TW201335100A - Optical glass, optical element, and preform - Google Patents
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Description
本發明係關於一種光學玻璃、光學元件及預成形體。 The present invention relates to an optical glass, an optical element, and a preform.
光學設備之透鏡系統通常組合設計有具有不同光學性質之複數個玻璃透鏡。近年來,為進一步拓寬多樣化之光學設備之透鏡系統的設計自由度,將具有先前未曾使用之光學特性之光學玻璃用作球面及非球面透鏡等光學元件。尤其是於進行光學設計時,根據減小光學系統整體之色像差等目的,業界開發有折射率或分散傾向不同者。 Lens systems for optical devices are typically designed in combination with a plurality of glass lenses having different optical properties. In recent years, in order to further broaden the degree of freedom in designing a lens system of a variety of optical devices, an optical glass having optical characteristics not previously used has been used as an optical element such as a spherical surface and an aspherical lens. In particular, in optical design, the industry has developed a refractive index or a dispersion tendency depending on the purpose of reducing chromatic aberration of the entire optical system.
製作光學元件之光學玻璃中,尤其是可謀求光學元件之輕量化及小型化之具有較高折射率(nd)與較高阿貝數(νd)的玻璃需求非常高。作為此種高折射率低分散玻璃,例如,作為具有1.53以上之折射率且具有60以上之阿貝數之光學玻璃,已知有如專利文獻1所代表之玻璃。 Among the optical glasses for producing optical elements, in particular, glass having a high refractive index (nd) and a high Abbe number (νd) which is lightweight and small in size can be used. As such a high refractive index low-dispersion glass, for example, an optical glass having a refractive index of 1.53 or more and having an Abbe number of 60 or more is known as a glass represented by Patent Document 1.
[專利文獻1]日本專利特開2007-055883號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-055883
然而,如專利文獻1中記載之先前之光學玻璃折射率之高度不足。即,期待開發具有60以上之較高阿貝數同時折射率更高之光學玻璃。 However, the height of the refractive index of the prior optical glass described in Patent Document 1 is insufficient. That is, it is expected to develop an optical glass having a higher Abbe number of 60 or more and a higher refractive index.
另一方面,作為由光學玻璃製作光學元件之方法,例如 已知:對由光學玻璃形成之坯或玻璃塊進行研削及研磨而獲得光學元件之形狀的方法,對將由光學玻璃形成之坯或玻璃塊再加熱使其成形(再加熱壓製成形)而獲得之玻璃成形體進行研削及研磨的方法,及以經超精密加工之模具使由坯或玻璃塊獲得之預成形體材成形(精密模具壓製成形)而獲得光學元件之形狀的方法。任一種方法均要求於由熔融之玻璃原料形成坯或玻璃塊時可獲得穩定之玻璃。此處,於對於構成所獲得之坯或玻璃塊之玻璃之失透的穩定性(耐失透性)下降而於玻璃之內部產生結晶之情形時,已無法獲得作為光學元件較佳之玻璃。 On the other hand, as a method of producing an optical element from optical glass, for example It is known that a method of obtaining a shape of an optical element by grinding and polishing a billet or a glass block formed of optical glass is obtained by reheating a billet or a glass block formed of optical glass to form (reheat press forming). A method of grinding and polishing a glass molded body, and a method of forming a shape of an optical element by molding a preform (a precision mold press molding) obtained from a blank or a glass block by an ultra-precision machined mold. Either method requires that a stable glass be obtained from the formation of a billet or glass block from the molten glass frit. Here, in the case where the stability (devitrification resistance) of the devitrification of the glass constituting the obtained green or glass block is lowered to cause crystallization in the inside of the glass, a glass which is preferable as an optical element has not been obtained.
本發明之目的在於解決上述課題。 The object of the present invention is to solve the above problems.
即,本發明之目的在於提供一種具有所需之較高阿貝數同時折射率更高、且耐失透性較高之光學玻璃及使用其之預成形體及光學元件。 That is, an object of the present invention is to provide an optical glass having a desired higher Abbe number and a higher refractive index and higher devitrification resistance, and a preform and an optical element using the same.
本發明者等人為解決上述課題進行銳意研究,已完成本發明。具體而言,本發明提供如下所述者。 The inventors of the present invention have made intensive studies to solve the above problems, and have completed the present invention. In particular, the invention provides the following.
(1)一種光學玻璃,其含有P5+及Al3+作為陽離子成分,Al3+之含量為25.0%以下,含有O2-及F-作為陰離子成分,且折射率(nd)為1.53以上。 (1) An optical glass containing P 5+ and Al 3+ as a cationic component, having a content of Al 3+ of 25.0% or less, containing O 2 and F - as an anion component, and having a refractive index (nd) of 1.53 or more .
(2)如(1)之光學玻璃,其中以陽離子%(莫耳%)表示計含有P5+ 10.0~70.0%。 (2) The optical glass according to (1), which contains P 5 + 10.0 to 70.0% in terms of cation % (% by mole).
(3)如(1)或(2)之光學玻璃,其中以陽離子%(莫耳%)表示計進而含有B3+ 0.1~15.0%。 (3) The optical glass according to (1) or (2), which further contains B 3+ 0.1 to 15.0% in terms of cation % (% by mole).
(4)如(1)至(3)中任一項之光學玻璃,其中以陽離子%(莫耳%)表示計,Mg2+之含有率為0~20.0%,Ca2+之含有率為0~30.0%,Sr2+之含有率為0~30.0%,Ba2+之含有率為0~50.0%。 (4) The optical glass according to any one of (1) to (3), wherein the content of Mg 2+ is 0 to 20.0%, and the content of Ca 2+ is represented by % of cation (% by mole) 0~30.0%, the content of Sr 2+ is 0~30.0%, and the content of Ba 2+ is 0~50.0%.
(5)如(4)之光學玻璃,其中以陽離子%(莫耳%)表示計含有Ba2+ 20.0%以上。 (5) The optical glass according to (4), which contains Ba 2+ 20.0% or more in terms of cation % (% by mole).
(6)如(1)至(5)中任一項之光學玻璃,其中P5+、B3+及Ba2+之合計含有率(陽離子%)為30.0~80.0%。 (6) The optical glass according to any one of (1) to (5), wherein a total content (cation %) of P 5+ , B 3+ and Ba 2+ is from 30.0 to 80.0%.
(7)如(1)至(6)中任一項之光學玻璃,其中P5+、B3+、Ba2+及Al3+之合計含有率(陽離子%)為95.0%以下。 The optical glass of any one of (1) to (6), wherein the total content (cation %) of P 5+ , B 3+ , Ba 2+ and Al 3+ is 95.0% or less.
(8)如(1)至(7)中任一項之光學玻璃,其中鹼土金屬之合計含有率(R2+:陽離子%)為60.0%以下。 (8) The optical glass according to any one of (1) to (7), wherein a total content (R 2+ : cation %) of the alkaline earth metal is 60.0% or less.
(9)如(1)至(8)中任一項之光學玻璃,其中以陽離子%(莫耳%)表示計,La3+之含有率為0~10.0%,Gd3+之含有率為0~10.0%,Y3+之含有率為0~10.0%,Yb3+之含有率為0~20.0%,Lu3+之含有率為0~10.0%。 (9) The optical glass according to any one of (1) to (8), wherein the content of La 3+ is 0 to 10.0%, and the content of Gd 3+ is represented by % of cation (% by mole). 0 to 10.0%, the content of Y 3+ is 0 to 10.0%, the content of Yb 3+ is 0 to 20.0%, and the content of Lu 3+ is 0 to 10.0%.
(10)如(1)至(9)中任一項之光學玻璃,其中La3+、Gd3+、Y3+、Yb3+及Lu3+之合計含有率(Ln3+:陽離子%)為20.0%以下。 (10) The optical glass of any one of (1) to (9), wherein a total content of La 3+ , Gd 3+ , Y 3+ , Yb 3+ , and Lu 3+ (Ln 3+ : cationic % ) is 20.0% or less.
(11)如上述(1)至(10)中任一項之光學玻璃,其中以陽離子%(莫耳%)表示計,Li+之含有率為0~20.0%,Na+之含有率為0~10.0%,K+之含有率為0~10.0%。 (11) The optical glass according to any one of (1) to (10) above, wherein the content of Li + is 0 to 20.0%, and the content of Na + is 0, expressed as % of cation (% by mole). ~10.0%, the content of K + is 0~10.0%.
(12)如(1)至(11)中任一項之光學玻璃,其中鹼金屬之合計含有率(Rn+:陽離子%)為20%以下。 The optical glass of any one of (1) to (11), wherein the total content (Rn + : cation %) of the alkali metal is 20% or less.
(13)如(1)至(12)中任一項之光學玻璃,其中以陽離子%(莫耳%)表示計,Si4+之含有率為0~10.0%,Zn2+之含有率為0~30.0%,Nb5+之含有率為0~10.0%,Ti4+之含有率為0~10.0%,Zr4+之含有率為0~10.0%,Ta5+之含有率為0~10.0%,W6+之含有率為0~10.0%,Ge4+之含有率為0~10.0%,Bi3+之含有率為0~10.0%,Te4+之含有率為0~15.0%。 (13) The optical glass according to any one of (1) to (12), wherein the content of Si 4+ is 0 to 10.0%, and the content of Zn 2+ is represented by % of cation (% by mole) 0~30.0%, the content of Nb 5+ is 0~10.0%, the content of Ti 4+ is 0~10.0%, the content of Zr 4+ is 0~10.0%, and the content of Ta 5+ is 0~ 10.0%, the content of W 6+ is 0 to 10.0%, the content of Ge 4+ is 0 to 10.0%, the content of Bi 3+ is 0 to 10.0%, and the content of Te 4+ is 0 to 15.0%. .
(14)如(1)至(13)中任一項之光學玻璃,其中以陰離子%(莫耳%)表示計,F-之含有率為20.0~70.0%,O2-之含有率為30.0~80.0%。 (14) (1) to (13) of the optical glass according to any, wherein the anionic% (mole%) indicates the count, F - content ratio of 20.0 ~ 70.0%, O 2- content was of 30.0 ~80.0%.
(15)如(1)至(14)中任一項之光學玻璃,其具有60以上之 阿貝數(νd)。 (15) The optical glass according to any one of (1) to (14) which has 60 or more Abbe number (νd).
(16)如(1)至(15)中任一項之光學玻璃,其中折射率(nd)與阿貝數(νd)之間滿足nd≧-0.00254×νd+1.760之關係。 (16) The optical glass according to any one of (1) to (15), wherein the relationship between the refractive index (nd) and the Abbe number (νd) satisfies the relationship of nd ≧ - 0.00254 × νd + 1.760.
(17)一種光學元件,其包含如(1)至(16)中任一項之光學玻璃。 (17) An optical element comprising the optical glass of any one of (1) to (16).
(18)一種研磨加工用及/或精密壓製成形用之預成形體,其包含如(1)至(16)中任一項之光學玻璃。 (18) A preform for polishing processing and/or precision press molding, comprising the optical glass according to any one of (1) to (16).
(19)一種光學元件,其係將如(18)之預成形體精密壓製而成。 (19) An optical member obtained by precisely pressing a preform such as (18).
根據本發明,可提供一種具有所需之較高阿貝數同時具有更高之折射率、且耐失透性較高之光學玻璃及使用其之預成形體及光學元件。 According to the present invention, it is possible to provide an optical glass having a desired higher Abbe number and having a higher refractive index and having higher devitrification resistance, and a preform and an optical element using the same.
本發明之光學玻璃含有P5+及Al3+作為陽離子成分,Al3+之含量為25.0%以下,含有O2-及F-作為陰離子成分,折射率(nd)為1.53以上。藉由減少陽離子成分之Al3+之含量,可提高玻璃之折射率及阿貝數。又,藉由含有P5+作為陽離子成分、且含有F-作為陰離子成分,可獲得所需之較高阿貝數,同時可提高玻璃之耐失透性。因此,可獲得具有所需之較高阿貝數同時具有更高之折射率、且耐失透性較高之光學玻璃。 The optical glass of the present invention contains P 5+ and Al 3+ as a cationic component, and has a content of Al 3+ of 25.0% or less, O 2 and F - as an anion component, and a refractive index (nd) of 1.53 or more. By reducing the content of Al 3+ of the cationic component, the refractive index and Abbe number of the glass can be increased. Further, by comprising P 5+ as a cationic component, and containing F - as an anion component, the desired high Abbe number can be obtained, while improving the devitrification resistance of glass. Therefore, an optical glass having a desired higher Abbe number while having a higher refractive index and having higher devitrification resistance can be obtained.
以下,對本發明之光學玻璃進行說明。本發明並不限定於以下之態樣,可於本發明之目標之範圍內添加適當變更 而實施。再者,有對說明重複之部分省略說明之情況,但並不限定發明之主旨。 Hereinafter, the optical glass of the present invention will be described. The present invention is not limited to the following aspects, and may be appropriately changed within the scope of the object of the present invention. And implementation. In addition, the description of the overlapping part is omitted, but the gist of the invention is not limited.
對構成本發明之光學玻璃之各成分進行說明。 The components constituting the optical glass of the present invention will be described.
於本說明書中,各成分之含有率於無特別說明之情形時,均以基於莫耳比之陽離子%或陰離子%表示。此處,「陽離子%」及「陰離子%」(以下,有時記為「陽離子%(莫耳%)」及「陰離子%(莫耳%)」)係將本發明之光學玻璃之玻璃構成成分分成陽離子成分及陰離子成分,分別將合計比例設為100莫耳%而記玻璃中所含之各成分之含有率的組成。 In the present specification, the content of each component is expressed by the percentage of cation or anion % based on the molar ratio, unless otherwise specified. Here, "cation %" and "anion %" (hereinafter, referred to as "cation % (mole %)" and "anion % (mole %)") are the glass constituents of the optical glass of the present invention. The composition was divided into a cationic component and an anionic component, and the total ratio was set to 100 mol%, and the composition of each component contained in the glass was recorded.
再者,各成分之離子價為方便起見僅使用代表值,因此並非與其他離子價者進行區分。存在於光學玻璃中之各成分之離子價有可能為代表值以外。例如,P通常以離子價為5價之狀態存在於玻璃中,因此本說明書中表示為「P5+」,但亦有可能以其他離子價之狀態存在。如此,嚴格而言,即便為以其他離子價之狀態存在者,本說明書中亦將各成分作為以代表值之離子價存在於玻璃中者進行處理。 Furthermore, the ion valence of each component uses only representative values for convenience, and thus is not distinguished from other ion valences. The ion valence of each component present in the optical glass may be other than the representative value. For example, P is usually present in the glass in a state in which the ionic value is pentad. Therefore, in the present specification, P is represented as "P 5+ ", but it may exist in the state of other ion valence. As described above, strictly speaking, even if it exists in the state of another ion value, in this specification, each component is processed in the glass as the ion value of a representative value.
P5+為玻璃形成成分,因此作為必需成分應含有超過0%。尤其是藉由含有P5+ 10.0%以上,可提高玻璃之耐失透性。因此,P5+之含有率較佳為以10.0%作為下限,更佳為以20.0%作為下限,進而較佳為以30.0%作為下限。 Since P 5+ is a glass forming component, it should contain more than 0% as an essential component. In particular, by containing P 5 + 10.0% or more, the devitrification resistance of the glass can be improved. Therefore, the content of P 5+ is preferably 10.0% as the lower limit, more preferably 20.0% as the lower limit, and still more preferably 30.0% as the lower limit.
另一方面,藉由將P5+之含量設為70.0%,可抑制由P5+引起之折射率或阿貝數之下降。因此,P5+之含有率較佳為以70.0%作為上限,更佳為以60.0%作為上限,更佳為以50.0%作為上限,進而較佳為以45.0%作為上限。 On the other hand, by setting the content of P 5+ to 70.0%, the decrease in the refractive index or the Abbe number caused by P 5+ can be suppressed. Therefore, the content of P 5+ is preferably 70.0% as the upper limit, more preferably 60.0% as the upper limit, more preferably 50.0% as the upper limit, and still more preferably 45.0% as the upper limit.
P5+可使用Al(PO3)3、Ca(PO3)2、Ba(PO3)2、Zn(PO3)2、BPO4、H3PO4等作為原料。 P 5+ using Al (PO 3) 3, Ca (PO 3) 2, Ba (PO 3) 2, Zn (PO 3) 2, BPO 4, H 3 PO 4 and the like as a raw material.
Al3+藉由有助於玻璃之微細構造之骨架形成可提高耐失透性,因此作為必需成分應含有超過0%。因此,Al3+之含有率較佳為以超過0%作為下限,更佳為以1.0%作為下限,更佳為以5.0%作為下限,進而較佳為以10.0%作為下限。 Al 3+ can improve the devitrification resistance by forming a skeleton which contributes to the fine structure of glass, and therefore should contain more than 0% as an essential component. Therefore, the content of Al 3+ is preferably a lower limit of more than 0%, more preferably 1.0% as a lower limit, still more preferably 5.0% as a lower limit, and still more preferably 10.0% as a lower limit.
另一方面,藉由將Al3+之含量設為25.0%以下,可抑制由Al3+引起之折射率或阿貝數之下降。因此,Al3+之含有率之上限較佳為25.0%,更佳為以22.0%作為上限,進而較佳為以20.0%作為上限,進而較佳為設為未達17.0%。 On the other hand, by setting the content of Al 3+ to 25.0% or less, the decrease in the refractive index or the Abbe number caused by Al 3+ can be suppressed. Therefore, the upper limit of the content ratio of Al 3+ is preferably 25.0%, more preferably 22.0%, and further preferably 20.0%, and more preferably less than 17.0%.
Al3+可使用Al(PO3)3、AlF3、Al2O3等作為原料。 As Al 3+, Al(PO 3 ) 3 , AlF 3 , Al 2 O 3 or the like can be used as a raw material.
B3+其本身為提高折射率之成分,且於使用其他提高折射率之成分即Yb3+或Ba2+成分之情形時為可提高耐失透性之任意成分。即,於含有B3+超過0%之情形時,可提高玻璃之折射率與耐失透性。因此,B3+之含有率較佳為可以超過0%作為下限,更佳為可以0.1%作為下限,進而較佳為可以1.0%作為下限,進而較佳為可以3.0%作為下限。 B 3+ itself is a component for increasing the refractive index, and is an optional component which can improve the devitrification resistance when a Yb 3+ or Ba 2+ component which is a component which increases the refractive index is used. That is, when B 3+ is contained in excess of 0%, the refractive index and devitrification resistance of the glass can be improved. Therefore, the content of B 3+ is preferably a lower limit of more than 0%, more preferably 0.1% as a lower limit, still more preferably 1.0% as a lower limit, and still more preferably 3.0% as a lower limit.
另一方面,藉由將B3+之含有率設為15.0%以下,可抑制化學耐久性之惡化。因此,B3+之含有率較佳為以15.0%作 為上限,更佳為以12.0%作為上限,進而較佳為以10.0%作為上限。 On the other hand, by setting the content ratio of B 3+ to 15.0% or less, deterioration of chemical durability can be suppressed. Therefore, the content of B 3+ is preferably 15.0% as an upper limit, more preferably 12.0% as an upper limit, and still more preferably 10.0% as an upper limit.
B3+可使用H3BO3、Na2B4O7、BPO4等作為原料。 As B 3+, H 3 BO 3 , Na 2 B 4 O 7 , BPO 4 or the like can be used as a raw material.
Mg2+為於含有超過0%之情形時可提高玻璃之耐失透性的任意成分。 Mg 2+ is an optional component which can improve the devitrification resistance of glass when it contains more than 0%.
另一方面,藉由將Mg2+之含有率設為20.0%以下,可抑制玻璃之折射率之下降。因此,Mg2+之含有率較佳為以20.0%作為上限,更佳為以10.0%作為上限,進而較佳為以7.0%作為上限,進而較佳為以3.0%作為上限。 On the other hand, by setting the content of Mg 2+ to 20.0% or less, the decrease in the refractive index of the glass can be suppressed. Therefore, the content of Mg 2+ is preferably 20.0% as an upper limit, more preferably 10.0% as an upper limit, still more preferably 7.0% as an upper limit, and still more preferably 3.0% as an upper limit.
Mg2+可使用MgO、MgF2等作為原料。 Mg 2+ can be used as a raw material using MgO, MgF 2 or the like.
Ca2+為於含有超過0%之情形時可提高玻璃之耐失透性、且可抑制折射率之下降的任意成分。因此,Ca2+之含有率較佳為可以超過0%作為下限,更佳為可以1.0%作為下限,進而較佳為可以2.0%作為下限。 When Ca 2+ is contained in an amount of more than 0%, it is possible to increase the resistance to devitrification of the glass and to suppress the decrease in the refractive index. Therefore, the content of Ca 2+ is preferably set to be less than 0% as the lower limit, more preferably 1.0% as the lower limit, and still more preferably 2.0% as the lower limit.
另一方面,藉由將Ca2+之含有率設為30.0%以下,可抑制由Ca2+之過量含有引起的玻璃之耐失透性或折射率之下降。因此,Ca2+之含有率較佳為以30.0%作為上限,更佳為以20.0%作為上限,進而較佳為以10.0%作為上限。 On the other hand, by setting the content of Ca 2+ to 30.0% or less, it is possible to suppress the devitrification resistance or the decrease in the refractive index of the glass caused by the excessive content of Ca 2+ . Therefore, the content of Ca 2+ is preferably an upper limit of 30.0%, more preferably an upper limit of 20.0%, and still more preferably an upper limit of 10.0%.
Ca2+可使用Ca(PO3)2、CaCO3、CaF2等作為原料。 Ca 2+ can be used as a raw material using Ca(PO 3 ) 2 , CaCO 3 , CaF 2 or the like.
Sr2+為於含有超過0%之情形時可提高玻璃之耐失透性、且可抑制折射率之下降的任意成分。 Sr 2+ is an optional component which can improve the devitrification resistance of the glass and suppress the decrease in the refractive index when it is more than 0%.
另一方面,藉由將Sr2+之含有率設為30.0%以下,可抑制由Sr2+之過量含有引起的玻璃之耐失透性或折射率之下降。因此,Sr2+之含有率較佳為以30.0%作為上限,更佳為 以20.0%作為上限,進而較佳為以10.0%作為上限。 On the other hand, when the content ratio of Sr 2+ is 30.0% or less, the devitrification resistance of the glass or the decrease in the refractive index due to the excessive content of Sr 2+ can be suppressed. Therefore, the content of Sr 2+ is preferably an upper limit of 30.0%, more preferably an upper limit of 20.0%, and still more preferably an upper limit of 10.0%.
Sr2+可使用Sr(NO3)2、SrF2等作為原料。 Sr 2+ can use Sr(NO 3 ) 2 , SrF 2 or the like as a raw material.
Ba2+為於含有超過0%之情形時可提高玻璃之耐失透性同時維持較低之分散性、且可提高折射率的任意成分。因此,Ba2+之含有率較佳為可以超過0%作為下限,更佳為可以10.0%作為下限,進而較佳為可以20.0%作為下限,進而較佳為可以超過25.0%作為下限,進而較佳為可以29.0%作為下限。 Ba 2+ is an optional component which can improve the devitrification resistance of the glass while maintaining a low dispersibility and can increase the refractive index when it exceeds 0%. Therefore, the content of Ba 2+ is preferably more than 0% as a lower limit, more preferably 10.0% as a lower limit, further preferably 20.0% as a lower limit, and further preferably 20.0% as a lower limit, and further preferably Jia can use 29.0% as the lower limit.
另一方面,藉由將Ba2+之含有率設為50.0%以下,可抑制由Ba2+之過量含有引起的玻璃之耐失透性之下降。因此,Ba2+之含有率較佳為以50.0%作為上限,更佳為以40.0%作為上限,更佳為以37.0%作為上限。 On the other hand, by setting the content of Ba 2+ to 50.0% or less, it is possible to suppress a decrease in the devitrification resistance of the glass due to the excessive content of Ba 2+ . Therefore, the content of Ba 2+ is preferably 50.0% as an upper limit, more preferably 40.0% as an upper limit, and more preferably 37.0% as an upper limit.
Ba2+可使用Ba(PO3)2、BaCO3、Ba(NO3)2、BaF2等作為原料。 As Ba 2+ , Ba(PO 3 ) 2 , BaCO 3 , Ba(NO 3 ) 2 , BaF 2 or the like can be used as a raw material.
本發明之光學玻璃之P5+、B3+及Ba2+之合計含有率較佳為30.0%以上且80.0%以下。 The total content of P 5+ , B 3+ and Ba 2+ in the optical glass of the present invention is preferably 30.0% or more and 80.0% or less.
尤其是藉由將該合計含有率設為30.0%以上,即便減少Al3+之含量,亦可提高耐失透性。因此,合計含有率(P5++B3++Ba2+)較佳為以30.0%作為下限,更佳為以50.0%作為下限,進而較佳為以55.0%作為下限,進而較佳為以60.0%作為下限,進而較佳為設為超過65.0%。 In particular, by reducing the total content rate to 30.0% or more, the devitrification resistance can be improved even if the content of Al 3+ is decreased. Therefore, the total content ratio (P 5+ + B 3+ + Ba 2+ ) is preferably 30.0% as the lower limit, more preferably 50.0% as the lower limit, still more preferably 55.0% as the lower limit, and further preferably The lower limit is 60.0%, and more preferably more than 65.0%.
另一方面,藉由將該合計含有率設為80.0%以下,可抑制由該等成分之過量含有引起的耐失透性之下降。因此,合計含有率(P5++B3++Ba2+)較佳為以80.0%作為上限,更佳 為以78.0%作為上限,進而較佳為以76.0%作為上限。 On the other hand, when the total content ratio is 80.0% or less, the deterioration of the devitrification resistance due to the excessive content of the components can be suppressed. Therefore, the total content ratio (P 5+ + B 3+ + Ba 2+ ) is preferably 80.0% as an upper limit, more preferably 78.0% as an upper limit, and still more preferably 76.0% as an upper limit.
又,本發明之光學玻璃之P5+、B3+、Ba2+及Al3+的合計含有率較佳為95.0%以下。藉此,具有所需之高折射率同時可維持較高之耐失透性。因此,合計含有率(P5++B3++Ba2++Al3+)較佳為以95.0%作為上限,更佳為以93.0%作為上限,進而較佳為以91.0%作為上限。 Moreover, the total content of P 5+ , B 3+ , Ba 2+ and Al 3+ of the optical glass of the present invention is preferably 95.0% or less. Thereby, the desired high refractive index is maintained while maintaining high resistance to devitrification. Therefore, the total content ratio (P 5+ + B 3+ + Ba 2+ + Al 3+ ) is preferably an upper limit of 95.0%, more preferably an upper limit of 93.0%, and still more preferably an upper limit of 91.0%.
另一方面,藉由將該合計含有率設為30.0%以上,可藉由該等成分提高耐失透性。因此,合計含有率(P5++B3++Ba2++Al3+)較佳為可以30.0%作為下限,更佳為可以50.0%作為下限,進而較佳為可以70.0%作為下限,進而較佳為可以80.0%作為下限,進而較佳為可以85.0%作為下限。 On the other hand, by setting the total content ratio to 30.0% or more, the devitrification resistance can be improved by the components. Therefore, the total content ratio (P 5+ + B 3+ + Ba 2+ + Al 3+ ) is preferably 30.0% as the lower limit, more preferably 50.0% as the lower limit, and further preferably 70.0% as the lower limit. Further preferably, 80.0% may be used as the lower limit, and further preferably 85.0% may be used as the lower limit.
鹼土金屬係指選自由Mg2+、Ca2+、Sr2+及Ba2+所組成之群中之一種以上。又,有將選自由Mg2+、Ca2+、Sr2+及Ba2+所組成之群中之一種以上表示為R2+的情況。 The alkaline earth metal refers to one or more selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ . Further, there is a case where one or more selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , and Ba 2+ is represented as R 2+ .
又,所謂R2+之合計含有率,係指該等四種離子中之一種以上之合計含有率(例如Mg2++Ca2++Sr2++Ba2+)。 In addition, the total content ratio of R 2+ means a total content ratio of one or more of the four types of ions (for example, Mg 2+ + Ca 2+ + Sr 2+ + Ba 2+ ).
R2+之合計含有率較佳為60.0%以下。藉此,可減少由R2+之過量含有引起的失透。因此,R2+之合計含有率較佳為以60.0%作為上限,更佳為以50.0%作為上限,更佳為以45.0%作為上限,進而較佳為以41.0%作為上限。 The total content of R 2+ is preferably 60.0% or less. Thereby, devitrification caused by excessive content of R 2+ can be reduced. Therefore, the total content of R 2+ is preferably 60.0% as the upper limit, more preferably 50.0% as the upper limit, more preferably 45.0% as the upper limit, and still more preferably 41.0% as the upper limit.
另一方面,R2+之合計含有率可設為超過0%。藉此,可獲得耐失透性更高之玻璃。因此,R2+之合計含有率較佳為可以超過0%作為下限,更佳為可以10.0%作為下限,進 而較佳為可以20.0%作為下限,進而較佳為可以30.0%作為下限。 On the other hand, the total content ratio of R 2+ can be set to exceed 0%. Thereby, a glass having higher devitrification resistance can be obtained. Therefore, the total content of R 2+ is preferably more than 0% as the lower limit, more preferably 10.0% as the lower limit, still more preferably 20.0% as the lower limit, and still more preferably 30.0% as the lower limit.
La3+、Gd3+、Y3+、Yb3+及Lu3+為於至少任一者含有超過0%之情形時維持高折射率及高阿貝數同時可提高耐失透性的任意成分。尤其是藉由含有La3+超過0%可容易地提高耐失透性,因此La3+之含有率較佳為可以超過0%作為下限,更佳為可以0.1%作為下限,進而較佳為可以0.5%作為下限,進而較佳為可以1.0%作為下限。又,藉由含有Yb3+超過0%,可提高折射率且可減少熔解時之F-等之揮發,因此Yb3+之含有率較佳為可以超過0%作為下限,更佳為可以0.1%作為下限,進而較佳為可以0.7%作為下限,進而較佳為可以2.0%作為下限。 La 3+ , Gd 3+ , Y 3+ , Yb 3+ , and Lu 3+ are arbitrarily capable of maintaining high refractive index and high Abbe number while at least one of them contains more than 0% while improving devitrification resistance. ingredient. In particular, since the devitrification resistance can be easily improved by containing La 3+ in excess of 0%, the content of La 3+ is preferably more than 0% as a lower limit, more preferably 0.1% as a lower limit, and further preferably 0.5% may be used as the lower limit, and further preferably 1.0% may be used as the lower limit. Further, by containing Yb 3+ in excess of 0%, the refractive index can be increased and the volatilization of F - or the like at the time of melting can be reduced. Therefore, the content of Yb 3+ is preferably more than 0% as a lower limit, more preferably 0.1. % is the lower limit, and further preferably 0.7% is the lower limit, and further preferably 2.0% is the lower limit.
另一方面,藉由將La3+、Gd3+、Y3+及Lu3+之各自含量設為10.0%以下、及/或將Yb3+之含量設為20.0%以下,可減少由該等成分之過量含有引起的失透。因此,La3+、Gd3+、Y3+及Lu3+之各自含量較佳為以10.0%作為上限,更佳為以8.0%作為上限,進而較佳為以5.0%作為上限,進而較佳為以3.0%作為上限。又,Yb3+之含量較佳為以20.0%作為上限,更佳為以15.0%作為上限,進而較佳為以10.0%作為上限,進而較佳為以5.0%作為上限。 On the other hand, by setting the respective contents of La 3+ , Gd 3+ , Y 3+ and Lu 3+ to 10.0% or less, and/or to set the content of Yb 3+ to 20.0% or less, it is possible to reduce Depletion caused by excessive content of the components. Therefore, the respective contents of La 3+ , Gd 3+ , Y 3+ and Lu 3+ are preferably 10.0% as an upper limit, more preferably 8.0% as an upper limit, and further preferably 5.0% as an upper limit, and further Jia is limited to 3.0%. Further, the content of Yb 3+ is preferably 20.0% as an upper limit, more preferably 15.0% as an upper limit, still more preferably 10.0% as an upper limit, and still more preferably 5.0% as an upper limit.
La3+、Gd3+、Y3+、Yb3+及Lu3+可使用La2O3、LaF3、Gd2O3、GdF3、Y2O3、YF3、Yb2O3、Lu2O3等作為原料。 La 3O 3 , Gd 3+ , Y 3+ , Yb 3+ , and Lu 3+ may be La 2 O 3 , LaF 3 , Gd 2 O 3 , GdF 3 , Y 2 O 3 , YF 3 , Yb 2 O 3 , Lu 2 O 3 or the like is used as a raw material.
Ln3+係指選自由Y3+、La3+、Gd3+、Yb3+及Lu3+所組成之群中之至少一種。又,有Ln3+之合計含有率表示該等5種 離子之合計含有率(Y3++La3++Gd3++Yb3++Lu3+)的情況。 Ln 3+ means at least one selected from the group consisting of Y 3+ , La 3+ , Gd 3+ , Yb 3+ , and Lu 3+ . In addition, the total content ratio of Ln 3+ indicates the total content ratio of these five kinds of ions (Y 3+ + La 3+ + Gd 3 + + Yb 3 + + Lu 3+ ).
尤其是藉由將Ln3+之合計含有率設為20.0%以下,可減少由Ln3+之過量含有引起的失透。因此,Ln3+之合計含有率較佳為以20.0%作為上限,更佳為以10.0%作為上限,進而較佳為以6.0%作為上限。 In particular, by setting the total content of Ln 3+ to 20.0% or less, devitrification caused by excessive content of Ln 3+ can be reduced. Therefore, the total content of Ln 3+ is preferably 20.0% as an upper limit, more preferably 10.0% as an upper limit, and still more preferably 6.0% as an upper limit.
另一方面,亦可不含Ln3+,但藉由含有Ln3+超過0%,可維持高折射率及高阿貝數同時可提高耐失透性。因此,Ln3+之合計含有率較佳為可以0.1%作為下限,更佳為可以1.0%作為下限,進而較佳為可以3.0%作為下限。 On the other hand, Ln 3+ may not be contained, but by containing Ln 3+ in excess of 0%, high refractive index and high Abbe number can be maintained while devitrification resistance can be improved. Therefore, the total content of Ln 3+ is preferably 0.1% as the lower limit, more preferably 1.0% as the lower limit, and still more preferably 3.0% as the lower limit.
Li+、Na+及K+為於含有超過0%之情形時可將玻璃形成時之耐失透性維持較高、且可降低玻璃轉移點的任意成分。尤其是Li+之提高耐失透性之作用較強,因此Li+之含有率較佳為可以超過0%作為下限,更佳為可以0.1%作為下限,進而較佳為可以0.3%作為下限。 Li + , Na + and K + are optional components which can maintain high devitrification resistance when the glass is formed and which can lower the glass transition point when the content exceeds 0%. In particular, Li + has a strong effect of improving resistance to devitrification, and therefore the content of Li + is preferably more than 0% as a lower limit, more preferably 0.1% as a lower limit, and further preferably 0.3% as a lower limit.
另一方面,藉由將Li+之含有率設為20.0%以下、及/或將Na+及K+中之一種以上之含有率設為10.0%以下,可抑制折射率之下降或化學耐久性之惡化。因此,Li+之含有率更佳為以20.0%作為上限,更佳為以10.0%作為上限,進而較佳為以5.0%作為上限。又,Na+及K+之各自含有率較佳為以10.0%作為上限,更佳為以5.0%作為上限,進而較佳為以3.0%作為上限。 On the other hand, when the content ratio of Li + is 20.0% or less, and/or the content ratio of one or more of Na + and K + is 10.0% or less, the decrease in refractive index or chemical durability can be suppressed. Deterioration. Therefore, the content of Li + is more preferably 20.0% as the upper limit, more preferably 10.0% as the upper limit, and still more preferably 5.0% as the upper limit. Further, the respective content ratios of Na + and K + are preferably 10.0% as an upper limit, more preferably 5.0% as an upper limit, and still more preferably 3.0% as an upper limit.
Li+、Na+及K+可使用Li2CO3、LiNO3、LiF、Na2CO3、NaNO3、NaF、Na2SiF6、K2CO3、KNO3、KF、KHF2、K2SiF6等作為原料。 As Li + , Na + and K + , Li 2 CO 3 , LiNO 3 , LiF, Na 2 CO 3 , NaNO 3 , NaF, Na 2 SiF 6 , K 2 CO 3 , KNO 3 , KF, KHF 2 , K 2 may be used. SiF 6 or the like is used as a raw material.
於本發明中,Rn+係指選自由Li+、Na+及K+所組成之群中之至少一種。又,有Rn+之合計含有率表示該等3種離子之合計含有率(Li++Na++K+)的情況。 In the present invention, Rn + means at least one selected from the group consisting of Li + , Na + and K + . In addition, the total content ratio of Rn + indicates the total content ratio (Li + +Na + +K + ) of the three kinds of ions.
尤其是藉由將Rn+之合計含有率設為20.0%以下,可抑制玻璃之折射率之下降或化學耐久性之惡化。因此,Rn+之合計含有率較佳為以20.0%作為上限,更佳為以10.0%作為上限,進而較佳為以5.0%作為上限。 In particular, by setting the total content of Rn + to 20.0% or less, it is possible to suppress a decrease in the refractive index of the glass or a deterioration in chemical durability. Therefore, the total content of Rn + is preferably 20.0% as an upper limit, more preferably 10.0% as an upper limit, and still more preferably 5.0% as an upper limit.
另一方面,亦可不含Rn+,但藉由含有Rn+超過0%可提高耐失透性,且可降低玻璃轉移點。因此,Rn+之合計含有率較佳為可以超過0%作為下限,更佳為可以0.1%作為下限,進而較佳為可以0.3%作為下限。 On the other hand, Rn + may not be contained, but the devitrification resistance may be improved by containing Rn + in excess of 0%, and the glass transition point may be lowered. Therefore, the total content of Rn + is preferably at least 0% as a lower limit, more preferably 0.1% as a lower limit, and further preferably 0.3% as a lower limit.
Si4+為於含有超過0%之情形時可提高玻璃之耐失透性、提高折射率、降低磨損度之任意成分。 Si 4+ is an optional component which can improve the devitrification resistance of the glass, increase the refractive index, and reduce the degree of wear when the content exceeds 0%.
另一方面,藉由將Si4+之含有率設為10.0%以下,可減少由Si4+之過量含有引起的失透。因此,Si4+之含有率較佳為以10.0%作為上限,更佳為以5.0%作為上限,進而較佳為以3.0%作為上限。 On the other hand, by setting the content ratio of Si 4+ to 10.0% or less, devitrification caused by excessive content of Si 4+ can be reduced. Therefore, the content of Si 4+ is preferably an upper limit of 10.0%, more preferably an upper limit of 5.0%, and still more preferably an upper limit of 3.0%.
Si4+可使用SiO2、K2SiF6、Na2SiF6等作為原料。 As Si 4+, SiO 2 , K 2 SiF 6 , Na 2 SiF 6 or the like can be used as a raw material.
Zn2+為於含有超過0%之情形時可提高玻璃之耐失透性之任意成分。 Zn 2+ is an optional component which can improve the resistance to devitrification of glass when it contains more than 0%.
另一方面,藉由將Zn2+之含有率設為30.0%以下,可抑制折射率之下降。因此,Zn2+之含有率較佳為以30.0%作為上限,更佳為以15.0%作為上限,進而較佳為以5.0%作為上限,進而較佳為以3.0%作為上限。 On the other hand, by setting the content of Zn 2+ to 30.0% or less, the decrease in the refractive index can be suppressed. Therefore, the content of Zn 2+ is preferably an upper limit of 30.0%, more preferably an upper limit of 15.0%, still more preferably an upper limit of 5.0%, and still more preferably an upper limit of 3.0%.
Zn2+可使用Zn(PO3)2、ZnO、ZnF2等作為原料。 Zn 2+ can be used as a raw material using Zn(PO 3 ) 2 , ZnO, ZnF 2 or the like.
Nb5+、Ti4+及W6+為於含有超過0%之情形時可提高玻璃之折射率的任意成分。另外,於含有Nb5+超過0%之情形時,可提高化學耐久性。又,於含有W6+超過0%之情形時,可降低玻璃轉移點。 Nb 5+ , Ti 4+ and W 6+ are arbitrary components which increase the refractive index of the glass when it contains more than 0%. Further, when Nb 5+ is contained in an amount exceeding 0%, chemical durability can be improved. Further, when W 6+ is more than 0%, the glass transition point can be lowered.
另一方面,藉由將Nb5+、Ti4+及W6+之各自含有率設為10.0%以下,可抑制阿貝數之下降,且可抑制由玻璃之著色引起之可見光穿透率之下降。因此,Nb5+、Ti4+及W6+之各自含有率較佳為以10.0%作為上限,更佳為以5.0%作為上限,進而較佳為以3.0%作為上限。 On the other hand, by setting the respective content ratios of Nb 5+ , Ti 4+ and W 6+ to 10.0% or less, it is possible to suppress the decrease in the Abbe number and suppress the visible light transmittance caused by the coloring of the glass. decline. Therefore, the respective content ratios of Nb 5+ , Ti 4+ and W 6+ are preferably 10.0% as an upper limit, more preferably 5.0% as an upper limit, and still more preferably 3.0% as an upper limit.
Nb5+、Ti4+及W6+可使用Nb2O5、TiO2、WO3等作為原料。 As Nb 5+ , Ti 4+ and W 6+ , Nb 2 O 5 , TiO 2 , WO 3 or the like can be used as a raw material.
Zr4+為於含有超過0%之情形時可提高玻璃之折射率之任意成分。 Zr 4+ is an optional component which increases the refractive index of the glass when it contains more than 0%.
另一方面,藉由將Zr4+之含有率設為10.0%以下,可抑制由玻璃中之成分之揮發引起的玻璃之條紋。因此,Zr4+之含有率較佳為以10.0%作為上限,更佳為以5.0%作為上限,進而較佳為以3.0%作為上限。 On the other hand, by setting the content ratio of Zr 4+ to 10.0% or less, it is possible to suppress streaking of the glass due to volatilization of the components in the glass. Therefore, the content of Zr 4+ is preferably an upper limit of 10.0%, more preferably an upper limit of 5.0%, and still more preferably an upper limit of 3.0%.
Zr4+可使用ZrO2、ZrF4等作為原料。 As Zr 4+, ZrO 2 , ZrF 4 or the like can be used as a raw material.
Ta5+為於含有超過0%之情形時可提高玻璃之折射率之任意成分。 Ta 5+ is an optional component which increases the refractive index of the glass when it contains more than 0%.
另一方面,藉由將Ta5+之含有率設為10.0%以下,可減少玻璃之失透。因此,Ta5+之含有率較佳為以10.0%作為上限,更佳為以5.0%作為上限,進而較佳為以3.0%作為上 限。 On the other hand, by setting the content ratio of Ta 5+ to 10.0% or less, the devitrification of the glass can be reduced. Therefore, the content of Ta 5+ is preferably an upper limit of 10.0%, more preferably an upper limit of 5.0%, and still more preferably an upper limit of 3.0%.
Ta5+可使用Ta2O5等作為原料。 Ta 5+ can use Ta 2 O 5 or the like as a raw material.
Ge4+為於含有超過0%之情形時可提高玻璃之折射率、且可提高耐失透性之任意成分。 Ge 4+ is an optional component which can increase the refractive index of the glass when it contains more than 0%, and can improve the devitrification resistance.
另一方面,藉由將Ge4+之含有率設為10.0%以下,可藉由昂貴之Ge4+之含量之減少而減少玻璃之材料成本。因此,Ge4+之含有率較佳為設為10.0%,更佳為設為5.0%,進而較佳為設為3.0%。 On the other hand, by setting the content of Ge 4+ to 10.0% or less, the material cost of the glass can be reduced by the decrease in the content of the expensive Ge 4+ . Therefore, the content of Ge 4+ is preferably set to 10.0%, more preferably 5.0%, and still more preferably 3.0%.
Ge4+可使用GeO2等作為原料。 Ge 4+ can use GeO 2 or the like as a raw material.
Bi3+及Te4+為於含有超過0%之情形時可提高玻璃之折射率、且可降低玻璃轉移點之任意成分。 Bi 3+ and Te 4+ are arbitrary components which can increase the refractive index of the glass when the content exceeds 0% and can lower the glass transition point.
另一方面,藉由將Bi3+之含有率設為10.0%以下、及/或將Te4+之含有率設為15.0%以下,可抑制由玻璃之失透或著色引起的可見光穿透率之下降。因此,Bi3+之含有率較佳為以10.0%作為上限,更佳為以5.0%作為上限,進而較佳為以3.0%作為上限。又,Te4+之含有率較佳為以15.0%作為上限,更佳為以10.0%作為上限,進而較佳為以5.0%作為上限。 On the other hand, by setting the content of Bi 3+ to 10.0% or less, and/or setting the content of Te 4+ to 15.0% or less, it is possible to suppress visible light transmittance due to devitrification or coloration of glass. The decline. Therefore, the content of Bi 3+ is preferably an upper limit of 10.0%, more preferably an upper limit of 5.0%, and still more preferably an upper limit of 3.0%. Further, the content of Te 4+ is preferably an upper limit of 15.0%, more preferably an upper limit of 10.0%, and still more preferably an upper limit of 5.0%.
Bi3+及Te4+可使用Bi2O3、TeO2等作為原料。 As Bi 2+ and Te 4+, Bi 2 O 3 , TeO 2 or the like can be used as a raw material.
本發明之光學玻璃含有F-。F-之含有率較佳為例如設為20.0%~70.0%。 The optical glass of the present invention contains F - . The content ratio of F - is preferably, for example, 20.0% to 70.0%.
尤其是藉由含有F- 20.0%以上,可提高玻璃之異常分散性或阿貝數,且可提高玻璃之耐失透性。因此,F-之含有 率較佳為設為20.0%,更佳為設為23.0%,進而較佳為設為26.0%。 In particular, by containing F - 20.0% or more, the abnormal dispersibility or Abbe number of the glass can be improved, and the devitrification resistance of the glass can be improved. Thus, F - set the content ratio is preferably 20.0%, more preferably set to 23.0%, and further preferably set to 26.0%.
另一方面,藉由將F-之含有率設為70.0%以下,可抑制磨損度低下。因此,F-之含有率較佳為以70.0%作為上限,更佳為以60.0%作為上限,更佳為以50.0%作為上限,進而較佳為以40.0%作為上限。 On the other hand, by setting the content ratio of F - to 70.0% or less, it is possible to suppress the deterioration of the degree of wear. Therefore, the content ratio of F - is preferably 70.0% as an upper limit, more preferably 60.0% as an upper limit, more preferably 50.0% as an upper limit, and still more preferably 40.0% as an upper limit.
F-可使用AlF3、MgF2、BaF2等各種陽離子成分之氟化物作為原料。 F - A fluoride of various cationic components such as AlF 3 , MgF 2 or BaF 2 can be used as a raw material.
本發明之光學玻璃含有O2-。O2-之含有率較佳為例如設為30.0%~80.0%。 The optical glass of the present invention contains O 2- . The content of O 2- is preferably, for example, 30.0% to 80.0%.
尤其是藉由含有O2- 30.0%以上,可抑制玻璃之失透或磨損度之上升。因此,O2-之含有率之下限較佳為設為30.0%,更佳為設為40.0%,進而較佳為設為50.0%,進而較佳為設為60.0%。 In particular, by containing O 2 - 30.0% or more, the devitrification of the glass or the increase in the degree of abrasion can be suppressed. Therefore, the lower limit of the content ratio of O 2- is preferably 30.0%, more preferably 40.0%, still more preferably 50.0%, and still more preferably 60.0%.
另一方面,藉由將O2-之含有率設為80.0%以下,可容易地獲得其他陰離子成分帶來之效果。因此,O2-之含有率之上限較佳為設為80.0%,更佳為設為77.0%,進而較佳為設為74.0%。 On the other hand, by setting the content of O 2 to 80.0% or less, the effect of other anionic components can be easily obtained. Therefore, the upper limit of the content ratio of O 2- is preferably 80.0%, more preferably 77.0%, and still more preferably 74.0%.
又,就抑制玻璃之失透之觀點而言,O2-之含有率與F-之含有率的合計較佳為以98.0%作為下限,更佳為以99.0%作為下限,進而較佳為設為100%。 Further, from the viewpoint of suppressing devitrification of the glass, the total content of O 2 and the content of F - are preferably 98.0% as a lower limit, more preferably 99.0% as a lower limit, and further preferably a lower limit. It is 100%.
O2-可使用Al2O3、MgO、BaO等各種陽離子成分之氧化物或Al(PO)3、Mg(PO)2、Ba(PO)2等各種陽離子成分之磷酸鹽等作為原料。 Using O 2- Al 2 O 3, various cationic components of MgO, BaO or oxides such as Al (PO) 3, Mg ( PO) 2, Ba (PO) 2 , and other like phosphate as a raw material of the cationic component.
於本發明之光學玻璃中,可於無損本案發明之玻璃之特性的範圍內視需要添加其他成分。 In the optical glass of the present invention, other components may be added as needed within the range which does not impair the characteristics of the glass of the present invention.
繼而,對本發明之光學玻璃中不應含有之成分、及若含有則欠佳之成分進行說明。 Next, the components which should not be contained in the optical glass of the present invention and the components which are not preferable if they are contained will be described.
關於除Ti、Zr、Nb、W、La、Gd、Y、Yb、Lu以外之V、Cr、Mn、Fe、Co、Ni、Cu、Ag及Mo等過渡金屬之陽離子,於分別單獨或複合地少量含有之情形時玻璃亦會著色,且具有對可見光範圍之特定波長產生吸收之性質,因此較佳為尤其是使用可見光範圍之波長之光學玻璃中實質上不含有。 Regarding cations of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo other than Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu, respectively, individually or in combination In the case where a small amount is contained, the glass is also colored, and has a property of absorbing a specific wavelength in the visible light range, and therefore it is preferably substantially not contained in the optical glass which particularly uses a wavelength in the visible light range.
Pb、Th、Cd、Tl、Os、Be及Se之陽離子近年來有作為有害化學物質而控制使用之傾向,不僅玻璃之製造步驟,及至加工步驟、及製品化後之處理,需要環境對策方面之措施。因此,於重視環境方面之影響之情形時,除不可避免之混入以外,較佳為實質上不含該等。藉此,光學玻璃中實質上不含污染環境之物質。因此,即便不採取特別之環境對策方面之措施,亦可製造、加工及廢棄該光學玻璃。 In recent years, cations of Pb, Th, Cd, Tl, Os, Be, and Se have been used as a harmful chemical substance, and not only the manufacturing steps of glass, but also the processing steps and the processing after productization require environmental countermeasures. Measures. Therefore, when it is important to pay attention to the influence of the environment, it is preferable that it is substantially not included in addition to the inevitable mixing. Thereby, the optical glass contains substantially no substances that pollute the environment. Therefore, the optical glass can be manufactured, processed, and discarded without taking special measures for environmental measures.
Sb或As之陽離子可用作脫泡劑,但作為對環境造成不利之成分,近年來有不含於光學玻璃中之傾向。因此,就該方面而言,本發明之光學玻璃較佳為不含Sb或As。 The cation of Sb or As can be used as a defoaming agent, but as a component which is disadvantageous to the environment, it has a tendency not to be contained in optical glass in recent years. Therefore, in this respect, the optical glass of the present invention is preferably free of Sb or As.
本發明之光學玻璃之製造方法並無特別限定。例如,可藉由如下方法製造:將上述原料以各成分成為特定含有率範圍內之方式均勻地混合,將所製作之混合物投入至石英坩堝或氧化鋁坩堝或鉑坩堝中進行粗熔融後,裝入至鉑坩堝、鉑合金坩堝或銥坩堝中,以900~1200℃之溫度範圍使其熔融2~10小時,攪拌均質化進行消泡等後,降低至850℃以下之溫度後進行最終攪拌去除條紋,澆鑄至模具中進行緩冷。 The method for producing the optical glass of the present invention is not particularly limited. For example, it can be produced by uniformly mixing the above-mentioned raw materials so that each component becomes within a specific content range, and putting the prepared mixture into quartz crucible or alumina crucible or platinum crucible for coarse melting, and then charging Into platinum rhodium, platinum alloy crucible or crucible, melt it at a temperature of 900~1200 °C for 2 to 10 hours, stir homogenize for defoaming, etc., then reduce to a temperature below 850 °C and then finally stir to remove Stripes are cast into the mold for slow cooling.
本發明之光學玻璃具有高折射率。又,本發明之光學玻璃較佳為具有高阿貝數(低分散)。 The optical glass of the present invention has a high refractive index. Further, the optical glass of the present invention preferably has a high Abbe number (low dispersion).
尤其是本發明之光學玻璃之折射率(nd)較佳為以1.53作為下限,更佳為以1.57作為下限,進而較佳為以1.59作為下限,進而較佳為以1.60作為下限,進而較佳為以1.607作為下限。該折射率之上限較佳為可為2.00,更佳為可為1.90,進而較佳為可為1.80。 In particular, the refractive index (nd) of the optical glass of the present invention is preferably 1.53 as a lower limit, more preferably 1.57 as a lower limit, further preferably 1.59 as a lower limit, and further preferably 1.60 as a lower limit, and further preferably. The lower limit is 1.607. The upper limit of the refractive index is preferably 2.00, more preferably 1.90, still more preferably 1.80.
又,本發明之光學玻璃之阿貝數(νd)較佳為以60作為下限,更佳為以63作為下限,進而較佳為以66作為下限,較佳為以90作為上限,更佳為以85作為上限,進而較佳為以80作為上限。 Further, the Abbe number (νd) of the optical glass of the present invention is preferably 60 as a lower limit, more preferably 63 as a lower limit, still more preferably 66 as a lower limit, more preferably 90 as an upper limit, more preferably The upper limit is 85, and it is more preferable to use 80 as the upper limit.
又,本發明之光學玻璃之阿貝數(νd)與折射率(nd)之間,較佳為滿足nd≧-0.00254×νd+1.760之關係,更佳為滿足nd≧-0.00254×νd+1.770之關係,最佳為滿足nd≧-0.00254×νd+1.790之關係。 Further, between the Abbe number (νd) and the refractive index (nd) of the optical glass of the present invention, it is preferable to satisfy the relationship of nd≧-0.00254×νd+1.760, and more preferably to satisfy nd≧-0.00254×νd+1.770. The relationship is best to satisfy the relationship of nd≧-0.00254×νd+1.790.
藉由具有此種高折射率,即便謀求光學元件之薄型化亦可獲得較大之光折射量。又,藉由具有此種低分散,即便為單透鏡亦減小由光之波長引起之焦點之偏移(色像差)。又,藉由折射率及阿貝數具有此種關係,於與近年來發表之具有高折射、高分散之光學特性之光學玻璃組合時,可獲得可進行高功率之光學設計之光學玻璃。 By having such a high refractive index, a large amount of light refraction can be obtained even if the optical element is made thinner. Moreover, by having such a low dispersion, even a single lens reduces the shift (chromatic aberration) of the focus caused by the wavelength of light. Further, by having such a relationship between the refractive index and the Abbe number, an optical glass capable of high-power optical design can be obtained when combined with an optical glass having high refractive index and high dispersion optical characteristics which has been published in recent years.
因此,本發明之光學玻璃於光學設計方面有用,可謀求光學系統之高精度化及小型化,因此可拓寬光學設計之自由度。 Therefore, the optical glass of the present invention is useful for optical design, and it is possible to increase the accuracy and size of the optical system, thereby broadening the degree of freedom in optical design.
再者,折射率(nd)及阿貝數(νd)係指基於日本光學玻璃工業會標準JOGIS01-2003進行測定而獲得之值。 Further, the refractive index (nd) and the Abbe number (νd) are values obtained by measurement based on the Japan Optical Glass Industry Association standard JOGIS01-2003.
本發明之光學玻璃較佳為自熔融狀態形成玻璃時之耐失透性較高。藉此,提高玻璃之穩定性、減少結晶化,因此可減少對由玻璃製作之光學元件之光學特性、尤其是對穿透率的不良影響。 The optical glass of the present invention preferably has a high resistance to devitrification when the glass is formed from a molten state. Thereby, the stability of the glass is improved and the crystallization is reduced, so that the optical characteristics of the optical element made of glass, in particular, the adverse effect on the transmittance can be reduced.
作為耐失透性之指標,可使用後述失透析出起始溫度(Tx)。本發明之光學玻璃之失透析出起始溫度(Tx)較佳為1200℃,更佳為1100℃以下,進而較佳為1000℃以下,進而較佳為950℃以下。 As an indicator of the resistance to devitrification, the de-dialysis starting temperature (Tx) described later can be used. The dialysis starting temperature (Tx) of the optical glass of the present invention is preferably 1200 ° C, more preferably 1100 ° C or less, further preferably 1000 ° C or less, and further preferably 950 ° C or less.
本發明之光學玻璃較佳為熔解玻璃原料時以F成分為代表之各種成分之揮發較少。藉此,減少對環境有害之氣體之產生,因此可更容易地改善製造光學玻璃時之作業環境。更具體而言,熔解玻璃原料時之揮發量(原料熔解時之揮發量)較佳為3.00%以下,更佳為2.50%以下,進而較 佳為2.30%以下。 The optical glass of the present invention preferably has less volatilization of various components represented by the F component when the glass raw material is melted. Thereby, the generation of gases harmful to the environment is reduced, so that the working environment in the production of the optical glass can be more easily improved. More specifically, the amount of volatilization when the glass raw material is melted (the amount of volatilization when the raw material is melted) is preferably 3.00% or less, more preferably 2.50% or less, and further Good is 2.30% or less.
此處,各種成分之揮發量例如可利用以下方法進行測定。 Here, the amount of volatilization of each component can be measured, for example, by the following method.
即,稱取調合之玻璃原料約200 mg,裝入至氧化鋁製之DTA(Differential Thermal Analysis,示差熱分析)坩堝中,以升溫速度40℃/分鐘加熱至1100℃,保持30分鐘。將該保持30分鐘之時設為起始點,以1100℃進而保持60分鐘。將起始點與自起始點起60分鐘後之質量變化量定義為揮發量,求出其量。 Specifically, about 200 mg of the blended glass raw material was weighed and placed in a DTA (differential thermal analysis) crucible made of alumina, and heated to 1,100 ° C at a temperature increase rate of 40 ° C / min for 30 minutes. The time of holding for 30 minutes was taken as the starting point, and further maintained at 1100 ° C for 60 minutes. The amount of mass change after the start point and 60 minutes from the start point was defined as the amount of volatilization, and the amount thereof was determined.
又,各種成分之揮發量亦可利用以下方法進行評價。 Further, the amount of volatilization of each component can also be evaluated by the following method.
即,以1000~1200℃使100 cm3之玻璃原料於加蓋之300 cc鉑坩堝中充分地熔解後,將所獲得之熔融液連同熔解容器取出至爐外,目測確認打開蓋後立即產生之白煙之量。此時,將白煙較少之情形評價為「◎非常良好」或「○良好」,將白煙較多之情形評價為「△較差」或「×非常差」。此處,將白煙較少之情形中白煙尤其少之情形評價為「◎非常良好」,將白煙較多之情形中白煙尤其多之情形評價為「×非常差」。 That is, 100 cm 3 of the glass raw material was sufficiently melted in a capped 300 cc platinum crucible at 1000 to 1200 ° C, and the obtained melt was taken out together with the melting vessel to the outside of the furnace, and visually confirmed that the lid was opened immediately after opening the lid. The amount of white smoke. In this case, the case where the white smoke is small is evaluated as "(very good) or "○ is good", and the case where the white smoke is large is evaluated as "poor" or "very bad". Here, the case where the white smoke is small is particularly small, and the case where the white smoke is particularly small is evaluated as "very good", and the case where the white smoke is particularly large is evaluated as "very bad".
本發明之光學玻璃對各種光學元件及光學設計有用,其中尤佳為由本發明之光學玻璃形成預成形體,對該預成形體使用研磨加工或精密壓製成形等方法而製作透鏡或稜鏡、反射鏡等光學元件。藉此,於用於如相機或投影儀等使可見光穿透光學元件之光學設備時,可實現高精細且高 精度之成像特性。尤其是本發明之光學玻璃由溫度變化引起之折射率之變動較小,因此例如即便用於如投影儀般於使用時成為高溫之用途中,亦可實現高精細且高精度之成像特性。此處,製造預成形體材之方法並無特別限定,例如可使用日本專利特開平8-319124中記載之玻璃坯之成形方法,或如日本專利特開平8-73229中記載之光學玻璃之製造方法及製造裝置般由熔融玻璃直接製造預成形體材的方法。又,亦可使用對由光學玻璃形成之帶材進行研削研磨等冷加工進行製造的方法。 The optical glass of the present invention is useful for various optical elements and optical designs. Among them, it is particularly preferable to form a preform from the optical glass of the present invention, and to form a lens or a flaw or a reflection by using a method such as grinding or precision press molding on the preform. Optical components such as mirrors. Thereby, high precision and high can be achieved when used for an optical device such as a camera or a projector that allows visible light to penetrate the optical element. Imaging characteristics of precision. In particular, since the optical glass of the present invention has a small variation in refractive index due to temperature change, it is possible to realize high-definition and high-precision imaging characteristics even in applications such as high temperature for use as a projector. Here, the method of producing the preform is not particularly limited, and for example, a method of forming a glass blank described in Japanese Patent Laid-Open No. Hei 8-319124, or an optical glass as described in Japanese Patent Laid-Open No. Hei 8-73229 A method of directly producing a preformed body from molten glass like the method and the manufacturing apparatus. Further, a method of performing cold working such as grinding and polishing on a strip formed of optical glass may be used.
將本發明之光學玻璃即實施例(No.1~No.38)及比較例(No.A)之玻璃的組成(以陽離子%表示或陰離子%表示之莫耳%表示)、折射率(nd)、阿貝數(νd)、及原料熔解時之揮發程度(表中僅稱為「揮發程度」)示於表1~表5。又,將實施例及比較例之玻璃的原料熔解時之揮發量與耐失透性示於表6。再者,以下之實施例原則上用於例示,並不僅限定於該等實施例。 The composition of the glass of the optical glass of the present invention (No. 1 to No. 38) and the comparative example (No. A) (indicated by the cation % or the % of the anion %), and the refractive index (nd) The Abbe's number (νd) and the degree of volatilization during melting of the raw materials (only referred to as "degree of volatilization" in the table) are shown in Tables 1 to 5. Further, the volatilization amount and the devitrification resistance at the time of melting the raw materials of the glass of the examples and the comparative examples are shown in Table 6. Furthermore, the following embodiments are for illustrative purposes and are not limited to the embodiments.
關於本發明之實施例及比較例之光學玻璃,均為作為各成分之原料選定各自相應之氧化物、碳酸鹽、硝酸鹽、氟化物、偏磷酸化合物等通常之氟磷酸鹽玻璃中使用之高純度原料,以成為表1~表5所示之各實施例之組成之比例的方式秤量並均勻地混合後,投入至鉑坩堝中,根據玻璃組成之熔融難易度,利用電爐以900~1200℃之溫度範圍熔解2~10小時,攪拌均質化進行消泡等後,將溫度降低至 850℃以下後澆鑄至模具中,進行緩冷而製作玻璃。 The optical glass of the examples and the comparative examples of the present invention are each used as a raw material of each component, and the respective fluorophosphate glasses such as oxides, carbonates, nitrates, fluorides, and metaphosphoric compounds are used. The purity raw materials were weighed and uniformly mixed in such a manner as to have a composition ratio of the respective examples shown in Tables 1 to 5, and then introduced into a platinum crucible, and the electric furnace was used at 900 to 1200 ° C according to the melting difficulty of the glass composition. The temperature range is melted for 2 to 10 hours, and the mixture is homogenized for defoaming, etc., and the temperature is lowered to After casting at 850 ° C or lower, it is cast into a mold and slowly cooled to prepare a glass.
此處,實施例及比較例之光學玻璃之折射率及阿貝數係基於日本光學玻璃工業會標準JOGIS01-2003進行測定。並且,針對所求出之折射率及阿貝數之值,求出關係式nd≧-0.00254×νd+b中之截距b(截距b於表中表示為「nd+0.00254*νd」)。再者,作為本測定所使用之玻璃,使用退火條件為緩冷下降速度設為-25℃/hr、利用緩冷爐進行處理者。 Here, the refractive indices and Abbe numbers of the optical glasses of the examples and the comparative examples were measured based on the Japan Optical Glass Industry Association standard JOGIS01-2003. Then, for the obtained refractive index and the value of the Abbe number, the intercept b in the relation nd ≧ 0.00 - 0.00254 × νd + b is obtained (the intercept b is expressed as "nd + 0.00254 * νd" in the table) . Further, as the glass used in the measurement, the annealing condition was such that the slow cooling rate was set to -25 ° C / hr, and the treatment was carried out in a slow cooling furnace.
又,關於實施例及比較例之玻璃原料熔解時之揮發程度,以1000~1200℃使100 cm3之玻璃原料於蓋上包含鉑或耐火物之蓋、內部直徑85 mm、高度65 mm之鉑坩堝(300 cc)中充分地熔解後,將所獲得之熔融液連同熔解容器取出至爐外,於坩堝之背面設置30 cm×30 cm之黑色板,目測確認打開蓋後立即產生之白煙量。此時,以黑色板之水平方向之中心線與坩堝之水平方向之中心線重合的方式進行設置。 Further, regarding the degree of volatilization during melting of the glass raw materials of the examples and the comparative examples, a glass material of 100 cm 3 was placed on the lid at 1000 to 1200 ° C, and a lid containing platinum or a refractory, a platinum having an inner diameter of 85 mm and a height of 65 mm was used. After fully melting in 坩埚 (300 cc), the obtained melt was taken out of the furnace together with the melting vessel, and a black plate of 30 cm × 30 cm was placed on the back of the crucible, and the amount of white smoke immediately after opening the lid was visually confirmed. . At this time, the center line of the horizontal direction of the black plate is arranged so as to coincide with the center line of the horizontal direction of the cymbal.
此時,將白煙較少之情形評價為「◎非常良好」或「○良好」,將白煙較多之情形評價為「△較差」或「×非常差」。此處,將白煙較少之情形中白煙尤其少之情形評價為「◎非常良好」,將白煙較多之情形中白煙尤其多之情形評價為「×非常差」。 In this case, the case where the white smoke is small is evaluated as "(very good) or "○ is good", and the case where the white smoke is large is evaluated as "poor" or "very bad". Here, the case where the white smoke is small is particularly small, and the case where the white smoke is particularly small is evaluated as "very good", and the case where the white smoke is particularly large is evaluated as "very bad".
又,實施例及比較例之玻璃的原料熔解時之揮發性亦藉由以下方法進行測定。 Further, the volatility at the time of melting the raw materials of the glasses of the examples and the comparative examples was also measured by the following method.
稱取調合之玻璃原料約200 mg,裝入至氧化鋁製之DTA 坩堝中,以升溫速度40℃/分鐘加熱至1100℃,保持30分鐘。將該保持30分鐘之時設為起始點,於1100℃下進而保持60分鐘。將起始點與自起始點起60分鐘後之質量變化量定義為揮發量,求出其量。 Weigh about 200 mg of blended glass material and put it into DTA made of alumina. In the crucible, it was heated to 1100 ° C at a heating rate of 40 ° C / min for 30 minutes. The time of holding for 30 minutes was taken as the starting point, and further maintained at 1,100 ° C for 60 minutes. The amount of mass change after the start point and 60 minutes from the start point was defined as the amount of volatilization, and the amount thereof was determined.
又,關於實施例及比較例之玻璃之耐失透性,將所獲得之玻璃粉碎為粒度425~600 μm,稱取經粉碎之玻璃試料約200 mg裝入至氧化鋁製之DTA坩堝中,以升溫速度10℃/分鐘加熱至950℃。於加熱溫度達到950℃後,以降溫速度5℃/分鐘冷卻至600℃,測定此時檢測到之示差熱曲線之最高發熱起始溫度Tx(-5)。又,同樣地,加熱溫度達到950℃後,以降溫速度2.5℃/分鐘冷卻至600℃,測定此時檢測到之示差熱曲線之最高發熱起始溫度Tx(-2.5)。將自測得之Tx(-5)與Tx(-2.5)之值外插至降溫速度0℃/分鐘的溫度定義為失透析出起始溫度(Tx),求出該溫度。 Further, regarding the devitrification resistance of the glass of the examples and the comparative examples, the obtained glass was pulverized to a particle size of 425 to 600 μm, and about 200 mg of the pulverized glass sample was weighed and placed in a DTA crucible made of alumina. The heating rate was heated to 950 ° C at a rate of 10 ° C / min. After the heating temperature reached 950 ° C, the temperature was cooled to 600 ° C at a cooling rate of 5 ° C / min, and the highest heat generation onset temperature Tx (-5) of the differential heat curve detected at this time was measured. Further, similarly, after the heating temperature reached 950 ° C, the temperature was cooled to 600 ° C at a temperature drop rate of 2.5 ° C / min, and the highest heat generation onset temperature Tx (-2.5) of the differential heat curve detected at this time was measured. The temperature at which the self-measured Tx(-5) and Tx(-2.5) were extrapolated to the temperature drop rate of 0 °C/min was defined as the dedialysis start temperature (Tx), and the temperature was determined.
如表1~表6所示,本發明之實施例之光學玻璃均為折射率1.53以上,更詳細而言為1.59以上,為所需之範圍內。另一方面,比較例(No.A)折射率低於1.53。因此,明確本發明之實施例之光學玻璃與比較例之玻璃相比折射率較高。 As shown in Tables 1 to 6, the optical glass of the examples of the present invention has a refractive index of 1.53 or more, and more specifically 1.59 or more, which is within a desired range. On the other hand, the refractive index of Comparative Example (No. A) was less than 1.53. Therefore, it is clear that the optical glass of the embodiment of the present invention has a higher refractive index than the glass of the comparative example.
又,本發明之實施例之光學玻璃均為阿貝數60以上,更詳細而言為65以上,同時該阿貝數為80以下,更詳細而言為70以下,為所需之範圍內。 Further, the optical glass of the embodiment of the present invention has an Abbe number of 60 or more, more specifically 65 or more, and the Abbe number is 80 or less, and more specifically 70 or less, which is within a desired range.
又,本發明之實施例之光學玻璃阿貝數(νd)與折射率(nd)之間,滿足nd≧-0.00254×νd+1.760之關係,更詳細而言滿足nd≧-0.00254×νd+1.767之關係,為所需之範圍內。 Further, between the optical glass Abbe number (νd) and the refractive index (nd) of the embodiment of the present invention, the relationship of nd ≧ - 0.00254 × νd + 1.760 is satisfied, and more specifically, nd ≧ - 0.00254 × νd + 1.767 is satisfied. The relationship is within the required range.
又,本發明之實施例之光學玻璃表中之「揮發之程度」為「◎」或「○」,明確熔解時之白煙之產生較少。又,本發明之實施例之光學玻璃揮發量為3.00%以下,更具體而 言為2.15%以下。另一方面,本發明之比較例之玻璃揮發量為3.15%。因此,推測本發明之光學玻璃與比較例之玻璃相比,熔解時以F成分為代表之各成分之揮發較少。 Further, the "degree of volatilization" in the optical glass watch of the embodiment of the present invention is "?" or "○", and it is clear that the generation of white smoke at the time of melting is small. Moreover, the amount of volatilization of the optical glass of the embodiment of the present invention is 3.00% or less, more specifically The statement is 2.15% or less. On the other hand, the glass volatile amount of the comparative example of the present invention was 3.15%. Therefore, it is presumed that the optical glass of the present invention has less volatilization of each component represented by the F component at the time of melting than the glass of the comparative example.
又,本發明之實施例之光學玻璃失透析出起始溫度為1200℃以下,更具體而言為940℃以下,為所需之範圍內。 Further, the optical glass has an dialysis starting temperature of 1200 ° C or less, more specifically 940 ° C or less, which is within a desired range.
因此,明確本發明之實施例之光學玻璃阿貝數處於所需之範圍內,同時折射率及耐失透性較高,且熔解時成分之揮發較少。 Therefore, it is clear that the optical glass Abbe number of the embodiment of the present invention is within the desired range, while the refractive index and the devitrification resistance are high, and the volatilization of the components at the time of melting is less.
進而,使用本發明之實施例之光學玻璃形成玻璃塊,對該玻璃塊進行研削及研磨,加工成透鏡及稜鏡之形狀。其結果為,可穩定地加工成各種透鏡及稜鏡之形狀。 Further, a glass block is formed using the optical glass of the embodiment of the present invention, and the glass block is ground and polished to be processed into a shape of a lens and a crucible. As a result, it can be stably processed into various lenses and shapes of the crucible.
以上,已為例示之目的詳細地說明本發明,但本實施例原則上僅用於例示,可理解為可由本領域業者不脫離本發明之思想及範圍而進行較多改變。 The present invention has been described in detail above for the purpose of illustration, and the embodiments of the present invention are to be construed as illustrative only.
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CN110156325B (en) * | 2019-05-31 | 2022-03-11 | 成都光明光电股份有限公司 | Fluorophosphate glass, glass preform, optical element and optical instrument having the same |
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CN110156324B (en) * | 2019-05-31 | 2022-05-24 | 成都光明光电股份有限公司 | Fluorophosphate glass, glass preform, optical element and optical instrument having the same |
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