JP2019202902A - Glass, glass filler, and resin mixture - Google Patents

Abstract

To provide a glass that hardly impairs the transparency of a resin mixture even when mixed with a resin.SOLUTION: A glass contains, in mass%, SiO35-75%, AlO0.1-30%, BO0-30%, SiO+AlO+BO55-90%, MgO+CaO+SrO+BaO+ZnO 2-15%, NbO+WO5-15%.SELECTED DRAWING: None

Description

  The present invention relates to glass, a glass filler, and a resin mixture.

  Conventionally, a method of obtaining a three-dimensional model by laminating resin materials or the like is known. For example, various methods such as an optical shaping method, a powder sintering method, and a hot melt lamination (FDM) method have been proposed and put into practical use.

  For example, stereolithography is excellent in fine modeling and accurate size expression, and is widely used. In this method, a three-dimensional model is produced as follows. First, a modeling stage is provided in a tank filled with a liquid photocurable resin, and a photocurable resin on the modeling stage is irradiated with an ultraviolet laser to produce a cured layer having a desired pattern. When one cured layer is formed in this way, the modeling stage is lowered by one layer, an uncured resin is introduced onto the cured layer, and similarly, the cured layer is irradiated with an ultraviolet laser. Stack a new hardened layer on top. By repeating this operation, a predetermined three-dimensional model is obtained. In addition, the powder sintering method has a modeling stage in a tank filled with resin, metal, ceramics, and glass powder, and the powder on the modeling stage is irradiated with a laser such as a semiconductor to form a desired pattern by softening deformation. A cured layer is produced.

Japanese Patent Laid-Open No. 7-26060

  It has been pointed out that a resin-made three-dimensional model produced by an optical modeling method is fine and precise, but is inferior in mechanical strength or the like. Therefore, Patent Document 1 proposes mixing a photocurable resin and an inorganic filler.

  However, when the resin and the inorganic filler particles are mixed, there is a problem that the transparency of the three-dimensional structure that is the resin mixture is impaired.

  In view of the above, an object of the present invention is to provide a glass that does not impair the transparency of a resin mixture even when mixed with a resin.

Glass of the present invention, in _{mass%, SiO 2 35~75%, Al} 2 O 3 0.1~30%, B 2 O 3 0~30%, SiO 2 + Al 2 O 3 + B 2 O 3 55~90 %, MgO + CaO + SrO + BaO + ZnO 2-15%, Nb ₂ O ₅ + WO ₃ 5-15%. The glass having such a composition easily matches the refractive index of the resin, and even when mixed with the resin, light scattering due to the refractive index difference between the glass and the resin hardly occurs, and as a result, the transparency of the resin mixture is increased. be able to. Here, “SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ” is the total amount of SiO ₂ , Al ₂ O ₃ , and B ₂ O ₃ , and “MgO + CaO + SrO + BaO + ZnO” is the total amount of MgO, CaO, SrO, BaO, and ZnO. , “Nb ₂ O ₅ + WO ₃ ” means the total content of Nb ₂ O ₅ and WO ₃ .

Glass of the present invention, in _mass%, preferably contains _{2 O 0~15% Li 2 O +} Na 2 O + K. Here, “Li ₂ O + Na ₂ O + K ₂ O” means the total content of Li ₂ O, Na ₂ O, and K ₂ O.

The glass of the present _invention contain Nb ₂ O 5 0.1~15%, by weight _ratio, it is preferable SiO 2 / _Nb 2 _{O 5} is from 2.4 to 20. Here, “SiO ₂ / Nb ₂ O ₅ ” means a value obtained by dividing the content of SiO _{2 by} the content of Nb ₂ O ₅ .

  The glass of the present invention preferably has a refractive index nd of 1.50 to 1.70 and an Abbe number νd of 40 to 60.

  The glass filler of the present invention is made of the above glass.

  The glass filler of the present invention preferably has a substantially spherical shape.

  The glass filler of the present invention preferably has an average particle size of 0.5 to 20 μm. Here, the “average particle diameter” indicates a 50% volume cumulative diameter in terms of the median diameter of primary particles, and is a value measured by a laser diffraction particle size distribution measurement method.

  The resin mixture of the present invention contains the glass filler and a resin.

  In the resin mixture of the present invention, the difference in refractive index nd between the glass filler and the resin is preferably within ± 0.05.

  The resin mixture of the present invention is preferably for three-dimensional modeling.

  ADVANTAGE OF THE INVENTION According to this invention, even if it mixes with resin, the glass which is hard to impair the transparency of a resin mixture can be provided.

The glass of the present invention has a glass composition of SiO ₂ 35 to 75%, Al ₂ O ₃ 0.1 to 30%, B ₂ O ₃ 0 to 30%, SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ 55 to 90. %, MgO + CaO + SrO + BaO + ZnO 2-15%, Nb ₂ O ₅ + WO ₃ 5-15%. Hereinafter, the reason why each component is limited as described above will be described. In the description regarding the content of each component, “%” means “mass%”.

SiO ₂ is a component that forms a glass skeleton. Further, it is a component capable of improving chemical durability and suppressing devitrification. The content of SiO ₂ is 35 to 75%, preferably 40 to 70%, 45 to 65%, 48 to 60%, and particularly preferably 50 to 58%. If the content of SiO ₂ is too small, the above effect is difficult to obtain. On the other hand, the fusible content of SiO ₂ is too large tends to decrease. Moreover, there is a possibility that the manufacturing becomes difficult due to difficulty in softening during molding.

Al ₂ O ₃ is a vitrification stable component. Further, it is a component capable of improving chemical durability and suppressing devitrification. The content of Al ₂ O ₃ is 0.1 to 30%, preferably 1 to 25%, 5 to 22%, 10 to 20%, particularly preferably 12 to 18%. When the content of Al ₂ O ₃ is too small, the effect is difficult to obtain. On the other hand, when the content of Al ₂ O ₃ is too large, the melting property tends to decrease. Moreover, there is a possibility that the manufacturing becomes difficult due to difficulty in softening during molding.

B ₂ O ₃ is a vitrification stable component. Further, it is a component capable of improving chemical durability and suppressing devitrification. The content of B ₂ O ₃ is 0 to 30%, preferably 1 to 26%, 5 to 22%, 10 to 20%, particularly preferably 12 to 18%. If the B ₂ O ₃ content is too large, the melting property tends to decrease. Moreover, it evaporates in a substantially spheroidizing step, and composition deviation from the design composition tends to occur.

The content of SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ is 55 to 90%, 60 to 89%, 65 to 88%, 70 to 87%, 75 to 86%, particularly 80 to 86%. Is preferred. When the content of _{SiO 2 + Al 2 O 3 +} B 2 O 3 is too small, it is difficult to vitrify. On the other _hand, when the content of _{SiO 2 + Al 2 O 3 +} B 2 O 3 is too large, the melting property tends to decrease. Moreover, there is a possibility that the manufacturing becomes difficult due to difficulty in softening during molding.

  MgO, CaO, SrO, BaO, and ZnO are components that act as intermediate substances in the glass, stabilize the glass, and lower the viscosity. The content of MgO + CaO + SrO + BaO + ZnO is 2 to 15%, preferably 2.2 to 12%, 2.4 to 10%, 2.6 to 8%, particularly preferably 2.8 to 6%. If the content of MgO + CaO + SrO + BaO + ZnO is too small, the above effect is difficult to obtain. On the other hand, if the content of MgO + CaO + SrO + BaO + ZnO is too large, the chemical durability tends to decrease, and the glass tends to be devitrified, making it difficult to manufacture.

  In addition, the preferable range of MgO, CaO, SrO, BaO, and ZnO is as follows.

  The content of MgO is preferably 0 to 15%, 0.5 to 10%, particularly 1 to 6%.

  The content of CaO is preferably 0 to 15%, 0.5 to 10%, particularly 1 to 6%.

  The content of SrO is preferably 0 to 15%, 0.5 to 10%, particularly 1 to 6%.

  The content of BaO is preferably 0 to 15%, 0.5 to 10%, particularly 1 to 6%.

  The content of ZnO is preferably 0 to 15%, 0.5 to 10%, particularly 1 to 6%.

Nb ₂ O ₅ and WO ₃ are components capable of adjusting the refractive index and the Abbe number. The content of Nb ₂ O ₅ + WO ₃ is 5 to 15%, preferably 5 to 12%, 5 to 10%, 6 to 9%, particularly preferably 7 to 8%. When the content of Nb ₂ O ₅ + WO ₃ is too small, the effect is difficult to obtain. On the other hand, if the content of Nb ₂ O ₅ + WO ₃ is too large, the refractive index tends to be too large and the Abbe number tends to be too small. Moreover, it becomes easy to devitrify glass.

A preferable range of _Nb 2 _{O 5,} and WO ₃ are as follows.

The content of Nb ₂ O ₅ is preferably 0 to 15%, 0.1 to 15%, 0.5 to 10%, particularly 1 to 5%. When the content of Nb ₂ O ₅ is too large, the refractive index becomes too large, there is a tendency that the Abbe number becomes too small. Moreover, it becomes easy to devitrify glass.

The content of WO ₃ is preferably 0 to 15%, 0.1 to 15%, 0.5 to 10%, particularly 1 to 5%. If the content of WO ₃ is too large, the refractive index tends to be too large and the Abbe number tends to be too small. Moreover, it becomes easy to devitrify glass. Furthermore, the glass tends to be easily colored.

SiO ₂ / _Nb 2 _{O 5} is 2.4～20,4～18,8～16,10～15, particularly preferably 12 to 14. By doing so, it becomes easy to obtain glass that matches the refractive index of the resin while improving chemical durability and devitrification resistance.

  In addition to the above components, the glass of the present invention can contain the following components.

Li ₂ O, Na ₂ O, and K ₂ O are components that reduce the viscosity of the glass and suppress devitrification. The content of Li ₂ O + Na ₂ O + K ₂ O is preferably 0 to 15%, 0.1 to 10%, 0.5 to 8%, 1 to 6%, particularly preferably 1 to 4%. When _{Li 2 O + Na 2 O +} K 2 _O content is too much, tends glass component evaporates at substantially spherical step of the glass, the composition deviation from a design composition is likely to occur. Moreover, chemical durability tends to be lowered, and Li ₂ O, Na ₂ O, and K ₂ O are eluted into the resin, and the resin is likely to be deteriorated.

_{Incidentally, Li 2 O, Na 2 O} , and _{K 2} O in the preferred ranges are as follows.

The content of Li ₂ O is preferably 0 to 10%, 0.1 to 9%, 0.5 to 7%, and particularly preferably 1 to 5%.

The content of Na ₂ O is preferably 0 to 10%, 0.1 to 7.5%, 0.5 to 5%, and particularly preferably 1 to 2.5%.

The content of K ₂ O is preferably 0 to 10%, 0.1 to 8%, 0.5 to 6%, particularly 1 to 4%.

TiO ₂ is a component that can adjust the refractive index and Abbe number, and is a component that lowers the viscosity of the glass. The content of TiO ₂ is preferably 0 to 15%, 0.1 to 12%, 0.5 to 10%, particularly 1 to 5%. If the content of TiO ₂ is too large, the refractive index tends to be too large and the Abbe number tends to be too small. Furthermore, it becomes easy to color glass.

  The glass of the present invention preferably has a refractive index nd of 1.50 to 1.70, 1.50 to 1.60, particularly 1.50 to 1.55, and an Abbe number νd of 40 to 60, 45. It is preferable that it is -60, especially 50-57. In this way, it becomes easy to match optical constants with many resins such as acrylic resins. If the optical constant deviates from the above range, it becomes difficult to obtain an optical constant consistent with the resin. The glass of the present invention preferably has a light transmittance of 30% or more, 50% or more, particularly 70% or more at a thickness of 0.5 mm at 588 nm from the viewpoint of enhancing the transparency of the resulting resin mixture.

  The glass filler of this invention consists of said glass.

  The shape of the glass filler of the present invention can be crushed, columnar, fibrous, or substantially spherical, but is preferably substantially spherical. If the shape is substantially spherical, when the amount of the glass filler contained in the resin is increased, an increase in the viscosity of the resin mixture can be suppressed, and the fluidity can be maintained. Moreover, since it can reduce the surface area which contacts with resin when it adds to resin, it is hard to produce light scattering and can improve the transparency of a resin mixture.

  The glass filler of the present invention preferably has an average particle size of 0.5 to 20 μm, 1 to 15 μm, particularly 3 to 12 μm. If it does in this way, when a glass filler is added to liquid resin, the sedimentation rate of a glass filler can be reduced. In particular, when the glass filler is added to the ultraviolet curable resin and the object is three-dimensional modeling that is cured by irradiating with ultraviolet rays, if the sedimentation occurs within the time required for modeling, unevenness occurs in the molded article, This can reduce this possibility.

  Next, an example of the manufacturing method of the glass and glass filler of this invention is demonstrated.

  First, a raw material batch obtained by blending glass raw materials at a predetermined ratio is melted at 1400 to 1700 ° C. to obtain molten glass. Next, the molten glass is formed into a predetermined shape (for example, a film), and then pulverized and classified to obtain glass powder. As a pulverization method, a ball mill, a bead mill, a jet mill, a vibration mill or the like is used, and wet pulverization or dry pulverization can be used. As a classification method, a known classification technique such as a net sieve or an airflow classifier can be used.

  The obtained glass powder is spheroidized by heating and melting. As a heating and melting method, there is a method in which glass powder is supplied into a furnace with a table feeder or the like, heated at 1400 to 2000 ° C. with an air burner or the like, melted, spheroidized by surface tension, cooled and recovered. Can be mentioned.

  Next, a glass filler is obtained by classifying the spheroidized glass powder to have a desired particle size distribution. As a classification method, a known classification technique such as a net sieve or an airflow classifier can be used.

  The surface of the glass filler is treated with a silane coupling agent. By treating with a silane coupling agent, it is possible to increase the bonding force between the glass filler and the resin, so that a resin mixture having excellent mechanical strength can be obtained. Furthermore, the familiarity between the glass filler and the resin is improved, the bubbles and voids at the interface are reduced, and the light scattering is reduced, so that the transparency of the resin mixture can be easily improved. As the silane coupling agent, aminosilane, epoxy silane, acrylic silane and the like are preferable. The silane coupling agent may be appropriately selected depending on the resin used.

  Next, the resin used in the present invention will be described.

  The resin may be either a photocurable resin or a thermosetting resin, and can be appropriately selected depending on the modeling method employed. For example, when using an optical modeling method, a liquid photocurable resin may be selected, and when a powder sintering method is used, a powdery thermosetting resin may be selected.

  Examples of the photocurable resin include polyamide resins, polyamideimide resins, polyacetal resins, (meth) acrylic resins, melamine resins, (meth) acrylic-styrene copolymers, polycarbonate resins, and styrene resins. , Polyvinyl chloride resin, benzoguanamine-melamine formaldehyde, silicone resin, fluorine resin, polyester resin, crosslinked (meth) acrylic resin, crosslinked polystyrene resin, crosslinked polyurethane resin, epoxy resin and the like.

  Examples of the thermosetting resin include epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, urea resins, allyl resins, silicon resins, benzoxazine resins, phenol resins, Examples include saturated polyester resins, bismaleimide triazine resins, alkyd resins, furan resins, melamine resins, polyurethane resins, aniline resins, and the like.

  Next, the resin mixture of the present invention will be described.

  The resin mixture of the present invention contains the above glass filler and resin. The amount of the glass filler is preferably 10 to 300 parts by mass, 20 to 280 parts by mass, particularly 30 to 260 parts by mass with respect to 100 parts by mass of the resin. When there is too little quantity of a glass filler, there exists a tendency for the mechanical strength of a resin mixture to become low. On the other hand, when there is too much quantity of a glass filler, the viscosity of a resin mixture will become high too much and the fluidity | liquidity of resin will fall easily.

  In the resin mixture of the present invention, the difference in refractive index nd between the glass filler and the resin is preferably within ± 0.05. In this way, light scattering caused by the difference in refractive index between the glass filler and the resin can be reduced, and thus the transparency of the resin mixture can be easily increased.

  The resin mixture of the present invention preferably has a light transmittance at a thickness of 0.5 mm and a wavelength of 588 nm of 50% or more, 70% or more, particularly 80% or more. Such a resin mixture is suitable for three-dimensional modeling.

  The resin mixture of the present invention may contain materials other than the glass filler of the present invention, such as a viscosity modifier, other glass fillers, ceramic fillers, metal materials, resin materials, carbon materials, and the like. The viscosity modifier may be liquid or solid. In particular, fumed silica can increase the viscosity of the resin mixture and suppress sedimentation of the glass filler by adding a small amount. By the way, fumed silica has many silanol groups on the surface, and each fumed silica is hydrogen bonded to form a three-dimensional network structure in the liquid resin, which has the effect of increasing the viscosity of the resin mixture. large. For example, fumed silica having an average particle size of 1 to 500 nm, 2 to 200 nm, 2 to 100 nm, 2 to 50 nm, 2 to 20 nm, and 2 to 10 nm can be used.

  Next, an example of the manufacturing method of a three-dimensional molded item is demonstrated. Specifically, the manufacturing method of the three-dimensional molded item using the resin mixture containing photocurable resin is demonstrated. The resin mixture is as described above, and the description is omitted here.

  First, one liquid layer made of a photocurable resin mixture is prepared. For example, a modeling stage is provided in a tank filled with a liquid photocurable resin mixture, and the stage upper surface is positioned so as to have a desired depth (for example, about 0.2 mm) from the liquid surface. By doing in this way, a liquid layer can be prepared on a stage.

  Next, the liquid layer is irradiated with an active energy ray, for example, an ultraviolet laser to cure the photocurable resin, thereby forming a cured layer having a predetermined pattern. As the active energy ray, laser light such as visible light and infrared light can be used in addition to ultraviolet light.

  Subsequently, a new liquid layer made of a photocurable resin mixture is prepared on the formed cured layer. For example, by lowering the modeling stage by one layer, a photocurable resin can be introduced onto the cured layer to prepare a new liquid layer.

  Thereafter, an active energy ray is irradiated to a new liquid layer prepared on the cured layer to form a new cured layer continuous with the cured layer.

  By repeating the above operation, the hardened layer is continuously laminated to obtain a predetermined three-dimensional object.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples.

  Table 1 shows Examples (No. 1 to 6) and Comparative Example (No. 7) of the present invention.

(Production of glass filler)
Raw material powders were prepared and mixed uniformly so as to have the composition shown in Table 1. The obtained raw material batch was melted at 1580 to 1600 ° C. until homogeneous, and then poured out between a pair of rollers to form a film. A part of the melted glass was cooled from 720 ° C. to room temperature over 5 hours, and the refractive index was measured with a refractive index measuring instrument (KPR-2000, manufactured by Shimadzu Corporation).

  Glass formed into a film was pulverized by jet mill to obtain glass powder. The obtained glass powder was supplied into the furnace with a table feeder, and the glass powder was heated to 1400 to 2000 ° C. with an air burner and melted to spheroidize the glass powder.

  Next, the fine particles adhering to the glass powder surface were removed by washing with water and then dried.

  Next, a glass filler was obtained by classifying the spheroidized glass powder with an airflow classifier so as to have an average particle diameter shown in Table 1. The average particle size was determined by a laser diffraction particle size distribution measurement method.

(Silane treatment)
In a beaker, 9 g of pure water and 1 g of a silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed. Further, 0.03 g of acetic acid was added and stirred for 30 minutes using a stirrer to hydrolyze the silane coupling agent.

  Next, glass filler: ethanol: hydrolyzed silane coupling agent was mixed at a weight ratio of 20: 19: 1 in another container and stirred for 1 hour.

  Next, ethanol was evaporated to dryness, and further maintained at 110 ° C. for 30 minutes.

(Production of resin mixture)
It measured so that it might become 46.5 mass parts of glass fillers which performed the silane process with respect to 100 mass parts of curable resin (Digital wax company DL360). Furthermore, the glass filler and the curable resin were mixed using a self-revolving mixer (ARE-310, manufactured by Shinky Corporation) to obtain a resin mixture. The refractive index nd of the curable resin after photocuring was 1.511.

(Light transmittance measurement)
An appropriate amount of the obtained resin mixture was collected on a slide glass, sandwiched between another glass slide with a glass plate having a thickness of 0.5 mm as a spacer, and irradiated with ultraviolet rays to cure the resin mixture.

  Next, the total light transmittance of the resin mixture including the slide glass was measured with a spectrophotometer (UV-3100 manufactured by Shimadzu Corporation), and the light transmittance at 588 nm was measured.

  As shown in Table 1, sample No. which is an example of the present invention. 1 to 6 had a high light transmittance of 80 to 84%. On the other hand, sample No. which is a comparative example. No. 7 had a refractive index nd of 1.725 and a large difference from the refractive index nd of the resin, so the light transmittance was as low as 22%.

Claims (10)

By _{mass%, SiO 2 35~75%, Al} 2 O 3 0.1~30%, B 2 O 3 0~30%, SiO 2 + Al 2 O 3 + B 2 O 3 55~90%, MgO + CaO + SrO + BaO + ZnO 2~15 %, Nb ₂ O ₅ + WO ₃ 5 to 15% glass. Moreover, in _mass%, the glass according to claim 1, characterized in that it contains _{2 O 0~15% Li 2 O +} Na 2 O + K. By _mass%, contains Nb ₂ O 5 0.1 to 15%, by mass _ratio, SiO 2 / _Nb 2 _{O 5} is as defined in claim 1 or 2, characterized in that a 2.4 to 20 Glass.   The glass according to any one of claims 1 to 3, wherein the refractive index nd is 1.50 to 1.70, and the Abbe number νd is 40 to 60.   It consists of the glass in any one of Claims 1-4, The glass filler characterized by the above-mentioned.   The glass filler according to claim 5, wherein the glass filler has a substantially spherical shape.   The glass filler according to claim 5 or 6, wherein an average particle diameter is 0.5 to 20 µm.   A resin mixture comprising the glass filler according to claim 5 and a resin.   The resin mixture according to claim 8, wherein a difference in refractive index nd between the glass filler and the resin is within ± 0.05.   The resin mixture according to claim 8 or 9, wherein the resin mixture is for three-dimensional modeling.