CN102923950B - Fluophosphate glass and manufacture method thereof and near-infrared absorption filter - Google Patents

Abstract

The present invention provides a kind of fluophosphate glass and manufacture method thereof and near-infrared absorption filter, even if described fluophosphate glass the most also has following O^2‑/P⁵⁺Ratio, and possess weatherability, described O^2‑/P⁵⁺Than being according to can add the Cu of amount of degree that absorbable near infrared light suppresses the absorption of visible ray simultaneously²⁺Mode and set.The fluophosphate glass of the present invention is because of containing Cu²⁺And the fluophosphate glass of near infrared light can be absorbed, and wherein, the O in described fluophosphate glass^2‑Content is relative to P⁵⁺Mol ratio (the O of content^2‑/P⁵⁺) it is 3.2 F less than 3.4, in described fluophosphate glass^‑Content is relative to O^2‑And F^‑The mol ratio (F of total content^‑/(O^2‑+ F^‑)) it is more than 0.05 and less than 0.25.

Description

Fluophosphate glass and manufacture method thereof and near-infrared absorption filter

Technical field

The present invention relates to fluophosphate glass and manufacture method thereof and near-infrared absorption filter, particularly to absorbable The fluophosphate glass of near infrared light and manufacture method thereof and near-infrared absorption filter.

Background technology

Fluophosphate glass is as having the glass of weatherability and low dispersing glass is highly useful, as this glass Know just like the glass described in patent documentation 1～6.

But, it is being based on obtaining the composition of required optical characteristics, frit is being concocted, adds hot melt Melt, in the case of thus manufacturing fluophosphate glass, be usually present following problem.

Fluophosphate glass demonstrates significant volatility the most during fabrication.Volatilization as melten glass is brought not Good impact exists: near surface or the internal generation such problem of brush line of glass；Glass is caused because of the carrying out of volatilization Glass composition changes, and therefore the characteristic of glass can change such problem over time.

It addition, in manufacturing process, because generating phosphorus oxyfluoride (POF₃) and produce volatilization.Further, the three of volatilization Fluorine phosphorous oxide also can produce fluohydric acid gas (HF) because of hydrolysis, thus results in the white cigarette containing these compounds.These are changed Compound likely produces infringement to glass manufacture equipment, therefore typically requires the countermeasure seeking problem above.Therefore, In order to deal with the by-product of volatilization, need to pay great expense, and the burden of operating personnel also can be increased.

In order to improve this situation, described volatile reason is investigated by the present inventor, and result is disclosed in In patent documentation 7～10.The summary of its content is as follows.

In the case of making fluophosphate glass, generally use phosphatic raw materials, but in order to make as anion component The import volume of fluorion is the most, and phosphate uses oxygen atom quantity ratio (oxygen atom/phosphorus relative to 1 phosphorus atoms Atom) little metaphosphate (oxygen atom (O)/phosphorus atoms (P)=3 i.e. PO₃).Due to this reason, up to now at fluorine phosphorus In the conventional glass of acid system, the amount of oxygen atom mostly is 3 with the ratio of the amount of phosphorus atoms.

But, the present inventor studies, it was found that only use metaphosphate to make oxygen as oxide raw material When/phosphorus ratio is the glass of 3, in melten glass, the Metaphosphoric acid from raw material reacts with fluorine, thus causes Generation demonstrates obvious volatile phosphorus oxyfluoride (POF₃).On the other hand, it is known that if adding beyond metaphosphate Oxide raw material or use pyrophosphate, by oxygen atom in melten glass relative to the atomic ratio of every 1 phosphorus atoms Be adjusted to more than 3.5 (oxygen atom/phosphorus atoms >=3.5), then the generation amount of volatile substance can be greatly reduced.It is thought that this Phosphoric acid in the presence of being because as melten glass, with oxygen atom relative to 1 phosphorus atoms quantity ratio (oxygen atom/ Phosphorus atoms) be 3 Metaphosphoric acid compare, oxygen atom/phosphorus atoms is diphosphonic acid (the pyrophosphoric acid i.e. P of 3.5₂O₇) more stable.

Based on above opinion, in order to suppress described volatilization, the present inventor is conceived to the O in fluophosphate glass^2-Content Relative to P⁵⁺Mol ratio (the O of content^2-/ P⁵⁺) or raw material in content containing relative to phosphorus atoms of contained oxygen atom The mol ratio (O/P) of amount, it is contemplated that making these values is more than 3.5 such methods, and public in patent documentation 7～10 Open the method.

It should be noted that in patent documentation 11, the applicant discloses too and makes these values is more than 3.5 Such method.

It addition, the present inventor discloses in patent documentation 12, make the O in fluophosphate glass^2-Content relative to P⁵⁺Mol ratio (the O of content^2-/ P⁵⁺) it is more than 3.4, make the F in fluophosphate glass^-Content is relative to O^2-And F^-Total content Mol ratio be more than 0.05 such method.

Hereinafter, for convenience of explanation, the oxygen in fluophosphate glass (is labeled as O^2-.) content (is labeled as relative to phosphorus P⁵⁺.) content mol ratio be referred to as " O^2-/ P⁵⁺Than ", oxygen contained in raw material (is labeled as O.) content relative to Phosphorus (is labeled as P.) mol ratio (O/P) of content is referred to as " raw material O/P than ".

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 10-139454 publication

Patent documentation 2: Japanese Unexamined Patent Publication 6-16451 publication

Patent documentation 3: Japanese Unexamined Patent Publication 8-253341 publication

Patent documentation 4: Japanese Unexamined Patent Publication 3-232735 publication

Patent documentation 5: Japanese Unexamined Patent Publication 1-219073 publication

Patent documentation 6: Japanese Unexamined Patent Publication 3-83834 publication

Patent documentation 7: Japanese Unexamined Patent Publication 2010-59019 publication

Patent documentation 8: Japanese Unexamined Patent Publication 2010-59021 publication

Patent documentation 9: Japanese Unexamined Patent Publication 2010-59022 publication

Patent documentation 10: Japanese Unexamined Patent Publication 2010-59023 publication

Patent documentation 11: Japanese Unexamined Patent Publication 2011-132077 publication

Patent documentation 12: Japanese Unexamined Patent Publication 2011-93757 publication

Summary of the invention

The problem that invention is to be solved

Before the present invention wants the problem solved illustrate, in terms of principle, at described patent documentation 7～ O is made in 10^2-/ P⁵⁺It is described in detail than the reason being more than 3.5.

Before described patent documentation 7～10 is open, as it has been described above, in the conventional glass of fluorophosphoric acid system, generally make O^2-/ P⁵⁺Ratio is 3.O^2-/ P⁵⁺Than when being 3, in glass, O with P is bonded thus forms the P-O-P chain of strip. Owing to these P-O-P chains multiple are orientated or are wound around, so that fluorophosphoric acid system glass is as the glass for reality application It is qualified.

But, at O^2-/ P⁵⁺Than the when of being 3, if there is fluorine (F), then there will be O and P in this P-O-P chain The probability cut off by F of key.It is as a result, it is possible to produce the above-mentioned volatile matter (POF as by-product₃And HF). In order to prevent this situation, in described patent documentation 7～10, employ following principle: compared with the past, carry further High O^2-/ P⁵⁺Ratio (that is, containing more oxygen (O)) such that it is able to before P-O-P chain is cut off by F, beforehand through O Cut off P-O-P chain, so that Metaphosphoric acid structure (i.e. PO₃) it is changed to pyrophosphoric acid structure (i.e. P₂O₇)。

On the other hand, the present inventors have additionally discovered that following problem: by improving O^2-/ P⁵⁺Ratio, can make containing Cu²⁺ C system glass absorb near infrared light, but also can cause the reality as optical filter because the absorbing too strong of visible ray Decline by property.Specifically, the inventors discovered that, when forming the fluophosphate glass of tabular of predetermined thickness, with energy The degree enough absorbing near infrared light adds Cu to raw material²⁺In the case of, if O^2-/ P⁵⁺Ratio is high, then with O^2-/ P⁵⁺Ratio is 3 Time compare, can exceedingly absorb visible ray, even put into the Cu of the amount that can absorb near infrared light degree²⁺As former Material, can cause exceedingly absorbing visible ray the most specifically.

In addition, the following opinion that the present inventor obtains: O^2-/ P⁵⁺Ratio can give the excessive absorption band for visible ray Affect, and in view of this impact, set for solving described problem in order to the fluophosphate glass after making manufacture has O^2-/ P⁵⁺Ratio, must be in view of the amount of the fluorine (F) in glass.Detailed content will be described later.

It is an object of the invention to provide a kind of fluophosphate glass and manufacture method thereof and near-infrared absorption filter, Even if described fluophosphate glass the most also has following O^2-/ P⁵⁺Ratio, and possess weatherability, described O^2-/ P⁵⁺ Than being according to can add the Cu of amount of degree that absorbable near infrared light suppresses the absorption of visible ray simultaneously²⁺Mode And set.

Means for solving the above

First, the present inventor has continued to use the policy of the technology described in patent documentation 7～10 of the present inventor as the most square Pin.That is, initially with following policy: compared with (3.0) in the past, O^2-/ P⁵⁺Than improving, thus suppress by-product Volatilization.Thus, as set forth above, it is possible to the cut-out of P-O-P chain is suppressed POF by advancing with O₃Generation. Additionally it is assumed that P-O-P chain is also possible to be cut because of hydrone contained in atmosphere when manufacturing fluophosphate glass Disconnected, therefore by weatherability being made to improve to be cut off by P-O-P chain the most in advance.

On the other hand, at O compared with the past^2-/ P⁵⁺In the case of improving, need to improve the F in fluophosphate glass^- Content is relative to O^2-And F^-The mol ratio of total content.This is because, by improving O^2-/ P⁵⁺Ratio, P-O-P chain is by O Cut off, therefore can form glass forming ability decline, the glass of the most notable crystallization.Therefore, by improving glass Interior above-mentioned F^-The mol ratio of content, can make F between pyrophosphoric acid structure, maintain what similar P-O-P chain was cut off Structure.Thus, during fluophosphate glass may be used for actual application.

Hereinafter, for convenience of explanation, by the F in fluophosphate glass^-Content (is labeled as O relative to oxygen^2-.) and fluorine (mark It is designated as F^-.) total content (O^2-+F^-) mol ratio (F^-/(O^2-+F^-)) it is referred to as " F^-Than ", by fluorine contained in raw material (it is labeled as F.) content (is labeled as O relative to oxygen.) and fluorine (be labeled as F.) the mol ratio (F/O of total content (O+F) + F) it is referred to as " raw material F ratio ".Wherein, it is described in detail later, the present invention have employed volatile material The method the most substantially produced.Therefore, above-mentioned raw materials F than with the F in product glass^-Ratio is substantially the same.

Return to topic in talk, by improving O^2-/ P⁵⁺Ratio, the P-O-P chain in glass mostly is pyrophosphoric acid structure (i.e. P₂O₇)。 Like this, other metal (Li etc.) in glass and pyrophosphoric acid structure bonding, it is also possible to form crystallization.If at glass Produce crystallization in glass, then can produce the result that optical characteristics is remarkably decreased.As its countermeasure, by improving in glass F^-Ratio, so that F is between pyrophosphoric acid structure.Thus, it is possible to suppress the formation of described crystallization.

Herein, the O in the embodiment in patent documentation 2～6 is selected^2-/ P⁵⁺Than for the numerical value more than 3.0 and less than 3.5 Embodiment, for O^2-/ P⁵⁺And F^-Ratio is fabricated to catalog, is shown in table 1.As shown in table 1, with conventional phase Than improving O^2-/ P⁵⁺Than time, if to possess sufficient weatherability as target, in any case generally F to be made^-Ratio is extremely Few for nearly more than 0.30, this is the general knowledge of those skilled in the art.

Table 1

	O2-/ P5+Ratio	F-Ratio	Remarks
				The embodiment 3 of patent documentation 2	3.473744	0.006025	Containing Pb
The comparative example 11 of patent documentation 2	3.068565	-	Containing B3+, without F-
				The comparative example 12 of patent documentation 2	3.182688	-	Without F-
The ratio embodiment 1 of patent documentation 3	3.134901	0.661544	-
				The embodiment 7 of patent documentation 3	3.149881	0.733764	-
The embodiment 8 of patent documentation 3	3.079777	0.337624	-
				The embodiment 11 of patent documentation 3	3.260386	0.467068	-
The embodiment 18 of patent documentation 3	3.394710	0.444594	-
				The comparative example 25 of patent documentation 3	3.020058	0.405389	-
The embodiment 2 of patent documentation 5	3.031390	0.215221	Containing Pb
				The embodiment 5 of patent documentation 5	3.480060	0.484436	-
The embodiment 8 of patent documentation 5	3.461567	0.558856	-
				The embodiment 9 of patent documentation 5	3.237104	0.609943	-
The embodiment 10 of patent documentation 5	3.359127	0.275487	Containing Pb
				The embodiment 1 of patent documentation 6	3.363245	0.343490	-
The embodiment 3 of patent documentation 6	3.011756	0.191647	Containing Pb
				The embodiment 5 of patent documentation 6	3.432149	0.541318	Containing Pb
The embodiment 6 of patent documentation 6	3.404429	0.375737	-
				The embodiment 7 of patent documentation 6	3.128491	0.292533	Containing Pb
The embodiment 8 of patent documentation 6	3.363245	0.338950	-
				The embodiment 9 of patent documentation 6	3.324640	0.405765	Containing Pb
The embodiment 10 of patent documentation 6	3.322762	0.400466	-

It should be noted that make O described in patent documentation 12^2-/ P⁵⁺Than being more than 3.4, making F^-Ratio is 0.05 Above, spectrophotometric transmittance during λ 50=615nm but near infrared light region (1200nm) (is the most also only called " thoroughly Cross rate ") reduction rest on about 23% (with reference to the embodiment (following table of table 1) of patent documentation 12).Former as it Cause, it is believed that there is following cause effect relation: even if the suction of certain light also can be carried out in visible region (615nm) The thickness of glass of receiving → cause λ 50=615nm is thinning → therefore cannot fully carry out near-infrared owing to thickness of glass is thinning The absorption of light.

The present inventor is while based on above-mentioned condition, being studied above-mentioned problem.As a result, to completing the present invention Till, obtain being divided into 3 opinions in general below.

[opinion 1] is for containing Cu²⁺Fluophosphate glass carry out absorption spectrum (transverse axis: wave number (K (kayser=cm^-1))) Analysis time, there is till near-infrared wavelength～visible wavelength a peak.But, this peak can be separated into 2 peaks: peak, infrared light side and peak, visible ray side.And, it is seen that the intensity at peak, light side can be by O^2-/ P⁵⁺The impact of ratio.

[opinion 2] at raw material F than high situation (or melt temperature high situation) and at least will in feed stage O^2-/ P⁵⁺In the case of being set near 3.0, even if there is predetermined O according to final glass composition^2-/ P⁵⁺Ratio Mode carries out mixture to the raw material of intended component, from feed stage to glass manufacture after-stage, and actually O^2-/ P⁵⁺ Than also changing because of by-product volatilization.That is, the O in product glass^2-/ P⁵⁺Than can be (or molten by raw material F ratio Melt temperature) impact.

[opinion 3] in [opinion 2], the O changed to glass manufacture after-stage from feed stage^2-/ P⁵⁺Than being about 3.3.This 3.3 this numeric representation tripolyphosphate structure (i.e. P₃O₁₀)。

Hereinafter, each opinion is described in detail, while combine that the present application completes through illustrating.

Illustrate first against [opinion 1], for containing Cu²⁺Fluophosphate glass carry out the analysis of absorption spectrum, Show the result in Fig. 1.Further, the absworption peak in this Fig. 1 is segmented into being Cu originally²⁺Infrared light side for Absorption Line Peak (little) and be positioned at the peak, visible ray side (greatly) of short wavelength side (the highest wave number side) compared with peak, infrared light side.Its result is shown In Fig. 2.It should be noted that in this Fig. 2 (a), make O^2-/ P⁵⁺Ratio is 3.5；In this Fig. 2 (b), make O^2-/ P⁵⁺ Ratio is 3.18.

From Figure 2 it can be seen that it is Cu originally that the absworption peak (with the solid line of ◇) in measured spectra is divided into²⁺For Absorption Line Peak, infrared light side (dotted line) and be positioned at the peak, visible ray side (solid line) of short wavelength side compared with peak, infrared light side.Except this it Outward, when Fig. 2 (a) and Fig. 2 (b) is compared, it is known that O^2-/ P⁵⁺Visible ray side than a low side (i.e. Fig. 2 (b)) The intensity at peak is low.It should be noted that for the width at peak, infrared light side and intensity, both sides are almost without difference, right Width both sides in peak, visible ray side are also almost without difference.It addition, for peak position, both sides are also almost without difference.

It should be noted that final calculated spectrophotometric transmittance contains the loss reflected and cause by surface.In order to In this loss being accounted for, it is accounted for being reflected, by surface, the loss (pecked line) caused in absorbance.But, In fig. 2, in general, the change of refractive index the variable quantity of the reflectance caused is little, and the most no matter wavelength how Reflectance will be calculated according to definite value.

It should be noted that product glass is surveyed the spectrum (with the solid line of ◇) obtained and to being divided into 2 Regular spread-spectrum (i.e. peak, infrared light side and peak, visible ray side) behind individual peak overlaps, and reflects in combination with by surface The loss that causes and the synthetic spectrum (dash line) that obtains is the most consistent.

Herein, it is judged that manufacture and there is certain thickness and certain near-infrared absorption ability (wavelength specifically Transmitance during 1200nm (about 8300K) is 10%) the situation of plate glass time, it is considered to O^2-/ P⁵⁺Than high glass (Fig. 2 (a)) and O^2-/ P⁵⁺Result than low glass (Fig. 2 (b)).That is, in order to obtain required plate glass, should The intensity at the peak, infrared light side in this raising absorption spectrum is so that the plate glass transmitance near infrared light region can Reach 10%, and need to add Cu further in feed stage²⁺。

So, Cu is being added further²⁺In the case of, for fluophosphate glass, its absorption spectrum is predicted, Show the result in Fig. 3.Further, based on Fig. 3, light transmitance in plate glass is predicted, by its result It is shown in Fig. 4.It should be noted that Fig. 3 (a) and Fig. 4 (a) represents predicting the outcome for Fig. 2 (a)；Fig. 3 (b) and figure 4 (b) represents predicting the outcome for Fig. 2 (b).

If as it is shown on figure 3, adding Cu further²⁺So that product glass has certain near-infrared absorption ability (ripple Transmitance during long 1200nm (about 8300K) is 10%) (dotted line → heavy line), the most not only intensity at peak, infrared light side Increase (two-dot chain line → fine line), it is seen that the intensity at peak, light side also can increase (chain-dotted line → solid line) further.Now, As shown in Fig. 2 (a), if O^2-/P⁵⁺Ratio is high, then, it is seen that peak, light side (near such as wavelength about 830nm's (about 12000K)) Intensity is the highest, by adding Cu further²⁺, it is seen that the absorption of light side becomes the strongest.Its result, as Shown in Fig. 4 (a), in visible region (such as wavelength 500nm), there is excessive absorbability, cause fluorophosphoric acid glass Glass transmitance in visible region declines.

On the contrary, if O^2-/P⁵⁺Ratio is low, then as shown in Fig. 2 (b), it is seen that the intensity at peak, light side is the lowest, by entering one Step adds Cu²⁺, transmitance when can make wavelength 1200nm (about 8300K) is 10%, and result can make visible ray side Absorption will not become the strongest.Its result, as shown in Fig. 4 (b), the transmitance of fluophosphate glass makes fluophosphate glass exist Having the absorbability of appropriateness in visible region, fluophosphate glass transmitance in visible region can maintain relatively High value.

By above result, and wholwe-hearted effort based on the present inventor, finally give following opinion: can making When absorbing the fluophosphate glass of near infrared light, O^2-/P⁵⁺Than producing impact to having absorption to visible ray.

The present inventor is not only somebody's turn to do [opinion 1], is additionally based upon this [opinion 1] and conducts in-depth research, and result is further Obtain above-mentioned [opinion 2].Hereinafter, [opinion 2] is described in detail.

Fig. 5 is that the raw material O/P representing the raw material moment in fluophosphate glass is than the transmitance after manufacturing with fluophosphate glass The chart of relation.Now, for each raw material F ratio, it is shown that a series of each plotting.It should be noted that Making melt temperature is 1000 DEG C.

It addition, in Fig. 5, for the plotting of each raw material F ratio, change thickness of glass, make the intensity at peak, visible ray side Equal, but (such as with Cu in addition to " raw material F ratio ", " thickness of glass ", " raw material O/P ratio "²⁺For represent Other composition), it is all same.

In Figure 5, it is known that when raw material F ratio is 0.04 and 0.08, as proved [opinion 1], peak, visible ray side is made Intensity when being constant in each plotting, along with raw material O/P ratio uprises, O^2-/ P⁵⁺Uprise than also, cause red therefrom The intensity at peak, outer smooth side declines (i.e. transmitance rising).Specifically, because adding and making the intensity at peak, visible ray side exist Each chart is constant restriction, if so raw material O/P is than high (i.e. O^2-/ P⁵⁺Ratio is high), then strong because of peak, visible ray side Spend the highest and cause adding a small amount of Cu²⁺.Its result causes the intensity at peak, infrared light side to decline, thoroughly Rate of crossing rises.

On the other hand, it is known that when raw material F ratio is 0.11 and 0.15, even if coming at feed stage change raw material O/P ratio Coordinating, when being ultimately formed into glass, transmitance is almost without difference.That is, if based on [opinion 1], then may be used Even if know feed stage change raw material O/P ratio coordinate, each plotting (such as raw material F than be 0.15 time In chart, raw material O/P is than point and the point of 3.09 being 3.05) between, the difference of composition when ultimately forming glass is little (i.e., Formed and there is almost identical O^2-/ P⁵⁺The glass of ratio).

In order to review its reason, the present inventor has carried out additional experiment further.Specifically, raw material in Figure 5 In the case of F ratio is 0.5, the situation (respectively 900 DEG C and 1000C) that melt temperature is different is tested. Figure as its result is shown in Fig. 6.

Observation Fig. 6 understands, and by making melt temperature rise, described tendency is the most obvious.I.e., it is known that melt by making Melt temperature to rise and promote reaction, even if thus coordinating at feed stage feed change O/P ratio, finally When forming glass, transmitance is identical, and then is nearly constant O^2-/ P⁵⁺Ratio.

Based on Fig. 5 and Fig. 6, the present inventor is studied for the reason of this phenomenon.Results presumption, this phenomenon Rise because of POF₃Volatilize thus cause glass composition to there occurs change compared with feed stage.Just because of this, thus it is speculated that if Raw material F ratio is high, then promote POF₃Volatilization, finally close to constant O^2-/ P⁵⁺Than (about 3.3).It addition, enter The supposition that row is same, by making melt temperature rise, promotes POF₃Volatilization, finally close to constant O^2-/ P⁵⁺ Ratio.That is, O^2-/P⁵⁺Than being affected because of raw material F ratio (or melt temperature).In other words, in product glass O^2-/P⁵⁺Than being controlled by raw material F ratio (or melt temperature).

Above idea is summarized, thus has obtained above-mentioned [opinion 2].

By this [opinion 2] being studied from diverse viewpoint, [opinion 3] can be obtained.That is, for [seeing Solve 2] in finally close to constant O^2-/ P⁵⁺Ratio (about 3.3) this situation, it can be envisaged that even if to fluophosphate glass It is O eventually^2-/ P⁵⁺Composition (pyrophosphoric acid structure) than=3.5, for fluophosphate glass O^2-/ P⁵⁺Ratio=3.3 such compositions (three Polyphosphoric acid structure) also it is a rock-steady structure as the interstage, optical characteristics etc. is difficult to because of the variation of manufacturing condition Change.[opinion 3] can be obtained by this imagination.

Based on so obtained [opinion 1]～[opinion 3], in order to obtain because of containing Cu²⁺And near infrared light can be absorbed but The most do not absorb the such fluophosphate glass of visible ray, present inventor has performed following research.

Can moderately contain Cu²⁺By O^2-/ P⁵⁺The impact of ratio.This O^2-/ P⁵⁺Than by raw material F ratio or melted temperature The impact of degree.This impact is caused by the volatilization of material present in feed stage.I.e., it is believed that if by raw material F ratio is set as originally will not producing the relatively low degree of volatilization, prevents O or P from departing from from raw material, then can eliminate Described impact, can make the fluophosphate glass after manufacture really have the Cu that can put into suitable amount²⁺O^2-/ P⁵⁺ Ratio.It should be noted that by doing so it is possible, volatilization will not substantially be produced, therefore raw material F than with manufacture after F in glass^-Ratio is substantially the same.Further, raw material O/P than with manufacture after glass in O^2-/ P⁵⁺Ratio Also it is substantially the same.

It should be noted that for F^-For Bi, although make O^2-/ P⁵⁺Ratio is higher than conventional, and has sufficient weatherability, But reduce F compared with patent documentation 2～6^-Ratio, this idea is and general knowledge phase to those skilled in the art Anti-idea.The most like that, by improving O^2-/ P⁵⁺Ratio, the key of O and P in P-O-P chain is by F Cutting off, strength of glass declines, it is possible to make weatherability deteriorate.It addition, other metal in glass and pyrophosphoric acid Structure is bonded, it is also possible to form crystallization.Therefore to prevent these situations, improve the F in glass^-Ratio is general knowledge.

But, the present inventor is not necessarily limited by such general knowledge, has carried out reducing the F in raw material F ratio and glass^- The trial of ratio.Further, the present inventor is to F^-Ratio and O^2-/ P⁵⁺Ratio is studied, so that along with F^-The decline of ratio, O^2-/ P⁵⁺Than higher than conventional and be suitable value, and appropriate Cu can be added²⁺.As concrete numerical example, Based on [opinion 3], establish O^2-/ P⁵⁺Ratio is that the numerical value near 3.3 is (in other words, with 3.3 or close to 3.3 Value centered by value one fixed width in the range of numerical value) target, and to compared with the past, by raw material F than with And F^-The method of the value less than being set as is studied.

It should be noted that for melt temperature and relative to its raw material F ratio and F^-Ratio and waving relative to them The degree of sending out, the present inventor furthers investigate.

O is made it should be noted that really record in above-mentioned patent documentation 12^2-/ P⁵⁺Ratio is more than 3.4, F^-Than being More than 0.05.But, in patent documentation 12, not about above-mentioned [opinion 1]～the disclosure of [opinion 3] or dark Show, also not to add Cu further²⁺Time visible region in light absorpting ability and near infrared light region In the record that absorbability is problem of light.In witness whereof, in the embodiment of patent documentation 12, near-infrared The reduction of the transmitance (λ 50=615nm) in light region (1200nm) rests on about 23%.

The mode of the present invention completed based on above opinion and result of study is as follows.

1st mode of the present invention is a kind of fluophosphate glass, and it is because of containing Cu²⁺And near infrared light can be absorbed Fluophosphate glass, it is characterised in that the O in described fluophosphate glass^2-Content is relative to P⁵⁺The mol ratio of content (O^2-/P⁵⁺) it is 3.2 F less than 3.4, in described fluophosphate glass^-Content is relative to O^2-And F^-Total content Mol ratio (F^-/(O^2-+F^-)) it is more than 0.05 and less than 0.25.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

2nd mode of the present invention is the mode described in the 1st mode, it is characterised in that dilute in described fluophosphate glass Great soil group ion concentration relative to the ratio of the content of whole cation constituents be more than 0.5 cation % and 2.0 sun from Sub-below %.

3rd mode of the present invention is the mode described in the 1st or the 2nd mode, it is characterised in that at fluophosphate glass In spectrophotometric transmittance, the thickness of the transmitance for demonstrating 50% in wavelength 615nm, its wavelength 1200nm Transmitance less than 15%.

4th mode of the present invention is a kind of near-infrared absorption filter, it is characterised in that this near-infrared absorption mistake Filter employs the fluophosphate glass described in either type of 1 to the 3rd.

The manufacture method that 5th mode is a kind of fluophosphate glass of the present invention, it is by adjusting frit Close, described frit is melted, thus manufactures because of containing Cu²⁺And the fluorophosphoric acid of near infrared light can be absorbed The method of glass, it is characterised in that

The composition of described fluophosphate glass is set as the O in described fluophosphate glass^2-Content is relative to P⁵⁺Content Mol ratio (O^2-/P⁵⁺) it is 3.2 less than the F in 3.4 and described fluophosphate glass^-Content is relative to O^2-With F^-The mol ratio (F of total content^-/(O^2-+F^-)) it is more than 0.05 and less than 0.25, based on the described composition set to glass Glass raw material is concocted, and thus produces glass.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

6th mode of the present invention is the mode described in the 5th mode, it is characterised in that

Described frit at least contains fluorine, oxygen, phosphorus,

It is more than 3.2 and little according to the content of oxygen contained in described frit relative to the mol ratio of the content of phosphorus Described frit is concocted and according to the Oil repellent in described frit relative to oxygen by the mode in 3.4 With the mode that the mol ratio of the total content of fluorine is more than 0.05 and less than 0.25, described frit is concocted, by This produces glass.

7th mode of the present invention is the mode described in the 5th or the 6th mode, it is characterised in that make described fluorophosphoric acid glass Terres rares ion concentration in glass relative to the ratio of the content of whole cation constituents be more than 0.5 cation % and Below 2.0 cationes %, make melt temperature be 1000 DEG C with foretell.

8th mode of the present invention is the mode described in the 5th to the 7th either type, it is characterised in that at fluorophosphoric acid glass In the spectrophotometric transmittance of glass, the thickness of the transmitance for demonstrating 50% in wavelength 615nm, its wavelength 1200nm Transmitance less than 15%.

Invention effect

According to the present invention it is possible to provide a kind of fluophosphate glass and manufacture method thereof and near-infrared absorption filter, Even if this fluophosphate glass the most also has following O^2-/P⁵⁺Ratio, and possess weatherability, described O^2-/P⁵⁺Ratio It is according to can add the Cu of amount of degree that absorbable near infrared light suppresses the absorption of visible ray simultaneously²⁺Mode and Set.

Accompanying drawing explanation

Fig. 1 is for O^2-/P⁵⁺Than the product glass of=3.5 (comparative examples 1), carry out the transmitance of 500nm～1500nm The chart during mensuration of spectrum, in this chart, is transformed to wave number (K i.e. cm by transverse axis^-1), the longitudinal axis be transformed to absorbance (arbitrary unit)。

In Fig. 2, (a) is at O^2-/P⁵⁺Than high situation (i.e. O^2-/P⁵⁺Ratio=3.5 (comparative examples 1)) chart in, by red Outer peak, smooth side and the chart of peak, visible ray side isolated.B () is at O^2-/P⁵⁺Than low situation (i.e. O^2-/ P⁵⁺Ratio =3.18 (reference examples 1)) chart in, by peak, infrared light side and the chart of peak, visible ray side isolated.

In Fig. 3, (a) is the chart relative to Fig. 2 (a), according to saturating in 1200nm (about 8300K) of product glass The rate of mistake be 10% mode make absorption spectrum be multiplied by the chart that coefficient obtains, herein, be equivalent to make the big of respective spectrum Little be 1.22 times, thickness be 1.22 times.B () is the chart relative to Fig. 2 (b), according to product glass at 1200nm (about Transmitance in 8300K) be 10% mode make absorption spectrum be multiplied by the chart that coefficient obtains, be equivalent to herein To make the size of respective spectrum be 1.4 times, thickness is 1.4 times.

In Fig. 4, (a) is that the chart of Fig. 3 (a) is transformed to transverse axis: wavelength (nm), the longitudinal axis: figure during transmitance (%) Table.B () is that the chart of Fig. 3 (b) is transformed to transverse axis: wavelength (nm), the longitudinal axis: chart during transmitance (%)

Fig. 5 is to regulate the situation of the thickness of product glass according to the mode that the transmitance in wavelength 615nm is 50% Under, using the transmitance in wavelength 1200nm as the longitudinal axis, raw material O/P is used for transverse axis, to each raw material F ratio The chart carrying out marking and drawing and obtain.

Fig. 6 is to regulate the situation of the thickness of product glass according to the mode that the transmitance in wavelength 615nm is 50% Under, using the transmitance in wavelength 1200nm as the longitudinal axis, raw material O/P is used for transverse axis, to each melt temperature The chart carrying out marking and drawing and obtain.

Detailed description of the invention

Hereinafter, for embodiments of the present invention, illustrate in the following order.

1. the manufacture method of fluophosphate glass

2. fluophosphate glass

3. the effect produced by embodiment

4. other

<the 1. manufacture method of fluophosphate glass>

The fluophosphate glass of present embodiment is by blending frit, and is melted by described frit and be made to Arrive.Further, this fluophosphate glass is because of containing Cu²⁺And there is the ability absorbing near infrared light.

In the making of this fluophosphate glass, according to the O in described fluophosphate glass^2-Content is relative to P⁵⁺Rubbing of content You are than (that is, O^2-/P⁵⁺) it is 3.2 less than the F in 3.4 and described fluophosphate glass^-Content is relative to O^2- And F^-Mol ratio (that is, the F of total content^-/ (O^2-+F^-)) be more than 0.05 and less than 0.25 mode to product glass rank The composition of the described fluophosphate glass in Duan is set, and concocts frit based on set described composition.

As described in above-mentioned [opinion 1]～[opinion 3], in the present embodiment, it is possible to will not be substantially Produce volatile matter (POF₃).Owing to will not substantially produce volatile matter, it is possible to from the stage of blending frit The main reason for fluctuation making the composition in glass to the warp melted stage obtaining product glass disappears.Therefore, for Obtain the product glass with above-mentioned composition, as long as using the frit with same composition.

Therefore, in described frit, at least contain fluorine, oxygen, phosphorus, as long as the composition in the product glass stage is full The above-mentioned condition of foot, and meet following condition further.That is, as long as according to the oxygen contained in described frit Content relative to the mol ratio (O/P) (that is, raw material O/P than) of phosphorus content be 3.2 less than 3.4 mode adjust Close described frit and according to the Oil repellent F that contains in described frit relative to the total content of oxygen and fluorine Mol ratio (F^-/ (F+O)) (that is, raw material F than) be that the mode of more than 0.05 and less than 0.25 is to concoct described frit ?.

Herein, if O^2-/P⁵⁺Ratio and raw material O/P ratio are more than 3.2, it becomes possible to moderately cut by P-O-P chain in advance Disconnected, therefore, it is possible to fully suppress the generation of volatile matter when being melted by frit.It addition, can suppress by hydrone The cut-out of the P-O-P chain caused, therefore can make product glass possess sufficient weatherability.

Further, 3.2 these numerical value are the O obtained by [opinion 3]^2-/P⁵⁺The value of the vicinity of ratio=3.3 these numerical value, because of This will not substantially produce volatile matter, moreover, is also to have more stable tripolyphosphate structure as structure, Stability as product glass also increases.

Herein, if O^2-/ P⁵⁺Ratio and raw material O/P ratio are less than 3.4, then as described in [opinion 1], even if in order to There is desired near-infrared absorption ability and make product glass contain Cu²⁺, it is also possible to suppression visible absorption energy Power excessively plays.It addition, also now be able to suppression to add Cu²⁺Time color development.

On the other hand, if F^-Than being more than 0.05 with raw material F ratio, even if assuming O^2-/ P⁵⁺Ratio and raw material O/P ratio For the values so the biggest close to 3.4, it is possible to (or the tripolyphosphate knot so that an adequate amount of F is situated between and is between pyrophosphoric acid structure Between structure), the homogeneous structure after P-O-P chain is cut off can be maintained.It is as a result, it is possible to fully suppression is by P-O-P chain The crystallization being cut off and cause, and then product glass can be made to possess sufficient weatherability.

If it addition, F^-Than and raw material F ratio be less than 0.25, as described in [opinion 2], at least can be former by glass In the low temperature that material is melted, it is possible to produce volatile matter the most substantively.It addition, do not make the oxygen relative quantity mistake relative to fluorine Many, therefore as a result, it is possible to moderately maintain higher O^2-/ P⁵⁺Ratio and raw material O/P ratio, and then can suppress Substantially produce volatile matter.It is as a result, it is possible to obtain product glass from the stage of blending frit to through melted The main reason for fluctuation making the composition in glass till stage disappears, can be to the O in product glass^2-/ P⁵⁺Than carrying out Control to make it have desired near-infrared absorption ability.

Summarizing above content, the present invention is conceived to the tripolyphosphate structure more stable with formation from initially O^2-/ P⁵⁺The value more close than=3.3 ([opinions 3]), O^2-/ P⁵⁺Even if adding Cu than for appropriateness during this value²⁺Also will not excessively inhale Receive visible ray ([opinion 1]).Further, in order to make product glass have this value (O^2-/ P⁵⁺Than) and make raw material F ratio (and F^-Than) it is above-mentioned scope, from without substantially producing volatile matter, eliminate main component fluctuation reason ([opinion 2]).

As it has been described above, just because of there is [opinion 1]～[opinion 3], make O so could derive^2-/ P⁵⁺Ratio and raw material O/P Than being 3.2 less than 3.4, making F simultaneously^-Ratio and raw material F ratio are more than 0.05 and less than 0.25 such composition. That is, each numerical range itself is the most meaningful, in the present embodiment, only combines both numerical rangies Real value can have been given play to.That is, just because of make glass composition be accommodated in both numerical rangies simultaneously, can Obtain playing the fluophosphate glass of following multi-effect: can add in fluophosphate glass and " can absorb the reddest Outer light " Cu of the amount of " suppression color development ", the absorption of visible ray " suppression " degree simultaneously²⁺, " can be from frit Stage starts the O so set^2-/ P⁵⁺Ratio is controlled ", and " possessing weatherability ".

Though it should be noted that carried out detailed narration in 2. fluophosphate glass described later, but described fluorine can be made Terres rares ion concentration in phosphoric acid glass relative to the ratio of whole cation constituent content be 0.5 cation % with Go up and below 2.0 cationes %.Thus, it is possible to the temperature allowing to carry out melting declines, manufacturing process's letter can be made Change.In the case of making terres rares ion concentration be above-mentioned scope, can make melt temperature is less than 1000 DEG C, therefore Preferably in this temperature, frit is melted.

Hereinafter, unless otherwise specified, the content of cation constituent, total content represent with cation %；Anion The content of composition represents with anion % or only represents with %.

It should be noted that hereinbefore, the composition being had for product glass after frit and manufacture is carried out Narration, but the concrete operation of melted grade in the manufacture method of fluophosphate glass can use casting, conduit outflow, The method that roller, pressurization etc. were used in the past.As the concrete example of this operation, enumerated in 4. other project.

But, when using above-mentioned conventional method, it is preferably based on the described composition of setting to concoct frit, will row Go out gas also to enclose in closed system, described frit is melted such that it is able to produce described mol ratio will not be made Glass is produced in the case of raw substantial variation.If present embodiment, then just can the most not from beginning Produce volatile matter, but in order to eliminate component fluctuation reason as much as possible, the most preferably by can close discharge gas this In the hermetic container of sample, described frit is carried out melted cooling, thus manufactures product glass.

2. fluophosphate glass

As it has been described above, the fluophosphate glass obtained by said method manufacture has the group almost identical with the frit stage Become.As a result, the fluophosphate glass in present embodiment is because of containing Cu²⁺And there is the ability absorbing near infrared light, with O in Shi Suoshu fluophosphate glass^2-Content is relative to P⁵⁺Mol ratio (the O of content^2-/ P⁵⁺) be 3.2 less than 3.4, the F in described fluophosphate glass^-Content is relative to O^2-And F^-The mol ratio (F of total content^-/ (O^2-+F^-)) it is 0.05 Above and less than 0.25.

It addition, the fluophosphate glass of present embodiment is it is particularly preferred that in the spectrophotometric transmittance of fluophosphate glass, The thickness of the transmitance for showing 50% in the wavelength of 615nm, the transmitance of its wavelength 1200nm is less than 15%. It should be noted that should less than 15% this numerical value be by the fact that and derive: raw material F ratio in Figure 5 Being in the plotting of 0.08, when raw material O/P ratio is 3.4, transmitance is less than 15%.

The composition of frit or product glass meets above-mentioned condition, such that it is able to obtain having near infrared light region filling The absorbability divided and the absorbability in visible region are suppressed and make the fluophosphate glass of visible light-transmissive. Only contrast the transmitance (table 2) of the fluophosphate glass of the present embodiment described later and the transmitance of the table 1 of patent documentation 12, It is known that the transmitance that the present embodiment is near infrared light region drops to about half (i.e., it is possible to absorb close to 2 Near infrared light again).Obtain this result nothing more than being because being met the fluophosphate glass of above-mentioned condition, enter And the Cu of the amount of the degree absorbing the absorption that near infrared light suppresses visible ray simultaneously can be added²⁺。

It addition, the terres rares ion concentration in fluophosphate glass is excellent relative to the ratio of the content of whole cation constituents Elect below more than 0.5 cation % and 2.0 cationes % as.

If the content as the terres rares ion contained by cation constituent is described scope, then can moderately suppress The melting temperature of frit, liquidus temperature, the outflow temperature of melten glass and the rising of forming temperature.In this enforcement In mode, by making O^2-/ P⁵⁺Than and raw material O/P ratio be 3.2 (to make F further less than 3.4^-Ratio and raw material F Ratio is more than 0.05 and less than 0.25), can actually substantially suppress the generation of volatile matter, and guarantee product glass The weatherability of glass.But, in addition, suppression melting temperature, liquidus temperature, forming temperature rising can also be more The most substantially suppress the generation of volatile matter, and guarantee the weatherability of product glass.

It addition, in the case of the glass that liquidus temperature is high, it is desirable to reduce and flow out temperature or forming temperature, then when flowing out Or the viscosity of glass during molding can uprise, be difficult to isolate from melten glass fused glass block or melten glass drips, Or it is difficult to molding.

On the other hand, from improving folding in the case of will not making glass coloration, heat stability will not be made to decline to a great extent From the viewpoint of penetrating rate, in fluophosphate glass, import terres rares ion situation preferably import Y, La, Gd, Any one or more than a kind of Yb.

Because of this reason, the total content preferably making described terres rares ion is more than 0.5 cation % and 2.0 cationes % Below.In other words, preferably make to comprise Y³⁺、La³⁺、Gd³⁺And Yb³⁺Total content be 0.5 cation % with Go up and below 2.0 cationes %.Wherein, Y is maintaining heat stability, is improving the aspect excellent effect of refractive index simultaneously, The most preferably make to comprise Y³⁺Total content be below more than 0.5 cation % and 2.0 cationes %.

And then, as an example, following fluophosphate glass can be enumerated, the composition of described fluophosphate glass meet on Condition (the O stated^2-/ P⁵⁺Ratio and raw material O/P ratio and F^-Than and the numerical range of raw material F ratio), wherein, with sun from Sub-% represents the composition of the fluophosphate glass of present embodiment.

Can enumerate a kind of fluophosphate glass, it contains:

P⁵⁺3%～50%,

Al³⁺5%～40%,

Lⁱ⁺0%～30%,

Na⁺0%～20%,

K⁺0%～20%,

Mg²⁺0%～10%,

Ca²⁺0%～30%,

Sr²⁺0%～30%,

Ba²⁺0%～40%,

Wherein, Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Total amount be more than 10%, possibly together with:

Zn²⁺0%～20%,

In²⁺0%～20%,

Y³⁺0%～10%,

La³⁺0%～10%,

Gd³⁺0%～10%,

Yb³⁺0%～10%,

Cu²⁺0.5%～13%,

And represent with anion %, possibly together with:

F^-20%～95%

O^2-5%～80%.

Hereinafter, above-mentioned each composition is illustrated.

P⁵⁺It it is the important component played a role as network forming component in glass.It addition, be also to determine this reality Execute the O of the characteristic of mode^2-/ P⁵⁺One of key element of ratio.Substantially, if P²⁺Amount be accommodated in above-mentioned O^2-/ P⁵⁺ The scope of ratio, when enumerating numerical value as an example, if more than 3%, fluophosphate glass is stable. If it addition, less than 50%, the low dispersibility of necessity can be obtained.It is therefore preferable that make P⁵⁺Content be 3%～ The scope of 50%.

Al³⁺Fluophosphate glass is the important component for improving stability, if more than 5% then fluophosphate glass It is stable.If it addition, less than 40%, it can be ensured that the total amount of other composition, fluophosphate glass is the most steady Fixed.It is therefore preferable that make Al³⁺The scope that content is 5%～40%.

Such as Li⁺、Na⁺、K⁺Such alkali metal is to make the viscosity of glass, glass transition temperature decline, and makes The composition carried out easy to manufacture of glass.It is therefore preferable that make Li⁺Amount be 0%～30%, the amount of Na+ be 0%～20%, The amount of K+ is 0%～20%.In alkali metal, Li⁺The effect of raising stability big, the most more preferably import 0.5% Above Li+, further preferably imports the Li of more than 1%⁺, particularly preferably import the Li of more than 2%⁺。

Such as Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺Such alkaline-earth metal is the stability of raising glass, makes in refractive index The composition risen, by making its total amount be more than 10%, such that it is able to improve the effect for stability.Need explanation It is, Mg²⁺、Ca²⁺It it is the useful composition making the devitrification resistance of glass, durability, processability improve.Sr²⁺、Ba²⁺ It it is the useful composition making the devitrification resistance of glass, meltbility improve.

But, if specific alkaline-earth metal composition becomes too much, then the balance with other composition is destroyed, therefore Preferably uniformly import, preferably import Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺At least two more than composition.Each composition Preferred content be: Mg²⁺Be 0%～10%, Ca²⁺Be 0%～30%, Sr²⁺Be 0%～30%, Ba²⁺Be 0%～ 40%.

Zn²⁺、In³⁺There is in the same manner as alkaline-earth metal the characteristic can being easily guided in glass, by importing Zn²⁺ Or In³⁺So that glass ingredient is Multiple components, the raising effect of stability thus can be expected, but not superfluous Importing.Therefore, Zn²⁺And In³⁺Import volume be respectively preferably 0%～20%, the most do not import Zn²⁺With In³⁺。

Y³⁺、La³⁺、Gd³⁺、Yb³⁺It is to maintain the low dispersibility of glass, simultaneously raising refractive index Deng rare earth element Composition, but the importing of surplus can make melting temperature rise, the stability of glass declines.It is therefore preferable that make described each one-tenth The amount divided is respectively 0%～10%.

It should be noted that for present embodiment, frit adds Cu²⁺.By adding Cu²⁺, can To give near-infrared absorption characteristic to product glass.In the present embodiment, interpolation can fully absorb near infrared light The Cu of the amount of the degree of the light in region²⁺, and, the Cu added²⁺Amount be also will not taken in excess visible region The amount of the light in territory.As it has been described above, this addition is by O^2-/ P⁵⁺Ratio and raw material O/P and F^-Determine than with raw material F ratio Fixed.Wherein, when enumerating a numerical example, it is desirable to add the Cu of 0.5%～13% by the way of outer interpolation²⁺。

It should be noted that containing Cu²⁺Glass as the color school of the semiconductor camera elements such as CCD or CMOS Positive filter material is suitable.Cu²⁺As long as addition in view of the thickness of described filter, be suitably specified in institute In the range of stating.

It follows that anion component, anion additive are illustrated.In the fluophosphate glass of present embodiment, F^-And O^2-It it is Main Anions composition.Substantially, F^-And O^2-As long as amount be accommodated in above-mentioned F^-The scope of ratio, When enumerating an example of numerical value, from the viewpoint of realizing desired optical characteristics and excellent weatherability, preferably Import the F of 20%～95%^-, 5%～the O of 80%^2-。

It addition, by importing a small amount of Cl^-、Br^-、I^-, then fluophosphate glass is difficult to when glass manufacture or outflow Time the platinum product such as the platinum container that used or platinum nozzle invade profit.Therefore, it is possible to easily carry out the manufacture of glass.But, Cl^-、Br^-、I^-Superfluous importing can cause the refractive index variation and the generation of platina matter caused because composition volatilization, therefore Import volume preferably adds up to 0%～3%, more preferably 0.1%～3%.

It should be noted that the quality of the fluophosphate glass in order to improve present embodiment, it is desirable to make F^-、O^2-、Cl^-、 The total amount of Br-and I-is more than 98%, it more desirable to be more than 99%, it is further desired that be 100%.

It should be noted that in the present embodiment, B is not contained³⁺.Originally, B³⁺It it is the durability improving glass Composition, but it is melting frit when, has the tendency forming fluoride and volatilize.Therefore, this reality Execute in the fluophosphate glass of mode and do not contain B³⁺。

There is also some and B³⁺Same, the composition not preferably comprised in the fluophosphate glass of present embodiment.Tool For body, it is contemplated that the load to environment, preferably do not contain Pb, As, Cd, Cr, U, Th, T1 and ion thereof With any one of compound.It should be noted that the fluophosphate glass of present embodiment does not at least contain Pb and T1.

<effect 3. produced by embodiment>

Following effect is served by present embodiment.

I.e., it is possible to obtain playing the fluophosphate glass of following multi-effect: can add in fluophosphate glass and " absorb Near infrared light " Cu of the amount of " suppression color development ", the absorption of visible ray " suppression " degree simultaneously²⁺, " can be from glass Feed stage starts the O so set^2-/ P⁵⁺Ratio is controlled ", and " making it possess weatherability ".

It is as a result, it is possible to provide fluophosphate glass and manufacture method thereof, even if described fluophosphate glass the most also has There is following O^2-/ P⁵⁺Ratio, and possess weatherability, described O^2-/ P⁵⁺Ratio is according to adding absorbable near infrared light Suppress the Cu of the amount of the degree of the absorption of visible ray simultaneously²⁺Mode and set.

Further, by making Cu²⁺Glass ingredient amount ratio in addition, for constant, changes Cu simultaneously²⁺Content, permissible Have both " absorption of near infrared light " and " the absorption suppression of visible ray ".Therefore, by making Cu²⁺Glass in addition becomes Component ratio, for constant, adjusts Cu simultaneously²⁺Content, the thickness of filter can be adjusted.By increasing Cu²⁺ Content, the lower thickness of filter can be made；By reducing Cu²⁺Content, the thickness of filter can be made to become Thick.That is, according to the present invention it is possible to provide a kind of Cu²⁺Glass ingredient amount ratio in addition, and can be right for constant Answer the glass material of the filter of various thickness.

Use Cu²⁺Glass ingredient amount in addition is than identical and Cu²⁺The different glass of content manufacture the feelings of filter Under condition, glass composition is almost identical, even if the most not changing the condition of molding of glass, processing conditions also is able to carry out good Molding well, processing.

4. other

Hereinafter, the concrete example of the operation such as melted in the manufacture method of fluophosphate glass is described.Now, as One example, below for by meeting the frit of above-mentioned essential condition to manufacture showing of near-infrared absorption filter Example describes.

It addition, in addition to above-mentioned embodiment, be also carried out narration during for being suitable for [opinion 1]～[opinion 3].

(concrete example of the manufacture method of fluophosphate glass)

First, the frit meeting above-mentioned essential condition is weighed, after mixing, at thermostability crucible, such as platinum Or platinum alloy crucible is carried out heat, melt.It should be noted that in the present embodiment, will not be substantially Produce volatile matter, but assume to produce a small amount of volatile matter, expect to cover at crucible the heat-resisting lids such as platinum to suppress volatilization On.

Further, the glass of molten condition is stirred, clarifies, glass outflow nozzle make not bubbles and homogenizing Glass melts flow out, thus be shaped, described glass outflow nozzle is platinum system, platinum alloy system, gold system, gold Any one nozzle of alloy.

When glass flows out, because of Cl contained in glass melts^-、Br^-、I^-At least one above halogen composition and The glass melts flowed out by nozzle tip that can be inhibited is invaded profit from spray nozzle front end to nozzle outer peripheral face and (is moistened Ga れ The effect of phenomenon ゐ).It is as a result, it is possible to reduce, prevent following phenomenon: the glass melts invading profit goes bad, and It is mixed into after Bian Zhi in the melten glass of outflow, produces the shortcoming such as brush line or devitrification.

But, for near-infrared absorption filter, in order to constitute the compact shooting possessing semiconductor image sensor System, it is desirable to improve the function of shielding of near infrared light, keep the transmitance of higher visible ray simultaneously.From such sight Point sets out, it is preferred that for the glass of the thickness that outside transmitance is 50% in wavelength 615nm, it is extremely Less will not the light of substantially absorbing wavelength 500nm.It should be noted that " substantially " bag described herein Containing the light not absorbing all this wavelength, also comprising the light assuming to absorb this wavelength is also will not to produce in reality application The situation of the absorption of the level of problem.

Additionally, it is preferred that the outside transmitance in wavelength 400nm is more than 80%.About the absorption of near infrared light, Transmitance in wavelength 1200nm is preferably smaller than 15%.

Under the making such as of described near-infrared absorption filter.

First, in order to obtain described glass, the melten glass after clarifying, homogenize melts so that it is flow out from conduit, Flow in mold, be shaped to the big glass blocks that thickness of slab is thicker.Such as, prepare mold, will all with the constant rate of outflow Melten glass after matter is cast to this mold by the conduit of platinum alloy, and described mold is by the smooth and end of level Face, clip this bottom surface the most parallel to pair of sidewalls, the peristome of side that is positioned between pair of sidewalls is plugged Weir plate is constituted.The melten glass of casting is at mold internal diffusion, and is defined as certain width by pair of sidewalls, Thus it is shaped to plate glass.Plate glass after molding is drawn out of continuously by the peristome of mold.Herein, pass through The conditions of molding such as the suitable rate of outflow setting the shape of mold, size, melten glass, can be big and wall thickness with molding Glass blocks.

It should be noted that the melted of frit can enter under the atmosphere of the noble gases such as nitrogen or dry air OK, it is also possible to carry out under air.According to the present invention it is possible to carry out under conditions of not affected by glassmelting atmosphere The manufacture of the fluophosphate glass of high-quality, supply.

Glass blocks after molding is transferred to be heated in advance in the annealing furnace near glass transition temperature, gradually cools down To room temperature.For eliminating the glass blocks of deformation by gradually cooling down, implement high-precision section, grinding, grinding Processing, thus two sides must be arrived and carried out the glass plate of optical grinding.This glass plate can act as near-infrared absorption and filters Device but it also may described glass plate is carried out laminating to make near-infrared absorption filter.Two sides has all been carried out light The crystal of the tabular learning grinding fits in the one of the near-infrared absorption glass of the tabular that two sides has carried out optical grinding On face.Then, on a face of crystal, laminating can make visible light-transmissive two sides all carry out the tabular of optical grinding Optical glass, such as BK-7 (borosilicate optical glass).Near-infrared absorption is may be constructed by this structure Filter but it also may on a face of described slab glass, another sheet of fitting can make visible light-transmissive and two Face has all carried out the optical glass (such as BK-7) of the tabular of optical grinding.As required, on the surface of filter Form optical multilayer.

So far, it is illustrated in the case of for glass blocks being processed as glass plate but it also may by glass blocks is entered Row grinding, grinding make lens or are processed as other shape.

The near-infrared absorption glass of present embodiment is fluophosphate glass, and its glass transition temperature is low, therefore passes through After precise compression molding (mould molding) is shaped, it is not necessary to photosensitiveness functional surfaces is implemented the machining such as grinding or grinding Just can form the optical element such as lens, diffraction grating.Such as, with high accuracy by known to SiC, superhard material etc. mould The forming surface of molded section bar is processed as the shape inverted by the lens face of non-spherical lens, thus makes upper die and lower die, Use this upper and lower mould or known body mould as required or upper and lower mould guide member, to by the near-infrared of present embodiment The glass preform that light heat absorbing glass is constituted carries out heating, precise compression molding.So, can by forming surface critically It is transferred to glass, makes non-spherical lens.This non-spherical lens is also that the near-infrared absorption of present embodiment filters Device.So obtained non-spherical lens may be constructed semiconductor image sensor for subject is imaged in light Part or all of the optical system in face, it is possible to reduce the optics number of packages in camera head, and for saving sky Between change, cost degradation be also effective.

With high accuracy, the forming surface of compression molding section bar is processed as the shape inverted by diffraction grating, thus on making Mould, lower mold, and use the method as described method that glass preform is carried out precise compression molding, it is possible to Make the near-infrared absorption filter possessing diffraction grating.

The near-infrared absorption filter possessing diffraction grating can be as the light being incident to semiconductor image sensor Optical low-pass filter and function.Therefore, it can near-infrared absorption filter and optical low-pass filter system As an element, therefore can reduce the optics number of packages in camera head, can carry out simultaneously space saving, Cost degradation.

If it should be noted that making the forming surface of compression molding section bar is the lens face (lens of such as non-spherical lens Face) shape that inverts, and it is processed as the shape inverted by the ditch of diffraction grating, use the side as described method Method carries out precise compression molding, then can make and have both near-infrared absorption function, optical functions of low-pass filter Near-infrared absorption filter with lens function.

As required, the forming surface of compression molding section bar can form known antiadhesion barrier.In addition, accurate mould Molded each condition can be suitable for known condition, simultaneously can be according to the near-infrared absorption filter as target Concrete specification suitably determine.

Near-infrared absorption filter is made thus by precise compression molding, such that it is able to based on higher productivity Manufacture and be unsuitable for based on grinding, the element of the volume production of grinding, such as non-spherical lens, possess the optics of diffraction grating Low pass filter, the non-spherical lens etc. with diffraction grating of performance optical low-pass filter function.Need explanation It is as required, the surface of near-infrared absorption filter to form the optical multilayers such as antireflection film.

Near-infrared absorption filter according to present embodiment, it is seen that the transmitance of light is high, the absorption of near infrared light is big, Therefore the response colo(u)r relation correction of semiconductor camera element can be carried out well.And also it is high to make optics homogeneity Filter.

It addition, by the near-infrared absorption filter of present embodiment and semiconductor image sensor are combined and can It is applicable to camera head.It should be noted that in semiconductor image sensor, by quasiconductors such as CCD or CMOS Imaging apparatus is installed in packaging body, and utilizes transparent member to be covered by light accepting part.Can be with near-infrared absorption mistake Filter is held concurrently as transparent member, it is possible to so that transparent member is different parts from near-infrared absorption filter.

It should be noted that the camera head of above-mentioned present embodiment can also possess for being become by the picture of subject As optical elements such as the lens on the sensitive surface of semiconductor image sensor or prisms.

It addition, according to above-mentioned camera head, be equipped with optics homogeneity transmitance excellent, visibility region high, the reddest Outer smooth region absorb big near-infrared absorption filter, therefore can provide that response colo(u)r relation correction is good, can obtain The camera head of the image that image quality is excellent.

It should be noted that if present embodiment, even if being then the optics unit outside near-infrared absorption filter Part (lens etc.) also can make.In addition, in order to be applied to the product of various glass, Various deformation can also be carried out.

([opinion 1]～the Application Example of [opinion 3])

In the present embodiment, for because of containing Cu²⁺And the fluophosphate glass that can absorb near infrared light is chatted State.But, with Cu²⁺Near-infrared absorption composition in addition (Al or In that enumerated, Sn, W or it The compound etc. such as oxide) replace Cu²⁺, or add, even if the most also can fit simultaneously Use the present invention.That is, when adding certain near-infrared absorption composition, optical absorption peak can be divided into as [opinion 1] 2, if its optical absorption peak is because of O^2-/P⁵⁺Compare and be affected, then the probability that above-mentioned problem occurs is high.It addition, [opinion 2] or [opinion 3] is and O^2-/P⁵⁺Ratio and F^-The relevant content of ratio, even if therefore for adding Cu²⁺Composition in addition Situation, it is possible to applicable probability is the highest.For reflecting the mode of foregoing, remarks is in the end of description.

Even if it addition, O^2-/P⁵⁺Ratio and raw material O/P ratio and F^-It is slightly offset from this embodiment party than with raw material F ratio Numerical range described in formula, it is also possible to the effect above can be played.For reflect foregoing mode, remarks in The end of description.

[embodiment]

Then, it is shown that embodiment, the present invention is specifically described.The present invention is certainly not limited to below example.

<embodiment 1～44>

In order to obtain each glass composition of the embodiment 1～44 shown in table 2, to phosphate such as diphosphonic acid zinc and The such raw material of the fluorides such as sodium fluoride is concocted, and puts in platinum crucible, in embodiment 1～11,16～41 with The melt temperature of 1000 DEG C, in embodiment 12 with the melt temperature of 900 DEG C, in embodiment 42～44 with 950 DEG C melt temperature, be stirred utilizing 2～3 hours and raw material is heated, melt, clarify, all Matter, after obtaining the glass melts of homogenizing, casts glass melts, i.e. melten glass to mold, thus obtains phase When in 44 kinds of fluophosphate glasses of embodiment 1～44.It should be noted that in described operation, not because of big Amount produces volatile ingredient and is difficult to glass manufacture.It addition, in the inside of the glass obtained, do not confirm crystallization Precipitation or residual bubble, impurity, brush line.

<comparative example 1～2>

Relative to embodiment 1～44, in comparative example 1～2, make raw material O/P ratio (i.e. O in product glass^2-/ P⁵⁺ Than) it is the glass of the comparative example of more than 3.4.In addition composition is as shown in table 2, as concrete manufacturing process with Embodiment is identical.

<reference example 1～10>

It should be noted that for having the O outside the numerical range of present embodiment^2-/ P⁵⁺Compare but also be able at near-infrared Light region reduces the example of transmitance, illustrates with the form of reference example.

Specifically, as a reference example 1～7, make raw material O/P ratio (i.e. O in product glass^2-/ P⁵⁺Than) be less than The glass of 3.2.In addition composition is as shown in table 2, and to make melt temperature in reference example 1～5 be 1000 DEG C, Making melt temperature in reference example 6～7 is 900 DEG C, and concrete manufacturing process in addition is identical with embodiment.

It addition, as a reference example 8～10, make raw material F ratio (i.e. F in product glass^-Than) less than 0.05 glass. In addition composition and concrete manufacturing process are as shown in table 2.Composition outside this is as shown in table 2, and conduct Concrete manufacturing process is identical with embodiment.

<transmitance>

For embodiment 1～44, comparative example 1～2 and each glass of reference example 1～10, by wavelength 615nm The thickness that outside transmitance is 50%, outside transmitance in wavelength 1200nm based on this thickness is (for some Embodiment is also shown for the transmitance in wavelength 400nm, 500nm) it is shown in table 2.

As shown in table 2, in the glass of embodiment, it is seen that the transmitance in region is high, in embodiment and reference example, The function of shielding of near infrared light is excellent, and the chromatic aberration correction filter glass as semiconductor image sensor is suitable 's.

In the fluophosphate glass of present embodiment, Cu²⁺Containing ratio be preferably greater than 1.00%.If it addition, considering Embodiment 1～44, then Cu²⁺Containing ratio more preferably above 2.50%.On the other hand, from maintaining the thermally-stabilised of glass From the viewpoint of property, Cu²⁺Containing ratio be preferably less than 5%.

Hereinafter, remarks has other preferred mode.

[remarks 1]

A kind of fluophosphate glass, it is because of containing Cu²⁺And there is the fluorophosphoric acid glass of optical absorption peak near infrared light region Glass, it is characterised in that

Described peak energy enough separates freely into 2 peaks, Cu²⁺Will not color development, it is possible to substantially absorbing wavelength 1200nm Light and will not the light of substantially absorbing wavelength 500nm；

F in described fluophosphate glass^-Content is relative to O^2-And F^-The mol ratio (F of total content^-/ (O^2-+F^-)) value POF is not the most produced when scope is to manufacture described near-infrared absorption filter₃The value of degree as the upper limit.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

[remarks 2]

A kind of fluophosphate glass, it is because of containing Cu²⁺And the fluophosphate glass of near infrared light can be absorbed, its feature It is,

O in described fluophosphate glass^2-Content is relative to P⁵⁺Mol ratio (the O of content^2-/ P⁵⁺) O^2-/ P⁵⁺The scope of ratio POF will not be substantially produced during to manufacture described near-infrared absorption filter₃The O of degree^2-/ P⁵⁺Under being Limit, with Cu²⁺Will not color development, can put into substantially absorbing wavelength 1200nm light and will not be substantially The Cu of the amount of the degree of the light of absorbing wavelength 500nm²⁺O^2-/ P⁵⁺Ratio is the upper limit,

F in described fluophosphate glass^-Content is relative to O^2-And F^-The mol ratio (F of total content^-/ (O^2-+F^-)) value POF is not the most produced when scope is to manufacture described near-infrared absorption filter₃The value of degree as the upper limit.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

[remarks 3]

A kind of fluophosphate glass, it is because of containing Cu²⁺And the fluophosphate glass of near infrared light can be absorbed, its feature It is,

O in described fluophosphate glass^2-Content is relative to P⁵⁺Mol ratio (the O of content^2-/ P⁵⁺) be 3.05 less than 3.40,

F in described fluophosphate glass^-Content is relative to O^2-And F^-The mol ratio (F of total content^-/ (O^2-+F^-)) it is 0.03 Above and less than 0.19.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

[remarks 4]

A kind of fluophosphate glass, it is characterised in that described F^-The ratio of content is not to produce by P₂O₇ ^4-And the crystallization caused The value of degree be lower limit.

[remarks 5]

A kind of manufacture method of fluophosphate glass, it is by concocting frit, and to described frit Melt, thus manufacture because of containing Cu²⁺And the method that the fluophosphate glass of near infrared light can be absorbed, its feature Be, in described fluophosphate glass as O^2-Content is relative to P⁵⁺Mol ratio (the O of content^2-/P⁵⁺) O^2-/P⁵⁺Ratio Scope will manufacture described near-infrared absorption filter time will not substantially produce POF₃The O of degree^2-/P⁵⁺ It is used for lower limit, on the other hand, by Cu²⁺Will not color development, can put into substantially absorbing wavelength 1200nm light, Simultaneously will not the Cu of the substantially amount of the degree of the light of absorbing wavelength 500nm²⁺O^2-/P⁵⁺Ratio is set as the upper limit,

F in described fluophosphate glass^-Content is relative to O^2-And F^-The mol ratio (F of total content^-/ (O^2-+F^-)) value Scope will not the most produce POF when will manufacture described near-infrared absorption filter₃The value of degree be set as on Limit,

Based on the described composition set, frit is concocted, thus manufacture glass.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

[remarks 6]

A kind of manufacture method of fluophosphate glass, it is by concocting frit, and to described frit Melt, thus manufacture because of containing Cu²⁺And the method that the fluophosphate glass of near infrared light can be absorbed, its feature It is,

In described fluophosphate glass as O^2-Content is relative to P⁵⁺Mol ratio (the O of content^2-/ P⁵⁺) O^2-/P⁵⁺Ratio POF will not be substantially produced when scope is to manufacture described near-infrared absorption filter₃The O of degree^2-/P⁵⁺Than being Lower limit, with Cu²⁺Will not color development, can put into substantially absorbing wavelength 1200nm light, simultaneously will not be substantive The Cu of the amount of the degree of the light of ground absorbing wavelength 500nm²⁺O^2-/P⁵⁺Ratio is the upper limit,

Based on the described composition set, frit is concocted, and discharge gas is enclosed in enclosed system, will Described frit melts, thus produces glass in the case of described mol ratio will not be made to produce substantial variation.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

[remarks 7]

A kind of fluophosphate glass, it is because absorbing the fluorophosphoric acid glass of near infrared light containing near-infrared absorption composition Glass, it is characterised in that in described fluophosphate glass as O^2-Content is relative to P⁵⁺Mol ratio (the O of content^2-/P⁵⁺) O^2-/P⁵⁺POF will not be substantially produced when the scope of ratio is to manufacture described fluophosphate glass₃The O of degree^2-/P⁵⁺ Than be lower limit, on the other hand, with near-infrared absorption composition will not color development, substantially absorbing wavelength can be put into The light of 1200nm, simultaneously will not the Cu of the substantially amount of the degree of the light of absorbing wavelength 500nm²⁺O^2-/P⁵⁺ Ratio is the upper limit,

F in described fluophosphate glass^-Content is relative to O^2-And F^-The mol ratio (F of total content^-/ (O^2-+F^-)) value POF is not the most produced when scope is to manufacture described near-infrared absorption filter₃The value of degree be the upper limit.

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and T1 and ion thereof and Its compound.

Claims (8)

1. a fluophosphate glass, it is because of containing Cu²⁺And the fluophosphate glass of near infrared light can be absorbed, it is special Levy and be,

O in described fluophosphate glass^2-Content is relative to P⁵⁺Mol ratio (the O of content^2-/P⁵⁺) be 3.2 less than 3.4,

F in described fluophosphate glass^-Content is relative to O^2-And F^-The mol ratio (F of total content^-/(O^2-+F^-)) it is 0.05 Above and less than 0.1533,

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and Tl and ion thereof and Its compound,

Al in described fluophosphate glass³⁺Content relative to the ratio of the total of the content of whole cation constituents is 5～40 cationes %, Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Adding up to of content become relative to described whole cation The ratio of the total of the content divided is more than 10%.

2. fluophosphate glass as claimed in claim 1, it is characterised in that the terres rares in described fluophosphate glass Ion concentration is more than 0.5 cation % and 2.0 cationes % relative to the ratio of the content of whole cation constituents Below.

3. fluophosphate glass as claimed in claim 1 or 2, it is characterised in that saturating in the light splitting of fluophosphate glass Crossing in rate, the thickness of the transmitance for demonstrating 50% in wavelength 615nm, its wavelength 1200nm passes through Rate is less than 15%.

4. a near-infrared absorption filter, it is characterised in that this near-infrared absorption filter employs right Require the fluophosphate glass described in 1～3 any one.

5. a manufacture method for fluophosphate glass, it is because of containing Cu²⁺And the fluorophosphoric acid of near infrared light can be absorbed The manufacture method of glass, described fluophosphate glass is by concocting frit, and enters described frit Row is melted and manufactures, and described manufacture method is characterised by,

The composition of described fluophosphate glass is set as the O in described fluophosphate glass^2-Content is relative to P⁵⁺Content Mol ratio (O^2-/P⁵⁺) it is 3.2 less than the F in 3.4 and described fluophosphate glass^-Content is relative to O^2-With F^-The mol ratio (F of total content^-/(O^2-+F^-)) it is more than 0.05 and less than 0.1533, right based on the described composition set Frit is concocted, and thus produces glass,

Wherein, described fluophosphate glass does not contains B³⁺, Pb and ion thereof and compound and Tl and ion thereof and Its compound,

Al in described fluophosphate glass³⁺Content relative to the ratio of the total of the content of whole cation constituents is 5～40 cationes %, Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺Adding up to of content become relative to described whole cation The ratio of the total of the content divided is more than 10%.

6. the manufacture method of fluophosphate glass as claimed in claim 5, it is characterised in that

Described frit at least contains fluorine, oxygen, phosphorus,

It is more than 3.2 and little according to the content of oxygen contained in described frit relative to the mol ratio of the content of phosphorus Described frit is concocted by the mode in 3.4, and according to the Oil repellent in described frit relative to oxygen With the mode that the mol ratio of the total content of fluorine is more than 0.05 and less than 0.1533, described frit is concocted, Thus produce glass.

7. the manufacture method of the fluophosphate glass as described in claim 5 or 6, it is characterised in that make described fluorine phosphorus Terres rares ion concentration in acid glass relative to the ratio of the content of whole cation constituents be 0.5 cation % with Go up and below 2.0 cationes %, making melt temperature is less than 1000 DEG C.

8. the manufacture method of the fluophosphate glass as described in any one of claim 5 or 6, it is characterised in that at fluorine In the spectrophotometric transmittance of phosphoric acid glass, the thickness of the transmitance for demonstrating 50% in wavelength 615nm, its ripple The transmitance of long 1200nm is less than 15%.