JP2013121905A - Resin composite substrate glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide resin composite substrate glass conforming with optical characteristics (refractive index nd, Abbe number νd) of a transparent resin, small in alkali elution amount and giving a resin composite substrate excellent in transparency and reliability.SOLUTION: This glass contains 45-65% SiO, 5-20% AlO, 13-25% BO, 10-30% total of MgO+CaO+SrO+BaO+ZnO, 5.5-9% MgO, 0-10% CaO, 0-10% SrO, 0-10% BaO, 0-1% total of LiO+NaO+KO, and 0.01-5.0% CeO.

Description

  The present invention relates to a glass used for a resin composite substrate in which a resin and glass are combined, and specifically relates to a glass for a resin composite substrate that is transparent to visible light and matches the optical characteristics of a transparent resin. It is.

  In recent years, as a substrate for flexible displays such as electronic paper, a resin composite substrate that is more flexible than a glass substrate, has better dimensional stability and mechanical strength than a resin substrate, and is transparent to visible light has attracted attention. Has been. Such a resin composite substrate is made of, for example, a composite material including a resin, a filler, and glass fibers as disclosed in Patent Documents 1 and 2.

  Examples of the resin constituting the resin composite substrate include epoxy resins, acrylic resins, cyclic olefin resins having a refractive index nd of 1.48 to 1.55 and an Abbe number νd of 50 to 65, from the viewpoint of transparency of the substrate. A mixture of

  The filler is added to control the thermal expansion characteristics of the resin composite substrate and to reduce the voids. For example, after the molten glass is formed into a film shape with a twin roller, it is pulverized with a ball mill or the like, The shape is used.

Glass fibers are added to increase the dimensional stability and mechanical strength of the resin composite substrate. For example, using a precious metal bushing device, the molten glass is continuously formed and spun, The fiber shape is used. The bushing structure has a container shape for retaining molten glass, and a number of nozzles are arranged in the vertical direction at the bottom. The glass fiber is formed into a fiber shape by drawing the molten glass from the nozzle near the forming temperature (spinning temperature, temperature at about 10 ³ dPa · s).

JP 2008-255002 A JP 2008-230949 A

  By the way, in order to improve the transparency of the resin composite substrate, it is necessary to match the optical characteristics (refractive index nd, Abbe number νd) of the constituent materials. Further, in order to increase the reliability of the resin composite substrate, it is necessary to increase the adhesive strength at the interface between the resin and the filler or between the resin and the glass fiber.

  However, it has been difficult for the glass for resin composite substrates used in the form of fillers, glass fibers and the like to increase the adhesive strength while matching the optical properties of the transparent resin.

  Specifically, conventional glass for resin composite substrates contained a large amount of alkali metal oxide in the glass composition. Therefore, when the resin and glass are compounded and processed into a resin composite substrate, curing of the resin may be hindered due to alkali elution, and after the resin composite substrate is manufactured, the interface between the resin and glass There was a problem that the adhesive strength of the resin was lowered with time due to alkali elution, and the mechanical strength of the resin composite substrate was likely to be lowered.

  If the alkali metal oxide is reduced from the filler and the glass fiber, the problems due to alkali elution can be solved, but it becomes difficult to match the optical characteristics (refractive index nd, Abbe number νd) of the transparent resin.

  The present invention provides a resin composite capable of obtaining a resin composite substrate that matches the optical characteristics (refractive index nd, Abbe number νd) of a transparent resin, has a small amount of alkali elution, and is excellent in transparency and reliability. It is a technical problem to provide glass for a body substrate.

  As a result of various experiments, the present inventors have found that the above technical problem can be solved by strictly limiting the total amount of each of the alkali metal oxide component and the alkaline earth metal oxide component. It is what we propose.

That is, the resin composite glass substrate of the present _{invention, SiO 2 45~65%, Al 2} O 3 5~20%, B 2 O 3 13~25%, MgO + CaO + SrO + BaO + 10~30% ZnO, MgO 5.5~9 _{%, CaO 0~10%, SrO 0~10} %, BaO 0~10%, Li 2 O + Na 2 O + K 2 O 0~1%, characterized in that it contains CeO 2 0.01 to 5.0%. Here, “MgO + CaO + SrO + BaO + ZnO” means the total amount of MgO, CaO, SrO, BaO and ZnO. “Li ₂ O + Na ₂ O + K ₂ O” means the total amount of Li ₂ O, Na ₂ O and K ₂ O.

  By doing in this way, it becomes easy to match | combine with the optical characteristics (refractive index nd, Abbe number (nu) d) of resin, such as an epoxy resin, an acrylic resin, and a cyclic olefin resin, and alkali elution can be reduced. As a result, it can be suitably used as a glass for a resin composite substrate.

In the present invention, it is desirable that the refractive index nd is 1.48 to 1.55 and the Abbe number νd is 50 to 65. Here, “refractive index nd” can be measured by, for example, a refractometer (KPR-200 manufactured by Karnew Co., Ltd.), and indicates a measured value at d-line (wavelength: 587.56 nm) of a helium lamp. Further, the “Abbe number νd” can be measured with a refractometer (KPR-200, manufactured by Kalnew). Helium lamp d-line, hydrogen lamp F-line (wavelength: 486.13 nm), and hydrogen lamp C-line The value calculated by the calculation formula {(nd-1) / (nF-nC)} after measuring the refractive index (nd, nF, nC) at (wavelength: 656.27 nm). Further, the refractive index nd and Abbe number νd were cast to a size such that the molten glass was poured onto a carbon plate to have a length of 12 cm, a width of 6 cm, and a thickness of 1.5 cm. The temperature is maintained for 1 hour at a temperature at which the viscosity becomes 10 ^13.0 dPa · s + 30 ° C., and a rate of 3 ° C./min from this temperature to (the temperature at which the viscosity of the glass becomes 10 ^14.5 dPa · s−100 ° C.). The sample obtained by slowly cooling the sample at a rate of 10 ° C./min from this temperature to 25 ° C. is measured.

  According to the said structure, matching with the optical characteristics (refractive index nd, Abbe number (nu) d) of resin, such as an epoxy resin, an acrylic resin, and a cyclic olefin resin, becomes easy.

  By the way, the glass for resin composite substrates is designed so that the optical characteristics of the glass match the resin. However, when the molten glass is molded while being rapidly cooled, the refractive index of the glass tends to decrease, and it may be difficult to obtain a refractive index as designed. As a result, the resin composite substrate may not be transparent even though the refractive indexes of the glass and the resin are matched in design. Further, the width of decrease in refractive index is proportional to the cooling rate during glass forming. Since the cooling rate is different between the case where glass is formed into a film shape and the case where glass is formed into a fiber shape, the refractive index of the filler and the glass fiber may not be the same even with the same composition. Therefore, even if a filler and glass fiber of the same material are used in combination, the refractive indexes of the two may be different and the transparency of the resin composite substrate may be impaired.

When such a situation is concerned, it is preferable to adjust so that (MgO + CaO + SrO + BaO + ZnO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) is 0.18 to 0.25 on a mass% basis. . Here, “(MgO + CaO + SrO + BaO + ZnO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ )” means that the total amount of MgO, CaO, SrO, BaO and ZnO is the amount of SiO ₂ , Al ₂ O ₃ and B ₂ O ₃ . It means the value divided by the total amount.

  According to the above configuration, desired optical characteristics can be easily obtained. Moreover, the refractive index change of the glass by rapid cooling can be suppressed effectively.

Moreover, in this invention, it is preferable that the linear thermal expansion coefficient in 30-380 degreeC is 40-50 * 10 < ^-7 > / degreeC.

  According to the said structure, the refractive index change of glass by rapid cooling can be suppressed more effectively.

  Moreover, in this invention, it is preferable that the amount of alkali elution is 0.35 mg or less.

  By doing in this way, at the time of the heat processing in the manufacturing process of the resin composite substrate, it becomes difficult for alkali ions to move from the surface layer of the glass to the resin, so that the adhesive strength between the resin and the glass is hardly lowered. In addition, after the production of the resin composite substrate, the adhesive strength at the interface between the resin and the filler or the resin and the glass fiber becomes difficult to decrease over time due to alkali elution. As a result, the mechanical strength of the resin composite substrate is reduced. The strength is difficult to decrease. Furthermore, the chemical resistance of the resin composite substrate is difficult to decrease. Here, “alkaline elution amount” refers to a value measured by a method based on JIS R3502 (1995).

In the present invention, the temperature corresponding to a viscosity of 10 ³ dPa · s is preferably 1300 ° C. or lower.

  According to the above configuration, melting of the glass is facilitated, and bubbles existing as defects in the molten glass are easily removed from the molten glass, so that a glass with less bubbles is easily obtained.

In the present invention, the difference between the temperature corresponding to a viscosity of 10 ³ dPa · s and the liquidus temperature is preferably 100 ° C. or more. Here, “liquidus temperature” refers to the maximum temperature at which crystals precipitate from the molten glass.

  According to the said structure, glass can be shape | molded easily to a fiber form.

  In the present invention, the resin composite substrate glass preferably has a powder shape.

  In the present invention, the glass for a resin composite substrate has a fiber shape.

  The method for using the glass for a resin composite substrate of the present invention uses the resin composite glass having a refractive index nd difference of 0.01 or less and an Abbe number νd difference of 3 or less. It is used as a composite substrate material.

  According to the said structure, the composite substrate transparent with respect to visible light can be produced easily.

  The resin composite substrate of the present invention is manufactured using the above glass for a resin composite substrate and a resin having a refractive index nd difference of 0.01 or less and an Abbe number νd difference of 3 or less. It is characterized by that.

  According to the said structure, a composite substrate is transparent with respect to visible light, and can be used suitably as a board | substrate etc. of flexible displays, such as electronic paper.

  The glass for a resin composite substrate of the present invention has optical characteristics (refractive index nd, Abbe number νd) matching with a transparent resin and a small amount of alkali elution. Therefore, it is suitable as glass for a resin composite substrate.

  In the glass for a resin composite substrate of the present invention, the reason for defining the content range of each component as described above will be described below. In addition, in description of the containing range of each component,% display points out the mass%.

SiO ₂ is a main component that forms a glass skeleton structure, and its content is 45% or more, preferably 48% or more, particularly preferably 50% or more, and 65% or less, preferably 60% or less, more Preferably it is 57% or less, Most preferably, it is 56% or less. When the content of SiO ₂ is too small, the mechanical strength tends to decrease. On the other hand, if the content of SiO ₂ is too large, higher high temperature viscosity, easily meltability and moldability is deteriorated and as a result, the manufacturing cost of the fillers and glass fibers increasing too high. In particular, if the content of SiO ₂ is regulated to 48 to 56%, meltability and formability can be improved without impairing mechanical strength.

Al ₂ O ₃ is a component that increases chemical durability and mechanical strength, is a component that increases devitrification resistance by addition of an appropriate amount, and further is a component that increases the elastic modulus and stabilizes the spinning state. Its content is 5 to 20%, preferably 7 to 18%, more preferably 10 to 15%. When the content of Al ₂ O ₃ is too small, the effect becomes difficult to obtain. On the other hand, when the content of Al ₂ O ₃ is too large, higher high temperature viscosity, easily meltability and moldability is deteriorated and as a result, the manufacturing cost of the fillers and glass fibers increasing too high. In particular, if the content of Al ₂ O ₃ is restricted to 10 to 15%, it becomes difficult for crystals to precipitate in the molten glass during molding, and the spinning state is easily stabilized.

B ₂ O ₃ is, in the same manner as SiO _2, is a component for forming a glass network structure, different from the SiO _2, a component to lower the high temperature viscosity, the content thereof is 13 to 25%, preferably Is 13 to 20%, more preferably 15 to 20%. When B ₂ O ₃ content is too small, higher high temperature viscosity, easily meltability and moldability is deteriorated and as a result, the manufacturing cost of the fillers and glass fibers increasing too high. On the other hand, if the content of B ₂ O ₃ is too large, the tendency of phase separation becomes prominent. Once phase separation occurs, it becomes difficult to secure desired optical characteristics, and chemical durability is lowered. It becomes easy to do. In particular, if the content of B ₂ O ₃ is regulated to 15 to 20%, the tendency of phase separation can be suppressed and the melting cost and the like can be easily reduced.

  MgO + CaO + SrO + BaO + ZnO is a component that lowers the viscosity at high temperature and increases the meltability, and is a component that optimizes optical properties (refractive index nd, Abbe number νd), and its content is 10 to 30%, preferably It is 10 to 25%, more preferably 15 to 25%. If the content of MgO + CaO + SrO + BaO + ZnO is too small, the high-temperature viscosity becomes high and the meltability and moldability are liable to decrease. As a result, the production cost of fillers and glass fibers increases, and the optical properties are transparent resins. It becomes difficult to match with epoxy resin, acrylic resin, cyclic olefin resin and the like. On the other hand, when the content of MgO + CaO + SrO + BaO + ZnO is too large, the refractive index nd becomes too large, the devitrification resistance is lowered, and the glass is more likely to be phase separated. Moreover, the thermal expansion coefficient of glass becomes too high. In particular, if the content of MgO + CaO + SrO + BaO + ZnO is restricted to 15 to 25%, not only the optical properties are easily matched to epoxy resins, acrylic resins, cyclic olefin resins, etc., which are transparent resins, but also meltability is improved, and phase separation is further improved. While weakening the tendency, it becomes easy to prevent precipitation of crystals from the molten glass.

  MgO is a component that lowers the high-temperature viscosity and improves the meltability, and is a component that optimizes optical properties (refractive index nd, Abbe number νd), and its content is 5.5 to 9%, Preferably it is 5.5 to 8%, more preferably 6 to 8%. If the content of MgO is too small, the high-temperature viscosity becomes high and the meltability and moldability are likely to deteriorate, resulting in a high manufacturing cost of fillers and glass fibers, and a transparent resin with optical properties. It becomes difficult to match with epoxy resin, acrylic resin, cyclic olefin resin and the like. On the other hand, when there is too much content of MgO, it will become easy to phase-separate glass. Moreover, the thermal expansion coefficient of glass becomes too high.

  CaO is a component that lowers the high-temperature viscosity and improves the meltability, and is a component that optimizes optical properties (refractive index nd, Abbe number νd), and its content is 0 to 10%, preferably 0 to 8%, more preferably 1 to 8%. When there is too much content of CaO, the crystal | crystallization containing Ca will precipitate easily from molten glass. Moreover, the thermal expansion coefficient of glass becomes too high.

  SrO is a component that lowers the high-temperature viscosity and increases the meltability, and is a component that optimizes optical properties (refractive index nd, Abbe number νd), and its content is 0 to 10%, preferably 0 to 8%, more preferably 1 to 8%. When there is too much content of SrO, the crystal | crystallization containing Sr will precipitate easily from molten glass. Moreover, the thermal expansion coefficient of glass becomes too high.

  BaO is a component that lowers the high-temperature viscosity and increases the meltability, and is a component that optimizes optical characteristics (refractive index nd, Abbe number νd), and its content is 0 to 10%, preferably 0 to 8%, more preferably 1 to 8%. When there is too much content of BaO, it will become easy to precipitate the crystal | crystallization containing Ba from molten glass. Moreover, the thermal expansion coefficient of glass becomes too high.

  ZnO is a component that lowers the high-temperature viscosity and increases the meltability, and is a component that optimizes optical properties (refractive index nd, Abbe number νd), and its content is 0 to 10%, preferably 0 to 8%, more preferably 0 to 5%. When there is too much content of ZnO, it will become easy to phase-separate glass.

Li ₂ O + Na ₂ O + K ₂ O is a component that lowers the high-temperature viscosity and increases the meltability. And if the meltability is good, it becomes easy to produce a homogeneous glass at a low temperature. The content of Li ₂ O + Na ₂ O + K ₂ O is 0 to 1%, preferably 0 to 0.8%, more preferably 0 to 0.5%, still more preferably 0 to less than 0.5%. When the content of Li ₂ O + Na ₂ O + K ₂ O is too large, curing of the resin may be inhibited by alkali elution when the resin, the filler, and the glass fiber are combined and processed into a resin composite substrate. . In addition, after the production of the resin composite substrate, the adhesive strength at the interface between the resin and the filler or the resin and the glass fiber decreases with time due to alkali elution, and the mechanical strength of the resin composite substrate is likely to decrease. . Furthermore, the coefficient of thermal expansion of the glass increases, and the refractive index change due to rapid cooling during molding increases. However, in order to reduce the high-temperature viscosity, it is preferable that the content of Li ₂ O + Na ₂ O + K ₂ O is 0.1% or more. Also, be equal the value of _{Li 2 O + Na 2 O +} K 2 O, by containing two or more components simultaneously, it is possible to suppress the alkaline elution than when containing only any one.

Li ₂ O is a component that lowers the high temperature viscosity and increases the meltability, and its content is 0 to 1%, preferably 0 to 0.5%, more preferably 0 to 0.4%. The content of Li 2 _O is too large, Li component from the glass surface in addition to being easily eluted, crystals are liable to precipitate containing Li from the molten glass. Moreover, the thermal expansion coefficient of glass becomes too high.

Na ₂ O is a component that lowers the high-temperature viscosity and enhances the meltability, and its content is 0 to 1%, preferably 0 to 0.5%, more preferably 0 to 0.4%. When the content of Na 2 _O is too large, easily Na component eluted from the glass surface. Na ₂ O is more likely to be eluted from the glass surface than other alkali metal oxides. Moreover, the thermal expansion coefficient of glass becomes too high.

K ₂ O is a component that increases the meltability by lowering the high temperature viscosity, and its content is 0 to 1%, preferably 0 to 0.5%, more preferably 0 to 0.4%. When the content of K 2 _O is too large, easily K components are eluted from the glass surface. Moreover, the thermal expansion coefficient of glass becomes too high.

CeO ₂ functions to remove bubbles present as defects in the molten glass, and is added in an appropriate amount as a clarifier that is not an environmental load substance, and its content is 0.01 to 5%, preferably It is 0.02 to 5%, more preferably 0.05 to 5%. When the content of CeO ₂ is too small, bubbles are likely to remain in the glass, and as a result, it is difficult to obtain uniform transparency of the resin composite substrate. On the other hand, when the content of CeO ₂ is too large, the molten glass tends to be devitrified.

In addition to the above components, other components may be added. For example, ZrO ₂ , TiO ₂ , P ₂ O ₅ , Cr ₂ O ₃ , Sb ₂ O ₃ , SO ₃ , Cl ₂ , La ₂ O ₃ are used to improve optical properties, chemical durability, high temperature viscosity, and the like. , WO ₃ , Nb ₂ O ₅ , Y ₂ O ₃ or the like may be added up to 3% each.

In addition, when it is desired to further increase the transparency of the resin composite substrate, the content of Fe ₂ O ₃ is preferably regulated to 0.5% or less, particularly 0.1% or less. In particular, when Fe ₂ O ₃ and TiO ₂ are contained simultaneously, the coloring of the glass with Fe ₂ O ₃ tends to increase, and the transparency of the resin composite substrate may be impaired. For this reason, the content of TiO ₂ is preferably regulated to 0.5% or less, particularly 0.1% or less. Further, trace components such as H ₂ , CO ₂ , CO, H ₂ O, He, Ne, Ar, and N ₂ may be included up to 0.1%, respectively. Further, the content of noble metal elements such as Pt, Rh, Au and the like is preferably 500 ppm or less, particularly preferably 300 ppm or less, respectively, so as not to adversely affect the characteristics of the resin composite substrate.

Similar to CeO ₂ , SO ₃ is a component that works to remove bubbles present as defects in the molten glass, and in particular, when reducing the bubbles remaining in the glass and making the resin composite substrate uniform in transparency. The content of SO ₃ is preferably 0.0001 to 0.5%, particularly preferably 0.0001 to 0.3%.

The value of (MgO + CaO + SrO + BaO + ZnO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) is a value that serves as an index for controlling the thermal expansion coefficient, refractive index nd, and Abbe number νd of the glass to appropriate values. The value is preferably 0.18 to 0.25, 0.19 to 0.24, particularly preferably 0.20 to 0.24. If the value of (MgO + CaO + SrO + BaO + ZnO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) is too small, the refractive index nd may become too small to match the resin. Further, there is a possibility that the Abbe number νd becomes too large to match the resin. On the other hand, if (MgO + CaO + SrO + BaO + ZnO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) is too large, the coefficient of thermal expansion becomes too high and the refractive index decreases greatly when the molten glass is made into a film shape or fiber shape. Therefore, it may be difficult to align with the resin. In addition, the cooling rate dependence of the refractive index drop when making glass or fiber from molten glass becomes stronger, making it difficult to stabilize the refractive index of the filler and glass fiber that pulverized the film, while matching with the resin. Can be difficult to do.

In the glass for a resin composite substrate of the present invention, the linear thermal expansion coefficient at 30 to 380 ° C. is preferably 40 to 50 × 10 ⁻⁷ / ° C., more preferably 42 to 48 × 10 ⁻⁷ / ° C., further preferably. 43 to 47 × 10 ⁻⁷ / ° C. When the linear thermal expansion coefficient is too small, the content of the alkaline earth metal oxide becomes very small, and the meltability may be deteriorated. On the other hand, if the linear thermal expansion coefficient at 30 to 380 ° C. is too large, the range of decrease in the refractive index when the molten glass is rapidly cooled increases, making it difficult to match the refractive index with the resin. In addition, the cooling rate dependency of the width of decrease in the refractive index becomes strong, making it difficult to stabilize the refractive index of the filler and the glass fiber and at the same time making it difficult to match the refractive index with the resin.

The glass for a resin composite substrate of the present invention having the above composition and expansion hardly changes in refractive index even when the molten glass is rapidly cooled. Specifically, the difference in the refractive index nd of the glass when it is sufficiently cooled and when it is rapidly cooled and formed into a film shape or fiber shape is 0.005 or less, particularly 0.003 or less. it can. If the difference in refractive index is too large, it will be difficult to match the refractive index of the filler and glass fiber obtained by pulverizing the film with the resin. Moreover, the cooling rate dependency of the refractive index drop width becomes strong, and the refractive index values of the filler and the glass fiber become unstable. “When sufficiently annealed” means that the molten glass is poured onto a carbon plate and formed into a size of 12 cm in length, 6 cm in width, and 1.5 cm in thickness. Is kept for 1 hour at (temperature at which the viscosity of the glass becomes 10 ^13.0 dPa · s + 30 ° C.), and from this temperature to 3 ° C. from (temperature at which the viscosity of the glass becomes 10 ^14.5 dPa · s−100 ° C.). It means a case where the temperature is lowered at a rate of 10 minutes per minute and gradually cooled from this temperature to 25 ° C. at a rate of 10 ° C./minute. “When formed into a film shape” means a glass formed by supplying molten glass to a double roller to form a film having a thickness of 1 mm. “When formed into a fiber shape” means a glass obtained by feeding molten glass to a platinum bushing furnace and spinning it into a fiber having a diameter of 5 μm.

  In the resin composite substrate glass of the present invention, it is important to adjust the refractive index nd to 1.48 to 1.55 (particularly 1.50 to 1.55) and the Abbe number νd to 50 to 65. If the refractive index nd is 1.48, particularly smaller than 1.50, the refractive index nd of the transparent resin such as epoxy resin, acrylic resin, cyclic olefin resin, etc. is much smaller, so that the visible light that has entered the transparent resin goes straight. As a result, incident light rays are dispersed, and as a result, a colorless and transparent resin composite substrate cannot be obtained, and the translucency of the resin composite substrate tends to be lowered. On the other hand, if the refractive index nd is larger than 1.55, it becomes difficult to match the refractive index nd of epoxy resin, acrylic resin, cyclic olefin resin, etc., which are transparent resins. It becomes difficult to obtain. Further, since the Abbe number νd of the glass becomes too small, even if it is transparent, it tends to be a resin composite substrate colored in blue, red, purple or the like. In order to achieve translucency in a visible wavelength range other than the wavelength of 587.56 nm, it is preferable to limit the Abbe number νd to a predetermined range. If the Abbe number νd is less than 50 or exceeds 65, it becomes difficult to match the Abbe number νd of epoxy resin, acrylic resin, cyclic olefin resin, etc., which are transparent resins. Therefore, a colorless and transparent resin composite substrate is obtained. It becomes difficult to obtain, or even if it is transparent, it tends to be a resin composite substrate colored in blue, red, purple or the like. If the glass composition is within the above range, it is easy to design a glass having a refractive index nd of 1.48 to 1.55 and an Abbe number νd of 50 to 65.

  The alkali elution amount is preferably 0.35 mg or less, 0.30 mg or less, 0.20 mg or less, 0.15 mg or less, particularly preferably less than 0.10 mg. When the amount of alkali elution is too large, alkali ions move from the surface layer of the glass to the resin during the heat treatment in the manufacturing process of the resin composite substrate, and the adhesive strength between the resin and the glass tends to decrease. In addition, after the production of the resin composite substrate, the adhesive strength at the interface between the resin and the filler or the resin and the glass fiber decreases with time due to alkali elution, and the mechanical strength of the resin composite substrate is likely to decrease. Furthermore, the chemical resistance of the resin composite substrate is likely to decrease.

Further, the temperature (spinning temperature) at which the glass has a viscosity of 10 ³ dPa · s is preferably 1300 ° C. or less, particularly preferably 1250 ° C. or less. If the temperature at which the viscosity of the glass becomes 10 ³ dPa · s is 1300 ° C. or lower, not only the melting of the glass is facilitated, but also the bubbles present as defects in the molten glass are easily removed from the molten glass, It becomes easy to obtain glass with few bubbles. As a result, uniform transparency of the resin composite substrate is easily obtained.

  The glass for a resin composite substrate of the present invention preferably has a powder shape. If it does in this way, it will become easy to apply to a filler. As described above, the filler can be produced by forming molten glass into a film shape with a twin roller and then grinding the glass film into a powder shape with a ball mill or the like. It can also be produced by water granulating molten glass.

  In addition, when applying the glass for resin composite substrates of this invention as a filler, it is preferable that the chemical | medical agent is apply | coated to the surface of the filler. A coupling agent can be used as the drug. When the surface of the filler is subjected to a coupling treatment, the familiarity with the resin component is improved and the adhesive strength between the resin and the filler is improved. Moreover, the deterioration with respect to moisture is suppressed and the product life is improved. The coupling treatment is preferably performed in a weak acid to neutral region.

The average particle diameter D50 of the filler is preferably 0.1 to ₅₀ μm, 1 to 20 μm, and particularly preferably 2 to 10 μm. If it does in this way, while it becomes easy to control a thermal expansion characteristic, it becomes easy to reduce the space | gap of a resin composite board | substrate. When the average particle diameter D ₅₀ is too small, handling properties and material yield is likely to decrease. On the other hand, when the average particle diameter D ₅₀ is too large, when combined with a resin or the like, with uniformly becomes difficult to mix, irregularities easily occur in the surface of the resin complex substrate. Here, the “average particle diameter D ₅₀ ” is a value measured by the laser diffraction method. In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. The particle size is 50%.

  Moreover, it is preferable that the glass for resin composite substrates of this invention has a fiber shape. If it does in this way, it can be used as glass fiber. As described above, the glass fiber can be produced by continuously forming and spinning using a noble metal bushing. Further, as a molding method, a direct molding method (direct melt method), an indirect molding method (marble melt method), or the like can be employed.

  In the case of forming into a fiber shape, the difference between the spinning temperature and the liquidus temperature is preferably 100 ° C. or higher, 125 ° C. or higher, particularly 150 ° C. or higher. The difference between the spinning temperature and the liquidus temperature is a value that is an indicator of productivity especially when spinning molten glass into glass fiber. If this value is too small, crystals from the molten glass are spun when spinning the molten glass. Precipitates and the spinning becomes easy to cut.

  In addition, when the glass for resin composite substrates of the present invention is applied as a glass fiber, it is preferable that a chemical is applied to the surface of the glass fiber. As the agent, a sizing agent, an antistatic agent, a surfactant, a polymerization initiator, a polymerization inhibitor, an antioxidant, a film forming agent, a coupling agent, and a lubricant can be used.

  The length of the glass fiber is not particularly limited as long as it has a fiber shape. The glass fiber may be milled fiber, chopped strand, yarn, roving or the like. The diameter of the glass fiber is not particularly limited as long as it has a fiber shape, and is generally in the order of angstroms to microns, but when used for a thin resin composite substrate, it may be 30 μm, particularly 10 μm or less. preferable. The cross-sectional shape of the glass fiber is not particularly limited as long as it has a fiber shape. Examples of the cross-sectional shape of the glass fiber include a perfect circle shape, a flat shape, a rectangular shape, and a polygonal shape.

  In the case of glass fiber, the refractive index nd can be adjusted by heat treatment. Moreover, a chemical strengthening process (ion exchange process) can also be performed with heat processing. Furthermore, even if fine crystals are precipitated in the glass fiber, they can be used as long as they do not adversely affect the characteristics of the resin composite substrate.

  Next, the usage method of the glass for resin composite substrates of this invention is demonstrated.

  First, the glass for a resin composite substrate of the present invention formed into a powder form and / or a fiber form is prepared. A resin having a refractive index difference with this glass of 0.01 or less and an Abbe number difference of 3 or less is prepared.

  Next, the resin composite substrate glass is impregnated in the resin, and the resin is cured while being bonded together. In this way, a resin composite substrate that is transparent to visible light can be obtained.

  Hereinafter, based on an Example, this invention is demonstrated in detail.

  Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 7 and 9 to 14) and comparative examples (samples No. 8 and 15).

  Each sample in the table was prepared as follows.

First, various glass raw materials, such as a natural raw material and a chemical raw material, were weighed and mixed so that it might become the glass composition in a table | surface, and the glass batch was produced. Next, after putting this glass batch into a crucible made of platinum rhodium alloy, it was heated in an indirect heating electric furnace at 1550 ° C. for 8 hours to obtain a molten glass. In order to obtain a homogeneous molten glass, the molten glass was stirred a plurality of times using a heat-resistant stirring rod during heating. Subsequently, the molten glass obtained was poured into a refractory mold to form a plate-like glass, and then annealed in a slow cooling furnace (heated at a temperature 30 to 50 ° C. higher than the temperature at 10 ¹³ dPa · s for 30 minutes) Then, the temperature range from the annealing point to the strain point was lowered at 1 ° C./min).

For each of the obtained samples, the thermal expansion coefficient, optical characteristics (refractive index nd, Abbe number νd), alkali elution amount, temperature (Tx) at 10 ³ dPa · s, and liquidus temperature (TL) were measured. Sample No. About 3-6, since the alkali metal oxide is not included in the glass composition, the alkali elution amount is not evaluated.

  Moreover, the molten glass was shape | molded in the film shape and the fiber shape, the optical characteristic was measured, and the characteristic difference with the said plate-shaped sample was calculated | required. The film-shaped sample was produced by supplying molten glass to a double roller and forming it into a film having a thickness of 1 mm. The fiber-shaped sample was supplied to a platinum bushing furnace and spun into a fiber having a diameter of 5 μm.

As apparent from Tables 1 and 2, Sample No. 1 to 7 and 9 to 14 have a refractive index nd of 1.518 to 1.55, an Abbe number νd of 58 to 65, and an alkali elution amount of 0.004 mg or less, which is very transparent. In addition, a resin composite substrate having excellent reliability can be obtained. Furthermore, the temperature (Tx) at 10 ³ dPa · s was 1250 ° C. or less, and the glass had excellent meltability. Sample No. 1-4, 9-14, (MgO + CaO + SrO + BaO + ZnO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) is in the range of 0.18 to 0.25, and slowly cooled plate-like sample, film or fiber It was confirmed that the difference in optical characteristics with the sample was small.

  In contrast, sample no. No. 8 has a refractive index nd of 1.46, an Abbe number νd of 67, and an alkali elution amount of 0.40 mg. No. 15 has a refractive index nd of 1.562 and an alkali elution amount of 0.4 mg. When used as a substrate glass for a resin composite substrate, it is expected that the transparency and mechanical strength of the resin composite substrate will decrease. Is done.

  In addition, the thermal expansion coefficient measured the average linear thermal expansion coefficient in 30-380 degreeC using the thermal expansion coefficient measuring apparatus by MAC SCIENCE.

  The refractive index nd of the plate-like sample is a value measured with a Kalnew refractometer KPR-200, and is a measured value at the d-line (wavelength: 587.56 nm) of the helium lamp. In addition, “Abbe number νd” is calculated by Kalnew refractometer KPR-200, using helium lamp d-line, hydrogen lamp F-line (wavelength: 486.13 nm), and hydrogen lamp C-line (wavelength: 656.27 nm). ) And the refractive index (nd, nF, nC), and the value calculated by the calculation formula {(nd-1) / (nF-nC)}. The refractive index nd of the film-shaped sample was measured with a Karnuo refractometer KPR-200 by stacking several layers of films. The refractive index nd of the fibrous sample was measured by the Becke line method.

  The alkali elution amount was measured by a method based on JIS R3502 (1995).

Regarding the measurement of the temperature (Tx) at which the viscosity of the glass becomes 10 ³ dPa · s, the plate-like glass is crushed to an appropriate size, put into an alumina crucible so as to avoid entrainment of bubbles, and heated again. Then, it is calculated by interpolating a viscosity curve obtained by a plurality of measurements of the respective viscosity values measured based on the platinum ball pulling method in the glass melt state.

  For the measurement of the liquid phase temperature (TL), a plate-like glass is crushed and filled in a fire-resistant container with an appropriate bulk density in a state adjusted to a particle size in the range of 300 to 500 μm. Then, it was placed in an indirect heating type temperature gradient furnace set at a maximum temperature of 1250 ° C. and left to stand for 16 hours in an air atmosphere. Thereafter, the test specimen was taken out together with the refractory container, cooled to room temperature, and then the liquidus temperature was specified by a polarizing microscope.

Claims (11)

By _{mass%, SiO 2 45~65%, Al} 2 O 3 5~20%, B 2 O 3 13~25%, MgO + CaO + SrO + BaO + 10~30% ZnO, MgO 5.5~9%, CaO 0~10%, SrO _{0~10%, BaO 0~10%, Li} 2 O + Na 2 O + K 2 O 0~1%, CeO 2 0.01~5.0% resin complex glass substrate which is characterized by containing.   The glass for a resin composite substrate according to claim 1, wherein the refractive index nd is 1.48 to 1.55, and the Abbe number νd is 50 to 65. 3. The glass for a resin composite substrate according to claim 1, wherein (MgO + CaO + SrO + BaO + ZnO) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) is 0.18 to 0.25 on a mass% basis. .
The linear thermal expansion coefficient in 30-380 degreeC is 40-50 * 10 < ^-7 > / degreeC, The glass for resin composite board | substrates in any one of Claims 1-3 characterized by the above-mentioned. 5. The glass for a resin composite substrate according to claim 1, wherein a temperature corresponding to a viscosity of 10 ³ dPa · s is 1300 ° C. or lower. The glass for an over-resin composite substrate according to claim 1, wherein a difference between a temperature corresponding to a viscosity of 10 ³ dPa · s and a liquidus temperature is 100 ° C. or more.
The glass for a resin composite substrate according to any one of claims 1 to 6, wherein an alkali elution amount is 0.35 mg or less.   It has a powder shape, The glass for resin composite substrates in any one of Claims 1-7 characterized by the above-mentioned.   The glass for a resin composite substrate according to any one of claims 1 to 7, which has a fiber shape.   The glass for a resin composite substrate according to claim 1 as a material for a composite substrate using a resin having a difference in refractive index nd of 0.01 or less and a difference in Abbe number νd of 3 or less from the glass. A method of using a glass for a resin composite substrate, characterized by being used.   A resin composite substrate glass according to any one of claims 1 to 9, and a resin having a difference in refractive index nd of 0.01 or less and a difference in Abbe number νd of 3 or less between the glass and the glass. Resin composite substrate.