# Patent

## Title
Optical glass

## Abstract

Provided is an optical glass that has desired optical properties, superior resistance to devitrification, and superior mass productivity. An optical glass is made of a SiO2—Nb2O5—TiO2-based glass having a refractive index (nd) of 1.75 to 1.95 and an Abbe's number (νd) of 15 to 35 and has an operation temperature range (ΔT=(temperature at 100.5 poise)−(liquidus temperature)) of 20° C. or more. The optical glass preferably contains, in percent by mass, 15% to 45% SiO2, 15% to 40% (but excluding 40%) Nb2O5 and 1% to 30% TiO2 as glass components.

## Background
TECHNICAL FIELD
This invention relates to optical glasses suitable as optical lenses for digital cameras and video cameras or as lenses for optical communication.
BACKGROUND ART
In recent years, performances of digital cameras and video cameras have increasingly been enhanced and, more specifically, their miniaturization is becoming greater and greater and their magnification and definition are becoming higher and higher. To achieve these enhanced performances, optical lens glasses used for digital cameras and video cameras have been increasingly required to have properties, such as high refractive index, high dispersion, and anomalous dispersion.
An example of glasses proposed which meets the above properties is a SiO2—Nb2O5-based glass having a refractive index (nd) of 1.78 or more and an Abbe's number (νd) of 30 or less (see, for example, Patent Literature 1). This glass can be used as a lens for optical communication by taking advantage of its properties, including high refractive index and high weatherability.
Known methods for producing an optical lens used for a digital camera, a video camera or the like includes a method of first molding a molten glass into an ingot, cutting the ingot into a glass material of appropriate size, polishing the glass material, and then press-molding it; and a method of forming a molten glass into a glass material by dropping a molten glass from a nozzle tip and forming it in a droplet shape, i.e., by so-called droplet forming, and then press-molding the formed glass material following or without polishing of the formed glass material.
CITATION LIST
Patent Literature


    Patent Literature 1: JP-A-2009-179538


SUMMARY OF INVENTION
Technical Problem
The conventional SiO2—Nb2O5-based glass has a high degree of devitrification and therefore tends to have poor mass productivity. Particularly, it presents a problem of difficulty in producing a glass material by droplet forming.
In view of the above problem, an object of the present invention is to provide an optical glass that has desired optical properties, superior resistance to devitrification, and superior mass productivity.
Solution to Problem
A first optical glass according to the present invention is made of a SiO2—Nb2O5—TiO2-based glass having a refractive index (nd) of 1.75 to 1.95 and an Abbe's number (νd) of 15 to 35 and has an operation temperature range (ΔT=(temperature at 100.5 poise)−(liquidus temperature)) of 20° C. or more.
Studies of the Inventor have revealed that occurrence of devitrification in SiO2—Nb2O5-based glasses is attributed mainly to the glasses containing a large amount of Nb2O5 which is a component for increasing the refractive index and dispersion. Therefore, it has been found that with the use of a SiO2—Nb2O5—TiO2-based glass in which part of Nb2O5 in a SiO2—Nb2O5-based glass is replaced with TiO2, devitrification can be reduced without decreasing the refractive index and dispersion so much. In addition, the use of a SiO2—Nb2O5—TiO2-based glass enables increase in weatherability, so that degradation in physical properties and surface alternation will be less likely to occur during the production process and the use of the product.
For example, in producing a glass material by droplet forming, a molten glass is dropped from a nozzle tip, which requires that the molten glass has a certain degree of viscosity. More specifically, if a molten glass of low viscosity is dropped, it takes the form of a continuous flow and cannot form droplets. Therefore, to achieve the formation of droplets, the molten glass must have a glass viscosity of about 100.5 poise or more, for example. However, the conventional SiO2—Nb2O5-based glass has the problem of ease of devitrification at a high viscosity of about 100.5 poise or more. In contrast, the optical glass of the present invention exerts the effect of enabling suitable implementation of forming, particularly droplet forming, since its operation temperature range is 20° C. or more.
Note that the term “SiO2—Nb2O5—TiO2-based glass” used herein refers to a glass containing SiO2, Nb2O5, and TiO2 as essential components.
Secondly, the first optical glass of the present invention preferably contains, in percent by mass, 15% to 45% SiO2, 15% to 40% (but excluding 40%) Nb2O5 and 1% to 30% TiO2 as glass components.
Thirdly, the first optical glass of the present invention preferably further contains, in percent by mass, 0% to 15% Li2O and 0% to 20% Na2O as glass components.
Fourthly, the first optical glass of the present invention preferably further contains, in percent by mass, 0% to 2% K2O, 0% to 20% (but excluding 20%) R2O (where R represents Li, Na or K), and 0% to 2% WO (where R′ represents Mg, Ca, Sr or Ba) as glass components and is preferably substantially free of PbO, As2O3, Cs2O, GeO2, and Bi2O3.
A second optical glass according to the present invention contains, in percent by mass, 15% to 45% SiO2, 15% to 40% (but excluding 40%) Nb2O5, 1% to 30% TiO2, 0% to 15% Li2O, 0% to 20% Na2O, 0% to 2% K2O, 0% to 20% (but excluding 20%) R2O (where R represents Li, Na or K), and 0% to 2% WO (where R′ represents Mg, Ca, Sr or Ba) as glass components and is substantially free of PbO, As2O3, Cs2O, GeO2, and Bi2O3.
Sixthly, the optical glass of the present invention is preferably for use in press molding.
Seventhly, the optical glass of the present invention is preferably used as a lens for optical communication.


DESCRIPTION OF EMBODIMENTS
An optical glass of the present invention is made of a SiO2—Nb2O5—TiO2-based glass having a refractive index (nd) of 1.75 to 1.95 and an Abbe's number (νd) of 15 to 35 and has an operation temperature range (ΔT=(temperature at 100.5 poise)−(liquidus temperature)) of 20° C. or more. The reasons why the present invention defines various properties as above are given below.
For example, when the optical glass is used as a lens, the lens can be more reduced in thickness as the refractive index is increased, which is advantageous for size reduction of an optical device. Therefore, the refractive index of the optical glass of the present invention is preferably not less than 1.75, more preferably not less than 1.765, still more preferably not less than 1.775, yet more preferably not less than 1.785, and particularly preferably not less than 1.80. Meanwhile, in order to increase the refractive index of the glass, it is necessary to increase the amount of component making the glass unstable, such as Nb2O5. Therefore, the upper limit of the refractive index must be defined in consideration of the stability of the glass. Specifically, the refractive index of the optical glass of the present invention is preferably not more than 1.95 and particularly preferably not more than 1.90.
The Abbe's number of the optical glass of the present invention is preferably not more than 35, more preferably not more than 30, still more preferably not more than 26, and particularly preferably not more than 24 in order to achieve a high dispersion property. Although smaller Abbe's number is desirable because of advantage for reduction of chromatic aberration in combination with another lens in an optical design, this is likely to decrease the refractive index or destabilize the glass. Therefore, the Abbe's number of the optical glass of the present invention is preferably not less than 20, more preferably not less than 21, and particularly preferably not less than 22.
When the operation temperature range is not less than 20° C., or not less than 30° C., or particularly not less than 40° C., a preform glass can be produced with a high yield. Larger operation temperature range is better and no particular limitation is placed on the upper limit of the operation temperature range. However, actually, the operation temperature range is preferably not more than 300° C. and particularly preferably not more than 200° C. Note that the temperature equivalent to 100.5 poise corresponds to the forming temperature in the droplet forming method. The droplet forming is known as one of forming methods whereby glass is most likely to be devitrified. Therefore, it can be considered that if the difference ΔT between the temperature at 100.5 poise and the liquidus temperature is not less than 20° C., glass forming is possible without the occurrence of devitrification in almost all of forming methods including the droplet forming method.
No particular limitation is placed on the composition of the SiO2—Nb2O5—TiO2-based glass so long as the glass is one meeting all of the above properties. Note that in order to obtain a SiO2—Nb2O5—TiO2-based glass having the above properties, an appropriate composition should be selected in consideration of the following points.
To increase the refractive index and reduce the Abbe's number in the SiO2—Nb2O5—TiO2-based glass, the contents of Nb2O5 and TiO2 should be increased. Besides these components, addition of Ta2O5, ZrO2, Y2O3, WO3 or the like can increase the refractive index and reduce the Abbe's number.
Furthermore, to increase the operation temperature range means to reduce the tendency of glass to devitrify. Therefore, in the SiO2—Nb2O5—TiO2-based glass, the contents of SiO2, B2O3, and TiO2 should be increased. Besides these components, addition of ZrO2, Y2O3, WO3 or the like can increase the operation temperature range.
Specifically, the optical glass of the present invention preferably contains, in percent by mass, 15% to 45% SiO2, 15% to 40% (but excluding 40%) Nb2O5 and 1% to 30% TiO2 as glass components. Within the above composition range, the properties of a refractive index of 1.75 to 1.95, an Abbe's number of 15 to 35, and an operation temperature range of 20° C. or more can be easily achieved.
The reasons why the composition range is defined as above are described below. Note that “%” used in the following description of the glass composition means “% by mass” unless otherwise stated.
SiO2 is a component for forming the glass network and a component having the effects of increasing the resistance to devitrification and widening the operation temperature range. SiO2 also has the effect of increasing the weatherability. The content of SiO2 is preferably 15% to 45%, more preferably 20% to 40%, and particularly preferably 25% to 37%. If the content of SiO2 is above 45%, there will be a tendency to significantly decrease the refractive index and a tendency to make the glass transition point excessively high (for example, above 700° C.) On the other hand, if the content of SiO2 is below 15%, there will be a tendency to make vitrification difficult.
Nb2O5 is a component for increasing the refractive index. The content of Nb2O5 is preferably 15% to 40% (but excluding 40%), more preferably 20% to 39.5%, and particularly preferably 25% to 39%. If the content of Nb2O5 is 40% or more, there will be a tendency to raise the liquidus temperature to decrease the stability of the glass. On the other hand, if the content of Nb2O5 is below 15%, a refractive index of 1.75 or more will become difficult to achieve.
TiO2 is a component for increasing the refractive index. In addition, TiO2 forms the glass as an intermediate oxide and, therefore, has the effects of increasing the resistance to devitrification and increasing the chemical durability. The content of TiO2 is preferably 1% to 30%, more preferably 5% to 25%, and particularly preferably 10% to 20%. If the content of TiO2 is above 30%, there will be, on the contrary, a strong tendency to cause devitrification and make vitrification difficult. On the other hand, if the content of TiO2 is below 1%, the chemical durability will be likely to significantly decrease.
When, besides the above components, one or more alkali metal oxides, such as Li2O, Na2O, and K2O, are added, a glass having a desired refractive index, a desired Abbe's number, and a desired operation temperature range can be more easily produced. These components are generally difficult to add into the SiO2—Nb2O5-based glass because they are likely to degrade the weatherability. However, when the content of Nb2O5 is reduced (for example, to below 40%), a relatively large amount of these components can be contained in the glass, which makes it easy to design a low-softening-point glass.
Li2O is a component for reducing the phase separation to increase the stability of the glass. The content of Li2O is preferably 0% to 15%, more preferably 0.1% to 10%, and particularly preferably 0.5% to 5%. If the content of Li2O is above 15%, there will be a tendency to significantly decrease the weatherability and a tendency to decrease the refractive index.
Na2O, like Li2O, is a component for reducing the phase separation to increase the stability of the glass. The content of Na2O is preferably 0% to 20%, more preferably 0.1% to 18%, still more preferably 0.5% to 15%, and particularly preferably 1% to 14%. If the content of Na2O is above 20%, there will be a tendency to significantly decrease the weatherability and a tendency to decrease the refractive index.
K2O, like Li2O and Na2O, is a component for reducing the phase separation to increase the stability of the glass. The content of K2O is preferably 0% to 2%, more preferably 0.1% to 1%, and particularly preferably 0.2% to 0.5%. If the content of K2O is above 2%, there will be a tendency to significantly decrease the weatherability and a tendency to decrease the refractive index.
The total content of Li2O, Na2O, and K2O is preferably 0% to 20%, more preferably 0.1% to 18%, still more preferably 0.5% to 15%, and particularly preferably 1% to 14%. If the total content of these components is above 20%, there will be a tendency to significantly decrease the weatherability and a tendency to decrease the refractive index.
Furthermore, in addition to the above components, ZrO2, WO3, B2O3, ZnO, and/or Ta2O5 may be added.
ZrO2 is a component for increasing the refractive index. In addition, ZrO2 forms the glass as an intermediate oxide and, therefore, has the effects of increasing the resistance to devitrification and increasing the chemical durability. The content of ZrO2 is preferably 0% to 15%, more preferably 0.5% to 10%, and particularly preferably 1% to 8%. If the content of ZrO2 is above 15%, there will be, on the contrary, a strong tendency to cause devitrification and make vitrification difficult.
WO3 is a component for increasing the refractive index. In addition, WO3 forms the glass as an intermediate oxide and, therefore, has the effect of increasing the resistance to devitrification. The content of WO3 is preferably 0% to 15%, more preferably 0.5% to 10%, and particularly preferably 1% to 8%. If the content of WO3 is above 15%, there will be, on the contrary, a strong tendency to cause devitrification and make vitrification difficult. In addition, there will be a tendency to decrease the ultraviolet region transmittance and a tendency to increase the affinity to the pressing mold to make the glass easily fusion bond to the mold upon press molding.
B2O3 is a component for forming the glass network and has the effect of increasing the resistance to devitrification. B2O3 also has the effects of increasing the Abbe's number and decreasing the softening point. In addition, B2O3 also has the effect of preventing fusion bonding to the mold upon press molding. The content of B2O3 is preferably 0% to 30%, more preferably 1% to 20%, and particularly preferably 5% to 15%. If the content of B2O3 is above 30%, there will be a tendency to decrease the chemical durability of the glass and a tendency to significantly degrade the weatherability thereof.
ZnO is a component for increasing the refractive index and the chemical durability and decreasing the softening point. The content of ZnO is preferably 0% to 20%, more preferably 0.5% to 15%, and particularly preferably 1% to 10%. If the content of ZnO is above 20%, there will be, on the contrary, a strong tendency to cause devitrification and make vitrification difficult.
Ta2O5 has the effects of increasing the refractive index, increasing the chemical durability, and increasing the resistance to devitrification. The content of Ta2O5 is preferably 0% to 20%, more preferably 0.5% to 15%, and particularly preferably 1% to 10%. If the content of Ta2O5 is above 20%, there will be, on the contrary, a strong tendency to cause devitrification and make vitrification difficult. In addition, the cost will be likely to increase.
Various components other than the above components may be added. For example, Sb2O3 may be added as a fining agent or a decolorizing agent. To avoid excessive coloration of the glass, the content of Sb2O3 is preferably 1% or less.
Alkaline earth metal oxides, such as MgO, CaO, SrO, and BaO, significantly decrease the weatherability and significantly increase the liquidus temperature. Therefore, the content of these components is preferably 2% or less and particularly preferably 1% or less and, most preferably, none of them is contained in the glass.
PbO, Cs2O, As2O3, GeO2, and Bi2O3 have a large effect on the environment and cause concerns about coloration of the glass. Therefore, the glass is preferably substantially free of these components (specifically, the content of each component is preferably less than 0.1% by mass).
La2O2, Ce2O2, Gd2O2, and Yb2O3 are preferably not contained in the glass because they are likely to increase the cost.
Besides the previously-described properties, the optical glass of the present invention should preferably achieve a low glass transition point. Thus, fusion bonding of the glass to the mold upon press molding can be prevented to increase the mass productivity. In addition, as the glass transition point decreases, the glass components become less likely to volatilize during press molding, so that problems of decrease in molding accuracy and deterioration or contamination of the mold become less likely to occur. Specifically, the glass transition point of the optical glass of the present invention is preferably not higher than 630° C. and particularly preferably not higher than 600° C.
Next, a description will be given of a method for producing an optical lens used for a digital camera, a video camera or the like using the optical glass of the present invention.
First, glass raw materials mixed together to give a desired composition are melted into a molten glass. Next, the molten glass is dropped from a nozzle tip and formed in a droplet shape (droplet-formed) to obtain a glass material. Subsequently, the formed glass material is press-molded after or without being polished, resulting in a lens having a desired shape. Alternatively, instead of performing the droplet forming, a method may be employed in which the molten glass is molded into an ingot, the ingot is cut into a glass material of appropriate size, and the glass material is polished and then press-molded.
The optical lens produced from the optical glass of the present invention can also be used as a lens cap assembled with a metallic part.
EXAMPLES
Hereinafter, the present invention will be described in detail with reference to examples but is not at all limited to the examples.
Tables 1 to 3 show examples of the present invention (Samples Nos. 1 to 22) and comparative examples (Samples Nos. 23 and 24).















TABLE 1





(% by mass)
1
2
3
4
5
6
7
8























SiO2
24.4
29.6
28.1
27.1
27.8
28.0
28.4
28.2


B2O3


1.7


ZnO





1.9


Li2O
4.7
5.7
5.7
5.5
5.6
5.7
6.4
5.7


Na2O
9.4
11.3
11.3
10.9
11.2
11.3
11.4
12.8


TiO2
6.5
13.9
13.8
13.3
13.6
13.8
14.0
13.9


Nb2O5
39.0
39.5
39.4
37.9
38.9
39.3
39.8
39.4


ZrO2




2.9


Ta2O5
16.0


WO3



5.3


Sb2O3
0.1


nd
1.8482
1.8201
1.8206
1.8284
1.8300
1.8258
1.8219
1.8162


νd
25.1
25.4
25.4
25.1
25.3
25.3
25.5
25.7


Tg [° C.]

530
519
526
538
521
522
524


Forming

1134
1098
1100
1118
1100
1086
1107


Temperature Tw [° C.]


Liquidus

1015
1002
1015
1036
1031
1031
1056


Temperature TL [° C.]


  T [° C.]

119
96
85
82
69
55
51
























TABLE 2





(% by mass)
9
10
11
12
13
1 4
15
16























SiO2
28.1
33.2
36.1
38.8
33.8
32.1
31.5
25.9


B2O3


ZnO


Li2O
5.7
3.5
1.7

1.7
1.7
1.7
5.2


Na2O
11.3
11.1
10.9
10.7
10.8
10.5
10.8
10.4


TiO2
15.7
13.6
13.3
13.1
16.0
13.7
18.5
12.7


Nb2O5
39.2
38.6
38.0
37.4
37.7
36.7
37.5
36.2


ZrO2





2.7


Ta2O5







9.6


WO3





2.6


Sb2O3




0.08
0.08
0.08


nd
1.8337
1.8090
1.7959
1.7766
1.8201
1.8223
1.8438
1.8432


νd
24.7
25.2
24.9
24.4
23.8
24.1
22.8
24.7


Tg [° C.]
532



582
576
579
544


Forming
1097



1377
1349
1283
1165


Temperature Tw [° C.]


Liquidus
1019



1071
1034
1114
1112


Temperature TL [° C.]


  T [° C.]
78



306
315
169
53
























TABLE 3





(% by mass)
17
18
19
20
21
22
23
24























SiO2
34.2
27.2
30.3
26.1
27.4
25.0
25.0
32.5


B2O3


ZnO


Li2O
2.7
1.5
6.8
6.3
2.4
1.4
5.0


Na2O
8.8
9.5
9.3
8.5
7.7
8.9

5.0


K2O






8.0
15.0


BaO






2.0
2.0


TiO2
16.1
14.0
14.1
12.8
14.2
13.1
8.0
15.0


Nb2O5
38.2
39.0
39.5
36.6
39.4
31.0
50.0
30.0


ZrO2






2.0


Ta2O5

8.8

9.7
8.9
20.6


WO3







0.5


Sb2O3
0.08
0.08


0.08
0.08


nd
1.8263
1.8720
1.8242
1.8504
1.8789
1.8793
1.8838
1.7401


νd
23.6
22.2
25.5
24.6
22.2
22.4
26.6
27.9


Tg [° C.]
569
588




565
840


Forming
1325
1295


1277

1310
1256


Temperature Tw [° C.]


Liquidus
1127
1098


1185

1298
1198


Temperature TL [° C.]


  T [° C.]
198
197


92

12
58









The individual samples were prepared in the following manner: First, each set of glass raw materials were mixed together to give a corresponding composition shown in the above tables and melted at 1400° C. for two hours using a platinum crucible. After the melting, the molten glass was allowed to flow on a carbon plate and annealed and, then, glass samples suitable for the respective measurements were produced.
The resultant samples were measured in terms of refractive index (nd), Abbe's number (νd), glass transition point (Tg), forming temperature for droplet forming (Tw), liquidus temperature (Tl), and operation temperature range (ΔT). The results are shown in Tables 1 to 3.
The refractive index is represented by a value measured for the d-line (587.6 nm) of a helium lamp.
The Abbe's number was calculated using the refractive index at the d-line of the helium lamp and the respective refractive indices at the F-line (486.1 nm) and C-line (656.3 nm) of a hydrogen lamp and in accordance with the formula: Abbe's number={(nd−1)/(nF−nC)}.
The glass transition point was measured using a method of measuring the linear expansion coefficient of glass based on Japanese Industrial Standards R-3102 and ISO 7991.
The operation temperature range was determined in the following manner: First, the temperature equivalent to 100.5 poise was determined by the platinum ball pulling-up method and the temperature determined was regarded as the forming temperature. On the other hand, the glass sample was ground and classified to obtain a 297-μm to 500-μm powder, the glass powder was put into a platinum boat, and the platinum boat containing the glass powder was held for 24 hours in an electric furnace having a temperature gradient and then cooled in air. The position of the glass powder in the boat where a devitrified substance precipitated was found with an optical microscope to thereby determine the liquidus temperature. The difference between the forming temperature and liquidus temperature obtained in the above manners was regarded as the operation temperature range.
As seen from Tables 1 to 3, Samples Nos. 1 to 22, examples of the present invention, have desired optical properties of a refractive index of 1.7766 to 1.8793 and an Abbe's number of 22.2 to 25.7. In addition, these samples have a low glass transition point of not higher than 588° C. and are therefore suitable for press molding. Furthermore, these samples have an operation temperature range of not less than 51° C., which shows that they are superior in workability.
On the other hand, Sample No. 23, a comparative example, has an operation temperature range as small as 12° C. and is therefore inferior in workability. Sample No. 24 has a refractive index as low as 1.7401, which does not fall within the desired range. In addition, this sample has a glass transition point as high as 840° C. and is therefore unsuitable for press molding.
INDUSTRIAL APPLICABILITY
The optical glass of the present invention can be used as a glass material for press molding and a glass material for polishing and is suitable for optical pickup lenses in various optical disc systems including CD, MD, DVD and the like; image pickup lenses in video cameras, digital cameras, and other general cameras; and lenses for optical communication.

## Claims

1. An optical glass made of a SiO2—Nb2O5—TiO2-based glass having a refractive index (nd) of 1.75 to 1.95 and an Abbe's number (νd) of 15 to 35, the optical glass containing, in percent by mass, 15% to 40% (but excluding 40%) Nb2O5, 1% to 18.5% TiO2, and 0% to 1% R′O (where R′ represents Mg, Ca, Sr, or Ba) as glass components, and having an operation temperature range (ΔT=(temperature at 100.5 poise)−(liquidus temperature)) of 20° C. or more, and
in percent by mass, 0% to 2% K2O, and 0% to 20% (but excluding 20%) R2O (where R represents Li, Na or K), as glass components and being substantially free of PbO, As2O3 Cs2O GeO2 and Bi2O3.

2. The optical glass according to claim 1, further containing, in percent by mass, 15% to 45% SiO2, as a glass component.

3. The optical glass according to claim 2, further containing, in percent by mass, 0% to 15% Li2O and 0% to less than 20% Na2O as glass components.

4. The optical glass according to claim 1, being for use in press molding.

5. The optical glass according to claim 1, being used as a lens for optical communication.

6. An optical lens defined by the optical glass according to claim 1.

7. A lens cap comprising:
the optical lens according to claim 6; and
a metallic part connected to the optical lens.

8. An optical glass containing, in percent by mass, 15% to 45% SiO2, 15% to 40% (but excluding 40%) Nb2O5, 1% to 18.5% TiO2, 0% to 15% Li2O, 0% to less than 20% Na2O, 0% to 2% K2O, 0% to 20% (but excluding 20%) R2O (where R represents Li, Na or K), and 0% to 1% R′O (where R′ represents Mg, Ca, Sr or Ba) as glass components and being substantially free of PbO, As2O3, Cs2O, GeO2, and Bi2O3.

9. The optical glass according to claim 8, being used as a lens for optical communication.

10. An optical lens defined by the optical glass according to claim 8.

11. A lens cap comprising:
the optical lens according to claim 10; and
a metallic part connected to the optical lens.