Low melting point glass

Abstract

The purpose of the present invention is to provide glass that has a low Tg, allowing for low-temperature molding, and in which bubbling and crystallization during molding are suppressed. The present invention pertains to glass that contains, indicated in mol% of the elements, 8-25% P, 8-40% Sn, 20-80% O, and 1-50% F, the glass transition temperature Tg being 300°C or lower, and A3240 / A3100 being 1.2 or below, where A3100 is the absorbance per 1 mm thickness at the wavenumber 3100 cm-1, and A3240 is the absorbance per 1 mm thickness at the wavenumber 3240 cm-1, in the infrared absorption spectrum.

Description

[Technical Field]

[0001] The present invention relates to glass, and more particularly to glass having a low glass transition temperature (Tg), enabling low-temperature molding, and suppressing foaming and crystallization during molding; to composite members of the glass and resin; and to molded articles thereof. [Background technology]

[0002] Organic polymers (resins) are inferior to glass in terms of heat resistance, light resistance, light transmittance, and gas barrier properties, but they are used in a variety of applications because they have a low molding temperature and are inexpensive. On the other hand, glass has excellent heat resistance, light resistance, light transmittance, and gas barrier properties, but ordinary glass has a high Tg, making it difficult to mold freely.

[0003] Low-melting-point glass refers to glass materials with a lower melting temperature than ordinary glass, and is used for coating metal surfaces and glass surfaces, bonding them together, and as sealing materials for electronic products and other items that require higher airtightness than resin-based materials (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japan Special Publication No. 2010-505727 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, conventional low-melting-point glass has drawbacks: it is prone to crystallization and foaming, making it difficult to achieve transparency after low-temperature molding, and the molding temperature margin is narrow due to crystallization. Therefore, conventional low-melting-point glass is generally unsuitable as a material for low-temperature molding processes such as extrusion, injection, blow molding, and press molding, which are commonly used in resin molding.

[0006] Therefore, an object of the present invention is to provide a glass having a low Tg, capable of being formed at a low temperature, and suppressing foaming and crystallization during molding.

Means for Solving the Problems

[0007] As a result of studying the above problems, the present inventors have found that the above problems can be solved by controlling the structure around the OH group in the glass, and thus have completed the present invention.

[0008] The present invention relates to a glass containing, in terms of molar percentage of elements, 8 to 25% of P, 8 to 40% of Sn, 20 to 80% of O, and 1 to 50% of F, having a glass transition temperature Tg of 300°C or lower, and having an absorbance per 1 mm thickness at a wavenumber of 3100 cm , , , [Figure 2] , [Figure 1] ,

[0010] in the infrared absorption spectrum designated as A3100, and an absorbance per 1 mm thickness at a wavenumber of 3240 cm -1 designated as A3240, wherein A3240 / A3100 is 0.6 to 1.2.

Advantages of the Invention

[0009] The glass of the present invention has a Tg of 300°C or lower and excellent formability. Also, in the infrared absorption spectrum, when the absorbance per 1 mm thickness at a wavenumber of 3100 cm -1 is designated as A3100, and the absorbance per 1 mm thickness at a wavenumber of 3240 cm -1 is designated as A3240, A3240 / A3100 is within a specific range, and crystallization and foaming are suppressed by controlling the structure around the OH group in the glass. Accordingly, the glass of the present invention has the advantage of exhibiting excellent transparency after low-temperature molding.

Brief Description of the Drawings

[0010] [Figure 1] FIG. 1(A) and FIG. 1(B) are schematic cross-sectional views of one embodiment of a glass resin laminate. FIG. 1(C) is a schematic cross-sectional view of one embodiment of a glass resin sea-island composite. [Figure 2] FIGS. 2(A) to (C) show schematic views of one embodiment of a method for producing a glass resin sea-island composite. [Figure 3] Figure 3 shows a DSC curve. [Figure 4] Figure 4 is a diagram showing an example of the measurement results of an infrared absorption spectrum. [Figure 5] Figure 5 is a diagram showing an example of the measurement results of parallel light transmittance.

Mode for Carrying Out the Invention

[0011] In this specification, "~" indicating a numerical range is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value. Unless otherwise specified, hereinafter, "~" in this specification is used with the same meaning.

[0012] In this specification, unless otherwise specified, the glass composition is simply represented by "%" for mol%.

[0013] Also, in this specification, "substantially not contained" means that it is below the impurity level contained in raw materials, etc., that is, it is not intentionally added. When it is described in this specification that a certain component is substantially not contained, specifically, the content of the component is, for example, less than 0.1%.

[0014] In this specification, "parallel light transmittance" is the ratio of the parallel light beam emitted from the sample to the parallel light beam incident on the sample, and scattered light is not included. Also, "haze ratio" means the value measured in accordance with JIS K3761:2000 using a C light source.

[0015] <Glass> (Composition) The glass of the present invention is in terms of mol% of elements P 8 to 25%, Sn 8 to 40%, O 20 to 80%, F 1 to 50%, and contains. The following describes each composition range.

[0016] The P content is 8% or more, preferably 10% or more, and more preferably 12% or more. By setting the P content to 8% or more, the glass transition temperature Tg and molding temperature can be lowered. The P content is 25% or less, preferably 20% or less, and more preferably 17% or less. By setting the P content to 25% or less, water resistance and gas barrier properties can be improved.

[0017] The Sn content is 8% or more, preferably 10% or more, and more preferably 13% or more. A Sn content of 8% or more can improve water resistance and gas barrier properties. The Sn content is 40% or less, preferably 30% or less, and more preferably 20% or less. A Sn content of 40% or less can lower the glass transition temperature (Tg) and molding temperature.

[0018] The ratio of Sn content to P content, i.e., Sn / P, is preferably 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 increased, 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.

[0019] The oxygen content is 20% or more, preferably 30% or more, and more preferably 40% or more. By setting the oxygen content to 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 setting the oxygen content to 80% or less, the glass transition temperature Tg and the molding temperature can be lowered.

[0020] The fluorine (F) content is 1% or more, preferably 3% or more, more preferably 10% or more, and even more preferably 15% or more. By setting the fluorine content to 1% or more, the glass transition temperature (Tg) and molding temperature can be lowered, and crystallization can be suppressed. The fluorine (F) content is 50% or less, preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less. By setting the fluorine (F) content to 50% or less, the glass manufacturing process can be simplified, and the generation of HF gas during melting and low-temperature molding can be suppressed. Here, the fluorine (F) content is not the amount added during the glass raw material preparation, but a value obtained by analyzing the glass using the ion electrode method or ion chromatography method. In addition, the content of each element other than F and O is a value obtained by ICP emission spectrometry. The O content is calculated from the difference between the sum of the concentrations of other elements and the total.

[0021] The glass of the present invention only needs to contain the above-mentioned components within the above range, and insofar as it achieves the effects of the present invention, it may also contain any compounds and additives used in glass in addition to the above-mentioned components. For example, it may contain the following components.

[0022] The glass of the present invention may contain 0 to 30% Zn. By including Zn, crystallization can be suppressed while keeping the glass transition temperature (Tg) low, and the coefficient of thermal expansion can be reduced. The Zn content may be 5% or more, or 10% or more. Furthermore, the Zn content may be 25% or less, or 20% or less.

[0023] The glass of the present invention may contain 0 to 30% Ba. By including Ba, crystallization can be suppressed while keeping the glass transition temperature (Tg) low, and water resistance can be improved. The Ba content may be 5% or more, or 10% or more. Furthermore, the Ba content may be 25% or less, or 20% or less.

[0024] The glass of the present invention may contain a total of 0 to 30% of Mg, Ca, and Sr. The inclusion 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. Furthermore, the total content of Mg, Ca, and Sr may be 25% or less, or 20% or less.

[0025] The glass of the present invention may contain a total of 0 to 30% of Li, Na, and K. The inclusion of Li, Na, and K can lower the glass transition temperature (Tg) and the molding temperature. The total content of Li, Na, and K may be 5% or more, or 10% or more. Furthermore, the total content of Li, Na, and K may be 25% or less, or 20% or less.

[0026] The glass of the present invention may contain 0 to 20% Al. The inclusion of Al can improve water resistance and gas barrier properties. The Al content may be 3% or more, or 6% or more. Furthermore, the Al content may be 15% or less, or 10% or less.

[0027] The glass of the present invention may contain 0 to 20% of B. By including B, crystallization can be suppressed and chemical resistance can be improved. The B content may be 5% or more, or 10% or more. Furthermore, the B content may be 17% or less, or 13% or less.

[0028] The glass of the present invention may contain 0 to 10% Si. The inclusion of Si can suppress crystallization and improve water resistance and chemical resistance. The Si content may be 2% or more, or 5% or more. Furthermore, the Si content may be 8% or less, or 7% or less.

[0029] The glass of the present invention may contain 0 to 10% Zr. The inclusion of Zr can suppress crystallization and improve water resistance and chemical resistance. The Zr content may be 2% or more, or 4% or more. Furthermore, the Zr content may be 8% or less, or 6% or less.

[0030] The glass of the present invention may contain a total of 0 to 10% Ce and Y. The inclusion of Ce and Y improves water resistance and chemical resistance. The total content of Ce and Y may be 2% or more, or 4% or more. Furthermore, the total content of Ce and Y may be 8% or less, or 6% or less.

[0031] The glass of the present invention may contain a total of 0 to 20% of Nb, W, Mo, and Ta. The inclusion of Nb, W, Mo, and Ta can improve water resistance and chemical resistance. However, care must be taken to prevent crystallization and discoloration. The total content of Nb, W, Mo, and Ta may be 2% or more, or 4% or more. Furthermore, the total content of Nb, W, Mo, and Ta may be 15% or less, or 10% or less.

[0032] The glass of the present invention may contain a total of 0 to 20% of Fe, Ti, Mn, Cr, Cu, and Ag. By including 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 prevent crystallization and discoloration. 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.

[0033] The glass of the present invention may contain a total of 0 to 20% of Cl, Br, I, and S. The presence of Cl, Br, I, and S can suppress crystallization. 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.

[0034] (Glass transition temperature Tg) 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. The lower limit of Tg is not particularly limited, but it is preferably 50°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher in order to improve weather resistance and water resistance. Because the glass transition temperature is 300°C or less, the glass has a low melting point and can be used as a material for low-temperature molding processes such as extrusion, injection, blow molding, and press molding, which are commonly used in resin molding.

[0035] (Infrared absorption spectrum) The glass of the present invention exhibits an infrared absorption spectrum of wavenumber 3100 cm⁻¹. -1 Absorbance per 1 mm thickness in this region is calculated using A3100 and wavenumber 3240 cm⁻¹. -1 When the absorbance per 1 mm thickness is A3240, the ratio of A3240 / A3100 is 1.2 or less, preferably 1 or less, and more preferably 0.9 or less. By having an A3240 / A3100 ratio of 1.2 or less, crystallization can be suppressed and foaming can be suppressed by appropriately controlling the structure around the OH group, so a transparent molded article can be obtained. The A3240 / A3100 ratio is 0.6 or more, preferably 0.7 or more, and more preferably 0.8 or more. By having an A3240 / A3100 ratio of 0.6 or more, the glass manufacturing process can be simplified.

[0036] Wave number 3100cm -1 and wave number 3240cm -1The infrared absorption spectrum in the vicinity originates from OH groups in the glass, but its shape changes under the influence of the glass's skeletal structure. When the glass's skeletal structure is a PO-Sn-O structure, during low-temperature molding, elements rearrange with the volatilization of F and OH associated with the glass skeleton, making it easy to form crystals of tin phosphate compounds. When the glass's skeletal structure takes the PO-Sn-O structure, the A3240 peak in the infrared absorption spectrum tends to protrude, and A3240 / A3100 becomes greater than 1.2. By preferably using a POPO structure for the glass's skeletal structure, A3240 / A3100 can be set to 0.6 or more and 1.2 or less. F and OH associated with the POPO 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. In addition, since the volatilization of F and OH can be suppressed, foaming is also less likely to occur.

[0037] By making ammonium dihydrogen phosphate (NH4H2PO4) account for 51% or more of the total weight of the glass phosphate raw materials, the structure forming the glass skeleton becomes a PO-Sn-O structure, making it easier to form crystals of tin phosphate compounds, and the A3240 / A3100 ratio becomes greater than 1.2. Furthermore, the use of ammonium dihydrogen phosphate is undesirable because it generates a large amount of ammonia gas during glass melting, resulting in a high environmental burden, and foaming due to ammonia gas also occurs during low-temperature molding. On the other hand, by using orthophosphoric acid (H3PO4) as the weight ratio of 51% or more of the total weight of the glass phosphate raw materials, the structure forming the glass skeleton becomes a POPO structure, resulting in a highly transparent glass that is less prone to crystallization and foaming after melting and low-temperature molding, and the A3240 / A3100 ratio becomes between 0.6 and 1.2. In addition, the water contained in orthophosphoric acid suppresses crystallization during low-temperature molding in the glass, so it is preferable to use orthophosphoric acid as the glass phosphate raw material.

[0038] Of the total weight of the glass phosphate raw materials, it is more preferable that the weight ratio of orthophosphoric acid (H3PO4) is 70% or more, more preferably 80% or more, and even more preferably 90% or more. As the phosphate raw materials, ammonium hexafluorophosphate (NH4PF6), stannous pyrophosphate (Sn2P2O7), phosphorus pentoxide (P2O5), tin tris(orthophosphate) (Sn3(PO4)2), zinc pyrophosphate (Zn2P2O7), aluminum phosphate (AlPO4), etc. can be used in combination. However, the phosphate raw materials are not limited to those exemplified here. It is preferable to use a chemical solution with a concentration of 75% to 90% for orthophosphoric acid (H3PO4), and the total weight of the chemical solution is used for calculating the weight ratio.

[0039] The glass of the present invention has an absorbance of 0.2 to 4 per millimeter thickness at a wavenumber of 3100 cm -1 in the infrared absorption spectrum, more preferably 0.3 to 3, and even more preferably 0.5 to 2. Also, the absorbance per millimeter thickness at a wavenumber of 3240 cm -1 is preferably 0.12 to 4.8, more preferably 0.18 to 3.6, and even more preferably 0.3 to 2.4. When the absorbance per millimeter thickness at a wavenumber of 3100 cm -1 and the absorbance per millimeter thickness at a wavenumber of 3240 cm -1 [[ID=:12]]are within the above ranges, the structure of the glass is controlled, and it is difficult to crystallize or foam during low-temperature molding, so a molded body with excellent transparency can be obtained.

[0040] The infrared absorption spectrum is measured using a Fourier transform infrared spectrophotometer. Let the transmittance at a wavenumber of 400 cm -1 be T400, the transmittance at a wavenumber of 3100 cm -1 be T3100, the transmittance at a wavenumber of 3240 cm -1 be T3240, and when the thickness of the measurement sample is D (mm), the absorbance A3 -1 per millimeter thickness at a wavenumber of 3100 cm is A3100 = -log -1 (T3100 / T400) / D, and at a wavenumber of 3240 cm 10 ...-1 The absorbance A3240 per 1 mm thickness is calculated as A3240 = -log 10 The calculation is performed using (T3240 / T400) / D. Dividing by T400 is done to correct the baseline during measurement. It is preferable to process the measurement sample into a 1mm thick flat plate using cerium oxide free abrasive as a finishing agent.

[0041] (Raman scattering spectrum) The glass of the present invention exhibits a Raman scattering spectrum of 1020-1060 cm⁻¹. -1 It is preferable that the main peak be observed within the range of P's Q. 1 These peaks originate from the structure and contribute to the stability of the glass. Furthermore, the glass of the present invention exhibits peaks of 960-1000 cm⁻¹ in its Raman scattering spectrum. -1 It is preferable that the peak is observed within the range of P's Q. 0 These peaks originate from the structure and contribute to improving the water resistance of the glass. Furthermore, the glass of the present invention exhibits peaks of 1080-1170 cm⁻¹ in its Raman scattering spectrum. -1 It is preferable that no peak is observed within the range of P's Q. 2 This peak is structural and degrades the water resistance of the glass.

[0042] (Differential scanning calorimetry) The glass of the present invention preferably has a difference of 150°C or more between the crystallization peak temperature Tc and the glass transition temperature Tg, determined by differential scanning calorimetry, more preferably 160°C or more, and even more preferably 170°C or more. Most preferably, Tc is not observed, in which case the difference between Tc and Tg can be interpreted as infinite. A difference of 150°C or more between Tc and Tg allows for a wider gap between the moldable temperature and the crystallization temperature, i.e., a wider molding temperature margin, resulting in glass with superior transparency after low-temperature molding. At temperatures above Tc, low-temperature molding becomes difficult due to a rapid increase in viscosity caused by glass crystallization.

[0043] The glass of the present invention preferably has a difference of 140°C or more between the crystallization onset temperature Tx and the glass transition temperature Tg, determined by differential scanning calorimetry, more preferably 150°C or more, and even more preferably 160°C or more. Most preferably, Tx is not observed, in which case the difference between Tx and Tg can be interpreted as infinite. A difference of 140°C or more between Tx and Tg widens the gap between the moldable temperature and the crystallization onset temperature, resulting in glass with superior transparency after low-temperature molding.

[0044] For differential scanning calorimetry (DSC) measurements, a powder with a median diameter of less than 3 microns, ground in an agate mortar, is used as the sample for measurement. The measurement is performed under conditions where the temperature is increased from 25°C to 500°C at a rate of 2°C / min in an air atmosphere. As shown in Figure 3, in the DSC curve, Tg is the temperature at which the curve first undergoes an endothermic shift during the heating process, Tx is the temperature at which exothermic reaction due to crystallization first begins during the heating process, and Tc is the peak temperature of the exothermic reaction due to crystallization that first occurs during the heating process.

[0045] (Weight change during molding) The glass of the present invention preferably has a weight change of -2% or more, more preferably -1% or more, and even more preferably -0.7% or more, before and after heat treatment at (Tg+150)°C for 1 hour. (Tg+150)°C is the same temperature as the temperature during low-temperature molding, and a weight change of -2% or more ensures that the amount of moisture in the glass is not too high, suppressing foaming during low-temperature molding and resulting in a molded article with excellent transparency. The upper limit of the weight change is preferably +0.5% or less, more preferably -0.1% or less, and even more preferably -0.3% or less. A weight change of +0.5% or less suppresses crystallization during low-temperature molding due to the presence of moisture in the glass, resulting in a molded article with excellent transparency.

[0046] The weight change before and after heat treatment at (Tg+150)℃ for 1 hour is measured under the following conditions. The weight of the sample is measured using a thermogravimetric differential thermal analyzer. The sample used for measurement is a powder with a median diameter of less than 3 microns, ground in an agate mortar. The measurement conditions are as follows: heating from 25°C to (Tg+150)°C at 2°C / min in an air atmosphere, and holding at (Tg+150)°C for 1 hour. The rate of weight change relative to the initial weight is evaluated during this process.

[0047] (Parallel light transmittance) 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, of the parallel light transmittance measured in the thickness direction of a 1 mm thick flat plate at wavelengths of 400 to 700 nm. An average value of 70% or more results in glass with excellent transparency and suppressed crystallization. Furthermore, a highly transparent molded body can be obtained by low-temperature molding using glass with an average value of 70% or more. While there is no particular upper limit to the average value, it is typically 92% or less. For measurement, it is preferable to process the sample into a 1 mm thick flat plate using cerium oxide free abrasive as a finishing agent.

[0048] (Hay rate) The glass of the present invention preferably has a haze rate of 20% or less, more preferably 15% or less, and even more preferably 10% or less, measured in the thickness direction of a 1 mm thick flat plate. A haze rate of 20% or less results in glass with excellent transparency and suppressed crystallization. While there is no particular lower limit to the haze rate, it is typically 0.2% or more. For measurement, it is preferable to process the sample into a 1 mm thick flat plate using cerium oxide free abrasive as a finishing agent.

[0049] (Manufacturing method) The glass of the present invention can be manufactured by a method of mixing, melting, and cooling glass raw materials. Preferably, orthophosphoric acid (H3PO4) is used as the phosphate raw material for the glass of the present invention. Since orthophosphoric acid contains water, it may be dried at a temperature of 100-500°C for 10 minutes to 50 hours before use. Orthophosphoric acid may be dried alone and then mixed with other raw materials, or orthophosphoric acid may be mixed with some or all of the other raw materials and then dried. Melting is carried out by placing the raw materials in a container made of platinum, carbon, quartz, alumina, or nickel, and melting at a temperature of 400-700°C for 10 minutes to 10 hours. All raw materials may be melted together, or some or specific raw materials may be melted first, with the remainder melted later. If necessary, the molten glass may be molded into predetermined shapes such as pellets or flakes using various methods.

[0050] <Glass pellets> The glass of the present invention may be in the form of pellet-shaped glass pellets. The pellet shape makes it easier to load into a low-temperature molding machine. The major diameter of the glass pellet 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 pellet is preferably 0.1 mm to 5 mm, more preferably 0.5 to 4.5 mm, and even more preferably 1.5 to 4 mm. If the glass pellet is too small, problems may arise such as clogging in the molding machine, crystallization during low-temperature molding, and the inclusion of bubbles during low-temperature molding. On the other hand, if the glass pellet is too large, problems may arise such as not being conveyed by the screw in the molding machine and being easily broken. The ratio of the major diameter to the minor diameter of the glass pellet is preferably 0.2 to 1, more preferably 0.5 to 1, and even more preferably 0.7 to 1, from the viewpoint of preventing breakage in the molding machine.

[0051] The method for manufacturing glass pellets is not particularly limited, but examples include pressing using a mold, crushing glass with water, drop molding, remelting glass powder, and tearing the molten material into small pieces and throwing them.

[0052] (Low-temperature molding) The glass of the present invention is preferably used in at least one of extrusion molding, injection molding, blow molding, and press molding at a temperature of 450°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower. Roll-out molding is also included in press molding. As described above, the glass of the present invention has a Tg of 300°C or lower and an A3240 / A3100 of 1.2 or lower, so even when used in a low-temperature molding process of preferably 450°C or lower, crystallization and foaming are suppressed, and a molded article with excellent transparency is obtained. From the viewpoint of further suppressing foaming, the glass may be dried before low-temperature molding. The drying conditions are typically 10 minutes to 10 hours at a temperature near the Tg.

[0053] <<Glass resin composite pellets>> The glass pellets may be glass-resin composite pellets formed by compounding the glass of the present invention with a resin. Both thermosetting resins and thermoplastic resins are applicable as the resin. From the viewpoint of ease of compounding with glass, thermoplastic resins are preferred, and resins having acidic and amino groups are preferred. Resins having acidic and amino groups readily chemically bond with the low-melting-point glass of the present invention.

[0054] Examples of thermosetting resins include epoxy resins, phenolic resins, urea resins, melamine resins, silicone resins, unsaturated polyester resins, and polyurethane resins.

[0055] 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, acronitrile butadiene styrene, acrylic, polyvinyl chloride, polyarylate, polyoxybenzoyl polyester, cycloolefin polymer, and cycloolefin copolymer.

[0056] From the viewpoint of ease of compounding with glass, it is preferable that the viscosity of the glass and the resin are approximately the same in the molding temperature range. Specifically, it is preferable that the complex viscosity of the resin is 250 to 1000 Pa·s at the temperature in which the complex viscosity of the glass is 500 Pa·s.

[0057] The method for manufacturing glass-resin composite pellets is not particularly limited, but examples include a method of melt-mixing glass components, resin components, and other components as needed using a twin-screw compounding extruder or the like to obtain a molten product which is then pelletized, and a method of heat-pressing glass pellets and resin pellets together.

[0058] In the glass-resin composite pellets of the present invention, the mixing ratio of glass and resin can be appropriately set considering the intended use of the composite composition, and is not particularly limited. For example, glass and resin can be mixed and composited in a range of 1:99 to 99:1 (volume ratio).

[0059] <<Component B>> The glass pellets according to the present invention may optionally contain one or more fillers, additives, etc. The fillers may be plate-shaped fillers, spherical fillers, or other granular fillers. The fillers may be inorganic or organic fillers. Examples of additives include flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insecticides, deodorants, color inhibitors, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, antifoaming agents, viscosity modifiers, and surfactants.

[0060] <Molded body> The molded article according to the present invention contains the glass according to the present invention and is obtained by molding the glass pellets (glass pellets alone or glass-resin composite pellets) into a desired shape by low-temperature molding such as extrusion, injection, blow molding, or press molding. If the glass crystallizes or foams during molding, molding becomes difficult and the molded article loses its transparency. Since the glass of the present invention suppresses crystallization and foaming during molding, a molded article with excellent adhesive strength and transparency in composite with resin can be obtained. From the viewpoint 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 upper limit to the parallel light transmittance, but it is typically 92% or less. Also, from the viewpoint 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 lower limit to the haze rate, but it is typically 0.2% or more.

[0061] The molded article according to the present invention preferably has good gas barrier properties. Specifically, it has a water vapor transmission rate of 1 g / m³ under conditions of 40°C and 90% RH. 2 It is preferable that the value be less than or equal to / day, and 0.1 g / m² 2 It is more preferable that it be less than or equal to / day, and 0.01 g / m² 2 It is even more preferable that it be less than or equal to / day, and 0.001 g / m² 2 It is especially preferable that the value be less than or equal to / day.

[0062] Examples of the forms of molded articles according to the present invention include glass molded articles and glass resin composite molded articles. The shape of the molded article may be plate-like or film-like, or it may have a three-dimensional shape such as a cylinder, column, prism, bottle, syringe, or container. In the case of plate-like or film-like articles, it is not limited to rectangles, but may also be polygonal, circular, or elliptical. Furthermore, the surface may be smooth or may have irregularities.

[0063] 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 allows for weight reduction.

[0064] <<Glass resin composite molded body>> Examples of glass-resin composite molded articles include 1) glass-resin laminates and 2) glass-resin sea-island composites. When the glass component crystallizes or foams, low-temperature molding of the composite molded article becomes difficult, and the adhesive strength and transparency between the resin and glass decrease. Since the glass of the present invention suppresses crystallization and foaming during low-temperature molding, a molded article with excellent adhesive strength and transparency in composite formation with resin can be obtained. In terms 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 upper limit to the parallel light transmittance, but it is typically 92% or less.

[0065] 1) Glass resin laminate Figures 1(A) and (B) show schematic cross-sectional views of one embodiment of the glass-resin laminate. As shown in Figures 1(A) and (B), the glass-resin laminate 11 is a laminate consisting of two or more layers, with resin layers 13 laminated on one or both sides of a glass layer 12, and preferably three or more layers. From the viewpoint of moldability and strength, the outermost layer is preferably resin.

[0066] In a glass-resin laminate, the ratio (volume ratio) of the glass layer to the resin layer is preferably 0.1:99.9 to 80:20, and more preferably 10:90 to 60:40, from the viewpoint of gas barrier properties and weight reduction.

[0067] Glass resin laminates are obtained by separately melting glass components (e.g., the glass pellets mentioned above) and resin components (e.g., resin pellets), then laminating and compounding them, and finally performing low-temperature molding by extrusion molding, injection molding, blow molding, press molding, etc.

[0068] 2) Glass resin sea-island composite Figure 1(C) shows a schematic cross-sectional view of one embodiment of a glass-resin sea-island composite. As shown in Figure 1(C), the glass-resin sea-island composite 21 has a structure in which a particulate glass phase 23, which is a discontinuous phase with a closed interface, exists in a resin phase 22, which is a continuous phase made of resin. Although Figure 1(C) shows a schematic cross-sectional view of a single-layer glass-resin sea-island composite, it may also be a structure consisting of two or more layers. From the viewpoint of moldability and strength, the outermost layer is preferably made of resin.

[0069] In this specification, "sea-island structure" refers to a structure in which a discontinuous phase of particulate island phase components, having closed interfaces (boundaries between phases), exists within a continuous phase of components forming the sea phase.

[0070] In glass-resin sea-island composites, the ratio (volume ratio) of glass phase to resin phase is preferably 1:99 to 70:30, and more preferably 10:90 to 60:40, from the viewpoint of gas barrier properties and weight reduction.

[0071] As a method for manufacturing glass-resin sea-island composites, for example, a method is used in which a material (e.g., glass-resin composite pellets) and a resin component (e.g., resin pellets) are mixed and composited separately, then laminated and composited, followed by low-temperature molding by extrusion molding, injection molding, blow molding, press molding, etc., and then biaxial stretching.

[0072] Figure 2 shows a schematic diagram of one embodiment of a method for manufacturing a glass-resin sea-island composite. Figure 2(A) shows the lamination process. In the lamination process, a resin layer 27 is laminated on both sides of a layer 26 which is a composite of a glass component 24 and a resin component 25, in order to obtain a laminate 28. Figure 2(B) shows the stretching and tensile process. In the stretching and tensile process, the laminate obtained in the lamination process is stretched by biaxial stretching. This yields the glass-resin sea-island composite shown in Figure 2(C).

[0073] <Application> The molded articles according to the present invention have excellent transparency and barrier properties, and their applications include packaging for foods such as high-performance foods or pharmaceuticals, pharmaceutical containers such as syringes and ampoules, flexible displays such as organic field-effect transistor (OLET) covers, wearable devices, or high-frequency films / substrates used in mobile phones or 5G.

[0074] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. [Examples]

[0075] The present invention will be described below with reference to examples, but the present invention is not limited thereto.

[0076] <Glassmaking> As described below, based on the base glass composition, the glass raw materials were weighed, melted, and cast into a mold to obtain glass blocks. For Examples 1-6, the base glass composition was as follows: 15% P, 17.5% Sn, 42.5% O, and 25% F (expressed as mol%). For Example 7, the base glass composition was as follows: 15.4% P, 15.4% Sn, 38.5% O, and 30.7% F (expressed as mol%). For Example 8, the base glass composition was as follows: 18.2% P, 12.1% Sn, 45.5% O, and 24.2% F (expressed as mol%).

[0077] One or two P raw materials were selected from NH4H2PO4, Sn2P2O7, and H3PO4 (85% concentration) and weighed. If H3PO4 was used, it was dried at a specified temperature for 4 hours. Then, it was mixed with all other raw materials such as SnO and SnF2, and melted in a platinum crucible at 500°C for 2 hours. The melt was cast into a mold to obtain a glass block. The F concentration of the obtained glass was quantified by the ion electrode method, and the concentrations of each element except F and O were quantified by ICP emission spectrometry. The O concentration was calculated from the difference between the sum of the concentrations of the other elements and the overall concentration. The results of the compositional quantification are shown in Table 1, expressed in mole percent of each element.

[0078] <Rating> (Tx, Tg, Tc) The aforementioned glass block was crushed in an agate mortar to obtain a powder with a median diameter of 0.3 microns. 50 mg of the powder was weighed into an aluminum pan and measured using a differential scanning calorimetry analyzer (Bruker DSC3300SA) under conditions of heating from 25°C to 500°C at a rate of 2°C / min in an atmospheric environment. In the DSC curve, Tg is the temperature at which the curve first shifts endothermically during the heating process, Tx is the temperature at which exothermic reaction due to crystallization first begins during the heating process, and Tc is the peak temperature of exothermic reaction due to crystallization that occurs first during the heating process. If Tx and Tc were not observed, it was indicated as "none".

[0079] (Weight change at (Tg + 150)℃) The aforementioned glass block was crushed in an agate mortar to obtain a powder with a median diameter of 0.3 microns. 50 mg of the powder was weighed into an aluminum pan and measured using a thermogravimetric differential thermal analyzer (Bruker TG-DTA20000SA) under the conditions of heating from 25°C to (Tg+150)°C at 2°C / min in an air atmosphere, and holding at (Tg+150)°C for 1 hour. The rate of weight change relative to the initial weight was evaluated.

[0080] (Infrared absorption spectrum) The aforementioned glass block was processed into a 1 mm thick flat plate using cerium oxide free abrasive as a finishing agent, and then measured using a Fourier transform infrared spectrophotometer (Nicolet iS10, Thermo Scientific) at wavenumbers of 400 to 4000 cm⁻¹. -1 Measurements were taken within the range of wavenumber 400 cm. -1 The transmittance in this region is T400, wavenumber 3100 cm². -1 The transmittance in this region is T3100, wavenumber 3240 cm⁻¹. -1 When the transmittance at T3240 is assumed, the wavenumber is 3100 cm. -1 The absorbance A3100 per 1 mm thickness is given by A3100 = -log 10 (T3100 / T400), wave number 3240cm -1 The absorbance A3240 per 1 mm thickness is calculated as A3240 = -log 10 Calculated using (T3240 / T400).

[0081] (Parallel light transmittance) The aforementioned glass block was processed into a 1 mm thick flat plate using cerium oxide free abrasive grains as a finishing agent, and the parallel light transmittance at wavelengths of 400 to 700 nm was obtained using an ultraviolet-visible-near-infrared spectrophotometer (Hitachi High-Tech Corporation: U4100).

[0082] The results are shown in Table 1. In Table 1, Examples 1 and 2 are comparative examples, and Examples 3 to 8 are examples.

[0083] [Table 1]

[0084] As an example of infrared absorption spectrum measurement results, Figure 4 shows the measurement results for the glasses in Example 1 and Example 5.

[0085] As an example of the measurement results for parallel light transmittance, Figure 5 shows the measurement results for the glass in Example 1 and Example 3.

[0086] As shown in Table 1, in Examples 3-8, which are embodiments of the present invention, the A3240 / A3100 ratio was 1.2 or less, and since the moisture content was controlled and crystallization was difficult, transparent glass was obtained. In addition, in Examples 3-6, the difference between Tc and Tg was 150°C or more (or Tc was not observed), which widened the margin between the moldable temperature and the crystallization temperature, resulting in glass with superior transparency even when molded at low temperatures. On the other hand, in Comparative Examples 1 and 2, the A3240 / A3100 ratio was greater than 1.2, and since crystallization was not controlled, transparent glass could not be obtained.

[0087] <Fabrication of glass-resin composites> In Example 3, the glass was processed into a 2mm thick plate, sandwiched between two 0.3mm thick polyethylene terephthalate resin sheets, and press-molded at 260°C to create a composite. As a result, the adhesive strength between the glass and resin was good, and the average value of the parallel light transmittance in the thickness direction at wavelengths of 400-700nm was high at 75%, indicating transparency.

[0088] On the other hand, the glass produced in Example 1 was processed into a 2 mm thick plate, sandwiched between two 0.3 mm thick polyethylene terephthalate resins, and press-molded at 260°C to create a composite. As a result, although the adhesive strength between the glass and the resin was good, due to crystallization, the average value of the parallel light transmittance in the thickness direction at wavelengths of 400-700 nm was low at 45%, and the composite was opaque.

[0089] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications are possible without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2020-149137, filed on 4 September 2020, which is incorporated by reference in its entirety. All references incorporated herein are incorporated as a whole.

Claims

1. In terms of elemental mole percentages P 12-20%, Sn 10-19%, O 55.9-70%, F 3-8.9%, It contains, The ratio of Sn content to P content (Sn / P) is 0.5 to 1.

24. The glass transition temperature Tg is 300°C or less. In the infrared absorption spectrum, wavenumber 3100 cm⁻¹ －１ The absorbance per 1 mm thickness is A3100, wavenumber 3240 cm⁻¹. －１ A glass in which, when the absorbance per 1 mm thickness is A3240, the ratio A3240 / A3100 is 0.6 to 1.

2.

2. The glass according to claim 1, wherein A3100 is 0.2 to 4 and 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 150°C or more.

4. The glass according to any one of claims 1 to 3, wherein the weight change before and after heat treatment at (Tg + 150) °C for 1 hour is -2% or more and +0.5% or less.

5. The glass according to any one of claims 1 to 4, wherein the average value of the parallel light transmittance measured on a 1 mm thick flat plate at wavelengths of 400 to 700 nm is 70% or more.

6. The glass according to any one of claims 1 to 5, used in at least one of extrusion molding, injection molding, blow molding, and press molding at a temperature of 450°C or below.

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

8. The pellet 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 pellet according to claim 7 or 8, wherein the pellet is a glass pellet.

10. The pellet according to claim 7 or 8, wherein the pellet is a glass-resin composite pellet formed by a composite of glass and resin.

11. A molded body containing glass, formed using pellets according to any one of claims 7 to 10.

12. The molded article according to claim 11, which is a glass resin composite molded article.

13. A molded article according to claim 11 or 12, wherein the average value of the parallel light transmittance in the thickness direction at wavelengths of 400 to 700 nm is 60% or more, with a thickness of 1 mm.

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