JP4736465B2 - UV-infrared absorbing green glass - Google Patents

Description

  The present invention relates to an ultraviolet-infrared-absorbing green-based glass that has a relatively high transparency and infrared / ultraviolet shielding properties, thereby providing high functionality to a window glass and realizing a high living environment.

  Conventionally, from the viewpoint of energy saving represented by reduction of cooling load, there is a social demand for minimizing the influence of generation of radiant heat by infrared rays. This demand is in an increasing direction due to the growing awareness of global warming and environmental issues. This demand also affects the glass industry, and glass that reduces the transmission of infrared rays by developing light absorption and reflection functions on the glass itself or the glass surface has been developed. Commercialized as glass.

For example, in weight percent, 66-75% of _SiO 2, 12 to 20% of _Na 2 O, 7 to 12% of CaO, 0 to 5% of MgO, 0 to 4% of _Al 2 _O 3, 0 _~3 % K ₂ O, 0-1% Fe ₂ O ₃ , and CeO ₂ , TiO ₂ , V ₂ O ₅ or MoO ₃ in total 0-1.5% composition, at least 0.45 weight % of iron oxide, iron in the ferrous state or its 35% expressed as FeO, and a glass article having less than 0.02 wt% sulfur, expressed as SO _3, at least 65% of visible light An infrared absorbing type soda / lime / silica glass exhibiting a transmittance (400 to 770 nm) and an infrared transmittance (800 to 2100 nm) of 15% or less is known (for example, see Patent Document 1).

  On the other hand, there is a social demand for minimizing the adverse effects of ultraviolet rays, such as deterioration of organic materials typified by fading, and the increase in the incidence of skin cancer caused by exposure to ultraviolet rays. In order to satisfy such requirements, products that reduce ultraviolet light transmission by imparting ultraviolet absorption or reflection functions to the glass itself or the glass surface have been studied and commercialized. A typical example is ultraviolet absorbing glass.

For example, in _{wt%, SiO 2 65~75%, Al} 2 O 3 0.1~5, Na 2 O 10~18%, K 2 O 0~5%, CaO 5~15%, MgO 1~6% SO ₃ 0.05 to 1.0%, CeO ₂ converted Ce content 0.2 to 1.5%, TiO ₂ converted Ti content 0 to 1.0%, CoO 0.001 to 0.006%, Ultraviolet absorption having a composition consisting essentially of 0.3 to 1.6% Fe content in terms of Fe ₂ O ₃ and 5 to 18% by weight of Fe content in terms of Fe ₂ O ₃ being Fe ²⁺ Colored glass is known (see, for example, Patent Document 2).

  In this publication, the main wavelength measured with a C light source is 488 to 492 nm, the color purity is 3 to 4%, and the visible light transmittance is 70% with a thickness of 3 to 5 mm and measured with an A light source A. As described above, the UV transmittance specified in ISO is 15% or less, and if the CoO 2 content is less than 0.001%, the dominant wavelength becomes too long and the yellow tone is obtained. It is described that the wavelength becomes too short, and no blue glass can be obtained.

  The above social demands have changed to demands to reduce the occurrence of adverse effects of ultraviolet rays and infrared rays at the same time, and these demands tend to increase due to increasing awareness of global warming and environmental issues. . This demand prompted the development of so-called ultraviolet and infrared absorbing glass, which absorbs both ultraviolet and infrared rays, in addition to conventional infrared absorbing glass and ultraviolet absorbing glass.

For example, in terms of Fe ₂ O ₃ , 0.65 to 1.25 wt% Fe, 0.2 to 1.4 wt% CeO ₂ , or 0.1 to 1.36 wt% CeO ₂ and 0 0.02 to 0.85 wt% of TiO ₂ as a main component, and when having a thickness of 3 to 5 mm, the colorimetric light A visible light (wavelength 400 to 770 nm) has a transmittance of 70% or more, the whole sun Infrared ultraviolet absorbing soda in which the weight ratio of FeO to Fe ₂ O ₃ is determined so that the energy (wavelength 300 to 2130 nm) transmittance is 46% or less and the ultraviolet light (wavelength 300 to 400 nm) transmittance is 38% or less. Lime silica green glass is disclosed (for example, refer to Patent Document 3).

In this publication, the Fe is 0.48 to 0.92 wt% Fe ₂ O ₃ and 0.15 to 0.33 wt% FeO, and the FeO content is 23 of the total iron content. ˜29% is obtained by reduction, colorimetric light C dominant wavelength is 498 to 525 nm, color purity is 2 to 4%, and 65 to 75% by weight of SiO including _2, 10-15 wt% of Na ₂ O, 0 to 4 wt% of K ₂ O, 1 to 5 wt% of MgO, 5 to 15 wt% of CaO, 0 to 3% _Al 2 _{O 3} This is described.

Further, in effect, in terms of oxide, 65-75 wt% of _SiO 2, 0.1 to 5 wt% of _Al 2 _O 3, 10 to 18 wt% of Na ₂ O, 0-5 wt% K ₂ O, 5 to 15 wt% of CaO, 1 to 6 wt% of MgO, 0.1 to 3 wt% of _CeO 2, 0.5 to 1.2 wt% of _Fe 2 _O 3, _0.05~ 1.0 wt% of _SO 3, made from a composition of 0 to 1.0 wt% of TiO _2, and of the total iron content expressed as _Fe 2 _{O 3, 20~40%} by weight oxide An infrared / ultraviolet absorbing glass that is ferrous iron (FeO 2) is disclosed (for example, see Patent Document 4).

In this publication, NiO, CoO, MnO, V ₂ O ₅ , MoO ₃ or the like is added as a colorant to the glass having the above composition range in a range of 0 to 1.5% by weight in a total amount of one kind or two or more kinds. In addition, in order to prevent the deterioration of the color tone due to ultraviolet rays and the color development of the amber, 0 to 3% by weight of ZnO may be added as necessary, and in the embodiment, visible transmission at a thickness of 5 mm is possible. The rate (380 to 780 nm) is 66.1 to 66.8%, the solar heat transmittance (340 to 1800 nm) is 37.7 to 38.4%, the dominant wavelength is 501 to 503 nm (green), etc. ing.

Further, in weight percent, 65% to 75% of _SiO 2, 0 to 5% of _Al 2 _O 3, 10 to 18% of Na ₂ O, 0 to 5% of K ₂ O, 5 to 15% of CaO, 0 NiO, CoO, MnO, V ₂ O ₅ , MoO with a composition comprising ˜5% MgO, 0.1 to 3% CeO ₂ , 0.2 to 1% FeO, 0.1 to 3% SnO _{3 and the} like, 0 to 1.5% of a colorant, 0 to 3% of ZnO, 0.1 to 3% of SnO, and an ultraviolet and infrared ray absorbing glass having a dominant wavelength of 488 to 497 nm are disclosed (for example, (See Patent Document 5).

In addition, the present applicant also has 67 to 75% SiO ₂ , 0.05 to 5% Al ₂ O ₃ , 12 to 16% Na ₂ O, and 0.5 to 3% K ₂ O by weight%. 7 to 11 percent of CaO, 2 to 4.2 percent of MgO, 0.05 to 0.3% of the _SO 3, 1.0 to 2.5 percent _CeO 2, of 0.1% to 1.0% TiO _2, from 0.0010 to 0.0400 percent of MnO, from .0001 to 0.0009 percent CoO, comprises 0 to 1% of SnO, further 70 to 76% of _{SiO 2 + Al 2 O 3 +} TiO 2, 10 An ultraviolet-infrared-absorbing green glass having a composition of ˜15% CaO + MgO and 13-17% Na ₂ O + K ₂ O has been proposed (for example, see Patent Document 6).

  In addition, with respect to the visible light transmittance, a glass that is as high as possible is desired because of the demand for improvement in transparency. And even if it is a glass which has a function of absorbing ultraviolet and infrared rays, glasses with different color tones are considered as different products, and the color tone of the glass itself is also an important required characteristic for the glass. For example, in a building such as a building, in most cases, glass of the same color is used for the window, and at present, a green color tends to be preferred. Further, the colored glass used for the window of the vehicle glass tends to be preferred to be a glass of green color.

Considering the global environment, the use of raw materials that were not previously considered a problem may be restricted. Furthermore, an increase in the adjustment load applied to the production equipment when changing the production type at the time of glass production leads to an increase in energy consumption, so it is desirable to reduce this load.
Japanese Patent Publication No. 5-27578 JP-A-6-321677 Japanese Patent Publication No. 6-88812 JP-A-4-310539 JP-A-4-46031 JP-A-9-208254

  The ultraviolet-infrared-absorbing green glass targeted by the present invention is preferably produced by a float process. In the float process, a clear glass made of soda-lime-silica-based glass to which special functions such as ultraviolet and infrared absorption ability and coloring, which are the objectives of the present invention, has not been added is usually produced. In order to manufacture glass with a special function such as glass, it is necessary to change glass raw materials, change kiln operating conditions, plate making conditions, and the like.

  Making this adjustment easy leads to low-cost production of ultraviolet-infrared-absorbing green glass and, in turn, reduction of impediments to the global environment. Accordingly, in the present invention, not only to obtain a glass having a green color tone, a high visible light transmittance, and an excellent ability to absorb ultraviolet and infrared rays, but also in the production of the glass by the float method, the adjustment load as described above. It is an object of the present invention to provide a glass capable of reducing the above.

The ultraviolet-infrared-absorbing green glass of the present invention is a soda-lime-silica glass, expressed by weight%, and the Fe amount is 0.3% or more and 0.5% or less in terms of Fe ₂ O ₃ , and CeO ₂ 0.3%. 1% or less, TiO ₂ 0.7% or more and 1.6% or less, FeO 0.1% or more and 0.25% or less coloring components at least, and the glass is 5 mm thick, UV transmission by ISO / DIS9050 The rate (T _UV ) is 9% or less, the 350 nm wavelength transmittance (T ₃₅₀ ) is 5% or less, the 550 nm wavelength transmittance (T ₅₅₀ ) is 72% or more, and the 1100 nm wavelength transmittance (T ₁₁₀₀ ) is 25% or less. It is characterized by that. The coloring component here is defined as a component that causes glass to absorb ultraviolet rays, to absorb infrared rays, and to use green color.

Except for the coloring components in the glass, SiO ₂ 67% to 75%, Al ₂ O ₃ 0.5% to 3%, CaO 7% to 11%, MgO 2% to 4.2 in terms of% by weight. % Or less, Na ₂ O 12% or more and 16% or less, K ₂ O 0.5% or more and 3% or less, SO ₃ 0.05% or more and 0.3% or less. % Of SiO ₂ + Al ₂ O ₃ + TiO ₂ 70% to 76%, CaO + MgO 10% to 15%, Na ₂ O + K ₂ O 13% to 17%.

For Fe, Fe ²⁺ / (Fe ³⁺ + Fe ²⁺ ) in the weight ratio display is 0.3 or more and 0.6 or less, and CeO ₂ / TiO ₂ in the weight ratio display is 0.3 or more and 1 or less. Is preferred.

The glass of the present invention is 5 mm thick, has a visible light transmittance (T _V ) of 69% or more with an A light source, a solar transmittance (T _S ) of 50% or less, a stimulation purity (Pe) of 10% or less, and D ₆₅ It is preferable that the dominant wavelength (D) by the light source is 495 nm to 560 nm, and the ultraviolet ray further contains MnO 200 ppm or less, SnO 1.0% or less, and CoO 10 ppm or less in terms of weight% as the second coloring component. Infrared absorbing green glass. The second coloring component is introduced mainly for adjusting the glass color tone.

  According to the present invention, it is possible to obtain a glass that exhibits high infrared absorption ability and ultraviolet absorption ability, realizes a green color tone in a well-balanced manner, and has high visible light permeability. In addition, it is possible to reduce the adjustment load generated when changing the glass production type without greatly changing the operating conditions and the plate making conditions in the float process, and to make it possible to produce high quality and yield.

In the soda-lime-silica glass, the present invention is expressed in wt%, and the iron oxide is 0.3% to 0.5% in terms of Fe ₂ O ₃ , CeO ₂ 0.3% to 1%, TiO ₂ 0.7% or more and 1.6% or less, FeO 0.1% or more and 0.25% or less coloring component at least, and the glass is 5 mm thick, UV transmittance (T _UV ) according to ISO / DIS9050 Is 9% or less, and 350 nm wavelength transmittance (T ₃₅₀ ) is 5% or less, 550 nm wavelength transmittance (T ₅₅₀ ) is 72% or more, and 1100 nm wavelength transmittance (T ₁₁₀₀ ) is 25% or less. It is.

Fe ₂ O ₃ functions as a component that absorbs ultraviolet rays and ensures a green color tone, and is necessary for stably obtaining various optical characteristics. Fe ₂ O ₃ is partly reduced in the course of glass production, and is also mixed in the form of FeO, so it is preferable to express it as an equivalent amount of Fe ₂ O ₃ . FeO exhibits an action of absorbing infrared rays in glass. Then, a function of absorbing ultraviolet rays in a glass, together with _Fe 2 _{O 3} to ensure the green _tint, it is necessary with each coloring agent of CeO 2, TiO ₂ or the like.

That is, when the amount of Fe is less than 0.3% in terms of Fe ₂ O ₃ , the effect on the above is poor, and when it exceeds 0.5%, the visible light transmittance is particularly lowered. A more preferable amount of Fe is 0.35 to 0.45% by weight in terms of Fe ₂ O ₃ . FeO is preferably 0.1% or more and 0.25% or less. If it is less than 0.1%, there is almost no infrared absorption effect. On the other hand, if it exceeds 0.25%, a problem arises that the bluish color becomes too strong in the color tone of the glass.

CeO ₂ mainly has the effect of absorbing ultraviolet rays, but the amount thereof is 0.3% or more and 1.0% or less by weight. This is because there is a problem. On the other hand, if it exceeds 1%, the oxidizing effect by CeO ₂ tends to be strong, the visible light transmittance tends to be lowered, the yellow color is overemphasized in the color tone of the glass, and the raw material costs are increased. To do. More preferably, it is 0.4-0.85%, More preferably, it is 0.55-0.7%.

TiO ₂ also has the effect of absorbing ultraviolet rays in the same manner as CeO _2. However, the amount of the TiO ₂ is 0.7 to 1.6% in terms of weight% when less than 0.7%. This is because there is a problem that the color tone of the glass becomes too blue due to the lack of color and other coloring components. On the other hand, if it exceeds 1.6%, the color tone of the glass becomes yellowish, and the visible light transmittance becomes too low. More preferably, it is 0.9 to 1.5%, and more preferably 1 to 1.4%.

  The above range was adopted because each component is necessary for obtaining a green color tone considering the absorption of ultraviolet rays and infrared rays, visible light transmittance, and the dominant wavelength, but the balance is extremely important. Thus, a desired green-based ultraviolet and infrared absorbing glass can be obtained within the above range.

The reason why ultraviolet-ray-absorbing green glass having an ultraviolet transmittance (T _UV ) by ISO / DIS 9050 at a thickness of 5 mm of 9% or less is preferable is that when it exceeds 9%, various deterioration problems due to ultraviolet rays occur. Here, the ultraviolet transmittance (T _UV ) according to ISO / DIS9050 represents an average value of transmittance in a wavelength region of 297.5 to 377.5 nm. Here, the reason why the wavelength range is 297.5 to 377.5 nm is that both medium wavelength ultraviolet light (UVB) having a wavelength of about 290 to 320 and long wavelength ultraviolet light (UVA) of about 320 to 400 nm are considered.

In general, an ultraviolet-infrared-absorbing green glass having a 350 nm wavelength transmittance (T ₃₅₀ ) of 5% or less is preferable because it is easy to eliminate the adverse effects of ultraviolet rays when the glass having the physical properties is used as a window. Here, light having a wavelength of 350 nm is representative of long wavelength ultraviolet rays (UVA) having a wavelength of about 320 to 400 nm, for example, having a strong penetration power into human skin, such as collagen fibers and elastic fibers in the dermis of the skin. This is because the so-called A ultraviolet ray, which is well known to act on the fiber of the skin and cause wrinkles and tarmi and to act on the melanin present in the skin to worsen the spots and freckles, is considered.

The ultraviolet and infrared absorbing green-based glass having a 550 nm wavelength transmittance (T ₅₅₀ ) of 72% or more at a thickness of 5 mm is preferable if it is less than 72%, depending on the transparency performance, which is one of the major characteristics of the glass. This is because problems may occur. Here, the reason why the light having a wavelength of 550 nm is representative is to mainly consider the transmittance in green.

The UV-infrared-absorbing green glass having a 1100 nm wavelength transmittance (T ₁₁₀₀ ) of 5% or less at a thickness of 5 mm is preferably 25% or less. If it exceeds 25%, the infrared shielding effect becomes insufficient, and when used as a window. This is because the effect is reduced in reducing the cooling load.

Moreover, except the coloring component of the glass, SiO ₂ 67% to 75%, Al ₂ O ₃ 0.5% to 3%, CaO 7% to 11%, MgO 2% to 4% in terms of% by weight. 2% or less, Na ₂ O 12% or more and 16% or less, K ₂ O 0.5% or more and 3% or less, SO ₃ 0.05% or more and 0.3% or less, and the sum of these components and the coloring components 98% or more, and SiO ₂ + Al ₂ O ₃ + TiO ₂ 70% or more and 76% or less, CaO + MgO 10% or more and 15% or less, Na ₂ O + K ₂ O 13% or more and 17% or less Green glass is preferred.

The reason why the SiO ₂ component is 67 to 75% by weight is that if it is less than 67%, the surface is liable to be burned and the like, and the weather resistance is lowered, resulting in practical problems. Melting is also difficult. In consideration of the above, the component is preferably 69 to 72%.

The reason why the Al ₂ O ₃ component is 0.5 to 3% by weight is that when it is less than 0.5%, the weather resistance is lowered, and the surface is likely to be burned, resulting in practical problems. . On the other hand, if it exceeds 3%, devitrification tends to occur, and the molding temperature range becomes narrow, so that the production becomes difficult. In consideration of the above, the component is preferably 1.5 to 2.5%.

  The reason why the CaO component is 7 to 11% by weight is that if it is less than 7%, the flux becomes insufficient as a flux, so that the melting temperature becomes high and the flow temperature does not become low, so that it becomes difficult to produce. On the other hand, if it exceeds 11%, devitrification is likely to occur, and the molding work range is narrowed, which makes manufacturing difficult. In consideration of the above, the component is preferably 7.4 to 9%.

  The reason why the MgO component is 2 to 4.2% by weight is that if it is less than 2%, the melting temperature rises and the operating range is narrowed, making it difficult to manufacture, and if it exceeds 4.2%, the meltability deteriorates. is there. In consideration of the above, the component is preferably 3 to 4%.

The reason why the Na ₂ O component is 12 to 16% by weight is that if it is less than 12, the meltability deteriorates and the ease of strengthening decreases, the moldability becomes difficult, and devitrification easily occurs. This makes it difficult to manufacture. On the other hand, if it exceeds 16%, the weather resistance is lowered, and defects such as burns tend to occur on the surface, resulting in practical problems. In consideration of the above, the component is preferably 12.5 to 14%.

The reason why the K ₂ O component is 0.5 to 3% by weight is that if it is less than 0.5%, the easy strengthening property is lowered, and if it exceeds 3%, the weather resistance is lowered and the cost is increased. In consideration of the above, the component is preferably 0.6 to 1.5%.

The reason why the SO ₃ component is set to 0.05 to 0.3% by weight is less than 0.05%, for example, it can be made only to the extent that defoaming or homogeneity tends to be insufficient in normal melting. If it exceeds%, it particularly affects the coloring state of the glass, for example, it becomes easy to shift to a yellow or amberish color tone, and it becomes difficult to obtain a desired green color tone. Preferably it is 0.1 to 0.2%.

In addition, the sum of the components of SiO ₂ , Al ₂ O ₃ , CaO, MgO, Na ₂ O, K ₂ O, SO ₃ , Fe ₂ O ₃ , CeO ₂ , and TiO ₂ was set to 98% or more by weight percentage. In some cases, it may be added, for example, so that the total amount of trace components such as CoO, Cr ₂ O ₃ , and MnO does not exceed 2%.

Furthermore, the reason why SiO ₂ + Al ₂ O ₃ + TiO ₂ is 70 to 76% by weight is that if it is less than 70%, the weather resistance is lowered, and if it exceeds 76%, there is a problem that easy strengthenability is lowered. Is about 70 to 74%.

  The reason why CaO + Mgo is 10 to 15% by weight is that CaO and MgO components are used for lowering the melting temperature, and when the content is less than 10%, the easy strengthening is reduced. It becomes difficult, and it is preferably about 11.5 to 15%.

The reason why Na ₂ O + K ₂ O is 13 to 17% in percentage is that if it is less than 13%, the easy strengthening property decreases, devitrification easily occurs, the working temperature range at the time of molding becomes narrow, and manufacturing becomes difficult. is there. On the other hand, if it exceeds 17%, the weather resistance is lowered, causing a practical problem and increasing the cost.

In addition, an ultraviolet-infrared-absorbing green glass in which Fe ²⁺ / (Fe ³⁺ + Fe ²⁺ ) in a weight ratio display is 0.3 to 0.6 and CeO ₂ / TiO ₂ in a weight ratio display is 0.3 to 1. preferable. FeO and Fe ₂ O ₃ generally have different roles. Mainly, Fe ₂ O ₃ has a large influence on the ultraviolet region, and FeO has a large influence on the infrared region. For this reason, although it is the same iron component, it will be preferable to control the ratio. When Fe ²⁺ / (Fe ³⁺ + Fe ²⁺ ) in the weight ratio display is less than 0.3, there is a problem that the solar radiation transmittance becomes excessively high with little absorption in the infrared region. On the other hand, if Fe ²⁺ / (Fe ³⁺ + Fe ²⁺ ) in weight ratio exceeds 0.6, the solar radiation transmittance is lowered, but the visible light transmittance is too low, and the color tone of the glass becomes too blue. appear. More preferably, it is the range of 0.35-0.47.

CeO ₂ and TiO ₂ mainly have an ultraviolet absorption effect. However, the effects of both on the absorption of ultraviolet rays are different, and the color tone is also different. For this reason, it is preferable to define the range of CeO ₂ / TiO ₂ in terms of weight ratio. When CeO ₂ / TiO ₂ in the weight ratio display is less than 0.3, there arises a problem that the visible light transmittance is too low. On the other hand, when CeO ₂ / TiO ₂ in the weight ratio display exceeds 1, there arises a problem that the yellowness of the glass is excessively emphasized in relation to other coloring materials. More preferably, it is the range of 0.4-0.9, More preferably, it is the range of 0.5-0.8.

Further, it is preferably 5 mm thick and the visible light transmittance (T _V ) by the A light source is 69% or more. This is because if it is less than 69%, a problem may occur depending on the perspective performance, which is one of the major characteristics of glass. In particular, in the case of a front window glass of an automobile, the visibility of the glass, particularly at nightfall, at night or when it rains, is likely to cause a decrease in object identification, so it is more preferably 71% or more. Here, the visible light region refers to a wavelength region of 380 to 780 nm.

An ultraviolet and infrared ray absorbing green glass having a solar transmittance (T _S ) of 50% or less is preferable. If it exceeds 50%, for example, the cooling load will increase, and this will go against the global warming phenomenon and environmental problems. That is, if it exceeds 50%, the actual feeling of the effect of increasing the cooling load or improving the comfort in the vehicle or in the room is reduced, and it becomes difficult to eliminate discomfort particularly in midsummer. For this reason, a sufficient energy saving effect cannot be obtained.

_Furthermore, the dominant wavelength by illuminant _{D 65} (D) is 495～560Nm, excitation purity (Pe) is preferably ultraviolet and infrared radiation absorbing green glass is 10% or less. This dominant wavelength (D) and excitation purity (Pe) are useful for determining the hue of the ultraviolet and infrared absorbing green glass. The color _tone, it is preferable that the dominant wavelength by illuminant _{D 65} (D) is in 495～560Nm. If illuminant D ₆₅ by dominant wavelength (D) is in the region shorter than 495 nm, a green color tone becomes sweet called bluish color, it will not match the green market needs. On the other hand, the dominant wavelength by illuminant D ₆₅ (D) is it exceeds the 560 nm, increased yellow or amber color, which also does not meet the market needs prefer green. More preferably, it is the range of 500-550 nm. On the other hand, when the stimulus purity (Pe) exceeds 10%, it becomes too strong and does not meet the recent market needs for “classy” shades.

  Furthermore, it is preferable to add MnO at 200 ppm or less as the second coloring component. This is because MnO has a reducing effect. However, if it exceeds 200 ppm, the reduction effect becomes too strong, and a problem that amber tends to occur is not preferable.

  SnO is preferably added at 1% or less. This is because SnO has a reducing effect. However, if it exceeds 1%, the reducing action becomes too strong and amber is likely to be produced, and problems such as the color tone of the glass becoming a bluish color tone are undesirable.

  CoO is preferably added at 10 ppm or less. This is because CoO has a reducing effect. However, if it exceeds 10 ppm, the color tone of the glass tends to be a strong blue tone, which is not preferable.

Furthermore, for color tone adjustment, Se may be used at 5 ppm or less, Cr ₂ O ₃ at 100 ppm or less, and NiO at 10 ppm or less. However, if the above value is exceeded, it becomes difficult to put the dominant wavelength of the glass obtained in the range of 495 to 560 nm.

In producing the ultraviolet and infrared absorbing green glass of the present invention, Fe ₂ O ₃ , Frit glass or cullet containing coloring components such as CeO ₂ , TiO ₂ , FeO, MnO, SnO, Cr ₂ O ₃ , CoO, NiO, and Se may be used. It is easy to stabilize the quantitative adjustment of these components, and it is easy to incorporate FeO into the glass, and it is possible to operate the glass in a stable redox state without greatly changing the operating conditions of the actual kiln. it can. In addition to the above-described coloring components, carbon, Zn metal powder, oxides, or the like can be used as a trace amount raw material. For example, it is effective when securing a color tone while assisting the clarification effect by mirabilite (Na ₂ SO ₄ ) or the like. Further, in some cases, introduction of nitrogen gas, a mixed gas thereof, or combustion exhaust gas in the atmosphere of the adjustment region of the glass kiln may lead to stabilization.

  The ultraviolet-infrared-absorbing green glass of the present invention is a thin plate glass having a plate thickness of about 1.5 to 5 mm. In addition, it is effective for producing glass with improved safety, such as laminated glass, and can be used particularly as window glass for vehicles such as automobiles and railway vehicles. Moreover, as a single plate glass, a laminated glass, a laminated glass, a multi-layer glass, etc., it can be used also as a window material for constructions from a thin plate glass having a thickness of about 1 mm to a thick plate glass having a thickness of about 25 mm.

  Hereinafter, an example explains.

Silica sand, feldspar, soda ash, dolomite, limestone, mirabilite, bengara, titanium oxide, cerium carbonate were used as glass materials. Furthermore, in addition to ilmenite, carbon and slag, Al ₂ O ₃ , Fe ₂ O ₃ , CaCO ₃ , MgCO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , CeO ₂ and TiO ₂ chemical reagents were also used. . Using these, the desired glass composition was predetermined as the target composition and weighed and prepared. As raw material batches, mirabilite / (silica sand + feldspar) was about 1%, and cullet was about 50%.

The prepared raw material was put in a crucible and the same as the actual kiln using nitrogen gas or a mixed gas containing the gas or the like using an actual kiln (for example, the side wall portion of the inlet and the side wall of the condition portion) maintained at about 1450 ° C. Melt in an electric furnace for about 3-4 hours and vitrify, hold for about 2 hours at 1420-1430 ° C. for further homogenization and clarification, and then poured out into a mold as a glass block with a size of 100 mm × 100 mm. Cutting out as a glass plate of about 3.5 mm, or pouring the glass into a plate shape with a size of 100 mm × 100 mm to a thickness of about 3.5 mm, and then grinding and polishing, and Examples 1 to 7 and Comparative Examples 1 to 5 A sample was obtained. Table 1 shows the composition represented by weight% of each example and each comparative example, Table 2 shows the amount of chemical species added in ppm order, and Table 3 shows Fe ²⁺ / (Fe ³⁺ + Fe ²⁺ ) ratio and CeO ₂ / TiO ₂ ratio.

  The glass component composition (% by weight) of the sample is measured by a wet analysis method based on JIS R-3101. The optical characteristics are U4100 type self-recording spectrophotometer manufactured by Hitachi, Ltd., JIS Z-8722, JIS R-3106, ISO. / DIS 9050 (1990 edition).

Table 4 shows UV transmittance (T _UV /%) and 350 nm wavelength transmittance (T ₃₅₀ /%) according to ISO / DIS9050 when the glass obtained in Examples 1 to 7 and Comparative Examples 1 to 5 is 5 mm thick. 550 nm wavelength transmittance (T ₅₅₀ /%), 1100 nm wavelength transmittance (T ₁₁₀₀ /%), visible light transmittance (T _V /%) by A light source, solar transmittance (T _S /%), stimulation purity ( Pe /%) and the dominant wavelength (D / nm) by the _D65 light source. The glasses obtained in Examples 1 to 7 were excellent in ultraviolet and infrared shielding properties, and were excellent in visible light transmittance and green color tone.

Claims (3)

In soda-lime-silica glass, the amount of Fe in terms of wt% is 0.3% to 0.5% in terms of Fe ₂ O ₃ , CeO ₂ 0.3% to 1%, TiO ₂ 0.7 % To 1.6%, FeO 0.1% to 0.25%, Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) is 0.3 to 0.6, and CeO ₂ / TiO ₂ in terms of weight ratio is It contains at least a coloring component of 0.3 or more and 1 or less, and other than the coloring component, SiO ₂ 67% or more and 75% or less, Al ₂ O ₃ 0.5% or more and 3% or less, CaO 7% or more 11 %, MgO 2% to 4.2%, Na ₂ O 12% to 16%, K ₂ O 0.5% to 3%, SO ₃ 0.05% to 0.3%, a is the sum of the coloring components and these components are 98%, and SiO _{2 Al 2 O 3 + TiO 2 70} % or more 76% or less, CaO + MgO 10% or more than _15%, and a _{Na 2 O + K 2 O 13} % to 17% or less, and in the glass is 5mm thick, ultraviolet transmittance by ISO / DIS9050 (TUV) is 9% or less, 350 nm wavelength transmittance (T350) is 5% or less, 550 nm wavelength transmittance (T550) is 72% or more, and 1100 nm wavelength transmittance (T1100) is 25% or less. UV-infrared absorbing green glass. With a thickness of 5 mm, visible light transmittance (TV) by A light source is 69% or more, solar transmittance (TS) is 50% or less, stimulation purity (Pe) is 10% or less, and main wavelength (D) by D65 light source is 495 nm. The ultraviolet-infrared-absorbing green glass according to claim 1, wherein the glass is ultraviolet-infrared absorbing green glass. The ultraviolet and infrared ray absorbing green glass according to claim 1 or 2, further comprising, as a second coloring component, 200% or less of MnO, 1% or less of SnO, and 10ppm or less of CoO in terms of% by weight.