WO2022044962A1

WO2022044962A1 - Curable composition for antimicrobial and antiviral material, antimicrobial and antiviral material, and antimicrobial and antiviral laminate

Info

Publication number: WO2022044962A1
Application number: PCT/JP2021/030397
Authority: WO
Inventors: 剛美川▲崎▼; 潤二百田
Original assignee: 株式会社トクヤマ
Priority date: 2020-08-27
Filing date: 2021-08-19
Publication date: 2022-03-03
Also published as: JPWO2022044962A1; TW202208000A

Abstract

Provided are: a curable composition that is for an antimicrobial and antiviral material, and that contains a bismuth compound in which a phosphoric acid ester having a (meth)acryloyl group is bonded to bismuth, and a polymerizable monomer other than the bismuth compound; an antimicrobial and antiviral material obtained by curing the curable composition; and an antimicrobial and antiviral laminate obtained by layering a substrate and the antimicrobial and antiviral material together.

Description

Curing compositions for antibacterial / antiviral materials, antibacterial / antiviral materials, and antibacterial / antiviral laminates

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.

It is said that the plague that was prevalent from the 14th century to the 15th century halved the population of China, and in some countries it was reduced to 20%. Even in modern times, the influenza virus pandemic that occurred between 1918 and 1920 was called the Spanish flu, and one-third of the world's population of just under 2 billion at that time was infected, with 20 to 1 million people. It is estimated that 100 million people have died. Infectious diseases caused by such bacteria or viruses still pose a threat to humankind.

In recent years, SARS (Severe Acute Respiratory Syndrome) in 2002, MERS (Middle East Respiratory Syndrome) in 2013, etc. have been infected only in a relatively limited area, but Ebola hemorrhagic fever in 2014 is a multilateral pandemic. It became. In addition, COVID-19, a new coronavirus infection originating in China at the end of 2019, has finally caused a global pandemic.

These infectious diseases are caused by a chain of spreads by airborne infection, droplet infection, contact transmission, and oral infection.

Of these, in order to prevent contact infection, it is necessary to sufficiently disinfect the surface of various tools, utensils, furniture, etc. that humans come into contact with with bacteria and viruses, but once a pandemic occurs, it is for disinfection. Drugs and equipment will be exhausted from the market, and it will be difficult to obtain them, including alternatives. In COVID-19, an epidemiological survey on the cruise ship where the spread of the infection occurred revealed that contact infection was one of the major causes of the infection explosion. At first, many became difficult to obtain.

In order to overcome such a situation, it is desirable that 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.

For this purpose, resin materials used as many structural materials are blended with antibacterial or antiviral agents exhibiting antibacterial or antiviral properties, for example, slaked lime and fresh lime (for example, slaked lime and fresh lime (). Patent Document 1) and methods using quaternary ammonium salts (see Patent Document 2) have been proposed.

In addition, by using the photocatalytic activity of metal oxides such as titanium oxide (see Patent Document 3) and metal salts such as copper (see Patent Document 4) and coating with a paint containing it, the surface of the material is antibacterial. A method of imparting antiviral properties is also known.

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

However, when a large amount of non-polymerizable antibacterial / antiviral agent is added to the resin material, the mechanical properties of the resin material may be deteriorated. In addition, antibacterial and antiviral agents may bleed out on the surface of the resin material, resulting in deterioration of aesthetics and function, and there is room for improvement. In addition, resin materials containing antibacterial and antiviral agents are often opaque and cannot be used where transparency is required.

Also, when the method of coating the surface is used, it is difficult to process the inner surface of a complicated structure. For example, when a measuring instrument having a microchannel, a reaction device, or the like is manufactured by a 3D printer using a radically polymerizable composition, 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.

Further, in the case of an antibacterial / antiviral agent using a photocatalyst, there is a problem that it cannot be used in a dark place or an internal space where light does not reach.

Therefore, it is an object of the present invention to provide 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.

As a result of diligent studies to solve the above problems, the present inventors have found that bismuth, which has been generally considered to exhibit antibacterial activity in the bright light because its oxide has photocatalytic activity, is called bismuth ion. By forming a so-called 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. We have found that 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.

That is, 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.

Further, the third aspect of the present invention is an antibacterial / antiviral laminated body obtained by laminating a base material and the antibacterial / antiviral material.

According to the present invention, it is possible to provide 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. ..

Hereinafter, specific embodiments to which the present invention is applied will be described in detail.
Unless otherwise specified in the present specification, the notation "x to y" using the numerical values x and y means "x or more and y or less". When a unit is attached only to the numerical value y in such a notation, the unit shall be applied to the numerical value x as well.
Further, in the present specification, the term "(meth) acryloyl" means both "acryloyl" and "methacrylic acid", and the term "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". It means both "acid".
Further, in the present specification, the term "poly (thio) urethane" means both "polyurethane" and "polythiourethane", and the term "iso (thio) cyanate" means "isocyanate" and It means both "isothiocyanate".

≪Curable composition for antibacterial and antiviral materials≫
The curable composition for an antibacterial / antiviral material according to the present embodiment (hereinafter, also simply referred to as “curable composition”) 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.

<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.

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. It is considered that this is because 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. Specifically, salicylic acid and / or (meth) acrylic acid may be further bonded. When 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. When two or more kinds of phosphoric acid esters are present, 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. .. In addition, the number of bonds of phosphoric acid ester, salicylic acid, and (meth) acrylic acid can be known by these methods.

Examples of suitable phosphoric acid ester-bonded bismuth compounds include those represented by the following formulas (1) to (3).

In the formula, R independently represents a hydrogen atom or a methyl group. Further, in the above formula (1), a + x + y + z = 3, x is the number of moles of 2-((meth) acryloyloxy) ethyl residue of hydrogen phosphate, and 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, and a is the number of moles of (meth) acrylic acid residues. In the above formula (2), 2b + u + v + w = 3, u is the number of moles of 2-((meth) acryloyloxy) ethyl residue of hydrogen phosphate, and v is phenyl-2-((meth) acryloyloxy) ethyl phosphate. The number of moles of the residue, w is the number of moles of the bis [2-((meth) acryloyloxy) ethyl] residue, and b is the number of moles of the salicylate residue. In the above formula (3), 2c + q + r + 2s + t = 3, q is the number of moles of 2-((meth) acryloyloxy) ethyl residue of hydrogen phosphate, and r is phenyl-2-((meth) acryloyloxy) ethyl phosphate. The number of moles of the residue, s is the number of moles of 2-((meth) acryloyloxy) ethyl phosphate residue, t is the number of moles of bisphosphate phosphate [2-((meth) acryloyloxy) ethyl] residue, c. Indicates the number of moles of salicylic acid residue.

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.

In the above formula (1), considering that it is a phosphate ester-bonded bismuth compound that can be produced at a low temperature and has little coloring, when a = 0, x: y: z = 1: 0.05 to 3 : 0.5 to 30, more preferably x: y: z = 1: 0.1 to 2: 1 to 20, and x: y: z = 1: 0.15 to 1: It is more preferably 1.5 to 10. Further, a = 0 and y = 0 can be set from the viewpoint of reducing the coloring.

Further, in the above formula (1), when a = other than 0, a: (x + y + z) = 0.1 to 10: 1 is preferable, and a: (x + y + z) = 0.1 to 5: 1. It is more preferable, a: (x + y + z) = 0.1 to 1: 1 is more preferable, and a: (x + y + z) = 0.1 to 5: 1 is particularly preferable. Even in this case, x: y: z = 1: 0.05 to 3: 0.5 to 30 is preferable, and x: y: z = 1: 0.1 to 2: 1 to 1. It is more preferably 20 and even more preferably x: y: z = 1: 0.15 to 1: 1.5 to 10.

In the above equation (2), when b = 0, it is the same as in the above regulation, where x is replaced with u, y is replaced with v, and z is replaced with w.

Further, in the above formula (2), when b = other than 0, b: (u + v + w) = 1: 0.1 to 30 is preferable, and b: (u + v + w) = 1: 0.2 to 20. It is more preferable, b: (u + v + w) = 1: 0.3 to 10, and b: (u + v + w) = 1: 0.5 to 5. In this case, u: v: w = 1: 0.05 to 20: 0.1 to 40 is preferable, and u: v: w = 1: 0.1 to 10: 0.2 to 20. It is more preferable that there is u: v: w = 1: 0.2 to 5: 0.4 to 10.

Among them, it is preferable that a compound in which bismuth subsalicylate and phenyl-2-((meth) acryloyloxy) ethyl hydrogen phosphate are bonded is contained.

In the above formula (3), when c = 0, q: r: s: t = 1: 0.1 to 50: 0.05 to 20: 0.1 to 40 is preferable, and q: r: It is more preferable that s: t = 1: 0.3 to 30: 0.1 to 10: 0.2 to 20 and q: r: s: t = 1: 0.5 to 20: 0.2 to 20. It is more preferably 5: 0.4 to 10.

Further, in the above formula (3), when c: other than c = 0, c: (q + s + s + t) = 1: 0.1 to 30 is preferable, and c: (q + s + s + t) = 1: 0.2 to 20. It is more preferable, c: (q + s + s + t) = 1: 0.3 to 10, and c: (q + s + s + t) = 1: 0.5 to 5. Even in this case, q: s: s: t = 1: 0.1 to 50: 0.05 to 20: 0.1 to 40 is preferable, and q: s: s: t = It is more preferably 1: 0.3 to 30: 0.1 to 10: 0.2 to 20, and q: s: s: t = 1: 0.5 to 20: 0.2 to 5: 0. It is more preferably 4 to 10.

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.

It takes a lot of industrial labor to remove the phosphate compound and unreacted raw materials produced as by-products during the production of the phosphoric acid ester-bonded bismuth compound, and these by-produced phosphoric acid compounds and unreacted raw materials are radically polymerizable. 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.

Further, 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. Therefore, when a compound derived from bismuth oxide is by-produced, it is preferable to use it in a state containing the compound derived from bismuth oxide. When 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.

[Method for producing phosphate ester-bonded bismuth compound]
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.

[(Meta) bismuth acrylate and bismuth subsalicylate]
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.

[Phosphate ester having (meth) acryloyl group]
As 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.

Further, in the present embodiment, in order to improve compatibility, 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.

Among them, when a phosphoric acid triester having a phenyl group such as diphenyl-2-methacryloyloxyethyl phosphate or phenylbis [2- (methacryloyloxyethyl)] phosphate is used, the above formulas (1) to (3) can be used. It is possible to satisfactorily introduce a monovalent phenylphosphate diester having one (meth) acryloyl group.

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]
In the present embodiment, 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.

Examples of the aliphatic hydrocarbon solvent or aromatic solvent 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. In particular, considering the productivity of the phosphate ester-bonded bismuth compound, the ratio of the total of the aliphatic hydrocarbon solvent and the aromatic solvent to 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.

[Reaction conditions]
In the present embodiment, the method for reacting bismuth (meth) acrylic acid or bismuth subsalicylate with a phosphoric acid ester is not particularly limited. For example, 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. In addition, 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. It is also possible to adopt a method in which a phosphate ester diluted with a group hydrocarbon solvent or an aromatic solvent is added together, and the mixture is stirred and mixed for reaction. It is also possible to adopt a method in which one component is introduced into the reaction system in advance, the other component is added to the reaction system, and the mixture is stirred and mixed to cause a reaction. Above all, in order to reduce the coloring of the obtained phosphoric acid ester-bonded bismuth compound and improve the productivity, it is preferable to adopt the following method. First, the bismuth subsalicylate is dissolved or dispersed in an aliphatic hydrocarbon solvent or an aromatic solvent. At this time, 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.

Further, when the reaction temperature is 30 to 110 ° C., it is preferable to reduce the pressure inside the reaction system in order to remove (dehydrate) the water generated in the reaction system. At that time, bismuth subsalicylate and a phosphoric acid ester can be mixed and dehydrated, or both can be mixed and then dehydrated. However, considering the efficiency of the reaction, it is preferable to mix the two and then dehydrate while reacting.

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.

After reacting under the above conditions, 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.

<Polymerizable monomer other than phosphate-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. Examples of the non-radical polymerizable monomer include an addition-polymerizable monomer and a ring-opening polymerizable monomer. When radical polymerization and polymerization other than radical polymerization occur at the same time, the obtained cured product becomes an alternating penetration type polymer composite, and the characteristics as a cured product are further improved.

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.

[Radical polymerizable monomer]
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. Among these, it is preferable to use acrylonitrile and / or styrene, and it is more preferable to use both acrylonitrile and styrene, from the viewpoint of solubility, transparency, etc. in the phosphate ester-bonded bismuth compound. When both acrylonitrile and styrene are used, 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.

Further, as the radically polymerizable monomer, 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.

Commercially available polyfunctional radically polymerizable monomers can be used without limitation. Among them, 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.

(In the formula, l indicates an integer of 7 to 14.)

(In the equation, n and m independently represent integers of 1 to 15, and n + m = 2 to 30.)

Further, in consideration of improving the properties such as the surface hardness of the cured product, it is recommended to use the compound represented by the following formula (7) in addition to the compound represented by the above formula (5) or (6). Suitable.

(In the formula, p indicates an integer from 1 to 5.)

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.

[Additionally polymerizable monomer]
In the present embodiment, an addition-polymerizable monomer that produces a cured product by addition polymerization may be used together with the radically polymerizable monomer.

In general, 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. For example, when one molecule of alcohol reacts with one molecule of isothiocyanate, 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. At this time, if there are a plurality of hydroxyl groups or iso (thio) cyanate groups in each of the reacting molecules, 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. When a thiol group is used instead of a hydroxyl group, it is polythiourethane, and when an amino group is used, it is polyurea.

Of the above-mentioned addition polymerizations, 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.

In order to obtain poly (thio) urethane or polyurea, 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.

It is also known that thiols and alkenes cause an addition reaction (en-thiol reaction) under radical generation conditions. By using the radically polymerizable monomer and the polyfunctional thiol group-containing monomer described later, pseudopolymerization by an en-thiol reaction occurs, which contributes to the improvement of the mechanical properties of the cured product.

Hereinafter, the poly (thio) urethane polymerizable monomer used for poly (thio) urethane and the polyurea polymerizable monomer used for polyurea will be described.

[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.

(Polyfunctional iso (thio) cyanate compound)
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. As 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. As 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.

Examples of the aliphatic isocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. , Decamethylene diisocyanate, Buten diisocyanate, 1,3-butadiene-1,4-diisisethylene, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundecamethylene diisocyanate, 1,3,6-trimethyl Hexamethylene diisocyanate, 1,8-diisocyanis-4-isocyanismethyloctane, 2,5,7-trimethyl-1,8-diisocyanis-5-isocyanismethyloctane, bis (isocyanisethyl) carbonate, bis (isocyanisethyl) ether, Bifunctional isocyanates such as 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanis, lysine diisocyanate methyl ester, and 2,4,4, -trimethylhexamethylene diisocyanate can be mentioned.

Examples of the alicyclic isocyanate include isophorone diisocyanate, (bicyclo [2.2.1] heptane-2,5-diyl) bismethylene diisocyanate, and (bicyclo [2.2.1] heptane-2,6-diyl). Bismethylene diisocyanate, 2β, 5α-bis (isocyanate) norbornan, 2β, 5β-bis (isocyanate) norbornan, 2β, 6α-bis (isocyanate) norbornan, 2β, 6β-bis (isocyanate) norbornan, 2,6-di (isocyanate) Isocyanatemethyl) furan, bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, 4,4-isopropylidenebis (cyclohexylisocyanate), cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2' -Dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate-n-butylidene) pentaerythritol, diisocyanate dimerate, 2,5-bis (isocyanatemethyl) -bicyclo [2,2,1] -heptane, 2,6-bis ( Isocyanatemethyl) -bicyclo [2,2,1] -heptane, 3,8-bis (isocyanatemethyl) tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8-bis (isocyanatemethyl) Tricyclodecane, 4,9-bis (isocyanatemethyl) tricyclodecane, 1,5-diisocyanate decalin, 2,7-diisocyanate decalin, 1,4-diisocyanate decalin, 2,6-diisocyanate decalin, bicyclo [4.3] .0] Nonan-3,7-diisocyanate, bicyclo [4.3.0] nonan-4,8-diisocyanate, bicyclo [2.2.1] heptane-2,5-diisocyanate and bicyclo [2.2.1] ] Heptane-2,6-diisocyanate, bicyclo [2,2,2] octane-2,5-diisocyanate, bicyclo [2,2,2] octane-2,6-diisocyanate, tricyclo [5.2.1.02] .6] Bifunctional isocyanates such as decane-3,8-diisocyanate, tricyclo [5.2.1.02.6] decane-4,9-diisocyanate; 2-isocyanatemethyl-3- (3-isocyanatepropyl)- 5-Isocyanate Methyl-bicyclo [2,2,1]- Heptane, 2-isocyanatemethyl-3- (3-isocyanatepropyl) -6-isocyanatemethyl-bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -5-isocyanatemethyl -Vicyclo [2,2,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -6-isocyanatemethyl-bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-3-( 3-Isocyanatepropyl) -5- (2-Isocyanateethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-3- (3-isocyanatepropyl) -6- (2-isocyanateethyl) -bicyclo [2,1,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -5- (2-isocyanateethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatemethyl-2 -(3-Isocyanatepropyl) -6- (2-isocyanateethyl) -bicyclo [2,2,1] -heptane, 1,3,5-polyfunctional isocyanate such as tris (isocyanatemethyl) cyclohexane; and the like. ..

Examples of the aromatic isocyanate include xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylenediphenyl-4,4'-diisocyanate, 4-chlor-m-xylylene diisocyanate. , 4,5-Dichlor-m-xylylene diisocyanate, 2,3,5,6-tetrabrom-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis (Isocyanate ethyl) benzene, bis (isocyanate propyl) benzene, 1,3-bis (α, α-dimethylisocyanatemethyl) benzene, 1,4-bis (α, α-dimethylisocyanatemethyl) benzene, α, α, α ', α'-Tetramethylxylylene diisocyanate, bis (isocyanate butyl) benzene, bis (isocyanate methyl) naphthalin, bis (isocyanate methyl) diphenyl ether, bis (isocyanate ethyl) phthalate, 2,6-di (isocyanate methyl) furan, Phenylene diisocyanate (o-, m-, p-), tolylene diisocyanate, ethyl phenylenedi isocyanate, isopropyl phenylenedi isocyanate, dimethyl phenylenedi isocyanate, diethyl phenylenedi isocyanate, diisopropyl phenylenedi isocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3 5-Triisocyanate Methyl benzene, 1,5-naphthalenediocyanate, Methylnaphthalenedi isocyanate, Biphenyldiisocyanate, 2,4-Torrenji isocyanate, 2,6-Tolylene diisocyanate, 4,4'-Diphenylmethane diisocyanate, 2,2'- Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis (isocyanatephenyl) ethylene, 3,3'-dimethoxybiphenyl- 4,4'-diisocyanate, phenylisocyanate methyl isocyanate, phenylisocyanate ethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diph Enyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofrangisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, 2,4-tolylene diisocyanate , 2,6-Tolylene diisocyanate and other bifunctional isocyanates; mesityrylene triisocyanate, triphenylmethane triisocyanate, polypeptide MDI, naphthalin triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane- Polyfunctional isocyanate compounds such as 4,4', 6-triisocyanate, 4-methyl-diphenylmethane-2,3,4', 5,6-pentaisocyanate; and the like.

Examples of the isothiocyanate 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.).

(Polymer containing polyfunctional hydroxyl group)
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. of Nippon Embroidery Co., Ltd.), butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerytritor, tripentaerythritol , Sorbitol, erythritol, threitol, rivitol, arabinitol, xylitol, aritol, mannitol, dolsitol, imidazole, glycol, inositol, hexanetriol, triglycerol, diglycerol, triethylene glycol and the like.

Examples of the alicyclic alcohol include hydrogenated bisphenol A, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, and tricyclo [5,2,1,02]. , 6] Decane-dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,13,9] dodecanediol, bicyclo [4,3,0] nonanedimethanol , Tricyclo [5,3,1,13,9] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,13,9] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1 Bifunctional polyols such as'-bicyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, o-dihydroxyxylylene; tris (2-hydroxyethyl) Polyfunctional polyols such as isocyanurate, cyclohexanetriol, sucrose, martitol, and lactitol; and the like.

Examples of the aromatic alcohol 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) -Hydroxyphenyl) heptane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) tridecane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-Methyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2, 2-Bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) ) Propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4'-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (2,3,5,6-tetramethyl-4-hydroxyphenyl) propane, bis ( 4-Hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4-hydroxyphenyl) butane , 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4) -Hydroxyphenyl) cycloheptane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3) , 5-Dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -4-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 2,2-bis (4-hydroxyphenyl) adamantan, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'- Dimethyldiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenylsulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfide, 3,3'-dicyclohexyl-4,4' -Dihydroxydiphenylsulfide, 3,3'-diphenyl-4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfoxide, 4,4' -Dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3-methylphenyl) ketone, 7,7'-dihydroxy- 3,3', 4,4'-tetrahydro-4,4,4', 4'-tetramethyl-2,2'-spirobi (2H-1-benzopyran), trans-2,3-bis (4-hydroxy) Phenyl) -2-butene, 9,9-bis (4-hydroxyphenyl) fluorene, 3,3-bis (4-hydroxyphenyl) -2-butanone, 1,6-bis (4-hydroxyphenyl) -1, 6-Hexanedione, 4,4'-dihydroxybiphenyl, m-dihydroxyxylylene, p-dihydroxyxylylene, 1,4-bis (2-hydroxyethyl) benzene, 1,4-bis (3-hydroxypropyl) benzene , 1,4-Bis (4-hydroxybutyl) Benzene Zen, 1,4-bis (5-hydroxypentyl) benzene, 1,4-bis (6-hydroxyhexyl) benzene, 2,2-bis [4- (2'-hydroxyethyloxy) phenyl] propane, hydroquinone, Bifunctional polyols such as resorcin; polyfunctional polyols such as trihydroxynaphthalene, tetrahydroxynaphthalene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, and trihydroxyphenanthrene; and the like.

Examples of the polyester polyol 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.

Examples of the polyether polyol 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. 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.

Examples of the polycaprolactone polyol include a compound obtained by ring-opening polymerization of ε-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.

Examples of the polycarbonate polyol 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.

Examples of the polyacrylic polyol 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.

(Polymer containing polyfunctional thiol group)
The polyfunctional thiol group-containing monomer is a compound having at least two thiol groups in one molecule.

As the 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, 4,6-bis (mercaptomethylthio) -1,3-dithian, tris-{(3-mercaptopropionyloxy) ethyl} -Polyfunctional thiols such as isocyanurate; and the like.

[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.

(Polyfunctional amino group monomer)
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.

Examples of the aliphatic amine 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.

Examples of the alicyclic amine include bifunctional amines such as isophorone diamine and cyclohexyl diamine.

Examples of the aromatic amine include 4,4'-methylenebis (o-chloroaniline) (MOCA), 2,6-dichloro-p-phenylenediamine, 4,4'-methylenebis (2,3-dichloroaniline), and the like. 4,4'-Methylenebis (2-ethyl-6-methylaniline), 3,5-bis (methylthio) -2,4-toluenediamine, 3,5-bis (methylthio) -2,6-toluenediamine, 3 , 5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, trimethylene glycol-di-p-aminobenzoate, polytetramethylene glycol-di-p-aminobenzoate, 4, 4'-Diamino-3,3', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-Tetraisopropyldiphenylmethane, 1,2-bis (2-aminophenylthio) ethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, N, N '-Di-sec-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, m-xylylene diamine, N, N'-di-sec-butyl-p- Phenylene diamine, m-phenylenediamine, p-xylylene diamine, p-phenylenediamine, 3,3'-methylenebis (methyl-6-aminobenzoate), 2,4-diamino-4-chlorobenzoic acid-2-methylpropyl , 2,4-Diamino-4-chlorobenzoic acid-isopropyl, 2,4-diamino-4-chlorophenylacetic acid-isopropyl, terephthalic acid-di- (2-aminophenyl) thioethyl, diphenylmethanediamine, tolylene amine, piperazine, etc. Bifunctional amines; 1,3,5-benzenetriamines, polyfunctional amines such as melamine; and the like.

[Ring-opening polymerizable monomer]
In the present embodiment, a ring-opening polymerizable monomer that produces a cured product by ring-opening polymerization may be used together with the radically polymerizable monomer. In ring-opening polymerization, 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.

Examples of the cyclic ether 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.

Examples of the cyclic lactone include 4-membered ring lactones such as β-propiolactone, β-methylpropiolactone, and L-serine-β-lactone; γ-butyrolactone, γ-hexanolactone, and γ-heptanolactone. γ-Octanolactone, γ-decanolactone, γ-dodecanolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-hydroxy-γ-butyrolactone, γ-methyl-γ-decanolactone, α- Methylene-γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, D-erythronolactone, α-methyl-γ-butyrolactone, γ-nonanolactone, DL-pantolactone, γ-phenyl-γ-butyrolactone, γ-unde Canolactone, γ-valerolactone, 2,2-pentamethylene-1,3-dioxolan-4-one, α-bromo-γ-butyrolactone, γ-crotonolactone, α-methylene-γ-butyrolactone, α-methacryloyl Five-membered ring lactones such as oxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone; δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecano Lactone, δ-dodecanolactone, δ-tridecanolactone, δ-tetradecanolactone, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid δ-lactone, monomethyl-δ-valerolactone, monoethyl-δ-valero 6-membered ring lactones such as lactones, monohexyl-δ-valerolactone, 1,4-dioxane-2-one, 1,5-dioxepan-2-one; ε-caprolactone, monomethyl-ε-caprolactone, monoethyl-ε-caprolactone , Monohexyl-ε-caprolactone, dimethyl-ε-caprolactone, di-n-propyl-ε-caprolactone, di-n-hexyl-ε-caprolactone, trimethyl-ε-caprolactone, triethyl-ε-caprolactone, tri-n-ε -Caprolactone, ε-caprolactone, 5-nonyl-oxepan-2-one, 4,4,6-trimethyl-oxepan-2-one, 4,6,6-trimethyl-oxepan-2-one, 5-hydroxymethyl- 7-membered ring lactones such as oxepan-2-one; 8-membered ring lactones such as ζ-enant lactone; lactones, lactides, dilactides, tetramethylglycosides, 1,5-dioxepan-2- Other lactones such as on, t-butylcaprolactone; and the like.

Examples of the cyclic lactam include 4-membered ring lactams such as 4-benzoyloxy-2-azetidinone; γ-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 ε-caprolactam and DL-α-amino-ε-caprolactam; ω-heptalactam Eight-membered ring lactam; etc.;

Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, 1,2-butyleneglycerol carbonate-1,2-carbonate, 4- (methoxymethyl) -1,3-dioxolane-2-one, and (chloromethyl) ethylene carbonate. , Vinylene carbonate, 4,5-dimethyl-1,3-dioxolane-2-one, 4-chloromethyl-5-methyl-1,3-dioxolane-2-one, 4-vinyl-1,3-dioxolane-2 -On, 4,5-diphenyl-1,3-dioxolane-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, 1,3-dioxane-2-one, 5 -Methyl-5-propyl-1,3-dioxolane-2-one, 5,5-diethyl-1,3-dioxolane-2-one and the like can be mentioned.

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.

<Other compounding agents>
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. Examples of such 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.

The content of 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.

≪Antibacterial / antiviral material and antibacterial / antiviral laminate≫
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. When 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.

Further, 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. Examples of 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. For example, 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. In this case, another layer may be provided so that the antibacterial / antiviral material is the outermost layer. For example, 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.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The analysis method and measurement method in this example are as follows.

<Analysis method of phosphate ester-bonded bismuth compound>
[ ¹ H-, ³¹ P-NMR measurement]
A nuclear magnetic resonance apparatus (JEM-ECA400II manufactured by JEOL RESONANCE Co., Ltd.) was used. Deuterated acetone was used as a solvent, and the measurement was performed at a sample concentration of 1% by mass.

[XPS measurement]
An X-ray photoelectron spectroscope (ESCA5701ci / MC manufactured by ULVAC FI Co., Ltd.) was used. Monochromatic Al-Kα (14kV-330W) was used as the X-ray source. The aperture diameter was φ800 μm and the photoelectron extraction angle was 45 °. The sample was pulverized in an agate mortar, and the obtained powder was fixed to a substrate with carbon tape and introduced into a measurement chamber for measurement.

[MALDI-TOF-MS (Matrix Assisted Laser Desorption Ionization-Time-of-Flight Mass Spectrometry) Measurement]
A rapiflex TOF / TOF type manufactured by Bruker was used. CHCA (α-cyano-4-hydroxycinnamic acid), DIT (ditranol), and DHB (2,5-dihydroxybenzoic acid) were used as the matrix, and sodium trifluoroacetate was used as the cationizing agent. 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).

<Characteristic evaluation of cured / laminated body>
[Antibacterial performance evaluation test using bacteria]
An antibacterial performance evaluation test using bacteria was carried out using a separately prepared 2 mm thick laminated body or cured body. The measurement was performed according to JIS R 1702: 2020 (ultraviolet light responsive photocatalyst, antibacterial, film adhesion method). However, this test was conducted in a dark place.

The sample plate (7 cmφ, 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. In JIS R 1702: 2020, 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 cmφ, 2 mm) was wiped with absolute ethanol. 150 μL 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. In 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.

[Yellowness measurement]
The yellowness (YI) was measured using an SM color computer SM-T manufactured by Suga Test Instruments Co., Ltd.

[Haze, total light transmittance measurement]
The haze and total light transmittance were measured using HAZE METER NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

[Impact resistance test]
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.

<Synthesis Example 1: Synthesis of Phosphate-bonded Bismuth Compound>
Next bismuth salicylate (III): 94.27 g (manufactured by Sigma-Aldrich, 260.35 mmol in terms of bismuth), phosphate diester-bis [(2-methacryloyloxyethyl)] phosphate and phosphate monoester- (2-methacryloyloxy). Mixture with ethyl) phosphate: 33.06 g (MR-200 manufactured by Daihachi Chemical Industry Co., Ltd., phosphate value 162.04 mmol), phosphate triester-diphenyl-2-methacryloyloxyethyl phosphate: 33.09 g (Daihachi) MR-260, 91.33 mmol manufactured by Kagaku Kagaku Kogyo Co., Ltd.), Dibutyl hydroxytoluene as a polymerization inhibitor (BHT, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent): 6.17 g in a 1000 mL eggplant-shaped flask and 750 mL of toluene Was added. This was ultrasonically dispersed with a bath-type sonicator to obtain a cloudy solution.

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 μm 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. 3 g of activated carbon (Norit SX-Plus, manufactured by Norit) was added to the obtained pale yellow solution, and the mixture was centrifuged at 23830 × g for 12 hours. The centrifugal supernatant was pressure-filtered with a membrane filter having a pore size of 0.2 μm to obtain a pale yellow transparent filtrate. The obtained filtrate was concentrated to 100 mL by a vacuum evaporator. This acetone solution was poured into 800 mL of hexane in a 1000 mL conical beaker with stirring. 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. The structure of the obtained phosphate ester-bonded bismuth compound was b = u = v = w = 0.6 in the above formula (2).

<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.

Next, 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. To 100 parts by mass of this curable composition, 1,1'-azobis (cyclohexane-1-carbonitrile): 0.5 parts by mass was added and dissolved. The viscosity of the obtained curable composition was 3000 mPa · s, which was a viscosity capable of mass polymerization by casting.

Next, 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.

Next, 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. Got 1-Hydroxycyclohexylphenylketone: 0.375 parts by mass, bis (2,6-trimethoxybenzoyl) -2,4,4-trimethylpentylphos as a polymerization initiator with respect to 100 parts by mass of this curable composition. Finoxide: 0.125 parts by mass, and other compounding agents, bis (1,2,2,6,6-pentamethyl-4-piperidyl), which is a light stabilizer, sebacate: 5 parts by mass, N-methyldiethanolamine: 3 Parts by weight were added and mixed well to obtain a curable composition. When the viscosity of this curable composition was measured at 25 ° C. using an E-type viscometer, the viscosity was 150 mPa · s, which was a viscosity suitable for spin coating.

Next, 2 g of this curable composition was spin-coated on the surface of the cured product (base material) obtained in Comparative Example 1 using a spin coater 1H-DX2 manufactured by MIKASA. The spin coating conditions were adjusted so that the thickness of the cured product obtained by curing the curable composition was 40 ± 1 μm. Next, a D-bulb manufactured by Fusion UV Systems Co., Ltd. was prepared by spin-coating a substrate having a curable composition on the surface so that the output of the substrate surface at a wavelength of 405 nm was 200 mW / cm ² in a nitrogen gas atmosphere. Using the mounted F3000SQ, it was irradiated with light for 90 seconds and cured. Then, the heat treatment was carried out for 1 hour in the incubator of 100 degreeC, and the laminated body was obtained. This laminate was subjected to antibacterial / antiviral test, optical property test, and impact resistance test. The results are shown in Table 1.

As shown in Table 1, 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. In particular, 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. On the other hand, 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.

Claims

A curable composition 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.
The curable composition for an antibacterial / antiviral material according to claim 1, wherein the bismuth compound contains a bismuth compound in which salicylic acid or (meth) acrylic acid and a phosphate ester having a (meth) acryloyl group are bonded to bismuth. thing.
The curable composition for an antibacterial / antiviral material according to claim 1 or 2, wherein the polymerizable monomer other than the bismuth compound contains a radically polymerizable monomer.
The curable composition for an antibacterial / antiviral material according to claim 3, wherein the radically polymerizable monomer contains at least one selected from acrylonitrile and styrene.
The antibacterial / antiviral material according to claim 3 or 4, wherein the polymerizable monomer other than the bismuth compound further contains at least one selected from the addition polymerizable monomer and the ring-opening polymerizable monomer. Curable composition.
An antibacterial / antiviral material obtained by curing the curable composition for an antibacterial / antiviral material according to any one of claims 1 to 5.
An antibacterial / antiviral laminate obtained by laminating a base material and the antibacterial / antiviral material according to claim 6.