JPH0624789A - High-refractive-index opthalmic and optical glass - Google Patents
High-refractive-index opthalmic and optical glassInfo
- Publication number
- JPH0624789A JPH0624789A JP5087759A JP8775993A JPH0624789A JP H0624789 A JPH0624789 A JP H0624789A JP 5087759 A JP5087759 A JP 5087759A JP 8775993 A JP8775993 A JP 8775993A JP H0624789 A JPH0624789 A JP H0624789A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass
- cao
- zno
- refractive index
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005304 optical glass Substances 0.000 title claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 94
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 9
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000006025 fining agent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 abstract 1
- 229910005979 Ge2O3 Inorganic materials 0.000 abstract 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 abstract 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 15
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 238000004031 devitrification Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000006066 glass batch Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- DSSRNNGLLCLIPR-QHGLUPRGSA-N (2s)-2-amino-n-(1,2,3,4-tetrahydronaphthalen-2-yl)propanamide Chemical compound C1=CC=C2CC(NC(=O)[C@@H](N)C)CCC2=C1 DSSRNNGLLCLIPR-QHGLUPRGSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高屈折性ガラスに関
し、さらに詳しくは、光学及び／又は眼科用レンズの製
造に適する高屈折性ガラスに関する。FIELD OF THE INVENTION The present invention relates to high-refractive-index glass, and more particularly to high-refractive-index glass suitable for manufacturing optical and / or ophthalmic lenses.
【０００２】[0002]
【従来の技術】例えば眼鏡用などのガラスレンズの光学
作用は、本質的にガラスレンズの境界を形成する面の曲
率半径及びガラスの屈折率により決定される。ディオプ
ター数が増す（およそ±４ディオプターから上に）程、
レンズの端縁領域及び中央領域は相対的に厚く作製せね
ばならないので、その重量は眼鏡装着者にとって不快に
なる。そのため、例えば低密度及び比較的に高い屈折率
（ｎｄ）を有するガラスの開発により矯正がなされてお
り、これにより、同等の高い焦点力を有するより薄くか
つ軽いガラスの製造が可能になっている。屈折率（ｎ
ｄ）＞１．７７のガラスが上記目的に特に適しており、
工業上の標準となっている。しかしながら、高い屈折率
（ｎｄ）を有するガラスは充分に高いアッベ数（νｄ）
を有さないのが一般的である。アッベ数は、高ければ高
い程、レンズ又は光学系における像欠陥を取り除くのに
特に有利に働く。特に眼鏡用レンズにとって、アッベ数
＞３４のガラスを用いるのが有利である。The optical behavior of glass lenses, for example for spectacles, is essentially determined by the radius of curvature of the surfaces forming the boundaries of the glass lens and the refractive index of the glass. As the number of diopters increases (up to about ± 4 diopters),
Since the edge and center regions of the lens must be made relatively thick, their weight is uncomfortable for the spectacle wearer. Therefore, for example, the development has been made by the development of glass having a low density and a relatively high refractive index (nd), which enables the production of thinner and lighter glass having an equivalent high focal power. . Refractive index (n
d)> 1.77 glasses are particularly suitable for the above purposes,
It has become an industrial standard. However, a glass having a high refractive index (nd) has a sufficiently high Abbe number (νd).
It is common to not have. The higher the Abbe number, the more advantageous it is to remove image defects in the lens or optical system. Especially for spectacle lenses, it is advantageous to use glass with an Abbe number> 34.
【０００３】屈折率（ｎｄ）及びアッベ数（νｄ）に関
する要求を全体的に又は部分的に満たす全系列のガラス
が、今では眼科用又は光学用の用途として知られるよう
になっている。特開昭５８−２２９９４９号には、１．
７７〜１．８１の屈折率（ｎｄ）を有するＳｉＯ2 （Ｂ
2 Ｏ3 ）−ＣａＯ−Ｎｂ2 Ｏ5 系から成るガラスが記載
されている。特開昭５８−２２９９４９号によるガラス
は、従って眼鏡レンズとして好適な非常に良好な屈折率
を示すけれども、このガラスの化学的安定性は充分とは
言えない。これは、なかんずく、ガラス組成物中の非常
に高いＢ2 Ｏ3 含量及び比較的に小さいＴｉＯ2 含量に
よるものである。The entire family of glasses, which fulfills the requirements in whole or in part on the refractive index (nd) and the Abbe number (νd), is now known for ophthalmic or optical applications. JP-A-58-229949 discloses 1.
SiO 2 (B) having a refractive index (nd) of 77 to 1.81
Glasses based on the 2 O 3 ) -CaO-Nb 2 O 5 system are described. The glass according to JP-A-58-229949 therefore exhibits a very good refractive index suitable for spectacle lenses, but the chemical stability of this glass is not sufficient. This is due, inter alia, to the very high B 2 O 3 content and the relatively low TiO 2 content in the glass composition.
【０００４】特開昭６４−７０１２号には、同様にＳｉ
Ｏ2 （Ｂ2 Ｏ3 ）−ＣａＯ−Ｎｂ2Ｏ5 系から成る眼鏡
レンズ用のガラスが記載されており、このガラスは１．
７９０〜１．８１３の屈折率及び３２．２〜３７．０の
アッベ数を有するが、上記公報に記載の実施例により溶
融された大部分のガラスは３４未満のアッベ数を有す
る。特開昭６４−７０１２号によるガラスは、比較的に
ＣａＯ及び／又はＭｇＯに富み（ＣａＯ＋ＭｇＯ合計＝
１６〜４２重量％）、またＣｓ2 Ｏを含有しないが、一
方では比較的に僅かのＬａ2 Ｏ3 を含有する（最大１４
重量％まで）。上記公報の例示されたガラスにおいて
は、僅かに最大１０重量％のＬａ2 Ｏ3 が同時に溶融さ
れている。しかしながら、その結果、全ての場合におい
て、要求される高いアッベ数を達成することは困難にな
る。さらに、上記特開昭６４−７０１２号に記載のガラ
スは一般に特に高いＮｂ2 Ｏ5 含量を有し（１〜３５重
量％と記載されているが、実施例によれば慨ね２８〜３
３重量％である）、この含量は要求されかつ望ましい高
い屈折率を達成するのには適しているかも知れないが、
所望のアッベ数を得るには不充分である。これもまた、
特開昭６４−７０１２号のガラスにおいて特に１９重量
％までの非常に高い潜在的なＴｉＯ2 含量によってお
り、ＴｉＯ2 含量を増大することはガラスのアッベ数を
著しく低下させる。同様に、ＴｉＯ2 及びＮｂ2 Ｏ5 の
比較的高い割合はガラスの比較的に低い失透安定性につ
ながり、即ち、特開昭６４−７０１２号に記載のガラス
は低いＴｉＯ2 及びＮｂ2 Ｏ5 含量を有する比較し得る
ガラスよりもさらに結晶化され易くなる。前記したこと
はまた本質的にドイツ特許第３４ ２０ ３０６号に開
示されているガラスについても言え、ここに記載のガラ
スは２０．４重量％以上のＭｇＯ＋ＣａＯ含量及び最大
６．８重量％のＬａ2 Ｏ3 含量を有し、また同様にＣｓ
2Ｏを含有していない。Japanese Unexamined Patent Publication (Kokai) No. 64-7012 also discloses Si.
A glass for an eyeglass lens composed of the O 2 (B 2 O 3 ) -CaO-Nb 2 O 5 system is described, and the glass is 1.
Although having a refractive index of 790 to 1.813 and an Abbe number of 32.2 to 37.0, most glasses fused according to the examples described in the above publication have an Abbe number of less than 34. The glass according to Japanese Unexamined Patent Publication No. 64-7012 is relatively rich in CaO and / or MgO (CaO + MgO total =
16-42% by weight) and also does not contain Cs 2 O, but on the other hand contains a relatively small amount of La 2 O 3 (maximum 14).
Up to wt%). In the glass exemplified in the above publication, only a maximum of 10% by weight of La 2 O 3 is simultaneously melted. However, as a result, it is difficult to achieve the required high Abbe number in all cases. Further, the glass described in JP-A-64-7012 generally has a particularly high Nb 2 O 5 content (1 to 35% by weight, but according to the examples, heaviness 28 to 3).
3% by weight), although this content may be suitable to achieve the required and desired high refractive index,
Insufficient to obtain the desired Abbe number. This is also
Due to the very high potential TiO 2 content, especially up to 19% by weight, in the glass of JP-A 64-7012, increasing the TiO 2 content significantly reduces the Abbe number of the glass. Similarly, a relatively high proportion of TiO 2 and Nb 2 O 5 leads to relatively low devitrification stability of the glass, i.e., glass is low TiO 2 and Nb 2 O described in JP-A-64-7012 It is more likely to crystallize than a comparable glass with a 5 content. The foregoing also applies essentially to the glasses disclosed in DE 34 20 306, the glasses described here having a MgO + CaO content of 20.4% by weight and above and a La 2 content of up to 6.8% by weight. Has an O 3 content and also Cs
Does not contain 2 O.
【０００５】特開昭６０−２２１３３８号には、１．６
２〜１．８５の屈折率（ｎｄ）及び３５〜６５のアッベ
数（νｄ）を有するガラスが記載されている。Ｂ2 Ｏ3
−ＳｉＯ2 系から成るこのガラスにおいては、５０重量
％までの極めて高いＢ2 Ｏ3割合が可能であるが、最小
量１重量％は常にガラス組成物中に含まれている。さら
に、特開昭６０−２２１３３８号に記載のガラスにおい
ては、幾つかの例においては、酸化物はフッ化物により
多量置換され、それによって２０重量％までの比較的高
いフッ化物割合となっている。さらに、当該ガラスは必
然的に常に最小限のＹ2 Ｏ3 含量は有さねばならず、比
較的に高価なガラスバッチとなる。しかしながら、全て
の点から考察して、特開昭６０−２２１３３８号によれ
ば、多数のガラスバッチがその特許請求の範囲に記載さ
れた組成物範囲を基に製造できるが、例えば、唯単に広
範囲の割合のために生ずるのであるが、得られる非常に
多くのガラスはもはや工業上の要求を満たさない非常に
小さな屈折率を有する。Japanese Patent Laid-Open No. 60-221338 discloses 1.6.
Glasses having a refractive index (nd) of 2 to 1.85 and an Abbe number (νd) of 35 to 65 are described. B 2 O 3
In this glass, which is based on the —SiO 2 system, very high B 2 O 3 proportions of up to 50% by weight are possible, but a minimum amount of 1% by weight is always included in the glass composition. Furthermore, in the glass described in JP-A-60-221338, in some cases the oxides were largely replaced by fluorides, resulting in relatively high fluoride proportions of up to 20% by weight. . Furthermore, the glass must necessarily always have a minimum Y 2 O 3 content, which results in a relatively expensive glass batch. However, in all respects, according to JP 60-221338, a large number of glass batches can be produced on the basis of the composition range stated in the claims, for example, only a wide range. However, the resulting large number of glasses has a very small refractive index which no longer meets the industrial requirements.
【０００６】眼科及び／又は光学用のガラスはまたヨー
ロッパ特許出願公開第２２７２６９号にも開示されてお
り、ここに記載のガラスは１．７８〜１．８２の屈折率
（ｎｄ）及び３１を越えるアッベ数（νｄ）を有し、Ｓ
ｉＯ2 −Ｂ2 Ｏ3 −ＣａＯ−Ｎｂ2 Ｏ5 −Ｌａ2 Ｏ3 系
から成っている。ヨーロッパ特許出願公開第２２７２６
９号に記載のガラスは、１６〜３３重量％のアルカリ土
類酸化物含量を有する。しかしながら、これらの比較的
高いアルカリ土類酸化物含量により、前記したタイプの
ガラスにおいて比較的に劣った失透挙動を示すようにな
る。さらに、二価のガラス成分が高含量になると、カリ
ウム／ナトリウム交換について知られるようなアルカリ
酸化物の拡散を妨げるようになる（ラウシェンバッハ、
リッヒター「シリケートテクニーク」Rauschenbach,Ric
hter in "Silikattechnik"，３３（１９８２）、７０−
７２頁）。ヨーロッパ特許出願公開第２２７２６９号に
記載のガラスはまた、その耐薬品性は依然として改善さ
れる必要がある。上記公報の記載によれば、１０％ＨＣ
ｌと１０分間接触後のサンプルの重量損失により決定さ
れる耐薬品性は、例示されたガラスの場合１３ｍｇ／ｄ
ｍ2 まである。今日では慣例となっているかなりのより
苛酷な試験条件下で２ｍｇ／ｄｍ2 未満というガラスの
耐薬品性に関する厳重な要求は、上記ガラスで満たすに
は不十分であり、あるいは全く満たされない。Glasses for ophthalmology and / or optics are also disclosed in EP-A-227269, the glasses described therein having a refractive index (nd) of 1.78 to 1.82 and above 31. Has an Abbe number (νd), S
iO 2 -B 2 O 3 consists -CaO-Nb 2 O 5 -La 2 O 3 system. European Patent Application Publication No. 22726
The glass described in No. 9 has an alkaline earth oxide content of 16-33% by weight. However, these relatively high alkaline earth oxide contents lead to relatively poor devitrification behavior in glasses of the type mentioned above. Furthermore, the high content of divalent glass constituents prevents the diffusion of alkali oxides as is known for potassium / sodium exchange (Rauschenbach,
Richter "Silicate Technik" Rauschenbach, Ric
hter in "Silikattechnik", 33 (1982), 70-
P. 72). The glass described in EP-A-227269 also requires that its chemical resistance still be improved. According to the description in the above publication, 10% HC
The chemical resistance determined by the weight loss of the sample after contacting with 1 for 10 minutes is 13 mg / d for the exemplified glasses.
There is up to m 2 . The strict requirements for chemical resistance of the glass of less than 2 mg / dm 2 under the considerably more severe test conditions customary today are insufficient or not at all to be met by the glass.
【０００７】[0007]
【発明が解決しようとする課題】従って、本発明の目的
は、前記したような従来技術により公知のガラスの不利
益を解消し、屈折率（ｎｄ）＞１．７７及びアッベ数
（νｄ）＞３４を有し、同時に良好な結晶化抵抗性（耐
結晶化性）及び薬品の侵蝕に対する改善された耐性を有
するガラスを提供することにある。さらに、ガラスを化
学的に硬化させることが可能であり、また、バッチ価格
も比較的に好都合なものでなければならない。SUMMARY OF THE INVENTION Therefore, the object of the present invention is to eliminate the disadvantages of the glass known by the prior art as described above, and the refractive index (nd)> 1.77 and the Abbe number (νd)> It is intended to provide a glass having 34, and at the same time having good crystallization resistance (crystallization resistance) and improved resistance to chemical attack. Furthermore, the glass should be able to be chemically cured and the batch price should also be relatively convenient.
【０００８】[0008]
【課題を解決するための手段】前記目的を達成するため
に、本発明によれば、下記の組成 ＳｉＯ2 ２０〜３５重量％ ＧｅＯ2 ０〜７ 重量％ ΣＳｉＯ2 ＋ＧｅＯ2 ２０〜３５重量％ Ｂ2 Ｏ3 ０〜７ 重量％ Ｐ2 Ｏ5 ０〜３ 重量％ Ｌｉ2 Ｏ ０〜５ 重量％ Ｎａ2 Ｏ ０〜５ 重量％ Ｋ2 Ｏ ０〜５ 重量％ Ｃｓ2 Ｏ ０．１〜５ 重量％ ΣＭ2 Ｏ ０．１〜５ 重量％ ＭｇＯ ０〜５ 重量％ ＣａＯ ５〜１５重量％ ＳｒＯ ０〜７ 重量％ ＢａＯ ０〜７ 重量％ ＺｎＯ ０〜７ 重量％ ＰｂＯ ０〜５ 重量％ ΣＭＯ ５〜１５重量％ Ａｌ2 Ｏ3 ０〜５ 重量％ Ｌａ2 Ｏ3 １５〜２５重量％ Ｂｉ2 Ｏ3 ０〜２ 重量％ Ｇｄ2 Ｏ3 ０〜５ 重量％ ΣＭ2 Ｏ3 １５〜２５重量％ ＴｉＯ2 ５〜１３重量％ ＺｒＯ2 ０〜１０重量％ Ｔａ2 Ｏ5 ０〜５ 重量％ Ｎｂ2 Ｏ5 １０〜２５重量％ ＷＯ3 ０〜５ 重量％ Ｆ ０〜３ 重量％ ＳＯ3 ０〜１ 重量％ 及び必要に応じて慣用の量の清澄剤を有する（ここでＭ
2 Ｏはアルカリ酸化物、ＭＯはアルカリ土類酸化物とさ
らにＰｂＯ及びＺｎＯを表し、またＭ2 Ｏ3 はＬａ2 Ｏ
3 ，Ｇｄ2 Ｏ3 及びＢｉ2 Ｏ3 を表わす）ことを特徴と
する１．７７より大きい屈折率（ｎｄ）、３４より大き
いアッベ数（νｄ）、良好な耐薬品性及び非常に良好な
結晶化抵抗性を有する高屈折性眼科及び光学ガラスが提
供される。In order to achieve the above object, according to the present invention, the following composition SiO 2 20-35 wt% GeO 2 0-7 wt% ΣSiO 2 + GeO 2 20-35 wt% B 2 O 3 0 to 7% by weight P 2 O 5 0 to 3% by weight Li 2 O 0 to 5% by weight Na 2 O 0 to 5% by weight K 2 O 0 to 5% by weight Cs 2 O 0.1 to 5% by weight % ΣM 2 O 0.1-5 wt% MgO 0-5 wt% CaO 5-15 wt% SrO 0-7 wt% BaO 0-7 wt% ZnO 0-7 wt% PbO 0-5 wt% ΣMO 5-5 15% by weight Al 2 O 3 0-5% by weight La 2 O 3 15-25% by weight Bi 2 O 3 0-2% by weight Gd 2 O 3 0-5% by weight ΣM 2 O 3 15-25% by weight TiO 2 5-13 wt% ZrO 2 0 wt% Ta 2 O 5 0~5 wt% Nb 2 O 5 1 25 wt% WO 3 0 to 5 wt% F 0 to 3 having a weight% SO 3 0 to 1 wt% and a refining agent in conventional amounts if desired (where M
2 O is an alkali oxide, MO is an alkaline earth oxide and further PbO and ZnO, and M 2 O 3 is La 2 O.
3 , Gd 2 O 3 and Bi 2 O 3 ), a refractive index (nd) greater than 1.77, an Abbe number (νd) greater than 34, good chemical resistance and very good crystals. High refractive ophthalmic and optical glasses having aging resistance are provided.
【０００９】[0009]
【発明の効果】本発明に係るガラスは、特に今日慣例と
して要求されている屈折率＞１．７７という要求を満た
し、充分に高いアッベ数＞３４（低分散に相当する）を
有し、結晶化に対する良好な抵抗性、一般に好適なＣｓ
2 Ｏの存在下において薬品侵蝕に対する優れた耐性、及
び例えばイオン交換プロセスにおける良好な化学的硬化
性を有することを特徴とする。また、このように優れた
品質を有するガラスを、比較的有利なバッチコストで製
造することができる。Industrial Applicability The glass according to the present invention has a high refractive index> 1.77, which is conventionally required today, and has a sufficiently high Abbe number> 34 (corresponding to low dispersion). Resistance to oxidization, generally suitable Cs
It is characterized by having excellent resistance to chemical attack in the presence of 2 O and, for example, good chemical curability in ion exchange processes. In addition, glass having such excellent quality can be manufactured at a relatively advantageous batch cost.
【００１０】[0010]
【発明の作用及び態様】本発明に係るガラスにおいて、
ガラス系は成分ＳｉＯ2 、アルカリ酸化物、ＣａＯ，Ｌ
ａ2 Ｏ3 及びＴｉＯ2 を基礎としており、ここでＳｉＯ
2 は網状組織形成体として働く。上に挙げた他の成分は
ガラス変化成分として働き、それらの添加の結果として
変性された結合条件及び群配列が網状構造内に生じ、従
ってガラスの物理的及び化学的特性において対応する変
化を生ずる結果となる。本発明によれば、原則として、
網状組織形成体として２０〜３５重量％、好ましくは２
６〜３１重量％の量のＳｉＯ2 のみを用いることが可能
である。ＳｉＯ2 の７重量％までの量を本発明の範囲内
において同族のＧｅＯ2 で置き換えることができるが、
置換によりガラスのコストが著しく増大することになる
ので、関連するＧｅＯ2 による置換はない方が好まし
い。Action and Mode of the Invention In the glass according to the present invention,
Glass-based components are SiO 2 , alkali oxides, CaO, L
based on a 2 O 3 and TiO 2 , where SiO 2
2 acts as a network former. The other components listed above act as glass-altering components, and their addition results in modified bonding conditions and group arrangements within the network and thus corresponding changes in the physical and chemical properties of the glass. Will result. According to the invention, in principle,
20-35% by weight, preferably 2 as a network former
It is possible to use only SiO 2 in an amount of 6 to 31% by weight. Within the scope of the invention, up to 7% by weight of SiO 2 can be replaced by the cognate GeO 2 ,
Substitution with no associated GeO 2 is preferred, as substitution will significantly increase the cost of the glass.
【００１１】さらに、本発明の高屈折性の眼科及び光学
ガラスの場合には、３重量％以下の量のＰ2 Ｏ5 及び／
又は７重量％以下の量のＢ2 Ｏ3 もまた網状組織形成体
として好適である。しかしながら、この選択される二つ
の網状組織形成体のうち、比較的高濃度のＰ2 Ｏ5 では
ガラスは望ましくない不透明になり易いのでＢ2 Ｏ3が
好ましい。従って、もしＰ2 Ｏ5 が全く使用されない以
外の場合、上記網状組織形成体（Ｐ2 Ｏ5 ）はほんの１
重量％までの量で用いることが望ましい。これに対し
て、ガラスの好適な態様においては、低含量のＢ2 Ｏ3
によって溶融特性が改善されるために少なくとも２重量
％をＢ2 Ｏ3 必須含量とすることが望ましい。しかしな
がら、有利には、Ｂ2 Ｏ3 の割合は５重量％を越えるべ
きではない。何故ならば、上記割合を越えると所望の耐
薬品性がもはや充分ではなくなるという危険性があるか
らである。Further, in the case of the highly refractive ophthalmic and optical glass of the present invention, the amount of P 2 O 5 and /
Alternatively, B 2 O 3 in amounts up to 7% by weight are also suitable as network formers. However, of the two network formers selected, B 2 O 3 is preferred because relatively high concentrations of P 2 O 5 tend to make the glass undesirably opaque. Therefore, if P 2 O 5 is not used at all, the network former (P 2 O 5 ) is only 1%.
It is desirable to use in an amount up to wt%. On the other hand, in the preferred embodiment of glass, a low content of B 2 O 3
It is desirable to have at least 2% by weight as the essential content of B 2 O 3 in order to improve the melting properties. However, advantageously, the proportion of B 2 O 3 should not exceed 5% by weight. This is because there is a risk that the desired chemical resistance will no longer be sufficient if the above ratio is exceeded.
【００１２】アルカリ酸化物は、とりわけ融点をより好
都合な範囲に低下させるために、本発明のガラス中に
０．１〜５重量％の量で含有される。驚くべきことに、
本発明に係るガラス系においては、Ｃｓ2 Ｏが最良の効
果を示すということが見い出された。これが、何故この
成分が必須かという理由である。好適な態様において
は、アルカリ酸化物Ｌｉ2 Ｏ，Ｋ2 Ｏ及びＣｓ2 Ｏはガ
ラスバッチ中合計量で２．３〜５重量％含有される。合
計量が２．３重量％未満の場合、所望の融点に調節する
ことがより困難となり、一方、合計量が５重量％を越え
ると、所望の耐薬品性及び光学特性を得ることがより困
難になるという危険性がある。必須のＣｓ2 Ｏの好まし
い割合は０．５〜２重量％であり、その結果、ガラス密
度を過剰に大きく増大することなく、またガラスバッチ
のコストを大きく押し上げることもなく、融点を低下さ
せることができる。この必須のＣｓ2 Ｏ以外の他のアル
カリ酸化物の中では、Ｌｉ2 Ｏを１．８〜５重量％の量
で用いることが好ましい。Ｌｉ2 ＯはＮａ2 Ｏ又はＫ2
Ｏよりも好ましく、というのはこれら他のアルカリ酸化
物は眼科用ガラスの密度をかなり大きく増大させるから
である。Ｌｉ2 Ｏの割合は化学的硬化にとっても有利で
ある。各種用途にとって重量軽減が不十分なことは密度
増大から生じている。上記の点から鑑みて、Ｎａ2 Ｏ及
びＫ2 Ｏの最大含量を最大１重量％に制限することは特
に好ましく、また特にＮａ2 Ｏは全く使用しないのが望
ましい。Alkali oxides are included in the glasses according to the invention in an amount of 0.1 to 5% by weight, in particular in order to lower the melting point to a more convenient range. Amazingly,
It has been found that Cs 2 O has the best effect in the glass system according to the invention. This is why this ingredient is essential. In a preferred embodiment, the alkali oxides Li 2 O, K 2 O and Cs 2 O are contained in the glass batch in a total amount of 2.3 to 5% by weight. When the total amount is less than 2.3% by weight, it becomes more difficult to adjust to a desired melting point, while when the total amount exceeds 5% by weight, it is more difficult to obtain desired chemical resistance and optical properties. There is a risk of becoming. The preferable proportion of essential Cs 2 O is 0.5 to 2% by weight, and as a result, the melting point is lowered without excessively increasing the glass density and without significantly increasing the cost of the glass batch. You can Among the alkali oxides other than the essential Cs 2 O, it is preferable to use Li 2 O in an amount of 1.8 to 5% by weight. Li 2 O is Na 2 O or K 2
Preferred over O, because these other alkali oxides increase the density of the ophthalmic glass considerably. The proportion of Li 2 O is also advantageous for chemical curing. Inadequate weight reduction for various applications results from increased density. In view of the above, it is particularly preferable to limit the maximum content of Na 2 O and K 2 O to a maximum of 1% by weight, and it is particularly preferable not to use Na 2 O at all.
【００１３】二価の金属酸化物ＭｇＯ，ＣａＯ，Ｓｒ
Ｏ，ＢａＯ，ＺｎＯ及びＰｂＯは、ガラスの耐薬品性を
増大させるために、本発明の高屈折性ガラス中に少なく
とも５重量％の合計量で含有される。上に挙げた二価の
金属酸化物の割合の上限は１５重量％である。その理由
は、特にアルカリ土類酸化物を多量に使用すると、失透
性（失透感受性）が増大するためにガラスの安定性が低
下するためである。上記二価の金属酸化物の中でも、Ｃ
ａＯの使用はガラスの耐薬品性を改善するために必須で
あり、８〜１５重量％の割合が好ましい。ＣａＯの５重
量％まではＭｇＯで置換し得るが、ガラスの失透性はか
なり増大する。同様に、ＣａＯの７重量％までのＳｒ
Ｏ，ＢａＯ又はＺｎＯによる置換、あるいはまたＣａＯ
の５重量％までのＰｂＯによる置換は可能であるが、但
し、ＣａＯの最大１０重量％までが他の二価の酸化物の
混合物と置換し得る。さらに、二価の金属酸化物の各々
は、置換しようとする混合物中にそれぞれの上限までの
割合でのみ添加し得る。しかしながら、本発明により可
能なＣａＯのＳｒＯ及び／又はＢａＯによる置換は、ガ
ラスの密度に本発明による上限が生ずるように悪影響を
及ぼす。同様な状況は、ＣａＯが前記した範囲で置換さ
れ得るガラス成分ＺｎＯ及びＰｂＯにも当てはまる。好
適なガラス組成物においては、従って、ＰｂＯ及びＢａ
Ｏは全く使用されず、二価の酸化物ＭｇＯ，ＳｒＯ及び
ＺｎＯはそれぞれ最大２重量％、３重量％及び６重量％
まで用いられ、ここで、ＣａＯの合計７重量％までが上
記３つの酸化物の混合物と置換し得、該混合物中、３つ
の酸化物の各々はそのそれぞれの上限までの割合で存在
し得る。Divalent metal oxides MgO, CaO, Sr
O, BaO, ZnO and PbO are contained in the high refractive index glass of the present invention in a total amount of at least 5% by weight in order to increase the chemical resistance of the glass. The upper limit of the proportion of the divalent metal oxide mentioned above is 15% by weight. The reason for this is that, particularly when a large amount of alkaline earth oxide is used, devitrification (devitrification susceptibility) increases, so that the stability of the glass decreases. Among the above divalent metal oxides, C
The use of aO is essential for improving the chemical resistance of the glass, and a proportion of 8 to 15% by weight is preferable. Up to 5% by weight of CaO can be replaced by MgO, but the devitrification of the glass is considerably increased. Similarly, Sr up to 7% by weight of CaO
Substitution with O, BaO or ZnO, or also CaO
Up to 5% by weight of PbO is possible, provided that up to 10% by weight of CaO can be replaced with a mixture of other divalent oxides. Furthermore, each of the divalent metal oxides can only be added to the mixture to be replaced in proportions up to their respective upper limits. However, the substitution of CaO according to the invention with SrO and / or BaO has a detrimental effect on the density of the glass, so that the upper limit according to the invention occurs. A similar situation applies to the glass components ZnO and PbO, in which CaO can be substituted in the ranges mentioned above. In the preferred glass composition, therefore, PbO and Ba
O is not used at all, and the divalent oxides MgO, SrO and ZnO are 2% by weight, 3% by weight and 6% by weight, respectively.
Up to a total of 7% by weight of CaO can be replaced by the mixture of the three oxides, each of the three oxides being present in proportions up to their respective upper limits.
【００１４】１５〜２５重量％の割合のＬａ2 Ｏ3 は本
発明による眼科用ガラスにとって必須である。Ｌａ2 Ｏ
3 の割合がこの範囲未満あるいはこの範囲を超えた場
合、高屈折率＞１．７７及び所望のアッベ数＞３４は得
られ難くなる。必須成分ＣａＯの場合と同様に、Ｌａ2
Ｏ3 もまた或る限度内でＢｉ2 Ｏ3 又はＧｄ2 Ｏ3 など
同様な効果を有するガラス成分と置き換えることができ
る。全ての点から考察して、２重量％までのＢｉ2 Ｏ3
及び／又は５重量％までのＧｄ2 Ｏ3 により相当する重
量割合のＬａ2 Ｏ3 を置換し得る。しかしながら、置換
を全体的にみると、そのような置換はガラスの価格に悪
影響を及ぼすことに留意すべきである。さらに、Ｂｉ2
Ｏ3 の使用によりガラスが望ましくない黄色に着色され
得るようになり、そのためにＢｉ2 Ｏ3 による置換の上
限はまた比較的に低く僅かに２重量％に設定されるべき
である。好適な態様においては、Ｂｉ2 Ｏ3 及びＧｄ2
Ｏ3 は全く使用されず、排他的にＬａ2 Ｏ3 のみが１７
〜２４重量％の量で用いられる。A proportion of 15 to 25% by weight La 2 O 3 is essential for the ophthalmic glass according to the invention. La 2 O
When the ratio of 3 is less than this range or exceeds this range, it becomes difficult to obtain a high refractive index> 1.77 and a desired Abbe number> 34. As in the case of the essential component CaO, La 2
O 3 can also be replaced within certain limits with glass components with similar effects, such as Bi 2 O 3 or Gd 2 O 3 . Considering from all points, up to 2% by weight of Bi 2 O 3
And / or up to 5% by weight of Gd 2 O 3 may replace the corresponding weight proportion of La 2 O 3 . However, it should be noted that, when looking at substitutions as a whole, such substitutions adversely affect the price of glass. Furthermore, Bi 2
The use of O 3 allows the glass to be colored undesirably yellow, for which reason the upper limit of substitution with Bi 2 O 3 should also be relatively low and set to only 2% by weight. In a preferred embodiment, Bi 2 O 3 and Gd 2
O 3 is not used at all, and only La 2 O 3 is 17
Used in an amount of ~ 24% by weight.
【００１５】本発明に係るガラスにとっての他の２つの
必須成分はＴｉＯ2 とＮｂ2 Ｏ5 である。５〜１３重量
％（ＴｉＯ2 ）及び１０〜２５重量％（Ｎｂ2 Ｏ5 ）の
範囲において、両成分共に所望の屈折率増大に重要な役
割を果たす。必要に応じて本発明に係るガラスに添加し
得る同様に屈折率を増大する他の成分は、ＺｒＯ2 （１
０重量％以下）、及びＴａ2 Ｏ5 及びＷＯ3 （各々５重
量％以下）である。上記成分、特にＺｒＯ2 の使用は望
ましい。何故ならば、ＴｉＯ2 は屈折率を大きく増大す
るだけでなく、分散も増大し、従って、ＴｉＯ2 含量が
１３重量％を越える場合、所望のアッベ数＞３４を得ら
れないという危険性があるからである。従って、特に好
適なガラス組成物においては、ＴｉＯ2 含量の上限は１
０重量％であり、一方、ＺｒＯ2 は必須成分となり、こ
れは２〜７重量％の割合でガラスバッチ中に同時に溶解
される。この場合、ガラスはＷＯ3 又はＴａ2 Ｏ5 を含
有しないことが好ましい。何故ならば、Ｔａ2 Ｏ5 はガ
ラスの価格に悪影響を及ぼし、またＷＯ3 は着色注型品
を生じ易いからである。ＺｒＯ2 とＴｉＯ2 を同時に使
用することが望ましい他の理由としては、両成分共に全
体的にみてガラスの化学的性質にプラスの効果を有する
ことが挙げられる。１０重量％までのＺｒＯ2 割合はガ
ラスの耐アルカリ性を増大し、一方、１３重量％までの
ＴｉＯ2 割合はガラスの耐酸性を増大する。一方、Ｎｂ
2 Ｏ5 の好適な割合は１４〜２０重量％である。The two other essential constituents for the glass according to the invention are TiO 2 and Nb 2 O 5 . In the range of 5 to 13 wt% (TiO 2 ) and 10 to 25 wt% (Nb 2 O 5 ), both components play an important role in increasing the desired refractive index. Other components which likewise increase the refractive index, which can be added to the glass according to the invention, if desired, are ZrO 2 (1
0 wt% or less), and Ta 2 O 5 and WO 3 (each 5 wt% or less). The use of the above components, especially ZrO 2 , is desirable. Because TiO 2 not only greatly increases the refractive index, but also increases the dispersion and therefore there is a risk that the desired Abbe number> 34 cannot be obtained when the TiO 2 content exceeds 13% by weight. Because. Therefore, in a particularly preferred glass composition, the upper limit of the TiO 2 content is 1
0% by weight, while ZrO 2 becomes an essential component, which is simultaneously dissolved in the glass batch in a proportion of 2 to 7% by weight. In this case, the glass preferably does not contain WO 3 or Ta 2 O 5 . This is because Ta 2 O 5 adversely affects the price of glass, and WO 3 tends to produce a colored cast product. Another reason why it is desirable to use ZrO 2 and TiO 2 at the same time is that both components have a positive effect on the glass chemistry as a whole. A ZrO 2 proportion of up to 10% by weight increases the alkali resistance of the glass, whereas a TiO 2 proportion of up to 13% by weight increases the acid resistance of the glass. On the other hand, Nb
A suitable proportion of 2 O 5 is 14 to 20% by weight.
【００１６】本発明に係る高屈折性の眼科及び光学ガラ
スにおいては、５重量％以下、好ましくは２重量％以下
のＡｌ2 Ｏ3 を同様に含有でき、その結果としてガラス
の耐薬品性を改善し得る。しかしながら、Ａｌ2 Ｏ3 含
量が増加する程、特に２重量％を越える量の場合、ガラ
スの失透安定性が低下するため、ガラスに添加するＡｌ
2 Ｏ3 は最大１重量％までの割合とすることが特に好ま
しい。さらに、３重量％以下のＦ及び１重量％以下のＳ
Ｏ3 を本発明のガラス中に含有し得る。好適な態様にお
いては、フッ素含量の上限は１．５重量％であり、ＳＯ
3 含量は最大１重量％である。有利には、ＳＯ3 成分は
全く使用されない。Ｆ及びＳＯ3 共に、清澄剤として使
用される添加剤から生じ得る。上に挙げた上限よりも高
い含量の場合、特にＦの場合、不透明の徴候を生じ易く
なる。また、眼科用ガラス及び光学ガラスの製造におい
て慣用されているように、必要に応じて、従来公知の各
種清澄剤を１重量％以下の量でガラス中に添加すること
ができる。公知の清澄剤は、ヒ素及びアンチモンの酸化
物、化合物、ハロゲン化物、及び硫酸塩である。In the highly refractive ophthalmic and optical glass according to the present invention, 5% by weight or less, preferably 2% by weight or less of Al 2 O 3 can be similarly contained, and as a result, the chemical resistance of the glass is improved. You can However, as the content of Al 2 O 3 increases, particularly when the content exceeds 2% by weight, the devitrification stability of the glass decreases, so Al added to the glass
It is particularly preferred that the proportion of 2 O 3 be up to 1% by weight. Further, 3% by weight or less of F and 1% by weight or less of S
O 3 may be included in the glass of the present invention. In a preferred embodiment, the upper limit of fluorine content is 1.5% by weight,
3 Content is up to 1% by weight. Advantageously, no SO 3 component is used. Both F and SO 3 can result from additives used as fining agents. If the content is higher than the above-mentioned upper limit, especially in the case of F, it tends to cause signs of opacity. If necessary, various conventionally known fining agents can be added to the glass in an amount of 1% by weight or less, as conventionally used in the production of ophthalmic glass and optical glass. Known fining agents are arsenic and antimony oxides, compounds, halides, and sulfates.
【００１７】[0017]
【実施例】以下、実施例を示して本発明についてさらに
具体的に説明するが、本発明が下記実施例に限定される
ものでないことはもとよりである。The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited to the following examples.
【００１８】実施例１〜５ 本発明に係るガラスを製造するために、原材料（酸化
物、炭酸塩、硝酸塩、フッ化物等）を充分に混合し、１
４００℃で溶解し、精製し、均質化した。ガラスを約１
３００℃に予備加熱した金型中に注ぎ、冷却した。実施
例として溶融した５つのガラスの組成及び特性を表１に
示す。表中、ガラス成分の全ての割合は重量％で示す。Examples 1 to 5 In order to produce the glass according to the present invention, the raw materials (oxide, carbonate, nitrate, fluoride, etc.) were mixed thoroughly and
Melted at 400 ° C., purified and homogenized. About 1 glass
It was poured into a mold preheated to 300 ° C. and cooled. Table 1 shows the compositions and properties of five molten glasses as examples. In the table, all percentages of glass components are given in weight percent.
【表１】 [Table 1]
【００１９】実施例５において、酸化物は部分的にフッ
化物により置き換えられた。この実施例においてＦ2 −
Ｏはフッ素により置き換えられた酸素原子の割合を表わ
す。Ｆ2 −Ｏを記入することにより、フッ素が用いられ
ても実施例を１００％に標準化（換算）することが可能
である。具体的なケースにおいては、フッ素割合のＦ 2
−Ｏへの変換は以下の比率によって行われた。 Ｆ2 −Ｏ：Ｆ＝２２：３８ 従って、実施例５においては、これからフッ素原子によ
り置換された酸素原子の割合０．５９重量％が導かれ
る。従って、Ｆの行はＦ2 −Ｏに相当するフッ素の割合
のみを示し、一方、組成欄のＦ2 −Ｏの行から上の全て
の成分の含量は合計１００％になる。屈折率（ｎｄ）及
びアッベ数（νｄ）の測定は常法に従って行った。屈折
率（ｎｄ）を測定するために、Ｈｅの黄色線beo ５８７
ｎｍを用いた。In Example 5, the oxide was partially
Replaced by the compound. In this embodiment, F2 −
O represents the proportion of oxygen atoms replaced by fluorine
You F2 Fluorine is used by entering -O
Even if the embodiment is standardized (converted) to 100%
Is. In a specific case, the fluorine content F 2
Conversion to -O was done according to the following ratios. F2 -O: F = 22: 38 Therefore, in Example 5, the fluorine atom
A percentage of oxygen atoms replaced by 0.59% by weight is derived.
It Therefore, the row of F is F2 Ratio of fluorine equivalent to -O
Only, while F in the composition column2 Everything above the -O line
The total content of the ingredients is 100%. Refractive index (nd)
And the Abbe number (νd) were measured according to a conventional method. refraction
He yellow line beo 587 to determine the rate (nd)
nm was used.
【００２０】耐薬品性（表中、ｄｍ2 当りの減失ｍｇと
して示されている）は、酸／塩基組合せ試験による重量
損失（減失ｍｇ／ｄｍ2 ）により決定された。このため
に、被検ガラスを９０℃の５０重量％ＫＯＨ中で１５分
間処理し、次いで６０℃の０．０５Ｎ ＨＮＯ3 中で１
５分間また室温下の０．０５Ｎ ＨＮＯ3 中でさらに１
５分間処理した。ガラスはすすぎ、乾燥し、処理により
得られた重量損失をｍｇ／ｄｍ2 で決定した。表１から
明らかなように、各実施例により得られた本発明に係る
ガラスは、屈折率及びアッベ数について要求される値を
満足すると共に、酸／塩基組合せ試験において優れた耐
薬品性を示し、このことは減失が２ｍｇ／ｄｍ2 未満で
あること、あるいは２つの実施例（実施例１及び３）の
場合にはさらに１．０ｍｇ／ｄｍ2 未満であることから
明らかである。[0020] Chemical resistance (in the table, shown as the impairment mg per dm 2) it was determined by the weight loss due to the acid / base combination test (the impairment mg / dm 2). For this, the test glass is treated in 50% by weight KOH at 90 ° C. for 15 minutes and then in 0.05N HNO 3 at 60 ° C. for 1 min.
Further 1 minute in 0.05N HNO 3 at room temperature for 5 minutes
It was treated for 5 minutes. The glass was rinsed, dried and the weight loss obtained by the treatment was determined in mg / dm 2 . As is clear from Table 1, the glasses according to the present invention obtained by the respective examples satisfy the required values for the refractive index and the Abbe number and show excellent chemical resistance in the acid / base combination test. This is evident from the loss being less than 2 mg / dm 2 , or even less than 1.0 mg / dm 2 in the two examples (Examples 1 and 3).
───────────────────────────────────────────────────── フロントページの続き (72)発明者 マルク、クレメント ドイツ連邦共和国、6500 マインツ １、 ゼーメリングシュトラーセ 19 (72)発明者 フォルクマール、ガイラー ドイツ連邦共和国、6500 マインツ 21、 ゼルトリウスリング 239 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mark, Clement Germany, 6500 Mainz 1, Sömeringstraße 19 (72) Inventor Volkmar, Gailler Germany, 6500 Mainz 21, Sertorius Ring 239
Claims (3)
2 Ｏはアルカリ酸化物、ＭＯはアルカリ土類酸化物とさ
らにＰｂＯ及びＺｎＯを表し、またＭ2 Ｏ3 はＬａ2 Ｏ
3 ，Ｇｄ2 Ｏ3 及びＢｉ2 Ｏ3 を表わす）ことを特徴と
する１．７７より大きい屈折率（ｎｄ）、３４より大き
いアッベ数（νｄ）、良好な耐薬品性及び非常に良好な
結晶化抵抗性を有する高屈折性眼科及び光学ガラス。1. The following composition: SiO 2 20 to 35% by weight GeO 2 0 to 7% by weight ΣSiO 2 + GeO 2 20 to 35% by weight B 2 O 3 0 to 7% by weight P 2 O 5 0 to 3% by weight Li 2 O 0-5 wt% Na 2 O 0-5 wt% K 2 O 0-5 wt% Cs 2 O 0.1-5 wt% ΣM 2 O 0.1-5 wt% MgO 0-5 wt% CaO 5 to 15 wt% SrO 0 to 7 wt% BaO 0 to 7 wt% ZnO 0 to 7 wt% PbO 0 to 5 wt% ΣMO 5 to 15 wt% Al 2 O 3 0 to 5 wt% La 2 O 3 15 to 25 wt% Bi 2 O 3 0~2 wt% Gd 2 O 3 0~5 wt% ΣM 2 O 3 15~25 wt% TiO 2 5 to 13 wt% ZrO 2 0 wt% Ta 2 O 5 0~ 5% by weight Nb 2 O 5 10 to 25% by weight WO 30 0 to 5% by weight F 0 to 3% by weight SO 3 0 .About.1% by weight and optionally conventional amounts of fining agent (where M
2 O is an alkali oxide, MO is an alkaline earth oxide and further PbO and ZnO, and M 2 O 3 is La 2 O.
3 , Gd 2 O 3 and Bi 2 O 3 ), a refractive index (nd) greater than 1.77, an Abbe number (νd) greater than 34, good chemical resistance and very good crystals. High refractive index ophthalmic and optical glass having resistance to aging.
とする請求項１に記載のガラス。2. A composition SiO 2 26 to 31 wt% of the following B 2 O 3 2 to 5 wt% P 2 O 5 0 to 1 wt% Li 2 O 1.8 to 5 wt% ΣK 2 O + Na 2 O 0~ 1% by weight Cs 2 O 0.5 to 2% by weight ΣLi 2 O + K 2 O + Cs 2 O + Na 2 O 2.3 to 5% by weight MgO 0 to 2% by weight CaO 8 to 15% by weight SrO 0 to 3% by weight ZnO 0 0 6% by weight ΣMgO + CaO + ZnO + SrO 8-15% by weight Al 2 O 3 0-1% by weight La 2 O 3 17-24% by weight TiO 2 5-10% by weight ZrO 2 2-7% by weight Nb 2 O 5 14-20% by weight Glass according to claim 1, characterized in that it has 0 to 1.5% by weight F 0 to 1% by weight SO 3 and optionally conventional amounts of fining agents.
ｍ2 未満の重量損失（減失）を示すことを特徴とする請
求項１又は２に記載のガラス。3. 2 mg / d in acid / base combination test
Glass according to claim 1 or 2, exhibiting a weight loss (loss) of less than m 2 .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4210011A DE4210011C1 (en) | 1992-03-27 | 1992-03-27 | |
| DE4210011.9 | 1992-03-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0624789A true JPH0624789A (en) | 1994-02-01 |
| JP3247482B2 JP3247482B2 (en) | 2002-01-15 |
Family
ID=6455178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08775993A Expired - Fee Related JP3247482B2 (en) | 1992-03-27 | 1993-03-24 | High refractive ophthalmic and optical glass |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3247482B2 (en) |
| DE (1) | DE4210011C1 (en) |
| FR (1) | FR2689117B1 (en) |
| GB (1) | GB2265367B (en) |
| IT (1) | IT1260626B (en) |
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| JP2000016830A (en) * | 1998-04-30 | 2000-01-18 | Hoya Corp | Optical glass and optical product |
| JP2006219365A (en) * | 2005-01-17 | 2006-08-24 | Ohara Inc | Glass |
| JP2010189262A (en) * | 2009-02-13 | 2010-09-02 | Schott Ag | Barium-free radiopaque glass and the use thereof |
| US7897531B2 (en) | 2005-01-17 | 2011-03-01 | Kabushiki Kaisha Ohara | Glass |
| US8207075B2 (en) | 2008-01-31 | 2012-06-26 | Ohara Inc. | Optical glass |
| CN104496174A (en) * | 2014-11-21 | 2015-04-08 | 柳州创宇科技有限公司 | Optical glass with high refractive index and optical element |
| JP2018108920A (en) * | 2016-12-28 | 2018-07-12 | 株式会社オハラ | Optical glass, preform, and optical element |
| JPWO2017175552A1 (en) * | 2016-04-04 | 2019-02-14 | 株式会社オハラ | Optical glass, preform material and optical element |
| JP2019116414A (en) * | 2017-12-26 | 2019-07-18 | Hoya株式会社 | Optical glass and optical element |
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|---|---|---|---|---|
| JPS6021828A (en) * | 1983-07-14 | 1985-02-04 | Hoya Corp | Glass for spectacle lens |
| JPS60122746A (en) * | 1983-12-07 | 1985-07-01 | Hoya Corp | Optical glass |
| JPS60221338A (en) * | 1984-04-12 | 1985-11-06 | Ohara Inc | Optical glass |
| BR8605356A (en) * | 1985-11-29 | 1987-08-04 | Corning Glass Works | GLASS FOR OPTICAL AND / OR OPHTHALMIC APPLICATIONS |
| JPS647012A (en) * | 1987-06-30 | 1989-01-11 | Ricoh Kk | Zoom lens enabling close-up photography |
-
1992
- 1992-03-27 DE DE4210011A patent/DE4210011C1/de not_active Expired - Lifetime
-
1993
- 1993-03-01 GB GB9304049A patent/GB2265367B/en not_active Expired - Fee Related
- 1993-03-12 IT ITTO930169A patent/IT1260626B/en active IP Right Grant
- 1993-03-24 JP JP08775993A patent/JP3247482B2/en not_active Expired - Fee Related
- 1993-03-25 FR FR9303422A patent/FR2689117B1/en not_active Expired - Fee Related
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| JP2006219365A (en) * | 2005-01-17 | 2006-08-24 | Ohara Inc | Glass |
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| JP2010189262A (en) * | 2009-02-13 | 2010-09-02 | Schott Ag | Barium-free radiopaque glass and the use thereof |
| US8178595B2 (en) | 2009-02-13 | 2012-05-15 | Schott Ag | X-ray opaque barium-free glasses and uses thereof |
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| JPWO2017175552A1 (en) * | 2016-04-04 | 2019-02-14 | 株式会社オハラ | Optical glass, preform material and optical element |
| JP2018108920A (en) * | 2016-12-28 | 2018-07-12 | 株式会社オハラ | Optical glass, preform, and optical element |
| JP2019116414A (en) * | 2017-12-26 | 2019-07-18 | Hoya株式会社 | Optical glass and optical element |
| KR20210097127A (en) * | 2018-11-29 | 2021-08-06 | 코닝 인코포레이티드 | High refractive index silicate glass composition with reduced devitrification kinetics |
| JP2022509646A (en) * | 2018-11-29 | 2022-01-21 | コーニング インコーポレイテッド | High refractive index silicate glass composition with reduced devitrification rate |
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Also Published As
| Publication number | Publication date |
|---|---|
| ITTO930169A0 (en) | 1993-03-12 |
| JP3247482B2 (en) | 2002-01-15 |
| DE4210011C1 (en) | 1993-07-15 |
| GB9304049D0 (en) | 1993-04-14 |
| ITTO930169A1 (en) | 1994-09-12 |
| IT1260626B (en) | 1996-04-22 |
| FR2689117A1 (en) | 1993-10-01 |
| FR2689117B1 (en) | 1995-05-24 |
| GB2265367A (en) | 1993-09-29 |
| GB2265367B (en) | 1995-08-02 |
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