Composition, curable composition, cured product, optical article, lens, glasses, and antibacterial / antiviral agent

Abstract

The present invention provides a composition comprising: a first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and terpenes. The present invention also provides a curable composition comprising the composition; a cured product of the curable composition; and an optical article, a lens, eyeglasses, and an antibacterial / antiviral agent, each of which contains the cured product.

Description

Technical Field

[0001] The present invention relates to a composition, a curable composition, a cured product, an optical article, a lens, glasses, and an antibacterial / antiviral agent. Background Art

[0002] The International Commission on Radiological Protection (ICRP) has alerted the risk that radiation can cause cataracts. Affected by this, in Japan, the Ionizing Radiation Hazards Prevention Regulations have been revised, and since April 2021, the limit of the equivalent dose received by the eye lenses of workers engaged in radiation work has been lowered. Workers engaged in radiation work are more strongly required to effectively use appropriate eye protection materials to reduce the risk.

[0003] Generally, as raw materials for shielding materials for eye protection, lead glass and lead acrylate as lightweight materials are used. However, lead is harmful to the environment and the human body, and there is a strong expectation for a lead-free alternative in shielding materials based on inorganic glass or resin. As alternative elements to lead, the following can be cited: bismuth, barium, antimony, tin, tungsten, etc.; among them, research on materials using bismuth is underway. Bismuth has been used as a gastrointestinal medicine since ancient times, is harmless to the human body, and has the same radiation shielding ability as lead, making it a suitable element to replace lead.

[0004] Generally, bismuth compounds have low solubility in organic solvents containing polymerizable monomers, and their use is restricted. In recent years, it has been reported that a cured product having sufficient transparency as an optical material can be obtained by using a composition containing a bismuth compound and a radical polymerizable monomer other than the bismuth compound, wherein the bismuth of the bismuth compound is bonded to a phosphate ester having a (meth)acryloyl group (see Patent Documents 1 and 2). This cured product has a high concentration of bismuth components dispersed in a resin matrix, and not only has excellent ability to shield X-rays for medical use, but also has excellent ability to shield radiation such as β-rays, and can be used for radiation protection glasses lenses, shielding materials, screens, observation windows, etc.

[0005] In addition, it is also known that bismuth compounds have antibacterial and antiviral properties and can be used as structural materials or coating materials having antibacterial / antiviral properties. Transparency is not necessarily required for this use.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: International Publication No. 2022 / 014591

[0009] Patent Document 2: International Publication No. 2019 / 177084 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] An object of the present invention is to provide a composition with reduced odor, a curable composition, a cured product of the curable composition, and an optical article, a lens, glasses, and an antibacterial / antiviral agent containing the cured product.

[0012] Solution to the problem

[0013] Specific means for solving the above problems include the following embodiments.

[0014] <1> A composition comprising:

[0015] A first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and

[0016] Terpenes.

[0017] <2> The composition according to <1>, wherein the ratio M1 / M2 of the mass M1 of the aforementioned first bismuth compound to the mass M2 of the aforementioned terpenes is 4 or more and 4990 or less.

[0018] <3> The composition according to <1> or <2>, wherein the aforementioned terpenes contain at least one compound selected from the group consisting of hemiterpenes, hemiterpene derivatives, monoterpenes, monoterpene derivatives, sesquiterpenes, and sesquiterpene derivatives.

[0019] <4> The composition according to any one of <1> to <3>, wherein the aforementioned terpenes contain at least one compound selected from the group consisting of monocyclic monoterpenes, monocyclic monoterpene derivatives, polycyclic monoterpenes, and polycyclic monoterpene derivatives.

[0020] <5> The composition according to any one of <1> to <4>, wherein the aforementioned terpenes contain at least one compound selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-terpinene, limonene, phenyl ethyl ether, p-cymene, terpinolene, 1,8-cineole, linalool, (+)-camphor, l-menthol, d-menthol, 1,4-cineole, nopinene, α-phellandrene, fenchone, borneol, and citronellol.

[0021] <6> The composition according to any one of <1> to <5>, wherein the boiling point of the aforementioned terpenes at 1 atmospheric pressure is 95°C or more and 250°C or less.

[0022] <7> The composition according to any one of <1> to <6>, which further contains a coordinating organic compound having an acid dissociation constant pKa of 1.5 or more.

[0023] <8> The composition according to any one of <1> to <7>, wherein the first bismuth compound further has a phosphoric acid bond.

[0024] <9> The composition according to any one of <1> to <8>, wherein the first bismuth compound further has a phenyl group.

[0025] <10> A curable composition comprising:

[0026] The composition according to any one of <1> to <9>; and

[0027] A first polymerizable compound having at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

[0028] <11> The curable composition according to <10>, wherein the content of the first bismuth compound is 10% by mass or more and 90% by mass or less.

[0029] <12> A cured product which is a cured product of the curable composition according to <10> or <11>.

[0030] <13> An optical article comprising the cured product according to <12>.

[0031] <14> A lens comprising the cured product according to <12>.

[0032] <15> A pair of glasses comprising the lens according to <14>.

[0033] <16> An antibacterial / antiviral agent comprising the cured product according to <12>.

[0034] <17> A composition comprising:

[0035] A first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and

[0036] An azeotropic compound of phenol.

[0037] Effects of the Invention

[0038] According to the present invention, it is possible to provide a composition and a curable composition with reduced odor, a cured product of the curable composition, and an optical article, a lens, a pair of glasses, and an antibacterial / antiviral agent containing the cured product. Detailed Description of the Invention

[0039] Hereinafter, specific embodiments to which the present invention is applied will be described in detail.

[0040] In this specification, the term “(meth)acryloyl” means both “acryloyl” and “methacryloyl”, and the term “(meth)acrylate” means both “acrylate” and “methacrylate”. The same applies to terms such as “(meth)acrylic acid”.

[0041] 《Composition》

[0042] The composition of this embodiment contains a first bismuth compound and contains an azeotropic compound of terpenes or phenols. The first bismuth compound has bismuth and has at least one of acryloyl and methacryloyl. By using the composition of this embodiment, a cured product with reduced odor can be obtained. The reason is presumably as follows.

[0043] The cured product containing the first bismuth compound sometimes contains impurities. These impurities are derived from, for example, the raw materials of the first bismuth compound and by-products generated during the manufacture of the first bismuth compound. These impurities are difficult to completely remove during the purification operation and sometimes remain in the cured product. These impurities remaining in the cured product may be the cause of the odor of the cured product. The inventors conducted in-depth research and found that these impurities can be included in the cured product in a form coordinated to the bismuth of the first bismuth compound. That is, the bismuth element forms a valence state of 0, 3, or 5. In the composition of this embodiment, the bismuth of the first bismuth compound can also reversibly change to a state of 0, 3, or 5. Furthermore, even trivalent bismuth is 8-coordinated, so the impurities contained in the composition can be coordinated to the empty coordination sites of bismuth, or the impurities can be coordinated as substituents. The inventors found that the impurities coordinated to bismuth may be released into the atmosphere by dissociating from bismuth over time, which may be the cause of the odor.

[0044] For example, when a compound containing a phenyl ester moiety of phosphoric acid is used as a raw material for manufacturing the first bismuth compound, partial hydrolysis occurs during manufacture and phenol is released. The released phenol can be coordinated to bismuth. This phenol is an important example of a by-product that causes the above-mentioned odor. The phenol contained in the first bismuth compound or the phenol contained in the cured product containing the first bismuth compound can be analyzed using a headspace gas chromatography-mass spectrometry device (GC / MS), and its volatilization amount can be easily quantified using a gas detector tube for phenol.

[0045] As described above, the composition of the present embodiment contains a first bismuth compound and an azeotropic compound of a terpene or phenol. Since the terpene has a high compatibility with impurities, it is considered that during the production of a cured product based on the polymerization of the curable composition, it vaporizes from the curable composition or the cured product together with impurities such as phenol. In addition, since the azeotropic compound is a compound capable of forming an azeotrope with phenol, it is considered that during the production of a cured product based on the polymerization of the curable composition, phenol vaporizes from the curable composition or the cured product together with the azeotropic compound. Therefore, if the composition of the present embodiment is used, a cured product with a reduced amount of impurities and a reduced odor can be achieved. Even if the residual amount of the by-product causing the odor contained in the first bismuth compound is several tens of ppm, the amount of volatile odorants in the present embodiment, although it also depends on the characteristics of its molecules, can still be 5 ppm or less, and can be made below the detection limit under optimal conditions.

[0046] Hereinafter, each component used in the composition of the present embodiment will be described.

[0047] <First Bismuth Compound>

[0048] The first bismuth compound has bismuth and at least one of an acryloyl group and a methacryloyl group. Since the first bismuth compound contains bismuth, it can be used as a radiation shielding material. Radiation includes electromagnetic radiation and particle radiation. Electromagnetic radiation includes X-rays and γ-rays. Particle radiation includes α-rays, β-rays, neutron rays, and proton beams. Since the first bismuth compound has excellent X-ray shielding ability, it is particularly suitable as an X-ray shielding material and a shielding material for β-rays that can generate X-rays.

[0049] The first bismuth compound has a high solubility in a radically polymerizable compound having at least one radical polymerization group selected from the group consisting of a nitrile group, an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group. Therefore, if the first bismuth compound is used, a curable composition and its cured product containing a high concentration of bismuth can be obtained. The solubility of the first bismuth compound in the radically polymerizable compound is more excellent than that of bismuth subsalicylate monomer.

[0050] The first bismuth compound can be in any form as long as it has bismuth and a (meth)acryloyl group. For example, bismuth and the (meth)acryloyl group can be directly bonded or can be bonded via a bonding group. Examples of the bonding group include an oxygen atom, a sulfur atom, a nitrogen atom, a phosphate group, etc.

[0051] The first bismuth compound preferably further has a phosphate bond. Additionally, it is more preferable that the bismuth in 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 form between the bismuth and the first phosphate ester is not particularly limited and can be any of an ionic bond, a coordination bond, and a covalent bond. That is, the first bismuth compound can be a phosphate or complex salt having bismuth (Bi 3+ or Bi 5+ ) as the cation and the first phosphate ester as the anion, can also be a phosphoric acid compound, or can be a complex.

[0052] The first bismuth compound can be a mono(meth)acrylate having 1 (meth)acryloyl group, a di(meth)acrylate having 2 (meth)acryloyl groups, a tri(meth)acrylate having 3 (meth)acryloyl groups, or a polyfunctional (meth)acrylate having 4 or more (meth)acryloyl groups.

[0053] In the first bismuth compound, the first phosphate ester is represented by the following formula (2), for example.

[0054]

[0055] In the above formula (2), Q 1 is a hydrogen atom or a methyl group. Q 1 is preferably a methyl group.

[0056] Q 2 is a hydrogen atom, a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 4 or more and 16 or less carbon atoms, or a (meth)acryloyloxyalkylene group. The number of carbon atoms of the alkyl group is preferably 1 or more and 6 or less. The number of carbon atoms of the aryl group is preferably 5 or more and 8 or less. The aryl group is preferably a phenyl group. The number of carbon atoms of the alkylene group contained in the (meth)acryloyloxyalkylene group is, for example, 1 or more and 10 or less, preferably 1 or more and 3 or less. The (meth)acryloyloxyalkylene group is preferably a (meth)acryloyloxyethylene group.

[0057] a 3 is 0 or 1. When a 3 is 0, the oxygen atom to which Q 2 is bonded is O - .

[0058] Q 3 is a linear or branched alkylene group having 1 or more and 10 or less carbon atoms, or a linear or branched alkoxyalkylene group having 1 or more and 10 or less carbon atoms.

[0059] In addition to the first phosphate ester, other compounds may be further bonded to the first bismuth compound. The bonding form between bismuth and other compounds can be any of an ionic bond, a coordination bond, and a covalent bond. That is, the first bismuth compound may be a phosphate or complex salt having bismuth (Bi 3+ or Bi 5+ ) as a cation and the first phosphate ester and other compounds as anions, or may be a phosphoric acid compound or a complex.

[0060] As a specific example of other compounds, at least one selected from the group consisting of salicylic acid and (meth)acrylic acid can be cited.

[0061] In order to improve the solubility in the radically polymerizable compound, the ratio of the first phosphate ester to other compounds is preferably such that, relative to 1 mole of the first phosphate ester, other compounds are 0.1 to 10 moles, more preferably 0.1 to 5 moles, still more preferably 0.1 to 1 mole, and particularly preferably 0.1 to 0.5 moles. It should be noted that when there are two or more types of the first phosphate ester, the above range is based on the total number of moles of the first phosphate ester.

[0062] It can be confirmed by infrared (IR) analysis that the first phosphate ester is bonded to bismuth. That is, in the infrared analysis measurement of the first bismuth compound, for example, when a peak is confirmed at 1670 to 1700 cm -1 , it can be said that the first phosphate ester is bonded to bismuth. This peak is considered to be a characteristic peak of the stretching vibration of Bi-O-P. This peak was not confirmed in bismuth and the first phosphate ester before bonding.

[0063] The IR spectrum is measured, for example, using Spectrum One manufactured by PerkinElmer by the ATR method with one reflection and four accumulations.

[0064] In addition, 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 spectroscopy), etc., the number of bonds of salicylic acid or (meth)acrylic acid and each phosphate ester in the first bismuth compound can be confirmed.

[0065] 1 H-, 31 When performing P-NMR measurement, a nuclear magnetic resonance apparatus (JNM-ECA400II manufactured by JEOL Ltd.) is used, deuterated acetone is used as a solvent, and the measurement is performed at a sample concentration of 1 mass%.

[0066] When performing XPS measurement, an X-ray photoelectron spectroscopy apparatus (manufactured by ULVAC-PHI, INCORPORATED., ESCA5701ci / MC) was used. Monochromatic Al-Kα (14 kV - 330 W) was used as the X-ray source, and the measurement was carried out with an aperture diameter of and a photoelectron emission angle of 45 degrees. The sample was pulverized using an agate mortar, and the obtained powder was fixed to a substrate using carbon tape, and then introduced into the measurement chamber for measurement.

[0067] The first bismuth compound preferably further has a phenyl group. The first bismuth compound having a phenyl group tends to have high compatibility with a radically polymerizable monomer. For example, it can be confirmed by FT-IR (Fourier transform infrared spectroscopy) that the first bismuth compound has a phenyl group.

[0068] The first bismuth compound is, for example, a phosphate or a complex salt represented by the following formula (1).

[0069]

[0070] In the above formula (1), Q 1 , Q 2 , Q 3 and a 3 are the same as those in the above formula (2).

[0071] In the above formula (1), X is (meth)acrylic acid represented by the following formula (1a) or salicylic acid represented by the following formula (1b). In formula (1a), R is a hydrogen atom or a methyl group. X is preferably salicylic acid represented by the following formula (1b).

[0072]

[0073] a 1 is a number from 0 or more and 1 or less.

[0074] a 2 is a number from 0.1 or more and 3 or less.

[0075] a 1 + a 2 is a number from 2 or more and 3 or less.

[0076] Regarding the first bismuth compound having the structure represented by the above formula (1), for example, it can be confirmed by detecting the protonated molecular ion or sodium adduct ion of the compound in MALDI-TOF-MS measurement. For example, when a 1 is a number from 1 to 2, X is salicylic acid, a 2 is a number from 1 to 3, Q 1 is methyl, Q 2 is methacryloyloxyalkyl, Q 3When measuring a compound having a straight-chain alkyl group with 2 carbon atoms, a protonated ion with m / z = 667 is detected.

[0077] In MALDI-TOF-MS measurement, a Bruker rapiflex TOF / TOF type is used. CHCA (α-cyano-4-hydroxycinnamic acid), DIT (Dithranol), and DHB (2,5-Dihydroxybenzoic acid) are used as matrices, and sodium trifluoroacetate is used as a cationizing agent. The measurement is carried out in Reflector / Positive mode, and the mass range is set to m / z = 20 - 4000.

[0078] The first bismuth compound can be a mixture in which a plurality of first phosphates and a plurality of other compounds are bonded to bismuth. Preferably, the first bismuth compound is formed by bonding both a first phosphate having 1 (meth)acryloyl group and a first phosphate having 2 (meth)acryloyl groups to bismuth. Such a first bismuth compound tends to have high compatibility with the polymerizable compound.

[0079] In such a first bismuth compound, the ratio of the first phosphate having 2 (meth)acryloyl groups to 1 mole of the first phosphate having 1 (meth)acryloyl group is preferably 0.05 - 3 moles, more preferably 0.10 - 2 moles, and further preferably 0.15 - 1 mole.

[0080] As suitable first bismuth compounds, the compounds represented by the following formulas (III) - (V) can be cited.

[0081]

[0082]

[0083] In formulas (III) - (V), each R is independently a hydrogen atom or a methyl group.

[0084] In the above formula (III), a + x + y + z = 3. x represents the number of moles of 2-((meth)acryloyloxy)ethyl hydrogen phosphate residue. y represents the number of moles of 2-((meth)acryloyloxy)ethyl phenyl phosphate residue. z represents the number of moles of bis[2-((meth)acryloyloxy)ethyl] phosphate residue. a represents the number of moles of (meth)acrylic acid residue.

[0085] In the above formula (IV), 2b + u + v + w = 3. u represents the number of moles of 2-((methacryloyloxy)ethyl) hydrogen phosphate residue. v represents the number of moles of 2-((methacryloyloxy)ethyl) phenyl phosphate residue. w represents the number of moles of bis[2-((methacryloyloxy)ethyl)] phosphate residue. b represents the number of moles of salicylic acid residue.

[0086] In the above formula (V), 2c + q + r + 2s + t = 3. q represents the number of moles of 2-((methacryloyloxy)ethyl) hydrogen phosphate residue. r represents the number of moles of 2-((methacryloyloxy)ethyl) phenyl phosphate residue. s represents the number of moles of 2-((methacryloyloxy)ethyl) phosphate residue. t represents the number of moles of bis[2-((methacryloyloxy)ethyl)] phosphate residue. c represents the number of moles of salicylic acid residue.

[0087] It should be noted that each of the first bismuth compounds represented by the above formulas (III) to (V) can be a mixture of multiple compounds, rather than a single compound. In this case, the number of moles of each of the above residues is set to represent the number of moles of the mixture as a whole.

[0088] In the above formula (III), considering the first bismuth compound that can be manufactured at low temperature and has less coloring, when a = 0, preferably x:y:z = 1:0.05 - 3:0.5 - 30, more preferably x:y:z = 1:0.1 - 2:1 - 20, and further preferably x:y:z = 1:0.15 - 1:1.5 - 10. In addition, from the viewpoint of further reducing coloring, it can also be set that a = 0 and y = 0.

[0089] In addition, in the above formula (III), when a is other than 0, preferably a:(x + y + z) = 0.1 - 10:1, more preferably a:(x + y + z) = 0.1 - 5:1, and further preferably a:(x + y + z) = 0.1 - 1:1. At this time, preferably x:y:z = 1:0.05 - 3:0.5 - 30, more preferably x:y:z = 1:0.1 - 2:1 - 20, and further preferably x:y:z = 1:0.15 - 1:1.5 - 10.

[0090] In the above formula (IV), when b = 0, it is the same as that obtained by substituting x with u, y with v, and z with w in the above regulations.

[0091] In addition, in the above formula (IV), when b is other than 0, it is preferred that b:(u + v + w) = 1:0.1 to 30, more preferably b:(u + v + w) = 1:0.2 to 20, still more preferably b:(u + v + w) = 1:0.3 to 10, and particularly preferably b:(u + v + w) = 1:0.5 to 5. At this time, it is preferred that u:v:w = 1:0.05 to 20:0.1 to 40, more preferably u:v:w = 1:0.1 to 10:0.2 to 20, still more preferably u:v:w = 1:0.2 to 5:0.4 to 10.

[0092] In the above formula (V), when c = 0, it is preferred that q:r:s:t = 1:0.1 to 50:0.05 to 20:0.1 to 40, more preferably q:r:s:t = 1:0.3 to 30:0.1 to 10:0.2 to 20, still more preferably q:r:s:t = 1:0.5 to 20:0.2 to 5:0.4 to 10.

[0093] In addition, in the above formula (V), when c is other than 0, it is preferred that c:(q + r + s + t) = 1:0.1 to 30, more preferably c:(q + r + s + t) = 1:0.2 to 20, still more preferably c:(q + r + s + t) = 1:0.3 to 10, and particularly preferably c:(q + r + s + t) = 1:0.5 to 5. At this time, it is preferred that q:r:s:t = 1:0.1 to 50:0.05 to 20:0.1 to 40, more preferably q:r:s:t = 1:0.3 to 30:0.1 to 10:0.2 to 20, still more preferably q:r:s:t = 1:0.5 to 20:0.2 to 5:0.4 to 10.

[0094] The first bismuth compound is, for example, a phosphate or a complex salt represented by the following formula (3).

[0095]

[0096] In the above formula (3), Q 1 , Q 2 , Q 3 and a 3 are the same as those in the above formula (2).

[0097] a 4 is a number greater than 0 and 3 or less.

[0098] a 5 is a number greater than 0 and 3 or less.

[0099] a 4 + a 5 is 3.

[0100] In addition, the first bismuth compound may be a composition containing a compound other than the first bismuth compound. Hereinafter, this composition is also referred to as the first bismuth composition. The first bismuth composition may also contain a by-produced phosphoric acid compound or an unreacted raw material during production.

[0101] Removing these by-produced phosphoric acid compounds or unreacted raw materials from the first bismuth compound requires a large amount of labor industrially. In addition, these by-produced phosphoric acid compounds or unreacted raw materials can contribute to improving the solubility in the radically polymerizable monomer.

[0102] Examples of the by-produced phosphoric acid compound include: a dimer of a phosphate ester (phosphoric acid monoester) having one (meth)acryloyl group, a dimer of a phosphate ester (phosphoric acid diester) having two (meth)acryloyl groups, bismuth salicylate, or an ester of bismuth (meth)acrylate and phosphoric acid.

[0103] Examples of the unreacted raw material include: a phosphate ester (phosphoric acid monoester) having one (meth)acryloyl group, a phosphate ester (phosphoric acid diester) having two (meth)acryloyl groups, bismuth salicylate, bismuth (meth)acrylate, etc.

[0104] In the first bismuth composition, the proportion of the compound other than the first bismuth compound is, for example, 30% by mass or less. There is no lower limit for 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 confirmed by quantifying the by-produced phosphoric acid compound and the unreacted raw material in the first bismuth composition by the internal standard method using 1 1H NMR.

[0105] In addition, the first bismuth composition may also contain a compound derived from bismuth oxide. The compound derived from bismuth oxide is, for example, a compound formed by bonding bismuth oxide with a phosphate ester having a (meth)acryloyl group, (meth)acrylic acid, and / or salicylic acid. Although the structure of the compound derived from bismuth oxide is unclear, it is considered to be formed by bonding the hydroxyl group on the surface of bismuth oxide with the carboxyl group of the phosphate ester, (meth)acrylic acid, or salicylic acid. It should be noted that it is very difficult to separate the compound derived from bismuth oxide from the first bismuth compound. Therefore, when a compound derived from bismuth oxide is by-produced, it is preferably used in a state containing the compound derived from bismuth oxide. When a compound derived from bismuth oxide is by-produced, it is desirable to adjust the manufacturing conditions, etc., so that its amount is within a range that does not reduce the solubility of the first bismuth composition. It should be noted that it is possible to comprehensively judge the inclusion of the compound derived from bismuth oxide based on its manufacturing conditions or methods such as IR, NMR, and XPS.

[0106] [Manufacturing method of the first bismuth compound]

[0107] The method for manufacturing the first bismuth compound is not particularly limited, and it is preferably manufactured by reacting a second bismuth compound with a first phosphate ester. Specifically, it is preferably manufactured by the following method: adding a polymerization inhibitor as needed in an aliphatic hydrocarbon solvent or an aromatic solvent, and reacting the second bismuth compound with the first phosphate ester to dehydrate.

[0108] The second bismuth compound refers to an organic compound containing bismuth. The second bismuth compound contains bismuth (meth)acrylate or bismuth subsalicylate. There is no particular limitation on bismuth (meth)acrylate or bismuth subsalicylate, and commercially available products can be used.

[0109] It should be noted that bismuth subsalicylate is a compound in which salicylic acid is bonded to bismuth and is represented by the following formula (VI).

[0110]

[0111] There is no particular limitation on the method for manufacturing bismuth subsalicylate, and it can be manufactured by a known method.

[0112] As the first phosphate ester, commercially available products can be used. The first phosphate ester may be a phosphate ester having one (meth)acryloyl group, a phosphate ester having two (meth)acryloyl groups, or a mixture thereof.

[0113] Examples of the phosphate ester having one (meth)acryloyl group include 2-(methacryloyloxy)ethyl dihydrogen phosphate and 2-methacryloyloxyethyl diphenyl phosphate.

[0114] In addition, examples of the phosphate ester having two (meth)acryloyl groups include bis[2-(methacryloyloxy)ethyl] hydrogen phosphate and phenyl[2-(methacryloyloxy)ethyl] hydrogen phosphate.

[0115] In addition, in order to improve compatibility, it is preferable to add a phosphate triester such as 2-methacryloyloxyethyl diphenyl phosphate, phenylbis[2-(methacryloyloxyethyl)] phosphate, or tris[2-(methacryloyloxyethyl)] phosphate as the first phosphate ester. If a phosphate triester having a phenyl group is used, a monovalent phenyl phosphate diester having one (meth)acryloyl group in the above formulas (III) to (V) can be introduced well.

[0116] Relative to a total of 1 mole of the phosphate ester having one (meth)acryloyl group and the phosphate ester having two (meth)acryloyl groups, the usage amount of the phosphate triester is preferably 0.1 to 20 moles, more preferably 0.2 to 5 moles.

[0117] The amount of the first phosphate ester used may be determined as long as the desired first bismuth compound can be obtained. Specifically, relative to 1 mole of the second bismuth compound, the amount of the first phosphate ester used is preferably in the range of 0.3 to 10 moles.

[0118] (aliphatic hydrocarbon solvent or aromatic solvent)

[0119] In the present embodiment, it is preferable to stir and mix the second bismuth compound and the first phosphate ester in an aliphatic hydrocarbon solvent or an aromatic solvent to carry out the reaction. At this time, water is generated in the reaction system, so it is preferable to dehydrate the generated water. In order to make the generated water easily dehydrated, 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 to form a mixed solution for use.

[0120] Examples of the aliphatic hydrocarbon solvent or aromatic solvent include hexane, heptane, nonane, decane, undecane, dodecane, xylene, dimethoxybenzene and their isomers; benzene, toluene, chlorobenzene, bromobenzene, anisole; petroleum ether, petroleum benzine, benzoin, etc.

[0121] The amount of the aliphatic hydrocarbon solvent or aromatic solvent used is not particularly limited as long as it can sufficiently mix the second bismuth compound and the first phosphate ester. Considering the productivity of the first bismuth compound, it is preferable to use the aliphatic hydrocarbon solvent or aromatic solvent in a ratio of 5 to 100 mL relative to 1 g of the second bismuth compound.

[0122] (Reaction conditions)

[0123] The method for introducing the second bismuth compound and the first phosphate into the reaction system is not particularly limited. For example, the following methods can be adopted: The second bismuth compound diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed, and the first phosphate diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed are added to the reaction system together and stirred and mixed. In addition, the following method can also be adopted: An aliphatic hydrocarbon solvent or an aromatic solvent is introduced into the reaction system in advance, and then the second bismuth compound diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed, and the first phosphate diluted with an aliphatic hydrocarbon solvent or an aromatic solvent as needed are added thereto together and stirred and mixed. In addition, the following means can also be adopted: One of the components is introduced into the reaction system in advance, and then the other component is introduced into the reaction system and stirred and mixed. Among them, in order to reduce the coloring of the obtained first bismuth compound and improve the productivity, the following method is preferably adopted. First, the second bismuth compound is dispersed in an aliphatic hydrocarbon solvent or an aromatic solvent. At this time, the second bismuth compound may not dissolve, and in this case, it is preferable to use an ultrasonic device or the like to crush the lump so that the lump of the second bismuth compound does not exist. Then, the first phosphate is added to the turbid solution in which the second bismuth compound is dispersed, and stirring and heating are started.

[0124] The temperature (reaction temperature) when stirring the components can be the reflux temperature of the aliphatic hydrocarbon solvent or the aromatic solvent. In order to further reduce the coloring of the obtained first bismuth compound, it is desirable to carry out the reaction at the following temperature: preferably an oil bath temperature of 30 to 150 °C, more preferably a temperature of 40 to 140 °C, and further preferably a temperature of 45 to 120 °C.

[0125] In addition, when the reaction temperature is 30 to 110 °C, in order to remove (dehydrate) the water generated in the reaction system, it is preferable to set the reaction system under reduced pressure. At this time, dehydration can be carried out while mixing the second bismuth compound and the first phosphate, or dehydration can be carried out after mixing the two. However, considering the efficiency of the reaction, it is preferable to carry out dehydration while the two are reacting after mixing them.

[0126] The reaction time is not particularly limited and can generally be 1 hour or more and 6 hours or less.

[0127] Considering the operability, the atmosphere during the reaction can be any of an air atmosphere, an inert gas atmosphere, and a dry air atmosphere. Considering the operability, it is preferably carried out in an air atmosphere.

[0128] After the reaction is carried out under the conditions described above, when there are insoluble turbid components in the first bismuth compound obtained after distilling off the solvent for concentration, it is desirable to separate them by filtration or centrifugation. Further, in the concentrated reaction solution obtained by this treatment, a solvent that is soluble in the reaction solvent used and does not dissolve the first bismuth compound is added to perform reprecipitation for purification. When a high-boiling solvent remains, the above decantation operation is repeated to replace the solvent. Then, the remaining solvent is distilled off and vacuum drying is performed, whereby the first bismuth compound can be extracted.

[0129] In the composition of the present embodiment, the content rate of the first bismuth compound is, for example, 80.0% by mass or more and 99.8% by mass or less. If the content of the first bismuth compound is large, when using this composition to prepare a curable composition, there is a tendency for the radiation shielding ability of the cured product to increase. The content rate of the first bismuth compound is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. On the other hand, if the content of the first bismuth compound is excessive, the odor of the cured product may become strong. The content rate of the first bismuth compound is preferably 99.5% by mass or less.

[0130] <Terpenes>

[0131] Terpenes include terpenes and their derivatives. Terpenes are hydrocarbons having isoprene as a structural unit.

[0132] 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 groups and carbonyl groups.

[0133] Terpenes preferably include at least one compound selected from the group consisting of monocyclic monoterpenes, monocyclic monoterpene derivatives, polycyclic monoterpenes, and polycyclic monoterpene derivatives. If monoterpenes are included, when using the composition of the present embodiment to prepare a curable composition, there is a tendency for the odor of the cured product to be further reduced.

[0134] Examples of terpenes include (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-terpinene, limonene, phenyl ethyl ether, p-cymene, terpinolene, 1,8-cineole, linalool, (+)-camphor, l-menthol, d-menthol, 1,4-cineole, norpinene, α-phellandrene, fenchone, borneol, citronellol, etc.

[0135] The terpene preferably contains at least one selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-methylstyrene, α-terpinene, limonene, phenyl ethyl ether, p-cymene, terpinolene, 1,8-cineole, linalool, (+)-camphor, and l-menthol, and more preferably contains at least one selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-methylstyrene, limonene, phenyl ethyl ether, p-cymene, linalool, and (+)-camphor.

[0136] The boiling point of the terpene at 1 atmospheric pressure is preferably 95 °C or higher and 250 °C or lower. When a terpene having a boiling point within this range is used, the odor of the cured product is further reduced when the curable composition is prepared using the composition of the present embodiment. The boiling point of the terpene is more preferably 100 °C or higher and 220 °C or lower, and further preferably 150 °C or higher and 210 °C or lower. The boiling point of the terpene can be measured, for example, by a boiling point measuring device.

[0137] In the composition of the present embodiment, the ratio M1 / M2 of the mass M1 of the first bismuth compound to the mass M2 of the terpene is preferably 4 or more and 4990 or less. If the ratio M1 / M2 is high, the radiation shielding ability of the cured product tends to increase when the curable composition is prepared using the composition of the present embodiment. If the ratio M1 / M2 is low, the odor of the cured product tends to be reduced. The ratio M1 / M2 is more preferably 15 or more and 300 or less, and further preferably 20 or more and 100 or less. The ratio M1 / M2 can also be 10 or more and 700 or less.

[0138] In the composition of the present embodiment, when the proportion of the terpene is high, the odor of the cured product tends to be easily reduced when the curable composition is prepared using the composition. The proportion of the terpene is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. On the other hand, if the proportion of the terpene is too high, there is a concern that the radiation shielding ability of the cured product will decrease when the curable composition is prepared using the composition of the present embodiment. The proportion of the terpene is preferably 8% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less. These proportions can be measured, for example, by 1 H-MNR measurement.

[0139] <Azeotropic compound>

[0140] An azeotropic compound is a compound capable of azeotroping with phenol. Examples of the azeotropic compound include (-)-α-pinene (azeotropic point: 152.75 °C), (-)-β-pinene (azeotropic point: 159.00 °C), (±)-camphene (azeotropic point: 156.10 °C), α-terpinene (azeotropic point: 166.70 °C), limonene (azeotropic point: 169.00 °C), p-cymene (azeotropic point: 170.50 °C), terpinolene (azeotropic point: 173.00 °C), cineole (azeotropic point: 182.85 °C), etc.

[0141] The azeotropic compound preferably contains at least one compound selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-terpinene, limonene, and p-cymene.

[0142] In the composition of the present embodiment, the ratio M1 / M12 of the mass M1 of the first bismuth compound to the mass M12 of the azeotropic compound is preferably 4 or more and 4990 or less, more preferably 5 or more and 700 or less. If the ratio M1 / M12 is high, when the composition of the present embodiment is used to prepare a curable composition, the radiation shielding ability of the cured product tends to increase. If the ratio M1 / M12 is low, the odor of the cured product tends to decrease. The ratio M1 / M12 is further preferably 15 or more and 300 or less, and particularly preferably 20 or more and 100 or less.

[0143] In the composition of the present embodiment, if the proportion of the azeotropic compound is high, when the composition is used to prepare a curable composition, the odor of the cured product tends to be easily reduced. The proportion of the azeotropic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. On the other hand, if the proportion of the azeotropic compound is too high, when the composition of the present embodiment is used to prepare a curable composition, there is a concern that the radiation shielding ability of the cured product may decrease. The proportion of the azeotropic compound is preferably 8% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less. These proportions can be determined, for example, by 1 H-MNR measurement.

[0144] <Coordination organic compound>

[0145] The composition of this embodiment preferably further contains a coordinating organic compound having an acid dissociation constant pKa of 1.5 or more. The coordinating organic compound is an organic compound capable of coordinating to bismuth. This coordinating organic compound can coordinate to bismuth more preferentially than impurities. Therefore, if the composition contains a coordinating organic compound, the amount of the first bismuth compound coordinated with impurities can be reduced. Therefore, when using a composition containing a coordinating organic compound, when using this composition to prepare a curable composition, there is a tendency for the odor of the cured product to be further reduced.

[0146] The acid dissociation constant pKa refers to the acid dissociation constant in water. For example, experimentally, titration can be used, and under assumed conditions, the acid dissociation constant pKa can be calculated by calculation. Specifically, use the calculation results obtained by the software V11.02 of ACD / Lab company recorded in SciFinder-n. Assume the values in water as the unified physical property indexes of each compound.

[0147] The acid dissociation constant pKa of the coordinating organic compound is preferably 2.0 or more and 15.0 or less. If a coordinating organic compound with an acid dissociation constant pKa within this range is used, when using the composition of this embodiment to prepare a curable composition, there is a tendency to obtain a cured product with a low yellowness. The acid dissociation constant pKa of the coordinating organic compound can be 3 or more, can be 4 or more, or can be 6 or more. The acid dissociation constant pKa of the coordinating organic compound can be 14 or less, can be 11 or less, or can be 10 or less.

[0148] The molecular weight (relative molecular mass) of the coordinating organic compound is preferably 17 or more and 400 or less. It is considered that a coordinating organic compound with a molecular weight within this range is more likely to coordinate to bismuth. The molecular weight of the coordinating organic compound is more preferably 18 or more and 300 or less, and further preferably 28 or more and 200 or less.

[0149] The boiling point of the coordinating organic compound under 1 atmospheric pressure is preferably 20°C or more and 500°C or less. If a coordinating organic compound with a boiling point within this range is used, when using the composition of this embodiment to prepare a curable composition, there is a tendency to be able to further reduce the odor of the cured product. The boiling point of the coordinating organic compound is more preferably 30°C or more and 400°C or less, and further preferably 120°C or more and 360°C or less.

[0150] In the composition of the present embodiment, the ratio M1 / M11 of the mass M1 of the first bismuth compound to the mass M11 of the coordinating organic compound is preferably 4 or more and 4990 or less, more preferably 5 or more and 700 or less. If this ratio M1 / M11 is high, when the composition of the present embodiment is used to prepare a curable composition, the radiation shielding ability of the cured product tends to increase. If this ratio M1 / M11 is low, the odor of the cured product tends to decrease. This ratio M1 / M11 is further preferably 7 or more and 300 or less, and particularly preferably 10 or more and 100 or less.

[0151] In the composition of the present embodiment, the ratio M2 / M11 of the mass M2 of the terpene to the mass M11 of the coordinating organic compound is preferably 0.01 or more and 100 or less. This ratio M2 / M11 is more preferably 0.1 or more and 10 or less, and further preferably 0.3 or more and 5 or less.

[0152] In the composition of the present embodiment, the ratio M12 / M11 of the mass M12 of the azeotropic compound to the mass M11 of the coordinating organic compound is preferably 0.01 or more and 100 or less. This ratio M12 / M11 is more preferably 0.1 or more and 10 or less, and further preferably 0.3 or more and 5 or less. These ratios can be determined, for example, by 1 H-MNR measurement.

[0153] In the composition of the present embodiment, if the proportion of the coordinating organic compound is high, when the composition is used to prepare a curable composition, the odor of the cured product tends to be easily reduced. The proportion of the coordinating organic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. On the other hand, if the proportion of the coordinating organic compound is too high, when the composition of the present embodiment is used to prepare a curable composition, the radiation shielding ability of the cured product may decrease. The proportion of the coordinating organic compound is preferably 8% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less.

[0154] The coordinating organic compound includes, for example, at least one compound selected from the group consisting of the following, preferably two or more compounds: a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom and an unsaturated bond, an unsaturated dicarboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic anhydride.

[0155] The coordinating organic compound preferably includes at least one compound selected from the group consisting of a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a triazole skeleton, and a compound having a tetrazole skeleton.

[0156] Compounds having an imidazole skeleton have a skeleton represented by the following formula (a).

[0157]

[0158] Examples of the compounds having an imidazole skeleton include, for example: imidazole, 1-vinylimidazole, 1-allylimidazole, N-acetylimidazole, benzimidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-cyanomethylimidazole, 1-(3-aminopropyl)imidazole, 2-methylimidazole, 2-methyl-1-vinylimidazole, 2-hydroxymethyl-1-methylimidazole, 4-hydroxymethyl-5-methylimidazole, 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-imidazolecarboxylic acid, 4-imidazolecarboxylic acid, 1-isopropylimidazole, 2-isopropylimidazole, 1,2-dimethylimidazole, etc. The compounds having an imidazole skeleton preferably contain 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 contain imidazole.

[0159] Compounds having a pyrazole skeleton have a skeleton represented by the following formula (b).

[0160]

[0161] Examples of the compounds having a pyrazole skeleton include, for example: 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, 1,2-dihydropyrazol-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, 5-(hydroxymethyl)-1-methylpyrazole, etc. The compounds having a pyrazole skeleton preferably contain pyrazole.

[0162] Compounds having a triazole skeleton include compounds having a 1,2,3-triazole skeleton and compounds having a 1,2,4-triazole skeleton.

[0163] The compound having a 1,2,3-triazole skeleton has a skeleton represented by the following formula (c).

[0164]

[0165] Examples of the compound having a 1,2,3-triazole skeleton include 1,2,3-triazole, 1H-benzotriazole, 2H-benzotriazole, etc. The compound having a 1,2,3-triazole skeleton preferably contains 1,2,3-triazole.

[0166] The compound having a 1,2,4-triazole skeleton has a skeleton represented by the following formula (d).

[0167]

[0168] Examples of the compound having a 1,2,4-triazole skeleton include 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, methyl 1,2,4-triazole-3-carboxylate, etc. The compound having a 1,2,4-triazole skeleton preferably contains 1,2,4-triazole.

[0169] The compound having a tetrazole skeleton has a skeleton represented by the following formula (e).

[0170]

[0171] Examples of the compound having a tetrazole skeleton include tetrazole, 1-methyl-1H-tetrazole, 5-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 5-(2-pyridyl)-1H-tetrazole, etc. The compound having a tetrazole skeleton preferably contains tetrazole.

[0172] The coordination organic compound includes, for example, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom 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 a compound include, in addition to the above-mentioned compound having an imidazole skeleton, etc., allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, indole, carbazole, 1,2-benzisothiazol-3(2H)-one, piperonal, allyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, etc.

[0173] The coordinating organic compound includes, for example, unsaturated dicarboxylic acids. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentenedioic acid, methylenesuccinic acid, allylmalonic acid, mesitylenic acid, 2,4-hexadienedioic acid, acetylenedicarboxylic acid, etc. The unsaturated dicarboxylic acid preferably includes maleic acid.

[0174] The coordinating organic compound includes, for example, unsaturated carboxylic acid esters. Examples of the unsaturated carboxylic acid ester include 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, diallyl maleate, etc. The unsaturated carboxylic acid ester preferably includes at least one compound selected from the group consisting of 2-dimethylaminoethyl acrylate and 2-dimethylaminoethyl methacrylate.

[0175] The coordinating organic compound includes, for example, unsaturated carboxylic anhydrides. Examples of the unsaturated carboxylic anhydride include acrylic anhydride, methacrylic anhydride, maleic anhydride, etc.

[0176] Preferred specific examples of the coordinating organic compound include at least one compound selected from the group consisting of imidazole, 1-vinylimidazole, 1-allylimidazole, N-acetylimidazole, trimethylsilylimidazole, 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-methylimidazole, 4-methylimidazole, 1,2-benzisothiazol-3(2H)-one, 2-isopropylimidazole, 1,2-dimethylimidazole, L-menthol, piperonal, triallyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, 4-acryloylmorpholine, triacryloyl hexahydrotriazine, dimethylpyrazole, linalool, camphor, acrylic acid, methacrylic acid, maleic acid, acrylic anhydride, methacrylic anhydride, and maleic anhydride.

[0177] The coordinating organic compound preferably includes at least one compound selected from the group consisting of imidazole, 2-methylimidazole, 1-vinylimidazole, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, triallylamine, and maleic anhydride.

[0178] It should be noted that the carboxylic anhydride can be used as a carboxylic acid precursor. The acid dissociation constant pKa uses the value of the corresponding carboxylic acid.

[0179] The coordinating organic compound preferably contains a first coordinating organic compound and a second coordinating organic compound different from the first coordinating organic compound. If a plurality of coordinating organic compounds are included, the odor can be further reduced by their synergistic effect.

[0180] The coordinating organic compound preferably contains at least one compound selected from the group consisting of a compound having a pyrazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom and an unsaturated bond, an unsaturated dicarboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic anhydride, and contains a compound having an imidazole skeleton. If a compound having an imidazole skeleton is included, when the curable composition is prepared using the composition of the present embodiment, the viscosity of the curable composition tends to decrease and the processability tends to improve.

[0181] Among the plurality of coordinating organic compounds, the proportion of the compound having an imidazole skeleton is preferably 10% by mass or more, more preferably 25% by mass or more, and still more preferably 40% by mass or more. According to one example, the proportion of the compound having an imidazole skeleton is 90% by mass or less, and according to another example, it is 60% by mass or less.

[0182] The coordinating organic compound preferably contains at least one compound selected from the group consisting of a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom and an unsaturated bond, an unsaturated dicarboxylic acid, and an unsaturated carboxylic acid ester, and contains an unsaturated carboxylic anhydride. If an unsaturated carboxylic anhydride is included, the water absorption tends to increase.

[0183] Among the plurality of coordinating organic compounds, the proportion of the unsaturated carboxylic anhydride is preferably 10% by mass or more, more preferably 25% by mass or more, and still more preferably 40% by mass or more. According to one example, the proportion of the unsaturated carboxylic anhydride is 90% by mass or less, and according to another example, it is 60% by mass or less.

[0184] The coordinating organic compound preferably contains both a compound having an imidazole skeleton and an unsaturated carboxylic anhydride. The coordinating organic compound may contain only a compound having an imidazole skeleton and an unsaturated carboxylic anhydride, or may contain other compounds.

[0185] <Preparation method of the composition>

[0186] The composition of the present embodiment can be prepared, for example, by mixing the following substances: a first bismuth compound; a terpene or an azeotropic compound; and optionally a coordinating organic compound.

[0187] 《Curable Composition》

[0188] The curable composition of the present embodiment contains the composition of the present embodiment described above and a first polymerizable compound. That is, the curable composition of the present embodiment contains a first bismuth compound, a terpene or an azeotropic compound, a first polymerizable compound, and an optional coordinating organic compound. The first polymerizable compound has at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

[0189] In the curable composition of the present embodiment, the content rate of the first bismuth compound is, for example, 10% by mass or more and 90% by mass or less. If the content of the first bismuth compound is large, there is a tendency for the radiation shielding effect of the cured product to be improved. The content rate of the first bismuth compound is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. On the other hand, if the content of the first bismuth compound is excessive, the odor of the cured product may become strong. The content rate of the first bismuth compound is preferably 80% by mass or less.

[0190] In the curable composition of the present embodiment, if the proportion of the terpene is high, there is a tendency for the odor of the cured product to be easily reduced. The proportion of the terpene is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more. On the other hand, if the proportion of the terpene is too high, there is a concern that the radiation shielding ability of the cured product may be reduced. The proportion of the terpene in the curable composition is preferably 8% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less.

[0191] In the curable composition of the present embodiment, if the proportion of the azeotropic compound is high, there is a tendency for the odor of the cured product to be easily reduced. The proportion of the azeotropic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more. On the other hand, if the proportion of the azeotropic compound is too high, there is a concern that the radiation shielding ability of the cured product may be reduced. The proportion of the azeotropic compound in the curable composition is preferably 8% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less.

[0192] In the curable composition of the present embodiment, when the proportion of the coordinating organic compound is high, there is a tendency for the odor of the cured product to be easily reduced. The proportion of the coordinating organic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still 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 in the curable composition is preferably 8% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less. For example, 1 HNMR can be used to measure this proportion.

[0193] <First Polymerizable Compound>

[0194] The first polymerizable compound has at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

[0195] The boiling point of the first polymerizable compound at 1 atmospheric pressure is preferably 90 °C or higher. When a first polymerizable compound having a higher boiling point is used, there is a tendency for the odor of the cured product to be reduced. The boiling point of the first polymerizable compound is preferably 100 °C or higher, more preferably 140 °C or higher. There is no particular upper limit to the boiling point of the first polymerizable compound. According to one example, it is 200 °C or lower, and according to another example, it is 300 °C or lower. For example, the boiling point of the first polymerizable compound can be measured by thermogravimetric (TG) analysis. In TG measurement, a differential thermal thermogravimetric synchronous measurement device (TG8120, manufactured by Rigaku Corporation) is used, and scanning is performed in an air stream from room temperature to 500 °C at a heating rate of 10 °C / minute.

[0196] The content of the first polymerizable compound in the curable composition of the present embodiment is, for example, 10% by mass or more and 80% by mass or less. For example, 1 H NMR can be used to measure this content.

[0197] The first polymerizable compound preferably contains a monofunctional radical polymerizable compound having 1 radical polymerizable site in one molecule. When the curable composition contains a monofunctional radical polymerizable compound, there is a tendency for the compatibility of the first bismuth compound to be improved. The boiling point of the monofunctional radical polymerizable compound at 1 atmospheric pressure is preferably 150 °C or higher, more preferably 180 °C or higher.

[0198] Examples of the first polymerizable compound having an acryloyl group include various commercially available monofunctional radical polymerizable compounds such as acrylic acid, acrylamide, phenyl acrylate, benzyl acrylate, isobutyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, isocyanatoethyl acrylate, and acryloxymethyltrimethoxysilane.

[0199] Examples of the first polymerizable compound having a methacryloyl group include the following various commercially available monofunctional free-radical polymerizable compounds: methacrylic acid, methacrylamide, phenyl methacrylate, benzyl methacrylate, isobutyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, trimethoxysilylmethyl methacrylate, etc.

[0200] Examples of the first polymerizable compound having a vinyl group include the following various commercially available monofunctional free-radical polymerizable monomers: vinylpyridine, vinylpyrrolidone, methylstyrene and its structural isomers, methoxystyrene and its structural isomers, dimers of methylstyrene, chlorostyrene, bromostyrene, divinylbenzene, etc.

[0201] Examples of the first polymerizable compound having an allyl group include the following various commercially available monofunctional free-radical polymerizable monomers: methyl allyl carbonate, allyl phenyl ether, 4-allyloxytoluene, allyloxytrimethylsilane, allyl benzoate, allyl methacrylate, allyl glycidyl ether, etc.

[0202] Among them, from the viewpoints of the cured optical properties and impact resistance properties, examples of suitable monofunctional free-radical polymerizable compounds include (meth)acrylates represented by the following formula (I).

[0203]

[0204] In the above formula (I), R 1 is a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms, an aryl group having 4 to 10 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms.

[0205] R 1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a heterocycloalkyl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms, more preferably a linear or branched alkoxy group having 1 to 10 carbon atoms or a heterocycloalkyl group having 3 to 10 carbon atoms and 1 to 3 heteroatoms, and still more preferably a methoxy group or a tetrahydrofuranyl group.

[0206] R 2is a linear or branched alkylene group having 1 to 10 carbon atoms or an alkylene oxide group having 1 to 10 carbon atoms.

[0207] R 2 Preferably, it is a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably a methylene group or an ethylene group.

[0208] R 3 is a hydrogen atom or a methyl group.

[0209] a is 0 or 1. a is preferably 1.

[0210] Specific examples of the (meth)acrylate represented by the above formula (I) include at least one selected from the group consisting of methoxyethyl acrylate (MEMA), ethoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, tetrahydrofurfuryl acrylate (THFAA), and tetrahydrofurfuryl methacrylate (THFMA).

[0211] In the curable composition of the present embodiment, the content of the monofunctional radically polymerizable compound is preferably 10% by mass or more and 80% by mass or less. If this ratio is high, the compatibility of the first bismuth compound tends to increase. If this ratio is low, there is a tendency that the odor degree of the cured product decreases and the impact resistance increases. This ratio is more preferably 10% by mass or more and 30% by mass or less. For example, this ratio can be measured by NMR.

[0212] The curable composition of the present embodiment preferably contains a plurality of monofunctional radically polymerizable compounds. If a plurality of monofunctional radically polymerizable compounds are contained, the compatibility of the first bismuth compound tends to increase. The curable composition of the present embodiment may contain a monofunctional radically polymerizable compound having a (meth)acryloyl group and a monofunctional radically polymerizable compound having a vinyl group. The ratio M4 / M5 of the mass M4 of the monofunctional radically polymerizable compound having a (meth)acryloyl group to the mass M5 of the monofunctional radically polymerizable compound having a vinyl group is, for example, 0.1 or more and 10 or less, preferably 1 or more and 5 or less.

[0213] The curable composition of the present embodiment preferably contains two or more (meth)acrylates represented by the above formula (I), more preferably contains the (meth)acrylate in which R 1 in the above formula (I) is a tetrahydrofuranyl group and R 1 in the above formula (I) is a methoxy group. If it contains the (meth)acrylate in which R 1 in the above formula (I) is a tetrahydrofuranyl group, the compatibility of the first bismuth compound tends to increase. If it contains R 1In particular, it is more preferred to include R 1 R is a methoxy (meth)acrylate. 1 The mass of methoxy (meth)acrylate M6 and R 1 The ratio M6 / M7 of the mass M7 of the (meth)acrylate of the tetrahydrofuranyl group is preferably 0.1 or more and 10 or less. If the ratio M6 / M7 is within this range, the compatibility of the first bismuth compound in the curable composition is improved, and the hardness of the cured product is improved. The ratio M6 / M7 is more preferably 0.3 or more and 5 or less, and further preferably 0.5 or more and 3 or less.

[0214] The ratio M1 / M10 of the mass M1 of the first bismuth compound to the mass M10 of the monofunctional free radical polymerizable compound is preferably 0.25 or more and 100 or less. If the ratio is high, the radiation shielding ability of the cured product tends to be improved. If the ratio is low, the compatibility of the first bismuth compound tends to be improved. The ratio is more preferably 1 or more and 6 or less.

[0215] The first polymerizable compound also preferably includes a multifunctional free radical polymerizable compound having multiple free radical polymerizable sites in one molecule. If a multifunctional free radical polymerizable compound is included, the mechanical properties of the cured product of the curable composition, such as impact resistance, can be further improved. As the multifunctional free radical polymerizable compound, commercially available products can be used without limitation. The boiling point of the multifunctional free radical polymerizable compound at 1 atmosphere is preferably 100° C. or more, more preferably 140° C. or more.

[0216] In consideration of solubility, viscosity of the composition, and impact resistance of the cured product, a di(meth)acrylate represented by the following formula (II) is preferably used as the polyfunctional radical polymerizable compound.

[0217]

[0218] In the above formula (II), R 4 It is a linear or branched alkylene group having 1 to 10 carbon atoms, or a linear or branched alkyleneoxy group having 1 to 10 carbon atoms.

[0219] R 4 It is preferably a linear or branched alkyleneoxy group having 1 to 10 carbon atoms, and more preferably an ethyleneoxy group.

[0220] R 5 and R 6 Each is independently a hydrogen atom or a methyl group.

[0221] n is 1 to 50. n is preferably a number of 3 to 30.

[0222] As specific examples of the bis(meth)acrylate represented by the above formula (II), bifunctional (meth)acrylates selected from the group consisting of polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, polytetramethylene glycol dimethacrylate, and polytetramethylene glycol diacrylate can be cited.

[0223] In the curable composition of the present embodiment, the proportion of the polyfunctional radical polymerizable compound is preferably 0% by mass or more and 50% by mass or less. If this proportion is high, the impact resistance of the cured product tends to increase. If this proportion is low, the compatibility of the first bismuth compound tends to increase. This proportion is more preferably 5% by mass or more and 20% by mass or less. For example, this proportion can be measured by NMR. The measurement conditions of NMR are the same as above.

[0224] The ratio M1 / M3 of the mass M1 of the first bismuth compound to the mass M3 of the polyfunctional radical polymerizable compound is preferably 0 or more and 100 or less. If this ratio is high, the radiation shielding ability of the cured product tends to increase. If this ratio is low, the impact resistance of the cured product tends to increase. This ratio is more preferably 1 or more and 10 or less.

[0225] The curable composition of the present embodiment preferably contains both a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable composition. The ratio M10 / M3 of the mass M10 of the monofunctional radical polymerizable compound to the mass M3 of the polyfunctional radical polymerizable compound is preferably 0.1 or more and 300 or less. If this ratio is high, the compatibility of the first bismuth compound tends to increase. If this ratio is low, the impact resistance of the cured product tends to increase. This ratio is more preferably 0.1 or more and 10 or less.

[0226] The curable composition of the present embodiment preferably contains the (meth)acrylate in which R in the above formula (I) 1 is a tetrahydrofuranyl group, the (meth)acrylate in which R in the above formula (I) 1 is a methoxy group, and the bis(meth)acrylate represented by the above formula (II). By containing these three polymerizable compounds, a cured product with reduced odor and more excellent impact resistance can be obtained. The total mass M8 of the mass M6 of the (meth)acrylate in which R 1 is a methoxy group and the mass M7 of the (meth)acrylate in which R 1 is a tetrahydrofuranyl group and the mass M9 of the bis(meth)acrylate represented by the above formula (II), the ratio M8 / M9 is preferably 0.1 or more and 10 or less, more preferably 0.3 or more and 5 or less, and still more preferably 0.5 or more and 3 or less.

[0227] The curable composition of the present embodiment may contain 10% by mass or less of a nitrile compound. The content rate of the nitrile compound in the curable composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. If the content of the nitrile compound is small, there is a tendency for the odor degree of the cured product to decrease. Regarding the lower limit value of the content rate of the nitrile compound, according to one example, it is 100 ppm by mass or more, and according to another example, it is 0% by mass. For example, it is possible to use 1 1H NMR to measure this ratio. The measurement conditions of NMR are the same as those described above.

[0228] Examples of the nitrile compound include: acrylonitrile, methacrylonitrile, crotononitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, allyl cyanide, allyl cyanoacetate, fumaronitrile, 5-norbornene-2-carbonitrile, and the like.

[0229] The curable composition of the present embodiment may contain a second polymerizable compound. The second polymerizable compound refers to a polymerizable compound having a boiling point below 90 °C at 1 atmospheric pressure. The content rate of the second polymerizable compound in the curable composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. If the content of the second polymerizable compound is small, there is a tendency for the odor degree of the cured product to decrease. Regarding the lower limit value of the content of the second polymerizable compound, according to one example, it is 1% by mass or more, and according to another example, it is 0% by mass. For example, it is possible to use 1 1H NMR to measure this ratio.

[0230] Examples of the second polymerizable compound include, for example: methyl acrylate, allyl methyl ether, allyl ethyl ether, and the like.

[0231] In the curable composition of the present embodiment, with respect to 100 parts by mass of the first bismuth compound, the content of other radical polymerizable monomers is preferably 0 to 500 parts by mass, more preferably 0 to 400 parts by mass, and further preferably 0 to 300 parts by mass.

[0232] In consideration of the radiation shielding effect, dispersibility, coloring reduction effect, etc., the ratio of the total amount of the polymerizable compounds (hereinafter also referred to as "total amount of polymerizable compounds") in the curable composition of the present embodiment to the amount of the first bismuth compound preferably sets the total amount of polymerizable compounds to 1 to 500 parts by mass with respect to 100 parts by mass of the first bismuth compound, more preferably 5 to 300 parts by mass, and still more preferably 10 to 200 parts by mass.

[0233] In addition, when using the curable composition of the present embodiment as an antibacterial / antiviral material, considering its effects, it is preferable that the total amount of the polymerizable compound is 1 to 20,000 parts by mass, more preferably 25 to 15,000 parts by mass, and still more preferably 10 to 9,900 parts by mass with respect to 100 parts by mass of the first bismuth compound.

[0234] <Other compounding agents>

[0235] In addition to the first bismuth compound, terpenes, azeotropic compounds, coordinating organic compounds, and polymerizable compounds, the curable composition of the present embodiment may further contain known compounding agents generally compounded in free-radical polymerizable curable compositions. Examples of such compounding agents include free-radical polymerization initiators, antioxidants, release agents for improving the releasability from a mold, pigments for adjusting the color tone of the cured product, chain transfer agents for controlling polymerization, and the like.

[0236] The content of each compounding agent may be within a range that does not hinder the effects of the present invention. Specifically, with respect to 100 parts by mass of the curable composition, it is preferable to compound 0 to 30 parts by mass of each compounding agent, more preferably 0.01 to 20 parts by mass, and still more preferably 0.02 to 15 parts by mass.

[0237] <Method for preparing curable composition>

[0238] The curable composition of the present embodiment can be prepared, for example, by mixing the following substances: a first bismuth compound; terpenes or azeotropic compounds; a polymerizable compound; and, if necessary, a coordinating organic compound and various compounding agents.

[0239] <Cured product>

[0240] The cured product of the present embodiment is obtained by curing the curable composition of the present embodiment. As a method for manufacturing the cured product, a known method can be adopted. Specifically, a photopolymerization method, a thermal polymerization method, or a polymerization method combining these two methods can be adopted. The appropriate polymerization method is determined by a free-radical polymerization initiator compounded as needed.

[0241] <Physical properties of cured product>

[0242] The cured product of the present embodiment contains a high concentration of bismuth, has high transmittance, and less coloring, and has a high ability to shield radiation such as X-rays. The cured product has a transmittance of 80% or more at a thickness of 2 mm and a wavelength of 560 nm, an X-ray shielding ability equivalent to that of a lead foil of 0.02 mm or more, and a yellowness of 40 or less.

[0243] In addition, when the total mass of the cured product is set to 100 mass%, the content of bismuth contained in the cured product can be set to 5 to 40 mass%.

[0244] The cured product of this embodiment may be a resin composition containing bismuth and (meth)acrylic resin. In this resin composition, when quantified based on the polymerization inhibitor contained in the first bismuth compound in production, the content rate of phenol based on the gas chromatography-mass spectrometry (GC / MS) method may be 10 ppm or less. That is, since this resin composition is a cured product of a curable composition containing terpenes or azeotropic compounds, the content rate of phenol that may cause odors can be reduced. When quantified based on the polymerization inhibitor contained in the first bismuth compound in production, the content rate of phenol is preferably 5 ppm or less, and more preferably below the detection limit. It should be noted that when calculating the phenol content rate by the GC / MS method, 1 HNMR is used to measure the same sample for quantification, and the area ratio of two signals in the chromatogram is used as a reference.

[0245] When performing gas chromatography-mass spectrometry analysis, a headspace type GC / MS is used. Approximately 1 g of the resin sample is crushed and put into a vial as a sample, heated at 120 °C for 30 minutes, and the volatilized vapor is introduced into the GC to measure the MS.

[0246] <Use of the cured product>

[0247] Since the cured product of this embodiment has a light color and is transparent, it can be used as an optical article. Furthermore, although it has visible light transmittance, it has radiation shielding ability, so it can be used as a transparent radiation shielding material.

[0248] The optical article containing the cured product of this embodiment can be used as a radiation shielding window material and a radiation shielding lens.

[0249] In addition, the lens containing the cured product of this embodiment can be used as radiation shielding glasses.

[0250] In addition, the cured product of this embodiment has antibacterial / antiviral properties, so it can be used for applications where high hygiene is desired.

[0251] Examples

[0252] Hereinafter, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the following examples.

[0253] <Analysis method of the first bismuth compound>

[0254] A Fourier transform infrared spectrometer (manufactured by PerkinElmer, Spectrum One) was used in the IR measurement. The measurement was performed by the ATR method with one reflection and four accumulations.

[0255] In the TG-DTA measurement, a differential thermal gravimetric synchronous measurement device (TG8120, manufactured by Rigaku Corporation) was used. Scanning was performed in an air stream from room temperature to 500 °C at a heating rate of 10 °C / minute.

[0256] In the Raman scattering measurement, a microscopic Raman spectroscopy device (NRS-7100, manufactured by JASCO Corporation) was used. When exciting the sample, a 532 nm laser, a 100-fold objective lens, a 600 line / mm grating, and an aperture of [[]] were used, and the measurement was performed with an exposure time of 20 s × 2.

[0257] 1 H- 31 In the ³¹P-NMR measurement, a nuclear magnetic resonance device (JNM-ECA400II (trade name), manufactured by JEOL Ltd.) was used. Deuterated acetone was used as the solvent, and the measurement was performed at a sample concentration of 1 mass%.

[0258] In the XPS measurement, an X-ray photoelectron spectroscopy device (ESCA5701ci / MC, manufactured by ULVAC-PHI, INCORPORATED.) was used. Monochromatized Al-Kα (14 kV - 330 W) was used as the X-ray source, and the aperture diameter was set to The photoelectron emission angle was set to 45 degrees. The sample was pulverized using an agate mortar, the obtained powder was fixed to a substrate using carbon tape, and then introduced into the chamber for measurement.

[0259] For the MALDI-TOF-MS measurement, a rapiflex TOF / TOF type manufactured by Bruker was used. CHCA (α-cyano-4-hydroxycinnamic acid), DIT (Dithranol), 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 set to m / z = 20 - 4000.

[0260] <Manufacturing Example 1: Production of a composition containing bismuth bonded with a phosphate (first bismuth compound)>

[0261] 94.27 g of bismuth(III) subsalicylate (manufactured by Sigma-Aldrich, 260.35 mmol in terms of bismuth), 33.06 g of a mixture of bis[(2-methylacryloyloxyethyl)] phosphate as a phosphodiester and (2-methylacryloyloxyethyl) phosphate as a phosphomonoester (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD., MR-200, 162.04 mmol in terms of phosphoric acid value), 33.09 g of diphenyl 2-methylacryloyloxyethyl phosphate as a phosphotriester (manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD., MR-260, 91.33 mmol), and 6.17 g of dibutylhydroxytoluene (BHT, special grade reagent, manufactured by FUJIFILM Wako Pure Chemical Corporation) as a polymerization inhibitor were charged into a 1000 mL eggplant-shaped flask, and 750 mL of toluene was added. It was dispersed ultrasonically using a bath-type sonicator to form a turbid solution.

[0262] The obtained turbid 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 time point when no more water was generated was set as the end point of the reaction. A pale yellow scattering solution was obtained, and a little pale yellow precipitate was formed in this solution.

[0263] This solution was concentrated to 250 mL using a vacuum evaporator. 8 g of alumina powder was added, and after standing overnight, suction filtration was carried out using a 5B filter paper. 3 g of activated carbon (Darco G60, manufactured by Norit) was added to the obtained pale yellow suspension filtrate, and it was treated in a centrifuge at 23830×g for 8 hours. The centrifuged supernatant was pressure-filtered using a membrane filter with a pore size of 0.2 μm to obtain a pale yellow transparent filtrate. After distilling off the solvent from this solution using a vacuum evaporator, it was 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 it was treated in a centrifuge at 23830×g for 12 hours. The centrifuged supernatant was pressure-filtered using a membrane filter with a pore size of 0.2 μm to obtain a pale yellow transparent filtrate. The obtained filtrate was concentrated to 100 mL using a vacuum evaporator. This acetone solution was poured into 800 mL of hexane placed in a 1000 mL conical beaker with stirring. The generated white precipitate was filtered out by suction filtration using a 5B filter paper, and the obtained solid was dried under vacuum. Thus, 64.40 g of a composition containing bismuth bonded with phosphate ester was obtained in the form of a white powder. The synthesis was confirmed by the above-mentioned assay method.

[0264] <Example 1>

[0265] To 65 parts by mass of the composition containing bismuth bonded with phosphate ester (recorded as "the first bismuth compound" in the table) obtained in Production Example 1, 12.9 parts by mass of methoxyethyl methacrylate (hereinafter denoted as "MEMA") as a polymerizable compound, 6.6 parts by mass of tetrahydrofurfuryl acrylate (hereinafter referred to as "THFAA"), and 13.9 parts by mass of nonaethylene glycol dimethacrylate (hereinafter referred to as "9G") were added. To this, 1 part by mass of (-)-α-pinene as a terpene was added. Further, 0.6 part by mass of methylstyrene dimer as another compounding agent was added and uniformly dissolved to obtain a curable composition. To this curable composition, 0.9 part by mass of 2,2'-azobis(2-methylbutyronitrile) (V-59) and 0.05 part by mass of 1,1'-azobis(cyclohexane-1-carbonitrile) (V-40) were further added and completely dissolved. The curable composition was placed under reduced pressure using a vacuum pump to remove dissolved oxygen. Then, the curable composition was poured into two glass molds fixed to a spacer so as to maintain a gap of 2 mm in thickness, and the temperature was raised to the maximum temperature of 90°C over 15 hours and held at 90°C for 2 hours for polymerization to obtain a pale yellow transparent cured product.

[0266] <Example 2>

[0267] Instead of (-)-α-pinene, 1 part by mass of (-)-β-pinene was used, and the same operations as in Example 1 were carried out to obtain a pale yellow transparent cured product.

[0268] <Example 3>

[0269] Instead of (-)-α-pinene, 1 part by mass of (±)-camphene was used, and the same operations as in Example 1 were carried out to obtain a pale yellow transparent cured product.

[0270] <Example 4>

[0271] Instead of (-)-α-pinene, 1 part by mass of limonene was used, and the same operations as in Example 1 were carried out to obtain a pale yellow transparent cured product.

[0272] <Example 5>

[0273] Instead of (-)-α-pinene, 1 part by mass of p-cymene was used, and the same operations as in Example 1 were carried out to obtain a pale yellow transparent cured product.

[0274] <Example 6>

[0275] Instead of (-)-α-pinene, 1 part by mass of 1,8-cineole was used, and the same operations as in Example 1 were carried out to obtain a pale yellow transparent cured product.

[0276] <Example 7>

[0277] 1 part by mass of linalool was used instead of (-)-α-pinene, and the same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product.

[0278] <Example 8>

[0279] 1 part by mass of (+)-camphor was used instead of (-)-α-pinene, and the same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product.

[0280] <Example 9>

[0281] 1 part by mass of l-menthol was used instead of (-)-α-pinene, and the same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product.

[0282] <Example 10>

[0283] 1 part by mass of terpinolene was used instead of (-)-α-pinene, and the same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product.

[0284] <Example 11>

[0285] 1 part by mass of α-terpinene was used instead of (-)-α-pinene, and the same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product.

[0286] <Example 12>

[0287] 1 part by mass of phenetole was used instead of (-)-α-pinene, and the same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product.

[0288] <Example 13>

[0289] To 65 parts by mass of the composition containing bismuth bonded with phosphate obtained in Production Example 1, 12.5 parts by mass of MEMA as a polymerizable compound, 6.3 parts by mass of THFAA, and 13.6 parts by mass of 9G were added. 1 part by mass of (-)-α-pinene as a terpene and 1 part by mass of imidazole as a coordinating organic compound were added thereto, and the same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product. It should be noted that the acid dissociation constant pKa of imidazole is 13.89.

[0290] <Example 14>

[0291] (-)-β-pinene was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out except for this, to obtain a pale yellow transparent cured product.

[0292] <Example 15>

[0293] (±)-Camphene was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0294] <Example 16>

[0295] Limonene was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0296] <Example 17>

[0297] p-Cymene was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0298] <Example 18>

[0299] 1,8-Cineole was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0300] <Example 19>

[0301] Linalool was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0302] <Example 20>

[0303] (+)-Camphor was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0304] <Example 21>

[0305] l-Menthol was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0306] <Example 22>

[0307] Terpinolene was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0308] <Example 23>

[0309] α-Terpinene was used instead of (-)-α-pinene, and the same operations as in Example 13 were carried out, obtaining a pale yellow transparent solidified product.

[0310] <Example 24>

[0311] Phenetole was used in place of (-)-α-pinene, and the same operations as in Example 13 were carried out except for this, to obtain a pale yellow transparent cured product.

[0312] <Comparative Example 1>

[0313] To 65 parts by mass of the composition containing bismuth bonded with phosphate obtained in Production Example 1, 13 parts by mass of MEMA as a polymerizable compound, 6.7 parts by mass of THFAA, and 14 parts by mass of 9G were added. Terpenes were not added thereto, and 0.3 part by mass of methylstyrene dimer and 1 part by mass of α-methylstyrene were added as other compounding agents. The same operations as in Example 1 were carried out except for this, to obtain a pale yellow transparent cured product having a thickness of 2.42 mm.

[0314] <Evaluation Test>

[0315] [Measurement of X-ray shielding ability]

[0316] The X-ray shielding ability of the obtained cured product was evaluated as follows: The amount of transmitted X-rays was measured in accordance with JIS T 61331-1 "Protective appliances against diagnostic X-rays - Part 1: Method for determining the attenuation characteristics of materials" to obtain the lead equivalent. As the X-ray apparatus, an MG-45 type manufactured by YXLON International was used. The X-ray tube voltage was set to 120 kV, the tube current was set to 12.5 mA, and 2.5 mm Al was used as an additional filter plate. The distance from the X-ray tube focus to the specimen was set to 600 mm, and the distance from the specimen to the measuring machine was set to 900 mm. As the measuring instrument, an ionization chamber irradiation dose rate meter (manufactured by TOYOMEDIC CO., LTD., RAMTEC-Solo type A4 probe) was used. The X-ray shielding ability was evaluated in the form of the thickness (mm) of the equivalent lead plate, i.e., the lead equivalent (mmPb). The results were 0.10 ± 0.04 mmPb of the lead equivalent in the cured products of all Examples and Comparative Examples.

[0317] [Measurement of yellowness]

[0318] The yellowness of the obtained cured product was measured using a ColourMeter SM-T45 manufactured by Suga Test Instruments Co., Ltd. The measured yellowness was divided by the thickness (mm) of the cured product and evaluated as the Y.I. per unit thickness. The results are shown in Tables 1 to 4. It should be noted that the thickness of the cured product was measured using a digital micrometer.

[0319] [Measurement of turbidity]

[0320] The turbidity (haze) of the obtained cured product was measured using a haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. The measured haze value was divided by the thickness (mm) of the cured product to evaluate the haze per unit thickness. The results are shown in Tables 1 to 4.

[0321] [Odor intensity measurement]

[0322] To evaluate the odor of the obtained cured product, an odor intensity was measured using a portable odor detector XP-329m manufactured by NEW COSMOS ELECTRIC CO., LTD. First, the device was placed stationary with the device facing upward, i.e., the odor suction port facing upward, and the ring-shaped lens sample holder was horizontally fixed thereto using a clamp. When the lens was mounted with the convex surface facing downward on the ring-shaped sample holder, the suction port of the odor detector was opposed to the most convex part at the center of the lens (the lowermost part of the lens in this orientation), and the gap between the lowermost surface of the downward-facing lens and the suction port of the odor detector was 5 mm. Pre-operation was performed before mounting the lens, and the lens sample was mounted when the value was stable. The stopwatch was started with this time point set to 0 seconds, and the odor intensity displayed numerically was read. The odor intensity at this time point was read 60 seconds later, and the value at 0 seconds was subtracted from this value to obtain the odor intensity of the sample. After the measurement, the device was operated with the sample removed for more than 2 minutes, and after confirming that the value was stable, the next measurement was performed. The measurement was performed 5 times, and the average was used as the measured value. The results are shown in Tables 1 to 4.

[0323] [Impact resistance measurement]

[0324] To evaluate the impact resistance of the obtained cured product, a falling ball test was conducted. First, a support ring made of NBR was joined to a tube with an inner diameter of 25 mm, an outer diameter of 32 mm, and a height of 25 mm. The thickness of the support ring was 3 mm, and the inner diameter was 25 mm. The cured product was placed stationary on this support ring. A steel ball was dropped from a height of 1.27 m onto this cured product using a dropping device using 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, 261 g. The steel balls were dropped in order from the lighter ones, and the weight of the previous steel ball that caused cracks or fractures in the cured product was set as the maximum impact resistance. The results are shown in Tables 1 and 3.

[0325] [Phenol volatilization amount measurement]

[0326] The cured product obtained in Example 3 was placed in a polyethylene bag with a zip-lock and a side length of 10 cm and left stationary for 1 minute. Then, a gas detector tube for phenol was used to measure the concentration of phenol volatilized in the polyethylene bag. As a result, the concentration of phenol volatilized from the cured product of Example 3 was 5 ppm.

[0327] [Table 1]

[0328]

[0329] [Table 2]

[0330]

[0331] [Table 3]

[0332]

[0333] [Table 4]

[0334]

[0335] From the above results, it can be seen that by using terpenes, a cured product with low odor can be obtained.

[0336] <Reference Example 1>

[0337] To 65 parts by mass of the composition containing bismuth bonded with phosphate ester (recorded as "the first bismuth compound" in the table) obtained in Production Example 1, 12.9 parts by mass of methoxyethyl methacrylate (hereinafter marked as "MEMA") as a polymerizable compound, 6.6 parts by mass of tetrahydrofurfuryl acrylate (hereinafter recorded as "THFAA"), and 13.9 parts by mass of nonaethylene glycol dimethacrylate (hereinafter recorded as "9G") were added. 1 part by mass of 2-methylimidazole was added thereto as a coordinating organic compound. Further, 0.6 part by mass of methylstyrene dimer was added as other compounding agents and dissolved uniformly to obtain a curable composition. 0.9 part by mass of 2,2'-azobis(2-methylbutyronitrile) (V-59) and 0.05 part by mass of 1,1'-azobis(cyclohexane-1-carbonitrile) (V-40) were further added to the curable composition and completely dissolved. The curable composition was placed under reduced pressure using a vacuum pump to remove dissolved oxygen. The curable composition was poured into two glass molds fixed to a spacer so as to maintain a void with a thickness of 2 mm, heated to the maximum temperature of 90°C over 15 hours, and then held at 90°C for 2 hours for polymerization to obtain a pale yellow transparent cured product. The yellowness index (Y.I.) per unit thickness and the odor degree of the obtained cured product were measured. The results are shown in Table 5 together with the pKa of the coordinating organic compound used.

[0338] <Reference Example 2>

[0339] Instead of 2-methylimidazole, 1 part by mass of dimethylaminoethyl methacrylate was used, and the same operations as in Reference Example 1 were carried out to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0340] <Reference Example 3>

[0341] Using 1 part by mass of imidazole in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0342] <Reference Example 4>

[0343] Using 1 part by mass of pyrazole in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0344] <Reference Example 5>

[0345] Using 1 part by mass of 4-methylimidazole in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0346] <Reference Example 6>

[0347] Using 1 part by mass of N-acetylimidazole in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0348] <Reference Example 7>

[0349] Using 1 part by mass of triazole in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0350] <Reference Example 8>

[0351] Using 1 part by mass of 1-vinylimidazole in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0352] <Reference Example 9>

[0353] Using 1 part by mass of 2-isopropylimidazole in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0354] <Reference Example 10>

[0355] Using 1 part by mass of maleic acid in the form of maleic anhydride in place of 2-methylimidazole, and performing the same operations as in Reference Example 1, a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0356] <Reference Example 11>

[0357] Instead of using 2-methylimidazole, 1 part by mass of (trimethylsilyl)imidazole was used, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0358] <Reference Example 12>

[0359] Instead of using 2-methylimidazole, 1 part by mass of benzimidazole was used, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0360] <Reference Example 13>

[0361] Instead of using 2-methylimidazole, 1 part by mass of allylimidazole was used, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0362] <Reference Example 14>

[0363] Instead of using 2-methylimidazole, 1 part by mass of 2-(tert-butylamino)ethyl methacrylate was used, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0364] <Reference Example 15>

[0365] Instead of using 2-methylimidazole, 1 part by mass of methacrylic acid was used in the state of methacrylic anhydride, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0366] <Reference Example 16>

[0367] Instead of using 2-methylimidazole, 1 part by mass of 1,2-dimethylimidazole was used, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0368] <Reference Example 17>

[0369] Instead of using 2-methylimidazole, 1 part by mass of 3,5-dimethylpyrazole was used, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0370] <Reference Example 18>

[0371] Instead of using 2-methylimidazole, 1 part by mass of carbazole was used, and the same operations as in Reference Example 1 were carried out otherwise, to obtain a pale yellow transparent cured product. The results are shown in Table 5.

[0372] <Reference Example 19>

[0373] Instead of using 1 part by mass of 2-methylimidazole, 1 part by mass of indole was used, and the same operations as in Reference Example 1 were carried out except for this, and a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0374] <Reference Example 20>

[0375] To 65 parts by mass of the composition containing bismuth bonded with phosphate obtained in Production Example 1, 12.5 parts by mass of MEMA, 6.3 parts by mass of THFAA, and 13.6 parts by mass of 9G as polymerizable compounds were added. 1 part by mass of imidazole and 1 part by mass of maleic anhydride were added thereto as coordinating organic compounds, and the same operations as in Example 1 were carried out except for this, thereby obtaining a pale yellow transparent cured product. The results are shown in Table 6.

[0376] <Reference Example 21>

[0377] Instead of using 1 part by mass of maleic anhydride, 1 part by mass of methacrylic anhydride was used, and the same operations as in Reference Example 20 were carried out except for this, and a pale yellow transparent cured product was obtained. The results are shown in Table 6.

[0378] <Comparative Example 2>

[0379] Instead of using 1 part by mass of 2-methylimidazole, 1 part by mass of pyrazine was used, and the same operations as in Reference Example 1 were carried out except for this, and a pale yellow transparent cured product was obtained. The results are shown in Table 5.

[0380] <Evaluation Test>

[0381] [Measurement of X-ray Shielding Ability]

[0382] The X-ray shielding ability of the obtained cured product was evaluated as follows: The amount of transmitted X-rays was measured in accordance with JIS T 61331-1 "Protective Equipment against Diagnostic X-rays - Part 1: Determination Method of Attenuation Characteristics of Materials" to obtain the lead equivalent. As the X-ray apparatus, an MG-45 type manufactured by YXLON International was used, the X-ray tube voltage was set to 120 kV, the tube current was set to 12.5 mA, and 2.5 mm Al was used as an additional filter plate. The distance from the X-ray tube focal point to the specimen was set to 600 mm, the distance from the specimen to the measuring machine was set to 900 mm, and as the measuring instrument, an ionization chamber irradiation dose rate meter (manufactured by TOYOMEDIC CO., LTD., RAMTEC-Solo type A4 probe) was used. The X-ray shielding ability was evaluated in the form of the thickness (mm) of the equivalent lead plate, that is, the lead equivalent (mmPb). As a result, the lead equivalent was 0.10 ± 0.04 mmPb in the cured products of all the reference examples and comparative examples.

[0383] [Measurement of Yellowness]

[0384] The yellowness of the obtained cured product was measured using a ColourMeter SM-T45 manufactured by Suga Test Instruments Co., Ltd. The measured yellowness was divided by the thickness (mm) of the cured product and evaluated as the Y.I. per unit thickness. The results are shown in Tables 5 and 6. It should be noted that the thickness of the cured product was measured using a digital micrometer.

[0385] [Measurement of odor intensity]

[0386] To evaluate the odor of the obtained cured product, the odor intensity was measured using a portable odor detector XP-329m manufactured by NEW COSMOS ELECTRIC CO., LTD. First, the device was placed upright, i.e., with the odor intake facing upward, and the ring-shaped lens sample holder was horizontally fixed to it using a clamp. When the lens was mounted on the ring-shaped sample holder with the convex surface facing down, the intake of the odor detector was opposed to the most convex part at the center of the lens (the lowest part of the lens in this orientation), and the gap between the lowest surface of the downward-facing lens and the intake of the odor detector was 5 mm. Pre-operation was performed before mounting the lens, and when the value became stable, the lens sample was mounted. The stopwatch was started with this point set as 0 seconds, and at the same time, the odor intensity displayed digitally was read. The odor intensity at this time point was read 60 seconds later, and the value at 0 seconds was subtracted from it to obtain the odor intensity of the sample. After the measurement, the device was operated with the sample removed for more than 2 minutes, and after confirming that the value was stable, the next measurement was performed. The measurement was performed 5 times, and the average was taken as the measured value. The results are shown in Tables 5 and 6.

[0387] [Table 5]

[0388]

[0389] [Table 6]

[0390]

[0391] From the above results, it can be seen that by using a coordinating organic compound with an acid dissociation constant pKa of 1.5 or more, a cured product with a lower odor can be obtained.

[0392] In addition, it can be seen that by using a coordinating organic compound with an acid dissociation constant pKa in the range of 2.0 to 15.0, a cured product with a lower Y.I., i.e., less yellow color tone than when not used, and a lower odor can be obtained.

Claims

1. A composition comprising: A first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and Terpenes.

2. The composition according to claim 1, wherein The ratio M1 / M2 of the mass M1 of the first bismuth compound to the mass M2 of the terpenes is 4 or more and 4990 or less.

3. The composition according to claim 1, wherein The terpenes include at least one compound selected from the group consisting of hemiterpenes, hemiterpene derivatives, monoterpenes, monoterpene derivatives, sesquiterpenes, and sesquiterpene derivatives.

4. The composition according to claim 1, wherein The terpenes include at least one compound selected from the group consisting of monocyclic monoterpenes, monocyclic monoterpene derivatives, polycyclic monoterpenes, and polycyclic monoterpene derivatives.

5. The composition according to claim 1, wherein, The terpenes include at least one compound selected from the group consisting of (-)-α-pinene, (-)-β-pinene, (±)-camphene, α-terpinene, limonene, phenyl ethyl ether, p-cymene, terpinolene, 1,8-cineole, linalool, (+)-camphor, l-menthol, d-menthol, 1,4-cineole, norpinene, α-phellandrene, fenchone, borneol, and citronellol.

6. The composition according to claim 1, wherein, The boiling point of the terpenes at 1 atmospheric pressure is 95°C or higher and 250°C or lower.

7. The composition according to claim 1, further comprising a coordinating organic compound having an acid dissociation constant pKa of 1.5 or higher.

8. The composition according to claim 1, wherein, The first bismuth compound further has a phosphate bond.

9. The composition according to claim 1, wherein The first bismuth compound further has a phenyl group.

10. A curable composition comprising: The composition according to any one of claims 1 to 9; and A first polymerizable compound having at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

11. The curable composition according to claim 10, wherein, The content rate of the first bismuth compound is 10% by mass or more and 90% by mass or less.

12. A cured product which is a cured product of the curable composition according to claim 10.

13. An optical article comprising the cured product according to claim 12.

14. A lens comprising the cured product according to claim 12.

15. A pair of glasses comprising the lens according to claim 14.

16. An antibacterial / antiviral agent comprising the cured product according to claim 12.

17. A composition comprising: A first bismuth compound having bismuth and having at least one of an acryloyl group and a methacryloyl group; and An azeotropic compound of phenol.

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