Low melting point glass

Abstract

The present invention provides a glass having a low Tg, which can be formed at a low temperature, and which is inhibited from foaming and crystallizing during forming. The present invention relates to a glass containing, in terms of the mole % of elements, P: 8 to 25%, Sn: 8 to 40%, O: 20 to 80%, and F: 1 to 50%, and having a glass transition temperature Tg of 300°C or lower, and an absorbance A3240 at a wave number of 3240 cm －1 -1 mm thickness, and an absorbance A3100 at a wave number of 3100 cm －1 -1 mm thickness, and A3240 / A3100 is 1.2 or lower.

Description

Technical Field

[0001] This invention relates to glass, and more particularly to glass with a low glass transition temperature (Tg) that can be molded at low temperatures and can suppress foaming and crystallization during molding, composite components of the glass and resin, and molded bodies thereof. Background Technology

[0002] While organic polymers (resins) have inferior heat resistance, light resistance, light transmittance, and gas barrier properties compared to glass, they are used for various applications due to their lower molding temperature and lower cost. On the other hand, glass has excellent heat resistance, light resistance, light transmittance, and gas barrier properties, but typical glass has a high Tg, making it difficult to freely mold.

[0003] Low-melting-point glass is a glass material with a melting temperature lower than that of ordinary glass. It is used for coating metal surfaces and glass surfaces, bonding them, or as a sealing material for electronic products that require higher airtightness compared to resin-based materials (e.g., Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Publication No. 2010-505727 Summary of the Invention

[0007] However, conventional low-melting-point glasses are prone to crystallization and foaming, resulting in difficulties in achieving transparency after low-temperature molding and a narrow molding temperature margin due to crystallization. Therefore, conventional low-melting-point glasses are unsuitable as materials for low-temperature molding processes commonly used in resin molding, such as extrusion, injection molding, blow molding, and pressure molding.

[0008] Therefore, the purpose of this invention is to provide glass with low Tg that can be molded at low temperatures, suppresses foaming during molding, and crystallizes.

[0009] The inventors studied the above-mentioned problems and found that by controlling the structure around the OH groups in the glass, the above-mentioned problems could be solved, thus completing the present invention.

[0010] This invention relates to a glass containing, in molar percentages (P: 8-25%, Sn: 8-40%, O: 20-80%, F: 1-50%), with a glass transition temperature (Tg) below 300°C and an infrared absorption spectrum showing a wavenumber of 3100 cm⁻¹. －1 The absorbance per 1 mm thickness is set to A3100, and the wavenumber is 3240 cm⁻¹. －1 When the absorbance per 1 mm thickness is set to A3240, the ratio of A3240 / A3100 is 0.6 to 1.2.

[0011] The glass of this invention has a Tg below 300°C, excellent formability, and exhibits a wavenumber of 3100 cm⁻¹ in its infrared absorption spectrum. －1 The absorbance per 1 mm thickness is set to A3100, and the wavenumber is 3240 cm⁻¹. －1 When the absorbance per 1 mm thickness is set to A3240, the ratio of A3240 / A3100 is within a specific range. By controlling the structure around the OH groups in the glass, crystallization and foaming are suppressed. Therefore, the glass of this invention has the advantage of exhibiting excellent transparency after low-temperature forming. Attached Figure Description

[0012] Figure 1 (A) and Figure 1 (B) is a cross-sectional schematic diagram of one embodiment of the glass resin laminate. Figure 1 (C) is a cross-sectional schematic diagram of one embodiment of the glass-resin island composite.

[0013] Figure 2 (A) to (C) are schematic diagrams illustrating one embodiment of a method for manufacturing a glass-resin island composite.

[0014] Figure 3 This represents the DSC curve.

[0015] Figure 4 This is a graph representing an example of the measurement results of infrared absorption spectroscopy.

[0016] Figure 5 This is a graph representing an example of the measurement results for the transmittance of parallel light rays. Detailed Implementation

[0017] In this specification, the "~" indicating a numerical range is used to mean the lower and upper limits of the values ​​listed before and after it. Unless otherwise specified, "~" will be used with the same meaning in this specification below.

[0018] Unless otherwise specified, the glass composition in this instruction manual will be simply referred to as "%" in molar percentage.

[0019] Furthermore, in this specification, "substantially not containing" means below the level of impurities present in raw materials, etc.; in other words, it means that it was not intentionally added. In this specification, when a component is stated as substantially not containing a certain ingredient, the content of that component is specifically, for example, less than 0.1%.

[0020] In this specification, "parallel light transmittance" refers to the ratio of parallel light emitted from the sample to the parallel light incident on the sample, excluding scattered light. Additionally, "haze rate" is a value measured using a C light source according to JIS K3761:2000.

[0021] <Glass>

[0022] (composition)

[0023] The glass of the present invention contains, in mole percent, P: 8-25%, Sn: 8-40%, O: 20-80%, and F: 1-50%.

[0024] The following explains the scope of each component.

[0025] The phosphorus (P) content is 8% or more, preferably 10% or more, and more preferably 12% or more. By making the P content 8% or more, the glass transition temperature (Tg) and molding temperature can be reduced. The P content is 25% or less, preferably 20% or less, and more preferably 17% or less. By making the P content 25% or less, water resistance and gas barrier properties can be improved.

[0026] The Sn content is 8% or more, preferably 10% or more, and more preferably 13% or more. By making the Sn content 8% or more, water resistance and gas barrier properties can be improved. The Sn content is 40% or less, preferably 30% or less, and more preferably 20% or less. By making the Sn content 40% or less, the glass transition temperature Tg and molding temperature can be reduced.

[0027] The preferred ratio of Sn to P content is 0.3 to 3. By setting Sn / P to 0.3 to 3, the residual rate of F after melting and low-temperature molding can be improved, and crystallization during low-temperature molding can be suppressed. Sn / P is preferably 0.3 to 3, more preferably 0.5 to 2.5, and even more preferably 0.7 to 2.

[0028] The oxygen content is 20% or more, preferably 30% or more, and more preferably 40% or more. By making the oxygen content 20% or more, the glass manufacturing process can be simplified. The oxygen content is 80% or less, preferably 70% or less, and more preferably 60% or less. By making the oxygen content 80% or less, the glass transition temperature Tg and the forming temperature can be reduced.

[0029] The content of phosphorus (F) is 1% or more, preferably 3% or more, more preferably 10% or more, and even more preferably 15% or more. By making the F content 1% or more, the glass transition temperature (Tg) and forming temperature can be lowered, and crystallization can be suppressed. The F content is 50% or less, preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less. By making the F content 50% or less, the glass manufacturing process can be simplified, and the generation of HF gas during melting and low-temperature forming can be suppressed. Here, the F content is not determined by the amount of raw material fed into the glass mixture, but by analyzing the glass using an ion electrode method or ion chromatography. In addition, the contents of each element other than F and O are obtained by ICP-based luminescence spectrophotometry. The O content is calculated by the difference between the total concentration of other elements and the overall concentration.

[0030] The glass of the present invention only requires that the contents of the above-mentioned components are within the above-mentioned ranges. In addition to the above-mentioned components, it may also contain any compounds and additives used in glass, as long as the effects of the present invention are achieved. For example, it may contain the following components.

[0031] The glass of the present invention may contain 0 to 30% Zn. By containing Zn, the glass transition temperature Tg can be kept low, while crystallization is suppressed, and the coefficient of thermal expansion can be reduced. The Zn content may be 5% or more, or 10% or more. Alternatively, the Zn content may be 25% or less, or 20% or less.

[0032] The glass of the present invention may contain 0 to 30% Ba. By containing Ba, the glass transition temperature (Tg) can be kept low, while crystallization is suppressed, thereby improving water resistance. The Ba content may be 5% or more, or 10% or more. Alternatively, the Ba content may be 25% or less, or 20% or less.

[0033] The glass of the present invention may contain a total of 0 to 30% Mg, Ca, and Sr. The presence of Mg, Ca, and Sr improves water resistance. The total content of Mg, Ca, and Sr may be 7% or more, or 15% or more. Alternatively, the total content of Mg, Ca, and Sr may be 25% or less, or 20% or less.

[0034] The glass of the present invention may contain a total of 0 to 30% Li, Na, and K. By containing Li, Na, and K, the glass transition temperature (Tg) and forming temperature can be lowered. The total content of Li, Na, and K may be 5% or more, or 10% or more. Alternatively, the total content of Li, Na, and K may be 25% or less, or 20% or less.

[0035] The glass of the present invention may contain 0 to 20% Al. The presence of Al improves water resistance and gas barrier properties. The Al content may be 3% or more, or 6% or more. Alternatively, the Al content may be 15% or less, or 10% or less.

[0036] The glass of the present invention may contain 0 to 20% boron (B). The presence of boron inhibits crystallization and improves reagent resistance. The boron content may be 5% or more, or 10% or more. Alternatively, the boron content may be 17% or less, or 13% or less.

[0037] The glass of the present invention may contain 0 to 10% Si. The presence of Si inhibits crystallization and improves water resistance and reagent resistance. The Si content may be 2% or more, or 5% or more. Alternatively, the Si content may be 8% or less, or 7% or less.

[0038] The glass of the present invention may contain 0 to 10% Zr. The presence of Zr inhibits crystallization and improves water resistance and reagent resistance. The Zr content may be 2% or more, or 4% or more. Alternatively, the Zr content may be 8% or less, or 6% or less.

[0039] The glass of the present invention may contain a total of 0 to 10% Ce and Y. The presence of Ce and Y improves water resistance and reagent resistance. The total content of Ce and Y may be 2% or more, or 4% or more. Alternatively, the total content of Ce and Y may be 8% or less, or 6% or less.

[0040] The glass of the present invention may contain a total of 0 to 20% Nb, W, Mo, and Ta. The presence of Nb, W, Mo, and Ta improves water resistance and reagent resistance. However, care must be taken to avoid crystallization and coloration. The total content of Nb, W, Mo, and Ta may be 2% or more, or 4% or more. Alternatively, the total content of Nb, W, Mo, and Ta may be 15% or less, or 10% or less.

[0041] The glass of the present invention may contain a total of 0 to 20% Fe, Ti, Mn, Cr, Cu, and Ag. By containing Fe, Ti, Mn, Cr, Cu, and Ag, crystallization can be suppressed, and the glass transition temperature Tg can be lowered. However, care must be taken to avoid crystallization and coloration. The total content of Fe, Ti, Mn, Cr, Cu, and Ag may be 2% or more, or 4% or more. Furthermore, the total content of Fe, Ti, Mn, Cr, Cu, and Ag may be 15% or less, or 10% or less.

[0042] The glass of the present invention may contain a total of 0 to 20% Cl, Br, I, and S. By containing Cl, Br, I, and S, crystallization can be suppressed. The total content of Cl, Br, I, and S may be 3% or more, or 7% or more. Alternatively, the total content of Cl, Br, I, and S may be 17% or less, or 13% or less.

[0043] (Glass transition temperature Tg)

[0044] The glass of the present invention has a glass transition temperature (Tg) of 300°C or less, preferably 200°C or less, more preferably 150°C or less, and even more preferably 100°C or less. There is no particular limitation on the lower limit of Tg, but to improve weather resistance and water resistance, it is preferably 50°C or more, more preferably 70°C or more, and even more preferably 80°C or more. Because the glass transition temperature is 300°C or less, the glass has a low melting point and can be used as a material in low-temperature molding processes such as extrusion, injection molding, blow molding, and pressure molding commonly used in resin molding.

[0045] (Infrared absorption spectrum)

[0046] The glass of this invention exhibits a wavenumber of 3100 cm⁻¹ in the infrared absorption spectrum. －1 The absorbance per 1 mm thickness is set to A3100, and the wavenumber is 3240 cm⁻¹. －1 When the absorbance per 1 mm thickness is set to A3240, the ratio of A3240 / A3100 is 1.2 or less, preferably 1 or less, and more preferably 0.9 or less. By having A3240 / A3100 1.2 or less, the structure around the OH groups can be appropriately controlled, thereby suppressing crystallization and foaming, resulting in a transparent molded body. A3240 / A3100 is 0.6 or more, preferably 0.7 or more, and more preferably 0.8 or more. By having A3240 / A3100 0.6 or more, the glass manufacturing process can be simplified.

[0047] wave number 3100cm －1 Wavenumber 3240cm －1The nearby infrared absorption spectrum originates from the OH groups in the glass, but its shape varies due to the influence of the structure forming the glass framework. Since the structure forming the glass framework is a P-O-Sn-O structure, during low-temperature molding, the F and OH groups attached to the glass framework volatilize, causing elemental rearrangement and easily leading to the crystallization of tin phosphate compounds. When the glass framework structure is P-O-Sn-O, the A3240 peak in the infrared absorption spectrum is easily prominent, and the A3240 / A3100 ratio is greater than 1.2. By preferably using a P-O-P-O structure as the glass framework, the A3240 / A3100 ratio can be between 0.6 and 1.2. The F and OH groups attached to the P-O-P-O structure are less likely to volatilize during low-temperature molding, and even if they do volatilize, crystallization due to elemental rearrangement is less likely to occur. Furthermore, because the volatilization of F and OH groups can be suppressed, foaming is less likely to occur.

[0048] By ensuring that the weight ratio of ammonium dihydrogen phosphate (NH4H2PO4) in the total weight of the phosphate raw materials for glass is 51% or more, a P-O-Sn-O structure is formed in the glass framework, making it easier for tin phosphate compounds to crystallize, and the A3240 / A3100 ratio is greater than 1.2. However, the use of ammonium dihydrogen phosphate generates a large amount of ammonia gas during glass melting, resulting in a high environmental impact, and foaming can also occur during low-temperature forming due to ammonia gas, making it undesirable. On the other hand, by ensuring that the weight ratio of orthophosphoric acid (H3PO4) in the total weight of the phosphate raw materials for glass is 51% or more, a P-O-P-O structure is formed in the glass framework, resulting in a transparent glass that is less prone to crystallization and foaming after melting and low-temperature forming, and the A3240 / A3100 ratio is 0.6 or more and 1.2 or less. In addition, the moisture contained in orthophosphoric acid has the effect of inhibiting crystallization in the glass during low-temperature forming, therefore, orthophosphoric acid is preferred as the phosphate raw material for glass.

[0049] More preferably, the weight ratio of orthophosphoric acid (H3PO4) in the total weight of the phosphate raw materials for glass is 70% or more, more preferably 80% or more, and even more preferably 90% or more. As phosphate raw materials, ammonium hexafluorophosphate (NH4PF6), stannous pyrophosphate (Sn2P2O7), phosphorus pentoxide (P2O5), tritin diphosphoric acid (Sn3(PO4)2), zinc pyrophosphate (Zn2P2O7), aluminum phosphate (AlPO4), etc., can be used together. However, the phosphate raw materials are not limited to the substances illustrated herein. Preferably, a solution of orthophosphoric acid (H3PO4) with a concentration of 75% to 90% is used, and the weight of the entire solution is used when calculating the weight ratio.

[0050] The glass of this invention has a wavenumber of 3100 cm⁻¹ in the infrared absorption spectrum. －1The absorbance per 1 mm thickness is preferably 0.2 to 4, more preferably 0.3 to 3, and even more preferably 0.5 to 2. Additionally, the wavenumber is 3240 cm⁻¹. －1 The absorbance per 1 mm thickness is preferably 0.12–4.8, more preferably 0.18–3.6, and even more preferably 0.3–2.4. Passing through a wavenumber of 3100 cm⁻¹ －1 Absorbance and wavenumber per 1 mm thickness: 3240 cm⁻¹ －1 The absorbance per 1 mm thickness is within the above range. The structure of the glass is controlled, and it is not easy to crystallize or foam during low-temperature molding, thus obtaining a molded body with excellent transparency.

[0051] Infrared absorption spectra were measured using a Fourier transform infrared spectrophotometer. A wavenumber of 400 cm⁻¹ was used. －1 The transmittance is set to T400 and the wavenumber to 3100 cm⁻¹. －1 The transmittance is set to T3100 and the wavenumber to 3240cm. －1 When the transmittance is set to T3240 and the sample thickness is measured to be D (mm), the transmittance is obtained through A3100 = -log 10 (T3100 / T400) / D calculates wavenumber 3100cm －1 The absorbance A3100 per 1 mm thickness is obtained by A3240 = -log 10 (T3240 / T400) / D calculates wavenumber 3240cm －1 The absorbance A3240 per 1 mm thickness. Dividing by T400 is for baseline correction in the measurement. It should be noted that the test sample is preferably processed into a 1 mm thick plate using cerium oxide abrasive as the processing agent.

[0052] (Raman scattering spectrum)

[0053] The glass of the present invention preferably has a Raman scattering spectrum of 1020–1060 cm⁻¹ －1 The main peak was observed within the range of P. It is a Q peak originating from P. 1 The peaks in the structure contribute to the stability of the glass. Furthermore, the glass of the present invention preferably exhibits Raman scattering peaks in the range of 960–1000 cm⁻¹. －1 A peak was observed within the range of P. It is a Q peak originating from P. 0 The peaks in the structure contribute to improved water resistance of the glass. Furthermore, the glass of this invention preferably exhibits Raman scattering peaks in the range of 1080–1170 cm⁻¹. －1 No peak was observed within the range. It is Q originating from P. 2 The peaks in the structure deteriorate the water resistance of the glass.

[0054] Differential scanning calorimetry

[0055] The difference between the crystallization peak temperature Tc and the glass transition temperature Tg of the glass of the present invention, as determined by differential scanning calorimetry, is preferably 150°C or higher, more preferably 160°C or higher, and even more preferably 170°C or higher. It should be noted that, most preferably, Tc cannot be observed; in this case, it can be interpreted as the difference between Tc and Tg being infinitely large. Since the difference between Tc and Tg is 150°C or higher, the gap between the formable temperature and the crystallization temperature, i.e., the forming temperature margin, can be widened, resulting in glass with superior transparency after low-temperature forming. It should be noted that at temperatures above Tc, the viscosity increases sharply due to glass crystallization, making low-temperature forming difficult.

[0056] The difference between the crystallization initiation temperature Tx and the glass transition temperature Tg of the glass of the present invention, as determined by differential scanning calorimetry, is preferably 140°C or more, more preferably 150°C or more, and even more preferably 160°C or more. It should be noted that, most preferably, Tx is not observable; in this case, the difference between Tx and Tg can be interpreted as infinitely large. By ensuring that the difference between Tx and Tg is 140°C or more, the gap between the formable temperature and the crystallization initiation temperature can be widened, resulting in glass with superior transparency after low-temperature forming.

[0057] Differential scanning calorimetry (DSC) uses powder with a median particle size of less than 3 micrometers, pulverized in an agate mortar, as the sample for measurement. The measurement is conducted in an atmospheric atmosphere at a temperature increase of 2°C from 25°C to 500°C per minute. Figure 3 As shown in the DSC curve, Tg is the temperature at which the curve begins to absorb heat and shift during the heating process, Tx is the temperature at which heat release begins due to crystallization during the heating process, and Tc is the peak temperature at which heat release occurs due to the initial crystallization during the heating process.

[0058] (Weight changes during molding)

[0059] The glass of the present invention preferably exhibits a weight change of -2% or more before and after heat treatment at (Tg+150)°C for 1 hour, more preferably -1% or more, and even more preferably -0.7% or more. (Tg+150)°C is the same temperature as that used during low-temperature forming. With this weight change of -2% or more, the water content in the glass is not excessive, foaming during low-temperature forming is suppressed, and a molded body with excellent transparency is obtained. The upper limit of this weight change is preferably +0.5% or less, more preferably -0.1% or less, and even more preferably -0.3% or less. With this weight change of +0.5% or less, crystallization during low-temperature forming is suppressed due to the presence of water in the glass, resulting in a molded body with excellent transparency.

[0060] The weight change before and after heat treatment at (Tg+150)℃ for 1 hour was determined under the following conditions.

[0061] The weight of the sample was determined using a thermogravimetric differential calorimeter. The sample used was powder with a median particle size of less than 3 micrometers, pulverized in an agate mortar. The measurement conditions were: heating from 25°C to (Tg+150)°C at a rate of 2°C / min in atmospheric atmosphere, and holding at (Tg+150)°C for 1 hour. The rate of change of weight relative to the initial weight was evaluated.

[0062] (Parallel ray transmittance)

[0063] The glass of the present invention preferably has an average value of 70% or more, more preferably 80% or more, and even more preferably 85% or more, when measured along the thickness direction of a 1 mm thick plate with parallel light transmittance at wavelengths of 400-700 nm. With an average value of 70% or more, it becomes a glass with excellent transparency and suppressed crystallization. Furthermore, by using glass with an average value of 70% or more for low-temperature forming, a molded body with high transparency can be obtained. There is no particular upper limit to this average value; typically, it is 92% or less. It should be noted that the sample used for measurement is preferably processed into a 1 mm thick plate using cerium oxide abrasive as a processing agent.

[0064] (Haze rate)

[0065] The glass of the present invention, when measured in the thickness direction as a 1 mm thick plate, preferably has a haze rate of 20% or less, more preferably 15% or less, and even more preferably 10% or less. With an average haze rate of 20% or less, it becomes a glass with excellent transparency and suppressed crystallization. There is no particular limitation on the lower limit of this haze rate, but typically it is 0.2% or more. It should be noted that the sample used for measurement is preferably processed into a 1 mm thick plate using cerium oxide abrasive as a processing agent.

[0066] (Manufacturing method)

[0067] The glass of this invention can be manufactured by blending glass raw materials, melting, and cooling. Preferably, orthophosphoric acid (H3PO4) is used as the phosphate raw material for the glass. Since orthophosphoric acid contains moisture, it can be dried at a temperature of 100–500°C for approximately 10 minutes to 50 hours before use. The orthophosphoric acid can be dried and then mixed with other raw materials, or it can be mixed with a portion or all of the other raw materials and then dried. Melting can be performed by placing the raw materials in a container of platinum, carbon, quartz, alumina, or nickel, etc., at a temperature of 400–700°C for approximately 10 minutes to 10 hours. All raw materials can be melted at once, or only a portion or specific raw materials can be melted first, followed by the melting of the remaining materials. The molten glass can be formed into specified shapes such as granules or sheets using various methods as needed.

[0068] <Glass particles>

[0069] The glass of the present invention can be in the form of granular glass particles. By forming them into granular shapes, they are easier to feed into a cryogenic forming machine. The major diameter of the glass particles is preferably 0.1 mm to 5 mm, more preferably 1 mm to 4.5 mm, and even more preferably 2 mm to 4 mm. The minor diameter of the glass particles is preferably 0.1 mm to 5 mm, more preferably 0.5 mm to 4.5 mm, and even more preferably 1.5 mm to 4 mm. If the glass particles are too small, they may cause blockage in the forming machine, easily crystallize during cryogenic forming, and easily become entangled with air bubbles during cryogenic forming. On the other hand, if the glass particles are too large, they may be unable to be spirally conveyed in the forming machine and are prone to breakage. From the perspective of preventing breakage in the forming machine, the ratio of the major diameter to the minor diameter of the glass particles is preferably 0.2 to 1, more preferably 0.5 to 1, and even more preferably 0.7 to 1.

[0070] There are no particular limitations on the manufacturing methods of glass particles. Examples include using molds to apply pressure, using water to pulverize glass, drop casting, remelting glass powder, and breaking up molten liquid for dispersion.

[0071] (low temperature molding)

[0072] The glass of the present invention is preferably used in at least one of extrusion molding, injection molding, blow molding, and pressure molding at a temperature preferably below 450°C, more preferably below 350°C, and even more preferably below 300°C. It should be noted that roll forming also includes pressure molding. As described above, the glass of the present invention has a Tg of below 300°C and an A3240 / A3100 ratio of 1.2 or less. Therefore, when used in a low-temperature molding process preferably below 450°C, it is possible to obtain a molded body with crystallization, suppressed foaming, and excellent transparency. From the viewpoint of further suppressing foaming, the glass can be dried before low-temperature molding. Typical drying conditions are 10 minutes to 10 hours at a temperature near the Tg.

[0073] Glass Resin Composite Particles

[0074] The glass particles can also be glass-resin composite particles obtained by combining the glass and resin of the present invention. Both thermosetting and thermoplastic resins can be used as the resin. From the viewpoint of ease of composite with glass, thermoplastic resins are preferred, and resins having acid groups and amino groups are particularly preferred. Resins having acid groups and amino groups readily chemically bond with the low-melting-point glass of the present invention.

[0075] Examples of thermosetting resins include epoxy resins, phenolic resins, urea resins, melamine resins, silicone resins, unsaturated polyester resins, and polyurethane resins.

[0076] In addition, examples of thermoplastic resins include nylon, polyacetal, polysulfone, polyetherimide, polyamideimide, liquid crystal polymer, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, aromatic polyether, polyphenylene ether, polyetheretherketone, polyphenylene oxide, polycarbonate, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethersulfone, polypropylene, polystyrene, acrylonitrile butadiene styrene, acrylic acid, polyvinyl chloride, polyarylate, polyoxybenzoyl polyester, cyclic olefin polymers, and cyclic olefin copolymers.

[0077] From the viewpoint of ease of composite with glass, it is preferable that the viscosity of the glass and the resin is approximately the same within the molding temperature range. Specifically, at a temperature where the complex viscosity of the glass is 500 Pa·s, the complex viscosity of the resin is preferably 250 to 1000 Pa·s.

[0078] There are no particular limitations on the manufacturing method of glass-resin composite granules. For example, methods such as using a biaxial compounding extruder to melt-blend glass components with resin components and other components as needed, and granulating the resulting melt; or hot-pressing glass granules and resin granules.

[0079] In the glass-resin composite particles of the present invention, the mixing ratio of glass to resin can be appropriately set considering the intended use of the composite material, and is not particularly limited. For example, it can be mixed and used in a composite ratio within the range of glass:resin = 1:99 to 99:1 (volume ratio).

[0080] Other Ingredients

[0081] The glass particles of the present invention may contain one or more fillers, additives, etc., as needed. The filler may be plate-shaped, spherical, or other granular fillers. The filler may be inorganic or organic. Examples of additives include flame retardants, conductivity enhancers, nucleating agents, ultraviolet absorbers, antioxidants, damping agents, antibacterial agents, insect repellents, deodorizers, anti-coloring agents, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foam control agents, viscosity modifiers, and surfactants.

[0082] Molded Body

[0083] The molded article of the present invention comprises the glass of the present invention, which can be obtained by molding the aforementioned glass particles (glass particles alone or glass-resin composite particles) into a desired shape through low-temperature molding such as extrusion, injection, blow molding, or pressure molding. If the glass crystallizes or foams during molding, molding becomes difficult, and the molded article loses its transparency. The glass of the present invention suppresses crystallization and foaming during molding, thus obtaining a molded article with excellent bonding strength with the resin and excellent transparency. From the perspective of ensuring transparency, the average value of the parallel light transmittance in the thickness direction of the molded article at wavelengths of 400 to 700 nm is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. There is no particular limitation on the upper limit of the parallel light transmittance, which is typically 92% or less. In addition, from the perspective of ensuring transparency, the haze rate in the thickness direction of the molded article is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. There is no particular limitation on the lower limit of this haze rate, which is typically 0.2% or more.

[0084] The molded article of the present invention preferably has good gas barrier properties. Specifically, under conditions of 40°C and 90% RH, the water vapor permeability is preferably 1 g / m. 2 For less than / day, 0.1g / m² is preferred. 2 Below / day, further preferably 0.01g / m 2 Below / day, preferably 0.001g / m 2 / day or less.

[0085] Examples of molded bodies according to the present invention include glass molded bodies and glass-resin composite molded bodies. The shape of the molded body can be plate-like or film-like, and can have three-dimensional shapes such as cylinders, prisms, bottles, syringes, and containers. In the case of plate-like or film-like shapes, it is not limited to rectangles, but can also be polygonal, circular, or elliptical. Furthermore, the surface can be smooth or uneven.

[0086] The thickness of the molded body is not particularly limited, but is preferably 0.01 to 5 mm, more preferably 0.02 to 3 mm, and even more preferably 0.05 to 1 mm. A thickness of 0.01 mm or more improves strength and gas barrier properties. A thickness of 5 mm or less enables lightweight construction.

[0087] <<Glass Resin Composite Molded Body>>

[0088] Examples of glass-resin composite molded bodies include 1) glass-resin laminates and 2) glass-resin island composites. If the glass components crystallize or foam, low-temperature molding of the composite becomes difficult, and the bond strength between the resin and the glass, as well as the transparency, decreases. The glass of this invention suppresses crystallization and foaming during low-temperature molding, thus obtaining a molded body with excellent bond strength and transparency in the resin composite. From the perspective of ensuring transparency, the average value of the parallel light transmittance in the thickness direction of the molded body at wavelengths of 400–700 nm is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. There is no particular upper limit to the parallel light transmittance, typically 92% or less.

[0089] 1) Glass resin laminate

[0090] A cross-sectional schematic diagram of one embodiment of the glass resin laminate is shown in Figure 1 (A) and (B). For example... Figure 1 As shown in (A) and (B), the glass resin laminate 11 is a laminate consisting of two or more layers, preferably three or more layers, obtained by laminating resin layers 13 on one or both sides of the glass layer 12. From the viewpoint of formability and strength, the outermost layer is preferably resin.

[0091] From the perspectives of gas barrier properties and lightweight design, the volume ratio (of glass layer to resin layer) of the glass-resin laminate is preferably 0.1:99.9 to 80:20, and more preferably 10:90 to 60:40.

[0092] Glass-resin laminates are composites made by melting glass components (e.g., the glass particles mentioned above) and resin components (e.g., resin particles) separately, then laminating them together, and finally forming them at low temperatures through extrusion molding, injection molding, blow molding, pressure molding, etc.

[0093] 2) Glass-resin island composite

[0094] A cross-sectional schematic diagram of one embodiment of the glass-resin island composite is shown in Figure 1 (C). For example Figure 1 As shown in (C), the glass-resin island composite 21 has a structure in which a discontinuous phase, namely a particle-shaped glass phase 23 with a closed interface, exists in the continuous phase 22 composed of resin, namely the resin phase 22. Figure 1 (C) shows a cross-sectional schematic diagram of a single-layer glass-resin island composite, but it can be a structure consisting of two or more layers. From the viewpoint of formability and strength, the outermost layer is preferably resin.

[0095] In this specification, "island structure" refers to the structure of a discontinuous phase of the components that constitute an island phase, which exists within a continuous phase of the marine phase and has closed interfaces (phase-to-phase boundaries).

[0096] From the perspectives of gas barrier properties and lightweight design, the ratio (volume ratio) of the glass phase to the resin phase in the glass-resin island composite is preferably 1:99 to 70:30, and more preferably 10:90 to 60:40.

[0097] As a method for manufacturing glass-resin island composites, examples include a method of mixing and combining glass components (e.g., the glass particles mentioned above) and resin components (e.g., resin particles) to form a composite material (e.g., glass-resin composite particles) and resin components (e.g., resin particles) separately, then laminating them together, and finally performing low-temperature molding by extrusion molding, injection molding, blow molding, pressure molding, etc., followed by biaxial stretching.

[0098] Figure 2 The diagram shows an embodiment of a method for manufacturing a glass-resin island composite. Figure 2 (A) indicates the lamination process. In the lamination process, a resin layer 27 is laminated on both sides of the layer 26 obtained by combining glass component 24 and resin component 25 to obtain a laminate 28. Figure 2 (B) indicates the stretching process. The stretching process involves stretching the laminate obtained from the lamination process using biaxial stretching. Thus, the following is obtained: Figure 2 (C) shows the glass-resin island composite.

[0099] <Uses>

[0100] The molded articles of the present invention have excellent transparency and barrier properties. As for their applications, examples include packaging for food or pharmaceutical products such as high-performance foods, pharmaceutical containers such as syringes and ampoules, flexible displays such as organic field-effect transistor (OLET) caps, and high-frequency films / substrates used in wearable devices or mobile phones or 5G.

[0101] The present invention will be specifically described below through embodiments, but the present invention is not limited to the following embodiments.

[0102] Example

[0103] The present invention will be described below through examples, but the present invention is not limited thereto.

[0104] <Glass Making>

[0105] As described below, after weighing the glass raw material according to the basic glass composition, the glass raw material is melted and cast into a mold to obtain a glass block. For Examples 1-6, the basic glass composition is expressed in mol% as a composition containing 15% P, 17.5% Sn, 42.5% O, and 25% F. For Example 7, the basic glass composition is expressed in mol% as a composition containing 15.4% P, 15.4% Sn, 38.5% O, and 30.7% F. For Example 8, the basic glass composition is expressed in mol% as a composition containing 18.2% P, 12.1% Sn, 45.5% O, and 24.2% F.

[0106] Two of the following were selected as phosphorus (P) raw materials: NH4H2PO4, Sn2P2O7, and H3PO4 (85% concentration). When using H3PO4, it was dried at a specified temperature for 4 hours. Subsequently, it was mixed with all other raw materials, including SnO and SnF2, and melted in a platinum crucible at 500°C for 2 hours. The melt was poured into a mold to obtain a glass block. The concentration of phosphorus (F) in the obtained glass was quantified using an ion-electrode method, and the concentrations of all elements except F and O were quantified using ICP-N (Inductively Coupled Phosphorus) spectroscopy. The concentration of oxygen (O) was calculated by the difference between the total concentrations of other elements and the total concentration. The quantitative results of the composition are shown in Table 1, expressed as molar percentage (%).

[0107] <Evaluation>

[0108] (Tx, Tg, Tc)

[0109] The glass block was pulverized in an agate mortar to obtain powder with a median particle size of 0.3 micrometers. 50 mg of the powder was placed in an aluminum dish and measured using a differential scanning calorimeter (Bruker DSC3300SA) in atmospheric conditions, with the temperature increased from 25°C to 500°C at a rate of 2°C / min. In the DSC curve, Tg is the temperature at which the endothermic shift begins during the heating process, Tx is the temperature at which the exothermic reaction due to crystallization begins during the heating process, and Tc is the peak temperature at which the exothermic reaction due to crystallization begins during the heating process. It should be noted that if Tx and Tc are not observed, they are recorded as "none".

[0110] (Weight change at (Tg+150)℃)

[0111] The glass block was pulverized in an agate mortar to obtain powder with a median particle size of 0.3 micrometers. 50 mg of the powder was placed in an aluminum pan and measured using a thermogravimetric differential calorimeter (Bruker TG-DTA20000SA) in atmospheric conditions, with the temperature increased from 25°C to (Tg+150)°C at a rate of 2°C / min and held at (Tg+150)°C for 1 hour. The rate of change of weight relative to the initial weight was evaluated.

[0112] (Infrared absorption spectrum)

[0113] The glass block was processed into a 1 mm thick plate using cerium oxide abrasive. A Fourier transform infrared spectrophotometer (Thermo Scientific Nicolet iS10) was then used to measure the plate at wavenumbers from 400 to 4000 cm⁻¹. －1 The range was measured. The wavenumber was 400 cm⁻¹. －1 The transmittance is set to T400, and the wavenumber is 3100cm. －1 The transmittance is set to T3100, and the wavenumber is 3240cm. －1 When the transmittance is set to T3240, the transmittance is A3100 = -log 10 (T3100 / T400) Calculate wavenumber 3100cm －1 The absorbance A3100 per 1 mm thickness is obtained by A3240 = -log 10 (T3240 / T400) Calculate wavenumber 3240cm －1 The absorbance per 1 mm thickness is A3240.

[0114] (Parallel ray transmittance)

[0115] After the glass block was processed into a 1mm thick plate using cerium oxide abrasive, the transmittance of parallel light with wavelengths of 400-700nm was obtained using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Hitachi High Technology Co., Ltd.: U4100).

[0116] The results are shown in Table 1. Examples 1 and 2 in Table 1 are comparative examples, and Examples 3 to 8 are exemplary examples.

[0117] [Table 1]

[0118]

[0119] As an example of the infrared absorption spectroscopy measurement results, the measurement results of the glasses in Examples 1 and 5 are shown below. Figure 4 .

[0120] As an example of the results of parallel light transmittance measurement, the measurement results of the glasses in Examples 1 and 3 are shown below. Figure 5 .

[0121] As shown in Table 1, in Examples 3 to 8, which are embodiments of the present invention, the A3240 / A3100 ratio is 1.2 or less, the moisture content is controlled, and crystallization is not easily achieved, thus resulting in transparent glass. Furthermore, in Examples 3 to 6, the difference between Tc and Tg is 150°C or more (or Tc is not observable), thus widening the difference between the formable temperature and the crystallization temperature, resulting in glass with even better transparency even during low-temperature forming. On the other hand, in Examples 1 and 2, which are comparative examples, the A3240 / A3100 ratio is greater than 1.2, crystallization is not controlled, and therefore transparent glass cannot be obtained.

[0122] <Fabrication of Glass-Resin Composites>

[0123] The glass manufactured in Example 3 was processed into a 2mm thick plate, sandwiched between two 0.3mm thick polyethylene terephthalate resin sheets, and then pressurized at 260°C to form a composite. As a result, the glass and resin exhibited good adhesion strength, and the average transmittance of parallel light in the thickness direction (wavelengths 400–700 nm) reached 75%, indicating transparency.

[0124] On the other hand, the glass manufactured in Example 1 was processed into a 2mm thick plate, sandwiched between two 0.3mm thick polyethylene terephthalate resin sheets, and then pressurized at 260°C to form a composite. As a result, the glass and resin had good bonding strength, but due to crystallization, the average value of the transmissivity of parallel light in the thickness direction (wavelength 400–700 nm) was as low as 45%, making it opaque.

[0125] The invention has been described in detail with reference to specific methods, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. It should be noted that this application is based on Japanese Patent Application No. 2020-149137, filed on September 4, 2020, the entire contents of which are incorporated herein by reference. Furthermore, all references cited herein are incorporated in their entirety.

Claims

1. A glass, containing, in mole percent, P: 8–25%, Sn: 8–40%, O: 20–80%, and F: 1–50%, In the total weight of phosphate raw materials for glass, orthophosphoric acid (H3PO4) accounts for more than 51% by weight. The glass transition temperature (Tg) is below 300℃, and the wavenumber in the infrared absorption spectrum is 3100 cm⁻¹. －1 The absorbance per 1 mm thickness is set to A3100, and the wavenumber is 3240 cm⁻¹. －1 When the absorbance per 1 mm thickness is set to A3240, the ratio of A3240 / A3100 is 0.6 to 1.

2.

2. The glass according to claim 1, wherein, The A3100 is 0.2 to 4, and the A3240 is 0.12 to 4.

8.

3. The glass according to claim 1 or 2, wherein, The difference between the crystallization peak temperature Tc and the glass transition temperature Tg, determined by differential scanning calorimetry, is greater than 150℃.

4. The glass according to claim 1, wherein, The weight change before and after heat treatment at (Tg+150)℃ for 1 hour is -2% to +0.5%.

5. The glass according to claim 1, wherein, The average transmittance of parallel light measured on a 1 mm thick plate at wavelengths of 400–700 nm is over 70%.

6. The glass according to claim 1, wherein it is used in at least one of extrusion molding, injection molding, blow molding and pressure molding at temperatures below 450°C.

7. A particle having a major diameter of 0.1 mm to 5 mm, comprising the glass described in any one of claims 1 to 6.

8. The particles according to claim 7, wherein, The minor diameter is 0.1 mm to 5 mm, and the ratio of the major diameter to the minor diameter is 0.2 to 1.

9. The particles according to claim 7 or 8, wherein, The particles are glass particles.

10. The particles according to claim 7 or 8, wherein, The particles are glass-resin composite particles made by combining glass and resin.

11. A molded body comprising glass, formed using the granules as described in any one of claims 7 to 10.

12. The molded body according to claim 11 is a glass resin composite molded body.

13. The molded article according to claim 11 or 12, wherein, The thickness of the molded body is 0.01 to 5 mm, and the average value of the parallel light transmittance in the thickness direction at wavelengths of 400 to 700 nm is above 60%.

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