Curable composition, cured product, optical article, lens, rubber sheet, eye protector, antibacterial / antiviral agent, and resin composition

Abstract

Provided is a curable composition containing: a first bismuth compound having bismuth, and having at least one of an acryloyl group and a methacryloyl group; and a first radical polymerizable monomer having a polyethylene glycol chain, the proportion of the polyethylene glycol chain being 13.5% by mass or more, and the proportion of the number average molecular weight N2 of the polyethylene glycol chain in the number average molecular weight N1 being N2 / N1 of 75% or more and 95% or less. Also provided are a cured product of the curable composition, and an optical article, a lens, a rubber sheet, an eye protector, and an antibacterial / antiviral agent containing the cured product.

Description

Technical Field

[0001] This disclosure relates to curable compositions, cured products, optical articles, lenses, rubber sheets, eye protection devices, antibacterial / antiviral agents, and resin compositions. Background Technology

[0002] Lead glass and lead acrylate are currently used as radiation protection materials to protect the eyes from radiation damage. However, lead is harmful to the environment and human health, and there is a strong need for a lead-free alternative. As such an alternative, a curable composition containing a bismuth compound has been developed, which is a phosphate ester with (meth)acryloyl groups bound to bismuth.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2022 / 014591

[0006] Patent Document 2: International Publication No. 2019 / 177084 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] The purpose of this disclosure is to provide curable compositions, cured products, optical articles, lenses, rubber sheets, eye protection devices, and antibacterial / antiviral agents that can provide resin compositions with antifogging properties.

[0009] Solution for solving the problem

[0010] According to this disclosure, a curable composition is provided. The curable composition comprises a first bismuth compound and a first radical polymerizable monomer. The first bismuth compound has bismuth and at least one of an acryloyl group and a methacryloyl group. The first radical polymerizable monomer has a polyethylene glycol chain. In the first radical polymerizable monomer, the ratio of the number average molecular weight N2 of the polyethylene glycol chain to the number average molecular weight N1 (N2 / N1) is 75% or more and 95% or less. In the curable composition, the proportion of the polyethylene glycol chain is 13.5% by mass or more.

[0011] According to this disclosure, a cured product is provided. The cured product is a cured product of the curable composition of this disclosure.

[0012] According to this disclosure, an optical article is provided. The optical article comprises a cured product of this disclosure.

[0013] According to this disclosure, a lens is provided. The lens comprises a cured product of this disclosure.

[0014] According to this disclosure, a rubber sheet is provided. The rubber sheet comprises a cured product of this disclosure.

[0015] According to this disclosure, an eye protection device is provided. The eye protection device comprises a cured product of this disclosure.

[0016] According to this disclosure, an antibacterial / antiviral agent is provided. The antibacterial / antiviral agent comprises a cured product of this disclosure.

[0017] According to this disclosure, a resin composition is provided. The resin composition comprises bismuth, a (meth)acrylic resin, and 16.0% by weight or more of polyethylene glycol chains.

[0018] The effects of the invention

[0019] According to this disclosure, there are curable compositions, cured products, optical articles, lenses, rubber sheets, eye protection devices, and antibacterial / antiviral agents that can provide resin compositions with antifogging properties. Detailed Implementation

[0020] For radiation protection materials used to protect the eyes, in addition to radiation protection capabilities, high transparency and surface smoothness are also required optical properties. For example, molded products of radiation protection materials used for eye protection, such as glasses and goggles, are sometimes used near the human eyeball. Therefore, the lenses may fog up due to human breathing, thus reducing the lens transparency. Thus, radiation protection materials with anti-fogging properties are needed.

[0021] According to this disclosure, a curable composition is provided. The curable composition comprises a first bismuth compound and a first radical polymerizable monomer. The first bismuth compound has bismuth and at least one of an acryloyl group and a methacryloyl group. The first radical polymerizable monomer has a polyethylene glycol chain. In the first radical polymerizable monomer, the number average molecular weight N2 of the polyethylene glycol chain accounts for a ratio N2 / N1 of 75% or more and 95% or less. In the curable composition, the proportion of the polyethylene glycol chain is 13.5% by mass or more.

[0022] If the curable composition disclosed herein is used, a resin composition with anti-fogging properties can be provided. That is, the curable composition contains a first radical polymerizable monomer in which the polyethylene glycol chain occupies most of the molecular weight, and contains a certain amount or more of polyethylene glycol chains. In the cured product of such a curable composition, the free energy of the hydrophilic polyethylene glycol chains is relatively high, so it is considered that a hydrophilic interface is formed on the surface of the cured product.

[0023] The components used in the curable compositions of this disclosure are described below. Each component described below may be used alone or in combination of two or more. It should be noted that in this specification, the term "(meth)acryloyl" refers to both "acryloyl" and "methacryloyl". The terms "(meth)acrylate" and "(meth)acrylic resin" are used in the same way.

[0024] <First Bismuth Compound>

[0025] The first bismuth compound contains bismuth and at least one of an acryloyl group and a methacryl group. Because it contains bismuth, the first bismuth compound can be used as a radiation shielding material. Radiation includes electromagnetic radiation and particle radiation. Electromagnetic radiation includes X-rays and gamma rays. Particle radiation includes alpha rays, beta rays, neutron rays, and proton beams. Due to its excellent X-ray shielding ability, the first bismuth compound is particularly suitable as an X-ray shielding material and a shielding material for beta rays that can generate X-rays.

[0026] The first bismuth compound exhibits high solubility for radical polymerizable compounds having at least one radical polymerizable group selected from the group consisting of nitrile, acryloyl, methacryl, vinyl, and allyl. Therefore, by using the first bismuth compound, a curable composition containing a high concentration of bismuth and its cured product can be obtained. The first bismuth compound demonstrates superior solubility for radical polymerizable compounds compared to bismuth basic salicylate alone.

[0027] The first bismuth compound can be formed in any manner as long as it contains both bismuth and a (meth)acryloyl group. For example, bismuth and the (meth)acryloyl group can be directly bonded or bonded via a linker. Examples of linkers include oxygen atoms, sulfur atoms, nitrogen atoms, and phosphate groups.

[0028] The first bismuth compound preferably also has a phosphate bond. Furthermore, it is more preferable that the first bismuth compound is bonded to a first phosphate ester having a (meth)acryloyl group. Such a first bismuth compound tends to have higher compatibility with various polymerizable compounds. The bonding mode between bismuth and the first phosphate ester is not particularly limited and can be any of ionic, coordinate, or covalent bonds. That is, the first bismuth compound can be bismuth (Bi... 3＋ Or Bi 5＋ Phosphates or complexes that are cations and have a first phosphate ester as an anion can be phosphoric acid compounds or complexes.

[0029] The first bismuth compound can be a mono(meth)acrylate having one (meth)acryloyl group, a di(meth)acrylate having two (meth)acryloyl groups, a tri(meth)acrylate having three (meth)acryloyl groups, or a polyfunctional (meth)acrylate having four or more (meth)acryloyl groups.

[0030] In the first bismuth compound, the first phosphate ester is represented, for example, by the following formula (2).

[0031]

[0032] In the above formula (2), Q 1 It is a hydrogen atom or a methyl group. Q 1 Methyl is preferred.

[0033] Q 2 It is a hydrogen atom, a straight-chain or branched alkyl group having 1 or more but 10 or fewer carbon atoms, an aryl group having 4 or more but 16 or fewer carbon atoms, or a (meth)acryloyloxyalkyl group. The alkyl group preferably has 1 or more but 6 or fewer carbon atoms. The aryl group preferably has 5 or more but 8 or fewer carbon atoms. The aryl group is preferably phenyl. The alkyl group comprising the (meth)acryloyloxyalkyl group has, for example, 1 or more but 10 or fewer carbon atoms, preferably 1 or more but 3 or fewer carbon atoms. The (meth)acryloyloxyalkyl group is preferably (meth)acryloyloxyethyl.

[0034] a 3 It can be 0 or 1. a 3 When Q is 0, 2 The bonded oxygen atom is O - .

[0035] Q 3 It is a straight-chain or branched alkylene group having 1 or more carbon atoms and 10 or fewer carbon atoms, or a straight-chain or branched alkoxyalkylene group having 2 or more carbon atoms and 10 or fewer carbon atoms.

[0036] The first bismuth compound, besides the first phosphate ester, can also be combined with other compounds. The other compounds can be bonded to bismuth via ionic, coordinate, or covalent bonds. That is, the first bismuth compound can be bismuth-based (Bi... 3＋ Or Bi 5＋ Phosphates or complexes that are cations and have a first phosphate ester and other compounds as anions can also be phosphoric acid compounds or complexes.

[0037] As specific examples of other compounds, at least one selected from the group consisting of salicylic acid and (meth)acrylic acid can be listed.

[0038] To improve solubility for free radical polymerizable compounds, the preferred ratio of the first phosphate ester to other compounds is: 0.1 to 10 moles of other compounds relative to 1 mole of the first phosphate ester, more preferably 0.1 to 5 moles, even more preferably 0.1 to 1 mole, and particularly preferably 0.1 to 0.5 moles. It should be noted that when two or more first phosphate esters are present, the above ranges are based on the total moles of the first phosphate esters.

[0039] The presence of a first phosphate ester bound to bismuth can be confirmed by infrared spectroscopy (IR) analysis. Specifically, in the IR spectral determination of the first bismuth compound, for example in the range of 1670–1700 cm⁻¹,... -1 The peak was confirmed to indicate that the first phosphate ester was bonded to the bismuth. This peak is considered to be characteristic of the stretching vibration of Bi-OP. This peak was not detected in the bismuth before bonding and in the first phosphate ester. Furthermore, this peak was not detected in the mixture of the second bismuth compound and the first phosphate ester, which are the raw materials for the first bismuth compound.

[0040] For IR spectroscopy, for example using the Spectrum One manufactured by PerkinElmer, the determination is performed by the ATR method with one reflection and four integrations.

[0041] In addition, the binding number of salicylic acid or (meth)acrylic acid and each phosphate ester in the first bismuth compound can be confirmed by combining NMR (nuclear magnetic resonance spectroscopy), MALDI-TOF-MS (matrix-assisted laser desorption / ionization-time-of-flight mass spectrometry), XPS (X-ray photoelectron spectroscopy) and elemental analysis based on EDS (energy dispersive X-ray spectrometer).

[0042] 1 H-、 31 For P-NMR determination, a nuclear magnetic resonance apparatus (manufactured by NEC Corporation, JNM-ECA400II) was used and deuterated acetone was used as the solvent, with a sample concentration of 1% by mass.

[0043] For XPS measurements, an X-ray photoelectron spectroscopy apparatus (manufactured by ULVAC-PHI Corporation, ESCA5701ci / MC) was used, employing a monochromatic Al-Kα (14kV-330W) X-ray source with an aperture diameter of φ800μm and a photoelectron extraction angle of 45 degrees. The sample was pulverized using an agate mortar, and the resulting powder was fixed onto a substrate using carbon tape before being introduced into the measurement chamber for analysis.

[0044] The first bismuth compound preferably also has a phenyl group. First bismuth compounds having a phenyl group tend to have high compatibility with radical polymerizable monomers. The presence of a phenyl group in the first bismuth compound can be confirmed, for example, by Fourier transform infrared spectroscopy (FT-IR).

[0045] The first bismuth compound is, for example, a phosphate or complex salt represented by the following formula (1).

[0046]

[0047] In the above formula (1), Q 1 Q 2 Q 3 and a 3 Same as equation (2) above.

[0048] In formula (1) above, X is (meth)acrylic acid represented by formula (1a) below, or salicylic acid represented by formula (1b) below. In formula (1a), R is a hydrogen atom or a methyl group. X is preferably salicylic acid represented by formula (1b).

[0049]

[0050]

[0051] a 1 A number that is greater than 0 and less than 1.

[0052] a 2 Numbers greater than 0.1 and less than 3.

[0053] a 1 +a 2 Numbers that are greater than 2 and less than 3.

[0054] The first bismuth compound has a structure represented by the above formula (1), which can be confirmed, for example, by detecting the protonated molecular ion or sodium adduct ion of the compound in a MALDI-TOF-MS assay. For example, when a 1 Numbers greater than 0 and less than 1, X is salicylic acid, a 2 Numbers greater than 1 and less than 3, Q 1 Methyl, Q 2 It is a methacryloyloxyalkyl group, Q 3 When measuring compounds that are straight-chain alkylene groups with two carbon atoms, a protonated ion with m / z = 667 is detected.

[0055] For MALDI-TOF-MS determination, a Bruker-manufactured rapiflex TOF / TOF type instrument was used. CHCA (α-cyano-4-hydroxycinnamic acid), DIT (dithranephenol), and DHB (2,5-dihydroxybenzoic acid) were used as the matrix, and sodium trifluoroacetate was used as the cationizing agent. The determination was performed in Reflector / Positive mode, with a mass range of m / z = 20–4000.

[0056] The first bismuth compound can be a mixture of various first phosphates and various other compounds bonded to bismuth. Preferably, the first bismuth compound is formed by bonding bismuth to both a first phosphate having one (meth)acryloyl group and a first phosphate having two (meth)acryloyl groups. Such a first bismuth compound tends to have high compatibility with polymerizable compounds.

[0057] In such a first bismuth compound, the ratio of a first phosphate having two (meth)acryloyl groups to 1 mole of a first phosphate having one (meth)acryloyl group is preferably 0.05 to 3 moles, more preferably 0.10 to 2 moles, and even more preferably 0.15 to 1 mole.

[0058] As suitable first bismuth compounds, compounds represented by the following formulas (III) to (V) can be listed.

[0059]

[0060]

[0061]

[0062] In the formula, R is either a hydrogen atom or a methyl group.

[0063] In formula (III) above, a + x + y + z = 3. x represents the molar number of 2-((meth)acryloyloxy)ethyl phosphate residues. y represents the molar number of 2-((meth)acryloyloxy)ethyl phosphate residues. z represents the molar number of bis[2-((meth)acryloyloxy)ethyl] phosphate residues. a represents the molar number of (meth)acrylic acid residues.

[0064] In formula (IV) above, 2b + u + v + w = ​​3. u represents the molar number of 2-((meth)acryloyloxy)ethyl phosphate residues. v represents the molar number of 2-((meth)acryloyloxy)ethyl phosphate residues. w represents the molar number of bis[2-((meth)acryloyloxy)ethyl] phosphate residues. b represents the molar number of salicylic acid residues.

[0065] In the above formula (V), 2c + q + r + 2s + t = 3. q represents the molar number of 2-((meth)acryloyloxy)ethyl phosphate residues. r represents the molar number of 2-((meth)acryloyloxy)ethyl phosphate residues. s represents the molar number of 2-((meth)acryloyloxy)ethyl phosphate residues. t represents the molar number of bis[2-((meth)acryloyloxy)ethyl] phosphate residues. c represents the molar number of salicylic acid residues.

[0066] It should be noted that the first bismuth compounds represented by formulas (III) to (V) above can each be a mixture of multiple compounds, rather than a single compound. In this case, the molar number of each residue is set to represent the molar number as a whole mixture.

[0067] In formula (III) above, considering that it is a first bismuth compound that can be manufactured at low temperatures and has minimal coloring, when a = 0, x:y:z = 1:0.05~3:0.5~30 is preferred, x:y:z = 1:0.1~2:1~20 is more preferred, and x:y:z = 1:0.15~1:1.5~10 is even more preferred. Furthermore, from the viewpoint of further reducing coloring, it is also possible to set a = 0 and y = 0.

[0068] Furthermore, in formula (III) above, when a = 0 or less, the preferred ratio is a:(x + y + z) = 0.1 to 10:1, more preferably a:(x + y + z) = 0.1 to 5:1, and even more preferably a:(x + y + z) = 0.1 to 1:1. In this case, the preferred ratio is 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 even more preferably x:y:z = 1:0.15 to 1:1.5 to 10.

[0069] In the above formula (IV), when b = 0, it is the same as the formula obtained by replacing x with u, y with v, and z with w in the above provisions.

[0070] Furthermore, in the above formula (IV), when b = 0 or less, b:(u + v + w) = 1:0.1 to 30 is preferred, b:(u + v + w) = 1:0.2 to 20 is more preferred, b:(u + v + w) = 1:0.3 to 10 is even more preferred, and b:(u + v + w) = 1:0.5 to 5 is particularly preferred. In this case, u:v:w = 1:0.05 to 20:0.1 to 40 is preferred, u:v:w = 1:0.1 to 10:0.2 to 20 is even more preferred, and u:v:w = 1:0.2 to 5:0.4 to 10 is even more preferred.

[0071] In the above formula (V), when c = 0, the preferred ratio is q:r:s:t = 1:0.1~50:0.05~20:0.1~40, more preferably q:r:s:t = 1:0.3~30:0.1~10:0.2~20, and even more preferably q:r:s:t = 1:0.5~20:0.2~5:0.4~10.

[0072] Furthermore, in the above formula (V), when c = 0 or less, c:(q + r + s + t) = 1:0.1 to 30 is preferred, c:(q + r + s + t) = 1:0.2 to 20 is more preferred, c:(q + r + s + t) = 1:0.3 to 10 is even more preferred, and c:(q + r + s + t) = 1:0.5 to 5 is particularly preferred. In this case, q:r:s:t = 1:0.1 to 50:0.05 to 20:0.1 to 40 is preferred, q:r:s:t = 1:0.3 to 30:0.1 to 10:0.2 to 20 is even more preferred, and q:r:s:t = 1:0.5 to 20:0.2 to 5:0.4 to 10 is even more preferred.

[0073] The first bismuth compound is, for example, a phosphate or complex salt represented by the following formula (3).

[0074]

[0075] In the above formula (3), Q 1 Q 2 Q 3 and a 3 Same as equation (2) above.

[0076] a 4 It is a number greater than 0 and less than 3.

[0077] a 5 It is a number greater than 0 and less than 3.

[0078] a 4 +a 5 The value is 3.

[0079] The first bismuth compound preferably comprises at least one compound selected from the group consisting of the compound shown in formula (3a), the compound shown in formula (3b), the compound shown in formula (3c), and the compound shown in formula (3d). The first bismuth compound more preferably comprises the compound shown in formula (3a).

[0080]

[0081]

[0082]

[0083]

[0084] In the first bismuth compound, the proportion of bismuth is, for example, 40% by mass or more and 60% by mass or less, preferably 45% by mass or more and 50% by mass or less. This proportion can be confirmed by inductively coupled plasma (ICP) spectroscopy.

[0085] Alternatively, the first bismuth compound may be a composition comprising compounds other than the first bismuth compound. This composition will also be referred to hereinafter as the first bismuth composition. The first bismuth composition may also contain phosphoric acid compounds or unreacted raw materials that are byproducts of manufacturing.

[0086] Removing these byproduct phosphoric acid compounds or unreacted raw materials from the first bismuth compound requires a significant amount of labor industrially. Furthermore, these byproduct phosphoric acid compounds or unreacted raw materials can contribute to improved solubility for free radical polymerizable monomers.

[0087] Phosphoric acid compounds that are byproducts include, for example, dimers of phosphate esters (monophosphates) having one (meth)acryloyl group, dimers of phosphate esters (diesters) having two (meth)acryloyl groups, esters of bismuth salicylate or bismuth (meth)acrylate with phosphoric acid, etc.

[0088] Examples of unreacted raw materials include: phosphate esters (monophosphates) having one (meth)acryloyl group, phosphate esters (diesters) having two (meth)acryloyl groups, bismuth salicylate, bismuth (meth)acrylate, etc.

[0089] In the first bismuth composition, the proportion of compounds other than the first bismuth compound is, for example, 30% by mass or less. There is no lower limit to this proportion; according to one example, it is 0% by mass, and according to another example, it is 5% by mass. This proportion can be determined by using… 1 The internal standard method of H-NMR was used to quantitatively identify byproduct phosphoric acid compounds and unreacted raw materials in the first bismuth composition.

[0090] Alternatively, the first bismuth composition may also contain a compound derived from bismuth oxide. Such a compound is, for example, a compound formed by bismuth oxide combined with a phosphate ester having a (meth)acryloyl group, (meth)acrylic acid, and / or salicylic acid. Although its structure is unknown, this bismuth oxide-derived compound is believed to be formed by the combination of hydroxyl groups formed on the surface of bismuth oxide with the carboxyl groups of the phosphate ester, (meth)acrylic acid, or salicylic acid. It should be noted that this bismuth oxide-derived compound is very difficult to separate from the first bismuth composition. Therefore, when a bismuth oxide-derived compound is produced as a byproduct, it is preferable to use the composition containing the bismuth oxide-derived compound. When a bismuth oxide-derived compound is produced as a byproduct, it is preferable to adjust the manufacturing conditions, etc., to keep its amount within a range that does not reduce the solubility of the first bismuth composition. It should be noted that the presence of a bismuth oxide-derived compound can be determined comprehensively based on its manufacturing conditions or methods such as IR, NMR, XPS, etc.

[0091] The first bismuth composition may also contain at least one compound selected from the group consisting of the compound shown in formula (3e) and the compound shown in formula (3f).

[0092]

[0093]

[0094] [Method for manufacturing the first bismuth compound]

[0095] The method for manufacturing the first bismuth compound is not particularly limited, but it is preferable to manufacture it by reacting a second bismuth compound with a first phosphate ester. Specifically, it is preferable to manufacture it by adding a polymerization inhibitor as needed to an aliphatic hydrocarbon solvent or an aromatic solvent, and then reacting the second bismuth compound with the first phosphate ester and dehydrating it.

[0096] Second bismuth compounds refer to organic compounds containing bismuth. Second bismuth compounds may contain bismuth (meth)acrylate or bismuth basic salicylate. There are no particular restrictions on whether bismuth (meth)acrylate or bismuth basic salicylate can be commercially available.

[0097] It should be noted that bismuth basic salicylate is a compound formed by salicylic acid bonded to bismuth, represented by the following formula (VI).

[0098]

[0099] There are no particular restrictions on the manufacturing method of basic bismuth salicylate, and it can be manufactured using well-known methods.

[0100] As the primary phosphate ester, commercially available products can be used. The primary phosphate ester can be a phosphate ester having one (meth)acryloyl group, a phosphate ester having two (meth)acryloyl groups, or a mixture thereof.

[0101] Examples of phosphate esters having one (meth)acryloyl group include: 2-(methacryloyloxy)ethyl dihydrogen phosphate, 2-methacryloyloxyethyl diphenyl phosphate, etc.

[0102] In addition, examples of phosphate esters having two (meth)acryloyl groups include: bis[2-(methacryloyloxy)ethyl] phosphate and phenyl[2-(methacryloyloxy)ethyl] phosphate.

[0103] Furthermore, to improve compatibility, it is preferable to add triphosphates such as diphenyl 2-methacryloyloxyethyl phosphate, phenyl bis[2-(methacryloyloxyethyl)] phosphate, and tri[2-(methacryloyloxyethyl)] phosphate as the first phosphate ester. If a triphosphate with a phenyl group is used, the monovalent phenyl phosphate diesters with one (meth)acryloyl group in formulas (III) to (V) above can be well introduced.

[0104] The amount of triphosphate mixed with 1 mole of phosphate ester having one (meth)acryloyl group and phosphate ester having two (meth)acryloyl groups is preferably 0.1 to 20 moles, more preferably 0.2 to 5 moles.

[0105] The amount of the first phosphate ester used can be determined in a manner that yields the desired first bismuth compound. Specifically, the amount of the first phosphate ester used is preferably set to a range of 0.3 to 10 moles relative to 1 mole of the second bismuth compound.

[0106] (Aliphatic hydrocarbon solvents or aromatic solvents)

[0107] When preparing the first bismuth compound, it is preferable to react the second bismuth compound with the first phosphate ester by stirring and mixing in an aliphatic hydrocarbon solvent or an aromatic solvent. Water will be generated in the reaction system during this process, and it is preferable to dehydrate the generated water. To facilitate the dehydration of the generated water, it is preferable to use an aliphatic hydrocarbon solvent or an aromatic solvent with a high boiling point, specifically above 100°C. Alternatively, a mixed solution can be prepared by mixing the aliphatic hydrocarbon solvent and the aromatic solvent for use.

[0108] Examples of aliphatic hydrocarbon solvents or aromatic solvents include: hexane, heptane, nonane, decane, undecane, dodecane, xylene, dimethoxybenzene and their isomers; benzene, toluene, chlorobenzene, bromobenzene, anisole; petroleum ether, petroleum benzine, benzoin, etc.

[0109] There is no particular limitation on the amount of aliphatic hydrocarbon solvent or aromatic solvent used, as long as it is sufficient to adequately mix the second bismuth compound and the first phosphate ester. Considering the yield of the first bismuth compound, it is preferable to use the aliphatic hydrocarbon solvent or aromatic solvent at a ratio of 5 to 100 mL relative to 1 g of the second bismuth compound.

[0110] (Reaction conditions)

[0111] There are no particular limitations on the method of introducing the second bismuth compound and the first phosphate ester into the reaction system. For example, the following method can be used: adding the second bismuth compound, diluted as needed with an aliphatic hydrocarbon solvent or an aromatic solvent, and the first phosphate ester, diluted as needed with an aliphatic hydrocarbon solvent or an aromatic solvent, together into the reaction system, and then stirring and mixing. Alternatively, the following method can be used: introducing an aliphatic hydrocarbon solvent or an aromatic solvent into the reaction system beforehand, and then adding the second bismuth compound, diluted as needed with an aliphatic hydrocarbon solvent or an aromatic solvent, and the first phosphate ester, diluted as needed with an aliphatic hydrocarbon solvent or an aromatic solvent, together into the reaction system, and then stirring and mixing. Alternatively, the following method can be used: introducing one component into the reaction system beforehand, then introducing the other component into the reaction system, and then stirring and mixing. Among these methods, in order to reduce the coloration of the obtained first bismuth compound and improve productivity, the following method is preferred: First, dispersing the second bismuth compound in an aliphatic hydrocarbon solvent or an aromatic solvent. At this point, the second bismuth compound may also remain insoluble. In this case, it is preferable to crush the lumps of the second bismuth compound using an ultrasonic device or the like, in a manner that eliminates any lumps of the second bismuth compound. Then, the first phosphate ester is added to the turbid solution in which the second bismuth compound is dispersed, and stirring and heating are then initiated.

[0112] The temperature (reaction temperature) during stirring of the components can be the reflux temperature of an aliphatic hydrocarbon solvent or an aromatic solvent. In order to further reduce the coloration of the obtained first bismuth compound, it is preferred to carry out the reaction at the following temperatures: preferably an oil bath temperature of 30 to 150°C, more preferably a temperature of 40 to 140°C, and even more preferably a temperature of 45 to 120°C.

[0113] Furthermore, when the reaction temperature is 30–110°C, it is preferable to place the reaction system under reduced pressure to remove (dehydrate) the water generated within the reaction system. In this case, dehydration can be carried out while mixing the second bismuth compound with the first phosphate ester, or the two can be mixed and then dehydrated. However, considering the efficiency of the reaction, it is preferable to mix the two and dehydrate them simultaneously during the reaction.

[0114] There is no particular limit to the reaction time; it can typically be more than 1 hour but less than 6 hours.

[0115] For operability, the atmosphere in which the reaction is carried out can be any of the following: air atmosphere, inert gas atmosphere, or dry air atmosphere. For operability, it is preferred to carry out the reaction in an air atmosphere.

[0116] After the reaction is carried out under the conditions described above, if insoluble turbid components are present after the obtained first bismuth compound is concentrated by distillation to remove the solvent, it is preferable to separate them by filtration or centrifugation. Then, a solvent is added to the concentrated reaction solution obtained by this treatment for reprecipitation to purify the solution; the solvent is soluble in the reaction solvent used and will not dissolve the first bismuth compound. If high-boiling-point solvent remains, the above decantation operation is repeated to replace the solvent. Then, the remaining solvent is distilled off and vacuum dried, thereby extracting the first bismuth compound.

[0117] In the curable composition, the content of the first bismuth compound is, for example, 30% by mass or more and 70% by mass or less. A higher content of the first bismuth compound tends to improve the radiation shielding ability of the cured product. The content of the first bismuth compound is preferably 40% by mass or more, more preferably 45% by mass or more. On the other hand, if the content of the first bismuth compound is too high, the anti-fogging properties of the cured product will decrease. The content of the first bismuth compound is preferably 60% by mass or less, more preferably 55% by mass or less. This content, for example, can be achieved by... 1 Measured by H-NMR.

[0118] <Polymerizing compounds>

[0119] The curable composition disclosed herein contains a first radical polymerizable monomer as a polymerizable compound (but other than the first bismuth compound described above). The first radical polymerizable monomer has a polyethylene glycol chain and a radical polymerizable group. The polyethylene glycol chain is an alkylene oxide unit (EO unit) represented by -(CH2CH2O)n-. n is the degree of polymerization.

[0120] The free radical polymerizable group includes, for example, at least one selected from the group consisting of (oxy)acryloyl, (oxy)methacryloyl, vinyl, and allyl. Preferably, the free radical polymerizable group includes at least one selected from the group consisting of (oxy)acryloyl and (oxy)methacryloyl. The number of free radical polymerizable groups can be one or more, two or more, three or more, or six or less. The number of free radical polymerizable groups is preferably one, two, or three, more preferably one or two.

[0121] In the first radical polymerizable monomer, the ratio of the number-average molecular weight N2 of the polyethylene glycol chain to the number-average molecular weight N1 (N2 / N1) is 75% or more and 95% or less. A higher N2 / N1 ratio tends to improve the anti-fogging properties of the cured product. This N2 / N1 ratio is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. This N2 / N1 ratio can be calculated, for example, from NMR spectral analysis and the structural formula of the first radical polymerizable monomer. Hereinafter, this N2 / N1 ratio will also be referred to as the EO ratio.

[0122] The number-average molecular weight N1 refers to the molecular weight of the first radical polymerizable monomer. The number-average molecular weight N1 of the first radical polymerizable monomer is, for example, 400 or more and 3000 or less. Preferably, the number-average molecular weight N1 is 500 or more and 1500 or less, more preferably 600 or more and 1400 or less, and even more preferably 800 or more and 1300 or less. The number-average molecular weight N1 can be calculated, for example, from NMR spectroscopy analysis and the structural formula of the first radical polymerizable monomer.

[0123] The number-average molecular weight N2 refers to the molecular weight of the polyethylene glycol chain portion in the first radical polymerizable monomer. The number-average molecular weight N2 of the polyethylene glycol chain portion of the first radical polymerizable monomer is, for example, 350 or more and 2200 or less, preferably 400 or more and 1500 or less, and more preferably 500 or more and 1200 or less. The number-average molecular weight N2 can be calculated, for example, from NMR spectroscopy analysis and the structural formula of the first radical polymerizable monomer.

[0124] The degree of polymerization of the polyethylene glycol chain of the first radical polymerizable monomer is, for example, 8 or more and 50 or less, preferably 10 or more and 30 or less, and more preferably 12 or more and 25 or less. The degree of polymerization can be calculated, for example, from NMR spectral analysis and the structural formula of the first radical polymerizable monomer.

[0125] The first radical polymerizable monomer preferably comprises a (meth)acrylate represented by the following formula (I).

[0126]

[0127] In the above formula (I), R 1 It can be a hydrogen atom or a methyl group. If R 1 If the first free radical polymerizable monomer is an acrylate, then there is a tendency for improved anti-fogging properties of the cured product. If R... 1 If the first free radical polymerizable monomer is methyl, that is, if the first free radical polymerizable monomer is methacrylate, there is a tendency for the hardness of the cured product to increase.

[0128] R 2 It can be acryloyl, methacryloyl, methyl, or phenyl. If R 2If the first free radical polymerizable monomer is acryloyl or methacryloyl, that is, if the first free radical polymerizable monomer is a bifunctional (meth)acrylate, there is a tendency for the hardness of the cured product to increase. If R 2 If the first free radical polymerizable monomer is methyl or phenyl, that is, if the first free radical polymerizable monomer is a monofunctional (meth)acrylate, there is a tendency for the cured product to have improved anti-fogging properties.

[0129] n refers to the degree of polymerization, which is an integer between 10 and 30. From the perspective of improving the anti-fogging properties of the cured product, n is preferably 12 or more, more preferably 13 or more, and even more preferably 20 or more. From the perspective of improving the hardness of the cured product, n is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.

[0130] The first radical polymerizable monomer preferably comprises at least one selected from the group consisting of monofunctional acrylates, difunctional acrylates, monofunctional methacrylates, and difunctional methacrylates, and may also comprise two or more, or three or more.

[0131] Specific examples of monofunctional acrylates include at least one selected from the group consisting of methoxy polyethylene glycol acrylate, phenoxy diethylene glycol acrylate, and ethoxylated o-phenylphenol acrylate.

[0132] Specific examples of monofunctional methacrylates include at least one selected from the group consisting of methoxy polyethylene glycol methacrylate, phenoxy diethylene glycol methacrylate, and ethoxylated o-phenylphenol methacrylate.

[0133] Specific examples of diacrylates include at least one selected from the group consisting of polyethylene glycol diacrylate, ethoxylated glycerol diacrylate, and pentaerythritol diacrylate.

[0134] Specific examples of dimethacrylates include at least one selected from the group consisting of polyethylene glycol dimethacrylate, ethoxylated glycerol dimethacrylate, and pentaerythritol dimethacrylate.

[0135] In the curable composition, the proportion of the first free radical polymerizable monomer is, for example, 15% by mass or more. From the perspective of improving anti-fogging properties, this proportion is preferably 17% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. From the perspective of improving the hardness of the cured product, this proportion is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. This proportion, for example, can be achieved by... 1 Measured by H-NMR.

[0136] When the first radical polymerizable monomer comprises both a bifunctional radical polymerizable monomer and a monofunctional radical polymerizable monomer, in the curable composition, from the perspective of improving the hardness of the cured product, the proportion of the bifunctional radical polymerizable monomer is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. From the perspective of improving the anti-fogging properties of the cured product, this proportion is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. In the curable composition, from the perspective of improving the anti-fogging properties of the cured product, the proportion of the monofunctional radical polymerizable monomer is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. From the perspective of improving the hardness of the cured product, this proportion is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0137] In the curable composition, the ratio M1 / M2 of the mass of the first bismuth compound (M1) to the mass of the first free radical polymerizable monomer (M2) is preferably 1 or more and 10 or less. A higher M1 / M2 ratio tends to improve the radiation shielding capability of the cured product. A lower M1 / M2 ratio tends to improve the anti-fogging properties of the first bismuth compound. A more preferred ratio M1 / M2 is 2 or more and 5 or less.

[0138] In the curable composition, the proportion of polyethylene glycol chains, i.e., the EO content, is 13.5% by mass or more. These polyethylene glycol chains are primarily derived from the first radical polymerizable monomer. From the perspective of improving the anti-fogging properties of the cured product, the proportion of polyethylene glycol chains in the curable composition is preferably 13.6% by mass or more, more preferably 14.0% by mass or more, even more preferably 16.0% by mass or more, particularly preferably 18.0% by mass or more, and extremely preferably 20.0% by mass or more. From the perspective of improving the hardness of the cured product, this proportion is preferably 40.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less. This proportion can be obtained, for example, by multiplying the proportion of the first radical polymerizable monomer in the curable composition by the EO rate of the first radical polymerizable monomer.

[0139] In addition to the first radical polymerizable monomer, the curable composition disclosed herein may also contain a second radical polymerizable monomer. The second radical polymerizable monomer is a radical polymerizable monomer that does not have an ethylene glycol chain but has a radical polymerizable group.

[0140] The free radical polymerizable group includes, for example, at least one selected from the group consisting of (oxy)acryloyl, (oxy)methacryloyl, vinyl, and allyl. Preferably, the free radical polymerizable group includes at least one selected from the group consisting of (oxy)acryloyl and (oxy)methacryloyl. The number of free radical polymerizable groups can be one or more, two or more, three or more, or six or less. The number of free radical polymerizable groups is preferably one, two, or three, more preferably one or two.

[0141] The number-average molecular weight of the second radical polymerizable monomer is, for example, 100 or more and 2000 or less. Preferably, the number-average molecular weight is 120 or more and 1500 or less, more preferably 130 or more and 1000 or less, and even more preferably 140 or more and 500 or less. The number-average molecular weight can be calculated, for example, from NMR spectroscopy analysis and the structural formula of the second radical polymerizable monomer.

[0142] The second radical polymerizable monomer preferably comprises a compound represented by the following formula (II).

[0143]

[0144] In equation (II) above, R 3 It can be a hydrogen atom or a methyl group. If R 3 If the second radical polymerizable monomer is an acrylate, it tends to improve the anti-fogging properties of the cured product. If R... 3 If the second free radical polymerizable monomer is methyl, that is, if the second free radical polymerizable monomer is methacrylate, there is a tendency to increase the hardness of the cured product.

[0145] R 4 It is an alkylene group having 1 or more but less than 5 carbon atoms. R 4 Preferably, it is methylene or ethylene. m is 0 or 1.

[0146] R 5 It is an alkyl, phenyl, dimethylamino, diethylamino, acryloyloxy, or methacryloyloxy group having 1 or more but 5 or fewer carbon atoms. If R 5 If the second radical polymerizable monomer is acryloyloxy or methacryloyloxy, that is, if the second radical polymerizable monomer is a bifunctional (meth)acrylate, there is a tendency for the hardness of the cured product to increase. If R 5 If the second radical polymerizable monomer is a monofunctional (meth)acrylate, then there is a tendency for the cured product to have improved anti-fogging properties.

[0147] The second radical polymerizable monomer preferably comprises at least one selected from the group consisting of monofunctional acrylates, difunctional acrylates, monofunctional methacrylates, and difunctional methacrylates, and may also comprise two or more, or three or more.

[0148] Specific examples of monofunctional acrylates include at least one selected from the group consisting of 2-(dimethylamino)ethyl acrylate, acrylic acid, acrylamide, phenyl acrylate, benzyl acrylate, isobutyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, isocyanate ethyl acrylate, and acryloyloxymethyltrimethoxysilane.

[0149] Specific examples of monofunctional methacrylates include at least one selected from the group consisting of 2-(dimethylamino)ethyl methacrylate, methacrylic acid, methacrylamide, phenyl methacrylate, benzyl methacrylate, isobutyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isocyanate ethyl methacrylate, and methacryloyloxymethyltrimethoxysilane.

[0150] Specific examples of diacrylates include at least one selected from the group consisting of ethylene glycol diacrylate, propylene glycol diacrylate, and tetramethylene glycol diacrylate.

[0151] Specific examples of dimethacrylates include at least one selected from the group consisting of ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and tetramethylene glycol dimethacrylate.

[0152] In the curable composition, the proportion of the second free radical polymerizable monomer is, for example, 10% by mass or more and 40% by mass or less. From the perspective of improving hardness, this proportion is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. From the perspective of improving the anti-fogging properties of the cured product, this proportion is preferably 35% by mass or less, more preferably 33% by mass or less, and even more preferably 30% by mass or less. This proportion, for example, can be achieved by... 1 Measured by H-NMR.

[0153] In the curable composition, the ratio M1 / M3 of the mass of the first bismuth compound (M1) to the mass of the second free radical polymerizable monomer (M3) is preferably 0.5 or more and 10 or less. A higher M1 / M3 ratio tends to improve the radiation shielding capability of the cured product. A lower M1 / M3 ratio tends to improve the formability of the first bismuth compound. A more preferred M1 / M3 ratio is 1 or more and 5 or less.

[0154] In the curable composition, the ratio M2 / M3 of the mass of the first free radical polymerizable monomer M2 to the mass of the second free radical polymerizable monomer M3 is preferably 0.1 or more and 10 or less. If this ratio M2 / M3 is higher, the anti-fogging properties of the cured product tend to improve. If this ratio M2 / M3 is lower, the formability of the first bismuth compound tends to improve. This ratio M2 / M3 is more preferably 0.2 or more and 2 or less, and even more preferably 0.5 or more and 1 or less.

[0155] In addition to the first and second free radical polymerizable monomers, the curable compositions disclosed herein may also contain other polymerizable compounds. Examples of other polymerizable compounds include compounds having vinyl groups and compounds having allyl groups.

[0156] Examples of polymerizable compounds containing vinyl groups include: vinylpyridine, vinylpyrrolidone; methylstyrene and its structural isomers, methoxystyrene and its structural isomers, methylstyrene dimer, chlorostyrene, bromostyrene, divinylbenzene and other styrene derivatives.

[0157] Examples of polymeric compounds containing an allyl group include allyl methyl carbonate, allyl phenyl ether, 4-allyloxytoluene, allyloxytrimethylsilane, allyl benzoate, allyl methacrylate, and allyl glycidyl ether.

[0158] The curable composition disclosed herein may also contain 10% by mass or less of a nitrile compound. The content of the nitrile compound in the curable composition is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. If the content of the nitrile compound is low, there is a tendency for the odor of the cured product to decrease. In one example, the lower limit of the nitrile compound content is 100 ppm by mass or more, and in another example, it is 0% by mass. This content can be achieved, for example, by... 1 Measured by H-NMR.

[0159] Examples of nitrile compounds include acrylonitrile, methacrylonitrile, crotonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, allyl cyanocyanate, allyl cyanoacetate, fumaric acid, 5-norbornene-2-carboxynitrile, etc.

[0160] <Other Compounding Agents>

[0161] In addition to the first bismuth compound and the polymerizable compound, the curable composition disclosed herein may also contain known compounding agents, coordination organic compounds, terpenes, etc.

[0162] Commonly known compounding agents include free radical polymerization initiators, antioxidants, release agents for improving release properties from molds, pigments for adjusting the color of cured products, chain transfer agents for controlling polymerization, plasticizers for improving the plasticity of cured products or giving them heat or cold resistance, antioxidants for improving durability, and anti-aging agents.

[0163] These compounding agents can be compounded within a range that does not impair the effects of the present invention. For example, relative to 100 parts by weight of the first bismuth compound and the polymerizable compound, it is preferable to compound 0 to 30 parts by weight of each compounding agent, more preferably 0.01 to 20 parts by weight, and even more preferably 0.02 to 15 parts by weight.

[0164] The curable composition disclosed herein can be manufactured by mixing a first bismuth compound, a polymerizable compound, and various compounding agents as needed.

[0165] [Coordination organic compounds]

[0166] Coordinating organic compounds are organic compounds that can be coordinated to bismuth and can function as odor suppressants and viscosity modifiers for cured products.

[0167] The acid dissociation constant pKa of coordination organic compounds is preferably 2.0 or higher and 15.0 or lower. Using coordination organic compounds with acid dissociation constant pKa within this range tends to yield solids with low yellowness and odor. The acid dissociation constant pKa of coordination organic compounds can be 3 or higher, 4 or higher, or 6 or higher. The acid dissociation constant pKa of coordination organic compounds can be 14 or lower, 11 or lower, or 10 or lower. It should be noted that the acid dissociation constant pKa refers to the acid dissociation constant in water. This acid dissociation constant pKa can be calculated experimentally, for example, by using titration and other assumed conditions. Specifically, the calculation results can be obtained using ACD / Lab software V11.02 as described in SciFinder-n. Although it is an assumed value in water, this value can be used as a uniform physical property index for each compound.

[0168] The molecular weight (relative molecular mass) of the coordination organic compound is preferably 17 or more and 400 or less. Coordination organic compounds with molecular weights in this range are considered to be more readily coordinated to bismuth. More preferably, the molecular weight of the coordination organic compound is 18 or more and 300 or less, and even more preferably 28 or more and 200 or less.

[0169] The boiling point of the coordination organic compound at 1 atmosphere is preferably 20°C or higher and 500°C or lower. Using a coordination organic compound with a boiling point within this range tends to further reduce the odor of the cured product. More preferably, the boiling point of the coordination organic compound is 30°C or higher and 400°C or lower, and even more preferably 120°C or higher and 360°C or lower.

[0170] In the curable composition, the ratio M1 / M4 of the mass of the first bismuth compound M1 to the mass of the coordinating organic compound is, for example, 4 or more and 4990 or less. If this ratio M1 / M4 is high, there is a tendency for the radiation shielding capability of the cured product to increase. If this ratio M1 / M4 is low, there is a tendency for the odor of the cured product to decrease. This ratio M1 / M4 is preferably 10 or more and 700 or less, more preferably 15 or more and 300 or less, and even more preferably 20 or more and 100 or less. This ratio, for example, allows for the utilization of… 1 Measured by H-NMR.

[0171] In curable compositions, a high proportion of the coordinating organic compound tends to reduce the odor of the cured product. The proportion of the coordinating organic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. On the other hand, if the proportion of the coordinating organic compound is too high, the radiation shielding ability of the cured product may decrease. The proportion of the coordinating organic compound is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0172] Examples of coordination organic compounds include: compounds with an imidazole skeleton, compounds with a pyrazole skeleton, compounds with a triazole skeleton, compounds with a tetraazole skeleton, compounds having at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms and an unsaturated bond, unsaturated dicarboxylic acids, unsaturated carboxylic esters, and unsaturated carboxylic anhydrides. It should be noted that even if a coordination organic compound has a free radical polymerizable group such as a (meth)acryloyl group, the coordination organic compound is still not included in the above-mentioned polymerizable compounds.

[0173] The coordinating organic compound preferably comprises at least one compound selected from the group consisting of compounds having an imidazole skeleton, compounds having a pyrazole skeleton, compounds having a triazole skeleton, and compounds having a tetraazole skeleton.

[0174] Compounds having an imidazole skeleton have a skeleton represented by the following formula (a).

[0175]

[0176] Compounds having an imidazole skeleton, such as those selected from imidazole, 1-vinylimidazol, 1-allylimidazol, N-acetylimidazol, benzimidazole, 1-methylimidazol, 1-ethylimidazol, 1-propylimidazol, 1-cyanomethylimidazol, 1-(3-aminopropyl)imidazol, 2-methylimidazol, 2-methyl-1-vinylimidazol, 2-hydroxymethyl-1-methylimidazol, 4-hydroxymethyl-5-methylimidazol, 2-formyl-1 - Vinylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-chloroimidazole, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole, 4-fluoroimidazole, 2-formylimidazole, 2-ethyl-4-imidazole, 4-formylimidazole, 4-ethylimidazole, 4-cyanomethylimidazole, 2-imidazolium carboxylic acid, 4-imidazolium carboxylic acid, 1-isopropylimidazole, 2-isopropylimidazole, and 1,2-dimethylimidazole. The compound having an imidazole skeleton preferably comprises at least one compound selected from the group consisting of imidazole, 1-vinylimidazole, 1-allylimidazole, 2-methylimidazole, N-acetylimidazole, trimethylsilylimidazole, and 1,2-dimethylimidazole, and more preferably includes imidazole.

[0177] Compounds having a pyrazole skeleton have a skeleton represented by the following formula (b).

[0178]

[0179] Compounds having a pyrazole skeleton, such as those selected from pyrazole, 1-methylpyrazole, 1-ethylpyrazole, 1-isopropylpyrazole, 1-nitropyrazole, 3-methylpyrazole, 3-aminopyrazole, 3-nitropyrazole, 4-methylpyrazole, 4-aminopyrazole, 4-chloropyrazole, 4-nitropyrazole, 3-amino-1-methylpyrazole, 3-amino-5-methylpyrazole, 3-amino-5-hydroxypyrazole, 5-amino-1-methylpyrazole, 5-hydroxy-1-methylpyrazole, 1 At least one compound from the group consisting of 2-dihydropyrazole-3-one, 3-formylpyrazole, 1,3-dimethylpyrazole, 1,5-dimethylpyrazole, 3,5-dimethylpyrazole, 3-amino-4-cyanopyrazole, 4-formyl-1-methylpyrazole, 1,3,5-trimethylpyrazole, 5-amino-1,3-dimethylpyrazole, 5-amino-1-ethylpyrazole, pyrazole-4-carboxylic acid, pyrazole-3-carboxylic acid, and 5-(hydroxymethyl)-1-methylpyrazole. Compounds having a pyrazole skeleton preferably contain pyrazole.

[0180] Compounds with a triazole skeleton include compounds with a 1,2,3-triazole skeleton and compounds with a 1,2,4-triazole skeleton.

[0181] Compounds having a 1,2,3-triazole skeleton have a skeleton represented by the following formula (c).

[0182]

[0183] Compounds having a 1,2,3-triazole skeleton, for example comprising at least one compound selected from the group consisting of 1,2,3-triazole, 1H-benzotriazole, and 2H-benzotriazole. Compounds having a 1,2,3-triazole skeleton preferably comprise 1,2,3-triazole.

[0184] Compounds having a 1,2,4-triazole skeleton have a skeleton represented by the following formula (d).

[0185]

[0186] Compounds having a 1,2,4-triazole skeleton, for example comprising at least one compound selected from the group consisting of 1,2,4-triazole, 3-methyl-1H-1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 1-hydroxymethyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3,5-amino-1,2,4-triazole, and methyl 1,2,4-triazole-3-carboxylate. Compounds having a 1,2,4-triazole skeleton preferably comprise 1,2,4-triazole.

[0187] Compounds with a tetrazolium skeleton have a skeleton represented by the following formula (e).

[0188]

[0189] Compounds having a tetrazolium skeleton, for example, comprising at least one compound selected from the group consisting of tetrazolium, 1-methyl-1H-tetrazole, 5-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, and 5-(2-pyridyl)-1H-tetrazole. Compounds having a tetrazolium skeleton preferably comprise a tetrazolium.

[0190] Coordinative organic compounds include, for example, compounds having at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and an unsaturated bond. The number of heteroatoms is, for example, 1 or more and 5 or less, preferably 1 or 2. Examples of such compounds, in addition to compounds having an imidazole skeleton as described above, include at least one compound selected from the group consisting of allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, indole, carbazole, 1,2-benzisothiazol-3(2H)-one, piperaldehyde, allyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, and 2-(tert-butylamino)ethyl methacrylate.

[0191] Coordinating organic compounds may include, for example, unsaturated dicarboxylic acids. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citralic acid, mesonic acid, 2-pentenic acid, methylene succinic acid, allyl malonic acid, isopropylidene succinic acid, 2,4-hexadienoic acid, and acetylene dicarboxylic acid. Maleic acid is preferred among the unsaturated dicarboxylic acids.

[0192] Coordinating organic compounds may include, for example, unsaturated carboxylic acid esters. Examples of unsaturated carboxylic acid esters include 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, diallyl maleate, etc. Preferably, the unsaturated carboxylic acid ester comprises at least one compound selected from the group consisting of 2-dimethylaminoethyl acrylate and 2-dimethylaminoethyl methacrylate.

[0193] Coordinative organic compounds include, for example, unsaturated carboxylic anhydrides. Examples of unsaturated carboxylic anhydrides include methacrylic anhydride and maleic anhydride.

[0194] Preferred examples of coordinating organic compounds include imidazole, 1-vinylimidazolium, 1-allylimidazolium, N-acetylimidazolium, trimethylsilylimidazolium, pyrazole, triazole, 1H-tetrazole, 1,2,3-benzotriazole, benzimidazole, allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, indole, carbazole, 2-methylimidazolium, 4-methylimidazolium At least one compound from the group consisting of azole, 1,2-benzisothiazol-3(2H)-one, 2-isopropylimidazol, 1,2-dimethylimidazol, L-menthol, piperonal, triallyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, 4-acryloylmorpholine, triacryloylhexahydrotriazine, dimethylpyrazole, linalool, camphor, acrylic acid, methacrylic acid, maleic acid, acrylic anhydride, methacrylic anhydride and maleic anhydride.

[0195] The coordination organic compound preferably comprises at least one compound selected from the group consisting of imidazole, 2-methylimidazolium, 1-vinylimidazolium, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, triallylamine, and maleic anhydride.

[0196] It should be noted that carboxylic anhydrides can be used as precursors for carboxylic acids. The acid dissociation constant pKa is given using the value corresponding to the carboxylic acid.

[0197] The coordination organic compound preferably includes a first coordination organic compound and a second coordination organic compound of a different type than the first coordination organic compound. If multiple coordination organic compounds are included, the odor can be further reduced through their synergistic effect.

[0198] The coordinating organic compound preferably comprises a compound having an imidazole skeleton, and includes compounds selected from those having a pyrazole skeleton, compounds having a triazole skeleton, compounds having a tetraazole skeleton, compounds having at least one heteroatom and an unsaturated bond selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and at least one compound selected from the group consisting of unsaturated dicarboxylic acids, unsaturated carboxylic esters, and unsaturated carboxylic anhydrides. If a compound with an imidazole skeleton is included, the viscosity of the curable composition tends to decrease, and its processability to improve.

[0199] In the complex of various coordinating organic compounds, the proportion of compounds having an imidazole skeleton is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. According to one example, the proportion of compounds having an imidazole skeleton is 90% by mass or less, and according to another example, it is 60% by mass or less.

[0200] The coordinating organic compound preferably comprises unsaturated carboxylic anhydrides, and includes compounds selected from those having an imidazole skeleton, compounds having a pyrazole skeleton, compounds having a triazole skeleton, compounds having a tetraazole skeleton, compounds having at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms and an unsaturated bond, and at least one compound selected from the group consisting of unsaturated dicarboxylic acids and unsaturated carboxylic acid esters. If unsaturated carboxylic anhydrides are included, the hygroscopicity tends to increase.

[0201] In the complex of various coordinating organic compounds, the proportion of unsaturated carboxylic anhydrides is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. According to one example, the proportion of unsaturated carboxylic anhydrides is 90% by mass or less, and according to another example, it is 60% by mass or less.

[0202] The coordination organic compound preferably comprises both a compound having an imidazole skeleton and an unsaturated carboxylic anhydride. The coordination organic compound may also comprise only a compound having an imidazole skeleton and an unsaturated carboxylic anhydride, or it may comprise other compounds.

[0203] [Terpenes]

[0204] Terpenes, including terpenes and their derivatives, can function as odor suppressants in solidified products. Terpenes are hydrocarbons with isoprene as their structural unit.

[0205] Terpenes include, for example, at least one compound selected from the group consisting of hemiterpenes, hemiterpene derivatives, monoterpenes, monoterpene derivatives, sesquiterpenes, and sesquiterpene derivatives. Terpenes preferably include at least one compound selected from the group consisting of monoterpenes, monoterpene derivatives, sesquiterpenes, and sesquiterpene derivatives, and more preferably include at least one compound selected from the group consisting of monoterpenes and monoterpene derivatives. Various derivatives may have functional groups such as hydroxyl and carbonyl groups.

[0206] The terpenes preferably include at least one compound selected from the group consisting of monocyclic monoterpenes, monocyclic monoterpenes derivatives, polycyclic monoterpenes, and polycyclic monoterpenes derivatives. Including these monoterpenes tends to further reduce the odor of the cured product.

[0207] Specific examples of terpenes include at least one selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-terpinene, limonene, phenethyl ether, p-isopropyltoluene, terpinene, 1,8-cineole, linalool, (+)-camphor, L-menthol, D-menthol, 1,4-cineole, β-pinene, α-phellandrene, fennel, borneol, and citronellol.

[0208] The terpenes preferably comprise at least one selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-methylstyrene, α-terpinene, limonene, phenethyl ether, p-isopropyltoluene, terpinene, 1,8-cineole, linalool, (+)-camphor, and L-menthol. More preferably, the terpenes comprise at least one selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-methylstyrene, limonene, phenethyl ether, p-isopropyltoluene, linalool, and (+)-camphor.

[0209] The boiling point of terpenes at 1 atmosphere is preferably 95°C or higher and 250°C or lower. Using terpenes with boiling points within this range tends to further reduce the odor of the cured product. More preferably, the boiling point of terpenes is 100°C or higher and 220°C or lower, and even more preferably 150°C or higher and 210°C or lower. The boiling point of terpenes can be determined, for example, using a boiling point apparatus.

[0210] In the curable composition, the ratio M1 / M5 of the mass of the first bismuth compound (M1) to the mass of the terpene (M5) is, for example, 4 or more and 4990 or less. If this ratio M1 / M5 is high, there is a tendency for the radiation shielding ability of the cured product to improve. If this ratio M1 / M5 is low, there is a tendency for the odor of the cured product to decrease. This ratio M1 / M5 is preferably 10 or more and 700 or less, more preferably 15 or more and 300 or less, and even more preferably 20 or more and 100 or less. This ratio, for example, allows for...1 Measured by H-NMR.

[0211] If the proportion of terpenes in the curable composition is high, the odor of the cured product tends to be reduced more easily. The proportion of terpenes is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. On the other hand, if the proportion of terpenes is too high, the radiation shielding ability of the cured product may be reduced. The proportion of terpenes is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. These proportions can be achieved, for example, by... 1 Measured by H-NMR.

[0212] <Methods for manufacturing solidified products>

[0213] As a method for curing the curable composition of this disclosure to obtain a cured product, known methods can be employed. Specifically, photopolymerization, thermal polymerization, or both can be used. The preferred polymerization method is determined by the free radical polymerization initiator formulated as needed.

[0214] <Physical Properties of Solidified Materials>

[0215] The curable composition disclosed herein can be used to produce a cured product containing a high concentration of bismuth with high radiation shielding capabilities, such as X-rays, and exhibiting high transmittance and flexibility with minimal coloring. The cured product obtained by curing the curable composition can be, for example, 2 mm thick, with a transmittance of 80% or more at a wavelength of 560 nm, an X-ray shielding capability equivalent to 0.02 mm of lead foil or more, and a yellowness of 40 or less.

[0216] Furthermore, when the total mass of the cured product is set to 100% by mass, the bismuth content in the cured product can be set to 5% to 40% by mass. The amount of bismuth is preferably 20% by mass or more, and more preferably 25% by mass or more. The proportion of bismuth in the cured product (resin composition) can be determined, for example, by fluorescence X-ray analysis.

[0217] The cured product can be a resin composition comprising bismuth, a (meth)acrylic resin, and at least 16.0% by mass of polyethylene glycol chains. The polyethylene glycol chains constitute a portion of the (meth)acrylic resin. The proportion of polyethylene glycol chains in the resin composition can be at least 17.0% by mass or at least 19.0% by mass. There is no particular upper limit to the proportion of polyethylene glycol chains in the resin composition; in one example, it is 30.0% by mass or less, and in another example, it is 25.0% by mass or less. The proportion of polyethylene glycol chains in the resin composition can be determined, for example, using NMR spectroscopy.

[0218] <Applications of solidified products>

[0219] The cured product obtained by curing the curable composition of this disclosure is transparent due to its light color, and therefore can be used as an optical article. Furthermore, although it has visible light transmittance, it also has radiation shielding capability, and therefore can be used as a transparent radiation shielding material. Moreover, since a large and flexible sheet can be obtained, it can be easily manufactured into a form that matches the application and the object.

[0220] Optical articles containing the cured material disclosed herein can be used as sheets for purposes such as radiation shielding window materials, radiation shielding lenses, and radiation protection curtains.

[0221] Lenses or sheets containing the cured material of this disclosure can be used as radiation shielding glasses or radiation shielding shields.

[0222] In addition, the cured product disclosed herein has antibacterial and antiviral properties, and therefore can be used in applications requiring high hygiene standards.

[0223] Example

[0224] The present invention will now be described in detail using examples and comparative examples, but the present invention is not limited to the following examples.

[0225] <Example 1>

[0226] (Preparation of the first bismuth compound)

[0227] 94.27 g of bismuth(III) basic salicylate (manufactured by Sigma-Aldrich, equivalent to 260.35 mmol of bismuth), 33.06 g of a mixture of bis[(2-methacryloyloxyethyl)] phosphate (a phosphate diester) and (2-methacryloyloxyethyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., MR-200, phosphoric acid value 162.04 mmol), 33.09 g of diphenyl-2-methacryloyloxyethyl phosphate (a phosphate trister) (manufactured by Daihachi Chemical Industry Co., Ltd., MR-260, 91.33 mmol), and 6.17 g of butylated hydroxytoluene (BHT, manufactured by FUJIFILM Wako Pure Chemical Corporation, premium reagent) as a polymerization inhibitor were placed in a 1000 mL round-bottom flask, and 750 mL of toluene was added. The solution in the flask was ultrasonically dispersed using a bath ultrasonic shaker to prepare a turbid solution.

[0228] The resulting turbid solution was transferred to a 1000 mL four-necked flask equipped with a Dean-Stark Trap separator. The reaction was carried out in an oil bath at 130 °C with stirring, and the generated water was removed from the system. The point at which no more water was generated was defined as the reaction endpoint. A pale yellow scattering solution with a small amount of pale yellow precipitate was obtained.

[0229] The solution was concentrated to 250 mL using a vacuum evaporator. 8 g of alumina powder was added, and the mixture was allowed to stand overnight. Then, it was filtered using 5B filter paper. 3 g of activated carbon (Norit Darco G60) was added to the obtained pale yellow scattering filtrate, and the mixture was centrifuged at 23830 × g for 8 hours. The supernatant was then pressure-filtered through a 0.2 μm membrane filter to obtain a pale yellow transparent filtrate. The solvent was removed from this solution by vacuum evaporation, and the solution was then dissolved in 250 mL of acetone. 3 g of activated carbon (Norit SX-Plus) was added to the obtained pale yellow solution, and the mixture was centrifuged at 23830 × g for 12 hours. The supernatant was then pressure-filtered through a 0.2 μm membrane filter to obtain a pale yellow transparent filtrate. The obtained filtrate was concentrated to 100 mL using a vacuum evaporator. The acetone solution was added to 800 mL of hexane in a 1000 mL conical beaker with stirring. The resulting white precipitate was filtered off using 5B filter paper, and the obtained solid was dried under vacuum. 64.40 g of the first bismuth compound (a composition containing bismuth bound to a phosphate ester) was obtained as a white powder.

[0230] (Analysis of the first bismuth compound)

[0231] IR measurements were performed using a Fourier transform infrared spectrometer (PerkinElmer, Spectrum One). Determination was performed by a single-reflectance ATR method with four integrations. The results showed that the spectrum of the first bismuth compound obtained was [value missing] at 1697 cm⁻¹. -1 Peak confirmed.

[0232] MALDI-TOF-MS determination was performed using a Bruker-manufactured rapiflex TOF / TOF model. CHCA (α-cyano-4-hydroxycinnamic acid), DIT (dithranephenol), and DHB (2,5-dihydroxybenzoic acid) were used as matrices, and sodium trifluoroacetate was used as a cationizing agent. Determination was performed in Reflector / Positive mode, with a mass range of m / z = 20–4000. The results confirmed the presence of compounds represented by formulas (3a), (3b), and (3f) above.

[0233] (The proportion of bismuth in the first bismuth compound)

[0234] The proportion of bismuth in the first bismuth compound was determined by ICP-N (Inductively Coupled Phosphorescent) spectroscopy. The result showed that bismuth accounted for 46% by mass.

[0235] (Preparation of curable composition)

[0236] A mixture of 52 parts by mass of the first bismuth compound obtained above, 16 parts by mass of methoxy polyethylene glycol methacrylate (M-130G) with a degree of polymerization of 13 (ethylene glycol chains), 24.8 parts by mass of methoxyethyl methacrylate (MEMA), and 6 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMAEMA) was prepared. 0.9 parts by mass of imidazole (IMD), 0.3 parts by mass of methylstyrene dimer (MSD), and 0.01 parts by mass of modified silicone oil (KF353A) were added to the above solution and allowed to dissolve uniformly to obtain a curable composition. The curable composition was then subjected to reduced pressure using a vacuum pump to remove dissolved oxygen. The proportion of ethylene glycol chains in the curable composition, i.e., the EO content, was 13.6% by mass.

[0237] (Manufacturing of solidified products)

[0238] The cured composition obtained above was injected into two glass plates (110mm×300mm) fixed in the middle by a 3mm square rope made of silicone resin with a 3mm gap. The temperature was raised to the maximum temperature of 90°C over 15 hours and maintained at 90°C for 2 hours to polymerize, resulting in a pale yellow transparent cured product.

[0239] <Examples 2-12 and Comparative Examples 1-3>

[0240] As shown in Table 1, the curing composition was modified, but the cured product was manufactured using the same method as in Example 1. In Comparative Examples 2 and 3, the amount of methylstyrene dimer (MSD) was set at 0.9 parts by mass.

[0241] The materials are summarized in Table 1 below.

[0242] (First radical polymerizable monomer)

[0243] M-130G: Methoxylated polyethylene glycol methacrylate, with a degree of polymerization of ethylene glycol chains of 13, a number-average molecular weight (N1) of 673, and an ethylene glycol chain content (EO ratio) of 85%;

[0244] M-230G: Methoxylated polyethylene glycol methacrylate, with a degree of polymerization of ethylene glycol chains of 23, a number-average molecular weight N1 of 1113, and an ethylene glycol chain content (EO ratio) of 91%;

[0245] A-1000: Polyethylene glycol diacrylate, with a degree of polymerization of ethylene glycol chains of 23, a number-average molecular weight N1 of 1139, and an ethylene glycol chain content (EO ratio) of 89%;

[0246] 9G: Polyethylene glycol dimethacrylate, with a degree of polymerization of 9 for its ethylene glycol chains, a number-average molecular weight N1 of 551, and an ethylene glycol chain content (EO ratio) of 72%;

[0247] 14G: Polyethylene glycol dimethacrylate, with a degree of polymerization of ethylene glycol chains of 14, a number-average molecular weight (N1) of 771, and an ethylene glycol chain content (EO ratio) of 80%;

[0248] 23G: Polyethylene glycol dimethacrylate, with a degree of polymerization of ethylene glycol chains of 23, a number-average molecular weight (N1) of 1167, and an ethylene glycol chain content (EO ratio) of 87%;

[0249] AM-130G: Methoxylated polyethylene glycol acrylate, with a degree of polymerization of ethylene glycol chains of 13, a number-average molecular weight N1 of 659, and an ethylene glycol chain ratio (EO rate) of 88%.

[0250] (Second radical polymerizable monomer)

[0251] MEMA: Methoxyethyl methacrylate

[0252] DMAEMA: 2-(dimethylamino)ethyl methacrylate

[0253] THFAA: Tetrahydrofurfuryl acrylate

[0254] <Evaluation Trial>

[0255] [Impact resistance test]

[0256] A drop ball test was conducted to evaluate the impact resistance of the cured material. First, a support ring made of nitrile butadiene rubber (NBR) was attached to a tube with an inner diameter of 25 mm, an outer diameter of 32 mm, and a height of 25 mm. The support ring was 3 mm thick and had an inner diameter of 25 mm. The cured material was then placed on the support ring. A steel ball was dropped from a height of 1.27 m onto the cured material using a drop device employing an electromagnet. The weights of the steel balls were 4.5 g, 6.9 g, 14 g, 16 g, 32 g, 50 g, 67 g, 80 g, 95 g, 112 g, 130 g, 151 g, 174 g, 198 g, 225 g, and 261 g. The steel balls were dropped sequentially from lightest to heaviest, and the weight of the steel ball preceding the one that caused the cured material to crack and break was defined as the maximum impact resistance. This test was performed three times, and the average value was defined as the maximum impact resistance of the cured material. The results are shown in Table 1.

[0257] [Shore D Hardness Test]

[0258] The Shore D hardness of the cured material was determined according to JIS K 7215. As an apparatus, a digital hardness tester (manufactured by Polymer Instruments Co., Ltd., DD4) was used, mounted on a motor-driven constant pressure load cell (manufactured by Polymer Instruments Co., Ltd., CLE-150). The pointer was lowered at a rate of 1 cm / s, and the value was read. Three measurements were performed, and the average value was taken as the Shore D hardness of the cured material. The results are shown in Table 1.

[0259] [Refrigeration Test]

[0260] The cured material was left to stand in a constant temperature bath at 4°C for 30 minutes. Afterward, the cured material was removed from the bath and placed in a room at 25°C. The surface of the cured material was visually observed for fogging, and evaluated according to the following three levels. The results are shown in Table 1.

[0261] -Evaluation Benchmarks-

[0262] 1: Fog not confirmed.

[0263] 2: After removal, fog was observed on a portion of the solidified surface, which disappeared after a few seconds.

[0264] 3: After removing it, fog was observed on the entire surface of the solidified material. The fog did not disappear after standing for 1 minute.

[0265] [Fog Disappearance Experiment]

[0266] The following method was used to conduct a fog disappearance test on the solidified material. First, a steam generating device was prepared. The steam generating device included: a water tank; a storage tank located in the water tank to store water; a first pipe connecting the external space (external atmosphere) to the water in the storage tank (aqueous phase); and a second pipe connecting the upper part of the water stored in the storage tank (gas phase) to the external space (external atmosphere). Air was blown into the 50°C distilled water stored in the storage tank at a flow rate of 1.0 mL / min through the first pipe to generate steam in the storage tank. The steam was then ejected into the external space through the second pipe. The solidified material was placed 1 cm away from the steam outlet, and the solidified material was immersed in the steam for 1 second. After 1 second, the steam outlet was plugged, and the time until the fog on the solidified material disappeared was measured. This test was performed 10 times, and the average value was taken as the fog disappearance time of the solidified material. The results are shown in Table 1.

[0267] [Table 1]

[0268]

[0269] As shown in Table 1, a cured product with anti-fogging properties can be obtained according to the curable compositions of Examples 1 to 12. The curable compositions of Examples 1 to 12 contain a first bismuth compound and a first free radical polymerizable monomer in which the proportion (EO rate) of the polyethylene glycol chain is 75% or more and 95% or less, and the proportion (EO amount) of the polyethylene glycol chain in the composition is 13.5% by mass or more.

[0270] The following are preferred embodiments.

[0271] [1] A curable composition comprising:

[0272] A first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and

[0273] The first free radical polymerizable monomer has polyethylene glycol chains, wherein the number-average molecular weight N2 of the aforementioned polyethylene glycol chains accounts for a ratio N2 / N1 of more than 75% and less than 95%.

[0274] The aforementioned polyethylene glycol chain accounts for more than 13.5% by mass.

[0275] [2] The curable composition according to [1], wherein the aforementioned ratio N2 / N1 is 85% or more and 95% or less.

[0276] [3] The curable composition according to [1] or [2], wherein the number average molecular weight N1 of the first free radical polymerizable monomer is 500 or more and 1500 or less.

[0277] [4] The curable composition according to any one of [1] to [3], wherein the proportion of the aforementioned first free radical polymerizable monomer is 15% by mass or more.

[0278] [5] The curable composition according to any one of [1] to [4], wherein the first free radical polymerizable monomer is a monofunctional (meth)acrylate.

[0279] [6] The curable composition according to any one of [1] to [5], wherein the aforementioned first free radical polymerizable monomer comprises a (meth)acrylate represented by the following formula (I):

[0280]

[0281] In the aforementioned formula (I),

[0282] R 1 It can be a hydrogen atom or a methyl group;

[0283] R 2 Acryloyl, methacryloyl, methyl, or phenyl;

[0284] n is an integer greater than 10 and less than 30.

[0285] [7] The curable composition according to any one of [1] to [6], wherein the proportion of the aforementioned first bismuth compound is 30% by mass or more and 70% by mass or less.

[0286] [8] The curable composition according to any one of [1] to [7] further contains a second radical polymerizable monomer that does not have a polyethylene glycol chain.

[0287] [9] The curable composition according to [8], wherein the aforementioned second radical polymerizable monomer comprises a compound represented by the following formula (II):

[0288]

[0289] In the aforementioned formula (II),

[0290] R 3 It can be a hydrogen atom or a methyl group;

[0291] R 4 It is an alkylene group having 1 or more but less than 5 carbon atoms;

[0292] R 5 It is an alkyl, phenyl, dimethylamino, diethylamino, acryloyloxy, or methacryloxy group having 1 or more but less than 5 carbon atoms;

[0293] m is 0 or 1.

[0294]

[10] The curable composition according to [8] or [9], wherein the proportion of the aforementioned second free radical polymerizable monomer is 10% by mass or more and 40% by mass or less.

[0295]

[11] The curable composition according to any one of [1] to

[10] , wherein the proportion of the aforementioned polyethylene glycol chain is 13.6% by mass or more and 30.0% by mass or less.

[0296]

[12] A cured product, which is a cured product of any one of the curable compositions described in [1] to

[11] .

[0297]

[13] An optical article comprising the cured material described in

[12] .

[0298]

[14] A lens comprising the cured material described in

[12] .

[0299]

[15] A rubber sheet comprising the cured material described in

[12] .

[0300]

[16] An eye protection device comprising the solidified material described in

[12] .

[0301]

[17] An antibacterial / antiviral agent comprising a solidified material as described in

[12] .

[0302]

[18] A resin composition comprising bismuth, (meth)acrylic resin and 16.0% by weight or more of polyethylene glycol chains.

Claims

1. A curable composition comprising: A first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and The first radical polymerizable monomer has polyethylene glycol chains, wherein the number-average molecular weight N2 of the polyethylene glycol chains accounts for a ratio N2 / N1 of 75% or more and 95% or less. The proportion of the polyethylene glycol chain is 13.5% by mass or more.

2. The curable composition according to claim 1, wherein, The ratio N2 / N1 is above 85% and below 95%.

3. The curable composition according to claim 1, wherein, The number average molecular weight N1 of the first free radical polymerizable monomer is greater than 500 and less than 1500.

4. The curable composition according to claim 1, wherein, The proportion of the first free radical polymerizable monomer is 15% by mass or more.

5. The curable composition according to claim 1, wherein, The first free radical polymerizable monomer is a monofunctional (meth)acrylate.

6. The curable composition according to claim 1, wherein, The first radical polymerizable monomer comprises a (meth)acrylate represented by the following formula (I): In the aforementioned formula (I), R 1 It can be a hydrogen atom or a methyl group; R 2 Acryloyl, methacryloyl, methyl, or phenyl; n is an integer greater than 10 and less than 30.

7. The curable composition according to claim 1, wherein, The proportion of the first bismuth compound is more than 30% by mass and less than 70% by mass.

8. The curable composition according to claim 1, further comprising a second radical polymerizable monomer that does not have a polyethylene glycol chain.

9. The curable composition according to claim 8, wherein, The second radical polymerizable monomer comprises a compound represented by the following formula (II): In the aforementioned formula (II), R 3 It can be a hydrogen atom or a methyl group; R 4 It is an alkylene group having 1 or more but less than 5 carbon atoms; R 5 It is an alkyl, phenyl, dimethylamino, diethylamino, acryloyloxy, or methacryloxy group having 1 or more but less than 5 carbon atoms; m is 0 or 1.

10. The curable composition according to claim 8, wherein, The proportion of the second free radical polymerizable monomer is more than 10% by mass and less than 40% by mass.

11. The curable composition according to claim 1, wherein, The proportion of the polyethylene glycol chain is more than 13.6% by mass and less than 30.0% by mass.

12. A cured product, which is a cured product of the curable composition according to any one of claims 1 to 11.

13. An optical article comprising the cured material of claim 12.

14. A lens comprising the cured material of claim 12.

15. A rubber sheet comprising the cured material of claim 12.

16. An eye protection device comprising the solidified material of claim 12.

17. An antibacterial / antiviral agent comprising the cured product of claim 12.

18. A resin composition comprising bismuth, a (meth)acrylic resin, and 16.0% by weight or more of a polyethylene glycol chain.

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