阅读说明：本技术 玻璃材料 (Glass material ) 是由 毛露路 郝良振 匡波 于 2020-05-27 设计创作，主要内容包括：本发明提供一种玻璃材料,其组分以重量百分比表示,含有：SiO<Sub>2</Sub>：50～70％；B<Sub>2</Sub>O<Sub>3</Sub>：3～15％；TiO<Sub>2</Sub>：0.5～10％；ZnO：1～12％；Al<Sub>2</Sub>O<Sub>3</Sub>：0.5～10％；Na<Sub>2</Sub>O+K<Sub>2</Sub>O：5～22％,其中B<Sub>2</Sub>O<Sub>3</Sub>/SiO<Sub>2</Sub>为0.06～0.26,(TiO<Sub>2</Sub>+ZnO)/Al<Sub>2</Sub>O<Sub>3</Sub>为0.5～8.0。通过合理的组分设计,本发明获得的玻璃材料具有较高的光透过率和优异的化学稳定性,满足感光器件封装等领域的应用。(The invention provides a glass material, which comprises the following components in percentage by weight: SiO 2 2 ：50～70％；B 2 O 3 ：3～15％；TiO 2 ：0.5～10％；ZnO：1～12％；Al 2 O 3 ：0.5～10％；Na 2 O+K 2 O: 5 to 22% of B, wherein 2 O 3 /SiO 2 0.06 to 0.26 (TiO) 2 +ZnO)/Al 2 O 3 0.5 to 8.0. Through reasonable component design, the glass material obtained by the invention has higher light transmittance and excellent chemical stability, and meets the application in the fields of photosensitive device packaging and the like.)

1. The glass material is characterized by comprising the following components in percentage by weight: SiO 2₂：50～70％；B₂O₃：3～15％；TiO₂：0.5～10％；ZnO：1～12％；Al₂O₃：0.5～10％；Na₂O+K₂O: 5 to 22% of B, wherein₂O₃/SiO₂0.06 to 0.26 (TiO)₂+ZnO)/Al₂O₃0.5 to 8.0.

2. The glass material according to claim 1, wherein the glass material further contains MgO + CaO + SrO + BaO in an amount of 0 to 10% by weight and/or L i₂O: 0 to 5 percent; and/or P₂O₅: 0 to 5 percent; and/or ZrO₂0 to 5%, and/or L a₂O₃: 0 to 5 percent; and/or Y₂O₃: 0 to 5 percent; and/or Gd₂O₃: 0 to 5 percent; and/or Nb₂O₅: 0 to 5 percent; and/or WO₃: 0 to 5 percent; and/or a clarifying agent: 0 to 1 percent.

3. Glass material, characterized in that its composition, expressed in weight percentage, is represented by SiO₂：50～70％；B₂O₃：3～15％；TiO₂：0.5～10％；ZnO：1～12％；Al₂O₃：0.5～10％；Na₂O+K₂O：5～22％；MgO+CaO+SrO+BaO：0～10％；Li₂O：0～5％；P₂O₅：0～5％；ZrO₂：0～5％；La₂O₃：0～5％；Y₂O₃：0～5％；Gd₂O₃：0～5％；Nb₂O₅：0～5％；WO₃: 0 to 5 percent; a clarifying agent: 0 to 1% of a component B₂O₃/SiO₂0.06 to 0.26 (TiO)₂+ZnO)/Al₂O₃0.5 to 8.0.

4. According to claims 1 to 3The glass material of any one of claims, wherein the composition is expressed in weight percent, wherein: b is₂O₃/SiO₂0.08 to 0.2; and/or (TiO)₂+ZnO)/Al₂O₃0.7 to 7.0; and/or (SiO)₂+TiO₂)/(Na₂O + ZnO) is 3.0 to 12.0; and/or ZnO/B₂O₃0.2 to 1.8; and/or (Na)₂O+K₂O)/Al₂O₃0.8 to 8.0; and/or (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.2 to 2.5; and/or (B)₂O₃+K₂O)/Al₂O₃Is 1.0 to 10.0.

5. A glass material according to any one of claims 1 to 3, characterised in that its composition is expressed in weight percentages in which: (MgO + CaO + SrO + BaO)/ZnO is less than 1.0; and/or (MgO + CaO + SrO + BaO)/Al₂O₃Is 1.0 or less; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 1.0 or less.

6. A glass material according to any one of claims 1 to 3, characterised in that its composition is expressed in weight percentages in which: SiO 2₂: 55-68%; and/or B₂O₃: greater than 5% but less than or equal to 13%; and/or TiO₂: 1.5-8%; and/or ZnO: 2-10%; and/or Al₂O₃: 1-8%; and/or Na₂O+K₂6-20% of O, and/or 0-5% of MgO + CaO + SrO + BaO, and/or L i₂O: 0 to 3 percent; and/or P₂O₅: 0 to 3 percent; and/or ZrO₂0 to 3%, and/or L a₂O₃: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or Gd₂O₃: 0 to 3 percent; and/or Nb₂O₅: 0 to 3 percent; and/or WO₃: 0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent.

7. The method according to any one of claims 1 to 3The glass material is characterized by comprising the following components in percentage by weight: b is₂O₃/SiO₂0.1 to 0.18; and/or (TiO)₂+ZnO)/Al₂O₃1.0 to 5.0; and/or (SiO)₂+TiO₂)/(Na₂O + ZnO) is 3.0 to 10.0; and/or ZnO/B₂O₃0.3 to 1.0; and/or (Na)₂O+K₂O)/Al₂O₃1.0 to 6.0; and/or (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.3 to 2.0; and/or (B)₂O₃+K₂O)/Al₂O₃1.5 to 8.0.

8. A glass material according to any one of claims 1 to 3, characterised in that its composition is expressed in weight percentages in which: (MgO + CaO + SrO + BaO)/ZnO is less than 0.5; and/or (MgO + CaO + SrO + BaO)/Al₂O₃Is less than 0.5; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 0.5 or less.

9. A glass material according to any one of claims 1 to 3, characterised in that its composition is expressed in weight percentages in which: SiO 2₂: 60-68%; and/or B₂O₃: 6-12%; and/or TiO₂: 2-7%; and/or ZnO: 3-8%; and/or Al₂O₃: 2-7%; and/or Na₂O+K₂8 to 18% of O, and/or L a₂O₃: 0 to 1 percent; and/or Y₂O₃: 0 to 1 percent; and/or Gd₂O₃: 0 to 1 percent; and/or Nb₂O₅: 0 to 1 percent; and/or WO₃：0～1％。

10. A glass material according to any one of claims 1 to 3, characterised in that its composition is expressed in weight percentages in which: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 4.0 to 8.0; and/or ZnO/B₂O₃0.4 to 0.8; and/or (Na)₂O+K₂O)/Al₂O₃1.5 to 5.0; and/or (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.5 to 1.5; and/or (B)₂O₃+K₂O)/Al₂O₃Is 2.0 to 6.0.

11. A glass material according to any one of claims 1 to 3, characterised in that its composition is expressed in weight percentages in which: (MgO + CaO + SrO + BaO)/ZnO is less than 0.2; and/or (MgO + CaO + SrO + BaO)/Al₂O₃Is 0.2 or less; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 0.2 or less.

12. A glass material according to any one of claims 1 to 3, characterised in that its composition is expressed in weight percentages in which: na (Na)₂O: 2-12%, preferably Na₂O: 3 to 10%, more preferably Na₂O: 4-9%; and/or K₂O: 2 to 12%, preferably K₂O: 3 to 10%, more preferably K₂O: 4-9%; and/or MgO: 0-5%, preferably MgO: 0 to 3%, more preferably MgO: 0-2%; and/or CaO: 0-5%, preferably CaO: 0-3%, more preferably CaO: 0-2%; and/or SrO: 0 to 5%, preferably SrO: 0 to 3%, more preferably SrO: 0-2%; and/or BaO: 0-5%, preferably BaO: 0 to 3%, more preferably BaO: 0 to 2 percent.

13. The glass material according to any one of claims 1 to 3, wherein the composition is represented by weight percentage, wherein L a₂O₃、Y₂O₃、Gd₂O₃、Nb₂O₅、WO₃The total content of (a) is 5% or less, preferably 3% or less, and more preferably 1% or less.

14. The glass material according to any one of claims 1 to 3, wherein F is not contained in the composition; and/or does not contain Ta₂O₅And/or do not contain L i₂O; andor does not contain P₂O₅(ii) a And/or does not contain ZrO₂。

15. The glass material according to any of claims 1 to 3, wherein the glass material has a refractive index of 1.48 to 1.56, preferably 1.50 to 1.55, more preferably 1.51 to 1.54, and/or an Abbe number of 50 to 58, preferably 51 to 57, more preferably 53 to 56, and/or a coefficient of thermal expansion of α_20-300℃Is 60 × 10^-7/K～90×10^-7Preferably 65 × 10K^-7/K～85×10^-7/K, more preferably 68 × 10^-7/K～80×10^-7a/K and/or a Young's modulus of 6000 × 10⁷Pa or more, preferably 6500 × 10⁷Pa～8500×10⁷Pa, more preferably 7000 × 10⁷Pa～8000×10⁷Pa; and/or a transition temperature of 500 ℃ to 610 ℃, preferably 520 ℃ to 600 ℃, more preferably 530 ℃ to 580 ℃; and/or the degree of bubbling is class A or more, preferably class A₀More preferably A or more₀₀A stage; and/or the stripes are of grade C or more, preferably of grade B or more.

16. The glass material according to any one of claims 1 to 3, wherein the glass material has an acid-resistance stability of 2 or more, preferably 1; and/or a stability against water action of more than 2 types, preferably 1 type; and/or alkali action resistance stability the glass sample after measurement according to the test conditions and requirements of ISO 10629 loses less than 9mg, preferably less than 7mg, more preferably less than 5 mg; and/or light transmission rate tau_360nmIs 78% or more, preferably 82% or more, and more preferably 85% or more.

17. Use of a glass material according to any one of claims 1 to 16 in the field of encapsulation.

18. A glass member made of the glass material according to any one of claims 1 to 16.

19. An apparatus comprising the glass material according to any one of claims 1 to 16, or comprising the glass member according to claim 18.

Technical Field

The invention relates to a glass material, in particular to a glass material suitable for the field of packaging of photosensitive devices.

Background

Photoelectric conversion devices such as cmos and CCD generally use a glass material as a window material, and the window glass functions to transmit light and protect the photoelectric conversion chip. The early photosensitive devices such as cmos and CCD are usually used in cameras in a comfortable environment, and thus have no high requirements on chemical stability (acid resistance, water resistance, alkali resistance, etc.), weather resistance and temperature impact resistance of the protective window of the photosensitive device. In recent years, with the development of vehicle security, deep space ocean exploration and machine vision, the photosensitive device is required to have higher reliability under very severe conditions. For example, a photosensitive device applied to a high-temperature fire scene needs to bear an extreme temperature environment of 100-200 ℃ or even higher; the photoreceptors observed in marine environments need to be able to withstand long-term alkaline or acidic attacks; the photosensitive device applied to the observation of chemical (chemical) experiments needs to be capable of bearing the corrosion of strong acid and strong alkali; the photosensitive device applied to vehicle-mounted and security needs to be exposed in outdoor environment for a long time. For the photosensitive devices such as COMS, the main component of the photosensitive chip is silicon single crystal material, and the packaging shell is mainly ceramic material. Ceramic materials have very good chemical stability and impact resistance, but have the disadvantage of being opaque, requiring brittle glass materials for the light-transmitting window. Glass materials have a great gap in chemical stability and thermal shock resistance compared to ceramic materials. Therefore, the chemical stability and the temperature impact resistance of the window glass material are the best way for improving the reliability of the photosensitive device in the severe external environment.

As a window of a photosensitive chip, a glass material is required to have higher transmittance in the range of 360 nm-2000 nm so as to meet the requirements of ultraviolet-visible-near infrared different wave band sensitization. In general, the transmittance of the glass material is gradually increased in the range of 360nm to 2000nm, so that the internal transmittance (tau) at 360nm can be used_360nm) To characterize the minimum transmittance of the glass as tau_360nmWhen the content is more than 78%, the representative sealing glass can satisfy the transmittance requirement of the above wavelength band. Since the glass for encapsulation is required to avoid reflection loss as much as possible, if the refractive index exceeds 1.60, the glass reflection loss increases. Although reflection loss can be reduced by plating an antireflection film, it causes problems of cost increase and stray light interference.

Disclosure of Invention

The invention aims to provide a glass material with high light transmittance and excellent chemical stability.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) the glass material comprises the following components in percentage by weight: SiO 2₂：50～70％；B₂O₃：3～15％；TiO₂：0.5～10％；ZnO：1～12％；Al₂O₃：0.5～10％；Na₂O+K₂O: 5 to 22% of B, wherein₂O₃/SiO₂0.06 to 0.26 (TiO)₂+ZnO)/Al₂O₃0.5 to 8.0.

(2) The glass material according to (1) further comprising, in terms of weight%, MgO + CaO + SrO + BaO in an amount of 0 to 10%, and/or L i₂O: 0 to 5 percent; and/or P₂O₅: 0 to 5 percent; and/or ZrO₂0 to 5%, and/or L a₂O₃: 0 to 5 percent; and/or Y₂O₃: 0 to 5 percent; and/or Gd₂O₃: 0 to 5 percent; and/or Nb₂O₅: 0 to 5 percent; and/or WO₃: 0 to 5 percent; and/or a clarifying agent: 0 to 1 percent.

(3) A glass material having a composition expressed in weight percent by SiO₂：50～70％；B₂O₃：3～15％；TiO₂：0.5～10％；ZnO：1～12％；Al₂O₃：0.5～10％；Na₂O+K₂O：5～22％；MgO+CaO+SrO+BaO：0～10％；Li₂O：0～5％；P₂O₅：0～5％；ZrO₂：0～5％；La₂O₃：0～5％；Y₂O₃：0～5％；Gd₂O₃：0～5％；Nb₂O₅：0～5％；WO₃: 0 to 5 percent; a clarifying agent: 0 to 1% of a component B₂O₃/SiO₂0.06 to 0.26 (TiO)₂+ZnO)/Al₂O₃0.5 to 8.0.

(4) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: b is₂O₃/SiO₂0.08 to 0.2; and/or (TiO)₂+ZnO)/Al₂O₃0.7 to 7.0; and/or (SiO)₂+TiO₂)/(Na₂O + ZnO) is 3.0 to 12.0; and/or ZnO/B₂O₃0.2 to 1.8; and/or (Na)₂O+K₂O)/Al₂O₃0.8 to 8.0; and/or (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.2 to 2.5; and/or (B)₂O₃+K₂O)/Al₂O₃Is 1.0 &10.0。

(5) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: (MgO + CaO + SrO + BaO)/ZnO is less than 1.0; and/or (MgO + CaO + SrO + BaO)/Al₂O₃Is 1.0 or less; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 1.0 or less.

(6) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: SiO 2₂: 55-68%; and/or B₂O₃: greater than 5% but less than or equal to 13%; and/or TiO₂: 1.5-8%; and/or ZnO: 2-10%; and/or Al₂O₃: 1-8%; and/or Na₂O+K₂6-20% of O, and/or 0-5% of MgO + CaO + SrO + BaO, and/or L i₂O: 0 to 3 percent; and/or P₂O₅: 0 to 3 percent; and/or ZrO₂0 to 3%, and/or L a₂O₃: 0 to 3 percent; and/or Y₂O₃: 0 to 3 percent; and/or Gd₂O₃: 0 to 3 percent; and/or Nb₂O₅: 0 to 3 percent; and/or WO₃: 0 to 3 percent; and/or a clarifying agent: 0 to 0.5 percent.

(7) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: b is₂O₃/SiO₂0.1 to 0.18; and/or (TiO)₂+ZnO)/Al₂O₃1.0 to 5.0; and/or (SiO)₂+TiO₂)/(Na₂O + ZnO) is 3.0 to 10.0; and/or ZnO/B₂O₃0.3 to 1.0; and/or (Na)₂O+K₂O)/Al₂O₃1.0 to 6.0; and/or (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.3 to 2.0; and/or (B)₂O₃+K₂O)/Al₂O₃1.5 to 8.0.

(8) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: (MgO + CaO + SrO + BaO)/ZnO is less than 0.5; and/or (MgO + CaO + SrO + BaO)/Al₂O₃Is less than 0.5; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 0.5 or less.

(9) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: SiO 2₂: 60-68%; and/or B₂O₃: 6-12%; and/or TiO₂: 2-7%; and/or ZnO: 3-8%; and/or Al₂O₃: 2-7%; and/or Na₂O+K₂8 to 18% of O, and/or L a₂O₃: 0 to 1 percent; and/or Y₂O₃: 0 to 1 percent; and/or Gd₂O₃: 0 to 1 percent; and/or Nb₂O₅: 0 to 1 percent; and/or WO₃：0～1％。

(10) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: (SiO)₂+TiO₂)/(Na₂O + ZnO) is 4.0 to 8.0; and/or ZnO/B₂O₃0.4 to 0.8; and/or (Na)₂O+K₂O)/Al₂O₃1.5 to 5.0; and/or (Na)₂O+K₂O)/(B₂O₃+ ZnO) is 0.5 to 1.5; and/or (B)₂O₃+K₂O)/Al₂O₃Is 2.0 to 6.0.

(11) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: (MgO + CaO + SrO + BaO)/ZnO is less than 0.2; and/or (MgO + CaO + SrO + BaO)/Al₂O₃Is 0.2 or less; and/or (MgO + CaO + SrO + BaO)/(Na)₂O+K₂O) is 0.2 or less.

(12) The glass material according to any one of (1) to (3), which comprises the following components in percentage by weight: na (Na)₂O: 2-12%, preferably Na₂O: 3 to 10%, more preferably Na₂O: 4-9%; and/or K₂O: 2 to 12%, preferably K₂O: 3 to 10%, more preferably K₂O: 4-9%; and/or MgO: 0-5%, preferably MgO: 0 to 3%, more preferably MgO: 0-2%; and/or CaO: 0-5%, preferably CaO: 0-3%, more preferably CaO: 0-2%; and/or SrO: 0 to 5%, preferably SrO: 0 to 3%, more preferably SrO: 0-2%; and/or BaO: 0-5%, preferably BaO: 0 to 3% of a solvent,more preferably BaO: 0 to 2 percent.

(13) The glass material according to any one of (1) to (3), wherein the composition is represented by weight percentage, wherein L a₂O₃、Y₂O₃、Gd₂O₃、Nb₂O₅、WO₃The total content of (a) is 5% or less, preferably 3% or less, and more preferably 1% or less.

(14) The glass material according to any one of (1) to (3), wherein F is not contained in the composition; and/or does not contain Ta₂O₅And/or do not contain L i₂O; and/or does not contain P₂O₅(ii) a And/or does not contain ZrO₂。

(15) The glass material according to any one of (1) to (3), wherein the glass material has a refractive index of 1.48 to 1.56, preferably 1.50 to 1.55, more preferably 1.51 to 1.54, and/or an Abbe number of 50 to 58, preferably 51 to 57, more preferably 53 to 56, and/or a thermal expansion coefficient of α_20-300℃Is 60 × 10^-7/K～90×10^-7Preferably 65 × 10K^-7/K～85×10^-7/K, more preferably 68 × 10^-7/K～80×10^-7a/K and/or a Young's modulus of 6000 × 10⁷Pa or more, preferably 6500 × 10⁷Pa～8500×10⁷Pa, more preferably 7000 × 10⁷Pa～8000×10⁷Pa; and/or a transition temperature of 500 ℃ to 610 ℃, preferably 520 ℃ to 600 ℃, more preferably 530 ℃ to 580 ℃; and/or the degree of bubbling is class A or more, preferably class A₀More preferably A or more₀₀A stage; and/or the stripes are of grade C or more, preferably of grade B or more.

(16) The glass material according to any one of (1) to (3), wherein the glass material has an acid-resistance stability of 2 or more, preferably 1; and/or a stability against water action of more than 2 types, preferably 1 type; and/or alkali action resistance stability the glass sample after measurement according to the test conditions and requirements of ISO 10629 loses less than 9mg, preferably less than 7mg, more preferably less than 5 mg; and/or light transmission rate tau_360nmIs 78% or more, preferably 82% or more, and more preferably 85% or more.

(17) Use of the glass material according to any one of (1) to (16) in the field of packaging.

(18) A glass member made of the glass material according to any one of (1) to (16).

(19) An apparatus comprising the glass material according to any one of (1) to (16), or comprising the glass element according to (18).

The invention has the beneficial effects that: through reasonable component design, the glass material obtained by the invention has higher light transmittance and excellent chemical stability, and meets the application in the fields of photosensitive device packaging and the like.

Detailed Description

The following describes in detail embodiments of the glass material of the present invention, but the present invention is not limited to the embodiments described below, and can be implemented by making appropriate changes within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the gist of the present invention is not limited thereto, and the glass material of the present invention may be simply referred to as glass in the following description.

[ glass Material ]

The ranges of the components of the glass material of the present invention are explained below. In the present specification, unless otherwise specified, the contents of the respective components and the total content are all expressed in terms of weight percentage with respect to the total amount of glass substances converted into the composition of oxides. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the glass material composition component of the present invention are decomposed in the melt and converted to oxides, the total weight of the oxides is 100%.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.

< essential Components and optional Components >

SiO₂Is one of the main components of the glass, in which a suitable amount of SiO is present₂Can ensure that the glass has higher water resistance and acid resistance, and can realize high light transmittance. If SiO₂The content of the glass is less than 50 percent, and the water resistance, the acid resistance and the ultraviolet transmittance of the glass are lower than the design requirements. If SiO₂The content of (A) is higher than 70%, and the refractive index of the glass cannot meet the design requirement. The melting temperature of the glass is sharply increased, and it is difficult to obtain high quality glass in production, and the thermal expansion coefficient of the glass is lowered. Thus, SiO in the present invention₂The content of (B) is limited to 50 to 70%, preferably 55 to 68%, more preferably 60 to 68%.

Appropriate amount of B₂O₃When the glass is added into glass, the structure of the glass can be converted to a compact direction, the refractive index of the glass is improved, and meanwhile, high water resistance and acid resistance are realized, and if the content of the glass is lower than 3%, the effect is not obvious. If B is₂O₃The content of the glass is higher than 15%, and the water resistance and acid resistance of the glass are reduced. Thus, B₂O₃The content of (B) is limited to 3 to 15%, preferably more than 5% but not more than 13%, more preferably 6 to 12%.

In the present invention, B₂O₃/SiO₂The value of (A) affects the difficulty of glass production, when B₂O₃/SiO₂When the melting temperature is less than 0.06, the glass melting temperature is increased, the corrosion to refractory materials is intensified, more coloring impurities and inclusions are easily introduced into the glass, the transmittance of the glass cannot meet the design requirement, and the probability of generating defects inside products is increased. When B is present₂O₃/SiO₂Above 0.26, the melting temperature does not drop significantly, while B₂O₃The corrosion to refractory materials is increased, more coloring impurities and inclusions are easily introduced into the glass, the short-wave transmittance of the glass cannot meet the design requirement, and the probability of generating defects on the surface of a product is increased. Thus, in the present invention, B₂O₃/SiO₂The value of (b) is 0.06 to 0.26, preferably 0.08 to 0.2, and more preferably 0.1 to 0.18.

An appropriate amount of Al₂O₃The addition of the glass into the glass can improve the water resistance and acid resistance of the glass and simultaneously can reduce the thermal expansion coefficient of the glass, especially in the presence of alkali metal oxide. If Al is present₂O₃The content of (A) is higher than 10%, the thermal expansion coefficient of the glass is rapidly reduced, and the design requirement cannot be met. Thus, Al₂O₃The content of (b) is limited to 0.5 to 10%, preferably 1 to 8%, more preferably 2 to 7%.

Appropriate amount of TiO₂The glass can be added into glass to improve the refractive index of the glass, improve the water resistance, acid resistance and alkali resistance of the glass, simultaneously reduce the thermal expansion coefficient of the glass, and improve the thermal shock resistance of the glass, if TiO is added into the glass₂The content of (a) is less than 0.5%, the above effects are not obvious; if TiO₂The content of (A) exceeds 10%, the Abbe number of the glass is lower than the expected number, and the short-wave transmittance is rapidly reduced, especially in the environment that the smelting atmosphere is unstable. More importantly, a high content of TiO₂The refractive index of the glass is rapidly increased, the reflection loss of short-wave wavelength is increased under the condition of not plating an antireflection film, the short-wave transmittance is further reduced, and meanwhile, the thermal expansion coefficient of the glass is reduced, so that the design requirement cannot be met. Thus, TiO in the present invention₂The content of (b) is limited to 0.5 to 10%, preferably 1.5 to 8%. In some embodiments, TiO is more preferred in view of the combination of the glass' refractive index, Abbe number, and difficulty of controlling the atmosphere during melting₂The content of (a) is 2-7%.

The field strength of ZnO in divalent metal oxide is high, and the ZnO added into the glass can improve the acid resistance, water resistance and alkali resistance of the glass, improve the refractive index of the glass, and simultaneously can reduce the thermal expansion coefficient of the glass, and is particularly obvious in a glass system containing alkali metal. If the content of ZnO is less than 1%, the above effect is not significant. If the content of ZnO exceeds 12%, the transition temperature of the glass is rapidly reduced, so that the glass is easy to soften and deform in a high-temperature working environment, and the glass device which needs to work in a high-temperature state is fatally influenced. If the content exceeds 12%, the dispersion of the glass rapidly increases and the Abbe number does not satisfy the design requirements. Therefore, the content of ZnO is limited to 1 to 12%, preferably 2 to 10%, and more preferably 3 to 8%.

In the present invention, (TiO) is₂+ZnO)/Al₂O₃When the value of (D) is more than 8.0, the ultraviolet transmittance of the glass is lowered and the tendency of devitrification is increased, if (TiO)₂+ZnO)/Al₂O₃When the value of (A) is less than 0.5, the meltability of the glass is lowered, the difficulty of discharging bubbles is increased, and the inherent quality is deteriorated. Thus, (TiO)₂+ZnO)/Al₂O₃The value of (D) is 0.5 to 8.0, preferably (TiO)₂+ZnO)/Al₂O₃The value of (B) is 0.7 to 7.0, more preferably (TiO)₂+ZnO)/Al₂O₃The value of (A) is 1.0 to 5.0.

Through a great deal of experimental research of the inventor, the glass contains B₂O₃In the meantime, the existence of ZnO further reduces the melting temperature of the glass, and high-quality products are easier to obtain, if ZnO/B₂O₃The above effect is not significant, if the value of (a) is less than 0.2; if ZnO/B₂O₃Above 1.8, the glass transition temperature is rapidly reduced and the heat resistance does not meet the design requirements. On the other hand, when ZnO/B₂O₃When the value of (A) is 0.2-1.8, the water resistance, acid resistance and alkali resistance of the glass are compared with those of the glass which is singly added with B₂O₃The time is more excellent. Therefore, ZnO/B is preferred in the present invention₂O₃The value of (b) is 0.2 to 1.8, more preferably 0.3 to 1.0, and still more preferably 0.4 to 0.8.

MgO, CaO, SrO and BaO belong to alkaline earth metal oxides, and when the MgO, CaO, SrO and BaO are added into glass, the refractive index and the transition temperature of the glass can be improved, and the stability and the thermal expansion coefficient of the glass can be adjusted. However, the addition of the alkaline earth metal oxide causes a rapid increase in the Young's modulus of the glass, and when the glass materials have the same coefficient of thermal expansion, the glass having a low Young's modulus has better thermal shock resistance. Therefore, in view of the above, the total amount of addition of MgO + CaO + SrO + BaO of the alkaline earth metal oxide is preferably 10% or less, more preferably 5% or less. In some embodiments, it is further preferred that no alkaline earth oxide be added if the glass has a stability, coefficient of thermal expansion and transition temperature that meet design requirements.

In some embodiments of the invention, the metal oxide is prepared by reacting an alkaline earth metal oxide with Al₂O₃In the ratio of (MgO + CaO + SrO + BaO)/Al₂O₃At most 1.0, devitrification resistance and chemical stability of the glass can be improved, and (MgO + CaO + SrO + BaO)/Al is preferable₂O₃Is 0.5 or less, more preferably (MgO + CaO + SrO + BaO)/Al₂O₃Is 0.2 or less.

In some packaging applications, a higher refractive index is required to achieve matching of the optical system, or a higher transition temperature is required, which requires the addition of small amounts of alkaline earth oxides to achieve. In order to avoid rapid deterioration of the water-, acid-and alkali-resistance properties of the glass while adding the alkaline earth metal oxide, it is conceivable to add MgO, CaO, SrO, BaO singly or in combination in this order. If the content of the alkaline earth metal oxides such as MgO, CaO, SrO, BaO and the like is more than 5 percent, the devitrification resistance of the glass is rapidly reduced, and a large-caliber high-quality product is not easy to obtain. Therefore, the contents of MgO, CaO, SrO, and BaO are each limited to 5% or less, preferably 3% or less, and more preferably 2% or less.

As a result of extensive experimental studies by the inventors, it has been found that when a certain amount of alkaline earth metal oxide is present in the glass, it is considered that the ZnO content can be adjusted to reduce the loss of the chemical stability and thermal shock resistance of the glass. In some embodiments, when the value of (MgO + CaO + SrO + BaO)/ZnO is 1.0 or less, preferably 0.5 or less, and more preferably 0.2 or less, a glass having a higher refractive index and satisfying the chemical stability, thermal expansion coefficient and thermal shock resistance required for the design of the present invention can be obtained more easily.

Li₂O、Na₂O、K₂O is an alkali metal oxide, and its content in the glass of the present invention is closely related to the thermal expansion coefficient, chemical stability and intrinsic quality of the glass.

Li₂Addition of O to the glass lowers the melting temperature and raises the bubble content of the glass, while minimizing the loss of chemical stability to the glass over the other two alkali metal oxides, however, L i₂The content of O is more than 5%, and the glass is cooled from liquid state to solid state in the forming processThe curing speed is slow, which is disadvantageous for the production of large-size high-quality products (such as the products with width or diameter larger than 340mm and thickness larger than 40mm are easy to have unqualified striae and internal crystallization)₂The content of O is limited to 5% or less, preferably 3% or less, and it is more preferable not to add L i₂O。

In the present invention, Na₂O and K₂Total content Na of O₂O+K₂When the O content exceeds 22%, the Abbe number of the glass is lower than the design requirement, the thermal expansion coefficient of the glass exceeds the design requirement, and the dielectric constant of the glass rapidly rises, so that the insulating property of the glass is rapidly reduced, which is unfavorable for some applications requiring insulation. If Na₂O+K₂O is less than 5 percent, the thermal expansion coefficient of the glass can not meet the design requirement, the coloring capability of the valence-changing component in the glass is enhanced, and the short-wave transmittance of the glass can not meet the design requirement. Thus, Na₂O and K₂Total content Na of O₂O+K₂O is 5 to 22%, preferably 6 to 20%, more preferably 8 to 18%.

Na₂The addition of O to the glass can significantly increase the coefficient of thermal expansion of the glass and at the same time can reduce the high temperature viscosity of the glass, making it easier to obtain glass products having a width greater than 330mm that can be processed into 12 inch packaged wafers. If however Na₂The content of O exceeds 12%, the refractive index of the glass is reduced, the chemical stability of the glass is rapidly reduced, and the design requirement cannot be met. If Na₂The content of O is less than 2%, the thermal expansion coefficient of the glass does not meet the design requirements, and the chemical stability is also seriously deteriorated. Thus, Na₂The content of O is limited to 2 to 12%, preferably 3 to 10%, more preferably 4 to 9%.

Appropriate amount K₂The addition of O into the glass can improve the thermal expansion coefficient of the glass, reduce the high-temperature viscosity of the glass and improve the bubble degree of the glass, especially the temperature of Na₂In the case where O coexists, an appropriate amount of K₂The addition of O to the glass does not significantly impair the chemical stability of the glassAnd (4) sex. However, if the content exceeds 12%, the water, acid and alkali resistance of the glass is deteriorated. If K₂The content of O is less than 2%, and the effects of increasing the thermal expansion coefficient and reducing the high-temperature viscosity are not obvious. Thus, K₂The content of O is limited to 2 to 12%, preferably 3 to 10%, more preferably 4 to 9%.

In some embodiments of the invention, if (B)₂O₃+K₂O)/Al₂O₃A value of more than 10.0, the alkali resistance of the glass decreases, and the thermal expansion coefficient increases; if (B)₂O₃+K₂O)/Al₂O₃A value of less than 1.0 lowers the melting property of the glass and raises the transition temperature. Therefore, (B) is preferred₂O₃+K₂O)/Al₂O₃The value of (B) is 1.0 to 10.0, more preferably (B)₂O₃+K₂O)/Al₂O₃The value of (A) is 1.5 to 8.0, and (B) is more preferable₂O₃+K₂O)/Al₂O₃The value of (b) is 2.0 to 6.0.

In some embodiments of the invention, (Na) is₂O+K₂O)/(B₂O₃+ ZnO) below 0.2, insufficient free oxygen in the glass system, resulting in B₂O₃And the probability of components such as ZnO entering the glass network is reduced, so that the chemical stability is reduced rapidly, and meanwhile, the expansion coefficient of the glass is reduced, and the design requirement cannot be met. If (Na)₂O+K₂O)/(B₂O₃+ ZnO) is greater than 2.5, the excess of free oxygen in the glass system results in a sharp decrease in the chemical stability of the glass, and the coefficient of expansion of the glass exceeds the design requirements. Thus, when (Na)₂O+K₂O)/(B₂O₃+ ZnO) is between 0.2 and 2.5, preferably between 0.3 and 2.0, more preferably between 0.5 and 1.5, the chemical stability and thermal expansion coefficient of the glass are the most balanced.