JP6410077B2 - Crystallized glass, window glass, bulletproof window glass, and method for producing crystallized glass - Google Patents

Crystallized glass, window glass, bulletproof window glass, and method for producing crystallized glass Download PDF

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JP6410077B2
JP6410077B2 JP2014126928A JP2014126928A JP6410077B2 JP 6410077 B2 JP6410077 B2 JP 6410077B2 JP 2014126928 A JP2014126928 A JP 2014126928A JP 2014126928 A JP2014126928 A JP 2014126928A JP 6410077 B2 JP6410077 B2 JP 6410077B2
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小川 修平
修平 小川
晋作 西田
晋作 西田
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日本電気硝子株式会社
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Description

  The present invention relates to crystallized glass, window glass, bulletproof window glass, and a method for producing crystallized glass. In detail, it is related with the window glass and bulletproof window glass suitable for the use of the window glass for aircraft, and the window glass for protection.

  Traditionally, soda-lime glass and transparent resin such as polycarbonate and acrylic are alternately used for window glass such as bulletproof window glass that protects against bullets, aircraft window glass, and protective window glass that protects against scattered objects. Laminated glass laminated is used. Soda lime glass moves the shape of a projectile in a crash by changing the shape of the tip of bullets and flying objects (hereinafter referred to as “projectile”) to increase the resistance applied to the projectile. The energy is attenuated. In addition, the composition of soda lime glass is improved, and the kinetic energy of the projector is attenuated during the crash by increasing the resistance (hereinafter referred to as “crack resistance”) that causes the crack to progress during the crash of the projector. ing.

  However, although soda lime glass is inexpensive, its crack resistance is not so high. In order to improve the crack resistance of the glass and improve the protection performance from the projector, crystallized glass obtained by baking crystalline glass is used instead of soda lime glass (for example, Patent Document 1).

The crystallized glass, such as in Patent Documents 2 to 4, primary crystal as β- quartz solid solution (Li 2 O · Al 2 O 3 · nSiO 2 [ provided that n ≧ 2]) Li 2 O -Al 2 O such as 3 -SiO 2 based crystal can be used a Li 2 O-Al 2 O 3 -SiO 2 based crystalline crystallized glass glass baking to crystallize the formed by suitably precipitated. With crystallized glass, first, Li 2 O—Al 2 O 3 —SiO 2 crystalline glass is heated to the nucleation temperature, held for a certain period of time to precipitate minute crystal nuclei in the glass, and then crystallized. It is a glass in which crystals are precipitated by multi-stage heat treatment in which the temperature is raised to a growth temperature and held for a certain time to grow crystal nuclei.

Special table 2010-505718 gazette Japanese Examined Patent Publication No. 39-21049 Japanese Patent Publication No. 40-20182 JP-A-1-308845

  In recent years, the power of bullets has increased due to the improvement of bullet performance. In addition, hurricanes and typhoons with powers that could not be considered in the past have occurred, and the weight of scattered objects has increased. Therefore, the kinetic energy of the projectile tends to increase. Further, bulletproof window glass has been increasingly used as a window glass for luxury automobiles and the like, and there is a tendency for glass with less coloring to be demanded.

  In general, in order to improve the protective performance from the projector, a method of increasing the hardness of the crystallized glass and a method of increasing the thickness of the crystallized glass are conceivable.

  Examples of the former method include a method of improving the crystallinity of crystallized glass (the proportion of crystals in the crystallized glass). However, if the crystallinity is increased by simply changing the heat treatment conditions, the crystal grain size tends to increase. Therefore, the crystallized glass tends to become cloudy. Further, in order to increase the crystallinity of the crystallized glass, it is necessary to increase the heat treatment temperature or lengthen the heat treatment time, which causes an increase in production cost.

  The latter method increases the weight and volume of the window glass. And the increase in the weight of a bullet-proof window glass or an aircraft window glass may lead to a reduction in fuel consumption and a restriction on the place of use.

Further, as another problem, when impurities such as Fe 2 O 3 are mixed into the glass raw material of Li 2 O—Al 2 O 3 —SiO 2 crystalline glass, the crystallized glass is colored more strongly by crystallization. There is a problem of end up.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a window glass having high protection performance from a projector tile and less coloring.

As a result of intensive studies on the above problems, the present inventors have found that the crack resistance is improved by adding SnO 2 to the crystallized glass. On the other hand, when SnO 2 is crystallized, it acts to strengthen yellow coloring caused by Fe 2 O 3 and the like contained in Li 2 O—Al 2 O 3 —SiO 2 crystalline glass, It is necessary to take measures to suppress this. Therefore, a method of containing copper oxide that causes blue color development in general soda lime glass and suppressing the yellow color tone by complementary color is also conceivable, but Li 2 O—Al 2 O 3 —SiO 2 based crystalline glass is considered. At the time of crystallization, the valence of copper oxide changes due to the oxidation-reduction reaction with SnO 2 and changes to a color other than blue, and it is difficult to maintain the performance as a complementary colorant. Therefore, as a result of further studies, the inventors have included a chromium compound that changes to various colors due to a change in valence, whereby Li 2 O—Al 2 O 3 —SiO 2 crystalline glass is crystallized. As a result, it was found that the color tone of the chromium compound becomes a complementary color of yellow.

That is, the crystallized glass of the present invention, as represented by mass percentage, SiO 2 55~75%, Al 2 O 3 10~35%, Li 2 O 0.1~5%, ZrO 2 0~5%, SnO 2 0.01~0.5%, Cr 2 O 3 0.05~10ppm , BaO 0~10%, 0~5% MgO, 0~5% ZnO, TiO 2 0~5%, P 2 O 5 0~ It has a composition of 4%, As 2 O 3 0-0.4%, and has β-quartz solid solution crystals.

  By using such crystallized glass, it is possible to obtain a window glass having a high protection performance from a projectile and having little coloring.

  The window glass of the present invention is characterized by comprising the crystallized glass described above.

  By setting it as such a structure, the window glass with the high protection performance from a projectile and little coloring can be obtained.

  The bulletproof glass of the present invention includes the window glass described above.

  By setting it as such a structure, the bulletproof glass with very high protection performance from a bullet and little coloring can be obtained.

Method for producing a crystallized glass of the present invention, as represented by mass percentage, SiO 2 55~75%, Al 2 O 3 10~35%, Li 2 O 0.1~5%, ZrO 2 0~5%, SnO 2 0.01~0.5%, Cr 2 O 3 0.05~10ppm, BaO 0~10%, 0~5% MgO, 0~5% ZnO, TiO 2 0~5%, P 2 O 5 0 To crystallize β-quartz solid solution by heat-treating Li 2 O—Al 2 O 3 —SiO 2 crystalline glass containing ˜4% and As 2 O 3 0 to 0.4%. Features.

Here, “Li 2 O—Al 2 O 3 —SiO 2 based crystalline glass” means crystalline glass containing Li 2 O, Al 2 O 3 and SiO 2 as essential components.

  By using the crystallized glass produced by such a method for a window glass, a window glass having high protection performance from a projector and having little coloring can be obtained.

  According to the present invention described above, it is possible to provide a window glass having a high protection performance from a projectile and being less colored.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described. However, the present invention is not limited to the following embodiments, and is based on ordinary knowledge of a person skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

Since the crystallized glass of the present invention contains SnO 2 , the crack resistance of the crystallized glass is improved. On the other hand, SnO 2 works to strengthen yellow due to Fe 2 O 3 or the like contained as a trace component. In particular, when the content of Fe 2 O 3 is 10 to 200 ppm, the problem of coloring of crystallized glass is likely to occur. Since the crystallized glass of the present invention contains an appropriate amount of Cr 2 O 3 exhibiting a complementary color tone of yellow by crystallization, a crystallized glass with little coloring can be obtained.

Specifically, the crystallized glass of the present invention, as represented by mass percentage, SiO 2 55~75%, Al 2 O 3 10~35%, Li 2 O 0.1~5%, 0~5% MgO, ZnO 0~5%, BaO 0~10%, TiO 2 0~5%, ZrO 2 0~5%, P 2 O 5 0~4%, SnO 2 0.01~0.5%, As 2 O 3 0 0.4%, and containing a composition of Cr 2 O 3 0.05-10, characterized by having a crystal β- quartz solid solution.

The crystals of β- quartz solid solution, meaning crystallized glass precipitated Li 2 O as a constituent component, Al 2 O 3 and SiO 2 required to crystals (LAS-based crystals) as a main crystal, Li 2 O · Al 2 O 3 .nSiO 2 (where 4> n ≧ 2). Crystallized glass of the present invention, in addition to crystals of β- quartz solid solution, is LAS-based crystals β- spodumene [Li 2 O · Al 2 O 3 · nSiO 2 ( provided that n ≧ 4)] and, LAS-based crystals Other crystals may be precipitated. In addition, it is preferable that 80% or more of all the crystals are β-quartz solid solution crystals. Thereby, it becomes transparent crystallized glass.

  The reason why the composition of the glass is limited as described above in the present invention will be described below.

SiO 2 forms a glass skeleton and is a component constituting an LAS crystal. The content of SiO 2 is 55 to 75% in terms of mass percentage. When the content of SiO 2 is too small, the thermal expansion coefficient tends to be high, and it becomes difficult to obtain crystallized glass excellent in thermal shock resistance. In addition, chemical durability tends to decrease. On the other hand, when the content of SiO 2 is too large, the meltability of the glass deteriorates, the viscosity of the glass melt increases, and it tends to be difficult to clarify or form the glass. A preferable range of SiO 2 is 57 to 73%, a more preferable range is 59 to 71%, and a further preferable range is 60 to 70%.

Al 2 O 3 forms a glass skeleton and is a component constituting an LAS crystal. The content of Al 2 O 3 is 10 to 35% in terms of mass percentage. When the content of Al 2 O 3 is too small, the thermal expansion coefficient tends to be high, and it becomes difficult to obtain crystallized glass excellent in thermal shock resistance. In addition, chemical durability tends to decrease. On the other hand, when the content of Al 2 O 3 is too large, deteriorated the meltability of the glass, increases the viscosity of the glass melt, or not easily clarified, there is a tendency to forming of glass difficult. Further, mullite crystals are precipitated, and the glass is devitrified and easily broken. A preferable range of Al 2 O 3 is 12 to 33%, a more preferable range is 15 to 30%, and a further preferable range is 18 to 27%.

Li 2 O is a component that constitutes an LAS-based crystal, and has a great influence on crystallinity, and is a component that lowers the viscosity of glass and improves glass meltability and formability. The content of Li 2 O is 0.1 to 5% in terms of mass percentage. When the Li 2 O content is too small, or easily broken it through glass loses crystal mullite is precipitated, there is a tendency that transparency is lost. Further, when the glass is crystallized, LAS-based crystals are difficult to precipitate, and it becomes difficult to obtain crystallized glass excellent in thermal shock resistance. Further, the viscosity of the glass melt tends to increase, and the meltability and moldability of the glass and the ease of fining tend to deteriorate. On the other hand, when the content of Li 2 O is too large, crystallinity becomes too strong, the tendency of the glass to devitrification. A preferable range of Li 2 O is 0.1 to 4.5%, a more preferable range is 0.5 to 4%, and a further preferable range is 1 to 3%.

ZrO 2 is a nucleation component for precipitating crystals in the crystallization process. The content of ZrO 2 is 0 to 5% in terms of mass percentage. When the content of ZrO 2 is too large, there is a tendency to devitrification during melting the glass, forming the glass becomes difficult. A preferable range of ZrO 2 is 0.1 to 4.5%, a more preferable range is 0.5 to 4%, and a further preferable range is 1 to 3%.

SnO 2 is a component that works as a fining agent, and is also a component that improves heat resistance. SnO 2 is a component that improves the crack resistance of crystallized glass. The cause is not clear, but it is presumed that SnO 2 acts as a nucleating agent and the proportion of the crystal phase having stronger bonds between atoms than the glass phase increases, leading to an improvement in crack resistance. The content of SnO 2 is 0.01 to 0.5% in terms of mass percentage. When the content of SnO 2 is too small, it is difficult to obtain the effect as the heat resistance improved and a fining agent. Furthermore, the crack resistance is lowered. On the other hand, when the content of SnO 2 is too large, in addition to the glass tends to be devitrified, leading to increase in raw material costs. Furthermore, the discoloration tends to become stronger when crystallized. A preferable range of SnO 2 is 0.01 to 0.45%, a more preferable range is 0.05 to 0.42%, and a further preferable range is 0.1 to 0.4%.

Cr 2 O 3 is a component that functions as a colorant. In the present invention, Cr 2 O 3 is also a component that suppresses coloring of crystallized crystallized glass by making use of coloring characteristics. In general, chromium ions in glass cause green coloration when trivalent and yellow color when hexavalent. Even if a trivalent chromium compound is added when the glass is melted, the crystallized glass may cause yellow coloration because chromium ions are oxidized and replaced with hexavalent during crystallization. Therefore, when trivalent Cr 2 O 3 and SnO 2 coexist at the time of melting, tin ions act as a reducing agent, and even when crystallized, chromium ions remain trivalent and cause green color development. For this reason, there exists an effect | action which cancels yellow color and can suppress coloring of crystallized glass. The content of Cr 2 O 3 is 0.05 to 10 ppm in terms of mass percentage. A preferable range of Cr 2 O 3 is 1 to 8 ppm, a more preferable range is 1.5 to 7 ppm, and a further preferable range is 2 to 6 ppm.

  BaO is a component that lowers the viscosity of the glass and improves the meltability and moldability of the glass. The content of BaO is 0 to 10% in terms of mass percentage. When there is too much BaO content, the crystal | crystallization containing Ba will precipitate easily and glass will devitrify. A preferable range of BaO is 0 to 7%, and a more preferable range is 0 to 5%.

  MgO is a component that has the effect of being dissolved in the LAS crystal and increasing the thermal expansion coefficient of the LAS crystal. The content of MgO is 0 to 5% in terms of mass percentage. When the content of MgO is too large, the crystallinity becomes too strong and tends to devitrify, and the glass is easily broken. A preferable range of MgO is 0 to 4.5%, a more preferable range is 0 to 4%, and a further preferable range is 0 to 3.5%.

  ZnO, like MgO, is a component that dissolves in the LAS crystal. The content of ZnO is 0 to 5% in terms of mass percentage. If the ZnO content is too large, the crystallinity becomes too strong, and thus the glass tends to devitrify when molded while being slowly cooled. As a result, the glass tends to be broken, so that it becomes difficult to form by, for example, the float process. A preferable range of ZnO is 0 to 4.5%, a more preferable range is 0 to 4%, and a further preferable range is 0 to 3.5%.

TiO 2 is a component that serves as a nucleating agent for precipitating crystals. The content of TiO 2 is 0 to 5% in terms of mass percentage. When the content of TiO 2 is too large, the interaction between Fe 2 O 3 is a minor component, tend to enhance the coloration of crystallized glass. Moreover, it exists in the tendency for glass to devitrify, and shaping | molding of glass becomes difficult. A preferable range of TiO 2 is 0 to 4.5%, a more preferable range is 0 to 4%, and a further preferable range is 0 to 3.5%.

Incidentally, ZrO 2 and TiO 2 is a nucleation agent is preferably 0.1% to 5% in total. When the total amount of ZrO 2 and TiO 2 is too small, crystals are difficult to precipitate. On the other hand, when the total amount of ZrO 2 and TiO 2 is too large, the glass tends to devitrify, forming of glass difficult. A more preferable range of the total amount of ZrO 2 and TiO 2 is 0.1 to 4.5%, and a more preferable range is 0.5 to 4%.

P 2 O 5 is a component that promotes the phase separation of glass and assists the formation of crystal nuclei. The content of P 2 O 5 is 0 to 4% in terms of mass percentage. When the content of P 2 O 5 is too large, the glass tends to undergo phase separation in the melting process, the homogeneity of the glass tends to decrease. A preferable range of P 2 O 5 is 0 to 3.5%, a more preferable range is 0 to 3%, and a further preferable range is 0 to 2.5%.

As 2 O 3 is a component that acts as a fining agent. The content of As 2 O 3 is 0 to 0.4% in terms of mass percentage. If the content of As 2 O 3 is too large, it is not preferable in view of environmental problems. A preferable range of As 2 O 3 is 0 to 0.2%, a more preferable range is 0 to 0.1%, and a further preferable range is 0 to 0.01%.

  Furthermore, in addition to the above, the crystallized glass of the present invention may contain various components as shown below within a range not impairing the required properties.

Na 2 O is a component that decreases the viscosity of the glass and improves the glass meltability and moldability. The content of Na 2 O is preferably 0 to 1.0% in terms of percentage. When the content of Na 2 O is too large, when molding with gentle cooling, tend to glass is devitrified, glass tends to break. In addition, the coefficient of thermal expansion tends to increase, making it difficult to obtain glass with excellent thermal shock resistance. A more preferable range of Na 2 O is 0 to 0.6%, and a more preferable range is 0.05 to 0.5%.

K 2 O, like Na 2 O, is a component that lowers the viscosity of the glass and improves the meltability and moldability of the glass. The content of K 2 O is preferably expressed as a percentage and is 0 to 1.0%. When the content of K 2 O is too large, the coefficient of thermal expansion tends to increase, and it becomes difficult to obtain a glass excellent in thermal shock resistance. In addition, the creep resistance tends to decrease, and if the crystallized glass is used for a long time at a high temperature, the crystallized glass tends to be deformed. A more preferable range of K 2 O is 0 to 0.6%, and a more preferable range is 0.05 to 0.5%.

In the case of combination of Na 2 O and K 2 O, the content of these components is preferably set to 0.05% to 1.0% in total. When the total content of Na 2 O and K 2 O is too small, it is difficult to obtain the effect of reducing the viscosity of the glass and improving the glass meltability and moldability. On the other hand, if the total content of Na 2 O and K 2 O is too large, the coefficient of thermal expansion tends to increase, making it difficult to obtain a glass with excellent thermal shock resistance. Moreover, it becomes easy to devitrify when forming molten glass, or the creep resistance is lowered. If the crystallized glass is used for a long time at a high temperature, the crystallized glass is likely to be deformed.

  Moreover, it is possible to add CaO, SrO, and BaO as a component which lowers | hangs the viscosity of glass and improves the meltability and moldability of glass, and adds up to 10% by mass percentage display. In addition, since CaO, SrO, and BaO are components which devitrify the glass when the glass is melted, it is more preferable that these components are combined in an amount of 7% or less.

B 2 O 3 is a component that suppresses the growth of coarse crystals. The content of B 2 O 3 is expressed by mass percentage and is preferably 0 to 2.0%. If the B 2 O 3 content is too large, heat resistance tends to decrease. A more preferable range of B 2 O 3 is 0 to 1.5%, and a more preferable range is 0.1 to 1.2%.

Further, a clarifying agent such as Cl and SO 3 can be added up to 2.0% in terms of mass percentage.

In addition to the above components, various components can be contained. For example, trace components such as H 2 , CO 2 , CO, H 2 O, He, Ne, Ar, N 2 , noble metal elements such as Ag, Au, Pd, Ir, and rare earths such as La 2 O 3 , Y 2 O 3 Oxides, other network-forming oxides, modified oxides, intermediate oxides, and the like may be included.

Further, Fe 2 O 3 is preferably 10 to 200 ppm, more preferably from 20~120Ppm, further preferably 30~110Ppm.

  The crystallized glass of the present invention can be produced as follows.

First, as represented by mass percentage, SiO 2 55~75%, Al 2 O 3 10~35%, Li 2 O 0.1~5%, ZrO 2 0~5%, SnO 2 0.01~0.5% , Cr 2 O 3 0.05~10ppm, BaO 0~10%, 0~5% MgO, 0~5% ZnO, TiO 2 0~5%, P 2 O 5 0~4%, As 2 O 3 0 The glass raw material is formulated to have a composition of ˜0.4%. In addition, you may add the component for improving the meltability and moldability of glass, a clarifying agent, etc. as needed.

Next, after the prepared glass raw material is melted at a temperature of 1550 to 1750 ° C., the molten glass is formed into a predetermined shape such as a plate shape. Examples of the forming method include forming methods such as a float method, a roll-out method, a press method, and a fusion method. In this way, the Li 2 O—Al 2 O 3 —SiO 2 based crystalline glass of the present invention is obtained.

Li 2 O—Al 2 O 3 —SiO 2 crystalline glass obtained by the above procedure was heat-treated at 600 to 800 ° C. for 1 to 5 hours to form crystal nuclei, and further at 800 to 950 ° C. A heat treatment is performed for 0.5 to 3 hours to precipitate a β-quartz solid solution crystal as a main crystal. In this way, the crystallized glass of the present invention is obtained. In addition, before or during the crystallization treatment, bending may be performed by a method such as applying a load to the heated crystalline glass.

  The obtained crystallized glass is subjected to post-processing such as cutting and polishing. Then, it is fitted into the window frame and processed into the window glass of the present invention.

  The window glass of the present invention is used as a window glass for buildings or automobiles. The window glass of the present invention is particularly preferably used as a bulletproof glass because it has a very high protection performance against a projector tile.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to a following example.

(Examples 1-6 and Comparative Examples 1-4)
First, each raw material was prepared in the form of an oxide, hydroxide, carbonate, nitrate, etc. so as to be a glass having the composition described in Tables 1-2, and mixed uniformly to obtain a glass batch 1. . Separately from the glass batch 1, a glass batch 2 was prepared in which the amounts of Cr 2 O 3 and Fe 2 O 3 were 0 ppm, and other compositions were substantially the same as the glass batch 1. Each of the obtained glass batches 1 and 2 was melted in a glass melting furnace at a melting efficiency of 2.5 m 2 / (t / day). Thereafter, it formed into a plate shape to prepare a Li 2 O-Al 2 O 3 -SiO 2 based crystallized glass was gradually cooled. Thereafter, the Li 2 O—Al 2 O 3 —SiO 2 crystalline glass was heated at 400 ° C./hour from room temperature to 780 ° C., which is the nucleation temperature, with a roller hearth kiln, and held at 780 ° C. for 3 hours, The crystal growth temperature was raised to 890 ° C. at 120 ° C./hour, held at 890 ° C. for 1 hour, and crystallized by lowering to 25 ° C. at 440 ° C./hour to produce crystallized glass. And the measurement of the crack resistance of the crystallized glass obtained from the glass batch 1, and the b * of the crystallized glass obtained from the glass batch 1 and the crystallized glass obtained from the glass batch 2, and the difference between them Δb * value, which is the absolute value of. Moreover, the coloring of the crystallized glass obtained from the glass batch 1 was evaluated by visual observation.

  The crack resistance measurement was performed according to the following procedure. First, a crystallized glass sample obtained from the glass batch 1 was processed into a plate shape of 25 mm × 30 mm, and both surfaces were finished to a thickness of 3 mm by parallel and mirror polishing. This was placed in an air atmosphere at a temperature of 25 ° C. and a relative humidity of 30% so that the sample surface was horizontal on the test stage. Then, a Vickers indenter was driven into the sample surface with an arbitrary load, and the number of cracks generated from the four vertices of the indentation within 15 seconds after the completion of the driving was counted (maximum of 4 per time). This was repeated 20 times for one load, and the load at which the probability of occurrence of cracks was 50% (40/80) was measured as crack resistance. For the measurement, a micro hardness tester MTX-50 manufactured by Matsuzawa Seiki Co., Ltd. was used.

The measurement of Δb * was performed according to the following procedure. First, the crystallized glass samples obtained from the glass batch 1 and the glass batch 2 were processed into a plate shape of 25 mm × 30 mm, and both surfaces were finished in parallel and mirror polished to a thickness of 3 mm. These crystallized glass samples, using a spectrophotometer to measure the transmittance at a wavelength of 380 to 780 nm, b * color values of the CIE standard from the transmission, the absolute value of the difference between b * values △ b * Valued.

  In addition, the evaluation of the coloration of the crystallized glass is performed by visually confirming the presence or absence of coloration of the crystallized glass obtained from the glass batch 1, and when it is not possible to recognize that the crystallized glass is colored, When the coloration of crystallized glass was recognized, it was set as x.

Tables 1 and 2 show the measurement results of the crack resistance of the crystallized glass obtained from the glass batch 1, the Δb * value of the crystallized glass, and the evaluation result of the coloration of the crystallized glass.

The crystallized glass of each example had a high crack resistance value and little coloration. The reason for little coloring is considered that the crystallized glass was not colored by Fe 2 O 3 contained as a trace component.

Claims (4)

  1. In terms of mass percentage, SiO 2 55 to 75%, Al 2 O 3 10 to 35%, Li 2 O 0.1 to 5%, ZrO 2 0 to 5%, SnO 2 0.01 to 0.5%, Cr 2 O 3 0.05~10ppm, BaO 0~10% , 0~5% MgO, 0~5% ZnO, TiO 2 0~5%, P 2 O 5 0~4%, As 2 O 3 0~0 A crystallized glass comprising a composition of 4%, Fe 2 O 3 10 to 200 ppm , and having crystals of β-quartz solid solution.
  2.   A window glass comprising the crystallized glass according to claim 1.
  3.   A bulletproof glazing comprising the glazing according to claim 2.
  4. Represented by mass percentage, SiO 2 55~75%, Al 2 O 3 10~35%, Li 2 O 0.1~5%, ZrO 2 0.1~5%, SnO 2 0.01~0.5% , Cr 2 O 3 0.05~10ppm, BaO 0~10%, 0~5% MgO, 0~5% ZnO, TiO 2 0~5%, P 2 O 5 0~4%, As 2 O 3 0 It is characterized by precipitating β-quartz solid solution crystals by heat-treating Li 2 O—Al 2 O 3 —SiO 2 crystalline glass containing up to 0.4%, Fe 2 O 3 10-200 ppm. A method for producing crystallized glass.
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FR2990690B1 (en) * 2012-05-15 2016-01-01 Eurokera Quartz-beta vitroceramics, transparent, essentially colorless and non-diffusing; articles thereof vitroceramic; precursor glasses
JP2013249221A (en) * 2012-05-31 2013-12-12 Nippon Electric Glass Co Ltd Li2O-Al2O3-SiO2-BASED CRYSTALLIZED GLASS AND METHOD FOR PRODUCING THE SAME
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