WO2022201919A1 - Moderately water-soluble glass, moderately water-soluble glass product, composition, and water quality improvement method - Google Patents

Moderately water-soluble glass, moderately water-soluble glass product, composition, and water quality improvement method Download PDF

Info

Publication number
WO2022201919A1
WO2022201919A1 PCT/JP2022/004749 JP2022004749W WO2022201919A1 WO 2022201919 A1 WO2022201919 A1 WO 2022201919A1 JP 2022004749 W JP2022004749 W JP 2022004749W WO 2022201919 A1 WO2022201919 A1 WO 2022201919A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
glass
soluble glass
ions
mol
Prior art date
Application number
PCT/JP2022/004749
Other languages
French (fr)
Japanese (ja)
Inventor
俊治 明渡
林也 苅部
久倫 福島
政樹 石田
剛志 稲葉
Original Assignee
東洋ガラス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋ガラス株式会社 filed Critical 東洋ガラス株式会社
Publication of WO2022201919A1 publication Critical patent/WO2022201919A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M21/00—Apparatus for the destruction of unwanted vegetation, e.g. weeds
    • A01M21/04—Apparatus for destruction by steam, chemicals, burning, or electricity
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
    • A01M29/30—Scaring or repelling devices, e.g. bird-scaring apparatus preventing or obstructing access or passage, e.g. by means of barriers, spikes, cords, obstacles or sprinkled water
    • A01M29/34—Scaring or repelling devices, e.g. bird-scaring apparatus preventing or obstructing access or passage, e.g. by means of barriers, spikes, cords, obstacles or sprinkled water specially adapted for insects
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass

Definitions

  • the present invention relates to a moderately water-soluble glass, a moderately water-soluble glass product, a composition, and a method for improving water quality.
  • Patent Documents 1 and 2 In order to reduce the occurrence of mosquitoes that transmit infectious diseases such as dengue fever and Zika fever, it is desired to suppress the occurrence and growth of mosquito larvae, mosquito larvae. Since mosquito larvae occur and grow in water that is left unattended, various products made of copper or copper alloy that can leach out copper (Cu) ions and zinc (Zn) ions into water to suppress the occurrence and growth of mosquito larvae. has been proposed (Patent Documents 1 and 2).
  • Cu ions and Zn ions are also known to be effective in suppressing the growth of mosses and algae.
  • An antibacterial agent carrying a hydroxide has also been proposed (Patent Documents 3 and 4).
  • Cu ions and Zn ions are known to be effective in imparting antibacterial and antiviral properties to glass, and glass products containing CuO and ZnO have also been proposed (Patent Documents 5 and 6). ).
  • Patent Documents 1 and 2 are made of solid copper or copper alloy, they are not suitable for long-term use by spraying them in outdoor puddles, etc., and their uses are limited. be done.
  • the antibacterial agents described in Patent Documents 3 and 4 cannot be said to have sufficient initial antibacterial effect (immediately after use) and antibacterial effect over time (hereinafter referred to as "sustainability of antibacterial effect").
  • the antibacterial agent cannot elute Cu ions and Zn ions over a long period of time.
  • the glass products described in Patent Documents 5 and 6 do not dissolve the entire glass, so the effects cannot be said to be sufficiently sustained.
  • the glass product is difficult to dissolve, it is not suitable for use by spraying it in outdoor puddles, for example, and its usage is limited.
  • the present invention has been made to solve the above problems, and provides a slowly water-soluble glass capable of eluting Cu ions and Zn ions over a long period of time, a slowly water-soluble glass product, and a method for improving water quality. With the goal.
  • Another object of the present invention is to provide a composition capable of producing a slightly water-soluble glass product having the above characteristics.
  • the present inventors have made intensive studies to solve the above problems, and as a result, have found a glass composition that can gradually elute Cu ions and Zn ions as the glass melts, and have completed the present invention. reached.
  • the present invention provides a It is a moderately water-soluble glass containing at least one selected and 28.0 mol % or less of R'O (R' is an alkaline earth metal).
  • the present invention is a moderately water-soluble glass product comprising the moderately water-soluble glass.
  • the present invention also provides a composition containing the moderately water-soluble glass.
  • the present invention is a method for improving water quality by immersing the moderately water-soluble glass or the moderately water-soluble glass product in water to elute at least one type of ion selected from Cu ions and Zn ions into the water.
  • a slowly water-soluble glass a slowly water-soluble glass product, and a method for improving water quality, which are capable of eluting Cu ions and Zn ions over a long period of time.
  • a composition capable of producing a moderately water-soluble glass product having the above characteristics.
  • the moderately water-soluble glass (hereinafter sometimes simply referred to as “glass”) according to an embodiment of the present invention contains 40.0 to 75.0 mol% SiO 2 and 5.0 to 38.0 mol% K 2 O, 0.1 to 33.0 mol% of at least one selected from CuO and ZnO, and 28.0 mol% or less of R'O (R' is an alkaline earth metal) include.
  • the term "slowly water-soluble glass” means glass that dissolves slowly in water. Specifically, a moderately water-soluble glass satisfies the following conditions in dissolution (normal and accelerated) tests.
  • Ordinary test The glass does not completely dissolve in the ordinary test. A typical test is performed by immersing a 1 cm ⁇ 1 cm ⁇ 0.5 cm glass in 100 mL of distilled water at 20° C. for 12 hours.
  • Accelerated test The mass reduction rate of the glass in the accelerated test is 2% or more. The mass reduction rate is calculated by the following formula. (Mass of glass before accelerated test - Mass of glass after accelerated test)/Mass of glass before accelerated test x 100 Moreover, an accelerated test is performed as follows.
  • the glass After pulverizing the glass, it is ground using a sieve into glass particles having a particle diameter of 1.4 to 2.0 mm, and the mass (the mass of the glass before the acceleration test) is measured. Next, the ground glass particles are immersed in 100 mL of distilled water at 90° C. for 5 hours, and then sieved using a sieve with an opening of 0.5 mm. Sieving crushes and removes degraded material that is no longer glass. Next, the glass particles remaining on the sieve are dried and their mass (mass of the glass after the accelerated test) is measured.
  • Cu ions and Zn ions can be gradually eluted as the glass slowly dissolves in water. becomes. Therefore, the effects of Cu ions and Zn ions (for example, growth inhibitory or repellent effects on insect pests such as mosquito larvae, mosses, algae, etc., antibacterial effects, and antiviral effects) can be maintained for a long period of time.
  • the duration of the effect of Cu ions and Zn ions depends on the shape (especially surface area) of the slightly water-soluble glass, the amount of water, the water temperature, etc. For example, if the slightly water-soluble glass is visible, the effect can be sustained. The duration of the effect may be appropriately set according to the use of the mildly water-soluble glass, but it can be adjusted so that it can last for about 1 day to 10 years, for example.
  • SiO 2 is a component that forms the network structure of glass. If the SiO 2 content is less than 40.0 mol %, the strength of the glass will be insufficient. On the other hand, if the content of SiO 2 exceeds 75.0 mol %, the network structure becomes too strong. As a result, the dissolution rate of the glass decreases, so that the Cu ions and Zn ions are not sufficiently eluted into the water, and the effects of the Cu ions and Zn ions cannot be sufficiently obtained. Therefore, the content of SiO 2 is 40.0 to 75.0 mol %, preferably 42.0 to 72.0 mol %, more preferably 42.0 to 72.0 mol %, from the viewpoint of stably ensuring the balance between glass strength and dissolution rate. is controlled at 43.0 to 70.0 mol %.
  • K 2 O is a component that increases the melting rate of glass. If the content of K 2 O is less than 5.0 mol %, the dissolution rate of the glass decreases, so that the Cu ions and Zn ions are not sufficiently eluted into the water, and the effects of the Cu ions and Zn ions are reduced. can't get enough. On the other hand, if the K 2 O content exceeds 38.0 mol %, the dissolution rate of the glass becomes too fast, so Cu ions and Zn ions cannot be eluted for a long period of time. Therefore, the content of K 2 O is 5.0 to 38.0 mol%, preferably 7.0 to 37.0 mol%, more preferably 9.0 mol%, from the viewpoint of ensuring an appropriate dissolution rate of the glass. controlled to ⁇ 36.0 mol%.
  • CuO and ZnO are components contained in the network structure of the glass and eluted as Cu ions and Zn ions when the glass is brought into contact with water. Either one or both of CuO and ZnO can be used in combination. If the total content of CuO and ZnO is less than 0.1 mol %, the amounts of Cu ions and Zn ions eluted into water are insufficient, and the effects of Cu ions and Zn ions cannot be obtained sufficiently. On the other hand, when the total content of CuO and ZnO exceeds 33.0 mol%, it becomes easy to crystallize without vitrification. It becomes difficult to control within a certain range.
  • the total content of CuO and ZnO is 0.1 to 33.0 mol%, preferably 0.5 to 32 mol%, from the viewpoint of ensuring the balance between the elution amount of Cu ions and Zn ions and the solubility of the glass. 0 mol %, more preferably 0.8 to 31.0 mol %.
  • the molar ratio of CuO and ZnO is not particularly limited, but is preferably 35:1 to 1:35, more preferably 10:1 to 1:10, still more preferably 3:1 to 1:3.
  • the molar ratio within such a range, Cu ions and Zn ions can be eluted into water in a well-balanced manner over a long period of time.
  • R'O (R' is an alkaline earth metal) is a component that improves chemical durability such as hygroscopicity or water resistance of glass, and is contained in glass as necessary.
  • R′ include, but are not limited to, Mg, Ca, Sr, Ba, and the like.
  • R'O may be of a single type or multiple types.
  • the content of R'O is controlled to 28.0 mol% or less, preferably 25.0 mol% or less, more preferably 20.0 mol% or less, from the viewpoint of ensuring the solubility of the glass.
  • the lower limit of its content is not particularly limited. From the viewpoint of obtaining the above effects of R'O, the lower limit of R'O is generally 0.1 mol%.
  • the moderately water-soluble glass according to the embodiment of the present invention can further contain known components that can be contained in the glass, if necessary, as long as the effects of the present invention are not impaired.
  • known components are not particularly limited, for example, R 2 O (R is an alkali metal other than K) and Al 2 O 3 can be used.
  • R 2 O (R is an alkali metal other than K) is a component that lowers the melting point and viscosity of glass, and is contained in glass as necessary.
  • R include, but are not particularly limited to, Na, Li, Rb, and Cs. Among these, R is preferably Na or Li from the viewpoint of cost.
  • R 2 O may be of a single type or of multiple types. If the content of R 2 O exceeds 35.0 mol %, the glass will readily dissolve in water. Therefore, the content of R 2 O is controlled to 35.0 mol % or less, preferably 33.0 mol % or less, more preferably 31.0 mol % or less, from the viewpoint of ensuring the slow melting property of the glass. . Since R 2 O may not be contained in the glass, the lower limit of its content is not particularly limited. From the viewpoint of obtaining the above effects of R 2 O, the lower limit of R 2 O is generally 0.1 mol %.
  • Al 2 O 3 is a component that improves chemical durability such as hygroscopicity or water resistance of glass.
  • the content of Al 2 O 3 is preferably 30.0 mol % or less, more preferably 28.0 mol % or less, and still more preferably 25.0 mol % or less, from the viewpoint of ensuring the solubility of the glass. be.
  • the lower limit of the content of Al 2 O 3 is not particularly limited, it is generally 0.1 mol % from the viewpoint of obtaining the above effects of Al 2 O 3 .
  • the moderately water - soluble glass according to the embodiment of the present invention preferably does not contain at least one selected from B2O3 and P2O5 , and does not contain both B2O3 and P2O5 . is more preferred.
  • B 2 O 3 and P 2 O 5 are components with a large environmental load. Therefore, by making the glass composition free of these components, the glass can be used by scattering it in outdoor puddles and the like, and can be used for various purposes.
  • B 2 O 3 and P 2 O 5 are components that form a network structure of glass like SiO 2 , and may be contained in the glass as necessary within a range that does not affect the environment. .
  • the amount of B 2 O 3 and P 2 O 5 is less than 0.5 mol % each in a range that does not affect the environment.
  • the moderately water-soluble glass according to the embodiment of the present invention preferably has a specific gravity of 2.4 or more.
  • the specific gravity By controlling the specific gravity within such a range, for example, when the slowly water-soluble glass is used by scattering it in a puddle outdoors, it is possible to prevent the loosely water-soluble glass from being washed away by rain or the like.
  • the upper limit of the specific gravity is not particularly limited, it is preferably 10.0, more preferably 8.0, and still more preferably 5.0 in consideration of the transportability of the moderately water-soluble glass.
  • the specific gravity can be measured with a commercially available hydrometer using the Archimedes method.
  • the moderately water-soluble glass according to the embodiment of the present invention can elute Cu ions and/or Zn ions over a long period of time
  • various applications where it is desirable to obtain the effects of Cu ions and/or Zn ions over a long period of time.
  • can be used in Examples of such uses include growth inhibitors or repellents for pests, mosses, algae, etc., antibacterial agents, antiviral agents, and the like.
  • growth inhibitors or repellents for pests, mosses, algae, etc. are preferred.
  • the shape of the moderately water-soluble glass according to the embodiment of the present invention is not particularly limited, and can be appropriately set according to the application.
  • the slowly water-soluble glass itself is used as a growth inhibitor or repellent for pests, mosses, algae, etc.
  • the slowly water-soluble glass may be made into an appropriate dosage form.
  • the slowly water-soluble glass is blended with an existing drug such as a plant breeding agent as a growth inhibitor or a repellent
  • the slowly water-soluble glass may be powdered and blended with the existing drug.
  • the moderately water-soluble glass when using the moderately water-soluble glass as a raw material for a molding material or a coating material, the moderately water-soluble glass may be powdered and blended with the molding material or the coating material.
  • the concentration of Cu ions and/or Zn ions in water is 0.5 ppm or more, preferably 1.0 ppm or more, more preferably is preferably 2.0 ppm or more.
  • concentration of Cu ions and/or Zn ions is 0.5 ppm or more, it is possible to obtain the effect of suppressing or repelling the growth of mosquito larvae.
  • concentration of Cu ions and/or Zn ions is 2.0 ppm or more, mosquito larvae hardly grow.
  • the upper limit of the concentration of Cu ions and/or Zn ions is not particularly limited, and may be appropriately set according to environmental standards and the like.
  • the moderately water-soluble glass according to the embodiment of the present invention can be produced in the same manner as known glass production methods. That is, the moderately water-soluble glass according to the embodiment of the present invention is prepared by blending the above components so as to have a predetermined content, heating at a high temperature to melt, and then shaping the melt into a predetermined shape (for example, a plate shape) and cooled. Alternatively, the melt may be formed into a predetermined shape by pouring it into a predetermined mold and cooling it. In addition, when the moderately water-soluble glass is used as a raw material for a molding material, a coating material, or the like, the obtained moderately water-soluble glass may be pulverized into powder.
  • a moderately water-soluble glass product comprises the above-described moderately water-soluble glass. Since this moderately water-soluble glass product includes the aforementioned moderately water-soluble glass, Cu ions and Zn ions can be eluted over a long period of time. Therefore, this moderately water-soluble glass product can obtain the effects of Cu ions and Zn ions (for example, the growth inhibition or repelling effect against pests such as mosquito larvae, mosses, algae, etc., antibacterial effects, and antiviral effects) over a long period of time. It is possible.
  • An example of the moderately water-soluble glass product according to the embodiment of the present invention is a coated product comprising a base material and a coating layer formed on the surface of the base material, the coating layer containing the above-described moderately water-soluble glass. .
  • the moderately water-soluble glass is preferably dispersed in the coating layer.
  • the base material is not particularly limited, and those formed from metal, resin, or the like can be used.
  • Another example of the moderately water-soluble glass product according to the embodiment of the present invention is a resin molded product containing the moderately water-soluble glass. In the resin molded article, the moderately water-soluble glass is preferably dispersed in the resin.
  • a moderately water-soluble glass product such as the one described above can be produced using a composition containing a moderately water-soluble glass.
  • a coated product can be produced by using a composition containing a sparingly soluble glass as a coating material and coating a substrate with the coating material.
  • a resin molded article can be produced by using a composition containing a moderately water-soluble glass as a molding material and molding the molding material into a predetermined shape.
  • a composition used as a coating material can contain known components used for coating materials (for example, resin components, solvents, inorganic components, etc.) in addition to the moderately water-soluble glass.
  • the composition used as the molding material can contain known components used in molding materials (for example, resin components, inorganic components, etc.) in addition to the moderately water-soluble glass.
  • a method for improving water quality includes immersing the above-described moderately water-soluble glass or the above-described moderately water-soluble glass product in water to elute at least one type of ion selected from Cu ions and Zn ions into the water. .
  • the elution of Cu ions and/or Zn ions makes it possible to obtain the effect of suppressing or repelling the growth of pests such as mosquito larvae, mosses, algae, etc., so that it is possible to improve water quality. .
  • the elution concentration of Cu ions and/or Zn ions in water is not particularly limited, but is preferably 0.5 ppm or more, preferably 1.0 ppm or more, and more preferably 2.0 ppm or more.
  • the upper limit of the elution concentration of Cu ions and/or Zn ions is not particularly limited, and may be appropriately set according to environmental standards and the like.
  • the amount of the moderately water-soluble glass or the moderately water-soluble glass product added to water is not particularly limited, and the amount of water is adjusted so as to maintain a predetermined elution concentration of Cu ions and/or Zn ions for a long period of time. It may be set as appropriate.
  • ⁇ Dissolution test> As the dissolution test, the normal test and the accelerated test described above were performed.
  • the ground glass particles were immersed in 100 mL of distilled water at 90° C. for 5 hours, and then sieved using a sieve with an opening of 0.5 mm. Glass particles remaining on the sieve were thoroughly washed with distilled water. Next, the glass particles remaining on the sieve were dried, and the mass (mass of the glass after the acceleration test) was measured. Then, the mass reduction rate of the glass was determined by the above formula. In the evaluation of this accelerated test, ⁇ means that the mass reduction rate of the glass is 2% or more, and ⁇ means that the mass reduction rate of the glass is less than 2%. Table 1 shows the above evaluation results.
  • test no. Samples 2 to 8, 15, 19 to 21 and 23 to 24 are mildly water-soluble glasses according to the dissolution test results, and contain a predetermined amount of CuO and/or ZnO. Therefore, these samples can slowly elute Cu and/or Zn ions as the glass slowly dissolves in water.
  • Test No. Samples 1, 16 and 17 are water soluble glasses from the dissolution (normal) test results. Therefore, in these samples, the glass immediately dissolves in water, and Cu ions and/or Zn ions cannot be gradually eluted.
  • test no. Samples 11, 12, 18 and 22 are poorly water-soluble glasses from the results of the dissolution (acceleration) test.
  • the present invention it is possible to provide a slowly water-soluble glass, a slowly water-soluble glass product, and a method for improving water quality that can elute Cu ions and Zn ions over a long period of time. Further, according to the present invention, it is possible to provide a composition capable of producing a moderately water-soluble glass product having the above characteristics.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Insects & Arthropods (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Birds (AREA)
  • Glass Compositions (AREA)
  • Catching Or Destruction (AREA)

Abstract

Moderately water-soluble glass containing 40.0-75.0 mol% SiO2, 5.0-38.0 mol% K2O, 0.1-33.0 mol% of at least one substance selected from among CuO and ZnO, and at most 28.0 mol% R'O (R' being an alkali earth metal).

Description

緩水溶性ガラス、緩水溶性ガラス製品、組成物及び水質改善方法SLOWLY WATER-SOLUBLE GLASS, SLOWLY WATER-SOLUBLE GLASS PRODUCT, COMPOSITION, AND WATER QUALITY IMPROVEMENT METHOD
　本発明は、緩水溶性ガラス、緩水溶性ガラス製品、組成物及び水質改善方法に関する。 The present invention relates to a moderately water-soluble glass, a moderately water-soluble glass product, a composition, and a method for improving water quality.
　デング熱やジカ熱などの感染症を媒介する蚊の発生を少なくするために、蚊の幼虫であるボウフラの発生や成長を抑制することが望まれている。ボウフラは、放置された水中などで発生して成長することから、ボウフラの発生や成長を抑制する銅（Ｃｕ）イオンや亜鉛（Ｚｎ）イオンを水中に溶出可能な銅又は銅合金製の各種製品が提案されている（特許文献１及び２）。 In order to reduce the occurrence of mosquitoes that transmit infectious diseases such as dengue fever and Zika fever, it is desired to suppress the occurrence and growth of mosquito larvae, mosquito larvae. Since mosquito larvae occur and grow in water that is left unattended, various products made of copper or copper alloy that can leach out copper (Cu) ions and zinc (Zn) ions into water to suppress the occurrence and growth of mosquito larvae. has been proposed (Patent Documents 1 and 2).
　また、ＣｕイオンやＺｎイオンは、苔類、藻類などの発生抑制に有効であることも知られており、多孔質ガラスなどの多孔質物質に、ＣｕイオンやＺｎイオンを溶出可能な酸化物や水酸化物を担持させた抗菌剤も提案されている（特許文献３及び４）。
　さらに、ＣｕイオンやＺｎイオンは、ガラスに抗菌性や抗ウィルス性を付与するのに有効であることも知られており、ＣｕＯやＺｎＯを含むガラス製品も提案されている（特許文献５及び６）。 Cu ions and Zn ions are also known to be effective in suppressing the growth of mosses and algae. An antibacterial agent carrying a hydroxide has also been proposed (Patent Documents 3 and 4).
Furthermore, Cu ions and Zn ions are known to be effective in imparting antibacterial and antiviral properties to glass, and glass products containing CuO and ZnO have also been proposed (Patent Documents 5 and 6). ).
特開２０１６－２１６３７６号公報JP 2016-216376 A 特開２０１７－２１８４０６号公報JP 2017-218406 A 特開２００３－８１７２５号公報JP-A-2003-81725 特開２００３－１４６８１８号公報JP 2003-146818 A 特表２０１７－５０８７０５号公報Japanese translation of PCT publication No. 2017-508705 特開２０１９－９９５１４号公報JP 2019-99514 A
　特許文献１及び２に記載の各種製品は、固形の銅又は銅合金製であるため、例えば、屋外の水たまりなどに散布して長期間に渡り使用するのに適しておらず、使用用途が限定される。
　また、特許文献３及び４に記載の抗菌剤は、初期（使用直後）の抗菌効果や、時間が経過した場合の抗菌効果（以下、「抗菌効果の持続性」という）が十分とはいえない。特に、当該抗菌剤は、ＣｕイオンやＺｎイオンを長期間にわたって溶出することができない。
　さらに、特許文献５及び６に記載のガラス製品は、ガラス全体が溶解するわけではないため、効果の持続性が十分であるとはいえない。また、当該ガラス製品は、溶解し難いため、例えば、屋外の水たまりなどに散布して使用するのに適しておらず、使用用途も限定される。 Since the various products described in Patent Documents 1 and 2 are made of solid copper or copper alloy, they are not suitable for long-term use by spraying them in outdoor puddles, etc., and their uses are limited. be done.
In addition, the antibacterial agents described in Patent Documents 3 and 4 cannot be said to have sufficient initial antibacterial effect (immediately after use) and antibacterial effect over time (hereinafter referred to as "sustainability of antibacterial effect"). . In particular, the antibacterial agent cannot elute Cu ions and Zn ions over a long period of time.
Furthermore, the glass products described in Patent Documents 5 and 6 do not dissolve the entire glass, so the effects cannot be said to be sufficiently sustained. In addition, since the glass product is difficult to dissolve, it is not suitable for use by spraying it in outdoor puddles, for example, and its usage is limited.
　本発明は、上記のような問題を解決するためになされたものであり、ＣｕイオンやＺｎイオンを長期間にわたって溶出可能な緩水溶性ガラス、緩水溶性ガラス製品及び水質改善方法を提供することを目的とする。
　また、本発明は、上記の特徴を有する緩水溶性ガラス製品を製造可能な組成物を提供することを目的とする。 The present invention has been made to solve the above problems, and provides a slowly water-soluble glass capable of eluting Cu ions and Zn ions over a long period of time, a slowly water-soluble glass product, and a method for improving water quality. With the goal.
Another object of the present invention is to provide a composition capable of producing a slightly water-soluble glass product having the above characteristics.
　本発明者らは、上記のような問題を解決すべく鋭意研究を行った結果、ガラスの溶解に伴ってＣｕイオンやＺｎイオンを徐々に溶出可能なガラスの組成を見出し、本発明を完成するに至った。 The present inventors have made intensive studies to solve the above problems, and as a result, have found a glass composition that can gradually elute Cu ions and Zn ions as the glass melts, and have completed the present invention. reached.
　すなわち、本発明は、４０．０～７５．０モル％のＳｉＯ2と、５．０～３８．０モル％のＫ2Ｏと、０．１～３３．０モル％の、ＣｕＯ及びＺｎＯから選択される少なくとも一種と、２８．０モル％以下のＲ’Ｏ（Ｒ’はアルカリ土類金属である）とを含む緩水溶性ガラスである。 That is, the present invention provides a It is a moderately water-soluble glass containing at least one selected and 28.0 mol % or less of R'O (R' is an alkaline earth metal).
　また、本発明は、前記緩水溶性ガラスを備える緩水溶性ガラス製品である。 Further, the present invention is a moderately water-soluble glass product comprising the moderately water-soluble glass.
　また、本発明は、前記緩水溶性ガラスを含む組成物である。 The present invention also provides a composition containing the moderately water-soluble glass.
　さらに、本発明は、前記緩水溶性ガラス又は前記緩水溶性ガラス製品を水に浸漬し、Ｃｕイオン及びＺｎイオンから選択される少なくとも一種のイオンを前記水に溶出させる水質改善方法である。 Further, the present invention is a method for improving water quality by immersing the moderately water-soluble glass or the moderately water-soluble glass product in water to elute at least one type of ion selected from Cu ions and Zn ions into the water.
　本発明によれば、ＣｕイオンやＺｎイオンを長期間にわたって溶出可能な緩水溶性ガラス、緩水溶性ガラス製品及び水質改善方法を提供することができる。
　また、本発明によれば、上記の特徴を有する緩水溶性ガラス製品を製造可能な組成物を提供することができる。 According to the present invention, it is possible to provide a slowly water-soluble glass, a slowly water-soluble glass product, and a method for improving water quality, which are capable of eluting Cu ions and Zn ions over a long period of time.
Further, according to the present invention, it is possible to provide a composition capable of producing a moderately water-soluble glass product having the above characteristics.
　以下、本発明の実施形態について具体的に説明する。本発明は以下の実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施形態に対し変更、改良などが適宜加えられたものも本発明の範囲に入ることが理解されるべきである。 Hereinafter, embodiments of the present invention will be specifically described. The present invention is not limited to the following embodiments, and modifications and improvements can be made to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. are also within the scope of the present invention.
　本発明の実施形態に係る緩水溶性ガラス（以下、単に「ガラス」と略すことがある）は、４０．０～７５．０モル％のＳｉＯ2と、５．０～３８．０モル％のＫ2Ｏと、０．１～３３．０モル％の、ＣｕＯ及びＺｎＯから選択される少なくとも一種と、２８．０モル％以下のＲ’Ｏ（Ｒ’はアルカリ土類金属である）とを含む。 The moderately water-soluble glass (hereinafter sometimes simply referred to as “glass”) according to an embodiment of the present invention contains 40.0 to 75.0 mol% SiO 2 and 5.0 to 38.0 mol% K 2 O, 0.1 to 33.0 mol% of at least one selected from CuO and ZnO, and 28.0 mol% or less of R'O (R' is an alkaline earth metal) include.
　ここで、本明細書において「緩水溶性ガラス」とは、水に緩やかに溶解するガラスを意味する。具体的には、緩水溶性ガラスは、溶解（通常及び加速）試験において以下条件を満たす。
（１）通常試験
　通常試験においてガラスが完全に溶解しない。
　通常試験は、１ｃｍ×１ｃｍ×０．５ｃｍのガラスを２０℃の蒸留水１００ｍＬに１２時間浸漬することによって行う。
（２）加速試験
　加速試験におけるガラスの質量減少率が２％以上である。
　質量減少率は、次の式によって算出される。
　　（加速試験前のガラスの質量－加速試験後のガラスの質量）／加速試験前のガラスの質量×１００
　また、加速試験は、次のようにして行う。まず、ガラスを粉砕した後、篩を用いて粒子径１．４～２．０ｍｍのガラス粒子に紛級し、その質量（加速試験前のガラスの質量）を測定する。次に、紛級したガラス粒子を９０℃の蒸留水１００ｍＬに５時間浸漬した後、目開き０．５ｍｍの篩を用いて篩分けする。篩分けは、劣化してガラスではなくなったものを潰して除去する。次に、篩に残ったガラス粒子を乾燥させ、その質量（加速試験後のガラスの質量）を測定する。 As used herein, the term "slowly water-soluble glass" means glass that dissolves slowly in water. Specifically, a moderately water-soluble glass satisfies the following conditions in dissolution (normal and accelerated) tests.
(1) Ordinary test The glass does not completely dissolve in the ordinary test.
A typical test is performed by immersing a 1 cm×1 cm×0.5 cm glass in 100 mL of distilled water at 20° C. for 12 hours.
(2) Accelerated test The mass reduction rate of the glass in the accelerated test is 2% or more.
The mass reduction rate is calculated by the following formula.
(Mass of glass before accelerated test - Mass of glass after accelerated test)/Mass of glass before accelerated test x 100
Moreover, an accelerated test is performed as follows. First, after pulverizing the glass, it is ground using a sieve into glass particles having a particle diameter of 1.4 to 2.0 mm, and the mass (the mass of the glass before the acceleration test) is measured. Next, the ground glass particles are immersed in 100 mL of distilled water at 90° C. for 5 hours, and then sieved using a sieve with an opening of 0.5 mm. Sieving crushes and removes degraded material that is no longer glass. Next, the glass particles remaining on the sieve are dried and their mass (mass of the glass after the accelerated test) is measured.
　ガラスを緩水溶性とすることにより、ガラスが水に緩やかに溶解するにつれてＣｕイオンやＺｎイオンを徐々に溶出させることができるため、長期間にわたって水中にＣｕイオンやＺｎイオンを溶出することが可能となる。したがって、ＣｕイオンやＺｎイオンによる効果（例えば、ボウフラなどの害虫や、苔類、藻類などの成長抑制又は忌避効果、抗菌効果、抗ウィルス効果）を長期間にわたって持続させることができる。
　なお、ＣｕイオンやＺｎイオンによる効果の持続期間は、緩水溶性ガラスの形状（特に、表面積）、水量、水温などに依存するが、例えば、緩水溶性ガラスが視認できる状態であれば、その効果を持続させることができる。効果の持続期間は、緩水溶性ガラスの用途などに応じて適宜設定すればよいが、例えば、１日～１０年程度を持続できるように調整することができる。 By making the glass mildly soluble in water, Cu ions and Zn ions can be gradually eluted as the glass slowly dissolves in water. becomes. Therefore, the effects of Cu ions and Zn ions (for example, growth inhibitory or repellent effects on insect pests such as mosquito larvae, mosses, algae, etc., antibacterial effects, and antiviral effects) can be maintained for a long period of time.
The duration of the effect of Cu ions and Zn ions depends on the shape (especially surface area) of the slightly water-soluble glass, the amount of water, the water temperature, etc. For example, if the slightly water-soluble glass is visible, the effect can be sustained. The duration of the effect may be appropriately set according to the use of the mildly water-soluble glass, but it can be adjusted so that it can last for about 1 day to 10 years, for example.
　ＳｉＯ2は、ガラスの網目構造を形成する成分である。
　ＳｉＯ2の含有量が４０．０モル％未満であると、ガラスの強度が不足してしまう。一方、ＳｉＯ2の含有量が７５．０モル％を超えると、網目構造が強固になりすぎてしまう。その結果、ガラスの溶解速度が低下してしまうため、水中にＣｕイオンやＺｎイオンが十分に溶出せず、ＣｕイオンやＺｎイオンによる効果が十分に得られない。したがって、ＳｉＯ2の含有量は、ガラスの強度及び溶解速度のバランスを安定して確保する観点から、４０．０～７５．０モル％、好ましくは４２．０～７２．０モル％、より好ましくは４３．０～７０．０モル％に制御される。 SiO 2 is a component that forms the network structure of glass.
If the SiO 2 content is less than 40.0 mol %, the strength of the glass will be insufficient. On the other hand, if the content of SiO 2 exceeds 75.0 mol %, the network structure becomes too strong. As a result, the dissolution rate of the glass decreases, so that the Cu ions and Zn ions are not sufficiently eluted into the water, and the effects of the Cu ions and Zn ions cannot be sufficiently obtained. Therefore, the content of SiO 2 is 40.0 to 75.0 mol %, preferably 42.0 to 72.0 mol %, more preferably 42.0 to 72.0 mol %, from the viewpoint of stably ensuring the balance between glass strength and dissolution rate. is controlled at 43.0 to 70.0 mol %.
　Ｋ2Ｏは、ガラスの溶解速度を高める成分である。
　Ｋ2Ｏの含有量が５．０モル％未満であると、ガラスの溶解速度が低下してしまうため、水中にＣｕイオンやＺｎイオンが十分に溶出せず、ＣｕイオンやＺｎイオンによる効果が十分に得られない。一方、Ｋ2Ｏの含有量が３８．０モル％を超えると、ガラスの溶解速度が速くなりすぎてしまうため、ＣｕイオンやＺｎイオンを長期間にわたって溶出することができなくなる。したがって、Ｋ2Ｏの含有量は、ガラスの適切な溶解速度を確保する観点から、５．０～３８．０モル％、好ましくは７．０～３７．０モル％、より好ましくは９．０～３６．０モル％に制御される。 K 2 O is a component that increases the melting rate of glass.
If the content of K 2 O is less than 5.0 mol %, the dissolution rate of the glass decreases, so that the Cu ions and Zn ions are not sufficiently eluted into the water, and the effects of the Cu ions and Zn ions are reduced. can't get enough. On the other hand, if the K 2 O content exceeds 38.0 mol %, the dissolution rate of the glass becomes too fast, so Cu ions and Zn ions cannot be eluted for a long period of time. Therefore, the content of K 2 O is 5.0 to 38.0 mol%, preferably 7.0 to 37.0 mol%, more preferably 9.0 mol%, from the viewpoint of ensuring an appropriate dissolution rate of the glass. controlled to ~36.0 mol%.
　ＣｕＯ及びＺｎＯは、ガラスの網目構造内に含有され、ガラスを水と接触させた際にＣｕイオン及びＺｎイオンとして溶出する成分である。ＣｕＯ及びＺｎＯは、いずれか一方又は両方を組み合わせて用いることができる。
　ＣｕＯ及びＺｎＯの合計含有量が０．１モル％未満であると、水中にＣｕイオン及びＺｎイオンの溶出量が不足し、ＣｕイオンやＺｎイオンによる効果が十分に得られない。一方、ＣｕＯ及びＺｎＯの合計含有量が３３．０モル％を超えると、ガラス化せずに結晶化し易くなってしまう結果、水に溶解し難くなったり、Ｃｕイオン及びＺｎイオンの溶出量を適切な範囲に制御し難くなったりする。したがって、ＣｕＯ及びＺｎＯの合計含有量は、Ｃｕイオン及びＺｎイオンの溶出量とガラスの溶解性とのバランスを確保する観点から、０．１～３３．０モル％、好ましくは０．５～３２．０モル％、より好ましくは０．８～３１．０モル％に制御される。 CuO and ZnO are components contained in the network structure of the glass and eluted as Cu ions and Zn ions when the glass is brought into contact with water. Either one or both of CuO and ZnO can be used in combination.
If the total content of CuO and ZnO is less than 0.1 mol %, the amounts of Cu ions and Zn ions eluted into water are insufficient, and the effects of Cu ions and Zn ions cannot be obtained sufficiently. On the other hand, when the total content of CuO and ZnO exceeds 33.0 mol%, it becomes easy to crystallize without vitrification. It becomes difficult to control within a certain range. Therefore, the total content of CuO and ZnO is 0.1 to 33.0 mol%, preferably 0.5 to 32 mol%, from the viewpoint of ensuring the balance between the elution amount of Cu ions and Zn ions and the solubility of the glass. 0 mol %, more preferably 0.8 to 31.0 mol %.
　ＣｕＯ及びＺｎＯの両方がガラスに含まれる場合、ＣｕＯとＺｎＯとのモル比は、特に限定されないが、好ましくは３５：１～１：３５、より好ましくは１０：１～１：１０、更に好ましくは３：１～１：３である。このような範囲のモル比に制御することにより、水中にＣｕイオン及びＺｎイオンをバランス良く長期間にわたって溶出することが可能になる。 When both CuO and ZnO are contained in the glass, the molar ratio of CuO and ZnO is not particularly limited, but is preferably 35:1 to 1:35, more preferably 10:1 to 1:10, still more preferably 3:1 to 1:3. By controlling the molar ratio within such a range, Cu ions and Zn ions can be eluted into water in a well-balanced manner over a long period of time.
　Ｒ’Ｏ（Ｒ’はアルカリ土類金属である）は、ガラスの吸湿性又は耐水性などの化学的耐久性を向上させる成分であり、必要に応じてガラスに含有される。Ｒ’としては、特に限定されないが、Ｍｇ、Ｃａ、Ｓｒ、Ｂａなどが挙げられる。Ｒ’Ｏは単一種であっても複数種であってもよい。
　Ｒ’Ｏの含有量が２８．０モル％を超えると、ガラスが水に溶解し難くなる。したがって、Ｒ’Ｏの含有量は、ガラスの溶解性を確保する観点から、２８．０モル％以下、好ましくは２５．０モル％以下、より好ましくは２０．０モル％以下に制御される。
　なお、Ｒ’Ｏはガラスに含有されていなくてもよいため、その含有量の下限は特に限定されない。Ｒ’Ｏによる上記の効果を得る観点からは、Ｒ’Ｏの下限値は一般的に０．１モル％である。 R'O (R' is an alkaline earth metal) is a component that improves chemical durability such as hygroscopicity or water resistance of glass, and is contained in glass as necessary. Examples of R′ include, but are not limited to, Mg, Ca, Sr, Ba, and the like. R'O may be of a single type or multiple types.
When the content of R'O exceeds 28.0 mol%, the glass becomes difficult to dissolve in water. Therefore, the content of R'O is controlled to 28.0 mol% or less, preferably 25.0 mol% or less, more preferably 20.0 mol% or less, from the viewpoint of ensuring the solubility of the glass.
Since R'O does not have to be contained in the glass, the lower limit of its content is not particularly limited. From the viewpoint of obtaining the above effects of R'O, the lower limit of R'O is generally 0.1 mol%.
　本発明の実施形態に係る緩水溶性ガラスは、本発明の効果を阻害しない範囲において、ガラスに含有され得る公知の成分を必要に応じて更に含むことができる。このような公知の成分としては、特に限定されないが、例えば、Ｒ2Ｏ（Ｒは、Ｋ以外のアルカリ金属である）、Ａｌ2Ｏ3を用いることができる。 The moderately water-soluble glass according to the embodiment of the present invention can further contain known components that can be contained in the glass, if necessary, as long as the effects of the present invention are not impaired. Although such known components are not particularly limited, for example, R 2 O (R is an alkali metal other than K) and Al 2 O 3 can be used.
　Ｒ2Ｏ（Ｒは、Ｋ以外のアルカリ金属である）は、ガラスの融点や粘性を低下させる成分であり、必要に応じてガラスに含有される。Ｒとしては、特に限定されないが、Ｎａ、Ｌｉ、Ｒｂ、Ｃｓなどが挙げられる。これらの中でもコストの観点から、ＲはＮａ又はＬｉであることが好ましい。Ｒ2Ｏは単一種であっても複数種であってもよい。
　Ｒ2Ｏの含有量が３５．０モル％を超えると、ガラスが水に溶解し易くなる。したがって、Ｒ2Ｏの含有量は、ガラスの緩溶解性を確保する観点から、３５．０モル％以下、好ましくは３３．０モル％以下、より好ましくは３１．０モル％以下に制御される。
　なお、Ｒ2Ｏはガラスに含有されていなくてもよいため、その含有量の下限は特に限定されない。Ｒ2Ｏによる上記の効果を得る観点からは、Ｒ2Ｏの下限値は一般的に０．１モル％である。 R 2 O (R is an alkali metal other than K) is a component that lowers the melting point and viscosity of glass, and is contained in glass as necessary. Examples of R include, but are not particularly limited to, Na, Li, Rb, and Cs. Among these, R is preferably Na or Li from the viewpoint of cost. R 2 O may be of a single type or of multiple types.
If the content of R 2 O exceeds 35.0 mol %, the glass will readily dissolve in water. Therefore, the content of R 2 O is controlled to 35.0 mol % or less, preferably 33.0 mol % or less, more preferably 31.0 mol % or less, from the viewpoint of ensuring the slow melting property of the glass. .
Since R 2 O may not be contained in the glass, the lower limit of its content is not particularly limited. From the viewpoint of obtaining the above effects of R 2 O, the lower limit of R 2 O is generally 0.1 mol %.
　Ａｌ2Ｏ3は、Ｒ’Ｏと同様に、ガラスの吸湿性又は耐水性などの化学的耐久性を向上させる成分である。
　Ａｌ2Ｏ3の含有量が３０．０モル％を超えると、ガラスが水に溶解し難くなる。したがって、Ａｌ2Ｏ3の含有量は、ガラスの溶解性を確保する観点から、好ましくは３０．０モル％以下、より好ましくは２８．０モル％以下、更に好ましくは２５．０モル％以下である。なお、Ａｌ2Ｏ3の含有量の下限値は、特に限定されないが、Ａｌ2Ｏ3による上記の効果を得る観点から、一般的に０．１モル％である。 Al 2 O 3 , like R'O, is a component that improves chemical durability such as hygroscopicity or water resistance of glass.
When the content of Al 2 O 3 exceeds 30.0 mol %, the glass becomes difficult to dissolve in water. Therefore, the content of Al 2 O 3 is preferably 30.0 mol % or less, more preferably 28.0 mol % or less, and still more preferably 25.0 mol % or less, from the viewpoint of ensuring the solubility of the glass. be. Although the lower limit of the content of Al 2 O 3 is not particularly limited, it is generally 0.1 mol % from the viewpoint of obtaining the above effects of Al 2 O 3 .
　本発明の実施形態に係る緩水溶性ガラスは、Ｂ2Ｏ3及びＰ2Ｏ5から選択される少なくとも一種を含まないことが好ましく、Ｂ2Ｏ3及びＰ2Ｏ5の両方を含まないことがより好ましい。
　Ｂ2Ｏ3及びＰ2Ｏ5は、環境負荷が大きい成分である。そのため、これらの成分を含まない組成のガラスとすることにより、屋外の水たまりなどにガラスを散布して使用することもでき、様々な用途で用いることが可能となる。
　ただし、Ｂ2Ｏ3及びＰ2Ｏ5は、ＳｉＯ2と同様にガラスの網目構造を形成する成分であり、環境に影響を与えない範囲であれば必要に応じてガラスに含まれてもよい。環境に影響を与えない範囲の量としては、Ｂ2Ｏ3及びＰ2Ｏ5それぞれ０．５モル％未満である。 The moderately water - soluble glass according to the embodiment of the present invention preferably does not contain at least one selected from B2O3 and P2O5 , and does not contain both B2O3 and P2O5 . is more preferred.
B 2 O 3 and P 2 O 5 are components with a large environmental load. Therefore, by making the glass composition free of these components, the glass can be used by scattering it in outdoor puddles and the like, and can be used for various purposes.
However, B 2 O 3 and P 2 O 5 are components that form a network structure of glass like SiO 2 , and may be contained in the glass as necessary within a range that does not affect the environment. . The amount of B 2 O 3 and P 2 O 5 is less than 0.5 mol % each in a range that does not affect the environment.
　本発明の実施形態に係る緩水溶性ガラスは、比重が２．４以上であることが好ましい。このような範囲の比重に制御することにより、例えば、緩水溶性ガラスを屋外の水たまりなどに散布して使用する場合に、緩水溶性ガラスが雨などによって流出され難くすることができる。なお、比重の上限値は、特に限定されないが、緩水溶性ガラスの運搬性などを考慮すると、好ましくは１０．０、より好ましくは８．０、更に好ましくは５．０である。
　なお、比重は、アルキメデス法を用いた市販の比重計により測定することができる。 The moderately water-soluble glass according to the embodiment of the present invention preferably has a specific gravity of 2.4 or more. By controlling the specific gravity within such a range, for example, when the slowly water-soluble glass is used by scattering it in a puddle outdoors, it is possible to prevent the loosely water-soluble glass from being washed away by rain or the like. Although the upper limit of the specific gravity is not particularly limited, it is preferably 10.0, more preferably 8.0, and still more preferably 5.0 in consideration of the transportability of the moderately water-soluble glass.
The specific gravity can be measured with a commercially available hydrometer using the Archimedes method.
　本発明の実施形態に係る緩水溶性ガラスは、Ｃｕイオン及び／又はＺｎイオンを長期間にわたって溶出することができるため、Ｃｕイオン及び／又はＺｎイオンによる効果を長期間にわたって得ることが望ましい各種用途で用いることができる。当該用途の例としては、害虫、苔類、藻類などの成長抑制剤又は忌避剤、抗菌剤、抗ウィルス剤などが挙げられる。これらの中でも害虫、苔類、藻類など（特に、ボウフラ）の成長抑制剤又は忌避剤が好ましい。 Since the moderately water-soluble glass according to the embodiment of the present invention can elute Cu ions and/or Zn ions over a long period of time, various applications where it is desirable to obtain the effects of Cu ions and/or Zn ions over a long period of time. can be used in Examples of such uses include growth inhibitors or repellents for pests, mosses, algae, etc., antibacterial agents, antiviral agents, and the like. Among these, growth inhibitors or repellents for pests, mosses, algae, etc. (especially mosquito larvae) are preferred.
　本発明の実施形態に係る緩水溶性ガラスの形状は、特に限定されず、用途に応じて適宜設定することができる。
　例えば、緩水溶性ガラスそれ自体を害虫、苔類、藻類などの成長抑制剤又は忌避剤などとして用いる場合には、緩水溶性ガラスを適切な剤形とすればよい。なお、緩水溶性ガラスを成長抑制剤又は忌避剤などとして植物育成剤などの既存の薬剤に配合して用いる場合には、緩水溶性ガラスを粉末状にして既存の薬剤に配合すればよい。さらに、緩水溶性ガラスを成形材料やコーティング材料などの原料として用いる場合には、緩水溶性ガラスを粉末状にして成形材料やコーティング材料に配合すればよい。 The shape of the moderately water-soluble glass according to the embodiment of the present invention is not particularly limited, and can be appropriately set according to the application.
For example, when the slowly water-soluble glass itself is used as a growth inhibitor or repellent for pests, mosses, algae, etc., the slowly water-soluble glass may be made into an appropriate dosage form. In addition, when the slowly water-soluble glass is blended with an existing drug such as a plant breeding agent as a growth inhibitor or a repellent, the slowly water-soluble glass may be powdered and blended with the existing drug. Furthermore, when using the moderately water-soluble glass as a raw material for a molding material or a coating material, the moderately water-soluble glass may be powdered and blended with the molding material or the coating material.
　本発明の実施形態に係る緩水溶性ガラスをボウフラの成長抑制剤又は忌避剤に用いる場合、水中のＣｕイオン及び／又はＺｎイオンの濃度が０．５ｐｐｍ以上、好ましくは１．０ｐｐｍ以上、より好ましくは２．０ｐｐｍ以上となるように用いることが好ましい。Ｃｕイオン及び／又はＺｎイオンの濃度を０．５ｐｐｍ以上とすることにより、ボウフラの成長抑制効果又は忌避効果を得ることができる。特に、Ｃｕイオン及び／又はＺｎイオンの濃度を２．０ｐｐｍ以上とすれば、ボウフラはほとんど成長しない。
　なお、Ｃｕイオン及び／又はＺｎイオンの濃度の上限値は、特に限定されず、環境基準などに応じて適宜設定すればよい。 When the moderately water-soluble glass according to the embodiment of the present invention is used as a growth inhibitor or repellent for mosquito larvae, the concentration of Cu ions and/or Zn ions in water is 0.5 ppm or more, preferably 1.0 ppm or more, more preferably is preferably 2.0 ppm or more. By setting the concentration of Cu ions and/or Zn ions to 0.5 ppm or more, it is possible to obtain the effect of suppressing or repelling the growth of mosquito larvae. In particular, when the concentration of Cu ions and/or Zn ions is 2.0 ppm or more, mosquito larvae hardly grow.
Note that the upper limit of the concentration of Cu ions and/or Zn ions is not particularly limited, and may be appropriately set according to environmental standards and the like.
　本発明の実施形態に係る緩水溶性ガラスは、公知のガラスの製造方法と同様にして製造することができる。すなわち、本発明の実施形態に係る緩水溶性ガラスは、上記の成分を所定の含有量となるように配合し、高温で加熱して溶融させた後、溶融物を所定の形状（例えば、板状）に成形し、冷却することによって製造することができる。なお、溶融物を所定の型枠に流し込んで冷却することによって、所定の形状に成形してもよい。また、緩水溶性ガラスを成形材料やコーティング材料などの原料に用いる場合には、得られた緩水溶性ガラスを粉砕して粉末状とすればよい。 The moderately water-soluble glass according to the embodiment of the present invention can be produced in the same manner as known glass production methods. That is, the moderately water-soluble glass according to the embodiment of the present invention is prepared by blending the above components so as to have a predetermined content, heating at a high temperature to melt, and then shaping the melt into a predetermined shape (for example, a plate shape) and cooled. Alternatively, the melt may be formed into a predetermined shape by pouring it into a predetermined mold and cooling it. In addition, when the moderately water-soluble glass is used as a raw material for a molding material, a coating material, or the like, the obtained moderately water-soluble glass may be pulverized into powder.
　本発明の実施形態に係る緩水溶性ガラス製品は、上記の緩水溶性ガラスを備える。この緩水溶性ガラス製品は、上記の緩水溶性ガラスを備えているため、ＣｕイオンやＺｎイオンを長期間にわたって溶出することができる。したがって、この緩水溶性ガラス製品は、ＣｕイオンやＺｎイオンによる効果（例えば、ボウフラなどの害虫や、苔類、藻類などの成長抑制又は忌避効果、抗菌効果、抗ウィルス効果）を長期間にわたって得ることが可能である。 A moderately water-soluble glass product according to an embodiment of the present invention comprises the above-described moderately water-soluble glass. Since this moderately water-soluble glass product includes the aforementioned moderately water-soluble glass, Cu ions and Zn ions can be eluted over a long period of time. Therefore, this moderately water-soluble glass product can obtain the effects of Cu ions and Zn ions (for example, the growth inhibition or repelling effect against pests such as mosquito larvae, mosses, algae, etc., antibacterial effects, and antiviral effects) over a long period of time. It is possible.
　本発明の実施形態に係る緩水溶性ガラス製品の例としては、基材と、基材の表面に形成されたコーティング層とを備え、コーティング層が上記の緩水溶性ガラスを含むコーティング製品である。コーティング製品において、緩水溶性ガラスはコーティング層中に分散して存在していることが好ましい。基材としては、特に限定されず、金属、樹脂などから形成されるものを用いることができる。
　また、本発明の実施形態に係る緩水溶性ガラス製品の別の例としては、上記の緩水溶性ガラスを含む樹脂成形品である。樹脂成形品において、緩水溶性ガラスは樹脂中に分散して存在していることが好ましい。 An example of the moderately water-soluble glass product according to the embodiment of the present invention is a coated product comprising a base material and a coating layer formed on the surface of the base material, the coating layer containing the above-described moderately water-soluble glass. . In the coated product, the moderately water-soluble glass is preferably dispersed in the coating layer. The base material is not particularly limited, and those formed from metal, resin, or the like can be used.
Another example of the moderately water-soluble glass product according to the embodiment of the present invention is a resin molded product containing the moderately water-soluble glass. In the resin molded article, the moderately water-soluble glass is preferably dispersed in the resin.
　上記のような緩水溶性ガラス製品は、緩水溶性ガラスを含む組成物を用いて製造することができる。例えば、コーティング製品は、緩水溶性ガラスを含む組成物をコーティング材料として用い、基材をコーティング材料で被覆することによって製造することができる。また、樹脂成形品は、緩水溶性ガラスを含む組成物を成形材料として用い、成形材料を所定の形状に成形することによって製造することができる。 A moderately water-soluble glass product such as the one described above can be produced using a composition containing a moderately water-soluble glass. For example, a coated product can be produced by using a composition containing a sparingly soluble glass as a coating material and coating a substrate with the coating material. Also, a resin molded article can be produced by using a composition containing a moderately water-soluble glass as a molding material and molding the molding material into a predetermined shape.
　コーティング材料として用いられる組成物は、緩水溶性ガラス以外に、コーティング材料に用いられる公知の成分（例えば、樹脂成分、溶剤、無機成分など）を含むことができる。
　成形材料として用いられる組成物は、緩水溶性ガラス以外に、成形材料に用いられる公知の成分（例えば、樹脂成分、無機成分など）を含むことができる。 A composition used as a coating material can contain known components used for coating materials (for example, resin components, solvents, inorganic components, etc.) in addition to the moderately water-soluble glass.
The composition used as the molding material can contain known components used in molding materials (for example, resin components, inorganic components, etc.) in addition to the moderately water-soluble glass.
　本発明の実施形態に係る水質改善方法は、上記の緩水溶性ガラス又は上記の緩水溶性ガラス製品を水に浸漬し、Ｃｕイオン及びＺｎイオンから選択される少なくとも一種のイオンを水に溶出させる。この方法によれば、Ｃｕイオン及び／又はＺｎイオンの溶出によって、ボウフラなどの害虫や、苔類、藻類などの成長抑制又は忌避効果を得ることができるため、水質を改善することが可能となる。 A method for improving water quality according to an embodiment of the present invention includes immersing the above-described moderately water-soluble glass or the above-described moderately water-soluble glass product in water to elute at least one type of ion selected from Cu ions and Zn ions into the water. . According to this method, the elution of Cu ions and/or Zn ions makes it possible to obtain the effect of suppressing or repelling the growth of pests such as mosquito larvae, mosses, algae, etc., so that it is possible to improve water quality. .
　水におけるＣｕイオン及び／又はＺｎイオンの溶出濃度は、特に限定されないが、０．５ｐｐｍ以上、好ましくは１．０ｐｐｍ以上、より好ましくは２．０ｐｐｍ以上であることが好ましい。Ｃｕイオン及び／又はＺｎイオンの溶出濃度を０．５ｐｐｍ以上とすることにより、上記の効果を得ることができる。なお、Ｃｕイオン及び／又はＺｎイオンの溶出濃度の上限値は、特に限定されず、環境基準などに応じて適宜設定すればよい。 The elution concentration of Cu ions and/or Zn ions in water is not particularly limited, but is preferably 0.5 ppm or more, preferably 1.0 ppm or more, and more preferably 2.0 ppm or more. By setting the elution concentration of Cu ions and/or Zn ions to 0.5 ppm or more, the above effect can be obtained. The upper limit of the elution concentration of Cu ions and/or Zn ions is not particularly limited, and may be appropriately set according to environmental standards and the like.
　水に対する上記の緩水溶性ガラス又は上記の緩水溶性ガラス製品の投入量は、特に限定されず、所定のＣｕイオン及び／又はＺｎイオンの溶出濃度を長期間にわたって維持できるように水の量に応じて適宜設定すればよい。 The amount of the moderately water-soluble glass or the moderately water-soluble glass product added to water is not particularly limited, and the amount of water is adjusted so as to maintain a predetermined elution concentration of Cu ions and/or Zn ions for a long period of time. It may be set as appropriate.
　以下、本発明を実施例によって更に具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited by these examples.
　表１に示す組成となるように各原料を秤量して均一に攪拌混合し、この混合物を１３００～１４５０℃で２～３時間加熱して溶融させた後、溶融物を板状に成形し、冷却することによって板状サンプルを得た。なお、試験Ｎｏ．９、１０、１３及び１４のサンプルはガラス化せずに結晶化してしまったのに対し、その他の試験のサンプルはガラス化した。このようにして得られた板状サンプルについて、以下の評価を行った。 Each raw material was weighed so as to have the composition shown in Table 1 and was uniformly stirred and mixed, and the mixture was heated at 1300 to 1450 ° C. for 2 to 3 hours to melt, and then the melt was formed into a plate shape, Plate-like samples were obtained by cooling. In addition, test No. Samples 9, 10, 13 and 14 crystallized rather than vitrified, while the samples of the other tests vitrified. The plate-like samples thus obtained were evaluated as follows.
＜比重＞
　比重計（アルファーミラージュ株式会社製ＭＤ－２００Ｓ）を用いて比重を測定した。 <Specific gravity>
The specific gravity was measured using a hydrometer (MD-200S manufactured by Alpha Mirage Co., Ltd.).
＜溶解試験＞
　溶解試験として、上記した通常試験及び加速試験を行った。
（１）通常試験
　通常試験は、１ｃｍ×１ｃｍ×０．５ｃｍのガラスを２０℃の蒸留水１００ｍＬに１２時間浸漬した。この通常試験の評価において、ガラスが完全に溶解しなかったものを〇、ガラスが完全に溶解したものを×と表す。ガラスが完全に溶解したか否かは、目視観察によって行った。
（２）加速試験
　板状サンプルを粉砕した後、篩を用いて粒子径１．４～２．０ｍｍのガラス粒子に紛級し、その質量（加速試験前のガラスの質量）を測定した。次に、紛級したガラス粒子を９０℃の蒸留水１００ｍＬに５時間浸漬した後、目開き０．５ｍｍの篩を用いて篩分けした。篩に残ったガラス粒子は、蒸留水を用いて十分に洗浄した。次に、篩に残ったガラス粒子を乾燥させ、その質量（加速試験後のガラスの質量）を測定した。そして、上記した式によってガラスの質量減少率を求めた。この加速試験の評価において、ガラスの質量減少率が２％以上のものを〇、ガラスの質量減少率が２％未満であったものを×と表す。
　上記の各評価結果を表１に示す。 <Dissolution test>
As the dissolution test, the normal test and the accelerated test described above were performed.
(1) Ordinary Test In the ordinary test, a 1 cm×1 cm×0.5 cm glass was immersed in 100 mL of distilled water at 20° C. for 12 hours. In the evaluation of this ordinary test, ◯ indicates that the glass was not completely dissolved, and x indicates that the glass was completely dissolved. Whether or not the glass was completely melted was visually observed.
(2) Accelerated Test After pulverizing the plate-shaped sample, it was ground using a sieve into glass particles having a particle diameter of 1.4 to 2.0 mm, and the mass (mass of the glass before the accelerated test) was measured. Next, the ground glass particles were immersed in 100 mL of distilled water at 90° C. for 5 hours, and then sieved using a sieve with an opening of 0.5 mm. Glass particles remaining on the sieve were thoroughly washed with distilled water. Next, the glass particles remaining on the sieve were dried, and the mass (mass of the glass after the acceleration test) was measured. Then, the mass reduction rate of the glass was determined by the above formula. In the evaluation of this accelerated test, ◯ means that the mass reduction rate of the glass is 2% or more, and × means that the mass reduction rate of the glass is less than 2%.
Table 1 shows the above evaluation results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示されるように、試験Ｎｏ．２～８、１５、１９～２１及び２３～２４（本発明例）のサンプルは、溶解試験の結果から緩水溶性ガラスであり、所定量のＣｕＯ及び／又はＺｎＯを含有している。したがって、これらのサンプルは、ガラスが水に緩やかに溶解するにつれてＣｕイオン及び／又はＺｎイオンを徐々に溶出することができる。
　これに対して、試験Ｎｏ．１、１６及び１７（比較例）のサンプルは、溶解（通常）試験の結果から水溶性ガラスである。したがって、これらのサンプルは、ガラスが水に直ぐに溶解してしまい、Ｃｕイオン及び／又はＺｎイオンを徐々に溶出することができない。
　また、試験Ｎｏ．１１、１２、１８及び２２（比較例）のサンプルは、溶解（加速）試験の結果から難水溶性ガラスである。したがって、これらのサンプルは、ガラスが水に溶解し難く、Ｃｕイオン及び／又はＺｎイオンを徐々に溶出することができない。
　なお、試験Ｎｏ．９、１０、１３及び１４（比較例）のサンプルは、ガラス化せずに結晶化したため、水に溶解しないと考えられる。したがって、これらのサンプルは、Ｃｕイオン及び／又はＺｎイオンを徐々に溶出することができない。 As shown in Table 1, test no. Samples 2 to 8, 15, 19 to 21 and 23 to 24 (inventive examples) are mildly water-soluble glasses according to the dissolution test results, and contain a predetermined amount of CuO and/or ZnO. Therefore, these samples can slowly elute Cu and/or Zn ions as the glass slowly dissolves in water.
On the other hand, Test No. Samples 1, 16 and 17 (comparative) are water soluble glasses from the dissolution (normal) test results. Therefore, in these samples, the glass immediately dissolves in water, and Cu ions and/or Zn ions cannot be gradually eluted.
Also, test no. Samples 11, 12, 18 and 22 (comparative examples) are poorly water-soluble glasses from the results of the dissolution (acceleration) test. Therefore, in these samples, the glass is difficult to dissolve in water, and Cu ions and/or Zn ions cannot be gradually eluted.
In addition, test No. Samples 9, 10, 13 and 14 (comparative examples) crystallized without vitrification, and are therefore considered insoluble in water. Therefore, these samples cannot gradually elute Cu ions and/or Zn ions.
　以上の結果からわかるように、本発明によれば、ＣｕイオンやＺｎイオンを長期間にわたって溶出可能な緩水溶性ガラス、緩水溶性ガラス製品及び水質改善方法を提供することができる。また、本発明によれば、上記の特徴を有する緩水溶性ガラス製品を製造可能な組成物を提供することができる。 As can be seen from the above results, according to the present invention, it is possible to provide a slowly water-soluble glass, a slowly water-soluble glass product, and a method for improving water quality that can elute Cu ions and Zn ions over a long period of time. Further, according to the present invention, it is possible to provide a composition capable of producing a moderately water-soluble glass product having the above characteristics.

Claims (9)

  1. 　４０．０～７５．０モル％のＳｉＯ2と、５．０～３８．０モル％のＫ2Ｏと、０．１～３３．０モル％の、ＣｕＯ及びＺｎＯから選択される少なくとも一種と、２８．０モル％以下のＲ’Ｏ（Ｒ’はアルカリ土類金属である）とを含む緩水溶性ガラス。 40.0 to 75.0 mol% of SiO 2 , 5.0 to 38.0 mol% of K 2 O, and 0.1 to 33.0 mol% of at least one selected from CuO and ZnO , R′O (R′ is an alkaline earth metal) up to 28.0 mol %.
  2. 　３５．０モル％以下のＲ2Ｏ（Ｒは、Ｋ以外のアルカリ金属である）、３０．０モル％以下のＡｌ2Ｏ3から選択される少なくとも一種を更に含む、請求項１に記載の緩水溶性ガラス。 2. The method according to claim 1, further comprising at least one selected from 35.0 mol% or less of R2O (R is an alkali metal other than K) and 30.0 mol% or less of Al2O3 . Slightly water-soluble glass.
  3. 　Ｂ2Ｏ3及びＰ2Ｏ5から選択される少なくとも一種を含まない、請求項１又は２に記載の緩水溶性ガラス。 3. The moderately water-soluble glass according to claim 1, which does not contain at least one selected from B2O3 and P2O5.
  4. 　比重が２．４以上である、請求項１～３のいずれか一項に記載の緩水溶性ガラス。 The moderately water-soluble glass according to any one of claims 1 to 3, which has a specific gravity of 2.4 or more.
  5. 　害虫、苔類、藻類の成長抑制剤若しくは忌避剤、抗菌剤、又は抗ウィルス剤に用いられる、請求項１～４のいずれか一項に記載の緩水溶性ガラス。 The moderately water-soluble glass according to any one of claims 1 to 4, which is used as a growth inhibitor or repellent for pests, mosses, and algae, an antibacterial agent, or an antiviral agent.
  6. 　請求項１～５のいずれか一項に記載の緩水溶性ガラスを備える緩水溶性ガラス製品。 A slow water-soluble glass product comprising the slow water-soluble glass according to any one of claims 1 to 5.
  7. 　請求項１～５のいずれか一項に記載の緩水溶性ガラスを含む組成物。 A composition containing the moderately water-soluble glass according to any one of claims 1 to 5.
  8. 　成形材料又はコーティング材料である、請求項７に記載の組成物。 The composition according to claim 7, which is a molding material or coating material.
  9. 　請求項１～５のいずれか一項に記載の緩水溶性ガラス又は請求項６に記載の緩水溶性ガラス製品を水に浸漬し、Ｃｕイオン及びＺｎイオンから選択される少なくとも一種のイオンを前記水に溶出させる水質改善方法。 The moderately water-soluble glass according to any one of claims 1 to 5 or the moderately water-soluble glass product according to claim 6 is immersed in water, and at least one ion selected from Cu ions and Zn ions is added to the A method for improving water quality by eluting into water.
PCT/JP2022/004749 2021-03-22 2022-02-07 Moderately water-soluble glass, moderately water-soluble glass product, composition, and water quality improvement method WO2022201919A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-047821 2021-03-22
JP2021047821A JP2022146713A (en) 2021-03-22 2021-03-22 Moderately water-soluble glass, moderately water-soluble glass product, composition, and water quality improvement method

Publications (1)

Publication Number Publication Date
WO2022201919A1 true WO2022201919A1 (en) 2022-09-29

Family

ID=83395507

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/004749 WO2022201919A1 (en) 2021-03-22 2022-02-07 Moderately water-soluble glass, moderately water-soluble glass product, composition, and water quality improvement method

Country Status (2)

Country Link
JP (1) JP2022146713A (en)
WO (1) WO2022201919A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08245237A (en) * 1995-03-09 1996-09-24 Nippon Sheet Glass Co Ltd Composition for antibacterial glass
JP2006052918A (en) * 2004-08-16 2006-02-23 Toagosei Co Ltd Microorganism growth preventive method
JP2006520311A (en) * 2003-02-25 2006-09-07 ショット アクチエンゲゼルシャフト Antimicrobial action borosilicate glass
JP2014005194A (en) * 2012-06-01 2014-01-16 Ishizuka Glass Co Ltd Antibacterial glass and manufacturing method of the same
JP2015078085A (en) * 2013-10-16 2015-04-23 株式会社イチキコーポレーション Water soluble glass composition and water treatment method for improving water quality
JP2015124098A (en) * 2013-12-25 2015-07-06 旭硝子株式会社 Production method for antimicrobial glass, and antimicrobial glass

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08245237A (en) * 1995-03-09 1996-09-24 Nippon Sheet Glass Co Ltd Composition for antibacterial glass
JP2006520311A (en) * 2003-02-25 2006-09-07 ショット アクチエンゲゼルシャフト Antimicrobial action borosilicate glass
JP2006052918A (en) * 2004-08-16 2006-02-23 Toagosei Co Ltd Microorganism growth preventive method
JP2014005194A (en) * 2012-06-01 2014-01-16 Ishizuka Glass Co Ltd Antibacterial glass and manufacturing method of the same
JP2015078085A (en) * 2013-10-16 2015-04-23 株式会社イチキコーポレーション Water soluble glass composition and water treatment method for improving water quality
JP2015124098A (en) * 2013-12-25 2015-07-06 旭硝子株式会社 Production method for antimicrobial glass, and antimicrobial glass

Also Published As

Publication number Publication date
JP2022146713A (en) 2022-10-05

Similar Documents

Publication Publication Date Title
US6939820B2 (en) Antibacterial glass composition and antibacterial polymer composition using the same
JP5845209B2 (en) Antibacterial glass and method for producing antibacterial glass
JPH03146436A (en) Antimicrobial glass
JP2001247336A (en) Glass composition for imparting antimicrobial properties, antimicrobial polymer composite material using the same and formed bodies of antimicrobial polymer composite material
JP2000053451A (en) Antibacterial glass product and its production
DE10244783A1 (en) Apparatus for melting highly pure, aggressive or high melting point glass or glass ceramic comprises crucible, around which electromagnetic coil is wound, fitted with mixer or homogenizing device
WO2022201919A1 (en) Moderately water-soluble glass, moderately water-soluble glass product, composition, and water quality improvement method
JPH06191875A (en) Phosphate glass of alkaline metal and copper
JP2002037643A (en) Antimicrobial glass and its resin components
JP4874492B2 (en) Glass composition and glass-forming material containing the composition
JP2001247337A (en) Glass composition for imparting antimicrobial properties, antimicrobial polymer composite material using the same and formed bodies of antimicrobial polymer composite material
JP2000302478A (en) Microbicidal glass and polystyrene resin composition containing the same
US20230031976A1 (en) Antibacterial glass composition and method for preparing same
JP2001247726A (en) Glass composition for imparting antifungal property, and antifungal polymeric composite material
JPS63221175A (en) Coating wall and spraying material having mildewproofing and antibacterial performance
JP3271888B2 (en) Antibacterial polycarbonate resin products
JPH11236241A (en) Antibacterial crystallized glass beads for building material
JP2826984B2 (en) Antibacterial / antifungal / algaeproofing agent for cement admixture and hydraulic cement composition using the same
JP2002160937A (en) Low temperature-meltable glass
KR102549169B1 (en) Antibacterial glass powder and method of manufacturing thereof and domestic appliance including the same
JP4368966B2 (en) Dissolvable glass composition for adding resin moldings having antibacterial properties and resin moldings using the same
JP5170814B2 (en) Antifungal glass and resin composition thereof
JP3251376B2 (en) Antibacterial and antifungal agent and its manufacturing method
JPH10218641A (en) Antimicrobial and antifungal glass and resin composition containing the same glass
JP2004203774A (en) Repellant composition, repelling coating material and repelling method using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22774720

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22774720

Country of ref document: EP

Kind code of ref document: A1