JP5668322B2 - Optical glass, glass frit and translucent substrate with glass layer - Google Patents

Description

  The present invention relates to an optical glass, a glass frit, and a translucent substrate with a glass layer.

Conventionally, an optical glass containing P ₂ O ₅ , Bi ₂ O _3, and ZnO and having a high refractive index, a low-temperature softening property, and a low thermal expansion coefficient is known (for example, see Patent Document 1).

Japanese Patent No. 4059695

  However, the optical glass described in Patent Document 1 has a problem that it is easily devitrified during glass production. Further, the optical glass described in Patent Document 1 has a problem that it easily crystallizes when fired as a glass frit. When crystallized, the light transmittance is lowered and the smoothness of the glass surface may be impaired. In the following description, “crystallization” means crystallization when fired as a glass frit.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an optical glass, a glass frit, and a translucent substrate with a glass layer that are not easily devitrified and hardly crystallized.

According to one aspect of the invention,
A glass frit containing optical glass powder,
The optical glass is
In mol% display based on oxide,
P ₂ O ₅ and 0 to _20% B 2 _{O 3} 15 to 60% of _Bi 2 _{O 3} 15 to 28% of ZnO and containing 20-50%,
The value obtained by dividing the content of P ₂ O _{5 by} the content of ZnO is less than 0.48,
The total content of P ₂ O ₅ and B ₂ O ₃ is 30 to 60%,
When the total content of P ₂ O ₅ and B ₂ O ₃ exceeds 50% , a glass frit is provided, wherein the content of P ₂ O ₅ is 10% or less .

  According to the present invention, it is possible to provide an optical glass, a glass frit, and a light-transmitting substrate with a glass layer which are not easily devitrified and hardly crystallized.

It is sectional drawing which shows an example of a translucent board | substrate with a glass layer of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. The following embodiment is shown as an example, and various modifications can be made without departing from the object of the present invention.

  FIG. 1 is a cross-sectional view showing an example of a light-transmitting substrate with a glass layer of the present invention.

  In the example shown in FIG. 1, the light-transmitting substrate with a glass layer includes a light-transmitting substrate 110 and a glass layer 120 formed on the light-transmitting substrate 110.

(Translucent substrate)
The translucent substrate 110 is made of a material having a high transmittance for visible light, and is made of, for example, glass or plastic.

Examples of the glass constituting the light-transmitting substrate 110 include alkali glass, non-alkali glass, and quartz glass. Generally, soda lime glass is used. A general soda lime glass has an average linear expansion coefficient at 50 to 300 ° C. (hereinafter also simply referred to as “average linear expansion coefficient”) of about 87 × 10 ⁻⁷ / ° C., and an annealing point of about 550 ° C. is there. Since the translucent substrate 110 made of such soda-lime glass may be deformed when heat-treated at a temperature of 550 ° C. or higher, the glass layer 120 is preferably formed at a temperature lower than 550 ° C.

  In the case where the light-transmitting substrate 110 is formed of a plastic substrate, the plastic substrate may have a barrier property because the plastic substrate has lower moisture resistance than a glass substrate. For example, the translucent substrate 110 may have a configuration in which another glass layer is further formed on the side opposite to the glass layer 120 side on the plastic substrate.

  The thickness of the translucent substrate 110 is usually 0.1 mm to 2.0 mm. When the glass substrate which is the translucent substrate 110 is thin, the strength may be insufficient. As for the thickness of the glass substrate which is the translucent board | substrate 110, it is especially preferable that they are 0.5 mm-1.0 mm.

  A glass layer 120 is formed on the translucent substrate 110. The glass layer forming surface on the glass substrate which is the translucent substrate 110 may be subjected to a surface treatment such as silica coating. That is, a protective layer such as a silica film may be formed between the glass substrate that is the light-transmitting substrate 110 and the glass layer 120.

(Glass layer)
The glass layer 120 is expressed in mol% based on oxide, and P ₂ O ₅ is 0 to 20%, B ₂ O ₃ is 15 to 60%, Bi ₂ O ₃ is 10 to 37%, and ZnO is 5 to 50%. SiO ₂ 0-20%, Al ₂ O ₃ 0-10%, ZrO ₂ 0-5%, Gd ₂ O ₃ 0-10%, TiO ₂ 0-15%, Li ₂ O and Na 0 to 5% in total of ₂ O and K ₂ O, 0 to 10% in total of alkaline earth metal oxide, and a value obtained by dividing the content of P ₂ O _{5 by} the content of ZnO is 0.48. When the total content of P ₂ O ₅ and B ₂ O ₃ is 30 to 60% and the total content of P ₂ O ₅ and B ₂ O ₃ exceeds 50%, P The content of ₂ O ₅ includes optical glass that is 10% or less.

  Next, the glass composition of this optical glass will be described. The unit% means mol%.

P ₂ O ₅ is a component that becomes a skeleton of the glass, stabilizes the glass, and improves acid resistance, and may be contained up to 20%. If the content of P ₂ O ₅ exceeds 20%, devitrification tends to occur, crystallization tends to occur, and the refractive index may be lowered. When the effect of improving acid resistance is expected, the content is more preferably 2% or more, and further preferably 5% or more.

B ₂ O ₃ is a component that becomes a skeleton of the glass and stabilizes the glass, and is essential. The content of B ₂ O ₃ is 15% to 60%. If it is less than 15%, devitrification tends to occur, crystallization tends to occur, and the average linear expansion coefficient may increase. On the other hand, if it exceeds 60%, devitrification tends to occur, crystallization is likely to occur, and water resistance may be deteriorated.

Here, the total content of P ₂ O ₅ and B ₂ O ₃ is 30 to 60%. If it is less than 30%, devitrification tends to occur, crystallization tends to occur, and stability may be impaired. On the other hand, if it exceeds 60%, devitrification tends to occur, crystallization is likely to occur, and the refractive index may decrease. Here, when the total content of P ₂ O ₅ and B ₂ O ₃ exceeds 50%, the content of P ₂ O ₅ is preferably 10% or less. If it exceeds 10%, devitrification tends to occur and crystallization tends to occur.

  ZnO is a component that stabilizes the glass, is a component that raises the refractive index and lowers the glass transition point and the softening point, and is essential. The content of ZnO is 5 to 50%, preferably 20 to 50%. If it is less than 5%, devitrification tends to occur, crystallization tends to occur, and the glass transition point and softening point may be increased. In addition, the refractive index may decrease. On the other hand, if it exceeds 50%, the average linear expansion coefficient is excessively increased and devitrification easily occurs during glass forming.

Here, the value obtained by dividing the content of P ₂ O _{5 by} the content of ZnO is less than 0.48. If it is 0.48 or more, devitrification tends to occur and crystallization tends to occur. On the other hand, if it is 0.48 or more, the refractive index decreases, and the glass transition point and softening point may increase.

Bi ₂ O ₃ is a component that increases the refractive index and decreases the viscosity, and is essential. The content of Bi ₂ O ₃ is 10% to 37%, preferably 15 to 28%. If it is less than 10%, the refractive index may be too low. On the other hand, if it exceeds 37%, the average linear expansion coefficient becomes too large. There is also a risk of crystallization.

TiO ₂ is not essential, but is a component that increases the refractive index, and may be contained up to 15%. However, when it contains excessively, it will crystallize easily and there exists a possibility that a glass transition point and a softening point may rise. It is also possible to use WO ₃ instead of (or in addition to) TiO ₂ . The total content of TiO ₂ and WO ₃ is more preferably 0 to 12%.

ZrO ₂ is not essential, but is a component that increases the weather resistance and acid resistance of the glass, and may be contained up to 5%. If it exceeds 5%, crystallization tends to occur, and the glass transition point and softening point may be increased.

SiO ₂ is not essential, but is a component that stabilizes glass and suppresses crystallization, and may be contained up to 20%. If it exceeds 20%, the liquidus temperature rises and devitrification may occur.

Al ₂ O ₃ is not essential, but is a component that stabilizes the glass, and may be contained up to 10%. If it exceeds 10%, the liquidus temperature rises and devitrification may occur.

Gd ₂ O ₃ is not essential, but is a component that increases the refractive index while suppressing the average linear expansion coefficient low and suppresses crystallization near the softening point, and may be contained up to 10%. If it exceeds 10%, crystallization tends to occur and the glass transition point and softening point may be increased. In particular, when it is desired to achieve both low expansion and high refractive index, it is more desirable to contain 2% or more.

  MgO, CaO, SrO, and BaO are not essential, but are components that lower the viscosity, and are used in any one or a combination of two or more. Here, the total content of MgO, CaO, SrO and BaO is preferably 10% or less. If it exceeds 10%, the average linear expansion coefficient tends to be large, and the refractive index may be lowered. More preferably, it is 7% or less.

Li ₂ O, Na ₂ O, and K ₂ O are not essential, but are components that lower the viscosity, and are used alone or in combination of two or more. Here, the total content of Li ₂ O, Na ₂ O and K ₂ O is preferably 5% or less. If it exceeds 5%, the average linear expansion coefficient tends to be large, and the refractive index may be lowered. It is more desirable not to contain substantially.

  If these alkali metal oxides are contained, the alkali component may be diffused in the heat treatment step. The alkali component may adversely affect the electrical characteristics. Therefore, it is preferable that optical glass does not contain an alkali metal oxide substantially depending on a use. Here, “substantially not containing” means not actively containing, except for being contained as an impurity.

In addition to the above components, the optical glass is, for example, GeO ₂ , Nb ₂ O ₅ , Y ₂ O ₃ , Ce ₂ O ₃ , CeO ₂ , La ₂ O ₃ , TeO ₂ , SnO as long as the effects of the invention are not lost. SnO ₂ , Sb ₂ O ₃ , Ta ₂ O _{5 and the} like may be contained. However, it is preferable to limit them to 5% in total. Moreover, in order to adjust a color, you may contain a trace amount coloring agent. As the colorant, known ones such as transition metal oxides, rare earth metal oxides, and metal colloids are used. These colorants are used alone or in combination. In addition, it is preferable that optical glass does not contain PbO substantially.

  Next, the physical properties of this optical glass will be described.

Refractive index _{n d} of the optical glass, He lamp d-line (wavelength: 587.6 nm) when measured at 25 ° C., the preferred 1.75 or more, more preferably 1.80 or more, particularly 1.85 or more preferable.

  The glass softening point Ts of the optical glass is preferably 600 ° C. or less, more preferably 595 ° C. or less, and particularly preferably 590 ° C. or less.

  When the translucent substrate 110 is made of soda lime glass, the glass transition point Tg of the optical glass is preferably 500 ° C. or less, more preferably 495 ° C. or less, in order to suppress thermal deformation of the translucent substrate 110. 485 ° C. or lower is particularly preferable.

  In order to suppress crystallization, the crystallization peak temperature Tc of the optical glass is preferably 600 ° C. or higher, more preferably 650 ° C. or higher, and particularly preferably 700 ° C. or higher.

  The difference (Tc−Ts) between the crystallization peak temperature Tc and the glass softening temperature Ts of the optical glass is preferably 55 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 90 ° C. or higher in order to suppress crystallization.

The average linear expansion coefficient α of the optical glass at 50 to 300 ° C. is 60 × 10 ⁻⁷ / ° C. or more in order to prevent the soda lime glass from being damaged or warped when the translucent substrate 110 is made of soda lime glass. Is preferable, and 65 × 10 ⁻⁷ / ° C. or more is more preferable. Further, the average linear expansion coefficient α of the optical glass at 50 to 300 ° C. is preferably 100 × 10 ⁻⁷ / ° C. or less, and more preferably 90 × 10 ⁻⁷ / ° C. or less.

  In this optical glass, raw materials such as oxides, phosphates, metaphosphates, carbonates, nitrates and hydroxides are weighed and mixed, and then at a temperature of 900 to 1400 ° C. using a crucible such as platinum. It can be obtained by dissolving and cooling. Thereafter, it may be gradually cooled as necessary to remove distortion. The obtained optical glass is pulverized with a mortar, ball mill, jet mill or the like, and classified as necessary to obtain optical glass powder. The surface of the optical glass powder may be modified with a surfactant or a silane coupling agent.

(Method for producing glass layer)
The glass layer 120 can be manufactured by applying a glass frit on the translucent substrate 110 and baking it.

(1) Glass frit The glass frit contains the optical glass powder. The particle size of the optical glass powder is preferably 1 to 10 μm from the viewpoint of coatability. The surface of the optical glass powder may be modified with a surfactant or a silane coupling agent.

  The glass frit is preferably applied on the light-transmitting substrate 110 as a frit paste kneaded with a resin or a solvent from the viewpoint of coating properties.

(2) Frit paste A frit paste is obtained by mixing glass frit and a vehicle with a planetary mixer or the like and uniformly dispersing them with a three roll or the like. You may further knead | mix with a kneading machine for viscosity adjustment. Usually, the glass frit is mixed at a ratio of 70 to 80% by mass and the vehicle at a ratio of 20 to 30% by mass.

  Here, the vehicle means a mixture of a resin and a solvent, and includes a mixture of a surfactant. Specifically, a resin, a surfactant, or the like is put into a solvent heated to 50 to 80 ° C., and then allowed to stand for about 4 to 12 hours, followed by filtration.

  The resin is for retaining the frit paste film after application. Specific examples include ethyl cellulose, nitrocellulose, acrylic resin, vinyl acetate, butyral resin, melamine resin, alkyd resin, and rosin resin. There are ethyl cellulose and nitrocellulose as main agents. Butyral resin, melamine resin, alkyd resin, and rosin resin are used as additives for improving the strength of the coating film. The binder removal temperature during firing is 350 to 400 ° C. for ethyl cellulose and 200 to 300 ° C. for nitrocellulose.

  The solvent is for dissolving the resin and adjusting the viscosity of the frit paste. The solvent is preferably not dried during coating, but quickly dried during drying, and preferably has a boiling point of 200 to 230 ° C. Specific examples include ether solvents (butyl carbitol (BC), butyl carbitol acetate (BCA), diethylene glycol di-n-butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, butyl cellosolve acetate), alcohol solvents (α -Terpineol, pine oil, Dawanol), ester solvent (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), phthalate ester solvent (DBP (dibutyl phthalate), DMP (dimethyl phthalate) , DOP (dioctyl phthalate)). These solvents may be used alone or in combination for adjusting the viscosity, the solid content ratio, and the drying speed. Mainly used are α-terpineol and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate). DBP (dibutyl phthalate), DMP (dimethyl phthalate), and DOP (dioctyl phthalate) also function as a plasticizer.

(3) Application As a method for applying the frit paste onto the translucent substrate 110, screen printing, doctor blade printing, die coating printing, or the like is used. Alternatively, the frit paste may be applied to a PET film or the like and dried to obtain a green sheet, and the green sheet may be thermocompression bonded onto the light transmitting substrate 110.

  When screen printing is used, the film thickness of the frit paste film after coating can be controlled by adjusting the mesh mesh roughness of the screen plate, the emulsion thickness, the pressing pressure during printing, the squeegee indentation amount, and the like.

  When doctor blade printing or die coat printing is used, the thickness of the frit paste film after application can be increased compared with the case where screen printing is used.

  Note that the thickness of the frit paste film may be increased by repeating application and drying.

(4) Firing The frit paste applied on the translucent substrate 110 is fired. Firing includes a binder removal process for decomposing and disappearing the resin in the frit paste and a firing process for sintering and softening the frit paste after the binder removal process. The binder removal temperature is 350 to 400 ° C. for ethyl cellulose and 200 to 300 ° C. for nitrocellulose, and heating is performed in an air atmosphere for 30 minutes to 1 hour. The firing temperature (firing temperature) is set within the range of −40 ° C. to + 30 ° C. based on the glass softening point Ts of the glass frit, or within the range of + 50 ° C. to + 120 ° C. based on the glass transition point Tg of the glass frit. Is done. After baking, the glass layer 120 is formed on the translucent substrate 110 by cooling to room temperature.

  The shape and size of the bubbles remaining in the glass layer 120 can be adjusted by adjusting the firing temperature, firing atmosphere, particle size distribution of the glass frit, and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

(Experiment 1)
For Examples 1 to 46, H ₃ BO ₃ , ZnO, Bi ₂ O ₃ , TiO ₂ , WO ₃ , Zn (PO ₃ ) ₂ , Li so as to obtain glasses having the compositions in Tables 1 to 6 Each powder raw material of ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , MgO, CaCO ₃ , SrCO ₃ , BaCO ₃ , ZrO ₂ , Gd ₂ O ₃ , SiO ₂ , Al ₂ O ₃ will be 200 g in total. After being weighed and mixed, using a platinum crucible, melting was carried out for 1 hour at 1050 ° C. for Examples 1 to 26 and 1250 ° C. for Examples 27 to 46, followed by Examples 1 to 26 For Example 27 to Example 46 at 950 ° C., melt at 1100 ° C. for 1 hour, half of the melt is poured into a carbon mold to obtain bulk glass, and the rest is poured into a gap between twin rolls and quenched. Get flaky glass . The bulk glass was put in an electric furnace at 500 ° C., and the strain was removed by lowering the temperature to room temperature at a rate of 100 ° C. per hour.

  Here, Examples 1 to 23 and Examples 27 to 46 are examples, and Examples 24 to 26 are comparative examples.

About the obtained glass, the presence or absence of devitrification at the time of bulk production, the presence or absence of devitrification at the time of flake production, the presence or absence of crystallization at the time of frit baking, the refractive index n _d , the glass transition point Tg (unit: ° C.), 50- Average linear expansion coefficient α (unit: 10 ⁻⁷ / ° C.) at 300 ° C., glass softening point Ts (unit: ° C.), crystallization peak temperature Tc (unit: ° C.), peak height of crystallization peak temperature (unit: μV) was measured by the following measurement method.
1. Devitrification during bulk production:
Before the glass is poured into a carbon mold and solidified, ◯ indicates that crystal precipitation and phase separation cannot be confirmed inside the glass, and △ indicates that crystal precipitation and phase separation can be partially confirmed. The case where crystal precipitation or phase separation occurred was marked as x.
2. Devitrification when making flakes:
After the glass is poured into the gap between the twin rolls, rapidly cooled, and solidified, it is marked with ○ where crystal precipitation and phase separation cannot be visually confirmed inside the glass, and when crystal precipitation and phase separation can be partially confirmed with x. did.
3. Crystallization during frit firing:
After pulverizing the flaky glass in an agate mortar, the glass powder having a particle size of 74 μm to 106 μm was sieved, 120 mg of this was put into a platinum pan, and heated in an electric furnace from room temperature to 600 ° C. at a heating rate of 10 ° C./min. When the crystal precipitation could not be confirmed visually inside the glass, it was marked with ◯, and when the crystal was deposited and became opaque, the mark was marked with x.
4). Refractive index n _d :
After polishing the bulk glass, it was measured at 25 ° C. with a measurement wavelength of 587.6 nm by a V-block method using a precision refractometer KPR-2000 manufactured by Kalnew.
5. Glass transition point Tg (unit: ° C):
The bulk glass was processed into a round bar shape having a diameter of 5 mm and a length of 200 mm, and then measured with a thermal dilatometer TD5000SA manufactured by Bruker AXS, Inc. at a heating rate of 5 ° C./min.
6. Average linear expansion coefficient α (unit: 10 ⁻⁷ / ° C.) at 50 to 300 ° C .:
The bulk glass was processed into a round bar shape having a diameter of 5 mm and a length of 200 mm, and then measured with a thermal thermal expansion meter TD5000SA manufactured by Bruker AXS Co., Ltd. at a heating rate of 5 ° C./min. When the length of the glass rod at 50 ° C. is L ₅₀ and the length of the glass rod at 300 ° C. is L ₃₀₀ , the average linear expansion coefficient α at 50 ° C. to 300 ° C. is α = {(L ₃₀₀ / L ₅₀ ) -1} / (300-50).
7). Glass softening point Ts (unit: ° C):
After pulverizing the flaky glass in an agate mortar, the glass powder having a particle size of 74 μm to 106 μm is sieved, and 120 mg of this is put into a platinum pan. The glass softening point Ts was defined as the temperature at the inflection point of the DTA curve accompanying the softening flow appearing on the higher temperature side than the glass transition point Tg.
8). Crystallization peak temperature Tc (unit: ° C.):
After pulverizing the flaky glass in an agate mortar, the glass powder having a particle size of 74 μm to 106 μm is sieved, and 120 mg of this is put into a platinum pan. The temperature was measured at ° C / min, and the temperature of the exothermic peak of the DTA curve accompanying crystallization was defined as Tc. When there was no crystallization peak or it was not detected sufficiently low, it was marked as “−”.
9. Peak height of crystallization peak temperature (unit: μV):
After pulverizing the flaky glass in an agate mortar, the glass powder having a particle size of 74 μm to 106 μm is sieved, and 120 mg of this is put into a platinum pan. The measurement was performed at a temperature of ° C / min, and the height of the exothermic peak of the DTA curve accompanying crystallization was read. When there was no crystallization peak or it was not detected sufficiently low, it was marked as “−”.

  The results are shown in Tables 1-6. In addition, when the sample for a physical-property value measurement was not able to be produced by devitrification, it described as "N / A."

表１〜表６からわかるように、例１〜例２３及び例２７〜例４６のガラスは、高屈折率と低温軟化性と低熱膨張率を有し、かつ、ガラス作製時の失透やフリット焼成時の結晶化を抑制することができた。また、例１〜例２３及び例２７〜例４６のガラスは、いずれも、ガラス転移点Ｔｇが５００℃以下であり、平均線膨張係数αが６０×１０^−７〜１００×１０^−７／℃であるため、ソーダライムガラス基板上で焼成してガラス層を形成させることができる。

As can be seen from Tables 1 to 6, the glasses of Examples 1 to 23 and Examples 27 to 46 have a high refractive index, a low temperature softening property, and a low coefficient of thermal expansion, and devitrification and frit during glass production. Crystallization during firing could be suppressed. Further, the glass of Examples 1 to 23 and Examples 27 to Example 46, both the glass transition point Tg is not more 500 ° C. or less, an average linear expansion coefficient α is ^{60 × 10 -7 ~100 × 10 -7} / ℃ Therefore, it can be fired on a soda lime glass substrate to form a glass layer.

(Experiment 2)
Next, the flaky glass having the composition of Example 1 was dry pulverized for 2 hours with an alumina ball mill to obtain a glass frit. The mass average particle size of the glass frit was 3 microns. 75 g of the obtained glass frit was kneaded with 25 g of an organic vehicle (10% by mass of ethyl cellulose dissolved in α-terpineol) to prepare a glass paste. This glass paste was printed in the center at a size of 9 cm square on a soda lime glass substrate having a size of 10 cm × 10 cm and a thickness of 0.55 mm so that the thickness after firing was 30 μm. This was dried at 150 ° C. for 30 minutes, then returned to room temperature, heated to 450 ° C. in 30 minutes, and held at 450 ° C. for 30 minutes to decompose and disappear the resin of the organic vehicle. Thereafter, the temperature was raised to 515 ° C. in 7 minutes and held at 515 ° C. for 30 minutes to soften the glass frit. Thereafter, the temperature was lowered to room temperature in 3 hours, and a glass layer having the composition of Example 1 was formed on a soda lime glass substrate. As a result of the visual test, no cracks were found on both sides of the soda lime glass substrate and the glass layer. Moreover, as a result of observing a glass layer using the transmission microscope (Nikon Corporation ECLIPSE ME600), the crystal | crystallization was not discovered by the glass layer.

  Further, the glass flits were obtained by dry-grinding the flaky glass having the composition of Example 19 for 2 hours with an alumina ball mill. The mass average particle size of the glass frit was 3 microns. 75 g of the obtained glass frit was kneaded with 25 g of an organic vehicle (10% by mass of ethyl cellulose dissolved in α-terpineol) to prepare a glass paste. This glass paste was printed in the center at a size of 9 cm square on a soda lime glass substrate having a size of 10 cm × 10 cm and a thickness of 0.55 mm so that the thickness after firing was 30 μm. This was dried at 150 ° C. for 30 minutes, then returned to room temperature, heated to 450 ° C. in 30 minutes, and held at 450 ° C. for 30 minutes to decompose and disappear the resin of the organic vehicle. Thereafter, the temperature was raised to 520 ° C. in 7 minutes and held at 520 ° C. for 30 minutes to soften the glass frit. Thereafter, the temperature was lowered to room temperature in 3 hours, and a glass layer having the composition of Example 1 was formed on a soda lime glass substrate. As a result of the visual test, no cracks were found on both sides of the soda lime glass substrate and the glass layer. Moreover, as a result of observing a glass layer using the transmission microscope (Nikon Corporation ECLIPSE ME600), the crystal | crystallization was not discovered by the glass layer.

  The flake glass having the composition of Example 43 was dry pulverized with an alumina ball mill for 2 hours to obtain a glass frit. The mass average particle size of the glass frit was 3 microns. 75 g of the obtained glass frit was kneaded with 25 g of an organic vehicle (10% by mass of ethyl cellulose dissolved in α-terpineol) to prepare a glass paste. This glass paste was printed in the center at a size of 9 cm square on a soda lime glass substrate having a size of 10 cm × 10 cm and a thickness of 0.55 mm so that the thickness after firing was 30 μm. This was dried at 150 ° C. for 30 minutes, then returned to room temperature, heated to 450 ° C. in 30 minutes, and held at 450 ° C. for 30 minutes to decompose and disappear the resin of the organic vehicle. Thereafter, the temperature was raised to 545 ° C. over 10 minutes and held at 545 ° C. for 30 minutes to soften the glass frit. Thereafter, the temperature was lowered to room temperature in 3 hours, and a glass layer having the composition of Example 1 was formed on a soda lime glass substrate. As a result of the visual test, no cracks or warpage were found on both sides of the soda lime glass substrate and the glass layer. Moreover, as a result of observing a glass layer using the transmission microscope (Nikon Corporation ECLIPSE ME600), the crystal | crystallization was not discovered by the glass layer.

  As described above, it can be seen that the optical glass of the present embodiment has good adhesion to a soda lime glass substrate and does not cause problems such as cracking and crystallization.

110 Translucent substrate 120 Glass layer

Claims (21)

A glass frit containing optical glass powder,
The optical glass is
In mol% display based on oxide,
P ₂ O ₅ and 0 to _20% B 2 _{O 3} 15 to 60% of _Bi 2 _{O 3} 15 to 28% of ZnO and containing 20-50%,
The value obtained by dividing the content of P ₂ O _{5 by} the content of ZnO is less than 0.48,
The total content of P ₂ O ₅ and B ₂ O ₃ is 30 to 60%,
A glass frit characterized by that when the total content of P ₂ O ₅ and B ₂ O ₃ exceeds 50%, the content of P ₂ O ₅ is 10% or less. The optical glass is
In mol% display based on oxide,
The total content of TiO ₂ and WO ₃ is 0-12%,
The content of ZrO ₂ is 0-5%,
The total content of MgO, CaO, SrO and BaO is 0 to 10%,
Glass frit according to claim 1, total content of Li ₂ O, Na ₂ O and _{K 2} O is characterized in that 0 to 5%. 3. The glass frit according to claim 1 , wherein the optical glass has a refractive index of 1.85 or more measured at 25 ° C. with a He lamp d line (wavelength: 587.6 nm). The optical glass has a glass according to any one of claims 1 to 3, wherein the average linear expansion coefficient at 50 ° C. to 300 ° C. is ^{60 × 10 -7 ~100 × 10 -7} / ℃ Frit . 5. The glass frit according to claim 1 , wherein the optical glass has a P ₂ O ₅ content of 5 to 20% in terms of an oxide-based mol%. The glass frit according to any one of claims 1 to 4, wherein the optical glass does not substantially contain P ₂ O ₅ except that the optical glass is contained as an impurity. The optical glass, except that it is contained as an impurity, a glass according to any one of claims 1 to 6, characterized in that substantially does not contain Li 2 _O, Na 2 _O and K _{2 O} Frit . And the light-transmitting substrate, a light-transmitting substrate with a glass layer and a glass layer formed on the transparent substrate,
The glass layer is seen including an optical glass,
The optical glass is
In mol% display based on oxide,
P ₂ O ₅ and 0 to _20% B 2 _{O 3} 15 to 60% of _Bi 2 _{O 3} 15 to 28% of ZnO and containing 20-50%,
The value obtained by dividing the content of P ₂ O _{5 by} the content of ZnO is less than 0.48,
The total content of P ₂ O ₅ and B ₂ O ₃ is 30 to 60%,
P ₂ O ₅ and _B 2 _{O 3} glass layer with the light-transmitting substrate, wherein when the total content exceeds 50% _P 2 _{O 5} content is less than 10% of.   The optical glass is
  In mol% display based on oxide,
  TiO ₂ And WO ₃ The total amount of the contents is 0-12%,
  ZrO ₂ Content of 0 to 5%,
  The total content of MgO, CaO, SrO and BaO is 0 to 10%,
  Li ₂ O and Na ₂ O and K ₂ The translucent substrate with a glass layer according to claim 8, wherein the total content of O is 0 to 5%.   10. The translucent glass layer according to claim 8, wherein the optical glass has a refractive index of 1.85 or more measured at 25 ° C. with a He lamp d-line (wavelength: 587.6 nm). substrate.   The optical glass has an average coefficient of linear expansion of 60 × 10 5 at 50 ° C. to 300 ° C. ^-7 ~ 100 × 10 ^-7 It is / degreeC, The translucent board | substrate with a glass layer as described in any one of Claims 8-10 characterized by the above-mentioned.   The optical glass is expressed in terms of mol% based on oxide, and P ₂ O ₅ The translucent substrate with a glass layer according to any one of claims 8 to 11, wherein the content of is 5 to 20%.   The optical glass is P except that it is contained as an impurity. ₂ O ₅ The translucent board | substrate with a glass layer as described in any one of Claims 8-11 characterized by not containing substantially.   The optical glass is Li except that it is contained as an impurity. ₂ O and Na ₂ O and K ₂ The translucent substrate with a glass layer according to any one of claims 8 to 13, wherein O is not substantially contained. In mol% display based on oxide,
P ₂ O ₅ and 0 to _20% B 2 _{O 3} 15 to 60% of _Bi 2 _{O 3 10~37%,} a ZnO 5 to 50% of SiO ₂ 0 to 20% of _Al 2 _{O 3} 0-10%, a ZrO ₂ 0 to 5% of _Gd 2 _{O 3} 0-10%, the TiO ₂ 0 to 15% 0 to 5% of Li ₂ O, Na ₂ O and _{K 2} O in total, Contains a total of 0-10% alkaline earth metal oxides,
The value obtained by dividing the content of P ₂ O _{5 by} the content of ZnO is less than 0.48,
The total content of P ₂ O ₅ and B ₂ O ₃ is 30 to 60%,
An optical glass characterized in that when the total content of P ₂ O ₅ and B ₂ O ₃ exceeds 50%, the content of P ₂ O ₅ is 10% or less. The optical glass according to claim 15 , wherein the refractive index measured at 25 ° C. with a He lamp d-line (wavelength: 587.6 nm) is 1.75 or more. In mol% display based on oxide,
The optical glass according to claim 15 or 16 , wherein the content of P ₂ O ₅ is 2 to 20%. In mol% display based on oxide,
The optical glass according to any one of claims 15-17, wherein the content of Gd ₂ O ₃ is 2-10%. Except that it is contained as an impurity, Li ₂ O and Na ₂ O and the optical glass according to any one of claims 15-18, characterized in that substantially does not contain _{K 2} O. A glass frit containing the optical glass powder according to any one of claims 15 to 19 . And the light-transmitting substrate, a light-transmitting substrate with a glass layer and a glass layer formed on the transparent substrate,
The glass layer, the glass layer with the light-transmitting substrate comprising the optical glass according to any one of claims 15-19.

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