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WO2007116943A1 - Verre optique pour moulage par compression - Google Patents

Verre optique pour moulage par compression Download PDF

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Publication number
WO2007116943A1
WO2007116943A1 PCT/JP2007/057672 JP2007057672W WO2007116943A1 WO 2007116943 A1 WO2007116943 A1 WO 2007116943A1 JP 2007057672 W JP2007057672 W JP 2007057672W WO 2007116943 A1 WO2007116943 A1 WO 2007116943A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
press molding
mold
mold press
optical glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/057672
Other languages
English (en)
Japanese (ja)
Inventor
Fumio Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to KR1020087019892A priority Critical patent/KR101351450B1/ko
Publication of WO2007116943A1 publication Critical patent/WO2007116943A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the present invention relates to an optical glass for mold press molding.
  • Refractive index (nd) for optical lenses such as optical pickup lenses for various optical disk systems such as CD, MD, DVD, and video cameras, etc. for ordinary cameras is 1.57 to L 62
  • Abbe An optical glass having a number (vd) of 55 or more, more specifically a refractive index (nd) of 1.5575-1.610 and an Abbe number (vd) of 58.5-62.0 is used.
  • lead-containing glass based on SiO 2 —PbO—R ′ 0 (R and O are alkali metal oxides) has been used.
  • R'O-based non-lead glass is being switched (for example,
  • Patent Documents 1 and 2 are referred to Patent Documents 1 and 2.
  • Patent Document 1 JP-A-6-107425
  • Patent Document 2 JP 2000-302479 A
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-328068
  • These optical pickup lenses and photographing lenses are molded as follows. First, molten glass is dripped from the tip of the nozzle to produce a glass droplet once, then polished I ”, polished and washed to produce a preform glass. Alternatively, rapidly cool and forge molten glass and make glass blocks, and also polish and wash them to make preform glass. After that, the preform glass that has been softened again is pressed with a precision-processed mold, and the surface shape of the mold is transferred to the glass. Such a method is called a so-called mold press molding method and is widely used.
  • the conventional lead-free preform glass as described above often does not have sufficient weather resistance. If the weather resistance of the glass is not sufficient, glass components will elute into the polishing cleaning water and various cleaning solutions during the cutting and cleaning processes, and the surface will be altered. As a result, defects are generated in the glass where devitrification is easily generated in the molding process, and mass production becomes difficult. Even in the final product, when exposed to high temperature and humidity for a long time, the surface of the glass is altered, and there is a problem that the reliability is impaired.
  • An object of the present invention is to satisfy various properties required for optical glass for mold press molding, and particularly, the refractive index (nd) is 1.57 to L 62, and the Abbe number (vd) is 55 or more (preferably Is a refractive index (nd) force S1. 575 to 1.610, Abbe number (vd) force 58.5 to 62.0) It is to be.
  • the optical glass of the present invention is used for optical lenses such as optical pickup lenses for CD, MD, DVD and other various optical disk systems, and photographing lenses for video cameras and general cameras. And an Abbe number (vd) of 55 or more.
  • vd Abbe number
  • the molding accuracy is not lowered and the mold is not deteriorated or contaminated.
  • it is suitable as an optical glass for mold press molding.
  • This glass has a basic composition of 2 3 to 15%.
  • lead-free glass contains a large amount of alkaline earth metal oxide RO in order to obtain a high refractive index, which is a cause of lowering the weather resistance of this glass. Yes. Therefore, the glass of the present invention contains La O, which is a component that increases the refractive index, and Al O, which is a component that improves weather resistance, and contains RO.
  • the weather resistance of the glass is improved while maintaining the refractive index.
  • the Abbe number is low.
  • the softening point of the glass is preferably 650 ° C. or lower (preferably 640 ° C. or lower, more preferably 630 ° C. or lower).
  • SiO is a component constituting the skeleton of glass, and has an effect of improving weather resistance. That
  • the content is 41 to 56%, preferably 42 to 53%, more preferably 43 to 50.5%. If the amount of SiO increases, the refractive index tends to decrease and the soft spot tends to increase. Devitrification
  • B 2 O is a skeletal component of glass and is effective in improving devitrification resistance. Also increase the Abbe number
  • Al 2 O is a component that constitutes the glass skeleton together with SiO, and has the effect of improving weather resistance
  • Alkaline earth metal oxides such as CaO, BaO, and SrO act as fluxes, and do not reduce the Abbe number in SiO-BO-RO R'OLaO-based glasses.
  • the total amount of CaO, BaO, and SrO is preferably 10 to 30%, particularly 10 to 20%, and more preferably 12 to 18%.
  • devitrification black tends to precipitate during the melting and forming process of the preform glass, and the liquidus temperature rises, so that the working range becomes narrow and mass production tends to be difficult.
  • elution from the glass into polishing cleaning water and various cleaning solutions increases, and the surface of the glass changes significantly in a hot and humid state.
  • inconveniences such as a decrease in refractive index and an increase in softening point are likely to occur.
  • CaO is a component that increases the refractive index without decreasing the Abbe number. In addition, it is an essential component for improving the weather resistance because the effect of preventing precipitation of alkali or alkaline earth on the surface in a high temperature and high humidity state is enhanced.
  • the CaO content is preferably 0.1 to 10%, particularly 0.5 to 5%, and more preferably 1 to 4%. When CaO is increased, the liquidus temperature rises and devitrification easily occurs.
  • BaO is a component that increases the refractive index, and this glass system also has the effect of lowering the liquidus temperature and improving workability. However, the amount of precipitation from the glass surface in a hot and humid state Is significantly higher than other RO components, so adding a large amount may impair the weather resistance of the final product.
  • the BaO content is preferably 0 to 10%, more preferably 0.5 to 9.5%, and even more preferably 4 to 9%.
  • SrO is a component that increases the refractive index. Compared with BaO, the amount of precipitation from the glass surface in a high temperature and high humidity state is small. Therefore, by using SrO actively, a product with excellent weather resistance can be obtained. Its content is 0 to 10%, preferably 0.5 to 9%, more preferably 3 to 8%. As SrO increases, the liquidus temperature rises and the working range tends to narrow.
  • MgO may be added to increase the refractive index.
  • its content is preferably 0 to 5%, particularly preferably 0 to 3%. It becomes easy to devitrify when the amount of MgO increases.
  • ZnO has the effect of increasing the refractive index and improving the weather resistance. Further, since the tendency to devitrification is not strong, a homogeneous glass can be obtained even if it is contained in a large amount. Its content is 0 to 5%, preferably 0.5 to 4%, more preferably 1 to 3%. As the amount of ZnO increases, the number of hot stones tends to decrease.
  • Alkali metal oxides (R, O) such as Li 2 O and Na 2 O are components for lowering the softening point.
  • Li 2 O and Na 2 O are combined in 5 to 12%, especially 6 to: L l%, further 7 to 10%
  • the mass productivity may be adversely affected.
  • the weather resistance tends to be poor.
  • the soft spot increases as R'O decreases.
  • LiO has the greatest effect of lowering the soft saddle point. Its content is 1 ⁇
  • Li O is phase separation
  • the liquidus temperature tends to be high and workability tends to deteriorate.
  • it has a low field strength (hereinafter referred to as F. S.) and increases the basicity of the glass, which will be described later.
  • F. S. field strength
  • the soft saddle point increases as Li O decreases.
  • Na O has the effect of lowering the soft saddle point.
  • the content of 2 is preferably 0 to 5%, particularly preferably 0.5 to 3%.
  • K 2 O may be added to lower the softening point.
  • La O content is 5-1
  • the content of SiO and La 2 O is such that the value of SiO 2 / La 2 O is 3.2 to 15.0 on a mass% basis.
  • Sb 2 O can be added as a fining agent. However, excessive coloration on the glass
  • the Sb 2 O content should be 1% or less.
  • TiO and NbO reduced the force Abbe number, which is a component that increases the refractive index of glass.
  • the absorption in the ultraviolet region is large, the transmittance at 390 to 440 nm is reduced, and the use as a short wavelength lens may be hindered.
  • PbO, Bi 2 O and As 2 O are light for Ag and halogens for environmental reasons.
  • substantially avoid introduction into glass means that the content is 0.1% or less.
  • the basicity of the glass can be used to prevent the glass and mold from being fused at the time of mold press molding in the optical glass for mold press molding of the present invention. Is 11 or less (preferably 9.5 or less).
  • the basicity means (total number of moles of oxygen atoms Z d Sum of Strength) Defined as X 100, and Field Strength (hereinafter referred to as FS) is calculated by Equation 1 below.
  • Equation 1 FS Z / r 2
  • Z is the ion valence
  • r is the ion radius.
  • the values of Z and r used the values in Table 1 (values described in “Science Manual Basic Bias Revised 2nd Edition (issued by Maruzen Co., Ltd., 1975)”) According to the knowledge of the present inventor, the lower the basicity, the harder it is to fuse with the mold. The mechanism by which the basicity of the glass controls the fusion will be described below.
  • the number of moles of atoms is obtained, and the total is defined as “sum of moles of oxygen atoms”.
  • FS is obtained.
  • the basicity of glass is an index indicating how much oxygen electrons in glass are attracted to cations in glass. High basicity! In glass, oxygen is not attracted by cations in glass. Therefore, when a glass having a high basicity is in contact with a cation (mold component) that has a strong tendency to demand electrons, a cation from the mold enters into the glass compared to a glass having a low basicity. Easy! When the cation, which is a mold component, penetrates (diffuses) into the glass, the concentration of the mold component in the glass phase near the interface increases. This reduces the compositional difference between the glass phase and the mold phase, increasing the affinity between the two and making it easier for the glass to wet the mold. It is considered that the glass and the mold are fused by such a mechanism. Therefore, as the basicity decreases, the mold components enter the glass and the glass and the mold are not fused.
  • the basicity of the glass is 11 or less, preferably 9.5 or less, it is considered that fusion does not occur. If the basicity of the glass exceeds 9.5, there is a tendency to fuse with the mold, and if it exceeds 11, the surface accuracy of the product is impaired due to fusion between the glass and the mold, and the mass productivity is markedly deteriorated. There is a tendency to.
  • a glass raw material is prepared so as to have a desired composition, and then melted in a glass melting furnace.
  • molten glass is dripped from the tip of the nozzle to temporarily produce glass droplets to obtain preform glass.
  • the molten glass is rapidly cooled and fabricated to once produce a glass block, which is then ground, polished and washed to obtain a preform glass.
  • Tables 2, 4 and 5 show examples of the present invention (sample Nos. 1 to 4 and 7 to 13), and Table 3 shows comparative examples (samples No. 5 to 6).
  • Each sample was prepared as follows. First, glass raw materials were adjusted so as to have the composition shown in the table, and were melted at 1400 ° C for 3 hours using a platinum crucible. After melting, the melt was poured onto a carbon plate, and after annealing, samples suitable for each measurement were prepared.
  • the samples No. 1 to 4 and 7 to 13 which are examples of the present invention have a refractive index of 1.5821-1.6061 and an Abbe number force of 6.6 or more. , Softening point below 648 ° C, liquidus temperature The degree was 887 ° C or less.
  • the change in transmittance before and after the exposure test in a hot and humid state was 1.6% or less, and the weather resistance was small. It contains a lot of BO and has a basicity of 9.5.
  • each of the samples No. 5 and No. 6 which are comparative examples had a low weather resistance with a large change in transmittance of 3.1% or more before and after the exposure test.
  • the refractive index (nd) is a measured value with respect to d-line (587.6 nm) of a helium lamp.
  • the Abbe number (Vd) is obtained by using the refractive index values of the d-line and the F-line (486. lnm) of the hydrogen lamp and the C-line (656.3nm) of the hydrogen lamp.
  • Number (vd) ⁇ (nd— 1) / (n
  • the softening point T is determined by the fiber elongation method based on Japanese Industrial Standard R-3104.
  • the liquid phase temperature T is 297 to 500 / ⁇ ⁇ , and the sample is pulverized and classified before platinum.
  • the measurement was performed by determining the deposition position of devitrification with an optical microscope.
  • the weather resistance was evaluated by measuring the transmittance of the glass before and after the exposure test in a hot and humid state with a spectrophotometer, and evaluating the difference in the transmittance of the glass at a wavelength of 590 nm in the visible region.
  • the exposure test was conducted under the conditions of temperature 60 ° C, humidity 90%, and 300 hours.
  • Basicity is (total number of moles of oxygen atoms Z total field strength of cations) X
  • F. S. field strength
  • Z is the ion valence, and r is the ion radius.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un verre optique sans plomb pour moulage par compression qui possède les caractéristiques nécessaires aux verres optiques pour moulage par compression, en particulier un indice de réfraction (nd) de 1,57-1,62, et un nombre d'Abbe (νd) supérieur ou égal à 55, ainsi qu'une excellente tenue aux intempéries. Le verre optique sans plomb pour moulage par compression se caractérise par une composition contenant, en pourcentage massique, 41-56 % de SiO2, 1,5-5 % d'Al2O3, 7-16 % de B2O3, 0,1-10 % de CaO, 0-10 % de BaO, 0-10 % de SrO, 0-5 % de ZnO, 1-10 % de Li2O, 0-5 % de Na2O et 5-15 % de La2O3. De préférence, la composition du verre optique respecte en outre les conditions suivantes : MgO + CaO + BaO + SrO représentent 10-20 %, Li2O + Na2O + K2O représentent 5-12 % et 3,2 ≤ SiO2/La2O3 ≤ 15,0.
PCT/JP2007/057672 2006-04-05 2007-04-05 Verre optique pour moulage par compression Ceased WO2007116943A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020087019892A KR101351450B1 (ko) 2006-04-05 2007-04-05 몰드 프레스 성형용 광학 유리

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006103806 2006-04-05
JP2006-103806 2006-04-05
JP2007086412A JP5224087B2 (ja) 2006-04-05 2007-03-29 モールドプレス成形用光学ガラス
JP2007-086412 2007-03-29

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WO2007116943A1 true WO2007116943A1 (fr) 2007-10-18

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JP (1) JP5224087B2 (fr)
KR (1) KR101351450B1 (fr)
TW (1) TWI391358B (fr)
WO (1) WO2007116943A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102171152A (zh) * 2008-10-07 2011-08-31 日本电气硝子株式会社 光学玻璃
WO2016059854A1 (fr) * 2014-10-16 2016-04-21 オリンパス株式会社 Procédé de détermination d'étape dans un procédé de production d'élément optique, procédé de production d'élément optique et élément optique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6792806B2 (ja) * 2015-04-10 2020-12-02 日本電気硝子株式会社 ガラス板
CN112939455B (zh) * 2021-03-23 2022-04-15 成都光明光电股份有限公司 光学玻璃、光学元件和光学仪器
CN115028354B (zh) * 2022-06-22 2023-09-05 成都光明光电股份有限公司 光学玻璃及光学元件

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002187735A (ja) * 2000-12-15 2002-07-05 Nippon Electric Glass Co Ltd モールドプレス成形用光学ガラス
JP2002249341A (ja) * 2001-02-19 2002-09-06 Nippon Electric Glass Co Ltd モールドプレス成形用光学ガラス
JP2004075456A (ja) * 2002-08-19 2004-03-11 Nippon Electric Glass Co Ltd モールドプレス成形用光学ガラス

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5047449B2 (ja) * 2002-09-25 2012-10-10 日本電気硝子株式会社 モールドプレス成形用光学ガラス
DE10311802B4 (de) * 2003-03-12 2006-03-02 Schott Ag Boroaluminosilikatglas und dessen Verwendung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002187735A (ja) * 2000-12-15 2002-07-05 Nippon Electric Glass Co Ltd モールドプレス成形用光学ガラス
JP2002249341A (ja) * 2001-02-19 2002-09-06 Nippon Electric Glass Co Ltd モールドプレス成形用光学ガラス
JP2004075456A (ja) * 2002-08-19 2004-03-11 Nippon Electric Glass Co Ltd モールドプレス成形用光学ガラス

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102171152A (zh) * 2008-10-07 2011-08-31 日本电气硝子株式会社 光学玻璃
WO2016059854A1 (fr) * 2014-10-16 2016-04-21 オリンパス株式会社 Procédé de détermination d'étape dans un procédé de production d'élément optique, procédé de production d'élément optique et élément optique
JP2016079064A (ja) * 2014-10-16 2016-05-16 オリンパス株式会社 光学素子製造方法における工程決定方法、光学素子製造方法、および光学素子

Also Published As

Publication number Publication date
JP2007297269A (ja) 2007-11-15
KR20080108087A (ko) 2008-12-11
KR101351450B1 (ko) 2014-01-15
JP5224087B2 (ja) 2013-07-03
TW200800830A (en) 2008-01-01
TWI391358B (zh) 2013-04-01

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