JPH0433743B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a colored glass composition that is easy to strengthen, especially a neutral gray colored glass that is produced by a float method and is suitable for obtaining tempered glass by heat strengthening. Regarding the composition. The present invention can be employed in a wide range of fields including window glasses for automobiles, railway vehicles, etc., architectural window glasses and door glasses, furniture, cooking equipment, and electronic and electrical equipment. [Prior Art] Sheet glass and float glass have been used as base plates for reinforcement, but recently the specific gravity of float glass has been increasing, and the plate thickness has also been becoming thinner. Moreover, because of the surface smoothness, flatness, and uniformity of the plate thickness unique to float glass, it is used in various fields, and among them, it is widely used in automobile window glass. Strengthening methods and glass compositions have been proposed. In addition, sheet glass and float glass are
It is a soda lime glass whose main components are SiO ₂ , Al ₂ O ₃ , CaO, MgO, Na ₂ O, and K ₂ O. It is heated to near its softening point and then rapidly cooled with air from the surface. Tempered glass is made using a thermal strengthening method. For example, Japanese Patent Publication No. 57-7574 discloses a method for manufacturing sheet glass and float glass.
_SiO2 in weight percent as its composition ranges from 70 to
73.3, _Na2O15.5 ~19.0, CaO5.5~7.7, MgO3.5~
4.9, _{Al2O3 0.1} ~1.5, _{Fe2O3 0.03} ~0.7, _K2O0 ~
0.5, _SO3 0.2-0.5, _SiO2 , _Na2O , CaO,
The proportion of MgO, Al ₂ O ₃ , Fe ₂ O ₃ and SO ₃ is at least 98% by weight of the total composition, CaO/MgO
The weight ratio of _Na2O /CaO ranges from 1.3 to 1.9.
A flat glass sheet with a weight ratio of 2.0 to 3.2 is described. Furthermore, JP-A-46-1185 discloses an improved thermal strengthening treatment method, in which the sheet glass is cooled from a temperature above its deformation point to a low temperature by contact with a cooling fluid. and finally cooling it to room temperature.
SiO ₂ at least 60% by weight, alkaline earth metal oxide at least 5% by weight, K ₂ O + Na ₂ O total 5-25
%, and the temperature difference between the softening point and deformation point of the glass must be within about 117℃, or the change in specific volume when rapidly cooled glass is heated between the deformation point and the softening point is conventional. It is described that the change is greater than that which occurs when float glass is heated from its deformation point to its softening point. In addition,
Publication No. 49010 states that SiO ₂ 68-75%, Al _2
O3 0-5%, CaO5-15%, MgO0-10%, CaO
+MgO6~15%, _Na2O10 ~18%, K2O0 _~ 5%,
The basic composition is Na ₂ O + K ₂ O 10-20%, and the coloring components are Fe ₂ O ₃ 0.1-0.5% and CoO 0.003-0.02.
%, Se0.0005 to 0.001%, and NiO0 to 0.002%, and the ratio of the above coloring components was adjusted to produce a visible light transmittance of 57 to 63% and a solar radiation heat transmittance of 57% in terms of 5 mm thickness.
It is known that a neutral gray glass having a neutral gray transmitted light color tone with a transmitted light color purity of ~63% and a transmitted light color purity of 1.5% or less is described. [Problems to be Solved by the Invention] Although the glass component composition described in the above-mentioned Japanese Patent Publication No. 57-7574 has good formability, it does not have good temperability by the thermal strengthening method, and its raw material The price is also high, and the
As described in Publication No. 1185, it is difficult to keep the temperature difference between the softening point and the deformation point within 117°C with a normal float glass component composition, so B ₂ O ₃ and/or TiO ₂ are selectively added. This is indispensable, and the raw material costs are high, making it difficult to adopt it for use in ordinary architectural glass sheets, automobile window glasses, etc. Furthermore, in the neutral gray glass described in the above-mentioned Japanese Patent Publication No. 52-49010, both visible light transmittance and solar radiation transmittance are 63% or less (52% or less).
mm equivalent), and when trying to use this glass for automobile window glass,
It cannot clear visible light transmittance of 70% or more according to JISR3211, and cannot be used for automobile window glass.For example, in the composition range near the upper and lower limits of each, the normal float method has poor formability and Problems arise in sheet manufacturing due to devitrification, and even if it were made, it would be a float glass with poor weather resistance, and furthermore, in some composition ranges, it would not be easily strengthened. [Means for Solving the Problems] The present invention has been made in view of the above-mentioned drawbacks of the conventional glass. In addition, it has a unique component composition that has low thermal conductivity and takes into account viscosity, and has improved toughness, weather resistance, and moldability, and has a visible light transmittance of 70% or more. A tempered colored glass composition is provided. That is, the present invention has a weight percentage of SiO ₂ 68.0~
71.0%, _{Al2O3 1.6} ~3.0%, CaO8.5~11.0%,
MgO2.0~4.0%, _Na2O12.5 ~16.0%, _K2O0.5 ~
Consists of 3.0% oxide component, the sum of these components is 97% or more, and SiO ₂ + Al ₂ O ₃ 70.0 ~
73.0%, CaO+MgO12.0~15.0%, _Na2O + _K2
O13.5-17.0%, as a trace component
CoO0.0010~0.0040%, NiO0.0002~0.0030%,
The composition has a composition range of Se0.0003 to 0.0010%, and the viscosity temperature at ¹⁰⁹ poise is 650 to 685℃, the viscosity temperature at ¹⁰¹² poise is 555 to 585℃, and the temperature difference between the two is 96 to 685℃. The present invention provides an easily temperable colored glass composition characterized by a temperature of 103°C. Here, the SiO ₂ component is 68.0 to 71.0% by weight percentage.
The reason is that if it is less than 68.0%, it tends to cause surface burns, etc., and its weather resistance decreases, causing practical problems.If it exceeds 71%, its easy strengthening properties decrease and it becomes difficult to melt. The reason why the Al ₂ O ₃ component is set at 1.6 to 3.0% by weight is that if it is less than 1.6, the weather resistance will decrease and the surface will easily become stained, causing practical problems. If it exceeds 8.5%, devitrification tends to occur, the molding temperature range narrows, and manufacturing becomes difficult.The reason why the CaO component is set at 8.5 to 11.0% by weight is that if it is less than 8.5%, the easy strengthening property decreases, and the meltability decreases. If it exceeds 11%, devitrification tends to occur, the molding work range is narrowed, and manufacturing becomes difficult. 2.0 in weight percentage
~4.0% is because if it is less than 2.0%, the melting temperature will rise and the operating range will be narrowed, making it difficult to manufacture.
If it exceeds 4.0%, the ease of reinforcement decreases,
The reason why the Na ₂ O component is set at 12.5 to 16.0% by weight is that if it is less than 12.5%, the easy strengthening properties will be reduced, the moldability will be difficult, and devitrification will easily occur, which will narrow the operating range and make it difficult to manufacture. If the K ₂ O content exceeds 16.0%, the weather resistance will decrease, and the surface will easily become stained, leading to practical problems and increasing costs. The reason why it is set at 3.0% is that if it is less than 0.5%, the easy reinforcing properties will decrease, and if it exceeds 3.0%, the weather resistance will decrease and the cost will increase. Also, SiO ₂ , Al ₂ O ₃ , CaO, MgO, Na ₂ O,
The total weight percentage of K ₂ O and Fe ₂ O ₃ is 97.0%.
The reason for this is to control the amount of trace components such as TiO ₂ and SO ₃ to not exceed 3%. Furthermore, the weight percentage of SiO ₂ + Al ₂ O ₃ is 70.0 ~
The reason for setting it at 73.0% is that if it is less than 70%, weather resistance will decrease, and if it exceeds 73.0%, easy reinforcement will decrease and problems will occur.
The reason why the CaO and MgO components are set at 12.0 to 15.0% is that they are used to lower the melting temperature, and the 12.0% to 15.0%
If it is less than 15%, the ease of reinforcement will decrease, and if it exceeds 15%, devitrification will easily occur and manufacturing will be difficult.
The reason why the weight percentage of Na ₂ O + K ₂ O is set to 13.5 to 17.0% is because if it is less than 13.5, easy strengthening properties will decrease, devitrification will occur easily, the working temperature range will be narrow in molding, and manufacturing will be difficult. If it exceeds this, the weather resistance decreases, causing practical problems, and the cost also increases. Furthermore, the weight percentage of Fe ₂ O ₃ component is 0.1~
0.15% and 0.0010 CoO component as trace component
~0.0040%, the NiO component to 0.0002 to 0.0030%, and the Se component to 0.0003 to 0.0010%, because with the composition of the above coloring components, it is possible to maintain the transmittance of the glass in the visible wavelength range at approximately the same level. As a result, the glass always exhibits a neutral gray color, and the _three Fe ₂ O components have absorption in the short wavelength side and long wavelength side of the visible range, and the CoO, NiO, and Si components have absorption. Due to its interaction with absorption, it has the effect of keeping the glass neutral gray. If it is less than 0.1%, such an effect cannot be obtained, and the transmittance in the visible range becomes too high and the color tone of the glass becomes purple. If it exceeds 0.15%, the transmittance on both sides of the visible range will be low, and the glass will have a greenish tinge and will not be able to maintain a neutral gray color. Fe ₂ O ₃ ,
It has the effect of maintaining the glass in a neutral gray color due to the mutual effect with the absorption of each component of NiO and Se. If it is less than 0.0010%, the transmittance in the above wavelength range increases and the glass takes on a reddish tinge. become,
If it exceeds 0.0040%, the transmittance in the above wavelength range will decrease and the glass will take on a bluish tinge. Therefore, outside the range of 0.0010 to 0.0040%, it will not be possible to maintain the glass in a neutral gray color. , NiO
The component has absorption in the wavelength range of 400 to 500 nm, and Fe ₂
Due to the interaction effect with the absorption of O ₃ , CoO, and Se components,
It has the effect of keeping the glass neutral gray. If it is less than 0.0002%, the transmittance in the above wavelength range will be high and the glass will take on a bluish-purple tone. If it exceeds 0.0030%, the transmittance in the above wavelength range will be high. The transmittance of the glass becomes low and the glass takes on a brownish tinge. Therefore, outside the range of 0.0002% to 0.0030%, the glass cannot be maintained in a neutral gray color. It has absorption in the _{wavelength region} of
The transmittance in the above wavelength range becomes high and the glass takes on a bluish-green tone.If it exceeds 0.0010%, the transmittance in the above wavelength range becomes low and the glass takes on a reddish-purple tone. ,0.0003
Outside the range of ~0.0010%, the glass cannot be maintained at a neutral gray color. In addition, 10 ⁹ poise and viscosity temperature
The reason why 10 ¹² poise was chosen is that 10 ⁹ poise is practically the temperature at which strengthening starts, and 10 ¹² poise can be considered to be the temperature at which viscous flow becomes small and strengthening ends. It is important that the viscous temperature at which ¹⁰⁹ poise occurs is 650 to 685℃, and the viscosity temperature at which ¹⁰¹² poise occurs is 555 to 585℃, and the temperature difference between the two is 96 to 103℃. Although the easy-to-strengthen property improves, problems occur in at least one of weather resistance, devitrification, formability, cost, etc., and when the temperature exceeds 103°C, the easy-to-strengthen property decreases, making it difficult to achieve the desired easy-to-strengthen performance. It is something that cannot be obtained. [Function] As mentioned above, the easily strengthenable colored glass composition of the present invention, that is, the combination of specific composition ranges of Se and each oxide component, and also by considering a specific adhesion temperature, In terms of formability,
Considering weather resistance, devitrification, cost, meltability, visible light transmittance, heat absorption performance, color tone, etc.
For example, in addition to the properties of conventional float glass, it is possible to improve the ease of strengthening without changing the manufacturing conditions, etc. Furthermore, by incorporating a coloring factor into the glass, it is possible to improve the strength of the glass during thermal strengthening. As the internal temperature difference increases, the ease of strengthening will continue to increase, and it is now possible to obtain a sufficient degree of strengthening of thin glass, etc., for which it was not possible to obtain a sufficient degree of strengthening with conventional thermal strengthening methods. Since a glass plate with an improved degree of reinforcement can be obtained, it can be more easily adopted in fields such as electronic and electrical equipment and cooking equipment, which were previously considered difficult to adopt, and can satisfy JISR-3211 while maintaining heat ray absorption performance. Therefore, we can provide more reliable, stable, high-strength, and colored heat ray-absorbing tempered glass for thin or laminated window glass for automobiles, railway vehicles, etc., architectural window glass, door glass, furniture glass, etc. Furthermore, the present invention improves manufacturing productivity and provides sufficient weather resistance. [Examples] Examples of the present invention will be described below. Examples 1 to 11 Glasses were made of specially selected silica sand (manufactured by Kyoritsu Ceramics) and primary reagents such as Al ₂ O ₃ , Fe ₂ O ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₃ ,
Weigh and mix KNO ₃ , CoO, NiO, and Se to the desired target composition, put the mixed raw materials into a crucible, and add approximately
It was melted and vitrified for about 3 hours in an electric furnace maintained at 1450°C, and then 1420°C was melted for further homogenization and clarification.
After keeping it at ℃~1430℃ for 2 hours, pour it into a mold to make a glass block with a size of 100 mm x 100 mm and a thickness of 100 mm.
Each sample was cut into a 3.5 mm glass plate, ground and polished. A wet analysis based on JISR-3101 was performed on the prepared sample, and the values shown in each example in Table 1 were obtained. Regarding the viscosity temperature, the viscosity curve was measured using the bending arm method, and 10 ⁹ poise and
The temperature of 10 ^{to 12} poise was determined, and the numerical values shown in each example in Table 2 were obtained. For confirmation, the strain point was measured using the Lilly method and the softening point was measured using the Littleton method.
The temperature difference between the softening point and strain point of glass is approximately 200 to 240
It was in the range of ℃. For devitrification, hold at a predetermined temperature for 2 hours, then rapidly cool.
The presence or absence of crystals was examined using a microscope, and the devitrification temperature was found to be 1040°C or less, which was not a problem. Regarding the moldability, the glass was pressed at about 700° C., and the moldability was judged comprehensively by taking into account the molding accuracy, mold release properties, etc., and there were no problems. Regarding weather resistance, 99%
Exposure to an ambient temperature of 50℃ at RH for about 2 months,
The surface condition was observed and there were no problems. Regarding easy strengthening, the above sample was heated in a furnace at an ambient temperature of about 730°C for about 3 to 5 minutes, and then strengthened by normal air cooling at an air pressure of 1300 Ap.
A tempered glass plate of 100 mm and a thickness of 3.5 mm is obtained, and this plate is crushed by impact at a position 30 mm from the corner end face of the glass plate, and the entire area of the glass plate is 50 mm x 50 mm in the central area of the glass plate. When the number of fractures was counted, for example, in Example 2, the number of fractures was 121, which was within the range of 60 to 400 determined by JIS, which was sufficiently satisfactory. The visible light transmittance was measured using a spectrophotometer 340 manufactured by Hitachi, and pass/fail was determined based on the value converted to a thickness of 5 mm, which was satisfactory. Each is as shown in Table 2. Comparative Examples 1 to 9 Glass plates and their viscosity temperature, easy strengthening properties, devitrification properties, moldability, weather resistance, visible light transmittance, etc. were tested in the same manner as in the examples, and the results are shown in the same manner as in the examples. 1 and Table 2. That is, for example, in terms of ease of strengthening, Comparative Example 1 clearly differs from the Examples, as the number of fractures was 48. Further, the measured values of the transmittance curves of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIG. 1, and the optical characteristics thereof are shown in Table 3, respectively.

【table】

【table】

【table】

〔Effect of the invention〕

As is clear from the above-mentioned Examples and Comparative Examples of the present invention, the present invention allows SiO ₂ , Al ₂ O ₃ , CoO, MgO, Na ₂ O,
As a glass component composition containing K ₂ O as a major component, it provides easy strengthening properties and can be made into a problem-free heat-absorbing colored glass with a visible light transmittance of 70% or more. It is possible to produce float glass without making any changes, especially without causing any problems in production, and the produced glass also has excellent weather resistance. As described above, the present invention makes it possible to thermally strengthen thin glass, expand the scope of use of tempered glass by the thermal strengthening method, and comply with JIS R-3211.
It has the remarkable effect that it can also be used as window glass for automobiles.

[Brief explanation of drawings]

FIG. 1 shows spectral transmittance curves of Examples 1 and 2 and Comparative Examples 1 and 2 of the easily temperable colored glass of the present invention.

Claims (1)

[Claims] 1. The following oxides in weight percentage: SiO ₂ 68.0-71.0% Al ₂ O ₃ 1.6-3.0% CaO 8.5-11.0% MgO 2.0-4.0% Na ₂ O 12.5-16.0% K ₂ O 0.5-3.0% Fe ₂ O ₃ 0.1-0.15% The sum of these components is 97% or more, and SiO ₂ + Al ₂ O ₃ 70.0-73.0% CaO + MgO 12.0%-15.0% Na ₂ O + K ₂ O 13.5-17.0 %, and the composition range is CoO 0.0010 to 0.0040%, NiO 0.0002 to 0.0030%, Se 0.0003 to 0.0010% as minor components, and the viscosity temperature at which the temperature becomes ¹⁰⁹ poise is 650 to 685℃ and the viscosity temperature at which the temperature becomes ¹⁰¹² poise. is 555 to 585°C, and the temperature difference between the two is 96 to 103°C.