Abstract:
This invention relates to a method of performing an ion exchange of optical glass to produce an axial gradient index material having a good linear distributiion by bringing a glass body containing a monovalent cation component into contact with a medium containing a monovalent cation component and exchanging these cation components under a predetermined condition.

Description:
This is a continuation-in-part of application Ser. No. 507,881, filed Apr. 12, 1990, abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a method of manufacturing optical glass having a gradient index and, more particularly, a method of manufacturing optical glass having a gradient index in a direction of the optical axis. 
     2. Prior Art 
     Optical glass is generally required to have a uniform refractive index. Optical glass and lens materials having gradient indices having controlled profiles have been developed and commercially available in recent years. 
     Gradient index lenses are classified into the following three types of lens: 
     Radial gradient index lens; 
     Axial gradient index lens; and 
     Spherical gradient index lens. 
     An example of the axial gradient index lens is shown in FIG. 19. A lens 1 has a gradient index monotonously decreased from a vertex 1A of its convex spherical surface to almost perfectly correct spherical aberration occurring on the convex spherical surface. A function for the axial gradient index can greatly enhance the aberrational correction by defining a refractive index n(z) at a distance z, as shown in FIG. 19, as follows: 
     
         n(z)=n0-kz                                                 (1) 
    
     where n0 is the refractive index at the vertex 1A of the convex surface, z is the length in the direction of thickness along the optical axis when the vertex of the convex surface is defined as an origin, and k is a positive constant. The distribution defined by equation (1) is called a linear distribution hereinafter. In order to obtain a lens having excellent optical characteristics, axial gradient index glass having a linear distribution or a distribution close to a linear distribution is prepared, and the glass is formed into a lens. When a refractive index difference Δn shown in FIG. 19 is increased, freedom in lens design is increased to facilitate aberrational correction. Therefore, a larger refractive index difference Δn is preferred. 
     An ion exchange method is generally employed as a method of manufacturing axial gradient index glass. More specifically, a flat glass body containing a monovalent ion component is dipped in a molten salt such as KNO 3 , NaNO 3  or TlNO 3  to form a concentration distribution of Li+, Na+, K+ or Tl+ ions in the glass body, thereby obtaining a gradient index corresponding to the concentration distribution. 
     Since, however, a monovalent ion exchange is a diffusion phenomenon, a gradient index obtained by the ion exchange method is not linear as shown in FIG. 19, but has one of the following distribution curves as shown in FIG. 20: 
     Distribution curve having an upward convex shape; 
     Distribution curve having a downward convex shape; and 
     S-shaped distribution curve. 
     Even if a glass material having such a gradient index is formed into a lens, it is difficult to correct the aberration. 
     OBJECT AND SUMMARY OF THE INVENTION 
     It is an object of the present invention to solve the conventional drawbacks described above and to provide a method of performing an ion exchange of optical glass to produce an axial gradient index material having a good linear distribution. 
     According to the extensive studies of the present inventors, when a composition of a monovalent cation component contained in a glass body and a composition of a monovalent cation component contained in a medium satisfied a predetermined condition, it was found that an axial gradient index having almost a linear index distribution could be obtained by the ion exchange method. 
     The monovalent ion component contained in the glass body serves to increase a refractive index. Of all the monovalent ion components, Tl 2  O has a maximum effect for increasing the refractive index. In order to obtain a large refractive index difference, it is most suitable to form a concentration distribution of Tl 2  O. 
     In order to form a concentration distribution of Tl 2  O by the ion exchange method, 
     the Tlhd 2O concentration in the glass body is set to be higher than the Tl+ concentration in the medium to decrease the Tl 2  O concentration on the glass surface, or 
     the Tl 2  O concentration in the glass body is set to be lower than the Tl+ concentration in the medium to increase the Tl 2  O concentration on the glass surface. 
     Glass containing a large amount of Tl 2  O is unstable, and the latter method is therefore suitable. 
     Conditions to be satisfied by the glass and the medium prior to the ion exchange process will be described below. 
     As a total sum M 2  O(=Tl 2  O+K 2  O+Na 2  O+Li 2  O of the monovalent cation concentration in the glass body is increased, a larger refractive index difference can be obtained, thus deriving the following condition: 
     
         8 mol % ≦M.sub.2 O (=Tl.sub.2 O+K.sub.2 O +Na.sub.2 O+Li.sub.2 O)≦30 mol %                                        (2) 
    
     If the total sum M 2  O is smaller than 8 mol %, a sufficiently large refractive index difference cannot be obtained. However, if the total sum M 2  O exceeds 30 mol %, chemical resistance of glass is degraded. 
     When a Tl 2  O component is contained in a glass body, a refractive index difference obtained by the ion exchange process is disadvantageously decreased. According to the extensive studies of the present inventors, when a Tl 2  O component was contained in a glass body in a predetermined amount, it was effective to contain Tl 2  O in the glass body in the following range to improve linearity of the gradient index: 
     
         0 ≦(Tl.sub.2 O≦12 mol %                      (3) 
    
     When the content of Tl 2  O is increased, the refractive index difference is decreased and at the same time an amount of relatively expensive Tl 2  O to be used is increased. Therefore, the content Tl 2  O preferably falls within the range of 0.9 mol % or less. 
     Other major monovalent cation components except for Tl 2  O are Na 2  O, K 2  O and Li 2  O. Of these components, when the content of K 2  O is increased, a glass transition point Tg of the glass body is increased. In this case, the temperature of the ion exchange process can also be increased, and the ion exchange process time can be advantageously shortened. 
     Glass forming components in addition to the monovalent ion component are silicates, borates and phosphates. 
     As a medium of the ion exchange, molten salts, e.g., nitrates, sulfates or chlorides can be used. Of these components, a nitrate (e.g., a mixed salt of TlNO 3 , NaNO 3  and KNO 3 ) which can minimize glass erosion is suitable. When the content of TlNO 3  in the mixed salt is increased, a refractive index difference can be increased. When the content of TlNO 3  is excessively increased, linearity of the gradient index is degraded, and at the same time a decomposition reaction of TlNO 3  is excessively accelerated. Therefore, the TlNO 3  concentration falls within the following condition: 
     
         1≦TlNO.sub.3≦ 10 mol %                       (5) 
    
     The above problem typically occurs when the content of TlNO 3  exceeds 10 mol %. 
     In order to suppress the decomposition reaction of the nitrate and minimize glass erosion, the content of KNO 3  must be increased to satisfy the following condition: 
     
         78≦KNO.sub.3≦ 99 mol %                       (6) 
    
     In addition, when NaNO 3  is added to a salt mixture of KNO 3  and TlNO 3  within the following range: 
     
         0≦NaNO.sub.3≦ 12 mol %                       (7) 
    
     linearity of the gradient index can often be improved. 
     The gradient index of the glass upon the ion exchange process under the above-mentioned conditions is almost linear in the direction of depth from the surface. 
     The range of M 2  O content is 8 mol % ≦M 2  O ≦30 mol % (M 2  O represents an oxide of a monovalent element). 
     M 2  O includes Tl 2  O as previously stated. 
     N Tl  represents the ratio of Tl 2  O content to the whole of the M 2  O content. 
     N Tl  is defined by equation (3) as O≦NT 1  ≦0.4. 
     Thus, 30 mol % which is the maximum of Tl 2  O content ×0.4 which is the maximum value of N Tl  equals 12 mol %. 
     Similarly if NT 1  equals 0.3 30 mol % ×0.3=9 mol %. 
     M 2  O comprises Tl 2  O, K 2  O, Na 2  O and Li 2  O. 
     The total sum of M 2  O equals Tl 2  O+K 2  O+Na 2  O+Li 2  O. 
     Tl 2  O ≦12 mol %. 
     1≦TlHO 3  ≦10 mol %. 
     78 mol % ≦KNO 3  ≦99 mol %. 
     O ≦NaNO 3  ≦12 mol % and, 
     1≦TlNO 3 ≦ 10 mol %. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIGS. 1 to 16 are graphs showing gradient indices of Examples 1 to 16 according to the present invention, in which a light wavelength is set to be 587.6 nm; 
     FIGS. 17 and 18 are graphs showing gradient indices of Comparative Examples 1 and 2 except for the present invention, in which a light wavelength is set to be 587.6 nm; 
     FIG. 19 is a view showing an axial gradient index lens; 
     FIG. 20 is a graph showing a gradient index which is not suitable for an axial gradient index lens; 
     FIG. 21 is a view for explaining an ion exchange processing apparatus; and 
     FIG. 22 is a graph for explaining n d  and Δn in Table 2. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The present invention will be described in detail below with reference to an embodiment shown in the accompanying drawings. 
     As shown in FIG. 21, a nitrate was placed in a stainless steel vessel 3 having a lid and a volume of about 1,000 ml and was heated in an electric furnace to obtain a molten salt 4. Preheated flat glass (50×60 ×3 mm) 5 was dipped in the molten salt 4 to perform an ion exchange process at a predetermined temperature. The flat glass 5 was kept upright by a stainless steel holder. Upon completion of the ion exchange, the flat glass 5 was taken out from the molten salt 4, gradually cooled, and washed with water. The gradient index of the flat glass 5 was measured as follows: 
     The flat glass was cut into about 20 pieces each having a size of 5×5 mm; 
     The surfaces (one major surface) of the pieces were cut by different depths (e.g., 0 μm, 20 μm, 40 μm, . . . ); and 
     The cut surfaces were polished, and their refractive indices (λ=587.6 nm) were measured by a refractometer. 
     EXAMPLES 
     Compositions of flat glass samples and their N Tl  values prior to the ion exchange process are shown for Examples 1 to 16 in Table 1. The compositions of molten salts, ion exchange temperatures, ion exchange times, refractive indices n d  of glass samples prior to the ion exchange process and refractive index differences Δn after the ion exchange process are summarized in Table 2 (FIG. 22). 
     The gradient indices of the samples after the ion exchange process are almost linear, as shown in FIGS. 1 to 16. The samples can be used as materials for axial gradient index lenses. 
     COMPARATIVE EXAMPLES 
     Compositions of flat glass samples and ion exchange conditions are summarized for Comparative Examples 1 and 2 in Tables 1 and 2. The content of TlNO 3  of Comparative Examples 1 and 2 are 12 mol % each, and do not satisfy the following condition of the present invention: 
     
         1≦TlNO.sub.3≦ 10 mol % 
    
     The gradient indices of Comparative Examples 1 and 2 are shown in FIGS. 17 and 18, respectively. Since the gradient index is greatly deviated from a straight line, these samples of Comparative Examples 1 and 2 are not suitable as materials for axial gradient index lenses. 
     
                                           TABLE 1__________________________________________________________________________Unit: mol %                               Other                                    Other                    Tl.sub.2 O Compo-                                    Compo-Component SiO.sub.2    B.sub.2 O.sub.3       MgO          CaO             ZnO                ZrO.sub.2                    (N.sub.T1)                        Na.sub.2 O                            K.sub.2 O                               nents                                    nents__________________________________________________________________________Example 1 55.0    5.0       -- -- 20.0                --  4.0 11.0                            5.0                               --   --                    (0.20)Example 2 55.0    3.5       4.0          --  8.0                1.0 4.0 14.0                            4.0                               Li.sub.2 O                                    TiO.sub.2                    (0.16)     3.5  3.0Example 3 53.0    3.5       4.0          4.0              9.0                1.0 4.0 14.0                            4.0                               Li.sub.2 O                                    --                    (0.16)     3.5Example 4 50.0    -- 2.0          3.0             15.0                --  4.0 10.0                            6.0                               GeO.sub.2                                    --                    (0.20)     10.0Example 5 57.0    -- 5.0          5.0             10.0                --  3.0  8.0                            9.0                               Al.sub.2 O.sub.3                                    --                    (0.15)     3.0Example 6 50.0    5.0       5.0          -- 15.0                1.0 3.0  6.0                            6.0                               Li.sub.2 O                                    Sb.sub.2 O.sub.3                    (0.14)     7.0  2.0Example 7 60.0    5.0       -- -- 15.0                --  2.0 --  18.0                               --   --                    (0.10)Example 8 53.0    5.0       10.0          10.0             -- 2.0 2.0 14.0                            4.0                               --   --                    (0.10)Example 9 67.0    5.0       3.0          -- 15.0                --  1.5  2.5                            6.0                               --   --                    (0.15)Example 10 55.0    5.0       5.0          -- 15.0                --  --  14.0                            6.0                               --   --Example 11 53.0    5.0       10.0          -- 10.0                1.0 --  10.0                            10.0                               Sb.sub.2 O.sub.3                                    --                               1.0Example 12 60.0    5.0       -- -- 15.0                --  5.0 --  15.0                               --   --                    (0.25)Example 13 61.0    -- 3.0          -- 10.0                1.0 4.0  8.0                            10.0                               PbO  --                    (0.18)     3.0Example 14 61.0    -- 3.0          -- 10.0                1.0 4.0  8.0                            10.0                               BaO  --                    (0.18)     3.0Example 15 50.0    5.0       5.0          8.0              7.0                1.0 3.0  6.0                            8.0                               Li.sub.2 O                                    --                    (0.13)     7.0Example 16 55.0    5.0       -- -- 20.0                --  4.0 11.0                            5.0                               --   --                    (0.20)Compara- 61.0    -- 3.0          -- 10.0                1.0 4.0  8.0                            10.0                               PbO  --tive Ex-                 (0.18)     3.0ample 1Compara- 55.0    5.0       5.0          -- 15.0                --  --  14.0                            6.0                               --   --tive Ex-ample 2__________________________________________________________________________ 
    
     
                                           TABLE 2__________________________________________________________________________Molten Salt       Ion Exchange                    Ion Ex-Composition (mol %)             Temperature                    change       GradientKNO.sub.3 NaNO.sub.3         TlNO.sub.3             (°C.)                    Time (hr)                          n.sub.d                              Δn                                 Index__________________________________________________________________________Example 1 92.5     --  7.5 485    792   1.6045                              0.044                                 FIG. 1Example 2 93.5     --  6.5 470    840   1.5970                              0.056                                 FIG. 2Example 3 96.0     --  4.0 480    840   1.5927                              0.046                                 FIG. 3Example 4 82.0     10.0         8.0 470    648   1.6198                              0.049                                 FIG. 4Example 5 93.5     --  6.5 470    840   1.5759                              0.055                                 FIG. 5Example 6 96.0     --  4.0 480    840   1.6039                              0.039                                 FIG. 6Example 7 96.0     --  4.0 480    840   1.5489                              0.048                                 FIG. 7Example 8 93.5     --  6.5 470    840   1.5597                              0.070                                 FIG. 8Example 9 90.5     --  9.5 475    792   1.5394                              0.016                                 FIG. 9Example 10 96.0     --  4.0 480    840   1.5243                              0.050                                 FIG. 10Example 11 96.0     --  4.0 480    840   1.5349                              0.060                                 FIG. 11Example 12 96.0     --  4.0 480    840   1.5763                              0.021                                 FIG. 12Example 13 93.5     --  6.5 470    840   1.6036                              0.037                                 FIG. 13Example 14 82.0     10.0         8.0 470    648   1.5951                              0.070                                 FIG. 14Example 15 96.0     --  4.0 480    840   1.5819                              0.014                                 FIG. 15Example 16 90.5     --  9.5 485    480   1.6045                              0.065                                 FIG. 16Compara- 88.0     --  12.0             475    792   1.6036                              0.076                                 FIG. 17tive Ex-ample 1Compara- 88.0     --  12.0             475    792   1.5243                              0.091                                 FIG. 18tive Ex-ample 2__________________________________________________________________________ 
    
     According to the present invention, an axial gradient index material having a good linear distribution can be manufactured by the ion exchange process. Therefore, the present invention greatly contributes to the manufacture of axial gradient index lenses having excellent optical characteristics. 
     Having described a specific preferred embodiment of the present invention with reference to the accompanying drawings, it is to be understood that the invention is not limited to that precise embodiment, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined in the appended claims.