material that has fluidity that can be applied to the surface of the lens 1 and has a higher adhesion to the lens 1 than the light-shielding ink that forms the light-shielding film 6. For example, the lens 1 is made of a glass material. In this case, the material for the underlayer 8 can be exemplified by a silane coupling agent. And as a material of the base layer 8, the photocurable thing which can control the start of a polymerization reaction is preferable. Thereby, like the light-shielding ink, the material of the base layer 8 attached to the optical surface 2 can be easily and reliably removed. As a photocurable silane coupling agent, the silane coupling agent which contains an acrylic group as an organic functional group can be illustrated. Furthermore, a general silane coupling agent requires a drying step for film formation, but if it is a photocurable silane coupling agent, the drying step can be omitted, and the cost can be increased by simplifying the step. Can be suppressed.
下地層８の材料の塗布方法としてはインクジェット法が好ましく、インクジェット法によれば高い塗布精度が得られ、さらに遮光性インクもインクジェット法によって塗布される場合に、下地層８の材料及び遮光性インクを一連の工程で塗布することが可能となり、工程の簡素化によってコストの増加を抑制することができる。一般的なインクジェットヘッドを用いて下地層８の材料を吐出することを考慮すると、下地層８の材料の表面張力は２０ｍＮ／ｍ以上４０ｍＮ／ｍが好ましく、２５ｍＮ／ｍ以上３５ｍＮ／ｍがより好ましい。また、下地層８の材料の粘度は３ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下が好ましく、６ｍＰａ・ｓ以上１５ｍＰａ・ｓがより好ましい。 As a method for applying the material for the underlayer 8, the ink jet method is preferable. When the ink jet method is used, high application accuracy is obtained, and when the light shielding ink is also applied by the ink jet method, the material for the underlayer 8 and the light shielding ink are used. Can be applied in a series of steps, and an increase in cost can be suppressed by simplifying the steps. In consideration of discharging the material of the underlayer 8 using a general ink jet head, the surface tension of the material of the underlayer 8 is preferably 20 mN / m or more and 40 mN / m, and more preferably 25 mN / m or more and 35 mN / m. . The viscosity of the material of the underlayer 8 is preferably 3 mPa · s or more and 20 mPa · s or less, and more preferably 6 mPa · s or more and 15 mPa · s.
以下、実験例について説明する。 Hereinafter, experimental examples will be described.
実験例１〜実験例１１に共通して、硝材としてＬＡＨ−５３（オハラ社製）を用い、図１に示したとおり、凸曲面の光学面及び光学面の外側のフランジ面を有するレンズを用意した。 In common with Experimental Examples 1 to 11, using LAH-53 (manufactured by OHARA) as a glass material, a lens having a convex curved optical surface and a flange surface outside the optical surface is prepared as shown in FIG. did.
＜撥水膜の形成＞
実験例２、実験例４、及び実験例５〜実験例１１のレンズに対し、蒸着法によって、膜厚約２０ｎｍの薄膜を光学面にのみ形成した。実験例２及び実験例４のレンズの光学面に形成した薄膜は、フッ化マグネシウムからなり、実験例５のレンズの光学面に形成した薄膜は、フッ素を含有しない有機ケイ素化合物（以下、フッ素非含有有機ケイ素化合物という。）からなり、実験例６〜実験例１１のレンズの光学面に形成した薄膜は、いずれもフッ素含有有機ケイ素化合物からなる。実験例５のフッ素非含有有機ケイ素化合物の組成及び分子量、並びに実験例６〜実験例１１のフッ素含有有機ケイ素化合物の組成及び分子量を表１に示す。なお、実験例１及び実験例３のレンズに対しては、薄膜を形成しなかった。
<Formation of water repellent film>
A thin film having a thickness of about 20 nm was formed only on the optical surface by vapor deposition for the lenses of Experimental Example 2, Experimental Example 4, and Experimental Examples 5 to 11. The thin film formed on the optical surface of the lenses of Experimental Example 2 and Experimental Example 4 is made of magnesium fluoride, and the thin film formed on the optical surface of the lens of Experimental Example 5 is an organosilicon compound that does not contain fluorine (hereinafter referred to as “fluorine-free”). The thin films formed on the optical surfaces of the lenses of Experimental Examples 6 to 11 are all made of a fluorine-containing organic silicon compound. Table 1 shows the composition and molecular weight of the fluorine-free organosilicon compound of Experimental Example 5 and the composition and molecular weight of the fluorine-containing organosilicon compound of Experimental Examples 6 to 11. Note that no thin film was formed on the lenses of Experimental Example 1 and Experimental Example 3.
＜遮光性インクの調液＞
まず、下記の成分を、合計１００質量部に対して下記の割合にて混合することによってブラックミルベースを調製した。
・カーボンブラック（商品名：SPECIAL BLACK 250、デグサ社製） ４０質量部
・分散剤（商品名：BYK−168、ビックケミー社製） ２５質量部
・フェノキシエチルアクリレート(第一工業製薬社製) ３５質量部
なお、上記の成分の混合は、上記の成分を分散機（商品名：モーターミルＭ５０、アイガー社製）に投入し、分散機に投入された上記の成分を直径０．６５ｍｍのジルコニアビーズを用いて周速９ｍ／ｓにて撹拌することによって行った。
<Preparation of light-shielding ink>
First, a black mill base was prepared by mixing the following components in the following ratio with respect to a total of 100 parts by mass.
Carbon black (trade name: SPECIAL BLACK 250, manufactured by Degussa) 40 parts by mass Dispersant (trade name: BYK-168, manufactured by Big Chemie) 25 parts by mass Phenoxyethyl acrylate (Daiichi Kogyo Seiyaku Co., Ltd.) 35 parts by mass Part In addition, the above components are mixed by putting the above components into a disperser (trade name: Motor Mill M50, manufactured by Eiger), and adding the above components put into the disperser into zirconia beads having a diameter of 0.65 mm. And stirred at a peripheral speed of 9 m / s.
調製されたブラックミルベース及び下記の成分を、合計１００質量部に対して下記の割合にて配合することによって遮光性インクを調液した。
・N−ビニルカプロラクタム（ＮＶＣ）
（商品名：V-CAP、ＩＳＰ社製） ２０質量部
・フェノキシエチルアクリレート（ＰＥＡ）
（商品名：NKエステルAMP-10G、新中村化学工業社製） ４０質量部
・ジプロピレングリコールジアクリレート（ＤＰＤＡ）
（商品名：SR508、サートマー・ジャパン社製） １０質量部
・ウレタンアクリレートオリゴマー（平均官能基数２）
（商品名：CN964、サートマー・ジャパン社製） ５質量部
・ビス（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド
（商品名：IRGACURE819、チバ・スペシャルティ・ケミカルズ社製） １０質量部
・ブラックミルベース １５質量部
The light-shielding ink was prepared by blending the prepared black mill base and the following components in the following proportion with respect to 100 parts by mass in total.
・ N-Vinylcaprolactam (NVC)
(Product name: V-CAP, manufactured by ISP) 20 parts by mass phenoxyethyl acrylate (PEA)
(Product name: NK ester AMP-10G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 40 parts by mass-dipropylene glycol diacrylate (DPDA)
(Product name: SR508, manufactured by Sartomer Japan) 10 parts by mass Urethane acrylate oligomer (average number of functional groups: 2)
(Product name: CN964, manufactured by Sartomer Japan) 5 parts by mass Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Product name: IRGACURE819, manufactured by Ciba Specialty Chemicals) 10 parts by mass Black Mill base 15 parts by mass
遮光性インク中のカーボンブラック粒子の平均粒径は、ブラックミルベースを調製する際の撹拌時間を変更することによって調整し、ナノトラック粒度分布測定装置（商品名：UPA−EX150、日機装社製）によって測定した。実験例１、実験例２、及び実験例５〜実験例８に用いた遮光性インクＡ中のカーボンブラック粒子の平均粒径は２５０ｎｍであり、実験例３、実験例４、及び実験例９〜実験例１１に用いた遮光性インクＢ中のカーボンブラック粒子の平均粒径は４００ｎｍであった。 The average particle size of the carbon black particles in the light-shielding ink is adjusted by changing the stirring time when preparing the black mill base, and is measured by a nanotrack particle size distribution analyzer (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.). It was measured. The average particle size of the carbon black particles in the light-shielding ink A used in Experimental Example 1, Experimental Example 2, and Experimental Example 5 to Experimental Example 8 is 250 nm. Experimental Example 3, Experimental Example 4, and Experimental Example 9 to The average particle diameter of the carbon black particles in the light-shielding ink B used in Experimental Example 11 was 400 nm.
＜遮光膜の形成＞
図２Ａ〜図２Ｃに示したとおり、レンズを光軸まわりに回転させた状態で、調液された遮光性インクをインクジェット法によってレンズのフランジ面及び外周面に塗布した。次いで、塗布された遮光性インクに硬化用の光を照射して遮光性インクを硬化させることによって遮光膜を形成した。
<Formation of light shielding film>
As shown in FIGS. 2A to 2C, the prepared light-shielding ink was applied to the flange surface and the outer peripheral surface of the lens by an inkjet method in a state where the lens was rotated around the optical axis. Next, a light-shielding film was formed by irradiating the applied light-shielding ink with curing light to cure the light-shielding ink.
＜遮光性インクの付着度の評価＞
実験例１及び実験例３のレンズの光学面と同様に硝材が表面に露出されたガラス基板、実験例２及び実験例４のレンズの光学面と同様にフッ化マグネシウムからなる薄膜が表面に形成されたガラス基板、実験例５のレンズの光学面と同様にフッ素非含有有機ケイ素化合部からなる薄膜が表面に形成されたガラス基板、実験例６及び実験例９のレンズの光学面と同様にフッ素含有有機ケイ素化合物Ａからなる薄膜が表面に形成されたガラス基板、実験例７及び実験例１０のレンズの光学面と同様にフッ素含有有機ケイ素化合物Ｂからなる薄膜が表面に形成されたガラス基板、及び実験例８及び実験例１１のレンズの光学面と同様にフッ素含有有機ケイ素化合物Ｃからなる薄膜が表面に形成されたガラス基板を別に用意した。なお、ガラス基板を構成する硝材には、イーグルＸＧ（コーニング社製）を用いた。
<Evaluation of adhesion of light-shielding ink>
A glass substrate with a glass material exposed on its surface as in the optical surfaces of the lenses in Experimental Examples 1 and 3, and a thin film made of magnesium fluoride formed on the surface as in the optical surfaces of the lenses in Experimental Examples 2 and 4. Similar to the optical surface of the glass substrate, the glass substrate on which a thin film made of a fluorine-free organic silicon compound portion is formed on the surface in the same manner as the optical surface of the lens of Experimental Example 5, and the optical surface of the lenses of Experimental Example 6 and Experimental Example 9 A glass substrate on which a thin film made of fluorine-containing organosilicon compound A is formed, and a glass substrate on which a thin film made of fluorine-containing organosilicon compound B is formed on the surface in the same manner as the optical surfaces of the lenses of Experimental Examples 7 and 10. As with the optical surfaces of the lenses of Experimental Example 8 and Experimental Example 11, a glass substrate on which a thin film made of a fluorine-containing organosilicon compound C was formed was prepared. In addition, Eagle XG (made by Corning) was used for the glass material which comprises a glass substrate.
そして、これらのガラス基板の表面に遮光性インクＡ（カーボンブラック粒子の平均粒径２５０ｎｍ）及び遮光性インクＢ（カーボンブラック粒子の平均粒径４００ｎｍ）を１０ｎｌ滴下し、ガラス基板の表面に滴下された遮光性インクの液滴の転落角を測定した。転落角が小さいほど、ガラス基板の表面に対する遮光性インクの付着度（密着力）が低い、すなわちガラス基板の表面の遮光性インクに対する撥水効果が高いと言える。測定された転落角が４５°以下の場合にＡ評価とし、転落角が４５°より大きく９０°未満の場合にＢ評価とし、ガラス基板の傾斜角が９０°に達しても液滴の転落が生じない場合にＣ評価として、ガラス基板における遮光性インクの転落角に基づく評価を、実験例１〜実験例１１のレンズの光学面に対する遮光性インクの付着度の評価とした。評価結果を表２に示す。 Then, 10 nl of light-shielding ink A (carbon black particle average particle size of 250 nm) and light-shielding ink B (carbon black particle average particle size of 400 nm) are dropped onto the surface of the glass substrate and dropped onto the surface of the glass substrate. The falling angle of the light-shielding ink droplets was measured. It can be said that the smaller the falling angle, the lower the degree of adhesion (adhesion) of the light-shielding ink to the surface of the glass substrate, that is, the higher the water repellent effect to the light-shielding ink on the surface of the glass substrate. The evaluation is A when the measured falling angle is 45 ° or less, B is evaluated when the falling angle is greater than 45 ° and less than 90 °, and even if the inclination angle of the glass substrate reaches 90 °, the droplet falls. When C did not occur, the evaluation based on the falling angle of the light-shielding ink on the glass substrate was evaluated as the evaluation of the degree of adhesion of the light-shielding ink to the optical surfaces of the lenses of Experimental Examples 1 to 11. The evaluation results are shown in Table 2.
＜遮光膜の印刷適性評価＞
実験例１〜実験例１１のレンズの光学面における遮光性インクの硬化物の有無、及び光学面とフランジ面との境界の光学面側における遮光性インクの硬化物の有無を目視観察により確認した。光学面及び上記境界の光学面側に遮光性インクの硬化物が残存せず、又は上記境界の光学面側に残存する遮光性インクの硬化物が少ないものほど、レンズの回転に伴う遠心力に起因して、光学面に付着した遮光性インクの光学面外側への移動が促進されていると言える。光学面に遮光性インクの硬化物が全く確認されない場合にＡ評価とし、上記境界の光学面側に僅かに遮光性インクの硬化物が確認される場合にＢ評価とし、上記境界の光学面側に遮光性インクの硬化物が確認される場合にＣ評価とし、光学面に遮光性インクの硬化物が確認される場合にＤ評価とした。評価結果を表２に併せて示す。
<Printability evaluation of shading film>
The presence or absence of a cured product of light-shielding ink on the optical surface of the lenses of Experimental Examples 1 to 11 and the presence or absence of a cured product of light-shielding ink on the optical surface side of the boundary between the optical surface and the flange surface were confirmed by visual observation. . The hardened material of the light-shielding ink does not remain on the optical surface and the optical surface side of the boundary, or the less the cured product of the light-shielding ink remains on the optical surface side of the boundary, the more the centrifugal force accompanying the rotation of the lens is. As a result, it can be said that the movement of the light-shielding ink attached to the optical surface to the outside of the optical surface is promoted. The evaluation is A when no cured product of the light-shielding ink is confirmed on the optical surface, and the evaluation is B when the cured product of the light-shielding ink is slightly confirmed on the optical surface side of the boundary, and the optical surface side of the boundary. C was evaluated when a cured product of light-shielding ink was confirmed, and D evaluation was obtained when a cured product of light-shielding ink was confirmed on the optical surface. The evaluation results are also shown in Table 2.
表２に示したとおり、硝材が光学面に露出されている実験例１及び実験例３のレンズ、並びにフッ化マグネシウムからなる薄膜が光学面に形成された実験例２及び実験例４のレンズでは、遮光性インクの付着度がいずれも“Ｃ評価”であり、付着度の評価に相応するように遮光膜の印刷適性がいずれも“Ｄ評価”である。また、フッ素非含有有機ケイ素化合部からなる薄膜が光学面に形成された実験例５のレンズでは、遮光性インクの付着度が“Ｂ評価”であり、付着度の評価に相応するように遮光膜の印刷適性が“Ｃ評価”である。これに対し、フッ素含有有機ケイ素化合物からなる薄膜が光学面に形成された実験例６〜実験例１１のレンズでは、遮光性インクの付着度がいずれも “Ａ評価”であり、遮光膜の印刷適性評価は“Ａ評価”又は“Ｂ評価”である。この結果から、フッ素含有有機ケイ素化合物からなる薄膜は高い撥水効果を有し、フッ素含有有機ケイ素化合物からなる薄膜の撥水効果によって、光学面に付着した遮光性インクの光学面外側への移動が促進されていることがわかる。以上から、フッ素含有有機ケイ素化合物からなる撥水膜を光学面に形成することにより、遮光膜が光学面にかかることなく光学面の外側に形成されたレンズを、低コストにて提供できることが確認された。 As shown in Table 2, in the lenses of Experimental Example 1 and Experimental Example 3 in which the glass material is exposed on the optical surface, and the lenses of Experimental Example 2 and Experimental Example 4 in which the thin film made of magnesium fluoride is formed on the optical surface The degree of adhesion of the light-shielding ink is “C evaluation”, and the printability of the light-shielding film is “D evaluation” so as to correspond to the evaluation of the degree of adhesion. Further, in the lens of Experimental Example 5 in which a thin film made of a fluorine-free organic silicon compound portion was formed on the optical surface, the light-shielding ink adhesion was “B evaluation”, and the light shielding was performed in accordance with the evaluation of the adhesion. The printability of the film is “C evaluation”. On the other hand, in the lenses of Experimental Examples 6 to 11 in which a thin film made of a fluorine-containing organosilicon compound was formed on the optical surface, the degree of adhesion of the light-shielding ink was “A evaluation”, and the light-shielding film was printed. The aptitude evaluation is “A evaluation” or “B evaluation”. From this result, the thin film made of fluorine-containing organosilicon compound has a high water-repellent effect, and the water-repellent effect of the thin film made of fluorine-containing organosilicon compound moves the light-shielding ink attached to the optical surface to the outside of the optical surface. It can be seen that is promoted. From the above, it is confirmed that by forming a water repellent film made of a fluorine-containing organosilicon compound on the optical surface, a lens formed outside the optical surface can be provided at low cost without the light shielding film being applied to the optical surface. It was done.
また、分子量が２０００未満のフッ素含有有機ケイ素化合物Ａからなる薄膜が光学面に形成された実験例６のレンズの遮光膜の印刷適性が“Ｂ評価”であるのに対し、分子量が２０００以上のフッ素含有有機ケイ素化合物Ｂからなる薄膜が光学面に形成された実験例７、及び分子量が２０００以上のフッ素含有有機ケイ素化合物Ｃからなる薄膜が光学面に形成された実験例８のレンズの遮光膜の印刷適性は“Ａ評価”である。この結果から、フッ素含有有機ケイ素化合物の分子量は好ましくは２０００以上であり、これにより、フッ素含有有機ケイ素化合物からなる撥水膜の撥水効果を高め、光学面に付着した遮光性インクをより確実に光学面の外側に移動させることができることがわかる。 Further, the printability of the light-shielding film of the lens of Experimental Example 6 in which the thin film made of the fluorine-containing organosilicon compound A having a molecular weight of less than 2000 was formed on the optical surface was “B evaluation”, whereas the molecular weight was 2000 or more. Example 7 in which a thin film made of a fluorine-containing organosilicon compound B was formed on the optical surface, and a light-shielding film for a lens in Experimental Example 8 in which a thin film made of a fluorine-containing organosilicon compound C having a molecular weight of 2000 or more was formed on the optical surface The printability of “A” is “A”. From this result, the molecular weight of the fluorine-containing organosilicon compound is preferably 2000 or more, thereby enhancing the water-repellent effect of the water-repellent film made of the fluorine-containing organosilicon compound, and ensuring more reliable light-shielding ink attached to the optical surface. It can be seen that it can be moved outside the optical surface.
また、分子量が２０００以上のフッ素含有有機ケイ素化合物からなる薄膜が光学面に形成された実験例７及び実験例８並びに実験例１０及び実験例１１のレンズにおいて、カーボンブラック粒子の平均粒径が３００ｎｍより大きい遮光性インクＢを用いて遮光膜が形成された実験例１０及び実験例１１のレンズでは遮光膜の印刷適性が“Ｂ評価”であるのに対し、カーボンブラック粒子の平均粒径が３００ｎｍより小さい遮光性インクＡを用いて遮光膜が形成された実験例７及び実験例８のレンズでは遮光膜の印刷適性が“Ａ評価”である。この結果から、遮光性インク及び遮光性インクが硬化されてなる遮光膜におけるカーボンブラック粒子の平均粒径は好ましくは３００ｎｍ以下であり、これにより、フッ素含有有機ケイ素化合物からなる撥水膜の撥水効果を高め、光学面に付着した遮光性インクをより確実に光学面の外側に移動させることができることがわかる。 Further, in the lenses of Experimental Example 7, Experimental Example 8, Experimental Example 10, and Experimental Example 11 in which a thin film made of a fluorine-containing organosilicon compound having a molecular weight of 2000 or more was formed on the optical surface, the average particle size of the carbon black particles was 300 nm. In the lenses of Experimental Example 10 and Experimental Example 11 in which the light-shielding film is formed using the larger light-shielding ink B, the printability of the light-shielding film is “B evaluation”, whereas the average particle size of the carbon black particles is 300 nm. In the lenses of Experimental Example 7 and Experimental Example 8 in which the light-shielding film is formed using the smaller light-shielding ink A, the printability of the light-shielding film is “A evaluation”. From this result, the average particle diameter of the carbon black particles in the light-shielding ink and the light-shielding film obtained by curing the light-shielding ink is preferably 300 nm or less, whereby the water-repellent property of the water-repellent film made of a fluorine-containing organosilicon compound. It can be seen that the effect is enhanced and the light-shielding ink attached to the optical surface can be moved more reliably to the outside of the optical surface.
以上説明したとおり、本明細書に開示されたレンズは、光学面の外側に、遮光膜によって覆われている遮光部を備え、フッ素含有有機ケイ素化合物からなる撥水膜が、上記光学面を含み且つ上記遮光部を除く領域の表面に形成されている。 As described above, the lens disclosed in the present specification includes a light-shielding portion covered with a light-shielding film outside the optical surface, and the water-repellent film made of a fluorine-containing organosilicon compound includes the optical surface. And it is formed in the surface of the area | region except the said light-shielding part.
また、本明細書に開示されたレンズは、上記フッ素含有有機ケイ素化合物が、ポリフルオロポリエーテル基、ポリフルオロアルキレン基、及びポリフルオロアルキル基からなる群から選ばれる一つ以上の基を含む。 In the lens disclosed in the present specification, the fluorine-containing organosilicon compound includes one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group.
また、本明細書に開示されたレンズは、上記フッ素含有有機ケイ素化合物の分子量が２０００以上である。 In the lens disclosed in this specification, the molecular weight of the fluorine-containing organosilicon compound is 2000 or more.
また、本明細書に開示されたレンズは、上記遮光膜が有機又は無機の黒色粒子を含有しており、上記黒色粒子の平均粒径が３００ｎｍ以下である。 In the lens disclosed in the present specification, the light-shielding film contains organic or inorganic black particles, and the average particle size of the black particles is 300 nm or less.
また、本明細書に開示されたレンズは、上記黒色粒子が、カーボン粒子、チタン化合物粒子、酸化鉄粒子、酸化銅粒子、酸化クロム、及びシリコンカーバイド粒子からなる群から選ばれる一つ以上の粒子である。 Further, in the lens disclosed in the present specification, the black particles are one or more particles selected from the group consisting of carbon particles, titanium compound particles, iron oxide particles, copper oxide particles, chromium oxide, and silicon carbide particles. It is.
また、本明細書に開示されたレンズは、上記遮光膜が光硬化性樹脂を含有する。 In the lens disclosed in the present specification, the light shielding film contains a photocurable resin.
また、本明細書に開示されたレンズは、上記遮光部が下地層を有し、上記遮光膜が上記下地層の上に形成されている。 In the lens disclosed in the present specification, the light-shielding portion has a base layer, and the light-shielding film is formed on the base layer.
また、本明細書に開示されたレンズは、上記下地層が光硬化性樹脂を含有する。 In the lens disclosed in the present specification, the base layer contains a photocurable resin.
また、本明細書に開示されたレンズは、上記遮光部の内縁から光軸に向けて距離０．５ｍｍまでの領域において、上記光軸を含む断面内の表面各部の接線と上記光軸との交差角度が４５°以上１８０°未満である。 Further, in the lens disclosed in the present specification, in a region from the inner edge of the light-shielding portion to the optical axis at a distance of 0.5 mm, the tangent of each surface portion in the cross section including the optical axis and the optical axis The crossing angle is 45 ° or more and less than 180 °.
１ レンズ
２ 光学面
３ フランジ面
４ 外周面
５ 遮光部
６ 遮光膜
７ 撥水膜
８ 下地層
Ｅ 遮光部の内縁
Ｈ インクジェットヘッド
Ｉ 遮光性インク
Ｌ 光
ｔ 接線
ｘ 光軸
θ 光軸と接線との交差角度
DESCRIPTION OF SYMBOLS 1 Lens 2 Optical surface 3 Flange surface 4 Outer peripheral surface 5 Light-shielding part 6 Light-shielding film 7 Water-repellent film 8 Underlayer E Inner edge H of light-shielding part Inkjet head I Light-shielding ink L Light t Tangential x Optical axis θ Optical axis and tangent line Intersection angle
Claims (9)
フッ素含有有機ケイ素化合物からなる撥水膜が、前記光学面を含み且つ前記遮光部を除く領域の表面に形成されているレンズ。 Provided with a light-shielding part covered with a light-shielding film outside the optical surface,
A lens in which a water repellent film made of a fluorine-containing organosilicon compound is formed on the surface of a region including the optical surface and excluding the light shielding portion.
前記フッ素含有有機ケイ素化合物は、ポリフルオロポリエーテル基、ポリフルオロアルキレン基、及びポリフルオロアルキル基からなる群から選ばれる一つ以上の基を含むレンズ。 The lens according to claim 1,
The fluorine-containing organosilicon compound is a lens including one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group.
前記フッ素含有有機ケイ素化合物の分子量は２０００以上であるレンズ。 The lens according to claim 1 or 2,
The lens whose molecular weight of the said fluorine-containing organosilicon compound is 2000 or more.
前記遮光膜は有機又は無機の黒色粒子を含有しており、
前記黒色粒子の平均粒径は３００ｎｍ以下であるレンズ。 The lens according to any one of claims 1 to 3,
The light shielding film contains organic or inorganic black particles,
A lens having an average particle size of the black particles of 300 nm or less.
前記黒色粒子は、カーボン粒子、チタン化合物粒子、酸化鉄粒子、酸化銅粒子、酸化クロム、及びシリコンカーバイド粒子からなる群から選ばれる一つ以上の粒子であるレンズ。 The lens according to claim 4,
The lens, wherein the black particles are one or more particles selected from the group consisting of carbon particles, titanium compound particles, iron oxide particles, copper oxide particles, chromium oxide, and silicon carbide particles.
前記遮光膜は光硬化性樹脂を含有するレンズ。 The lens according to any one of claims 1 to 5,
The light shielding film is a lens containing a photocurable resin.
前記遮光部は下地層を有し、
前記遮光膜は前記下地層の上に形成されているレンズ。 The lens according to any one of claims 1 to 6,
The light-shielding portion has an underlayer;
The light shielding film is a lens formed on the base layer.
前記下地層は光硬化性樹脂を含有するレンズ。 The lens according to claim 7,
The underlayer is a lens containing a photocurable resin.
前記遮光部の内縁から光軸に向けて距離０．５ｍｍまでの領域において、前記光軸を含む断面内の表面各部の接線と前記光軸との交差角度が４５°以上１８０°未満であるレンズ。 The lens according to any one of claims 1 to 8,
A lens in which the intersection angle between the tangent of each surface portion in the cross section including the optical axis and the optical axis is 45 ° or more and less than 180 ° in the region from the inner edge of the light shielding portion to the optical axis at a distance of 0.5 mm. .
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| CN113238339A (en) * | 2019-07-11 | 2021-08-10 | 华为技术有限公司 | Lens, camera and electronic equipment |
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