JP3481067B2 - UV absorbing colored glass - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brown-colored ultraviolet-absorbing glass having a high ultraviolet-absorbing ability and a relatively high visible-light transmittance, and more particularly to a brown-tone gray-colored ultraviolet-absorbing glass having a very low stimulating purity.

[0002]

_2. Description of the Related Art Conventionally, FeO and Fe ₂ O have been used as glass for buildings or vehicles having a brown or gray color.
Those containing ₃ , ₃ , CeO ₂ , TiO ₂ , CoO and Se, and in some cases NiO are known.

For example, JP-A-5-58670 and JP-A-6-92678 disclose bronze glass in which TiO ₂ is introduced in an amount of 0 to 1% by weight in order to partially substitute the ultraviolet absorbing function of cerium oxide. Regarding the amount of TiO ₂ introduced, it is described that TiO ₂ coexists with iron oxide and also absorbs visible light on the short wavelength side to lower the visible light transmittance, so that the upper limit is 1%.

In the example of JP-A-5-58670, FeO, Fe ₂ O ₃ , CeO ₂ , Se and 0.1
0.5 wt% TiO ₂ , optionally CoO, NiO
To obtain an ultraviolet absorbing bronze glass. In the example of JP-A-6-92678, 0.2% by weight is used.
The total Fe ₂ O ₃ , CeO ₂ , and 0.24 to 0.
An ultraviolet absorbing bronze glass is obtained by using 4% by weight of TiO ₂ , and optionally, CoO and NiO together. However, the ultraviolet transmittance in the example of JP-A-6-92678 is at least 25% at a thickness of 4 mm.

Further, Japanese Patent Laid-Open Nos. 5-270855 and 6-1994
-40741 contains TiO ₂ limited to 0.15 to 0.45 wt% and Ce limited to 0.2 to 0.6 wt%.
O ₂ and by combining, and neutral gray glass with a reduced effect on the color tone is disclosed in its Example, neutral gray glass having an ultraviolet transmittance of about 18-22% by 4mm thick Is getting In addition, JP-A-6
In the example of -40741, 4 mm thick and 16.7.
A neutral gray glass having an ultraviolet transmittance of about 19.43% is obtained.

Further, Japanese Patent Laid-Open No. 6-345482 discloses a brown glass in which TiO ₂ is introduced in an amount of 0 to 1% by weight in order to partially replace cerium oxide. The ultraviolet transmittance of the glass of the example exceeds 10% in terms of 5 mm thickness.

[0007]

In recent years, particularly in vehicle windshields, there has been a demand for glass having a further reduced ultraviolet transmittance. In the above-mentioned conventional example, the ultraviolet transmittance exceeds 10% in terms of 5 mm thickness, which does not fully satisfy the recent demands.

An object of the present invention is to make a soda lime silica, which is a glass for ordinary construction or vehicles, a mother composition, and to contain various colorants in a controlled manner so as to sufficiently absorb an ultraviolet ray and to compare it. The present invention provides a glass having a brown or gray color tone having a characteristic of transmitting visible light.

[0009]

The present invention is based on 100 parts by weight of a mother component made of soda-lime glass, 0.12 to 0.7 parts by weight of total iron converted into Fe ₂ O ₃ , and CeO as coloring components. All of cerium from 0.2 to 1.5 parts by weight in terms of _2, the total titanium from 1.1 to 2.5 parts by weight in terms of TiO _2, CoO 0.0018 to 0.01 parts by weight, Se from .0001 to 0 The standard light source C has an ultraviolet ray transmittance of 10% or less defined by ISO-9050 converted to a thickness of 5 mm.
The main wavelength measured by the above is in the range of 565 to 600 nm, which is an ultraviolet absorbing colored glass.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises a mother component made of soda-lime glass and a predetermined amount of a coloring component. This coloring component will be described below.

If the total iron content converted to Fe ₂ O ₃ is less than 0.12 parts by weight with respect to 100 parts by weight of the mother component, the dominant wavelength becomes too short and a brown or gray glass cannot be obtained. Further, if it exceeds 0.7 parts by weight, the visible transmittance becomes small. In order to maintain a high visible light transmittance and obtain a glass having a low stimulating purity, it is preferably 0.4 parts by weight or less with respect to 100 parts by weight of the mother component.

Cerium mainly contains Ce ³⁺ and Ce ⁴⁺ , both of which are components having an ultraviolet absorbing effect. Ce
If the total amount of cerium converted to O ₂ is less than 0.2 parts by weight relative to 100 parts by weight of the mother component, the effect is small, and if it exceeds 1.5 parts by weight, the effect of visible light absorption is large. In order to impart a higher UV absorption capacity to glass, the mother component 10
It is preferably 0.4 parts by weight or more with respect to 0 parts by weight. On the other hand, when the amount of cerium added is large, the stimulation purity tends to increase. To be used for window glass to obtain brown-colored glass close to gray that more easily matches the color of the interior
In addition, the amount is 1.5 parts by weight or less based on 100 parts by weight of the mother component .

Further, by using titanium in combination with cerium, the ultraviolet absorbing ability can be increased. Cerium, which has absorption in the near-ultraviolet region, is Ce ³⁺ , so CeO ₂ is replaced by Ti ₂ O ₃
The effect of absorbing near-ultraviolet rays can be further enhanced by reducing with. Compared to cerium, titanium has a smaller degree of increase in stimulation purity due to addition. Therefore, it is a preferable component rather than cerium for obtaining a brown glass close to gray.

If the total titanium content converted to TiO ₂ is less than 1.1 parts by weight with respect to 100 parts by weight of the mother component, the ultraviolet transmittance becomes too large, and if it exceeds 2.5 parts by weight, the visible light transmittance decreases. May occur .

Se is a component for adjusting the color tone to brown or gray. This content is 100
If it is less than 0.0001 parts by weight with respect to parts by weight, the dominant wavelength becomes too short and a glass having a brown or gray color cannot be obtained. If it exceeds 0.02 parts by weight, the coloring effect is saturated and there is no effect. In order to set the dominant wavelength (hereinafter simply referred to as the dominant wavelength) measured by the standard light source C to 575 nm or more, 0.0004 parts by weight or more is preferable with respect to 100 parts by weight of the mother component. From the viewpoint of cost reduction, the mother component 1
It is preferably 0.01 parts by weight or less with respect to 00 parts by weight.

In general, brown glass is often obtained by shifting the green color produced by the presence of Fe to the long wavelength side by adding Se. In the present invention, since a relatively large amount of cerium and titanium are contained, brown color may not be easily obtained by simply adding Se in the extension line of the conventional brown glass.

[0017] Therefore, in the present invention, the percentage of divalent iron in terms of Fe ₂ O ₃ in the total iron in terms of Fe ₂ O ₃ 1
It is preferably 9% or less. More preferably 17%
It is below, especially preferably below 15%. By doing so, the dominant wavelength of the glass is shifted to a longer wavelength in combination with the effect of the addition of Se, a brown color is obtained, and the stimulation purity can be suppressed to be relatively small. The amount of divalent iron (FeO) typically contained in the glass of the present invention is, for example, 0.1 part by weight or less based on 100 parts by weight of the mother component.

[0018] CoO is mandatory, to lower the excitation purity
It This content is 0.0 with respect to 100 parts by weight of the mother component.
If it exceeds 1 part by weight, the dominant wavelength becomes too short and a glass exhibiting a brown or gray color cannot be obtained. Since CoO tends to lower the visible light transmittance, 0.005 parts by weight or less is preferable with respect to 100 parts by weight of the mother component in order to maintain a high visible light transmittance.

On the other hand, since the glass of the present invention contains a relatively large amount of cerium and titanium, it tends to have a high stimulation purity as compared with the conventional glass having a relatively large ultraviolet transmittance. Stimulation purity is low (12% or less, preferably 10)
%), CoO is contained in an amount of 0.002 parts by weight or more with respect to 100 parts by weight of the base component in order to obtain a glass exhibiting a relatively clear brown color (main wavelength measured by the standard light source C is 575 nm or more). It is preferable.

Further, it is preferable that the composition of the soda lime glass as the mother component essentially consists of the following components. SiO ₂ 65 to 75 wt%, Al ₂ O ₃ 0.1~ 5 wt%, Na ₂ O 10~18 wt%, K ₂ O 0~ 5 wt%, CaO 5 to 15 wt%, MgO 0 to 6 wt %, If the SiO ₂ content is less than 65% by weight, the weather resistance is poor, and if it exceeds 75% by weight, devitrification is likely to occur. If the Al ₂ O ₃ content is less than 0.1% by weight, the water resistance will decrease, and if it exceeds 5% by weight, the solubility will decrease. Na ₂ O and K ₂ O are components that promote the dissolution of raw materials, and the content of Na ₂ O is 10% by weight.
If it is less than 18% by weight, the effect is small, and if it exceeds 18% by weight, the weather resistance becomes poor. Further, K ₂ O is not an essential component but may be contained. If the content exceeds 5% by weight, the cost becomes high.

CaO and MgO are components that accelerate the dissolution of the raw materials and improve the weather resistance. If the content of CaO is less than 5% by weight, the above-mentioned effects are small, and if it exceeds 15% by weight, devitrification is likely to occur. MgO is not an essential component but may be included. If its content exceeds 6% by weight, devitrification tends to occur.
SO ₃ may be used as a fining agent. At such times, typically the amount of SO ₃ remaining in the glass is 0.0
It is between 5 and 1.0% by weight.

The glass of the present invention typically has a thickness of 5 m.
The UV transmittance at 10 m is 10% or less, and the dominant wavelength is 56
It becomes 5 to 600 nm. The stimulation purity can be adjusted depending on the application and can be set to 0 to 15%. Further, although not particularly limited, the solar radiation transmittance is typically 50 to 80%, particularly 60 to 80% in terms of 4 mm thickness. Especially for vehicle applications, the thickness is 2 to 6 mm, especially 3 to 5
mm, the visible light transmittance measured by the standard light source A is 7
It is preferably 0% or more.

Brown-tone gray glass, specifically, having a dominant wavelength of 570 to 600 nm, preferably 575 to 600
In order to obtain a glass having a stimulating purity of 12% or less, preferably 10% or less, the following composition is preferable.

That is, with respect to 100 parts by weight of a mother component made of soda-lime glass, 0.12 to 0.4 parts by weight of total iron converted into Fe ₂ O ₃ and 0.1% by weight of total cerium converted into CeO ₂ as coloring components. ₂ to 1.5 parts by weight, 1.1 to 2.5 parts by weight of total titanium converted to TiO ₂ , 0.002 to 0.01 parts by weight of CoO, and 0.0001 to 0.02 parts by weight of Se. , in the total iron in terms of Fe ₂ O _3, the proportion of the amount of divalent iron in terms of Fe ₂ O ₃ is less than 19%.

In the above composition, in order that the visible light transmittance measured by the standard light source A is 70% or more, the ratio of the amount of divalent iron to the total iron amount is 17%.
The following is preferable.

The glass plate made of the glass of the present invention is excellent in the ability to absorb ultraviolet rays and has ISO-9050 at the actual thickness of the glass plate.
The ultraviolet transmittance defined in 1. can be set to 10% or less, which is preferable for construction, vehicles, and the like. In particular, in addition to the above-mentioned dominant wavelength and ultraviolet absorbing ability of the glass of the present invention, the visible light transmittance measured by the standard light source A is 70% or more and the actual thickness is 2 to 6.
The mm glass plate is preferable for vehicles because it easily recognizes external objects and does not deteriorate the interior due to ultraviolet rays.

[0027]

[Examples] As raw materials, silica sand, feldspar, dolomite, soda ash, mirabilite, ferric oxide, cerium oxide, titanium dioxide,
By melting the blended batch using sodium selenite and coke in an atmosphere (O ₂ concentration of about 2.0%) that seems to be close to a real kiln, and by performing appropriate molding and slow cooling,
The mother composition (unit:% by weight) shown in Tables 1 to 3, the colorant composition (unit: parts by weight when the entire mother composition is 100 parts by weight), and REDOX (converted into Fe ₂ O ₃ in total iron) Fe
A brown or gray glass having a divalent iron weight ratio (reduction ratio) converted to ₂ O ₃ was obtained. However, in the table, t-Fe ₂ O ₃ means total iron converted to Fe ₂ O ₃ .

Then, with respect to this glass, the visible light transmittance T _va measured with a standard light source A in terms of a thickness of 4 mm and a thickness of 4 m
m-converted solar radiation transmittance T _E , dominant wavelength D _w , stimulus purity P _e converted to thickness of 4 mm, wavelength 370 nm converted to thickness of 3.5 mm
The transmittance T ₃₇₀ and the ultraviolet transmittance T _UV in terms of the thickness of 5 mm were measured. The results are shown in Tables 4 to 6. Visible light transmittance and solar radiation transmittance are according to JIS-R3160, dominant wavelength and stimulation purity are according to JIS-Z8701, and ultraviolet transmittance is ISO-.
9050.

Examples 5 to 44, Examples 47 to 51, Examples 53 and 54
Are Examples, and Examples 1-4, Examples 45, 46, 52, 5
Reference numerals 5 and 56 are comparative examples. As is apparent from the table, the glass according to the present invention has a brown to gray color tone,
Also, it has excellent UV absorption.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

Since the glass of the present invention has a relatively high visible light transmittance and sufficiently absorbs ultraviolet rays, it can prevent deterioration of interior materials and sheets due to ultraviolet rays and prevent sunburn of persons inside. Therefore, it is particularly useful as a window glass for buildings and vehicles.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-6-92678 (JP, A) JP-A-6-345482 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C03C 1/00-14/00

Claims (7)

(57) [Claims] 1. A total of 0.12 to 0.7 parts by weight of total iron converted to Fe ₂ O _3, and 0.1 to 0.7 parts by weight of total cerium converted to CeO ₂ as coloring components, relative to 100 parts by weight of a mother component made of soda-lime glass. 2 to 1.5 parts by weight, 1.1 to 2.5 parts by weight of total titanium converted to TiO ₂ , 0.0018 to 0.01 parts by weight of CoO, and 0.0001 to 0.02 parts by weight of Se. , The UV transmittance defined by ISO-9050 converted to a thickness of 5 mm is 10% or less, and the standard light source C
The ultraviolet-absorbing colored glass having a dominant wavelength in the range of 565 to 600 nm measured by. Wherein Fe ₂ O ₃ in the total iron as calculated as a divalent claim 1 UV absorbing colored glass according ratio of the amount of iron is not more than 19% in terms of Fe ₂ O _3. 3. As a coloring component, 0.12 to 0.4 parts by weight of total iron converted to Fe ₂ O ₃ and 0.1 to 0.4 parts by weight of total cerium converted to CeO ₂ are added to 100 parts by weight of a mother component made of soda-lime glass. ₂ to 1.5 parts by weight, 1.1 to 2.5 parts by weight of total titanium converted to TiO ₂ , 0.002 to 0.01 parts by weight of CoO, and 0.0001 to 0.02 parts by weight of Se. , claim 1 in the total iron in terms of Fe ₂ O _3, the proportion of the amount of divalent iron in terms of Fe ₂ O ₃ is not more than 19%
The ultraviolet absorbing colored glass described. 4. The dominant wavelength measured by the standard light source C is 570.
The ultraviolet absorbing colored glass according to claim 3, which has a stimulation purity of 12% or less in the range of ˜600 nm. 5. The visible light transmittance measured by the standard light source A is 70% or more with a thickness of 2 to 6 mm.
The ultraviolet absorbing colored glass according to any one of claims 1. 6. The ultraviolet absorbing colored glass according to claim 1, wherein the soda lime glass essentially consists of the following components. SiO ₂ 65 to 75 wt%, Al ₂ O ₃ 0.1~ 5 wt%, Na ₂ O 10~18 wt%, K ₂ O 0~ 5 wt%, CaO 5 to 15 wt%, MgO 0 to 6 wt %, 7. A glass plate comprising the ultraviolet-absorbing colored glass according to any one of claims 1 to 6, and having a UV transmittance of 10% or less defined by ISO-9050 at an actual thickness.