阅读说明：本技术 近红外线吸收玻璃 (Near infrared ray absorption glass ) 是由 永野雄太 村田哲哉 高山佳久 于 2018-07-30 设计创作，主要内容包括：本发明提供一种能够将光学器件薄型化并且耐候性、耐失透性和光学特性的各特性优异的近红外线吸收玻璃。上述近红外线吸收玻璃的特征在于,以阳离子％计含有10～70％的P<Sup>5+</Sup>、0％以上且低于7％的Na<Sup>+</Sup>、3％以上且低于31％的R<Sup>2+</Sup>(R为选自Mg、Ca、Sr和Ba中的至少1种)、0.1～20％的Mg<Sup>2+</Sup>、2～20％的Sr<Sup>2+</Sup>、0.1％以上且低于9％的Cu<Sup>2+</Sup>,且以阴离子％计含有14.5～90％的F<Sup>－</Sup>、10～85.5％的O<Sup>2－</Sup>,厚度为0.25mm以下。(The invention provides a near infrared ray absorbing glass which can make an optical device thin and has excellent weather resistance, devitrification resistance and optical characteristics. The near infrared ray absorbing glass is characterized by containing 10-70% of P in terms of cation% 5+ 0% or more and less than 7% of Na + R is more than 3% and less than 31% 2+ (R is at least 1 selected from Mg, Ca, Sr and Ba), 0.1-20% of Mg 2+ 2 to 20% of Sr 2+ 0.1% or more ofUp to and below 9% Cu 2+ And 14.5 to 90% of F in terms of anion% － 10 to 85.5% of O 2－ And a thickness of 0.25mm or less.)

1. A near-infrared ray absorption glass characterized in that:

10 to 70% of P in terms of cation%⁵⁺0% or more and less than 7% of Na⁺R is more than 3% and less than 31%²⁺0.1 to 20% of Mg²⁺2 to 20% of Sr²⁺0.1% or more and less than 9% of Cu²⁺And 14.5 to 90% of F in terms of anion%^－10 to 85.5% of O^2－Wherein R is at least 1 selected from Mg, Ca, Sr and Ba,

the thickness of the near infrared ray absorbing glass is 0.25mm or less.

2. The near-infrared ray absorption glass according to claim 1, wherein:

0 to 10% of Zn in terms of cation%²⁺。

3. The near-infrared ray absorption glass according to claim 1 or 2, wherein:

substantially free of Pb component and As component.

Technical Field

The present invention relates to a near-infrared ray absorbing glass capable of selectively absorbing near-infrared rays.

Background

In general, near infrared absorbing glass is used in a camera portion in an optical device such as a digital camera or a smartphone to correct visibility of a solid-state image pickup element such as a CCD or a CMOS. For example, patent document 1 discloses a phosphoric acid-based near-infrared absorbing glass containing fluorine.

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, thinning of optical devices is strongly desired, and thinning of near infrared ray absorption glass is required, but high resistance to devitrification is required to produce thin near infrared ray absorption glass. However, if the devitrification resistance is to be improved, a problem of deterioration in weather resistance, optical characteristics, and the like is likely to occur.

In view of the above-described situation, an object of the present invention is to provide a near-infrared ray absorbing glass which can make an optical device thin and is excellent in various properties such as resistance to devitrification, weather resistance, and optical properties.

Technical solution for solving technical problem

The near infrared ray absorbing glass of the present invention is characterized by containing 10 to 70% of P in terms of cation%⁵⁺0% or more and less than 7% of Na⁺R is more than 3% and less than 31%²⁺(R is at least 1 selected from Mg, Ca, Sr and Ba), 0.1-20% of Mg²⁺2 to 20% of Sr²⁺0.1% or more and less than 9% of Cu²⁺And in% of anionContaining 14.5 to 90% of F^－10 to 85.5% of O^2－And a thickness of 0.25mm or less.

The near infrared ray absorbing glass of the present invention is obtained by improving the devitrification resistance of R²⁺Na having a devitrification resistance reduced by 3% or more⁺Specified to be less than 7%, high resistance to devitrification is achieved. Therefore, the method can be applied to a molding method which is easily accompanied by devitrification, such as a Down draw method (Down draw) and a Redraw method (Redraw), which can efficiently produce infrared absorbing glass having a small thickness.

The near-infrared absorbing glass of the present invention preferably further contains 0 to 10% of Zn in terms of cation%²⁺。

The near-infrared absorbing glass of the present invention preferably contains substantially no Pb component and As component. The term "substantially free" means that the compound is not intentionally contained as a raw material, and objectively means that the content of each component is less than 0.1%.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a near-infrared absorbing glass which can make an optical device thin and is excellent in various properties such as resistance to devitrification, weather resistance, and optical properties.

Detailed Description

The near infrared ray absorbing glass of the present invention contains 10 to 70% of P in terms of cation%⁵⁺0% or more and less than 7% of Na⁺R is more than 3% and less than 31%²⁺(R is at least 1 selected from Mg, Ca, Sr and Ba), 0.1-20% of Mg²⁺2 to 20% of Sr²⁺0.1% or more and less than 9% of Cu²⁺. The reason why the glass composition is limited as described above will be described below.

P⁵⁺Is an essential component for forming the glass skeleton. P⁵⁺The content of (b) is 10 to 70%, preferably 15 to 63%, 18 to 51%, 25 to 50%, and particularly preferably 25 to 40%. P⁵⁺When the content of (b) is too small, the vitrification tends to become unstable. On the other hand, P⁵⁺When the content of (b) is too large, the weather resistance tends to be lowered.

Na⁺Is a component that lowers the melting temperature. Na (Na)⁺The content of (A) is 0%More than or equal to less than 7%, preferably 0.1 to 6%, 0 to 2%, and particularly preferably not containing Na⁺。Na⁺When the content of (b) is too large, resistance to devitrification and weather resistance tend to be lowered.

R²⁺(R is at least 1 selected from Mg, Ca, Sr and Ba) is a component for improving resistance to devitrification and weather resistance. R²⁺The content of (b) is 3% or more and less than 31%, preferably 8 to 28%, and particularly preferably 12 to 26% in total. R²⁺When the content of (B) is too small, the above-mentioned effects are hardly obtained. In another aspect, R²⁺When the content of (b) is too large, the vitrification stability is liable to be lowered.

Furthermore, R²⁺The contents of the respective components (a) and (b) are as follows.

Mg²⁺Is a component for improving resistance to devitrification and weather resistance. Mg (magnesium)²⁺The content of (b) is preferably 0.1 to 20%, particularly preferably 3 to 11%. Mg (magnesium)²⁺When the content of (B) is too small, the above-mentioned effects are hardly obtained. On the other hand, Mg²⁺When the content of (b) is too large, the vitrification stability is liable to be lowered.

Ca²⁺With Mg²⁺Similarly, the components improve resistance to devitrification and weather resistance. Ca²⁺The content of (b) is preferably 0 to 12%, particularly preferably 0.1 to 10%. Ca²⁺When the content of (b) is too large, the vitrification stability is liable to be lowered.

Sr²⁺Also with Mg²⁺Similarly, the components improve resistance to devitrification and weather resistance. Sr²⁺The content of (b) is preferably 2 to 20%, particularly preferably 2 to 10%. Sr²⁺When the content of (B) is too small, the above-mentioned effects are hardly obtained. On the other hand, Sr²⁺When the content of (b) is too large, the vitrification stability is liable to be lowered.

Ba²⁺Also with Mg²⁺Similarly, the components improve resistance to devitrification and weather resistance. Ba²⁺The content of (b) is preferably 0 to 10%, particularly preferably 0.1 to 9%. Ba²⁺When the content of (b) is too large, the vitrification stability is liable to be lowered.

Cu²⁺Is an essential component for absorbing near infrared rays. Cu²⁺The content of (A) is 0.1% or more and less than 9%, preferably 2%% or more and less than 9%, particularly preferably 5% or more and less than 9%. Cu²⁺When the content of (B) is too small, the above-mentioned effects are hardly obtained. On the other hand, Cu²⁺When the content of (b) is too large, the light transmittance in the ultraviolet to visible light region tends to be low. In addition, the devitrification resistance tends to be lowered.

In addition to the above components, various components shown below may be contained.

Al³⁺Is a component for improving chemical durability. Al (Al)³⁺The content of (b) is preferably 0 to 20%, 2 to 19%, 6 to 18%, 7 to 17%, and particularly preferably 8 to 16%. Al (Al)³⁺When the content of (b) is too large, the meltability tends to decrease and the melting temperature tends to increase. Further, when the melting temperature rises, Cu ions are easily reduced to separate from Cu²⁺Conversion to Cu⁺It is difficult to obtain desired optical characteristics. Specifically, the light transmittance in the near ultraviolet to visible light region is reduced, or the near infrared absorption characteristic is easily reduced.

Zn²⁺Is a component for improving resistance to devitrification and weather resistance. Zn²⁺The content of (b) is preferably 0 to 10%, particularly preferably 0.1 to 5%. Zn²⁺When the content of (b) is too large, the vitrification stability is liable to be lowered.

Li⁺Is a component that lowers the melting temperature. Li⁺The content of (b) is preferably 0 to 30%, particularly preferably 0.1 to 25%. Li⁺When the content of (b) is too large, the devitrification resistance tends to be lowered.

K⁺Is a component that lowers the melting temperature. K⁺The content of (b) is preferably 0 to 30%, particularly preferably 0.1 to 20%. K⁺When the content of (b) is too large, the devitrification resistance tends to be lowered.

In the optical glass of the present invention, Bi may be contained as a cationic component within a range not impairing the effects of the present invention³⁺、La³⁺、Y³⁺、Gd³⁺、Te⁴⁺、Si⁴⁺、Ta⁵⁺、Nb⁵⁺、Ti⁴⁺、Zr⁴⁺Or Sb³⁺And the like. Specifically, the content of each of these components is preferably 0 to 3%, more preferably 0 to 3%The concentration is selected to be 0-1%.

Pb component (Pb)²⁺Etc.) and As component (As)³⁺Etc.) are environmentally-friendly substances, and therefore, it is preferable in the present invention that they are not substantially contained.

The composition of the anionic component preferably contains 14.5 to 90% of F^－And 10 to 85.5% of O^2－Particularly preferably 20 to 70% of F^－And 30 to 80% of O^2－。F^－Too small a content of (O)^2－Too much) tends to lower resistance to devitrification and weather resistance. On the other hand, F^－Too much (O)^2－Too small content of (b) the stability of vitrification tends to be lowered.

The near-infrared absorbing glass of the present invention is generally used in a plate shape. The thickness is 0.25mm or less, preferably 0.2mm or less, 0.15mm or less, and particularly preferably 0.1mm or less. If the thickness is too large, it becomes difficult to make the optical device thin. The lower limit of the thickness is not particularly limited, but is preferably 0.01mm or more from the viewpoint of mechanical strength.

The near-infrared absorbing glass of the present invention has the above composition, and thus can achieve both high light transmittance in the visible region and excellent light absorption characteristics in the near-infrared region. Specifically, the light transmittance at a wavelength of 500nm is preferably 75% or more, and particularly preferably 77% or more. On the other hand, the light transmittance at a wavelength of 700nm is preferably 28% or less, particularly preferably 26% or less, and the light transmittance at a wavelength of 1200nm is preferably 39% or less, particularly preferably 37% or less.

The near-infrared ray absorption glass of the present invention preferably has a liquid phase viscosity of 10^0.8dPas or more, particularly preferably 10^1.0dPas or more. When the liquid phase viscosity is too low, devitrification is likely to occur during molding.

The near-infrared absorbing glass of the present invention can be produced by melting and molding a raw material powder master batch prepared to have a desired composition. The melting temperature is preferably 700-900 ℃. When the melting temperature is too low, it is difficult to obtain homogeneous glass. On the other hand, when the melting temperature is too high, Cu ions are easily reduced to separate Cu ions from Cu²⁺Transformation ofIs Cu⁺And thus it is difficult to obtain desired optical characteristics.

Thereafter, the molten glass is molded into a predetermined shape, and subjected to necessary post-processing, thereby being supplied to various applications. In order to efficiently produce a near-infrared-absorbing glass having a small thickness, a forming method such as a down-draw method or a redraw method is preferably applied. These molding methods are likely to involve devitrification, and therefore, the near-infrared ray absorbing glass of the present invention having excellent devitrification resistance can be easily obtained.