Abstract:
An optical glass has a large negative anomalous dispersion value and optical constants of refractive index (nd) within a range of 1.65-1.80 and Abbe number (νd) within a range of 28-42. The optical glass includes, as its essential ingredients, in weight percent, 20-50% SiO 2 , 6-20% B 2  O 3  where SiO 2  /B 2  O 3  ≦6, 0.5-15% ZrO 2  and 31-50% Nb 2  O 5 .

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to an optical glass having a large negative anomalous dispersion value and having optical constants of refractive index (nd) within a range from 1.65 to 1.80 and Abbe number (ν d) within a range from 28 to 42 and moreover having no PbO and As 2  O 3  ingredients. 
     In an optical lens system, chromatic aberration can be removed for two color light by combining two types of normal optical glasses having different Abbe numbers, namely optical glasses having no large anomalous dispersion. As regards light of other colors, however, there still exists a residual chromatic aberration which is expressed as secondary spectra. Correction of such secondary spectra, particularly spectra in the region from blue spectrum of visible region to the ultraviolet spectrum, is desired in the design of optical lenses and such secondary spectra can be reduced to a substantial degree by combining an optical lens having a large positive anomalous dispersion with an optical lens having a large negative anomalous dispersion. 
     As optical glasses having optical constants within the above described ranges and having also a negative anomalous dispersion, known in the art are a SiO 2  --B 2  O 3  --Al 2  O 3  --PbO glass disclosed in Japanese Patent Publication No. Sho-45-2311 and a SiO 2  --B 2  O 3  --Al 2  O 3  --PbO--Sb 3  O 3  glass disclosed in Japanese Patent Application Laid-open No. Sho-48-74516. Since, however, these glasses contain a fairly large amount of PbO, they have a high density and a large weight and therefore have a disadvantage in using them. Moreover, these glasses do not have sufficient chemical durability and are costly for coping with environmental problems they have in manufacturing, processing and disusing them. 
     As glasses containing no PbO, Japanese Patent Publication No. Sho-51-34407 discloses a glass which contains SiO 2 , B 2  O 3  and GeO 2  as glass-forming materials and also contains Li 2  O, ZnO, ZrO 2  and Ta 2  O 5 . This glass, however, is economically disadvantageous because, for achieving desired refractive index and negative anomalous dispersion, it introduces a large amount of GeO and Ta 2  O 5  which are very expensive. Besides, this glass has difficulty in melting and therefore it is hard to obtain a homogeneous glass. Japanese Patent Publication No. Sho-58-46459 discloses a SiO 2  --Nb 2  O 5  --R 2  O--RO glass but this publication does not suggest anything about negative anomalous dispersion of the glass. 
     It is, therefore, an object of the invention to provide an optical glass having negative anomalous dispersion and having optical constants of refractive index (nd) within a range from 1.65 to 1.80 and Abbe number (ν d) within a range from 28 to 42, having excellent chemical durability and homogeneity and containing no PbO or As 2  O 3  which increases cost for protecting the environment and containing no expensive GeO 2  or Ta 2  O 5  as an essential ingredient. 
     SUMMARY OF THE INVENTION 
     As a result of laborious studies and experiments made by the inventors of the present invention, it has been found, which has led to the present invention, that the above described object of the invention can be achieved by providing a SiO 2  --B 2  O 3  --ZrO 2  --Nb 2  O 5  glass of a specific composition. 
     For achieving the object of the invention, there is provided an optical glass having a negative anomalous dispersion consisting in weight percent of: 
     
         ______________________________________   SiO.sub.2    20-50%   B.sub.2 O.sub.3                6-20%______________________________________ 
    
     where SiO 2  /B 2  O 3  ≦6 in weight percent, 
     
         ______________________________________  ZrO.sub.2     0.5-15%  Nb.sub.2 O.sub.5                31-50%  Al.sub.2 O.sub.3                0-4%  GeO.sub.2     0-5%  Y.sub.2 O.sub.3                0-5%  La.sub.2 O.sub.3                0-5%  Gd.sub.2 O.sub.3                0-5%  Yb.sub.2 O.sub.3                0-5%  Ta.sub.2 O.sub.5                0-15%  WO.sub.3      0-10%  ZnO           0-14%  MgO           0-7%  CaO           0-7%  SrO           0-14%  BaO           0-14%  Li.sub.2 O    0-10%  Na.sub.2 O    0-15%  K.sub.2 O     0-15%  Sb.sub.2 O.sub.3                0-1%.______________________________________ 
    
     In one aspect of the invention, there is provided an optical glass having a negative anomalous dispersion consisting in weight percent of: 
     
         ______________________________________   SiO.sub.2    20-50%   B.sub.2 O.sub.3                6-20%______________________________________ 
    
     where SiO 2  /B 2  O 3  ≦6 in weight percent, 
     
         ______________________________________  ZrO.sub.2     0.5-15%  Nb.sub.2 O.sub.5                31-50%  Al.sub.2 O.sub.3                0-4%  GeO.sub.2     0-5%  Y.sub.2 O.sub.3                0-5%  La.sub.2 O.sub.3                0-5%  Gd.sub.2 O.sub.3                0-5%  Yb.sub.2 O.sub.3                0-5%  Ta.sub.2 O.sub.5                0-15%  WO.sub.3      0-10%  ZnO           0-14%  MgO           0-7%  CaO           0-7%  SrO           0-14%  BaO           0-14%  Li.sub.2 O    0-10%  Na.sub.2 O    0-15%  K.sub.2 O     0-15%  Sb.sub.2 O.sub.3                0-1%.______________________________________ 
    
     wherein Δθ g, F representing value of anomalous dispersion is -0.001 or below. 
     In another aspect of the invention, there is provided an optical glass having a negative anomalous dispersion consisting in weight percent of: 
     
         ______________________________________   SiO.sub.2    20-40%   B.sub.2 O.sub.3                6-20%______________________________________ 
    
     where SiO 2  /B 2  O 3  ≦6 in weight percent, 
     
         ______________________________________ZrO.sub.2               0.5-15%Nb.sub.2 O.sub.5        31-45%Al.sub.2 O.sub.3        0-4%GeO.sub.2               0-5%Y.sub.2 O.sub.3 + La.sub.2 O.sub.3 + Gd.sub.2 O.sub.3 + Yb.sub.2 O.sub.3                   0-5%______________________________________ 
    
     in which 
     
         ______________________________________Y.sub.2 O.sub.3         0-5%La.sub.2 O.sub.3        0-5%Gd.sub.2 O.sub.3        0-5%Yb.sub.2 O.sub.3        0-5%Ta.sub.2 O.sub.5        0-10%WO.sub.3                0-10%ZnO + MgO + CaO + SrO + BaO                   0.5-20%______________________________________ 
    
     in which 
     
         ______________________________________ZnO                    0-14%MgO                    0-7%CaO                    0.5-7%SrO                    0-14%BaO                    0-14%Li.sub.2 O + Na.sub.2 O + K.sub.2 O                  0.5-20%______________________________________ 
    
     in which 
     
         ______________________________________  Li.sub.2 O    0.5-10%  Na.sub.2 O    0-15%  K.sub.2 O     0-10%  Sb.sub.2 O.sub.3                0-1%______________________________________ 
    
     and having refractive index (nd) within a range from 1.65 to 1.80 and Abbe number (ν d) within a range from 28 to 42 and also having Δθg, F value representing anomalous dispersion of -0.001 or below. 
     The value of Δθ g, F which represents the anomalous dispersion is calculated in the following manner: 
     First, relative partial dispersion (θ g, F) is calculated by the formula ##EQU1## Then, in FIG. 1 in which the vertical axis represents the relative partial dispersion (θ g, F) and the horizontal axis represents the Abbe number (νd), two normal types of glasses NSL7 and PBM2 (both names of glasses made by Kabushiki Kaisha Ohara) having partial dispersion (θ g, F) and Abbe number (νd) shown in the following Table 1 are selected as reference. 
     
                       TABLE 1______________________________________Type            θg,F                   νd______________________________________NSL7            0.5436  60.49PBM2            0.5828  36.26______________________________________ 
    
     Coordinates (θ g, F; νd) of these two glasses designated by the black circle mark in FIG. 1 are connected by straight line L. Difference (Δθ g, F) in the vertical axis between this line L and a coordinate (θ g, F: νd) of a glass to be compared represents a value of deviation in the relative partial dispersion, i.e., anomalous dispersion. 
     In a case where the value of Δθ g, F thus calculated is of a negative value, i.e., a coordinate (θ g, F : νd) of a glass is located below the line L in FIG. 1, this glass has a negative anomalous dispersion. In a case where the value of Δθ g, F is of a positive value, i.e., a coordinate (θ g, F: νd) is above the line L, this glass has positive anomalous dispersion. In both cases of negative and positive values, the larger the absolute value of Δθ g, F, the larger is anomalous dispersion of the glass. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 is a θ g, F- νd diagram in which the vertical axis represents the relative partial dispersion (θ g, F) and horizontal axis represents the Abbe number (ν d). 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In the glass made according to the invention, the above described content ranges of the respective ingredients have been selected for the reasons stated below. In the following description, the content ranges of the respective ingredients are expressed in weight percent. 
     The SiO 2  ingredient is an indispensable ingredient as a glass forming oxide. If the amount of this ingredient is below 20%, a stable glass cannot be obtained and chemical durability of the glass is insufficient. If the amount of this ingredient exceeds 50%, it becomes difficult to obtain a glass having optical constants within the desired ranges and besides the melting property of the glass is deteriorated. For obtaining a glass having an excellent homogeneity, the content range of the SiO 2  ingredient should preferably be within a range from 20 to 40%. 
     The B 2  O 3  ingredient is an important ingredient as a glass forming oxide like the SiO 2  ingredient and is also very important as an ingredient which increases negative anomalous dispersion. If the amount of this ingredient is below 6%, this effect is not sufficiently achieved and the melting property of the glass is deteriorated with resulting difficulty in obtaining a homogeneous glass. If the amount of this ingredient exceeds 20%, the glass becomes instable and its chemical durability is deteriorated. In the present invention, it is most important, for maintaining Δθ g, F representing anomalous dispersion at a value of -0.001 or below, to restrict the weight ratio of SiO 2  /B 2  O 3  to 6 or below. 
     The ZrO 2  ingredient is effective for increasing refractive index and negative anomalous dispersion. If the amount of this ingredient is below 0.5%, a sufficient effect cannot be obtained whereas if the amount of this ingredient exceeds 15%, devitrification occurs and a stable glass cannot be obtained. 
     The Nb 2  O 5  ingredient is an indispensable ingredient for maintaining the desired optical constants. If the amount of this ingredient is below 31%, it becomes difficult to maintain the desired optical constants whereas if the amount of this ingredient exceeds 50%, devitrification occurs in the glass. For obtaining a particularly stable glass, the amount of this ingredient should preferably be within a range from 31% to 45%. 
     The Al 2  O 3  ingredient may be optionally added for adjusting the optical constants and improving chemical durability. The amount of this ingredient should be up to 4%. 
     The GeO 2  ingredient may be optionally added for adjusting the optical constants. It suffices to add this ingredient in the amount up to 5%. 
     The Y 2  O 3 , La 2  O 3 , Gd 2  O 3  and Yb 2  O 3  ingredients may be optionally added for adjusting the optical constants and improving chemical durability. These ingredients can be added to 5% respectively. These ingredients, however, tend to increase the devitrification tendency of the glass and, for obtaining a stable glass, the total amount of these ingredients should preferably be 5% or below. 
     The Ta 2  O 5  and WO 3  ingredients may be optionally added for adjusting the optical constants. The amount of the Ta 2  O 5  ingredient should be up to 15% and preferably up to 10% because this ingredient tends to produce an unmelted portion in a melted glass. The WO 3  ingredient tends to decrease the negative anomalous dispersion value and therefore the amount of this ingredient should be up to 10%. 
     The CaO ingredient is effective for improving chemical durability of the glass and increasing the negative anomalous dispersion value. If the amount of this ingredient exceeds 7%, devitrification tendency occurs in the glass. For achieving the above effects while maintaining stability of the glass, the amount of this ingredient should preferably be within a range from 0.5% to 7%. 
     The ZnO, MgO, SrO and BaO ingredients may be optionally added for adjusting the optical constants, stabilizing the glass and improving chemical durability. If the amounts of these ingredients exceed 14%, 7%, 14% and 14% respectively, the devitrification tendency increases rather than decreases. For obtaining a glass which is more stable and excellent in chemical durability, the total amount of one or more of the CaO, ZnO, MgO, SrO and BaO ingredients should preferably be within a range from 0.5% to 20%. 
     The Li 2  O, Na 2  O and K 2  O ingredients may be optionally added for enhancing melting of the glass and expanding the glassifying range. If the amounts of these ingredients exceed 10%, 15% and 15% respectively, the devitrification tendency increases rather than decreases. Among these ingredients, the Li 2  O ingredient is effective for increasing the negative anomalous dispersion value and therefore this ingredient should preferably be added in the amount of 0.5% or over. Conversely, the K 2  O ingredient decreases the negative anomalous dispersion value and therefore the amount of this ingredient should preferably be 10% or below. For maintaining an excellent chemical durability of the glass, the total amount of Li 2  O, Na 2  O and K 2  O ingredients should preferably be within a range from 0.5% to 20%. 
     The Sb 2  O 3  ingredient may be optionally added as a defoaming agent for refining and homogenizing the glass. The amount up to 1% will suffice for this ingredient. 
     For improving the melting property and resistivity to devitrification, preventing solarization and for other purposes, ingredients other than the above described ones such as Rb 2  O, Cs 2  O, TiO 2 , Bi 2  O 3  and F may be optionally added up to the total amount of 1%. 
     EXAMPLES 
     Tables 2 to 4 show preferred examples (No. 1 to No. 14) of the optical glass according to the invention having negative anomalous dispersion, comparative examples (No. a to No. c) of the prior art SiO 2  --Nb 2  O 5  --R 2  O--RO glass and comparative examples (No d and No. e) of the prior art SiO 2  --B 2  O 3  --Al 2  O--PbO glass together with optical constants (nd, νd), relative partial dispersion (θ g, F), anomalous dispersion ( Δθ g, F), acid-proof property (SR value) and weight ratio of SiO 2  /B 2  O 3  of these glasses. In FIG. 1 (θ g, F - νd diagram), coordinates of θ g, F and  νd of the glasses of Examples No. 1 to No. 14 are indicated by the circle mark, coordinates of θ g, F and d of the glasses of Comparative Examples No. a to No. c by the x mark and coordinates of θ g, F and νd of the glasses of Comparative Examples No. d and No. e by the black square mark. 
     The value of Δθ g, F representing anomalous dispersion was calculated by the above described method. The SR value representing anti-acid property shows results of measurement made by employing the measuring method according to ISO 8424: 1987(E). The SR value classifies glasses in accordance with time (h) required for eroding glass specimens by 0.1 micron in a predetermined acid solution. The SR values 1, 2, 3 and 4 indicate that time exceeding 100 h, 100 h-10 h, 10 h-1 h and 1 h-0.1 h respectively are required for the erosion by using a nitric acid solution of pH 0.3. The SR values 5, 51, 52 and 53 indicate that time exceeding 10 h, 10 h-1 h, 1 h-0.1 h and time below 0.1 h are required for the erosion by using an acetic acid buffer solution of pH 4.6. Accordingly, the smaller the SR value, the higher is the acid-proof property of the glass and therefore the more excellent is chemical durability of the glass. 
     
                                           TABLE 2__________________________________________________________________________                              weight %ExamplesNo.  1    2    3    4    5    6    7__________________________________________________________________________SiO.sub.220.0 40.0 30.0 33.0 25.3 21.3 27.4B.sub.2 O.sub.320.0 7.0  8.0  10.0 15.5 17.5 13.6Al.sub.2 O.sub.3    4.0GeO.sub.2                4.5Y.sub.2 O.sub.3La.sub.2 O.sub.3                   5.0Gd.sub.2 O.sub.3Yb.sub.2 O.sub.3ZrO.sub.28.0  0.5  8.0  0.5  14.5 1.9  3.6Nb.sub.2 O.sub.531.9 38.0 32.0 41.5 32.0 33.0 32.5Ta.sub.2 O.sub.5WO.sub.3ZnO                           10.9PbOMgO                                5.0CaO  0.5  0.5  4.0  1.0  0.5  7.0  1.4SrOBaO  13.0 1.0  2.0Li.sub.2 O0.5  9.5  5.0  10.0 0.5  1.5  0.5Na.sub.2 O5.0       7.0       7.1       10.9K.sub.2 O1.0  3.5  3.0            6.9Sb.sub.2 O.sub.30.1       1.0       0.1       0.1As.sub.2 O.sub.3SiO.sub.2 /B.sub.2 O.sub.31.0  5.7  3.8  3.3  1.6  1.2  2.0nd   1.70892     1.71503          1.65923               1.72142                    1.72656                         1.69072                              1.66778νd35.2 35.2 39.9 32.6 32.6 36.2 38.1θg, F0.5807     0.5822          0.5662               0.5867                    0.5842                         0.5775                              0.5741Δθg, F-0.0038     -0.0023          -0.0107               -0.0020                    -0.0045                         -0.0054                              -0.0057SR   1    1    1    1    1    1    1__________________________________________________________________________ 
    
     
                                           TABLE 3__________________________________________________________________________                              weight %ExamplesNo.  8    9    10   11   12   13   14__________________________________________________________________________SiO.sub.237.6 32.0 32.0 32.0 25.0 23.0 20.0B.sub.2 O.sub.36.5  11.5 6.0  8.0  12.0 4.0  17.5Al.sub.2 O.sub.3GeO.sub.2Y.sub.2 O.sub.3     5.0       2.0La.sub.2 O.sub.3              1.0Gd.sub.2 O.sub.34.0                      2.0Yb.sub.2 O.sub.3    5.0ZrO.sub.21.0  2.4  1.3  7.4  2.5  12.0 5.0Nb.sub.2 O.sub.536.2 31.1 45.0 32.1 34.9 31.0 31.4Ta.sub.2 O.sub.5     9.0                 1.0WO.sub.3                 9.8ZnO  0.9                           2.0PbOMgO       6.5                      7.0CaO  3.0  1.0  1.0  0.7  0.5  2.0  3.5SrO            14.0                7.0BaOLi.sub.2 O0.7  6.4  0.5  1.1  0.7  6.0  0.5Na.sub.2 O               14.5 12.0 6.0K.sub.2 O10.0           8.7       4.0Sb.sub.2 O.sub.30.1  0.1  0.2       0.1       0.1As.sub.2 O.sub.3SiO.sub.2 /B.sub.2 O.sub.35.8  2.8  5.3  4.0  2.1  5.8  1.1nd   1.72031     1.71151          1.77964               1.70233                    1.77327                         1.67305                              1.65911νd33.3 36.4 30.6 35.4 30.5 37.9 39.8θg, F0.5863     0.5782          0.5903               0.5811                    0.5901                         0.5736                              0.5680Δθg, F-0.0013     -0.0044          -0.0017               -0.0031                    -0.0020                         -0.0065                              -0.0091SR   1    1    1    1    1    1    1__________________________________________________________________________ 
    
     
                       TABLE 4______________________________________weight %Comparative ExamplesNo.     a        b        c      d      e______________________________________SiO.sub.2   26.0     20.0     28.0   13.7   16.9B.sub.2 O.sub.3   4.0               2.0    29.7   12.9Al.sub.2 O.sub.3                 12.7   8.8GeO.sub.2Y.sub.2 O.sub.3La.sub.2 O.sub.3          5.0    2.6    1.8Gd.sub.2 O.sub.3Yb.sub.2 O.sub.3ZrO.sub.2   5.0Nb.sub.2 O.sub.5   25.0     40.0     27.0Ta.sub.2 O.sub.6 10.0WO.sub.3ZnOPbO                              41.0   59.4MgOCaO     20.0     5.0SrOBaO                       30.0Li.sub.2 O   2.0      5.0      3.0Na.sub.2 O       15.0K.sub.2 O   18.0     5.0      5.0Sb.sub.2 O.sub.3As.sub.2 O.sub.3                 0.3    0.2SiO.sub.2 /B.sub.2 O.sub.3   6.5               14.0   0.5    1.3nd      1.6786   1.6985   1.6955 1.6389 1.7377νd   32.0     31.3     35.3   40.8   31.4θg,F   0.5920   0.5940   0.5840 0.5660 0.5860Δθg,F   +0.0023  +0.0032  -0.0004                            -0.0095                                   -0.0047SR      1        1        1      51     53______________________________________ 
    
     As shown in Tables 2, 3 and 4 and FIG. 1, the glasses of Examples No. 1 to No. 14 have negative anomalous dispersion Δθ g, F the absolute value of which is larger than that of the glasses of Comparative Examples No. a to No. c and therefore have a larger negative anomalous dispersion. The glasses of Comparative Examples No. d and No. e have a negative anomalous dispersion value which is about as large as those of the examples of the invention. However, as shown in Tables 2 to 4, the glasses of Examples No. 1 to No. 14 all have SR value of 1 and therefore are superior in the acid-proof property and chemical durability to the glasses of Comparative Examples No. d and No. e. 
     For manufacturing the glasses of Examples No. 1 to No. 14, normal raw materials for the optical glass including oxides, carbonates and nitrates are weighed and mixed and the mixture is melted in a platinum crucible at a temperature of 1300° C. to 1400° C. for about 3 to 4 hours depending upon the melting property of the raw materials. The melted glass is defoamed, stirred and homogenized and then the temperature is lowered to a proper temperature. The glass is formed to a glass product by casting in a metal mold and subsequent annealing. 
     As described in the foregoing, the optical glass having a negative anomalous dispersion of the invention is a SiO 2  --B 2  O 3  --ZrO 2  --Nb 2  O 5  glass of a specific composition, having optical constants of predetermined ranges and a large negative anomalous dispersion value. The optical glass of the invention contains no PbO or As 2  O 3  which is costly for protecting the environment. The optical glass of the invention besides has excellent chemical durability and homogeneity. Moreover, since the optical glass of the invention has a low glass transformation temperature, it is suitable for mold pressing, i.e., precision pressing of glass according to which pressed glass can be used directly as an optical element such as an optical lens without requiring grinding or polishing after press forming.