Glass having a colored layer and method for producing the same

Abstract

To provide a glass having a colored layer and a method for manufacturing the glass.SOLUTION: A glass contains at least one glass component selected from the group consisting of ions of Ti, Nb, W, and Bi, and has a colored layer of any shape.SELECTED DRAWING: Figure 10

Description

[Technical field]

[0001] The present invention relates to glass having a colored layer. [Background technology]

[0002] Patent Document 1 discloses an invention in which the transmittance of glass is changed by heat treating the glass in an oxidizing atmosphere or a non-oxidizing atmosphere, but does not disclose the formation of a colored layer on glass.

[0003] Patent Document 2 discloses a transparent substrate having a light-transmitting portion that transmits light and a light-shielding portion that is formed to surround the outer periphery of the light-transmitting portion and blocks a part of the light. This transparent substrate is suitable for, for example, a cover glass that is attached to the front of a package that houses a solid-state imaging element, and is used as a light-transmitting window while protecting the solid-state imaging element. The light-shielding portion functions to suppress flare and ghosts caused by stray light. An example is disclosed in which a film of a metal material such as Cr (chromium), Ta (tantalum), Mo (molybdenum), Ni (nickel), Ti (titanium), Cu (copper), or Al (aluminum), a resin material in which a black pigment such as carbon is dispersed, or a resin material in which multiple colored layers having light transparency are laminated, is formed on the surface of the transparent substrate to form a light-shielding portion, but there is no disclosure of coloring the glass itself to impart light-shielding properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2002-201041 A [Patent Document 2] JP 2015-179788 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide glass having a colored layer and a method for producing the same. [Means for solving the problem]

[0006] The gist of the present invention is as follows. (1) Contains one or more glass components selected from the group consisting of Ti ions, Nb ions, W ions, and Bi ions; Glass having a colored layer of any shape.

[0007] (2) It is plate-shaped, The glass according to (1), having a colored layer on one or both sides.

[0008] (3) It is plate-shaped, A colored layer is provided on the first and second main surfaces, The glass according to (1), wherein, in a plan view, the colored layer on the first principal surface does not overlap with the colored layer on the second principal surface.

[0009] (4) It is plate-shaped, A colored layer is provided on the first and second main surfaces, The glass according to (1), wherein, in a plan view, a part or all of the colored layer on the first principal surface overlaps with a part or all of the colored layer on the second principal surface.

[0010] (5) An optical element made of the glass according to any one of (1) to (4) above.

[0011] (6) Having a light-shielding portion and a light-transmitting portion, the light-shielding portion and the light-transmitting portion have the same glass composition; The light-shielding portion is made of a colored layer. A cover glass made of the glass according to any one of (1) to (4).

[0012] (7) forming a metal film of any shape on the glass surface; and Heat treatment in a reducing atmosphere. A method for producing glass having a colored layer of any shape, comprising one or more glass components selected from the group consisting of Ti ions, Nb ions, W ions, and Bi ions. Effect of the Invention

[0013] According to the present invention, it is possible to provide glass having a colored layer and a method for producing the same. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention. [Diagram 2] FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention. [Diagram 3] FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention. [Figure 4] FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention. [Diagram 5] FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention. [Figure 6] FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention. [Figure 7] 1 is a graph showing the transmittance of a portion of a glass sample in Example 1-1 having a colored layer. [Figure 8] 1 is a graph showing the transmittance of a portion of a glass sample in Example 1-2 having a colored layer. [Figure 9] 1 is a graph showing the transmittance of a portion of a glass sample having a colored layer in Example 1-3. [Figure 10] 1 is a graph showing the transmittance of a portion of a glass sample having a colored layer in Examples 1-4. [Figure 11] 1 is a graph showing the transmittance of a portion of a glass sample having a colored layer in Examples 1-5. [Figure 12] 1 is a graph showing the transmittance of a portion of a glass sample having a colored layer in Examples 1-6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In this embodiment, the glass according to the present invention will be described based on the content ratio of each component expressed in cation %. Therefore, hereinafter, unless otherwise specified, "%" for each content means "cation %".

[0016] The cationic % expression refers to the molar percentage when the total content of all cationic components is taken as 100%. The total content refers to the total content of multiple cationic components (including the case where the content is 0%). The cationic ratio refers to the ratio (ratio) of the content of each cationic component (including the total content of multiple cationic components) in the cationic % expression.

[0017] The content of the glass component can be quantified by known methods, such as inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), etc. In this specification and the present invention, the content of a component being 0% means that the component is substantially not contained, and it is acceptable for the component to be contained at an unavoidable impurity level.

[0018] In addition, in this specification, unless otherwise specified, the refractive index refers to the refractive index nd at the d line (wavelength 587.56 nm) of yellow helium.

[0019] Hereinafter, embodiments of the present invention will be described in detail.

[0020] The glass according to this embodiment has a colored layer of any shape. The colored layer is a portion in which the glass itself is colored, and is preferably present in a layer form from the glass surface toward the inside.

[0021] The colored layer is a portion having a low transmittance for light incident on the glass. Therefore, in the glass according to this embodiment, of the light incident on the glass, the light that enters the colored layer is absorbed partially or entirely, and the intensity of the transmitted light is attenuated compared to the light that does not enter the colored layer. In other words, the glass according to this embodiment can have portions with low transmittance and portions with high transmittance.

[0022] In the glass according to this embodiment, the colored layer can be removed by grinding or polishing. In the glass according to this embodiment, the transmittance of the glass after the colored layer is removed is greater than the transmittance before the colored layer is removed.

[0023] The glass according to the present embodiment has a colored layer of any shape. That is, the glass according to the present embodiment may have a colored layer on the entire surface of one or more surfaces of the glass, or may have a colored layer patterned into any shape. When patterning, the shape may be, for example, a pattern, a letter, a number, a figure, a design, an identification code, or a shape drawn with straight lines or curves. As shown in FIG. 1, a colored layer may be formed by freely patterning a pattern or design. FIG. 1 is a plan view of the glass according to the embodiment, in which the black part is the colored layer and the other part is a non-colored part. In the glass according to the present embodiment, the contrast between the colored layer and the non-colored part that is not colored is clear, and it is possible to form a colored layer patterned into any shape.

[0024] The glass according to the present embodiment may have a colored layer of any shape on the side surface and / or the main surface. That is, the glass according to the present embodiment may have a colored layer on the entire surface of the side surface, or may have a colored layer patterned into any shape. Similarly, the glass according to the present embodiment may have a colored layer on the entire surface of the main surface, or may have a colored layer patterned into any shape. The glass according to the present embodiment may have a colored layer of any shape on the side surface and the main surface. For example, as shown in FIG. 2, a colored layer can be formed on the entire side surface of the glass, and a colored layer patterned into any shape can be formed on the main surface. Such a glass can be used as a filter glass.

[0025] The glass according to the present embodiment is a plate-shaped glass, and may have a colored layer of any shape on one or both sides. The colored layer may be on the entire surface of one or both sides, or may have a colored layer patterned in any shape. The thickness of the glass is not particularly limited, but when a colored layer is formed on both sides of the glass, if the thickness of the glass is small, the colored layer formed on one side and the colored layer formed on the other side may overlap in the thickness direction. In this case, the colored layer may be formed so as to penetrate the glass in the thickness direction.

[0026] Furthermore, in the case of thin glass, the formation of the colored layer may cause deformation such as warping of the glass. The cause of this is not particularly limited, but it is thought to be due to some stress being generated in the glass by forming the colored layer. In the case where warping occurs when a colored layer is provided on only one side of the glass, the stress generated in the glass may be offset by providing a colored layer on both sides of the glass. The shape of the colored layer is not particularly limited. Warping and deformation caused by the colored layer are likely to occur when the glass is 1 mm thick or less.

[0027] The glass according to the present embodiment may be a plate-shaped glass having colored layers on the first and second main surfaces, in which the colored layer on the first main surface does not overlap the colored layer on the second main surface in a plan view. By providing the colored layers in this manner, warping and deformation of the glass caused by the formation of the colored layers can be reduced. For example, as shown in FIG. 3, warping and deformation of the glass may be reduced by providing the colored layers at different positions on the first and second main surfaces of the glass.

[0028] Alternatively, the glass according to the present embodiment may be a plate-shaped glass having colored layers on the first and second main surfaces, and in plan view, a part or all of the colored layer on the first main surface overlaps a part or all of the colored layer on the second main surface. Even with such glass, warping and deformation of the glass can be reduced. For example, as shown in FIG. 4, in a plate-shaped glass, colored layers of the same shape can be formed at the same positions in plan view on the first and second main surfaces of the glass. In this case, even if the degree of coloring is small in each of the colored layers formed on the first and second main surfaces, the colored layer on the first main surface and the colored layer on the second main surface appear to overlap in plan view, so that the colored layer appears to be dark. When the degree of coloring is small, the degree of warping and deformation is also small. And, when the degree of coloring does not need to be large, the heat treatment time in a reducing atmosphere described later can be shortened. When the heat treatment time in a reducing atmosphere is shortened, the transmittance of the non-colored portion other than the colored layer can be maintained high. As a result, the contrast between the colored layer and the non-colored portion can be made clearer in plan view.

[0029] The glass according to the present embodiment may be a plate-like glass having a non-colored central portion in a plan view and a colored layer provided so as to surround the non-colored portion. Such glass can be used as an optical element having the function of a cover glass.

[0030] A cover glass is an optical element disposed in front of a solid-state imaging element as disclosed in Patent Document 2, and is particularly attached to the front of a package that houses the solid-state imaging element, and is used as a light-transmitting window while protecting the solid-state imaging element. In recent years, imaging modules incorporating solid-state imaging elements such as CCDs and CMOSs ​​have been used in mobile phones, portable information terminal devices, and the like. Such imaging modules include a square-shaped package made of ceramic or resin that houses the solid-state imaging element, and a cover glass that is fixed to the periphery of the package with an ultraviolet-curing adhesive and seals the solid-state imaging element. However, when an optical component such as such a cover glass is disposed in front of the solid-state imaging element (i.e., in the optical path of light toward the solid-state imaging element), problems such as flare and ghosting occur due to light reflected by the side surface of the cover glass or the like being incident on the imaging surface of the solid-state imaging element.

[0031] For this reason, a configuration has been proposed in the past in which a light shielding plate is provided between the cover glass and the solid-state imaging element to block the optical path of light that causes ghosts and the like. For example, in Patent Document (JP Patent Publication 2006-141726), a black metal such as Cr (chromium) is vapor-deposited onto the cover glass, so that the light shielding plate is formed integrally with the cover glass. The so-called photolithography method is used as a method for vapor-depositing Cr onto the cover glass.

[0032] However, when forming a light shielding plate by etching in this way, the entire glass must be immersed in the etching solution for a relatively long time, which causes problems such as the etching solution scraping away not only the Cr but also the glass surface, resulting in roughening. When the glass surface becomes rough, the light traveling toward the solid-state imaging element is disturbed by the glass surface, resulting in problems such as a decrease in transmittance, the occurrence of flare, and a decrease in resolution.

[0033] In addition, a method of applying black ink to the surface of the cover glass to provide light blocking properties has also been used in the past. However, this method has the problem that light is reflected by the surface of the black ink at the boundary between the area where the black ink is applied and the area where the black ink is not applied, resulting in stray light. In addition, the ink degassing occurs when the temperature rises, causing the cover glass surface to become cloudy.

[0034] In the glass according to this embodiment, the colored layer has a light-shielding function. Therefore, when the glass according to this embodiment is used as a cover glass, the colored layer can suppress the occurrence of flare, ghost, and the like caused by light reflected on the side surface of the cover glass. In addition, since the colored layer is formed by heat treatment in a reducing atmosphere as described below, there is no problem of the glass surface becoming rough. Furthermore, since the colored layer has the same glass composition as the non-colored portion, there is no outgassing even when the temperature rises.

[0035] The glass according to this embodiment may be a plate-shaped glass having a non-colored central portion in a plan view, a colored layer surrounding the non-colored portion, and an edge portion of the glass being non-colored. The colored layer can be formed on one side or both sides. Such glass can also be used as an optical element having the function of a cover glass. When used as a cover glass, the colored layer can suppress the occurrence of flare, ghost, and the like caused by light reflected by the side surface of the cover glass. Specifically, a glass having a colored layer as shown in FIG. 4 can be mentioned.

[0036] The non-colored portion transmits light sufficiently compared to the colored layer. Therefore, it is possible to polymerize and harden a photocurable resin such as an ultraviolet-curable adhesive by transmitting light from the non-colored portion. That is, by making the portion using the photocurable resin a non-colored portion, adhesion by the photocurable resin becomes possible. When the edge of the glass is made a non-colored portion, light can be transmitted from this edge. Therefore, when such glass is used as a cover glass, light can be transmitted from the edge to fix the glass itself or other imaging elements with a photocurable resin or the like.

[0037] As described above, when the glass according to this embodiment is used as a cover glass, the colored layer can function as a light-shielding portion, and the non-colored portion can function as a light-transmitting portion (light-transmitting window). Here, in this embodiment, as described later, the glass surface in contact with the metal film is selectively colored by heat treatment in a reducing atmosphere, but the glass surface not in contact with the metal film (non-colored portion) may also be slightly colored. However, by shortening the heat treatment time in a reducing atmosphere, undesirable coloring in the non-colored portion can be reduced. For example, as shown in FIG. 4, in the case of forming a colored layer on the first and second main surfaces of a plate-shaped glass, the OD (optical density) of each of the colored layers on the first and second main surfaces is approximately halved by halving the heat treatment time, but by forming a colored layer on the first and second main surfaces of the glass in the same shape and at the same position in plan view, the sum of the OD of the colored layer on the first main surface and the OD of the colored layer on the second main surface can be set to the OD of the light-shielding portion. In addition, in the non-colored portion, by halving the heat treatment time in a reducing atmosphere, the coloring due to the heat treatment is halved and sufficiently reduced. As a result, the colored layer can ensure sufficient light-shielding properties as a light-shielding portion, and the non-colored portion can ensure sufficient light-transmitting properties as a light-transmitting portion. Note that, as long as it is possible to achieve both the light-transmitting properties of the non-colored portion and the light-shielding properties of the colored layer, the colored layer on the first principal surface and the colored layer on the second principal surface do not need to have exactly the same shape, and the positions of the two colored layers in a plan view do not need to be exactly the same.

[0038] The glass according to the present embodiment is a plate-shaped glass, and may have a colored layer of any shape on the side surface. The glass according to the present embodiment may have a colored layer on the entire side surface, or may have a colored layer patterned in any shape. The colored layer has a light-shielding function. Therefore, when the glass according to the present embodiment is used as a cover glass, stray light from the side surface of a lead frame or the like around the solid-state imaging element can be suppressed by providing a colored layer of any shape on the side surface.

[0039] As described above, the glass according to the present embodiment is a plate-shaped glass having colored layers on the first and second main surfaces, and when used as a cover glass, stray light from the front of the cover glass can be prevented. Furthermore, the glass according to the present embodiment may be a plate-shaped glass having colored layers of any shape on the first and second main surfaces and side surfaces. By using such glass as a cover glass, stray light generated on the front and side surfaces can be suppressed.

[0040] In the glass according to this embodiment, when the glass is in a plate shape, the thickness of the glass is not particularly limited, but may be 1 mm or less, 0.7 mm or less, or 0.5 mm or less. The glass according to this embodiment is in a plate shape having a thickness in the above range, and by appropriately arranging the colored layer as described above, it can be used as an optical element having the function of a cover glass.

[0041] The glass according to this embodiment may have a through hole and a colored layer of any shape on the inner periphery of the through hole. For example, as shown in FIG. 5, the glass may be a tube-shaped glass having a colored layer formed on the inner periphery of the through hole. There is no particular limitation on the position or length of the through hole. For example, in a plate-shaped glass, a through hole may be provided at any position, and a colored layer of any shape may be formed on the inner periphery of the through hole. In addition, a colored layer may or may not be formed in a portion other than the inner periphery of the through hole.

[0042] The glass according to this embodiment may have a recess and a colored layer of any shape on the inner wall surface of the recess. For example, in one or more recesses, the entire inner wall surface of the recess may have a colored layer, or the inner wall surface may have a colored layer patterned in any shape. There are no particular limitations on the shape, position, and size of the recess. For example, as shown in FIG. 6, a colored layer may be provided on the inner wall surfaces of a plurality of recesses.

[0043] The glass according to this embodiment has a convex portion, and the convex portion may have a colored layer of any shape. For example, one or more convex portions may have a colored layer on the entire surface, or the convex portion may have a colored layer patterned in any shape. There is no particular limitation on the shape, position, and size of the convex portion.

[0044] The glass according to this embodiment can be used as an optical element. From the viewpoint of use as an optical element, the glass according to this embodiment is preferably optical glass. However, the glass according to this embodiment can be used as an ornament or the exterior of a small electronic device by utilizing the decorativeness of the colored layer, so it is not limited to optical glass.

[0045] In the glass according to this embodiment, the colored layer and the non-colored portion have the same glass component composition, however, the valence of the glass components (cations) may differ between the colored layer and the non-colored portion.

[0046] The color of the colored layer is preferably a reduction color caused by a glass component, more preferably a reduction color caused by a transition metal. Examples of the transition metal include Ti, Nb, W, and Bi. Therefore, the glass according to this embodiment contains one or more glass components selected from the group consisting of Ti ions, Nb ions, W ions, and Bi ions, and preferably contains Bi ions.

[0047] Conventionally, in order to impart light-shielding properties to glass, coloring components such as CuO, CoO, and V2O5 were included as glass components according to the wavelength range of light to be absorbed (for example, International Publication No. 2015 / 125565). Therefore, it is necessary to adjust the glass components to be included depending on the wavelength range of light to be absorbed. For example, in order to use it as a light-shielding part of a cover glass, it was necessary to include various coloring components. On the other hand, the light-transmitting part of the cover glass is required to have sufficient light-transmitting properties in a wide wavelength range such as the visible range to the infrared range. As a result, it was necessary to greatly change the composition of the glass used as the light-shielding part and the glass used as the light-transmitting part. In general, the chemical and physical properties of glass depend greatly on the glass composition. In other words, if the glass composition is different, the properties such as the expansion coefficient of the glass will differ. Therefore, when attempting to join glasses with different compositions by a method such as fusion, there are problems such as distortion and deformation caused by residual stress, and a decrease in the strength of the joined glass. In addition, when integrating the glass by fusion, it is necessary to flow and deform the glass to join it, which requires a process of processing the glass into an appropriate shape. Furthermore, since the glass is flowed and deformed, it is difficult to control the shape of the glass to be joined with high precision.

[0048] In contrast, in this embodiment, since the colored layer can be formed on a part of the glass, the glass composition is the same in the colored layer and the non-colored portion, and the colored layer and the non-colored portion can be combined in one glass without bonding. In addition, in this embodiment, the colored layer has sufficient light-shielding properties, and the non-colored portion has sufficient light-transmitting properties. Furthermore, in this embodiment, the colored layer can be formed in any shape, and the contrast between the colored layer and the non-colored portion is clear, so the shape of the colored layer can be controlled with high precision. And, in the glass according to this embodiment, the refractive index is almost the same in the colored layer and the non-colored portion, so when used as a cover glass, the interface reflection between the colored layer and the non-colored portion can be suppressed, and stray light can be effectively suppressed.

[0049] Therefore, the glass according to this embodiment can be used as a cover glass having a light-shielding portion and a light-transmitting portion, the light-shielding portion and the light-transmitting portion having the same glass composition. In this case, the light-shielding portion is made of a colored layer, and the light-transmitting portion is a non-colored portion. The light-shielding portion can be of any shape. By making the light-shielding portion and the light-transmitting portion have the same composition, the refractive indexes of the light-shielding portion and the light-transmitting portion can be made almost the same, so that the interface reflection between the light-shielding portion and the light-transmitting portion can be suppressed, and stray light can be effectively suppressed.

[0050] (Thickness of colored layer) The thickness of the colored layer is not particularly limited, but is preferably 1 to 300 μm, more preferably 20 to 200 μm, and further preferably 30 to 150 μm.

[0051] (OD) In the glass according to this embodiment, the spectral transmittance of the colored layer in the wavelength range from the visible range (400 nm to 760 nm) to the infrared range increases as the wavelength increases. On the other hand, the OD of the colored layer decreases as the wavelength increases. OD is optical density, and is expressed as a negative value of the common logarithm of the ratio of the incident light intensity I0 to the transmitted light intensity I, as shown in the following formula. OD=-log 10 (I / I o )

[0052] When the glass according to the present embodiment is composed of a colored layer and a non-colored portion having a large visible transmittance, the OD of the colored layer is large while the OD of the non-colored portion is small. In measuring the OD, when the measurement light passes through both the colored layer and the non-colored portion, the OD of the non-colored portion is sufficiently small, so that the OD of the colored layer becomes dominant.

[0053] In the glass according to this embodiment, the OD at a wavelength of 1100 nm of the portion having the colored layer is preferably 0.3 or more, more preferably 0.4 or more, 0.5 or more, 0.7 or more, 1.0 or more, and 1.5 or more in that order. On the other hand, the OD at a wavelength of 1100 nm of the non-colored portion is preferably 0.15 or less, more preferably 0.1 or less.

[0054] Usually, the sensitivity range of optical sensors such as CCD and CMOS sensors extends from the visible range to around 1100 nm. By providing a colored layer having an OD in the above range, a glass capable of blocking light over the entire sensitivity range of the optical sensor can be obtained. Therefore, the glass according to this embodiment is preferably one capable of controlling the transmittance of light rays in the wavelength range from the visible range to 1100 nm.

[0055] In addition, when a glass has two opposing surfaces and a colored layer of the same thickness and the same degree of coloring is provided on both surfaces, the OD is approximately twice as large as when the same colored layer is provided on only one surface.

[0056] In the glass according to this embodiment, the OD decreases with increasing wavelength in the visible to near infrared wavelength range, so that in the portion having the colored layer, the OD at a wavelength of 780 nm is greater than the OD at a wavelength of 1100 nm.

[0057] Therefore, if there is a wavelength range that needs to be blocked, the glass is designed so that the OD is high at the longer wavelength side of that wavelength range. When designing glass that blocks only visible light, it is sufficient to set the OD high at the longer wavelength side of the visible light range (e.g., 780 nm). When designing glass that blocks light from the visible range to the near-infrared range, it is sufficient to set the OD high at a wavelength in the near-infrared range (e.g., 1100 nm). The OD can be controlled by adjusting the thickness of the colored layer and the degree of coloring.

[0058] In the glass according to this embodiment, the non-colored portion preferably has a high transmittance for light having a wavelength range from the visible region to the infrared region, and more preferably has a high transmittance for light having a wavelength range from the visible region to 1100 nm. In particular, the transmittance of the non-colored portion at a thickness of 1 mm for light having a wavelength of 400 to 800 nm is preferably 50% or more, more preferably 60% or more, 70% or more, 75% or more, 77% or more, and 80% or more in this order. In addition, the λ70 of the non-colored portion is preferably 550 nm or less, and more preferably 500 nm or less, 480 nm or less, 460 nm or less, and 450 nm or less in this order. In addition, λ70 is the wavelength at which the external transmittance is 70% when the spectral transmittance is measured for a glass sample having a thickness of 10.0 mm ± 0.1 mm.

[0059] (Refractive Index) In the glass according to this embodiment, the refractive index nd is preferably 1.70 or more, more preferably 1.73 or more, 1.75 or more, 1.76 or more, 1.77 or more, 1.78 or more, 1.79 or more, and 1.80 or more in that order. The upper limit of the refractive index nd is not particularly limited, but is usually 2.5, and preferably 2.3.

[0060] (Glass composition) Non-limiting examples of the composition of the glass according to this embodiment are shown below.

[0061] The glass according to the present embodiment is preferably a phosphate glass. Phosphate glass is a glass that contains mainly P as a network forming component. 5+ This refers to glass that contains P as a network forming component of glass. 5+ , B 3+ , Si 4+ , Al 3+ Here, the term "containing mainly phosphate as a glass network forming component" means that P 5+ The content of B 3+ , Si 4+ , Al 3+ The content of the phosphate glass can increase the degree of coloring in the colored layer.

[0062] In the glass according to this embodiment, P 5+ The lower limit of the content of P is preferably 10%, and more preferably 13%, 15%, 17%, and 20% in that order. 5+ The upper limit of the content is preferably 50%, and more preferably 45%, 40%, 38%, 35%, 33%, and 30%, in that order.

[0063] P 5+ is a glass network forming component. 5+ If it contains too much, the melting property will deteriorate. 5+ The content is preferably within the above range.

[0064] In the glass according to this embodiment, B 3+ The upper limit of the content of is preferably 30%, more preferably 25%, 20%, 15%, 13%, and 10%, in that order. 3+ The lower limit of the content of is preferably 0.1%, more preferably 0.5%, 1%, 3%, and 5% in that order. 3+ The content may be 0%.

[0065] B 3+ is a glass network forming component and has the function of improving the melting property of glass. 3+ If the content of B is too high, the chemical durability tends to decrease. 3+ The content is preferably within the above range.

[0066] In the glass according to this embodiment, P 5+ B content 3+ The cationic ratio of the content [B 3+ / P 5+ The upper limit of the cation ratio [B 3+ / P 5+ ] may be 0.

[0067] In the glass according to this embodiment, Si4+ The upper limit of the content of Si is preferably 10%, and more preferably 7%, 5%, 3%, 2%, and 1% in that order. 4+ The lower limit of the Si content is preferably 0.1%, and more preferably 0.2%, 0.3%, 0.4%, and 0.5%, in that order. 4+ The content may be 0%.

[0068] S 4+ is a glass network forming component, and has the function of improving the thermal stability, chemical durability, and weather resistance of glass. 4+ If the content of Si is too high, the melting property of the glass decreases and the glass raw material tends to remain unmelted. 4+ The content is preferably within the above range.

[0069] In the glass according to this embodiment, Al 3+ The upper limit of the Al content is preferably 10%, and more preferably 7%, 5%, 3%, and 1% in that order. 3+ The content may be 0%.

[0070] Al 3+ It has the function of improving the chemical durability and weather resistance of glass. 3+ If the content of Al is too high, the thermal stability of the glass decreases, the glass transition temperature Tg increases, and the melting property tends to decrease. 3+ The content is preferably within the above range.

[0071] In the glass according to this embodiment, P 5+ , B 3+ , Si 4+ and Al 3+ The total content of [P 5+ +B 3+ +Si 4+ +Al 3+ The lower limit of the total content [P 5+ +B 3+ +Si 4+ +Al3+ The upper limit of is preferably 60%, and more preferably 50%, 45%, 40%, 37%, and 35%, in that order.

[0072] The glass according to this embodiment preferably contains a transition metal as a glass component, more preferably contains at least one glass component selected from the group consisting of Ti ions, Nb ions, Bi ions and W ions, and further preferably contains Bi ions.

[0073] In the glass according to this embodiment, the lower limit of the Ti ion content is preferably 1%, more preferably 2% and 3% in that order. The upper limit of the Ti ion content is preferably 45%, more preferably 40%, 35%, 30%, 25%, 20%, 15%, and 12% in that order. Here, the Ti ion is Ti 4+ , Ti 3+ In addition, all Ti ions with different valences are included.

[0074] Ti ions, like Nb ions, W ions and Bi ions, contribute greatly to increasing the refractive index and also have the function of increasing the coloring of glass. On the other hand, if the content of Ti ions is too high, the melting property of glass decreases and the glass raw material tends to remain unmelted. Therefore, it is preferable that the content of Ti ions is within the above range.

[0075] In the glass according to this embodiment, the lower limit of the Nb ion content is preferably 1%, more preferably 5%, 10%, and 15% in that order. The upper limit of the Nb ion content is preferably 45%, more preferably 40%, 35%, 30%, 25%, 23%, and 20% in that order. Nb ions are Nb 5+ In addition, it includes all Nb ions with different valences.

[0076] Nb ions are a component that contributes to a high refractive index and increases the coloring of glass. They also have the function of improving the thermal stability and chemical durability of glass. On the other hand, if the content of Nb ions is too high, the thermal stability of glass tends to decrease. Therefore, it is preferable that the content of Nb ions is within the above range.

[0077] In the glass according to this embodiment, the upper limit of the W ion content is preferably 30%, more preferably 25%, 20%, 15%, and 13% in that order. The lower limit of the W ion content is preferably 0.5%, more preferably 1%, 2%, and 3% in that order. W ions are 6+ In addition, it includes all W ions with different valences.

[0078] W ions contribute to a high refractive index and also have the effect of increasing the coloring of the glass, so the content of W ions is preferably within the above range.

[0079] In the glass according to this embodiment, the upper limit of the content of Bi ions is preferably 40%, more preferably 35%, 30%, 28%, and 25% in that order. The lower limit of the content of Bi ions is preferably 0.5%, more preferably 1%, 2%, and 2.5% in that order. Bi ions are 3+ In addition, all Bi ions with different valences are included.

[0080] Bi ions contribute to a high refractive index and also have the effect of increasing the coloring of the glass, so the content of Bi ions is preferably within the above range.

[0081] In the glass according to this embodiment, the lower limit of the total content of Ti, Nb and W ions [Ti+Nb+W] is preferably 1%, more preferably 5%, 10%, 15%, 20% and 23% in that order. The upper limit of the total content [Ti+Nb+W] is preferably 60%, more preferably 55%, 50%, 45%, 40%, 38% and 35% in that order.

[0082] In the glass according to this embodiment, the upper limit of the total content of Ti, Nb, W and Bi ions [Ti+Nb+W+Bi] is preferably 80%, more preferably 75%, 70%, 68% and 65% in that order. The lower limit of the total content [Ti+Nb+W+Bi] is preferably 1%, more preferably 5%, 10%, 15%, 20%, 23% and 25% in that order.

[0083] In the glass according to this embodiment, P 5+ , B 3+ and Si 4+ The cation ratio of the total content of Ti ions, Nb ions, W ions and Bi ions to the total content of [(Ti + Nb + W + Bi) / (P 5+ +B 3+ +Si 4+ The lower limit of the cation ratio [(Ti+Nb+W+Bi) / (P 5+ +B 3+ +Si 4+ The upper limit of )] is preferably 4.0, and more preferably 3.5, 3.0, 2.7, and 2.5 in that order.

[0084] In the glass according to this embodiment, Ta 5+ The upper limit of the Ta content is preferably 5%, and more preferably 3%, 2%, and 1% in that order. 5+ The content may be 0%.

[0085] Ta 5+ has the function of improving the thermal stability of the glass. 5+ If the content of Ta is too high, the refractive index of the glass tends to be low and the melting property tends to be deteriorated. 5+ The content is preferably within the above range.

[0086] In the glass according to this embodiment, Li +The upper limit of the content of Li is preferably 35%, and more preferably 30%, 27%, 25%, 23%, and 20% in that order. + The lower limit of the content of Li is preferably 1%, and more preferably 2%, 3%, 5%, and 8% in that order. + The content may be 0%.

[0087] In the glass according to this embodiment, Na + The upper limit of the content of Na is preferably 40%, and more preferably 35%, 30%, 25%, 20%, and 18% in that order. + The lower limit of the Na content is preferably 0.5%, and more preferably 1%, 1.5%, 3%, and 5% in that order. + The content may be 0%.

[0088] Glass is Li + or Na + The inclusion of Li makes it easier to chemically strengthen the glass. + or Na + If the content of Li is too high, the thermal stability of the glass may decrease. + and Na + The content of each of the above is preferably within the above range.

[0089] In the glass according to this embodiment, Li + and Na + The total content of [Li + +Na + The upper limit of the total content [Li + +Na + The lower limit of is preferably 1%, and more preferably 5%, 10%, 15%, and 20% in that order.

[0090] In the glass according to this embodiment, K + The upper limit of the content of K is preferably 20%, and more preferably 15%, 13%, 10%, 8%, 5%, and 3% in that order. +The lower limit of the content of K is preferably 0.1%, more preferably 0.5%, 1.0%, and 1.2% in that order. + The content may be 0%.

[0091] K + has the function of improving the thermal stability of glass. + If the content is too high, the thermal stability tends to decrease. + The content is preferably within the above range.

[0092] In the glass according to this embodiment, Rb + The upper limit of the content of Rb is preferably 5%, more preferably 3%, 1%, and 0.5%, in that order. + The content may be 0%.

[0093] In the glass according to this embodiment, Cs + The upper limit of the Cs content is preferably 5%, more preferably 3%, 1%, and 0.5%, in that order. + The content may be 0%.

[0094] Rb + and Cs + On the other hand, if the content of these elements is too high, the refractive index nd decreases and the volatilization of glass components during melting may increase. + and Cs + The content of each of the above is preferably within the above range.

[0095] In the glass according to this embodiment, Mg 2+ The upper limit of the Mg content is preferably 15%, more preferably 10%, 5%, 3%, and 1% in that order. 2+ The content may be 0%.

[0096] In the glass according to this embodiment, Ca 2+The upper limit of the Ca content is preferably 15%, and more preferably 10%, 5%, 3%, and 1% in that order. 2+ The content may be 0%.

[0097] In the glass according to this embodiment, Sr 2+ The upper limit of the Sr content is preferably 15%, more preferably 10%, 5%, 3%, and 1% in that order. 2+ The content may be 0%.

[0098] In the glass according to this embodiment, Ba 2+ The upper limit of the Ba content is preferably 25%, and more preferably 20%, 18%, 15%, 10%, and 5% in that order. 2+ The content may be 0%.

[0099] Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ Each of these glass components functions to improve the thermal stability and meltability of the glass. On the other hand, if the content of these glass components is too high, the high refractive index may be lost and the thermal stability of the glass may be reduced. Therefore, it is preferable that the content of each of these glass components is within the above-mentioned range.

[0100] In the glass according to this embodiment, Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ The total content of [Mg 2+ +Ca 2+ +Sr 2+ +Ba 2+ The upper limit of is preferably 30%, and more preferably 25%, 20%, 18%, 15%, 10%, and 5%, in that order.

[0101] In the glass according to this embodiment, Zn 2+ The upper limit of the content of Zn is preferably 15%, and more preferably 10%, 8%, 5%, 3%, and 1% in that order. 2+The lower limit of the content of Zn is preferably 0.1%, more preferably 0.3%, and even more preferably 0.5%. 2+ The content may be 0%.

[0102] Zinc 2+ It has the function of improving the thermal stability of glass. On the other hand, Zn 2+ If the content is too high, the melting property may deteriorate. 2+ The content is preferably within the above range.

[0103] In the glass according to this embodiment, Zr 4+ The upper limit of the content of Zr is preferably 5%, more preferably 3%, 2%, and 1% in that order. 4+ The content may be 0%.

[0104] Zr 4+ has the function of improving the thermal stability of glass. 4+ If the content of Zr is too high, the thermal stability and meltability of the glass tend to decrease. 4+ The content is preferably within the above range.

[0105] In the glass according to this embodiment, Ga 3+ The upper limit of the Ga content is preferably 3%, more preferably 2% and further more preferably 1%. 3+ The lower limit of the content of Ga is preferably 0%. 3+ The content may be 0%.

[0106] In the glass according to this embodiment, In 3+ The upper limit of the content of In is preferably 3%, more preferably 2% and further more preferably 1%. 3+ The lower limit of the content of In is preferably 0%. 3+ The content may be 0%.

[0107] In the glass according to this embodiment, Sc 3+The upper limit of the content of Sc is preferably 3%, more preferably 2% and further more preferably 1%. 3+ The lower limit of the content of Sc is preferably 0%. 3+ The content may be 0%.

[0108] In the glass according to this embodiment, Hf 4+ The upper limit of the content of Hf is preferably 3%, more preferably 2% and further more preferably 1%. 4+ The lower limit of the content of Hf is preferably 0%. 4+ The content may be 0%.

[0109] In the glass according to this embodiment, Lu 3+ The upper limit of the content of Lu is preferably 3%, more preferably 2% and further more preferably 1%. 3+ The lower limit of the content of Lu is preferably 0%. 3+ The content may be 0%.

[0110] In the glass according to this embodiment, Ge 4+ The upper limit of the content of Ge is preferably 3%, more preferably 2% and further more preferably 1%. 4+ The lower limit of the content is preferably 0%. 4+ The content may be 0%.

[0111] In the glass according to this embodiment, La 3+ The upper limit of the content of La is preferably 5%, more preferably 4% and further more preferably 3%. 3+ The lower limit of the content of La is preferably 0%. 3+ The content may be 0%.

[0112] In the glass according to this embodiment, Gd 3+ The upper limit of the content of Gd is preferably 5%, more preferably 4% and further more preferably 3%. 3+ The lower limit of the content of Gd is preferably 0%. 3+ The content may be 0%.

[0113] In the glass according to this embodiment, Y 3+ The upper limit of the content of Y is preferably 5%, more preferably 4%, and even more preferably 3%. 3+ The lower limit of the content of Y is preferably 0%. 3+ The content may be 0%.

[0114] In the glass according to this embodiment, Yb 3+ The upper limit of the content of Yb is preferably 3%, more preferably 2% and further more preferably 1%. 3+ The lower limit of the content of Yb is preferably 0%. 3+ The content may be 0%.

[0115] The cationic components of the glass according to this embodiment are mainly the components mentioned above, i.e., P 5+ , B 3+ , Si 4+ , Al 3+ , Ti ions, Nb ions, W ions, Bi ions, Ta 5+ , Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , B.A. 2+ , Zn 2+ , Zr 4+ , Ga 3+ , In 3+ , Sc 3+ , Hf 4+ , Lu 3+ , Ge 4+ , La 3+ , Gd 3+ , Y 3+ and Yb 3+ The total content of the above components is preferably greater than 95%, more preferably greater than 98%, even more preferably greater than 99%, and even more preferably greater than 99.5%.

[0116] The glass according to this embodiment contains F as an anion component. - and O 2- It may contain ingredients other than F. - and O 2- The other anion components are Cl - , Br - , I - However, Cl - , Br - , I - All of these components are prone to volatilization during glass melting. The volatilization of these components causes problems such as fluctuations in glass properties, a decrease in glass homogeneity, and increased wear on melting equipment. - The content of Br is preferably less than 5 anion %, more preferably less than 3 anion %, even more preferably less than 1 anion %, particularly preferably less than 0.5 anion %, and even more preferably less than 0.25 anion %. - and I - The total content is preferably less than 5 anion %, more preferably less than 3 anion %, even more preferably less than 1 anion %, particularly preferably less than 0.5 anion %, even more preferably less than 0.1 anion %, and even more preferably 0 anion %.

[0117] The "anion %" refers to a molar percentage when the total content of all anion components is taken as 100%.

[0118] The glass according to this embodiment is preferably composed basically of the above-mentioned components, but may contain other components as long as the effects of the present invention are not impaired.

[0119] For example, the glass according to this embodiment may further contain an appropriate amount of copper (Cu) as a glass component in order to impart near-infrared light absorption properties to the glass. In addition, V, Cr, Mn, Fe, Co, Ni, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Ce, etc. may be contained. These increase the coloring of the glass and can be a source of fluorescence.

[0120] Further, the present invention does not exclude the inclusion of unavoidable impurities.

[0121] <Other ingredient composition> Pb, As, Cd, Tl, Be, and Se are all toxic, and therefore the glass of the present embodiment preferably does not contain these elements as glass components.

[0122] U, Th, and Ra are all radioactive elements, and therefore the glass of the present embodiment preferably does not contain these elements as glass components.

[0123] Sb 3+ , Sn 4+ , and Ce 4+ is a glass component that functions as a fining agent and can be added as an optional component. 3+ is a fining agent with a great fining effect.

[0124] Sb 3+ The content of Sb is converted to Sb2O3 and expressed as a percentage by mass. 3+ , Sn 4+ , and Ce 4+ The content ratio of the cationic components other than Sb is converted to oxide in the same manner as Sb2O3, and Sb 3+ , Sn 4+ , and Ce 4+ The content of Sb2O3 is expressed in mass% when the total content ratio of all cationic components other than Sb2O3 is 100 mass%. The content of Sb2O3 is preferably less than 2 mass%, more preferably less than 1 mass%, even more preferably less than 0.5 mass%, and even more preferably less than 0.2 mass%, less than 0.1 mass%, or less than 0.05 mass%. By setting the content of Sb2O3 in the above range, the clarity of the glass can be improved.

[0125] Sn 4+ and Ce 4+ The content of each element is also expressed as an oxide equivalent. 3+ , Sn 4+ , and Ce4+ The content ratio of the cationic components other than Sb is converted to oxide. 3+ , Sn 4+ , and Ce 4+ The SnO2 content and CeO2 content are expressed in mass% when the total content ratio of all cationic components other than are 100 mass%. Each of the SnO2 and CeO2 contents is preferably less than 2 mass%, more preferably less than 1 mass%, further preferably less than 0.5 mass%, and even more preferably less than 0.1 mass%. Each of the SnO2 and CeO2 contents may be 0 mass%. By setting each of the SnO2 and CeO2 contents within the above ranges, the clarity of the glass can be improved.

[0126] (Glass manufacturing) The glass according to the present embodiment is obtained by preparing uncolored glass and forming a colored layer of any shape thereon. Uncolored glass may be produced according to a known glass production method. For example, a plurality of compounds are mixed together to prepare a batch raw material, and the batch raw material is placed in a melting vessel to melt, clarify, and homogenize the raw material, and then the molten glass is formed and slowly cooled to obtain glass. Alternatively, the batch raw material is placed in a melting vessel to perform rough melting. The molten material obtained by rough melting is quenched and crushed to produce cullet. The cullet is further placed in a melting vessel to be heated and remelted to prepare molten glass, which is further clarified and homogenized, and then the molten glass is formed and slowly cooled to obtain glass. A known method may be applied to the forming and slow cooling of the molten glass.

[0127] Furthermore, the glass manufacturing process according to this embodiment may include a step of increasing the water content in the glass melt. Examples of steps of increasing the water content in the glass melt include a step of adding water vapor to the melting atmosphere and a step of bubbling a gas containing water vapor into the melt. Of these, it is preferable to include a step of adding water vapor to the melting atmosphere. By including a step of increasing the water content in the glass melt, the βOH value of the glass can be increased. By increasing the βOH value, glass with higher transparency can be obtained.

[0128] (Formation of colored layer) In the glass according to this embodiment, the colored layer can be formed by a step of forming a metal film of any shape on the glass surface, and a step of performing a heat treatment in a reducing atmosphere.

[0129] The metal constituting the metal film is preferably a metal that absorbs hydrogen ions in the atmosphere and reduces the glass components contained in the glass by transferring hydrogen ions and electrons. Among the glass components, a metal that reduces transition metals is more preferable. Specifically, Ni, Au, Ag, Pt, Pd, and alloys containing the above metals such as Pt-Pd alloys can be mentioned.

[0130] The colored layer may be formed using a metal paste containing the metal constituting the metal film as described above. The method for forming the metal film on the glass surface is not particularly limited as long as the metal film can be adhered to the glass surface, and examples of the method include vapor deposition, sputtering, plating, screen printing, and coating.

[0131] The reducing atmosphere may contain a gas having reducing power. An example of the gas having reducing power is hydrogen. Therefore, it is preferable to use a hydrogen-containing gas as the reducing atmosphere, and a forming gas containing hydrogen may be used. The forming gas is a mixed gas consisting of hydrogen and nitrogen, and usually contains about 3 to 5 volume % of hydrogen.

[0132] The heat treatment is performed at a temperature 200° C. lower than the glass transition temperature (Tg-200) and lower than the softening point. The heat treatment time can be appropriately adjusted depending on the desired degree of coloring, the area of ​​the colored layer, the thickness of the colored layer, etc.

[0133] After the heat treatment, the metal film is peeled off from the glass surface by any method, including, but not limited to, polishing or dissolving in an acidic liquid.

[0134] By the heat treatment in a reducing atmosphere, a colored layer is formed from the surface of the glass in contact with the metal film to the interior thereof.

[0135] The mechanism by which the colored layer is formed by the above method is not particularly limited, but is thought to be as follows. The color of the colored layer formed in this embodiment is considered to be a reduction color caused by glass components, and in particular, a reduction color caused by transition metals. Usually, even if a glass molded body is heat-treated in an atmosphere containing hydrogen at a low concentration of about 3 to 5 volume %, the glass hardly exhibits a reduction color. However, since the above-mentioned metal film absorbs hydrogen ions in the atmosphere, the portion of the glass in contact with the metal film is supplied with more hydrogen ions than the portion not in contact with the metal film, and as a result, the reduction reaction proceeds faster. Therefore, the portion of the glass in contact with the metal film is colored deeply. The amount of hydrogen ions absorbed by the metal film is large, so much that the hydrogen concentration in the atmosphere is reduced due to the absorption by the metal film. For this reason, the reduction reaction does not proceed easily in the portion not in contact with the metal film.

[0136] The reduction reaction of the glass components that causes coloring proceeds in all directions from the part in contact with the metal film. That is, when observed from the cross section of the glass, the colored layer is formed in the thickness direction from the glass surface in contact with the metal film, and when observed from the surface of the glass, it is formed radially from the part in contact with the metal film.

[0137] According to the above method, a colored layer that is more deeply colored can be formed. Therefore, even if the thickness of the colored layer is small, the transmittance can be sufficiently reduced. When the thickness of the colored layer is small, the range of the colored layer formed radially from the part that was in contact with the metal film, observed from the surface of the glass, is also small. In other words, according to the present embodiment, by adjusting the forming conditions of the colored layer, a colored layer having approximately the same shape as the metal film can be formed when observed from the surface of the glass.

[0138] (Manufacturing of optical elements, etc.) The optical element made of the glass according to this embodiment is obtained by preparing an uncolored optical element and forming a colored layer of any shape thereon. The uncolored optical element may be produced according to a known production method. For example, molten glass is poured into a mold and molded into a plate shape to produce a glass material. The obtained glass material is appropriately cut, ground, and polished to produce cut pieces of a size and shape suitable for press molding. The cut pieces are heated and softened, and press molded (reheat pressed) by a known method to produce an optical element blank that is similar to the shape of the optical element. The optical element blank is annealed, and then ground and polished by a known method to produce an optical element.

[0139] A colored layer can be formed on the produced optical element by the above-mentioned method. Alternatively, a colored layer may be formed during the production of the optical element.

[0140] The optically functional surface of the prepared optical element may be coated with an anti-reflection film, a total reflection film, or the like depending on the intended use.

[0141] According to one aspect of the present invention, an optical element made of the above glass can be provided. Examples of the type of optical element include lenses such as spherical lenses and aspherical lenses, and prisms. Examples of the lens shape include biconvex lenses, plano-convex lenses, biconcave lenses, plano-concave lenses, convex meniscus lenses, and concave meniscus lenses. The optical element can be manufactured by a method including a process of processing a glass molded body made of the above glass. Examples of the processing include cutting, machining, rough grinding, fine grinding, polishing, and the like.

[0142] Another example of an optical element is an optical element for blocking light that is obliquely incident on the light receiving surface of an image sensor such as a CCD or CMOS sensor. Specifically, a cover glass that blocks obliquely incident light on the light receiving surface of the image sensor can be given.

[0143] According to one embodiment of the present invention, the decorative property of the colored layer can be utilized to make it possible to use the product as a decorative item, an exterior of a small electronic device, or the like. EXAMPLES

[0144] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0145] Glass samples having the glass compositions shown in Table 1 were prepared by the following procedure, and various evaluations were carried out.

[0146] [Table 1]

[0147] [Glass manufacturing] Oxides, hydroxides, metaphosphates, carbonates, and nitrates corresponding to the constituent components of glass were prepared as raw materials, and the raw materials were weighed and mixed so that the composition of the resulting glass would be each composition shown in Table 1, and the raw materials were thoroughly mixed. The resulting mixed raw materials (batch raw materials) were placed in a platinum crucible and heated at 1100 to 1450°C for 2 to 3 hours to make molten glass. The molten glass was stirred to homogenize it and clarify it, and then cast into a mold preheated to an appropriate temperature. The cast glass was heat treated for about 1 hour near the glass transition temperature Tg, and allowed to cool to room temperature in a furnace. The glass was processed to a size of 40 mm long, 60 mm wide, and 15 mm thick, and two faces measuring 40 mm x 60 mm were precision polished (optical polished) to obtain a glass sample.

[0148] [Confirmation of glass composition] The content of each glass component in the obtained glass sample was measured by inductively coupled plasma atomic emission spectrometry (ICP-AES), and it was confirmed that each composition was as shown in Table 1.

[0149] [Optical property measurements] The refractive index nd, specific gravity and glass transition temperature Tg of the obtained glass samples were measured, and the results are shown in Table 1.

[0150] (i) Refractive index nd The refractive index nd was measured by the refractive index measurement method of JIS B 7071-1.

[0151] (ii) Specific gravity The specific gravity was measured by the Archimedes method.

[0152] (iii) Glass transition temperature Tg The glass transition temperature Tg was measured using a thermomechanical analyzer (TMA4000S) manufactured by MAC Sciences at a heating rate of 4° C. / min.

[0153] <Example 1-1> Of the obtained glass samples, the glass sample having the glass composition No. 1 was processed to a size of 20 mm length, 20 mm width, and 1.0 mm thickness, and two faces measuring 20 mm x 20 mm were precision polished (optically polished). On one of the optically polished faces, a metal film (Pt-Pd film) of an arbitrary shape was formed by sputtering (sputtering current 15 mA, film formation time 900 sec).

[0154] The glass sample on which the metal film was formed was heat-treated at 400° C. for 5 hours while supplying forming gas (hydrogen 3 vol %, nitrogen 97 vol %) as a reducing atmosphere at a flow rate of 0.2 L / min. The metal film was peeled off by polishing to obtain a glass sample having a colored layer having substantially the same shape as the formed metal film in plan view.

[0155] [Transmittance measurement] The external transmittance was measured at wavelengths of 300 to 2500 nm. The external transmittance is defined as the percentage of the transmitted light intensity relative to the incident light intensity when light is incident in the thickness direction of the glass sample [transmitted light intensity / incident light intensity x 100]. The external transmittance also includes the reflection loss of light rays on the sample surface. The results are shown in Figure 7. In the figure, the dotted line indicates the transmittance of the part with the colored layer, and the solid line indicates the transmittance of the same part before the colored layer was formed (before heat treatment in a reducing atmosphere).

[0156] [OD measurement] For the portion having the colored layer, the incident light intensity I0 and the transmitted light intensity I at a wavelength of 1100 nm were measured, and the OD (optical density) was calculated using the following formula. For the same portion, the OD before the colored layer was formed (before heat treatment in a reducing atmosphere) was also calculated in the same manner. The results are shown in Table 2. OD=-log 10 (I / I0)

[0157] [Measurement of λ70] Before the colored layer was formed (before heat treatment in a reducing atmosphere), the sample was processed to have a thickness of 10 mm and parallel, optically polished flat surfaces, and the spectral transmittance was measured. The intensity of the light beam perpendicularly incident on one of the optically polished flat surfaces was taken as intensity A, and the intensity of the light beam emerging from the other flat surface was taken as intensity B, and the spectral transmittance B / A was calculated. The wavelength at which the spectral transmittance was 70% was taken as λ70. The spectral transmittance also includes the reflection loss of the light beam on the sample surface. The results are shown in Table 3.

[0158] <Example 1-2> A glass sample having a colored layer was obtained in the same manner as in Example 1-1, except that a glass sample having the glass composition of No. 2 was used. The transmittance was measured in the same manner as in Example 1-1, and the results are shown in FIG. The OD was measured in the same manner as in Example 1-1, and the results are shown in Table 2. The λ70 was measured in the same manner as in Example 1-1. The results are shown in Table 3.

[0159] <Example 1-3> A glass sample having a colored layer was obtained in the same manner as in Example 1-1, except that a glass sample having the glass composition of No. 3 was heat-treated at 430° C. for 9 hours. The transmittance was measured in the same manner as in Example 1-1, and the results are shown in FIG. The OD was measured in the same manner as in Example 1-1, and the results are shown in Table 2. The λ70 was measured in the same manner as in Example 1-1. The results are shown in Table 3.

[0160] <Example 1-4> A glass sample having a colored layer was obtained in the same manner as in Example 1-1, except that a glass sample having the glass composition of No. 4 was processed to a thickness of 0.4 mm and heat-treated at 410° C. for 5 hours. The transmittance was measured in the same manner as in Example 1-1. The transmittance of the non-colored portion (the portion where no colored layer was formed) after heat treatment in a reducing atmosphere was also measured. The results are shown in Figure 10. In the figure, the dashed line indicates the transmittance of the non-colored portion after heat treatment in a reducing atmosphere. The OD was measured in the same manner as in Example 1-1. In addition, the OD of the non-colored portion (the portion where no colored layer was formed) after the heat treatment in the reducing atmosphere was also measured. The results are shown in Table 2. The λ70 was measured in the same manner as in Example 1-1. In addition, the λ70 of the non-colored portion (the portion where no colored layer was formed) after the heat treatment in the reducing atmosphere was also measured. The results are shown in Table 3.

[0161] <Example 1-5> A glass sample having a colored layer was obtained in the same manner as in Example 1-1, except that a glass sample having the glass composition of No. 5 was heat-treated at 440° C. for 12 hours. The transmittance was measured in the same manner as in Example 1-1. The transmittance of the non-colored portion (the portion where no colored layer is formed) after heat treatment in a reducing atmosphere was also measured. The results are shown in FIG. 11. In the figure, the dashed line indicates the transmittance of the non-colored portion (the portion where no colored layer is formed) after heat treatment in a reducing atmosphere. The OD was measured in the same manner as in Example 1-1. In addition, the OD of the non-colored portion (the portion where no colored layer was formed) after the heat treatment in the reducing atmosphere was also measured. The results are shown in Table 2. The λ70 was measured in the same manner as in Example 1-1. In addition, the λ70 of the non-colored portion (the portion where no colored layer was formed) after the heat treatment in the reducing atmosphere was also measured. The results are shown in Table 3.

[0162] <Examples 1-6> A glass sample having a colored layer was obtained in the same manner as in Example 1-1, except that a Ni film was formed as a metal film on the glass sample having the glass composition of No. 3 and heat-treated at 430° C. for 9 hours. The transmittance was measured in the same manner as in Example 1-1. The transmittance of the non-colored portion (the portion where no colored layer is formed) after heat treatment in a reducing atmosphere was also measured. The results are shown in Figure 12. In the figure, the dashed line indicates the transmittance of the non-colored portion (the portion where no colored layer is formed) after heat treatment in a reducing atmosphere. The OD was measured in the same manner as in Example 1-1. In addition, the OD of the non-colored portion (the portion where no colored layer was formed) after the heat treatment in the reducing atmosphere was also measured. The results are shown in Table 2. The λ70 was measured in the same manner as in Example 1-1. In addition, the λ70 of the non-colored portion (the portion where no colored layer was formed) after the heat treatment in the reducing atmosphere was also measured. The results are shown in Table 3.

[0163] [Table 2]

[0164] [Table 3]

[0165] <Example 2-1> A glass sample having the composition of No. 3 in Table 1 was processed into a circle with a diameter of 30 mm and a thickness of 2.0 mm, and the two main surfaces were precision polished (optically polished). On one of the optically polished surfaces (main surface), a metal film (Ni film) patterned into an arbitrary shape was formed using a metal paste. In addition, a metal film (Ni film) was formed on the entire surface of the side of the same sample.

[0166] The sample on which the metal film was formed was heat-treated at 430° C. for 9 hours while supplying forming gas (hydrogen 3 volume %, nitrogen 97 volume %) as a reducing atmosphere at a flow rate of 0.2 L / min.

[0167] The metal film was removed to obtain a sample having colored layers on the main surface and side surfaces as shown in FIG.

[0168] <Example 2-2> A glass sample having the composition No. 3 in Table 1 was processed into a square shape with a length of 50 mm, a width of 50 mm, and a thickness of 1.0 mm, and two surfaces measuring 50 mm x 50 mm were precision polished (optically polished). A metal film (Pt-Pd film) patterned into an arbitrary shape was formed on one of the optically polished surfaces (first main surface) using a metal paste. In addition, a metal film (Pt-Pd film) was formed on the other optically polished surface (second main surface) of the same sample so as not to overlap with the metal film formed on the first main surface in a plan view.

[0169] The sample on which the metal film was formed was heat-treated at 430° C. for 9 hours while supplying forming gas (hydrogen 3 volume %, nitrogen 97 volume %) as a reducing atmosphere at a flow rate of 0.2 L / min.

[0170] The metal film was removed. As shown in Fig. 3, a sample having colored layers on the first and second principal surfaces was obtained. It was confirmed that the obtained sample can be suitably used as a cover glass for a CCD or CMOS sensor (solid-state image sensor) as disclosed in Patent Document 2.

[0171] <Example 2-3> A glass sample having the composition No. 3 in Table 1 was processed into a rectangular shape of 50 mm long, 50 mm wide, and 1.0 mm thick, and two surfaces of 50 mm x 50 mm were precisely polished (optically polished). A metal film (Pt-Pd film) patterned into an arbitrary shape was formed on one surface (first main surface) of the optically polished surface using a metal paste. In addition, a metal film (Pt-Pd film) was formed on the other optically polished surface (second main surface) of the same sample, in the same shape and at the same position in plan view as the metal film formed on the first main surface. Then, heat treatment was performed in a reducing atmosphere in the same manner as in Example 2-2, except that the heat treatment time was 4.5 hours.

[0172] The metal film was removed to obtain a sample having colored layers on both sides as shown in Figure 4. It was confirmed that the obtained sample, like the sample of Example 2-2, can be suitably used as a cover glass for an image sensor.

Claims

1. Contains one or more glass components selected from the group consisting of Ti ions, Nb ions, W ions, and Bi ions; The content of Bi ions is 0.5 cation % or more, P 5+ A glass having a content of 10 cation % or more, A colored layer and a non-colored portion of any shape are included, The colored layer and the non-colored portion have the same glass composition.

2. It is plate-shaped, 10. The glass of claim 1 having a tinted layer on one or both sides.

3. It is plate-shaped, A colored layer is provided on the first and second main surfaces, 2. The glass of claim 1, wherein, in a plan view, the colored layer on the first major surface does not overlap with the colored layer on the second major surface.

4. It is plate-shaped, A colored layer is provided on the first and second main surfaces, 2. The glass according to claim 1, wherein, in a plan view, a part or all of the colored layer on the first principal surface overlaps a part or all of the colored layer on the second principal surface.

5. 5. The glass according to claim 1, wherein the portion having the colored layer has an OD of 0.3 or more at a wavelength of 1,100 nm.

6. An optical element comprising the glass according to any one of claims 1 to 4.

7. The light-shielding portion and the light-transmitting portion are included. the light-shielding portion and the light-transmitting portion have the same glass composition; The light-shielding portion is made of a colored layer. A cover glass comprising the glass according to any one of claims 1 to 4.

8. forming a metal film of any shape on a glass surface, and heat-treating the glass in a reducing atmosphere to form a colored layer of any shape from the glass surface in contact with the metal film to the inside of the glass; The glass contains one or more glass components selected from the group consisting of Ti ions, Nb ions, W ions, and Bi ions, the content of Bi ions being 0.5 cation % or more, and P 5+ A method for producing glass having a colored layer of any shape, wherein the content of is 10 cation % or more.

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