CN113603361B - Phosphate optical glass - Google Patents
Phosphate optical glass Download PDFInfo
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- CN113603361B CN113603361B CN202111075454.1A CN202111075454A CN113603361B CN 113603361 B CN113603361 B CN 113603361B CN 202111075454 A CN202111075454 A CN 202111075454A CN 113603361 B CN113603361 B CN 113603361B
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- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/253—Silica-free oxide glass compositions containing germanium
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- 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
- C03C4/00—Compositions for glass with special properties
Abstract
The invention provides phosphate optical glass, which comprises the following components in percentage by weight: p 2 O 5 ：10～30％；Bi 2 O 3 ：16～35％；Nb 2 O 5 ：20～40％；WO 3 ：5～20％；TiO 2 :0 to 10% of, wherein (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) Is 0.4 to 1.5. Through reasonable component design, the optical glass obtained by the invention has lower transition temperature while having the expected refractive index and Abbe number.
Description
Technical Field
The present invention relates to optical glass, and particularly relates to phosphate optical glass having a refractive index of 1.87 or more and an abbe number of 24 or less.
Background
The optical glass with the refractive index of more than 1.87 and the Abbe number of less than 24 belongs to high-refraction high-dispersion optical glass, and the glass can be coupled with low-dispersion optical glass for use, so that chromatic aberration and secondary spectrum are effectively eliminated, the total optical length of a lens can be effectively shortened, and an imaging system is miniaturized, therefore, the glass has wide application prospect in optical design.
Currently, the mainstream manufacturing method of optical elements is precision press molding (including direct press molding and secondary press molding), and lenses manufactured by using precision press molding technology are generally not ground and polished, thereby reducing raw material consumption, reducing costs of manpower and material resources, and reducing environmental pollution, and the technology can produce aspheric elements in large quantities at low cost. Precision press molding is a process of press-molding a glass preform with a high precision mold having a predetermined product shape under a certain temperature and pressure to obtain a glass product having a final product shape and an optical function. Various optical glass products such as spherical lenses, aspherical lenses, prisms, diffraction gratings, etc. can be manufactured by precision press-molding techniques.
In precision press molding, in order to transfer a high-precision mold surface to a glass product, it is necessary to press-mold a glass preform at a high temperature (usually 20 to 60 ℃ or higher at a glass transition temperature) while a molding die is under a high temperature and pressure, that is, under a high temperature and pressureThe mold surface is also susceptible to oxidation and erosion when exposed to a protective atmosphere. Since the press temperature must be lowered in order to extend the life of the mold and suppress damage to the mold due to a high-temperature environment, the transition temperature T of the glass material used for press molding is set to be lower than the press temperature T g It needs to be as low as possible. Patent document CN103663961A discloses a phosphate optical glass having a refractive index of 1.75 or more and an abbe number of 10 or more and 35 or less, which has a high transition temperature and is not favorable for prolonging the service life of a mold. With the progress of science and technology, the demand of photoelectric information products is increasing, and the performance of optical glass is also required.
Disclosure of Invention
The invention aims to solve the technical problem of providing phosphate optical glass with a refractive index of more than 1.87, an Abbe of less than 24 and a low transition temperature.
The technical scheme adopted by the invention for solving the technical problems is as follows:
phosphate optical glass, the components of which are expressed by weight percentage and comprise: p 2 O 5 ：10～30％；Bi 2 O 3 ：16～35％；Nb 2 O 5 ：20～40％；WO 3 ：5～20％；TiO 2 :0 to 10% of (Nb), wherein 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.4 to 1.5.
Further, the phosphate optical glass comprises the following components in percentage by weight: b 2 O 3 :0 to 8 percent; and/or Li 2 O:0 to 10 percent; and/or Na 2 O:0 to 10 percent; and/or K 2 O:0 to 10 percent; and/or RO:0 to 10 percent; and/or SiO 2 :0 to 5 percent; and/or ZrO 2 :0 to 5 percent; and/or Al 2 O 3 :0 to 5 percent; and/or Ln 2 O 3 :0 to 8 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, the RO is one or more of MgO, caO, srO, baO and ZnO, and the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as a clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
Phosphate optical glass, the composition of which is expressed in weight percentage by P 2 O 5 ：10～30％；Bi 2 O 3 ：16～35％；Nb 2 O 5 ：20～40％；WO 3 ：5～20％；TiO 2 ：0～10％；B 2 O 3 ：0～8％；Li 2 O：0～10％；Na 2 O：0～10％；K 2 O：0～10％；RO：0～10％；SiO 2 ：0～5％；ZrO 2 ：0～5％；Al 2 O 3 ：0～5％；Ln 2 O 3 ：0～8％；GeO 2 :0 to 5 percent; a clarifying agent: 0 to 1% of a composition of (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.4 to 1.5, the RO is one or more of MgO, caO, srO, baO and ZnO, and the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
Further, the phosphate optical glass has the following components in percentage by weight, and satisfies one or more of the following 5 conditions:
1)Bi 2 O 3 /Nb 2 O 5 0.5 to 1.5, preferably Bi 2 O 3 /Nb 2 O 5 0.6 to 1.2, and Bi is more preferable 2 O 3 /Nb 2 O 5 0.65 to 1.15, and Bi is more preferable 2 O 3 /Nb 2 O 5 0.7 to 1.1;
2)(Nb 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) Is 0.6 to 1.2, preferably (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) Is 0.72 to 1.0, more preferably (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.75 to 0.92;
3)(WO 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) From 0.4 to 1.5, preferably (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) Is 0.5 to 1.2, more preferably (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) Is 0.6 to 1.0, and is more preferably (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) 0.7 to 1.0;
4)WO 3 /Bi 2 O 3 0.2 to 1.0, preferably WO 3 /Bi 2 O 3 0.25 to 0.8, more preferably WO 3 /Bi 2 O 3 0.3 to 0.6, and further preferably WO 3 /Bi 2 O 3 0.35 to 0.46;
5)P 2 O 5 /(Nb 2 O 5 +TiO 2 ) Is 0.3 to 1.2, preferably P 2 O 5 /(Nb 2 O 5 +TiO 2 ) Is 0.4 to 1.0, more preferably P 2 O 5 /(Nb 2 O 5 +TiO 2 ) Is 0.45 to 0.9, and P is more preferably 2 O 5 /(Nb 2 O 5 +TiO 2 ) 0.5 to 0.8.
Further, the phosphate optical glass comprises the following components in percentage by weight, and one or more of the following 4 conditions are met:
1)(Li 2 O+Na 2 O+K 2 O)/Bi 2 O 3 0.05 to 1.0, preferably (Li) 2 O+Na 2 O+K 2 O)/Bi 2 O 3 Is 0.1 to 0.8, more preferably (Li) 2 O+Na 2 O+K 2 O)/Bi 2 O 3 Is 0.15 to 0.6, and (Li) is more preferable 2 O+Na 2 O+K 2 O)/Bi 2 O 3 0.2 to 0.5;
2)TiO 2 /(Li 2 O+Na 2 O+K 2 o) is 1.0 or less, preferably TiO 2 /(Li 2 O+Na 2 O+K 2 O) is 0.02 to 0.8, more preferably TiO 2 /(Li 2 O+Na 2 O+K 2 O) is 0.05 to 0.6, and TiO is more preferable 2 /(Li 2 O+Na 2 O+K 2 O) is 0.1 to 0.38;
3)RO/Li 2 o is 1.0 or less, preferably RO/Li 2 O is 0.7 or less, and RO/Li is more preferable 2 O is 0.5 or less, and RO/Li is more preferable 2 O is 0.4 or less;
4)(Na 2 O+TiO 2 )/WO 3 0.1 to 2.0, preferably (Na) 2 O+TiO 2 )/WO 3 Is 0.2 to 1.5, more preferably (Na) 2 O+TiO 2 )/WO 3 Is 0.3 to 1.2, and (Na) is more preferable 2 O+TiO 2 )/WO 3 0.4 to 1.0.
Further, the phosphate optical glass comprises the following components in percentage by weight: p 2 O 5 :15 to 25%, preferably P 2 O 5 :17 to 23 percent; and/or Bi 2 O 3 :18 to 32%, preferably Bi 2 O 3 :22 to 29.5 percent; and/or Nb 2 O 5 :25 to 35%, preferably Nb 2 O 5 :27 to 33 percent; and/or WO 3 :7 to 17%, preferably WO 3 :9 to 15 percent; and/or TiO 2 :0.5 to 8%, preferably TiO 2 :1 to 5 percent; and/or B 2 O 3 :0 to 5%, preferably B 2 O 3 :0 to 3 percent; and/or Li 2 O:0.5 to 8%, preferably Li 2 O:1 to 5 percent; and/or Na 2 O:1 to 8%, preferably Na 2 O:2 to 7 percent; and/or K 2 O:0 to 8%, preferably K 2 O:0 to 5 percent; and/or RO:0 to 8%, preferably RO:0 to 4 percent; and/or SiO 2 :0 to 3%, preferably SiO 2 :0 to 2 percent; and/or ZrO 2 :0 to 3%, preferably ZrO 2 :0 to 2 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 2 percent; and/or Ln 2 O 3 :0 to 5%, preferably Ln 2 O 3 :0 to 3 percent; and/or GeO 2 :0 to 3%, preferably GeO 2 :0 to 2 percent; and/or a clarifying agent: 0 to 0.5%, preferably clarifying agent: 0 to 0.2 percent of the total weight of the catalyst, wherein the RO is one or more of MgO, caO, srO, baO and ZnO, and the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
Furthermore, the refractive index n of the phosphate optical glass d Is 1.87 or more, preferably 1.88 to 1.96, more preferably 1.90 to 1.94; abbe number v d Is 24 or less, preferably 16 to 23, more preferably 19 to 22.
Further, the acid-resistance stability D of the phosphate optical glass A Is 2 or more, preferably 1; and/or stability against water action D W Is 2 or more, preferably 1; and/or coefficient of thermal expansion alpha -30/70℃ Is 100 x 10 -7 Preferably 95X 10 or less,/K -7 A value of less than or equal to K, more preferably 90X 10 -7 below/K; and/or transition temperature T g Is 500 ℃ or lower, preferably 490 ℃ or lower, more preferably 480 ℃ or lower; and/or degree of wear F A 310 to 400, preferably 320 to 380, more preferably 340 to 370; and/or lambda 70 470nm or less, preferably 460nm or less; and/or lambda 5 410nm or less, preferably 400nm or less; and/or a Young's modulus E of 8000X 10 7 /Pa or more, preferably 8500X 10 7 /Pa～10000×10 7 /Pa, more preferably 8700X 10 7 /Pa～9500×10 7 Pa; and/or a density p of 4.70g/cm 3 Hereinafter, it is preferably 4.60g/cm 3 Hereinafter, more preferably 4.50g/cm 3 The following; and/or the upper crystallization temperature is 980 ℃ or lower, preferably 970 ℃ or lower, more preferably 960 ℃ or lower, and still more preferably 950 ℃ or lower.
The glass preform is made of the phosphate optical glass.
An optical element made of the phosphate optical glass or the glass preform.
An optical device comprising the phosphate optical glass and/or comprising the optical element.
The beneficial effects of the invention are: through reasonable component design, the optical glass obtained by the invention has lower transition temperature while having the expected refractive index and Abbe number.
Detailed Description
The phosphate optical glass of the present invention is obtained by the following method, which is a method for producing a phosphate optical glass according to the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. In the following, the phosphate optical glass of the present invention is sometimes simply referred to as optical glass or glass.
[ optical glass ]
The ranges of the respective components (ingredients) of the phosphate optical glass of the present invention are explained below. In the present invention, the contents and total contents of the respective components are all expressed in weight percent (wt%), that is, the contents and total contents of the respective components are expressed in weight percent with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed and converted to oxides when melted, the total amount of the oxides is 100%.
Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include end-point values, as well as all integers and fractions within the range, and are not limited to the specific values recited in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means only A, or only B, or both A and B.
< essential Components and optional Components >
P 2 O 5 The glass forming agent has the functions of lowering the melting temperature of the glass raw material and improving the stability and visible light transmittance of the glass, and in the present invention, P is contained by 10% or more 2 O 5 To obtain the above effects, P is preferred 2 O 5 Is 15% or more, more preferably P 2 O 5 The content of (B) is more than 17%. On the other hand, P is 2 O 5 The content of (A) is controlled to be 30% or less to prevent the glass from lowering in refractive index and deterioration in devitrification resistance. Thus, in the present invention P 2 O 5 The content of (b) is 30% or less, preferably 25% or less, and more preferably 23% or less.
Bi 2 O 3 Can improve the refractive index and partial dispersion ratio of the glass, reduce the softening temperature of the glass and improve the weather resistance and stability of the glass. In the present invention, 16% or more of Bi is contained 2 O 3 In order to obtain the above-mentioned effects, bi is preferably contained in an amount of 18% or more 2 O 3 More preferably 22% or more of Bi 2 O 3 . On the other hand, by adding Bi 2 O 3 The content of (A) is controlled to be less than 35%, so that the glass has excellent anti-devitrification performance and Young modulus. Thus, bi 2 O 3 The content of (b) is 35% or less, preferably 32% or less, more preferably 29.5% or less.
Nb 2 O 5 The refractive index and dispersion of the glass can be improved, and the chemical stability and devitrification resistance of the optical glass can be improved. In the invention, more than 20 percent of Nb is contained 2 O 5 In order to obtain the above effects, it is preferable to contain 25% or more of Nb 2 O 5 More preferably 27% or more of Nb 2 O 5 . If Nb 2 O 5 When the content exceeds 40%, the devitrification resistance of the glass is lowered and the abrasion degree is deteriorated. Therefore, in the optical glass of the present invention, nb 2 O 5 The content is 40% or less, preferably 35% or less, and more preferably 33% or less.
In some embodiments, by reacting Bi 2 O 3 Content of (2) and Nb 2 O 5 Ratio between contents of Bi 2 O 3 /Nb 2 O 5 The thermal expansion coefficient of the glass can be reduced while the chemical stability of the glass is improved by controlling the temperature within the range of 0.5-1.5. Therefore, bi is preferred 2 O 3 /Nb 2 O 5 Is 0.5 to 1.5, and Bi is more preferable 2 O 3 /Nb 2 O 5 0.6 to 1.2. Further, by controlling Bi 2 O 3 /Nb 2 O 5 In the range of 0.65-1.15, the crystallization resistance of the glass is improved, and the abrasion degree is optimized. Therefore, bi is more preferable 2 O 3 /Nb 2 O 5 0.65 to 1.15, and Bi is more preferable 2 O 3 /Nb 2 O 5 0.7 to 1.1.
WO 3 Can improve the refractive index and mechanical strength of the glass, reduce the transition temperature of the glass, and in the precise profiling process, WO 3 The wettability between the glass material and the mold can be suppressed, and the releasability of the glass can be improved. The invention contains more than 5% of WO 3 To obtain the above effects, WO is preferred 3 The lower limit of the content of (B) is 7%, and WO is more preferable 3 The lower limit of the content of (B) is 9%. If WO 3 The content of (b) exceeds 20%, the thermal stability of the glass is reduced, the glass is easily colored in the precision die pressing process, the high-temperature viscosity of the glass is reduced, and the molding difficulty is increased. Thus, WO 3 The upper limit of the content of (b) is 20%, preferably 17%, more preferably 15%.
In some embodiments, WO is 3 Content of (A) and Bi 2 O 3 Ratio between contents of WO 3 /Bi 2 O 3 The crystallization resistance and the streak degree of the glass can be improved by controlling the temperature within the range of 0.2-1.0. Thus, WO is preferred 3 /Bi 2 O 3 0.2 to 1.0, more preferably WO 3 /Bi 2 O 3 0.25 to 0.8, and further preferably WO 3 /Bi 2 O 3 0.3 to 0.6. Further, by controlling WO 3 /Bi 2 O 3 In the range of 0.35 to 0.46, the glass transition temperature and the thermal expansion coefficient can be further reduced. Therefore, W is more preferableO 3 /Bi 2 O 3 0.35 to 0.46.
In some embodiments, WO is 3 And Bi 2 O 3 WO in total 3 +Bi 2 O 3 And Nb 2 O 5 And P 2 O 5 Total content of (2) Nb 2 O 5 +P 2 O 5 Ratio therebetween (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) The chemical stability of the glass can be improved and the light transmittance of the glass can be improved at the same time when the control is within the range of 0.4-1.5. Therefore, preferred (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) Is 0.4 to 1.5, more preferably (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) 0.5 to 1.2. Further, by control (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) In the range of 0.6 to 1.0, the temperature coefficient of refractive index and the thermal expansion coefficient of the glass can be reduced. Therefore, further preferred (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) Is 0.6 to 1.0, and more preferably (WO) 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) Is 0.7 to 1.0.
TiO 2 Has the function of improving the refractive index and dispersion of the glass, and the proper content of the additive can ensure that the glass obtains proper Young modulus and prevent the thermal expansion coefficient of the glass from increasing. If TiO 2 2 Too large of (b) results in deterioration of abrasion, transmittance and chemical stability of the glass. Thus, in the present invention, tiO 2 The content of (b) is 10% or less, preferably 0.5 to 8%, more preferably 1 to 5%.
In some embodiments, nb is 2 O 5 And TiO 2 Total content of (B) Nb 2 O 5 +TiO 2 With WO 3 And Bi 2 O 3 WO in total 3 +Bi 2 O 3 Ratio (Nb) between 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) The glass transition temperature can be reduced while the chemical stability of the glass is optimized by controlling the temperature to be in the range of 0.4-1.5. Therefore, (Nb) is preferable 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) Is 0.4 to 1.5, more preferably (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.6 to 1.2. Further, by controlling (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) The Young's modulus and density of the glass can also be optimized within the range of 0.72 to 1.0. Therefore, (Nb) is more preferable 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) Is 0.72 to 1.0, more preferably (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.75-0.92.
In some embodiments, P is 2 O 5 Content of (2) and Nb 2 O 5 And TiO 2 2 Total content of (B) Nb 2 O 5 +TiO 2 Ratio P therebetween 2 O 5 /(Nb 2 O 5 +TiO 2 ) The control is in the range of 0.3-1.2, the thermal expansion coefficient of the glass can be reduced, and the light transmittance of the glass can be improved. Therefore, P is preferred 2 O 5 /(Nb 2 O 5 +TiO 2 ) Is 0.3 to 1.2, more preferably P 2 O 5 /(Nb 2 O 5 +TiO 2 ) 0.4 to 1.0. Further, by controlling P 2 O 5 /(Nb 2 O 5 +TiO 2 ) Within the range of 0.45-0.9, the abrasion degree and the streak degree of the glass can be further optimized. Therefore, P is more preferable 2 O 5 /(Nb 2 O 5 +TiO 2 ) Is 0.45 to 0.9, and P is more preferably 2 O 5 /(Nb 2 O 5 +TiO 2 ) 0.5 to 0.8.
B 2 O 3 Which can improve the melting and devitrification resistance of the glass, are optional components of the glass of the present invention. By mixing B 2 O 3 The content of (B) is limited to 8% or less, and the prevention of the occurrence of the above-mentioned problemsB 2 O 3 Excessive content results in lowering of glass stability and refractive index. Thus, B 2 O 3 The content of (b) is 8% or less, preferably 5% or less, more preferably 3% or less.
Li 2 O can lower the glass transition temperature and adjust the viscosity of the glass, but its high content is disadvantageous in chemical stability and thermal expansion coefficient of the glass, and therefore Li in the present invention 2 The content of O is 10% or less, preferably 0.5 to 8%, more preferably 1 to 5%.
Na 2 O has the effects of improving glass meltability, increasing glass melting effect, and lowering glass transition temperature, and Na is added 2 The O content exceeds 10%, the chemical stability and weather resistance of the glass are lowered, and therefore Na 2 The content of O is 0 to 10%, preferably Na 2 The content of O is 1 to 8%, more preferably Na 2 The content of O is 2-7%.
In some embodiments, na is substituted with sodium hydroxide 2 O and TiO 2 Total content of (3) Na 2 O+TiO 2 With WO 3 Ratio between contents of (Na) 2 O+TiO 2 )/WO 3 The Young's modulus of the glass can be improved while the glass has a low thermal expansion coefficient by controlling the temperature to be within the range of 0.1-2.0. Therefore, (Na) is preferred 2 O+TiO 2 )/WO 3 Is 0.1 to 2.0, more preferably (Na) 2 O+TiO 2 )/WO 3 0.2 to 1.5. Further, mixing (Na) 2 O+TiO 2 )/WO 3 The hardness and the transition temperature of the glass can be optimized by controlling the range of 0.3-1.2. Therefore, (Na) is more preferable 2 O+TiO 2 )/WO 3 Is 0.3 to 1.2, and more preferably (Na) 2 O+TiO 2 )/WO 3 Is 0.4 to 1.0.
K 2 O has an effect of improving the thermal stability and meltability of the glass, but the content thereof exceeds 10%, and the resistance to devitrification and chemical stability of the glass are deteriorated, so that K in the present invention 2 The content of O is 10% or less, preferably K 2 The content of O is 8% or less, more preferably 5% or less.
In some embodiments of the present invention, the substrate is,by adding Li 2 O、Na 2 O、K 2 Total content of O Li 2 O+Na 2 O+K 2 O and Bi 2 O 3 Ratio between contents of (Li) 2 O+Na 2 O+K 2 O)/Bi 2 O 3 The control is within the range of 0.05-1.0, thus preventing the light transmittance of the glass from reducing and simultaneously improving the anti-crystallization performance of the glass. Therefore, (Li) is preferable 2 O+Na 2 O+K 2 O)/Bi 2 O 3 Is 0.05 to 1.0, more preferably (Li) 2 O+Na 2 O+K 2 O)/Bi 2 O 3 0.1 to 0.8. Further, by controlling (Li) 2 O+Na 2 O+K 2 O)/Bi 2 O 3 The bubble degree and abrasion degree of the glass can be further optimized within the range of 0.15 to 0.6. Therefore, (Li) is more preferable 2 O+Na 2 O+K 2 O)/Bi 2 O 3 Is 0.15 to 0.6, more preferably (Li) 2 O+Na 2 O+K 2 O)/Bi 2 O 3 0.2 to 0.5.
In some embodiments, by reacting TiO with a catalyst 2 With Li 2 O、Na 2 O、K 2 Total content of O Li 2 O+Na 2 O+K 2 Ratio between O TiO 2 /(Li 2 O+Na 2 O+K 2 O) is controlled below 1.0, which is beneficial to reducing the density of the glass and optimizing the streak degree and the transmittance of the glass. Therefore, tiO is preferred 2 /(Li 2 O+Na 2 O+K 2 O) is 1.0 or less, and TiO is more preferable 2 /(Li 2 O+Na 2 O+K 2 O) is 0.02 to 0.8, and TiO is more preferable 2 /(Li 2 O+Na 2 O+K 2 O) is 0.05 to 0.6. Further, by controlling TiO 2 /(Li 2 O+Na 2 O+K 2 O) is in the range of 0.1 to 0.38, and the Young's modulus and abrasion of the glass can be further optimized. Therefore, tiO is more preferable 2 /(Li 2 O+Na 2 O+K 2 O) is 0.1 to 0.38.
RO (RO is one or more of MgO, caO, srO, baO and ZnO) can adjust the refractive index of the glass and improve the devitrification resistance of the glass, and is an optional component in the optical glass of the invention. By controlling the RO content to 10% or less, the glass can be inhibited from lowering in crystallization resistance and chemical stability. Therefore, in the optical glass of the present invention, the upper limit of the range of the RO content is 10%, preferably 8%, more preferably 4%.
In some embodiments, the RO content is determined by combining the RO content with Li 2 Ratio between the contents of O RO/Li 2 And the O is controlled below 1.0, so that the chemical stability and the thermal stability of the glass are improved. Therefore, RO/Li is preferable 2 O is 1.0 or less, and RO/Li is more preferable 2 O is 0.7 or less. Further, by controlling RO/Li 2 O is less than 0.5, and the devitrification resistance and the Young modulus of the glass can be further optimized. Therefore, RO/Li is more preferable 2 O is 0.5 or less, and RO/Li is more preferable 2 O is 0.4 or less.
Ln 2 O 3 (Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more) is a component for improving the refractive index and chemical stability of the glass by adding Ln 2 O 3 The content of (2) is controlled to 8% or less, and a decrease in devitrification resistance of the glass can be prevented, and Ln is preferred 2 O 3 The upper limit of the content range is 5%, and the more preferable upper limit is 3%.
SiO 2 Which can improve the devitrification resistance and chemical stability of the glass, are optional components of the glass of the present invention. When the content is too high, the transition temperature of the glass increases, the refractive index decreases, and calculus is liable to occur. Thus, siO in the present invention 2 The content of (b) is 5% or less, preferably 3% or less, more preferably 2% or less.
ZrO 2 Can improve the refractive index of glass, adjust the dispersion, and improve the devitrification resistance and strength of glass, if ZrO 2 If the content of (b) is too large, the difficulty of melting the glass increases and the transition temperature rises. Thus, zrO 2 The content is 5% or less, preferably 3% or less, and more preferably 2% or less.
Al 2 O 3 The chemical stability of the glass can be improved, but when the content is too high, the devitrification resistance and melting resistance of the glass decrease, so that the content is 5% or less, preferably 3% or less, more preferably 2% or less, and further preferably no Al is contained 2 O 3 。
GeO 2 The optical glass of the present invention has the effects of increasing the refractive index of the glass and increasing the devitrification resistance, but is an optional component of the optical glass of the present invention, however, it is expensive, contains too much, is disadvantageous in cost reduction, and the light transmittance of the glass is lowered, so that the content thereof is limited to 5% or less, preferably 3% or less, more preferably 2% or less. In some embodiments, it is further preferred that no GeO is present 2 。
In some embodiments, the optical glass can also contain 0-1% of a clarifying agent so as to improve the defoaming capability of the glass. The fining agent includes but is not limited to Sb 2 O 3 、SnO 2 SnO and CeO 2 Preferably Sb 2 O 3 As a clarifying agent. The upper limit of the content of the above-mentioned clarifying agent is preferably 0.5%, more preferably 0.2% when it is present alone or in combination.
< Components not to be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, cr, mn, fe, co, ni, cu, ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, cd, tl, os, be, and Se tend to Be used as harmful chemical substances under control, and measures for protecting the environment are required not only in the glass production process but also in the processing process and in the disposal after the production of products. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Thus, it is possible to provideThe optical glass of the present invention can be produced, processed and discarded without taking special measures for environmental measures. Meanwhile, in order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 And PbO.
"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.
The properties of the phosphate optical glass of the present invention will be described below:
< refractive index and Abbe number >
Refractive index (n) of optical glass d ) And Abbe number (. Nu.) d ) The test was carried out according to the method specified in GB/T7962.1-2010.
In some embodiments, the phosphate optical glass of the present invention has a refractive index (n) d ) The upper limit of (a) is 1.96, the preferred upper limit is 1.94, and the more preferred upper limit is 1.93.
In some embodiments, the phosphate optical glasses of the present invention have a refractive index (n) d ) The lower limit of (2) is 1.87, the preferred lower limit is 1.88, and the more preferred lower limit is 1.90.
In some embodiments, the phosphate optical glass of the present invention has an Abbe number (. Nu. d ) The upper limit of (2) is 24, preferably 23, more preferably 22.
In some embodiments, the Abbe number (v) of the phosphate optical glass of the present invention d ) The lower limit of (b) is 16, preferably 17, more preferably 18, and still more preferably 19.
< degree of coloration >
The coloring degree (. Lamda.) for the short-wave transmission spectrum characteristic of the phosphate optical glass of the present invention 70 And λ 5 ) And (4) showing. Lambda [ alpha ] 70 Refers to the wavelength corresponding to the glass transmittance of 70%. Lambda 70 Is measured by using a polishing solution having a plurality of parallel and optically polished surfacesOf glass having a thickness of 10 + -0.1 mm in two opposite planes, the spectral transmittance in the wavelength region from 280nm to 700nm is measured and a wavelength at which the transmittance is 70% is exhibited. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glass in Light transmitted through the glass and having an intensity I emitted from a plane out Under the condition of light of (1) through out /I in The quantity expressed and also the transmission of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glasses, λ 70 A small value of (A) means that the glass itself is rarely colored and has a high light transmittance.
In some embodiments, the phosphate optical glass of the present invention has a lambda 70 Is 470nm or less, preferably lambda 70 Is 460nm or less.
In some embodiments, the phosphate optical glass of the present invention has a lambda 5 Is 410nm or less, preferably λ 5 Is 400nm or less.
< stability against acid Effect >
Stability of acid resistance of optical glasses (D) A ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the phosphate optical glasses of the present invention are stable against acid action (D) A ) Is 2 or more, preferably 1.
< stability against Water Effect >
Stability to Water of optical glass (D) W ) (powder method) the test was carried out according to the method described in GB/T17129.
In some embodiments, the phosphate optical glass of the present invention has stability against water action (D) W ) Is 2 or more, preferably 1.
< upper limit temperature of crystallization >
The crystallization resistance of the optical glass is measured by adopting a gradient temperature furnace method, the glass is made into a sample of 180 multiplied by 10mm, the side surface of the sample is polished, the sample is put into a furnace with a temperature gradient (10 ℃/cm) and the highest temperature zone temperature of 1200 ℃ for heat preservation for 4 hours, then the sample is taken out and naturally cooled to the room temperature, the crystallization condition of the glass is observed under a microscope, and the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.
In some embodiments, the phosphate optical glass of the present invention has a crystallization upper limit temperature of 980 ℃ or lower, preferably 970 ℃ or lower, more preferably 960 ℃ or lower, and further preferably 950 ℃ or lower.
< Young's modulus >
The Young's modulus (E) of the optical glass is obtained by measuring the longitudinal wave velocity and the transverse wave velocity of the optical glass by ultrasonic waves and calculating according to the following formula.
G＝V S 2 ρ
In the formula: e is Young's modulus, pa;
g is shear modulus, pa;
V T is the transverse wave velocity, m/s;
V S is the longitudinal wave velocity, m/s;
rho is the density of the glass, g/cm 3 。
In some embodiments, the phosphate optical glass of the present invention has a Young's modulus (E) of 8000X 10 7 /Pa or more, preferably 8500X 10 7 /Pa～10000×10 7 /Pa, more preferably 8700X 10 7 /Pa～9500×10 7 /Pa。
< coefficient of thermal expansion >
Coefficient of thermal expansion (alpha) of optical glass -30/70℃ ) The data at-30 to 70 ℃ were measured according to the method specified in GB/T7962.16-2010.
In some embodiments, the phosphate optical glasses of the present invention have a coefficient of thermal expansion (α) -30/70℃ ) Is 100 x 10 -7 Preferably 95X 10,/K or less -7 A value of not more than 90X 10 is more preferable -7 The ratio of the sulfur to the sulfur is below K.
< Density >
The density (. Rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.
In some embodiments, the phosphate optical glass of the present invention has a density (. Rho.) of 4.70g/cm 3 Hereinafter, it is preferably 4.60g/cm 3 Hereinafter, more preferably 4.50g/cm 3 The following.
< degree of abrasion >
Degree of abrasion (F) of optical glass A ) The abrasion loss of the sample is multiplied by 100 under the same conditions, and the value is expressed by the following formula:
F A ＝V/V 0 ×100＝(W/ρ)/(W 0 /ρ 0 )×100
in the formula: v, the volume abrasion loss of the measured sample;
V 0 -the amount of wear of the standard sample volume;
w is the abrasion loss of the quality of the sample to be measured;
W 0 -abrasion loss of standard sample mass;
rho is the density of the sample to be measured;
ρ 0 -standard sample density.
In some embodiments, the phosphate optical glass of the present invention has an abrasion loss (F) A ) The upper limit of (2) is 400, preferably 380, more preferably 370.
In some embodiments, the phosphate optical glass of the present invention has an abrasion loss (F) A ) The lower limit of (b) is 310, the preferred lower limit is 320, and the more preferred lower limit is 340.
< transition temperature >
Transition temperature (T) of optical glass g ) The test was carried out according to the method specified in GB/T7962.16-2010.
In some embodiments, the transition temperature (T) of the phosphate optical glass of the present invention g ) Is 500 ℃ or lower, preferably 490 ℃ or lower, and more preferably 480 ℃ or lower.
[ production method ]
The method for producing the phosphate optical glass of the present invention comprises: the glass of the present invention is produced by using conventional materials and processes including but not limited to oxides, hydroxides, fluorides, various salts (carbonates, nitrates, sulfates, phosphates, metaphosphates), etc. as raw materials, blending by conventional methods, then melting the blended charge in a melting furnace (such as platinum, gold or platinum alloy crucible) at 800-1200 deg.C, and after fining and homogenizing, obtaining homogeneous molten glass without bubbles and undissolved substances, and casting and annealing the molten glass in a mold. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
[ glass preform and optical element ]
The glass preform can be produced from the phosphate optical glass produced by direct gob casting, grinding, or press molding such as hot press molding. That is, a glass preform can be produced by direct precision gob-molding of molten optical glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from optical glass, subjecting the preform to reheat press molding, and then performing polishing processing. It should be noted that the means for producing the glass preform is not limited to the above means.
As described above, the phosphate optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the phosphate optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
The glass preform and the optical element of the present invention are each formed of the above-described phosphate optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by phosphate optical glass; the optical element of the present invention has excellent characteristics of phosphate optical glass, and can provide various optical elements such as lenses and prisms having high optical values.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instruments ]
The optical element formed by the phosphate optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< phosphate optical glass example >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 1 to 4 were obtained by the above-described method for producing phosphate optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 4.
Table 1.
Table 2.
Table 3.
Table 4.
< glass preform example >
Various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses and plano-concave lenses, and preforms such as prisms were produced from the glasses obtained in phosphate optical glass examples 1 to 26 by, for example, polishing or press molding such as reheat press molding and precision press molding.
< optical element example >
The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to perform fine adjustment so that the optical properties such as the refractive index were adjusted to desired values.
Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be further coated with an antireflection film.
< optical Instrument embodiment >
The optical element obtained by the above-described optical element embodiment is used for, for example, an imaging device, a sensor, a microscope, a medical technology, a digital projection, a communication, an optical communication technology/information transmission, an optical/illumination in an automobile field, a lithography technology, an excimer laser, a wafer, a computer chip, and an integrated circuit and an electronic device including such a circuit and a chip, or an image pickup device and apparatus used in an in-vehicle field, by forming an optical component or an optical assembly by using one or more optical elements through an optical design.
Claims (23)
1. Phosphate optical glass, characterized in that its composition, expressed in weight percentages, contains: p 2 O 5 ：10～30％；Bi 2 O 3 ：16～35％；Nb 2 O 5 ：20～40％；WO 3 ：5～20％；TiO 2 :0 to 10% of, wherein (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.4 to 0.92% of TiO 2 /(Li 2 O+Na 2 O+K 2 O) is 0.38 or less.
2. A phosphate optical glass according to claim 1, characterized in that its components, expressed in weight percent, further comprise: b 2 O 3 :0 to 8 percent; and/or Li 2 O:0 to 10 percent; and/or Na 2 O:0 to 10 percent; and/or K 2 O:0 to 10 percent; and/or RO:0 to 10 percent; and/or SiO 2 :0 to 5 percent; and/or ZrO 2 :0 to 5 percent; and/or Al 2 O 3 :0 to 5 percent; and/or Ln 2 O 3 :0 to 8 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, the RO is one or more of MgO, caO, srO, baO and ZnO, and the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
3. Phosphate optical glass, characterized in that its components are heavyThe quantity percentage is expressed by P 2 O 5 ：10～30％；Bi 2 O 3 ：16～35％；Nb 2 O 5 ：20～40％；WO 3 ：5～20％；TiO 2 ：0～10％；B 2 O 3 ：0～8％；Li 2 O：0～10％；Na 2 O：0～10％；K 2 O：0～10％；RO：0～10％；SiO 2 ：0～5％；ZrO 2 ：0～5％；Al 2 O 3 ：0～5％；Ln 2 O 3 ：0～8％；GeO 2 :0 to 5 percent; a clarifying agent: 0 to 1% of a composition of (Nb) 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.4 to 0.92% of TiO 2 /(Li 2 O+Na 2 O+K 2 O) is less than 0.38, the RO is one or more of MgO, caO, srO, baO and ZnO, and Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
4. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 5 conditions:
1)Bi 2 O 3 /Nb 2 O 5 0.5 to 1.5;
2)(Nb 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.6 to 0.92;
3)(WO 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) 0.4 to 1.5;
4)WO 3 /Bi 2 O 3 0.2 to 1.0;
5)P 2 O 5 /(Nb 2 O 5 +TiO 2 ) Is 0.3 to 1.2.
5. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 5 conditions:
1)Bi 2 O 3 /Nb 2 O 5 0.6 to 1.2;
2)(Nb 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.72 to 0.92;
3)(WO 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) 0.5 to 1.2;
4)WO 3 /Bi 2 O 3 0.25 to 0.8;
5)P 2 O 5 /(Nb 2 O 5 +TiO 2 ) 0.4 to 1.0.
6. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 5 conditions:
1)Bi 2 O 3 /Nb 2 O 5 0.65 to 1.15;
2)(Nb 2 O 5 +TiO 2 )/(WO 3 +Bi 2 O 3 ) 0.75 to 0.92;
3)(WO 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) 0.6 to 1.0;
4)WO 3 /Bi 2 O 3 0.3 to 0.6;
5)P 2 O 5 /(Nb 2 O 5 +TiO 2 ) 0.45 to 0.9.
7. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 4 conditions:
1)Bi 2 O 3 /Nb 2 O 5 0.7 to 1.1;
2)(WO 3 +Bi 2 O 3 )/(Nb 2 O 5 +P 2 O 5 ) 0.7 to 1.0;
3)WO 3 /Bi 2 O 3 0.35 to 0.46;
4)P 2 O 5 /(Nb 2 O 5 +TiO 2 ) 0.5 to 0.8.
8. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 4 conditions:
1)(Li 2 O+Na 2 O+K 2 O)/Bi 2 O 3 0.05 to 1.0;
2)TiO 2 /(Li 2 O+Na 2 O+K 2 o) is 0.02 to 0.38;
3)RO/Li 2 o is 1.0 or less;
4)(Na 2 O+TiO 2 )/WO 3 is 0.1 to 2.0.
9. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 4 conditions:
1)(Li 2 O+Na 2 O+K 2 O)/Bi 2 O 3 0.1 to 0.8;
2)TiO 2 /(Li 2 O+Na 2 O+K 2 o) is 0.05 to 0.38;
3)RO/Li 2 o is 0.7 or less;
4)(Na 2 O+TiO 2 )/WO 3 0.2 to 1.5.
10. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 4 conditions:
1)(Li 2 O+Na 2 O+K 2 O)/Bi 2 O 3 is 0.15～0.6；
2)TiO 2 /(Li 2 O+Na 2 O+K 2 O) is 0.1 to 0.38;
3)RO/Li 2 o is 0.5 or less;
4)(Na 2 O+TiO 2 )/WO 3 0.3 to 1.2.
11. A phosphate optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 3 conditions:
1)(Li 2 O+Na 2 O+K 2 O)/Bi 2 O 3 0.2 to 0.5;
2)RO/Li 2 o is 0.4 or less;
3)(Na 2 O+TiO 2 )/WO 3 is 0.4 to 1.0.
12. A phosphate optical glass according to any one of claims 1 to 3, characterized in that its composition, expressed in weight percent, comprises: p 2 O 5 :15 to 25 percent; and/or Bi 2 O 3 :18 to 32 percent; and/or Nb 2 O 5 :25 to 35 percent; and/or WO 3 :7 to 17 percent; and/or TiO 2 :0.5 to 8 percent; and/or B 2 O 3 :0 to 5 percent; and/or Li 2 O:0.5 to 8 percent; and/or Na 2 O:1 to 8 percent; and/or K 2 O:0 to 8 percent; and/or RO:0 to 8 percent; and/or SiO 2 :0 to 3 percent; and/or ZrO 2 :0 to 3 percent; and/or Al 2 O 3 :0 to 3 percent; and/or Ln 2 O 3 :0 to 5 percent; and/or GeO 2 :0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent of RO, wherein the RO is one or more of MgO, caO, srO, baO and ZnO, and Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as a clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more ofAnd (4) a plurality of.
13. A phosphate optical glass according to any one of claims 1 to 3, characterized in that its composition, expressed in weight percent, comprises: p 2 O 5 :17 to 23 percent; and/or Bi 2 O 3 :22 to 29.5 percent; and/or Nb 2 O 5 :27 to 33 percent; and/or WO 3 :9 to 15 percent; and/or TiO 2 :1 to 5 percent; and/or B 2 O 3 :0 to 3 percent; and/or Li 2 O:1 to 5 percent; and/or Na 2 O:2 to 7 percent; and/or K 2 O:0 to 5 percent; and/or RO:0 to 4 percent; and/or SiO 2 :0 to 2 percent; and/or ZrO 2 :0 to 2 percent; and/or Al 2 O 3 :0 to 2 percent; and/or Ln 2 O 3 :0 to 3 percent; and/or GeO 2 :0 to 2 percent; and/or a clarifying agent: 0 to 0.2 percent of the total weight of the catalyst, wherein the RO is one or more of MgO, caO, srO, baO and ZnO, and the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO 2 、SnO、CeO 2 One or more of (a).
14. A phosphate optical glass according to any one of claims 1 to 3, wherein the refractive index n of the phosphate optical glass is d Is 1.87 or more; abbe number v d Is 24 or less.
15. A phosphate optical glass according to any one of claims 1 to 3, wherein the refractive index n of the phosphate optical glass is d 1.88 to 1.96; abbe number v d Is 16 to 23.
16. A phosphate optical glass according to any one of claims 1 to 3, wherein the refractive index n of the phosphate optical glass is d 1.90 to 1.94; abbe number v d Is 19 to 22.
17. A phosphate optical glass according to any one of claims 1 to 3, characterized in that the phosphate optical glass has an acid action resistance stability D A Is more than 2 types; and/or stability against water action D W Is 2 or more; and/or coefficient of thermal expansion alpha -30/70℃ Is 100 x 10 -7 below/K; and/or transition temperature T g Below 500 ℃; and/or degree of wear F A Is 310 to 400; and/or lambda 70 Is below 470 nm; and/or lambda 5 Is 410nm or less; and/or a Young's modulus E of 8000X 10 7 More than Pa; and/or a density rho of 4.70g/cm 3 The following; and/or the upper limit temperature of crystallization is 980 ℃ or lower.
18. A phosphate optical glass according to any one of claims 1 to 3, characterized in that the phosphate optical glass has an acid action resistance stability D A Is of type 1; and/or stability against water action D W Is of type 1; and/or coefficient of thermal expansion alpha -30/70℃ Is 95X 10 -7 below/K; and/or transition temperature T g At 490 ℃ or below; and/or degree of wear F A Is 320 to 380; and/or lambda 70 Is 460nm or less; and/or lambda 5 Is 400nm or less; and/or a Young's modulus E of 8500X 10 7 /Pa～10000×10 7 Pa; and/or a density rho of 4.60g/cm 3 The following; and/or the upper limit temperature of crystallization is 970 ℃ or lower.
19. A phosphate optical glass according to any one of claims 1 to 3, wherein the phosphate optical glass has a coefficient of thermal expansion α -30/70℃ Is 90X 10 -7 below/K; and/or transition temperature T g Below 480 ℃; and/or degree of wear F A 340 to 370; and/or a Young's modulus E of 8700X 10 7 /Pa～9500×10 7 Pa; and/or a density rho of 4.50g/cm 3 The following; and/or the upper crystallization temperature is 960 ℃ or lower.
20. A phosphate optical glass according to any one of claims 1 to 3, wherein the crystallization upper limit temperature of the phosphate optical glass is 950 ℃ or lower.
21. A glass preform made from the phosphate optical glass according to any one of claims 1 to 20.
22. An optical element produced using the phosphate optical glass according to any one of claims 1 to 20 or the glass preform according to claim 21.
23. An optical device comprising the phosphate optical glass according to any one of claims 1 to 20 and/or comprising the optical element according to claim 22.
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