WO2022044962A1 - Composition durcissable pour matériau antimicrobien et antiviral, matériau antimicrobien et antiviral, et stratifié antimicrobien et antiviral - Google Patents

Composition durcissable pour matériau antimicrobien et antiviral, matériau antimicrobien et antiviral, et stratifié antimicrobien et antiviral Download PDF

Info

Publication number
WO2022044962A1
WO2022044962A1 PCT/JP2021/030397 JP2021030397W WO2022044962A1 WO 2022044962 A1 WO2022044962 A1 WO 2022044962A1 JP 2021030397 W JP2021030397 W JP 2021030397W WO 2022044962 A1 WO2022044962 A1 WO 2022044962A1
Authority
WO
WIPO (PCT)
Prior art keywords
bismuth
antiviral
bis
antibacterial
curable composition
Prior art date
Application number
PCT/JP2021/030397
Other languages
English (en)
Japanese (ja)
Inventor
剛美 川▲崎▼
潤二 百田
Original Assignee
株式会社トクヤマ
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 株式会社トクヤマ filed Critical 株式会社トクヤマ
Priority to JP2022544521A priority Critical patent/JPWO2022044962A1/ja
Publication of WO2022044962A1 publication Critical patent/WO2022044962A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile

Definitions

  • the present invention relates to an antibacterial / antiviral material curable composition containing a bismuth compound, an antibacterial / antiviral material obtained by curing the composition, and an antibacterial / antiviral laminate containing the antibacterial / antiviral material.
  • infectious diseases are caused by a chain of spreads by airborne infection, droplet infection, contact transmission, and oral infection.
  • the surface of a substance that an unspecified number of people come into contact with originally has a function of inactivating bacteria and viruses adsorbed there. This provides a safe living environment without regular or appropriate disinfection and can break the chain of further infections.
  • Patent Document 1 slaked lime and fresh lime (for example, slaked lime and fresh lime ().
  • Patent Document 2 methods using quaternary ammonium salts (see Patent Document 2) have been proposed.
  • Japanese Patent No. 3802272 Japanese Unexamined Patent Publication No. 2020-7267 Japanese Patent Application Laid-Open No. 2003-275601 Japanese Unexamined Patent Publication No. 2019-44096
  • a coating agent is used to impart antibacterial and antiviral properties to the internal channels and chamber surface. It is necessary to modify the inner surface by circulating it inside, but it may be difficult to treat due to its viscosity and wettability. Further, if only the surface is modified, there is a problem in durability such that the active layer disappears due to abrasion.
  • an antibacterial / antiviral material that does not bleed out, can be used as a highly durable structural material having high mechanical properties, and can also have transparency. And.
  • bismuth which has been generally considered to exhibit antibacterial activity in the bright light because its oxide has photocatalytic activity
  • bismuth ion is called bismuth ion.
  • Werner-type metal complex composed of a specific organic ligand, it was found that it exhibits not only antibacterial properties but also antiviral properties in a solid state, and further, curability of the compound and a polymerizable monomer.
  • the cured product obtained by curing the composition has high mechanical properties and transparency while exhibiting high antibacterial and antiviral properties even in a dark place, and have completed the present invention.
  • the first aspect of the present invention is for an antibacterial / antiviral material containing a bismuth compound in which a phosphate ester having a (meth) acryloyl group is bonded to bismuth and a polymerizable monomer other than the bismuth compound. It is a curable composition.
  • the second aspect of the present invention is an antibacterial / antiviral material obtained by curing the curable composition.
  • the third aspect of the present invention is an antibacterial / antiviral laminated body obtained by laminating a base material and the antibacterial / antiviral material.
  • an antibacterial / antiviral material that does not bleed out, can be used as a highly durable structural material having high mechanical properties, and can further have transparency. ..
  • the notation "x to y" using the numerical values x and y means “x or more and y or less”.
  • the unit shall be applied to the numerical value x as well.
  • the term “(meth) acryloyl” means both “acryloyl” and “methacrylic acid”
  • the term “(meth) acrylic acid” means “acrylic acid” and “methacrylic acid”. It means both "acid”.
  • poly (thio) urethane means both “polyurethane” and “polythiourethane”
  • iso (thio) cyanate means “isocyanate” and It means both “isothiocyanate”.
  • the curable composition for an antibacterial / antiviral material according to the present embodiment is a bismuth compound in which a phosphate ester having a (meth) acryloyl group is bound to bismuth (hereinafter, bismuth). , Also referred to as "phosphate ester-bonded bismuth compound”) and a polymerizable monomer other than the phosphate ester-bonded bismuth compound.
  • the phosphate ester-bonded bismuth compound is a compound in which a phosphate ester having a (meth) acryloyl group (hereinafter, also simply referred to as “phosphate ester”) is bound to bismuth. Since the compound has high solubility, particularly solubility in a solution-like radically polymerizable monomer, a high concentration of bismuth can be contained in the cured product, and the physical properties of the cured product can be improved.
  • This phosphate ester-bonded bismuth compound has higher solubility in a radically polymerizable monomer than the bismuth subsalicylate described later.
  • the bond form between bismuth and the phosphate ester having a (meth) acryloyl group is not particularly limited, and may be either an ionic bond or a coordination bond.
  • Examples of the phosphoric acid ester-bonded bismuth compound include those in which the phosphoric acid ester is formed from a phosphoric acid monoester having one (meth) acryloyl group (for example, 2- (methacryloyloxy) ethyl phosphate dihydrogen). , (Meta) Phosphate diesters having two acryloyl groups (eg, hydrogen phosphate bis [2- (methacryloyloxy) ethyl]).
  • the phosphoric acid ester may be formed from only one of a phosphoric acid monoester having one (meth) acryloyl group and a phosphoric acid diester having two (meth) acryloyl groups, and is formed from both. It may be one.
  • the phosphoric acid ester When the phosphoric acid ester is formed from a phosphoric acid monoester having one (meth) acryloyl group and a phosphoric acid diester having two (meth) acryloyl groups, it has solubility in a radically polymerizable monomer. In order to improve and suppress the aggregation of the bismuth component, the following ratio is preferable. Specifically, 1 mol of a phosphate monoester derived from a phosphate monoester having one (meth) acryloyl group and 0.05 to 3 mol of a phosphate ester derived from a phosphate diester having two (meth) acryloyl groups. It is preferable that it consists of.
  • the phosphoric acid ester derived from the phosphoric acid diester is more preferably 0.1 to 2 mol, further preferably 0.15 to 1 mol.
  • the advantage of including both one having one (meth) acryloyl group and one having two (meth) acryloyl groups is that bismuth has one (meth) acryloyl group (divalent phosphate).
  • Those having a group) and those having two (meth) acryloyl groups (those having a monovalent phosphate group) have a suitable site to be bonded, and the suitable site to which the group is bonded is (meth) acryloyl.
  • the phosphoric acid ester derived from the one having two (meth) acryloyl groups is present in a ratio of 0.05 to 3 mol with respect to 1 mol of the phosphoric acid ester derived from the one having one group. Be done. Further, the presence of two (meth) acryloyl groups in the above ratio reduces the bismuth concentration but improves the solubility in the radically polymerizable monomer. As a result, there is an advantage that the bismuth component can be present in the cured product in a well-balanced and high concentration.
  • the phosphate ester-bound bismuth compound may be bound to other compounds as long as the phosphate ester is bound.
  • salicylic acid and / or (meth) acrylic acid may be further bonded.
  • the phosphate ester and salicylic acid and / or (meth) acrylic acid are bound to the same bismuth, the phosphate ester and salicylic acid and / or are used to improve the solubility in radically polymerizable monomers.
  • the ratio of (meth) acrylic acid to 1 mol of phosphoric acid ester is preferably 0.1 to 10 mol, and 0.1 to 5 mol of salicylic acid and / or (meth) acrylic acid. Is more preferable.
  • the above range is based on the total number of moles of the phosphoric acid esters.
  • the phosphate ester-bonded bismuth compound is a compound in which a phosphate ester having a (meth) acryloyl group is bonded to bismuth, and its production method, IR, NMR (nuclear magnetic resonance spectroscopy), MALDI-TOF-MS. (Matrix-assisted laser desorption / ionization-time-of-flight mass analysis), elemental analysis using an energy-dispersed X-ray spectrometer (EDS), etc., confirm that the phosphate ester having a (meth) acryloyl group is bound. ..
  • the number of bonds of phosphoric acid ester, salicylic acid, and (meth) acrylic acid can be known by these methods.
  • Suitable phosphoric acid ester-bonded bismuth compounds include those represented by the following formulas (1) to (3).
  • R independently represents a hydrogen atom or a methyl group.
  • a + x + y + z 3
  • x is the number of moles of 2-((meth) acryloyloxy) ethyl residue of hydrogen phosphate
  • y is phenyl-2- ((meth) acryloyloxy) phosphate.
  • the number of moles of ethyl residues, z is the number of moles of bis [2-((meth) acryloyloxy) ethyl] residues
  • a is the number of moles of (meth) acrylic acid residues.
  • the phosphate ester-bonded bismuth compounds represented by the above formulas (1) to (3) may not be a single compound but a mixture of a plurality of compounds. In that case, the number of moles of each residue described above shall indicate the number of moles of the mixture as a whole.
  • a compound in which bismuth subsalicylate and phenyl-2-((meth) acryloyloxy) ethyl hydrogen phosphate are bonded is contained.
  • the content of the phosphoric acid ester-bonded bismuth compound is, for example, preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on the total amount of the curable composition according to the present embodiment. , 15-85% by mass, more preferably.
  • the curable composition according to the present embodiment may contain a phosphoric acid compound or an unreacted raw material produced as a by-product during the production of the phosphoric acid ester-bonded bismuth compound, in addition to the phosphoric acid ester-bonded bismuth compound.
  • Examples of the phosphoric acid compound produced as a by-product during production include a dimer of a phosphoric acid monoester having one (meth) acryloyl group, a dimer of a phosphoric acid diester having two (meth) acryloyl groups, and bismuth salicylate. Alternatively, an ester of (meth) bismuth acrylate and phosphoric acid can be mentioned.
  • Examples of the unreacted raw material include a phosphoric acid monoester having one (meth) acryloyl group, a phosphoric acid diester having two (meth) acryloyl groups, bismuth salicylate, and bismuth (meth) acrylic acid.
  • the curable composition according to the present embodiment preferably contains these by-produced phosphoric acid compounds and unreacted raw materials because it contributes to the improvement of solubility in the monomer.
  • the curable composition according to the present embodiment is, for example, a compound in which bismuth oxide is bonded to a phosphoric acid ester having a (meth) acryloyl group, (meth) acrylic acid, and / or salicylic acid (hereinafter, “oxidation”). It may also contain "a compound derived from bismuth”). Although the structure of the compound derived from bismuth oxide is not clear, it is considered that the hydroxyl group formed on the surface of bismuth oxide is bonded to the carboxy group of phosphate ester, (meth) acrylic acid, or salicylic acid. It should be noted that this compound derived from bismuth oxide is very difficult to separate from the phosphate ester-bonded bismuth compound.
  • a compound derived from bismuth oxide when by-produced, it is preferable to use it in a state containing the compound derived from bismuth oxide.
  • a compound derived from bismuth oxide is produced as a by-product, it is desirable to adjust the production conditions and the like so that the amount thereof is within a range that does not reduce the solubility of the phosphate ester-bonded bismuth compound.
  • the inclusion of the compound derived from bismuth oxide can be comprehensively determined by the production conditions thereof or a method such as IR, NMR, X-ray photoelectron spectroscopy (XPS) or the like.
  • the phosphate ester-bonded bismuth compound is preferably produced by reacting, for example, bismuth (meth) acrylate or bismuth subsalicylate with a phosphate ester having a (meth) acryloyl group. More specifically, in an aliphatic hydrocarbon solvent or an aromatic solvent, a polymerization inhibitor is added as necessary to add bismuth (meth) acrylate or bismuth subsalicylate and a phosphate ester having a (meth) acryloyl group. It is preferable to produce a phosphate ester-bonded bismuth compound by reacting with and dehydrating.
  • Bismuth (meth) acrylate is a compound in which salicylic acid is bound to bismuth.
  • the bismuth subsalicylate is a compound in which salicylic acid is bound to bismuth and is represented by the following formula (4).
  • the (meth) bismuth acrylate and the bismuth subsalicylate are not particularly limited and can be produced by a known method, or commercially available ones can also be used.
  • the phosphoric acid ester having a (meth) acryloyl group a commercially available one can be used.
  • the phosphoric acid ester may be a phosphoric acid ester having one (meth) acryloyl group (hereinafter, also referred to as "monofunctional phosphoric acid ester”), or a phosphoric acid ester having two (meth) acryloyl groups. (Hereinafter, it may also be referred to as "bifunctional phosphoric acid ester").
  • Examples of the monofunctional phosphoric acid ester include 2- (methacryloyloxy) ethyl dihydrogen phosphate and diphenyl-2-methacryloyloxyethyl phosphate.
  • Examples of the bifunctional phosphate ester include hydrogen phosphate bis [2- (methacryloyloxy) ethyl] and hydrogen phenylphosphate [2- (methacryloyloxy) ethyl]. Of course, a mixture of monofunctional phosphate and bifunctional phosphate may be used in the reaction.
  • the amount of the phosphate ester used may be determined so that the desired phosphate ester-bonded bismuth compound can be obtained. Specifically, the amount of the phosphoric acid ester used is preferably in the range of 0.3 to 10 mol with respect to 1 mol of the total of bismuth (meth) acrylate and bismuth subsalicylate.
  • diphenyl-2-methacryloyloxyethyl phosphate and phenylbis [2- (methacryloyloxyethyl)] phosphate are used as phosphoric acid esters having a (meth) acryloyl group.
  • Tris [2- (methacryloyloxyethyl)] phosphate and the like may be further added.
  • the amount of the phosphoric acid triester used is 0.1 to 20 mol with respect to a total of 1 mol of the phosphoric acid ester having one (meth) acryloyl group and the phosphoric acid ester having two (meth) acryloyl groups. It is preferably 0.2 to 5 mol, and more preferably 0.2 to 5 mol.
  • [Aliphatic hydrocarbon solvent and aromatic solvent] it is preferable to stir and mix the (meth) bismuth acrylate or the bismuth subsalicylate and the phosphoric acid ester in an aliphatic hydrocarbon solvent or an aromatic solvent to react. At that time, water is generated in the reaction system, and it is preferable to dehydrate the generated water. In order to facilitate dehydration of the generated water, it is preferable to use an aliphatic hydrocarbon solvent or an aromatic solvent having a high boiling point, specifically, a boiling point of 100 ° C. or higher. It is also possible to mix an aliphatic hydrocarbon solvent and an aromatic solvent and use it as a mixed solution.
  • aliphatic hydrocarbon solvent or aromatic solvent examples include hexane, heptane, nonane, decane, undecane, dodecane, xylene, dimethoxybenzene, benzene, toluene, chlorobenzene, bromobenzene, anisole, petroleum ether, petroleum benzine, benzoin and the like. Can be mentioned.
  • the amount of the aliphatic hydrocarbon solvent or aromatic solvent used is not particularly limited as long as the amount of (meth) bismuth acrylate or bismuth subsalicylate and the phosphate ester can be sufficiently mixed.
  • the ratio of the total of the aliphatic hydrocarbon solvent and the aromatic solvent is 5 to 100 mL with respect to the total of 1 g of the (meth) bismuth acrylate and the bismuth subsalicylate. It is preferable to use in.
  • the method for reacting bismuth (meth) acrylic acid or bismuth subsalicylate with a phosphoric acid ester is not particularly limited.
  • bismuth hyposalicylate diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed and a phosphoric acid ester diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed are put together in the reaction system. It is possible to adopt a method of adding to and stirring and mixing to react.
  • an aliphatic hydrocarbon solvent or an aromatic solvent is introduced into the reaction system in advance, and the following bismuth salicylate diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as necessary, and fat as necessary.
  • the bismuth subsalicylate is dissolved or dispersed in an aliphatic hydrocarbon solvent or an aromatic solvent.
  • the bismuth subsalicylate may not be dissolved, but in that case, it is preferable to pulverize the bismuth subsalicylate with an ultrasonic device or the like so that the bismuth subsalicylate does not exist. Then, the phosphate ester is added to the solution in which bismuth salicylate is dissolved or the cloudy solution in which the bismuth salicylate is dissolved, and the mixture is stirred and mixed to react.
  • the reaction temperature may be the reflux temperature of the aliphatic hydrocarbon solvent or the aromatic solvent, but is preferably 30 to 150 ° C., more preferably in order to further reduce the coloring of the obtained phosphoric acid ester-bonded bismuth compound. Is preferably carried out at 40 to 140 ° C, more preferably 45 to 120 ° C.
  • reaction temperature is 30 to 110 ° C.
  • pressure inside the reaction system it is preferable to reduce the pressure inside the reaction system in order to remove (dehydrate) the water generated in the reaction system.
  • bismuth subsalicylate and a phosphoric acid ester can be mixed and dehydrated, or both can be mixed and then dehydrated.
  • the reaction time is not particularly limited and may be usually 1 to 6 hours.
  • the atmosphere at the time of carrying out the reaction may be any of an air atmosphere, an inert gas atmosphere, and a dry air atmosphere in consideration of operability, and the reaction may be carried out in an air atmosphere in consideration of operability. preferable.
  • the obtained phosphate ester-bonded bismuth compound is concentrated by distilling off the solvent, and if there is an insoluble turbid component, it should be separated by filtration or centrifugation. Is desirable. Further, it is desirable to add a solvent that is soluble in the reaction solvent used and does not dissolve the phosphate ester-bonded bismuth compound to the concentrated reaction solution obtained by this treatment, and perform reprecipitation for purification. If the high boiling point solvent remains, the above decantation operation may be repeated to replace the solvent. Then, the remaining solvent is distilled off and vacuum dried to obtain a phosphate ester-bonded bismuth compound.
  • the polymerizable monomer other than the phosphate ester-bonded bismuth compound may be only a radically polymerizable monomer that can be copolymerized with the phosphate ester-bonded bismuth compound, or a radically polymerizable monomer and a non-radical. It may be a mixture with a polymerizable monomer.
  • the non-radical polymerizable monomer include an addition-polymerizable monomer and a ring-opening polymerizable monomer.
  • the total content of the polymerizable monomer other than the phosphoric acid ester-bonded bismuth compound is based on 100 parts by mass of the phosphoric acid ester-bonded bismuth compound from the viewpoints of antibacterial / antiviral property, mechanical properties, transparency, coloring and the like. It is preferably 1 to 10000 parts by mass, more preferably 5 to 5000 parts by mass, and even more preferably 10 to 1000 parts by mass. Within this range, it becomes easy to have both mechanical strength as a structural material and light transmission as a transparent material while exhibiting sufficient antibacterial and antiviral properties.
  • the radically polymerizable monomer is not particularly limited, but it is preferable to use a monofunctional radically polymerizable monomer having one radically polymerizable carbon-carbon double bond.
  • Examples of the monofunctional radically polymerizable monomer include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, acrylonitrile, methacrylonitrile, and styrene.
  • Examples thereof include divinylbenzene and its structural isomer, methylstyrene and its structural isomer, methoxystyrene and its structural isomer, chlorostyrene, bromostyrene, vinylpyridine, vinylpyrrolidone and the like.
  • the blending amount of styrene is determined from the viewpoints of solubility in phosphate ester-bonded bismuth compound, viscosity after mixing, impact resistance of the cured product after curing, hardness, thermal properties, etc.
  • the amount is preferably 1 to 500 parts by mass, more preferably 2 to 400 parts by mass, and further preferably 3 to 300 parts by mass with respect to 100 parts by mass of acrylonitrile.
  • a polyfunctional radical having two or more radically polymerizable carbon-carbon double bonds in order to further improve the mechanical properties of the cured product after curing, for example, impact resistance. It is more preferable to use the polymerizable monomer together.
  • polyfunctional radically polymerizable monomers can be used without limitation.
  • those represented by the following formula (5) or (6) are preferably used in consideration of the solubility in the phosphate ester-bonded bismuth compound, the viscosity after mixing, the impact resistance of the cured product after curing, and the like. Will be done.
  • the blending amount of the polyfunctional radically polymerizable monomer is preferably 0 to 500 parts by mass, more preferably 0 to 400 parts by mass with respect to 100 parts by mass of the monofunctional radically polymerizable monomer. It is preferably 0 to 300 parts by mass, and more preferably 0 to 300 parts by mass.
  • the content of the radically polymerizable monomer in the curable composition according to the present embodiment is preferably 5 to 2000 parts by mass with respect to 100 parts by mass of the phosphoric acid ester-bonded bismuth compound, and is preferably 10 to 900 parts by mass. Is more preferable, and 15 to 600 parts by mass is further preferable.
  • an addition-polymerizable monomer that produces a cured product by addition polymerization may be used together with the radically polymerizable monomer.
  • addition polymerization refers to those in which there are no small molecules to be eliminated when two types of functional groups react to form a new bond.
  • a urethane bond is formed, and from the two molecules, one new molecule having a molecular weight obtained by adding the respective molecular weights is generated.
  • an intermolecular bond due to the reaction is formed between the plurality of molecules to become a macromolecule, and as a result, the molecule is cured.
  • This is polyurethane.
  • a thiol group is used instead of a hydroxyl group, it is polythiourethane, and when an amino group is used, it is polyurea.
  • the one particularly preferable is the addition polymerization which becomes poly (thio) urethane or polyurea.
  • the above-mentioned mixture of the phosphate ester-bonded bismuth compound and the radically polymerizable monomer becomes a cured product by radical polymerization, but when the polymerizable monomer that causes addition polymerization exists at the same time and causes different polymerization, both of them.
  • the polymer chains of the above are independent as chemical bonds, but as molecular chains, they are entangled with each other to form a mutually penetrating cured product.
  • This mutual intrusive hardened body may be in a state of being woven like a bamboo basket and may have strong resistance to external stress, which contributes to the improvement of the mechanical properties of the hardened body.
  • a catalyst such as a tin compound is usually required, but the bismuth contained in the phosphate ester-bonded bismuth compound functions as it is. Therefore, in the present embodiment, it is not necessary to add a catalyst separately, but if necessary, known catalysts may be used in combination without any limitation.
  • Poly (thio) urethane polymerizable monomer To obtain polyurethane, two types of poly (thio) urethane polymerizable monomers, that is, a polyfunctional iso (thio) cyanate monomer and a polyfunctional hydroxyl group-containing monomer or a polyfunctional thiol group-containing monomer are used. Is used. In order to obtain a higher molecular weight polyurethane, it is necessary to make the number of moles of the iso (thio) cyanate group contained and the total number of moles of the hydroxyl group or the thiol group as equal as possible.
  • a polyfunctional iso (thio) cyanate compound is a compound having at least two isocyanate groups and / or isothiocyanate groups in one molecule. Among them, a compound having 2 to 6 iso (thio) cyanate groups in the molecule is preferable, a compound having 2 to 4 is more preferable, and a compound having 2 to 3 is further preferable.
  • the polyfunctional iso (thio) cyanate compound has a bifunctional iso (thio) cyanate compound having two isocyanate groups and / or isothiocyanate groups in one molecule, and two active hydrogen-containing groups in one molecule. It may be a urethane prepolymer having an isothiocyanate group at both ends, which is produced by a reaction with a functionally active hydrogen-containing compound.
  • the urethane prepolymer one containing two or more unreacted isocyanate groups or isothiocyanate groups can be used without any limitation, and a urethane prepolymer containing two or more isocyanate groups is preferable.
  • the active hydrogen-containing group is a group selected from a hydroxyl group, a thiol group, and an amino group.
  • Polyfunctional iso (thio) cyanate compounds can be classified into aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, isothiocyanates, other isocyanates, and urethane prepolymers.
  • the polyfunctional iso (thio) cyanate compound one kind of compound may be used, or a plurality of kinds of compounds may be used. When a plurality of types of compounds are used, the reference mass is the total amount of the plurality of types of compounds.
  • aliphatic isocyanate examples include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate.
  • alicyclic isocyanate examples include isophorone diisocyanate, (bicyclo [2.2.1] heptane-2,5-diyl) bismethylene diisocyanate, and (bicyclo [2.2.1] heptane-2,6-diyl).
  • aromatic isocyanate examples include xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylenediphenyl-4,4'-diisocyanate, 4-chlor-m-xylylene diisocyanate.
  • isothiocyanate examples include bifunctional isothiocyanates such as p-phenylenedi isothiocyanate, xylylene-1,4-diisothiocyanate, and ethylidine diisothiocyanate.
  • Examples of other isocyanates include polyfunctional isocyanates having a bullet structure, a uretdione structure, and an isocyanurate structure using diisocyanates such as hexamethylene diisocyanate and trimethylolocyanate as main raw materials (for example, Japanese Patent Application Laid-Open No. 2004-534870).
  • a method for modifying the bullet structure, uretdione structure, and isocyanurate structure of an aliphatic polyisocyanate is disclosed); a polyfunctional adduct with a trifunctional or higher functional polyol such as trimethylolpropane; etc. (See “Keiji Iwata ed., Polyurethane Resin Handbook, Nikkan Kogyo Shimbun (1987)", etc.).
  • the polyfunctional hydroxyl group-containing monomer is a compound having at least two hydroxyl groups in one molecule.
  • Polyfunctional hydroxyl group-containing monomers can be classified into aliphatic alcohols, alicyclic alcohols, aromatic alcohols, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and polyacrylic polyols.
  • Examples of the aliphatic alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7-dihydroxyheptane, and 1,8-dihydroxyoctane.
  • 1,9-Dihydroxynonane 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glyceryl monooleate, monoeridine, polyethylene glycol, 3-methyl-1, Bifunctional polyols such as 5-dihydroxypentane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, 2-methyl-1,3-dihydroxypropane; glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, Trimethylolpropane Tripolyoxyethylene ether (for example, TMP-30, TMP-60, TMP-90, etc.
  • Examples of the alicyclic alcohol include hydrogenated bisphenol A, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, and tricyclo [5,2,1,02].
  • aromatic alcohol examples include dihydroxynaphthalene, dihydroxybenzene, bisphenol A, bisphenol F, xylylene glycol, tetrabrom bisphenol A, bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl) ethane.
  • 1,2-bis (4-hydroxyphenyl) ethane bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,1- Bis (4-hydroxyphenyl) -1-phenylethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-Bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4) -Hyl
  • polyester polyol examples include compounds obtained by a condensation reaction between a polyol and a polybasic acid. Among them, those having a number average molecular weight of 400 to 2000 are preferable, those having a number average molecular weight of 500 to 1500 are more preferable, and those having a number average molecular weight of 600 to 1200 are further preferable. Those having hydroxyl groups (two in the molecule) only at both ends of the molecule correspond to the above-mentioned bifunctional active hydrogen-containing compound constituting the urethane prepolymer.
  • polyether polyol examples include a compound obtained by ring-opening polymerization of an alkylene oxide or a reaction between a compound having two or more active hydrogen-containing groups in the molecule and an alkylene oxide, and a modified product thereof.
  • those having a number average molecular weight of 400 to 2000 are preferable, those having a number average molecular weight of 500 to 1500 are more preferable, and those having a number average molecular weight of 600 to 1200 are further preferable.
  • Those having hydroxyl groups (two in the molecule) only at both ends of the molecule correspond to the above-mentioned bifunctional active hydrogen-containing compound constituting the urethane prepolymer.
  • Examples of the polycaprolactone polyol include a compound obtained by ring-opening polymerization of ⁇ -caprolactone. Among them, those having a number average molecular weight of 400 to 2000 are preferable, those having a number average molecular weight of 500 to 1500 are more preferable, and those having a number average molecular weight of 600 to 1200 are further preferable. Those having hydroxyl groups (two in the molecule) only at both ends of the molecule correspond to the above-mentioned bifunctional active hydrogen-containing compound constituting the urethane prepolymer.
  • polycarbonate polyol examples include a compound obtained by phosgenating one or more kinds of low molecular weight polyols, or a compound obtained by transesterifying with ethylene carbonate, diethyl carbonate, diphenyl carbonate or the like. Among them, those having a number average molecular weight of 400 to 2000 are preferable, those having a number average molecular weight of 500 to 1500 are more preferable, and those having a number average molecular weight of 600 to 1200 are further preferable. Those having hydroxyl groups (two in the molecule) only at both ends of the molecule correspond to the above-mentioned bifunctional active hydrogen-containing compound constituting the urethane prepolymer.
  • polyacrylic polyol examples include a (meth) acrylic acid ester and a polyol compound obtained by polymerizing a vinyl monomer. Those having hydroxyl groups (two in the molecule) only at both ends of the molecule correspond to the above-mentioned bifunctional active hydrogen-containing compound constituting the urethane prepolymer.
  • the polyfunctional thiol group-containing monomer is a compound having at least two thiol groups in one molecule.
  • polyfunctional thiol group-containing monomer for example, those described in International Publication No. 2015/068798 can be used.
  • Preferred are tetraethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercaptopropionate), 1,6-hexanediol bis (3-mercaptopropionate), and the like.
  • Bifunctional polyols such as 1,4-bis (mercaptopropylthiomethyl) benzene; trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakiss (3) -Mercaptopropionate), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 2,2-bis (mercaptomethyl) -1,4-butanedithiol, 2,5-bis ( Mercaptomethyl) -1,4-dithian, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3- Tetrakiss (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane,
  • Polyurea polymerizable monomer In order to obtain polyurea, two kinds of polyurea polymerizable monomers, that is, the above-mentioned polyfunctional iso (thio) cyanate monomer and polyfunctional amino group monomer are used.
  • the polyfunctional amino group monomer is not particularly limited as long as it is a compound having two or more primary and / or secondary amino groups in one molecule.
  • Polyfunctional amino group-containing monomers can be classified into aliphatic amines, alicyclic amines, and aromatic amines.
  • aliphatic amine examples include bifunctional amines such as ethylenediamine, hexamethylenediamine, nonamethylenediamine, undecanemethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, and putresin; and polyamines such as diethylenetriamine. Polyfunctional amines; and the like.
  • alicyclic amine examples include bifunctional amines such as isophorone diamine and cyclohexyl diamine.
  • aromatic amine examples include 4,4'-methylenebis (o-chloroaniline) (MOCA), 2,6-dichloro-p-phenylenediamine, 4,4'-methylenebis (2,3-dichloroaniline), and the like.
  • a ring-opening polymerizable monomer that produces a cured product by ring-opening polymerization may be used together with the radically polymerizable monomer.
  • cyclic compounds such as cyclic ether, cyclic siloxane, cyclic lactone, cyclic lactam, cyclic acetal, cyclic amine, cyclic carbonate, cyclic imino ether, and cyclic thiocarbonate can be used as the ring-opening polymerizable monomer. .. Further, if necessary, a catalyst for ring-opening polymerization may be added.
  • cyclic ether examples include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, oxetane, and 3-methyloxetane.
  • examples thereof include 3,3-dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran and 3-methyltetrahydrofuran.
  • cyclic lactone examples include 4-membered ring lactones such as ⁇ -propiolactone, ⁇ -methylpropiolactone, and L-serine- ⁇ -lactone; ⁇ -butyrolactone, ⁇ -hexanolactone, and ⁇ -heptanolactone.
  • cyclic lactam examples include 4-membered ring lactams such as 4-benzoyloxy-2-azetidinone; ⁇ -butyrolactam, 2-azabicyclo (2,2,1) hepta-5-en-3-one, 5-methyl-.
  • 5-membered ring lactam such as 2-pyrrolidone
  • 6-membered ring lactam such as 2-piperidone-3-carboxylate ethyl
  • 7-membered ring lactam such as ⁇ -caprolactam and DL- ⁇ -amino- ⁇ -caprolactam
  • ⁇ -heptalactam Eight-membered ring lactam etc.
  • cyclic carbonate examples include ethylene carbonate, propylene carbonate, 1,2-butyleneglycerol carbonate-1,2-carbonate, 4- (methoxymethyl) -1,3-dioxolane-2-one, and (chloromethyl) ethylene carbonate.
  • the content of the non-radical polymerizable monomer such as the addition polymerizable monomer and the ring-opening polymerizable monomer in the curable composition according to the present embodiment is 100 parts by mass of the phosphate ester-bonded bismuth compound. , 0 to 5000 parts by mass, more preferably 0 to 1000 parts by mass, and even more preferably 0 to 500 parts by mass.
  • the curable composition according to the present embodiment may contain a known compounding agent other than the above, as long as the effect of the present invention is not impaired.
  • a compounding agent include a radical polymerization initiator, an antioxidant, a stabilizer, a mold release agent for improving mold releasability, a chain transfer agent for controlling the polymerizable property of radical polymerization, and a solvent.
  • examples include pigments.
  • each compounding agent is preferably 0 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, and 0.02 to 15 parts by mass with respect to 100 parts by mass of the curable composition. It is more preferable to be a part.
  • the curable composition according to the present embodiment can be produced by mixing the above-mentioned components by a known method.
  • the antibacterial / antiviral material according to the present embodiment is obtained by curing the curable composition according to the present embodiment.
  • This antibacterial / antiviral material has high mechanical strength and transparency while exhibiting high antibacterial and antiviral properties.
  • the method for curing the curable composition according to the present embodiment is not particularly limited, and known polymerization methods such as photopolymerization and thermal polymerization can be adopted.
  • the curable composition according to the present embodiment contains a non-radical polymerizable monomer, a method of polymerizing the non-radical polymerizable monomer is adopted.
  • the antibacterial / antiviral laminate according to the present embodiment is formed by laminating a base material and an antibacterial / antiviral material according to the present embodiment.
  • the base material include resin, metal, wood and the like, and resin is preferable.
  • the method for producing the antibacterial / antiviral laminate according to the present embodiment is not particularly limited as long as the base material and the antibacterial / antiviral material can be laminated.
  • a method is preferable in which the curable composition according to the present embodiment is applied to the surface of an arbitrary substrate by spin coating, dipping or the like, and then the curable composition is cured by UV irradiation, heating or the like. This makes it possible to impart antibacterial and antiviral properties to the surface of any substrate.
  • another layer may be provided so that the antibacterial / antiviral material is the outermost layer.
  • another layer may be provided between the base material and the cured product obtained by curing the curable composition according to the present embodiment.
  • the antibacterial / antiviral material and the antibacterial / antiviral laminate according to the present embodiment show high antibacterial and antiviral properties, and can be used as structural materials, transparent materials, and the like.
  • the analysis method and measurement method in this example are as follows.
  • MALDI-TOF-MS Measurement
  • a rapiflex TOF / TOF type manufactured by Bruker was used.
  • CHCA ⁇ -cyano-4-hydroxycinnamic acid
  • DIT ditranol
  • DHB 2,5-dihydroxybenzoic acid
  • the measurement was performed in the Reflector / Positive mode, and the mass range was m / z 20 to 4000.
  • ⁇ Viscosity measurement of curable composition The viscosity of the curable composition was measured at 25 ° C. using an E-type viscometer (Rheometer RST, manufactured by Brookfield).
  • the sample plate (7 cm ⁇ , 2 mm) was wiped with absolute ethanol.
  • the surface was inoculated with 0.1 mL of Staphylococcus aureus (NBRC 12732) having a concentration of 2.8 ⁇ 10 6 cfu / mL, and the viable cell count was measured 8 hours later.
  • the antibacterial property is evaluated as a comparison before and after the antibacterial treatment when the sample surface is treated with antibacterial treatment, but in this test, the viable cell count after 8 hours is simply below the detection limit.
  • the antibacterial property was evaluated based on whether or not it became. Specifically, if no viable bacteria can be detected, it has antibacterial properties, and if even a small amount of viable bacteria can be detected, it has no antibacterial properties.
  • Antiviral performance evaluation test using virus An antiviral performance evaluation test using a virus was carried out using a separately prepared 2 mm-thick laminated body or cured body. The measurement was performed according to JIS R 1706: 2020 (ultraviolet light responsive photocatalyst, antiviral, film adhesion method). However, this test was conducted in a dark place.
  • the sample plate (7 cm ⁇ , 2 mm) was wiped with absolute ethanol.
  • 150 ⁇ L of Influenza A virus (H3N2) A / HongKong / 8/68 strain (influenza A virus, ATCC VR-1679) at a concentration of 1.6 ⁇ 10 7 cfu / mL was inoculated on this surface, and the active virus was introduced after 4 hours. The number was measured.
  • MDCK cells ATCC CCL-34) were used as host cells.
  • JIS R 1706: 2020 the antiviral property is evaluated as a comparison before and after the antiviral treatment when the sample surface is treated with the antiviral treatment, but in this test, the number of active viruses after 4 hours is simply calculated. The antiviral property was evaluated based on whether or not it was below the detection limit. Specifically, if no active virus can be detected, it has antiviral properties, and if even a small amount of active virus can be detected, it has no antiviral properties.
  • the impact resistance test was performed according to the US FDA standard ball drop test. From a height of 50 inches (1.27 m), 4.5 g, 6.9 g, 14 g, 16.3 g, 32 g, 50 g, 67 g, 80 g, 95 g, 112 g, 130 g, 151 g, 174 g, 198 g, 225 g, 261 g. The steel balls were dropped freely in sequence and applied to the sample plate, and the weight immediately before cracks and cracks were taken as the maximum impact resistance.
  • the obtained cloudy solution was transferred to a 1000 mL four-necked flask equipped with a Dean-Stark trap, and the reaction was carried out while heating and stirring at 130 ° C. using an oil bath, and the generated water was removed from the system.
  • the reaction end point was defined as the time when no water was produced.
  • a pale yellow scattering solution was obtained with a slight pale yellow precipitate.
  • This solution was concentrated to 250 mL by vacuum evaporator. After adding 8 g of radiolite # 100, which is a fired diatomaceous earth product, and allowing it to stand overnight, suction filtration was performed with 5B filter paper. To the obtained pale yellow scattering filtrate, 3 g of activated carbon (Darco G60 manufactured by Norit) was added, and the mixture was centrifuged at 23830 ⁇ g for 8 hours. The centrifugal supernatant was pressure-filtered with a membrane filter having a pore size of 0.2 ⁇ m to obtain a pale yellow transparent filtrate. The solvent was distilled off from this solution by a vacuum evaporator and redissolved in 250 mL of acetone.
  • radiolite # 100 which is a fired diatomaceous earth product
  • the generated white precipitate was collected by suction filtration using 5B filter paper, and the obtained solid was vacuum-dried to obtain 64.40 g of a phosphate ester-bonded bismuth compound as a white powder.
  • the synthesis was confirmed by the above 1 H-NMR measurement method.
  • Example 1 A cured product obtained by curing a curable composition containing a phosphate ester-bonded bismuth compound and a radically polymerizable monomer> Phosphorus ester-bonded bismuth compound: 70 parts by mass, styrene: 9 parts by mass, acrylonitrile: 9 parts by mass, nonaethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 12 parts by mass was added to uniformly dissolve and cure. A sex composition was obtained. To 100 parts by mass of this curable composition, 2,2'-azobis (isobutyric acid): 0.4 parts by mass was added and dissolved. The viscosity of the obtained curable composition was 380 mPa ⁇ s, which was a viscosity suitable for mass polymerization by casting.
  • this curable composition was placed under reduced pressure by a vacuum pump to remove dissolved oxygen. Then, the curable composition was poured between two disk glass molds having a diameter of 7 cm, which were adjusted so as to form a gap having a thickness of 2 mm and fixed with an adhesive tape, and polymerized at a maximum temperature of 90 ° C. for 4 hours. went. After release from the mold, annealing was performed at 100 ° C. for 2 hours to obtain a pale yellow transparent cured product. The thickness of the obtained cured product was 2.03 mm. The cured product was subjected to antibacterial / antiviral test, optical property test, and impact resistance test. The results are shown in Table 1.
  • Example 2 A cured product obtained by curing a curable composition containing a phosphate ester-bonded bismuth compound, a radically polymerizable monomer, and a polyurethane polymerizable monomer> Phosphoric acid ester-bonded bismuth compound: 70 parts by mass, styrene: 3.7 parts by mass, acrylonitrile: 13.7 parts by mass, hexamethylene diisocyanate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 4 parts by mass, polyethylene glycol (molecular weight 300) : Wako Pure Chemical Industries, Ltd.): 7 parts by mass was added and uniformly dissolved to obtain a curable composition.
  • Phosphoric acid ester-bonded bismuth compound 70 parts by mass
  • styrene 3.7 parts by mass
  • acrylonitrile 13.7 parts by mass
  • hexamethylene diisocyanate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • this curable composition was placed under reduced pressure by a vacuum pump to remove dissolved oxygen. Then, this curable composition was poured between two disk glass molds having a diameter of 7 cm using a 2 mm gasket, and polymerization was carried out at a maximum temperature of 100 ° C. for 4 hours. After release from the mold, annealing was performed at 100 ° C. for 2 hours to obtain a dark yellow transparent cured product. The thickness of the obtained cured product was 2.44 mm. The cured product was subjected to antibacterial / antiviral test, optical property test, and impact resistance test. The results are shown in Table 1.
  • ⁇ Comparative Example 1 A cured product obtained by curing a curable composition that does not contain a phosphate ester-bonded bismuth compound> Styrene: 30 parts by mass, acrylonitrile: 30 parts by mass, nonaethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 40 parts by mass were added and uniformly dissolved to obtain a curable composition. To 100 parts by mass of this curable composition, 2,2'-azobis (isobutyric acid): 0.4 parts by mass was added and dissolved. The viscosity of the obtained curable composition was 90 mPa ⁇ s.
  • this curable composition was placed under reduced pressure by a vacuum pump to remove dissolved oxygen. Then, this curable composition was poured between two disk glass molds having a diameter of 7 cm, which were adjusted so as to form a gap having a thickness of 2 mm and fixed with an adhesive tape, and polymerized at a maximum temperature of 90 ° C. for 4 hours. went. After release from the mold, annealing was performed at 100 ° C. for 2 hours to obtain a pale yellow transparent cured product. The thickness of the obtained cured product was 2.01 mm. The cured product was subjected to antibacterial / antiviral test, optical property test, and impact resistance test. The results are shown in Table 1.
  • Example 3 A laminate having a cured product obtained by curing a curable composition containing a phosphate ester-bonded bismuth compound and a radically polymerizable monomer> Bismuth compound: 30 parts by mass, styrene: 24 parts by mass, acrylonitrile: 19 parts by mass, nonaethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 27 parts by mass is added and uniformly dissolved to form a curable composition.
  • Bismuth compound 30 parts by mass
  • styrene 24 parts by mass
  • acrylonitrile 19 parts by mass
  • nonaethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • the cured products of Examples 1 and 2 obtained by curing a curable composition containing a phosphoric acid ester-bonded bismuth compound and a radically polymerizable monomer, and Example 3 having the cured product thereof.
  • the laminate had high mechanical strength and transparency while exhibiting high antibacterial and antiviral properties.
  • the cured product of Example 2 obtained by curing the curable composition containing an addition-polymerizable monomer in addition to the radically polymerizable monomer was remarkably excellent in mechanical strength.
  • the cured product of Comparative Example 1 in which the curable composition containing no phosphate ester-bonded bismuth compound was cured did not show antibacterial and antiviral properties.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une composition durcissable qui est destinée à un matériau antimicrobien et antiviral, et qui contient un composé de bismuth dans lequel un ester d'acide phosphorique ayant un groupe (méth)acryloyle est lié au bismuth, et un monomère polymérisable autre que le composé de bismuth ; un matériau antimicrobien et antiviral obtenu par durcissement de la composition durcissable ; et un stratifié antimicrobien et antiviral obtenu par stratification d'un substrat et du matériau antimicrobien et antiviral ensemble.
PCT/JP2021/030397 2020-08-27 2021-08-19 Composition durcissable pour matériau antimicrobien et antiviral, matériau antimicrobien et antiviral, et stratifié antimicrobien et antiviral WO2022044962A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022544521A JPWO2022044962A1 (fr) 2020-08-27 2021-08-19

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-143643 2020-08-27
JP2020143643 2020-08-27

Publications (1)

Publication Number Publication Date
WO2022044962A1 true WO2022044962A1 (fr) 2022-03-03

Family

ID=80355114

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/030397 WO2022044962A1 (fr) 2020-08-27 2021-08-19 Composition durcissable pour matériau antimicrobien et antiviral, matériau antimicrobien et antiviral, et stratifié antimicrobien et antiviral

Country Status (3)

Country Link
JP (1) JPWO2022044962A1 (fr)
TW (1) TW202208000A (fr)
WO (1) WO2022044962A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6372768A (ja) * 1986-09-16 1988-04-02 Nippon Paint Co Ltd 防汚塗料
JPH11335487A (ja) * 1998-05-22 1999-12-07 Kuraray Co Ltd 抗菌・抗カビ性を有する有機重合体
WO2007105355A1 (fr) * 2006-02-23 2007-09-20 Mitsui Chemicals, Inc. Agent de demoulage interne pour la production d'un materiau optique polythiourethane
JP2010235553A (ja) * 2009-03-31 2010-10-21 Kuraray Medical Inc リン酸エステル化合物及びそれを含む重合性組成物
JP2012087070A (ja) * 2010-10-15 2012-05-10 Tokuyama Dental Corp 重合性単量体
WO2019177084A1 (fr) * 2018-03-16 2019-09-19 株式会社トクヤマ Composé de bismuth, composition durcissable et produit durci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6372768A (ja) * 1986-09-16 1988-04-02 Nippon Paint Co Ltd 防汚塗料
JPH11335487A (ja) * 1998-05-22 1999-12-07 Kuraray Co Ltd 抗菌・抗カビ性を有する有機重合体
WO2007105355A1 (fr) * 2006-02-23 2007-09-20 Mitsui Chemicals, Inc. Agent de demoulage interne pour la production d'un materiau optique polythiourethane
JP2010235553A (ja) * 2009-03-31 2010-10-21 Kuraray Medical Inc リン酸エステル化合物及びそれを含む重合性組成物
JP2012087070A (ja) * 2010-10-15 2012-05-10 Tokuyama Dental Corp 重合性単量体
WO2019177084A1 (fr) * 2018-03-16 2019-09-19 株式会社トクヤマ Composé de bismuth, composition durcissable et produit durci

Also Published As

Publication number Publication date
TW202208000A (zh) 2022-03-01
JPWO2022044962A1 (fr) 2022-03-03

Similar Documents

Publication Publication Date Title
US11059969B2 (en) Polymer compositions and methods
KR101970115B1 (ko) 자일릴렌 다이아이소사이아네이트 조성물, 자일릴렌 다이아이소사이아네이트 변성체 조성물, 이액형 수지 원료 및 수지
KR20190077322A (ko) 폴리로탁산을 사용한 우레탄 수지 및 연마용 패드
WO2017039019A1 (fr) Composition d'apprêt et corps en couches photochromique
JP7352540B2 (ja) 低水分量ポリロタキサンモノマー、および該モノマーを含む硬化性組成物
WO2019198675A1 (fr) Résine d'uréthane utilisant un polyrotaxane, et tampon à polir
WO2020032056A1 (fr) Composition durcissable contenant un monomère de polypseudorotaxane
TWI695041B (zh) 活性能量線硬化性聚合物組成物、使用其之硬化膜、及具有前述硬化膜之層合體
WO2018164194A1 (fr) Composition polymérisable et corps moulé
WO2022044962A1 (fr) Composition durcissable pour matériau antimicrobien et antiviral, matériau antimicrobien et antiviral, et stratifié antimicrobien et antiviral
WO2022030531A1 (fr) Composition durcissable, et corps durci associé
JP2022043679A (ja) フォトクロミック組成物
KR20120109052A (ko) 카다놀 유도체의 고분자 도막 형성방법 및 이를 통하여 제조된 도막
WO2022158348A1 (fr) Composition de résine, stratifié optique, article optique, lentilles et lunettes
EP4286434A1 (fr) Nouvelles particules creuses et fines comprenant une résine à base de mélamine
JP7219022B2 (ja) 水分散型ポリイソシアネート
WO2023012000A1 (fr) Composition de résine à double durcissement comprenant un composé contenant des uretdiones et son utilisation en impression 3d
EP4380990A1 (fr) Composition de résine à double durcissement comprenant un composé contenant des uretdiones et son utilisation en impression 3d
JP2015143291A (ja) ポリイソシアネート組成物
Eom Photopolymerizations of multicomponent epoxide and acrylate/epoxide hybrid systems for controlled kinetics and enhanced material properties
CN116745333A (zh) 由三聚氰胺系树脂形成的新型的微小中空颗粒

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: 21861390

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022544521

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21861390

Country of ref document: EP

Kind code of ref document: A1