Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
  • C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to a resin composition, a curable composition, a cured product, an optical article, a rubber sheet, eye protection equipment, and an antibacterial/antiviral agent.
• lead glass and acrylic lead which is a lightweight material, are used as shielding materials to protect the eyes.
• lead is harmful to the environment and the human body, and there is a strong demand for lead-free alternatives to shielding materials based on inorganic glass or resin.
• Lead alternatives include bismuth, barium, antimony, tin, and tungsten, among which materials using bismuth are being investigated. Bismuth has long been used as a gastrointestinal medicine and is harmless to the human body, yet has the same radiation shielding ability as lead, making it a suitable element to replace lead.
• This cured product has a high concentration of bismuth components dispersed in a resin matrix, and has excellent shielding capabilities not only for X-rays used in medical applications, but also for radiation such as beta rays, and can be used for radiation protection eyeglass lenses, shielding materials, screens, peepholes, etc.
• bismuth compounds are known to have antibacterial and antiviral properties, and can be used as structural or coating materials with antibacterial and antiviral properties. Transparency is not necessarily required for this application.
• the present invention aims to provide a resin composition having low hardness, a curable composition from which the resin composition can be obtained, a cured product of the curable composition, and an optical article, a rubber sheet, eye protection equipment, and an antibacterial and antiviral agent each containing the cured product.
• ⁇ 1> Contains bismuth and a (meth)acrylic resin, A resin composition having a Shore D hardness of 70 or less as measured in accordance with JIS K 7215.
• ⁇ 2> The resin composition according to ⁇ 1>, wherein the Shore D hardness is 20 or more and 60 or less.
• ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the elastic modulus obtained when one end of a test piece having a width of 20 mm, a length of 100 mm, and a thickness of 5.7 mm is pulled by a tensile tester at a speed of 10 mm/min is 5 MPa or more and 50 MPa or less.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the bismuth content measured by high-frequency inductively coupled plasma atomic emission spectrometry is 20% by mass or more and 50% by mass or less.
• the content of the first bismuth compound is 10% by mass or more and 65% by mass or less
• ⁇ 7> The curable composition according to ⁇ 5> or ⁇ 6>, in which a ratio M1/M6 of a mass M1 of the first bismuth compound to a mass M6 of the monofunctional acrylate is 0.25 or more and 5.5 or less.
• ⁇ 8> The curable composition according to any one of ⁇ 5> to ⁇ 7>, wherein the content of the first bismuth compound is 30% by mass or more and 55% by mass or less.
• ⁇ 9> The curable composition according to any one of ⁇ 5> to ⁇ 8>, wherein the first bismuth compound includes a compound having two or more (meth)acryloyl groups.
• ⁇ 12> The curable composition according to any one of ⁇ 5> to ⁇ 11>, wherein the polymerizable compound further contains a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups.
• ⁇ 13> The curable composition according to ⁇ 12>, wherein the content of the polyfunctional (meth)acrylate is 10% by mass or more and 35% by mass or less.
• ⁇ 14> The curable composition according to ⁇ 12> or ⁇ 13>, wherein the polyfunctional (meth)acrylate includes a bifunctional (meth)acrylate represented by the following formula (II):
• R3 and R4 each independently represent a hydrogen atom or a methyl group
• R5 is a linear or branched alkylene group having 1 to 10 carbon atoms
• n2 is an integer of 1 or more and 50 or less.
• ⁇ 15> The curable composition according to any one of ⁇ 5> to ⁇ 14>, further comprising a coordinating organic compound having an acid dissociation constant pKa of 2.0 or more and 15.0 or less.
• ⁇ 16> The curable composition according to ⁇ 15>, wherein the coordinating organic compound includes at least one 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.
• ⁇ 17> A cured product of the curable composition according to any one of ⁇ 5> to ⁇ 16>.
• ⁇ 18> An optical article comprising the cured product according to ⁇ 17>.
• ⁇ 19> A rubber sheet comprising the cured product according to ⁇ 17>.
• ⁇ 20> An eye protection device comprising the cured product according to ⁇ 17>.
• ⁇ 21> An antibacterial and antiviral agent comprising the cured product according to ⁇ 17>.
• the present invention can provide a resin composition having low hardness, a curable composition from which the resin composition can be obtained, a cured product of the curable composition, and an optical article, a rubber sheet, eye protection equipment, and an antibacterial and antiviral agent each containing the cured product.
• optical lenses containing bismuth can be manufactured in the same manner as ordinary plastic lenses in order to achieve high transparency, surface smoothness, and optical uniformity.
• optical lenses containing bismuth can be obtained by casting a composition containing a polymerizable bismuth compound into a glass mold and polymerizing it by thermal polymerization using a thermal polymerization initiator, photopolymerization using a photopolymerization initiator, or a combination of these.
• protective goggles made from thermoplastic resins such as polycarbonate resin are manufactured by injecting molten resin into a metal mold, and can be molded into any shape. This allows them to be shaped with a high degree of curvature to fit around the face, providing eye protection from multiple directions.
• thermosetting resin to manufacture protective goggles with such high curvature and large protective areas. It is technically difficult to obtain an optically uniform cured body due to insufficient adhesion to the mold surface, or conversely, the transfer of surface irregularities due to high transferability, peeling and cracking due to polymerization shrinkage, etc. Furthermore, there is also the practical problem that the current equipment used to manufacture glass molds for optical materials is not capable of handling large areas or unique shapes, and manufacturing new equipment would be extremely costly and time-consuming.
• thermosetting resin after the thermosetting resin has hardened, it can be adjusted to its final shape by heat processing, but if it contains a polyfunctional monomer, this acts as a crosslinking agent, making it less heat processable, and even if the shape can be adjusted, it will return to its original state over time.
• thermosetting resins that have the physical properties of normal plastic lenses into any size or shape.
• radiation protection materials with large areas and flexible shapes are required to protect doctors and nurses from scattered X-rays in IVR (imaging-guided therapy) that uses X-rays, or to protect workers engaged in decommissioning work at nuclear power plants from beta rays or X-rays.
• Radiation protection rubber sheets incorporating metal fillers are already on the market and are used as shielding materials, but their lack of transparency limits how they can be used.
• a resin composition contains bismuth and a (meth)acrylic resin, and has a Shore D hardness of 70 or less as measured in accordance with JIS K 7215.
• a curable composition in another embodiment, contains a first bismuth compound having bismuth and a (meth)acryloyl group, and a polymerizable compound (excluding the first bismuth compound), and the polymerizable compound contains a monofunctional acrylate.
• the content of the first bismuth compound is 10% by mass or more and 65% by mass or less.
• the content of the monofunctional methacrylate is 20% by mass or less.
• the curable composition according to this embodiment contains a first bismuth compound and a monofunctional acrylate as a polymerizable compound, and has a low content of monofunctional methacrylate.
• a resin composition cured body
• Such a resin composition has excellent moldability, and therefore it is possible to realize a bismuth-containing optical article having a large area and a desired shape.
• Such an optical article can be suitably used as a radiation protection component, such as the above-mentioned protective goggles.
• the resin composition according to this embodiment can be used as a transparent structural material or coating material having antibacterial and antiviral properties.
• (meth)acrylic resin means both “acrylic resin” and “methacrylic resin.” The same applies to terms such as “(meth)acryloyl” and “(meth)acrylate.”
• the curable composition according to this embodiment contains a first bismuth compound having bismuth and a (meth)acryloyl group, and a polymerizable compound (excluding the first bismuth compound), in which the polymerizable compound contains a monofunctional acrylate, the content of the first bismuth compound is 10% by mass or more and 65% by mass or less, and the content of the monofunctional methacrylate is 20% by mass or less.
• 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.
• the radiation includes electromagnetic radiation and particle radiation.
• the electromagnetic radiation includes X-rays and gamma rays.
• the particle radiation includes alpha rays, beta rays, neutron rays, and proton rays. Since the first bismuth compound has excellent X-ray shielding ability, it is particularly suitable for use as an X-ray shielding material and a beta ray shielding material that can generate X-rays.
• the first bismuth compound has high solubility in radically polymerizable compounds having at least one radically polymerizable group selected from the group consisting of a nitrile group, an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group. Therefore, by using the first bismuth compound, a hardenable composition containing a high concentration of bismuth and a hardened product thereof can be obtained.
• the first bismuth compound has better solubility in radically polymerizable compounds than bismuth subsalicylate alone.
• the first bismuth compound may be in any form as long as it contains bismuth and a (meth)acryloyl group.
• the bismuth and the (meth)acryloyl group may be directly bonded to each other, or may be bonded to each other via a bonding group.
• the bonding group include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphate group.
• the first bismuth compound preferably further has a phosphate bond.
• the first bismuth compound is more preferably a compound in which bismuth and a first phosphate ester having a (meth)acryloyl group are bonded.
• Such a first bismuth compound tends to have higher compatibility with various polymerizable compounds.
• the bond form between bismuth and the first phosphate ester is not particularly limited, and may be any of an ionic bond, a coordinate bond, and a covalent bond.
• 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 as an anion, a phosphate compound, or a complex.
• the first bismuth compound may be a mono(meth)acrylate having one (meth)acryloyl group, a di(meth)acrylate having two (meth)acryloyl groups, a tri(meth)acrylate having three (meth)acryloyl groups, or a multifunctional (meth)acrylate having four or more (meth)acryloyl groups.
• the first phosphate ester is represented, for example, by the following formula (2).
• Q1 is a hydrogen atom or a methyl group, and Q1 is preferably a methyl group.
• Q2 is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 16 carbon atoms, or a (meth)acryloyloxyalkylene group.
• the number of carbon atoms in the alkyl group is preferably 1 to 6.
• the number of carbon atoms in the aryl group is preferably 5 to 8.
• the aryl group is preferably a phenyl group.
• the number of carbon atoms in the alkylene group contained in the (meth)acryloyloxyalkylene group is, for example, 1 to 10, preferably 1 to 3.
• the (meth)acryloyloxyalkylene group is preferably a (meth)acryloyloxyethylene group.
• a3 is 0 or 1.
• the oxygen atom to which Q2 is bonded is O- .
• Q3 is a linear or branched alkylene group having from 1 to 10 carbon atoms, or a linear or branched alkyleneoxyalkylene group having from 2 to 10 carbon atoms.
• the first bismuth compound may further be bonded to other compounds in addition to the first phosphate ester.
• the bond between the other compounds and the bismuth may be any of ionic bonds, coordinate bonds, and covalent bonds. That is, the first bismuth compound may be a phosphate or complex salt having bismuth (Bi 3+ or Bi 5+ ) as the cation and the first phosphate ester and other compounds as the anions, a phosphate compound, or a complex.
• Specific examples of other compounds include at least one selected from the group consisting of salicylic acid and (meth)acrylic acid.
• the ratio of the primary phosphate ester to the other compounds is preferably 0.1 to 10 moles, more preferably 0.1 to 5 moles, even more preferably 0.1 to 1 mole, and particularly preferably 0.1 to 0.5 moles, of the other compounds per mole of the primary phosphate ester. Note that when two or more types of primary phosphate esters are present, the above range is based on the total number of moles of the primary phosphate esters.
• the fact that the first phosphate ester is bonded to bismuth can be confirmed by infrared spectroscopy (IR) analysis. That is, when a peak is confirmed, for example, at 1670 to 1700 cm ⁇ 1 in infrared spectroscopy analysis of the first bismuth compound, it can be said that the first phosphate ester is bonded to bismuth. This peak is considered to be a peak characteristic of the stretching vibration of Bi—O—P. This peak is not confirmed in the bismuth and the first phosphate ester before bonding. In addition, it is not confirmed in a mixture of the second bismuth compound and the first phosphate ester described below, which are the raw materials of the first bismuth compound.
• IR infrared spectroscopy
• the IR spectrum is measured, for example, using a PerkinElmer Spectrum One, using the single reflection ATR method and four-times accumulation.
• the 1 H- and 31 P-NMR measurements are performed using a nuclear magnetic resonance apparatus (JNM-ECA400II, manufactured by JEOL Ltd.) with deuterated acetone as the solvent and a sample concentration of 1% by mass.
• JNM-ECA400II manufactured by JEOL Ltd.
• an X-ray photoelectron spectrometer (ULVAC-PHI, Inc., ESCA5701ci/MC) is used, and the X-ray source is monochromatic Al-K ⁇ (14 kV-330 W), with an aperture diameter of ⁇ 800 ⁇ m and a photoelectron take-off angle of 45 degrees.
• the sample is crushed in an agate mortar, and the resulting powder is fixed to a substrate with carbon tape and introduced into the measurement chamber for measurement.
• the first bismuth compound preferably further contains a phenyl group.
• a first bismuth compound containing a phenyl group tends to have high compatibility with radically polymerizable monomers. Whether the first bismuth compound contains a phenyl group can be confirmed, for example, by FT-IR (Fourier transform infrared spectroscopy).
• the first bismuth compound is, for example, a phosphate or complex salt represented by the following formula (1):
• X is (meth)acrylic acid represented by the following formula (1a), or salicylic acid represented by the following formula (1b).
• R is a hydrogen atom or a methyl group.
• X is preferably salicylic acid represented by the following formula (1b).
• a1 is a number between 0 and 1.
• a2 is a number greater than or equal to 0.1 and less than or equal to 3.
• a 1 +a 2 is a number between 2 and 3 inclusive.
• the fact that the first bismuth compound has the structure represented by the above formula (1) can be confirmed, for example, by detection of a proton-added molecular ion or a sodium-added ion of the compound in MALDI-TOF-MS measurement.
• a compound in which a1 is a number from 0 to 1 X is salicylic acid
• a2 is a number from 1 to 3
• Q1 is a methyl group
• Q2 is a methacryloyloxyalkyl group
• Q3 is a linear alkyl group having 2 carbon atoms
• the first bismuth compound may be a mixture in which multiple types of first phosphate esters and multiple types of other compounds are bonded to bismuth.
• the first bismuth compound is preferably a mixture in which both a first phosphate ester having one (meth)acryloyl group and a first phosphate ester having two (meth)acryloyl groups are bonded to bismuth. Such a first bismuth compound tends to be highly compatible with polymerizable compounds.
• the ratio of the first phosphate ester having two (meth)acryloyl groups to 1 mole of the first phosphate ester having one (meth)acryloyl group is preferably 0.05 to 3 moles, more preferably 0.10 to 2 moles, and even more preferably 0.15 to 1 mole.
• Suitable first bismuth compounds include those represented by the following formulas (III) to (V).
• each R is independently a hydrogen atom or a methyl group.
• x represents the number of moles of 2-((meth)acryloyloxy)ethyl hydrogen phosphate residues.
• y represents the number of moles of phenyl-2-((meth)acryloyloxy)ethyl phosphate residues.
• z represents the number of moles of bis[2-((meth)acryloxyoxy)ethyl]phosphate residues.
• a represents the number of moles of (meth)acrylic acid residues.
• u represents the number of moles of 2-((meth)acryloyloxy)ethyl hydrogen phosphate residues.
• v represents the number of moles of phenyl-2-((meth)acryloyloxy)ethyl phosphate residues.
• w represents the number of moles of bis[2-((meth)acryloyloxy)ethyl]phosphate residues.
• b represents the number of moles of salicylic acid residues.
• q represents the number of moles of 2-((meth)acryloyloxy)ethyl hydrogen phosphate residues.
• r represents the number of moles of phenyl-2-((meth)acryloyloxy)ethyl phosphate residues.
• s represents the number of moles of 2-((meth)acryloyloxy)ethyl phosphate residues.
• t represents the number of moles of bis[2-((meth)acryloyloxy)ethyl]phosphate residues.
• c represents the number of moles of salicylic acid residues.
• first bismuth compounds represented by the above formulas (III) to (V) may not each be a single compound, but may be a mixture of multiple compounds.
• the number of moles of each of the above-mentioned residues refers to the number of moles of the entire mixture.
• the first bismuth compound is, for example, a phosphate or complex salt represented by the following formula (3):
• a4 is a number greater than 0 and equal to or less than 3.
• a5 is a number greater than 0 and equal to or less than 3.
• a4 + a5 is 3.
• the first bismuth compound preferably contains at least one compound selected from the group consisting of a compound represented by the following formula (3a), a compound represented by the following formula (3b), a compound represented by the following formula (3c), and a compound represented by the following formula (3d). It is more preferable that the first bismuth compound contains a compound represented by the following formula (3a).
• the first bismuth compound may also be a composition containing a compound other than the first bismuth compound.
• this composition is also referred to as the first bismuth composition.
• the first bismuth composition may contain a phosphate compound that is a by-product during production, or unreacted raw materials.
• Examples of by-product phosphoric acid compounds include dimers of phosphoric acid esters (phosphoric acid monoesters) having one (meth)acryloyl group, dimers of phosphoric acid esters (phosphoric acid diesters) having two (meth)acryloyl groups, and esters of bismuth salicylate or bismuth (meth)acrylate with phosphoric acid.
• unreacted raw materials include phosphate esters having one (meth)acryloyl group (phosphate monoesters), phosphate esters having two (meth)acryloyl groups (phosphate diesters), bismuth salicylate, bismuth (meth)acrylate, etc.
• the ratio of compounds other than the first bismuth compound is, for example, 30 mass% or less. There is no lower limit to this ratio, but in one example, it is 0 mass%, and in another example, it is 5 mass%. This ratio can be confirmed by quantifying the by-product phosphate compound and unreacted raw materials in the first bismuth composition by an internal standard method using 1H MNR.
• the first bismuth composition may also contain a compound derived from bismuth oxide.
• the compound derived from bismuth oxide is, for example, a compound in which bismuth oxide is bonded to a phosphate ester having a (meth)acryloyl group, (meth)acrylic acid, and/or salicylic acid.
• a hydroxyl group formed on the surface of the bismuth oxide is bonded to a carboxyl group of the phosphate ester, (meth)acrylic acid, or salicylic acid. It is very difficult to separate this compound derived from bismuth oxide from the first bismuth compound.
• a compound derived from bismuth oxide when a compound derived from bismuth oxide is by-produced, it is preferable to use the composition in a state in which the compound derived from bismuth oxide is included.
• a compound derived from bismuth oxide when a compound derived from bismuth oxide is by-produced, it is desirable to adjust the production conditions, etc. so that the amount of the compound derived from bismuth oxide is within a range that does not reduce the solubility of the first bismuth composition.
• the presence of a compound derived from bismuth oxide can be determined comprehensively by the production conditions or a method such as IR, NMR, or XPS.
• the first bismuth composition may contain at least one compound selected from the group consisting of a compound represented by the following formula (3e) and a compound represented by the following formula (3f).
• the method for producing the first bismuth compound is not particularly limited, but it is preferable to produce the first bismuth compound by reacting the second bismuth compound with a first phosphate ester. Specifically, it is preferable to produce the first bismuth compound by reacting the second bismuth compound with a first phosphate ester in an aliphatic hydrocarbon solvent or an aromatic solvent, optionally adding a polymerization inhibitor, and then dehydrating the resulting mixture.
• bismuth-containing compound refers to an organic compound containing bismuth.
• the bismuth-containing compound includes bismuth (meth)acrylate or bismuth subsalicylate. There are no particular limitations on the bismuth (meth)acrylate or bismuth subsalicylate, and commercially available products can be used.
• Bismuth subsalicylate is a compound in which salicylic acid is bonded to bismuth, and is represented by the following formula (VI).
• 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 of these.
• phosphate esters having one (meth)acryloyl group examples include 2-(methacryloyloxy)ethyl dihydrogen phosphate and diphenyl-2-methacryloyloxyethyl phosphate.
• phosphate esters having two (meth)acryloyl groups include bis[2-(methacryloxyoxy)ethyl] hydrogen phosphate and phenyl[2-(methacryloxyoxy)ethyl] hydrogen phosphate.
• a phosphate triester such as diphenyl-2-methacryloyloxyethyl phosphate, phenyl bis[2-(methacryloyloxyethyl)]phosphate, or tris[2-(methacryloyloxyethyl)]phosphate as the first phosphate ester.
• the amount of the phosphate triester is preferably 0.1 to 20 moles, and more preferably 0.2 to 5 moles, per mole of the total of the phosphate ester having one (meth)acryloyl group and the phosphate ester having two (meth)acryloyl groups.
• the amount of primary phosphate ester used may be determined so as to obtain the desired primary bismuth compound. Specifically, it is preferable to use an amount of primary phosphate ester in the range of 0.3 to 10 moles per mole of secondary bismuth compound.
• Aliphatic hydrocarbon solvents or aromatic solvents include, for example, hexane, heptane, nonane, decane, undecane, dodecane, xylene, dimethoxybenzene, and their isomers; benzene, toluene, chlorobenzene, bromobenzene, anisole; petroleum ether, petroleum benzine, benzoin; and the like.
• the amount of the aliphatic hydrocarbon solvent or aromatic solvent used is not particularly limited, so long as it is an amount that allows sufficient mixing of the bismuth dibasic compound and the first phosphate ester. Considering the productivity of the first bismuth compound, it is preferable to use 5 to 100 mL of the aliphatic hydrocarbon solvent or aromatic solvent per 1 g of the bismuth dibasic compound.
• the method of introducing the second bismuth compound and the first phosphate ester into the reaction system is not particularly limited.
• a method can be adopted in which the second bismuth compound diluted with an aliphatic hydrocarbon solvent or aromatic solvent as necessary and the first phosphate ester diluted with an aliphatic hydrocarbon solvent or aromatic solvent as necessary are added together into the reaction system and stirred and mixed.
• a method can be adopted in which an aliphatic hydrocarbon solvent or aromatic solvent is introduced into the reaction system in advance, and the second bismuth compound diluted with an aliphatic hydrocarbon solvent or aromatic solvent as necessary and the first phosphate ester diluted with an aliphatic hydrocarbon solvent or aromatic solvent as necessary are added together thereto and stirred and mixed.
• the second bismuth compound is dispersed in an aliphatic hydrocarbon solvent or aromatic solvent.
• the second bismuth compound may not dissolve, but in that case, it is preferable to crush the lumps of the second bismuth compound by an ultrasonic device or the like so that no lumps or the like of the second bismuth compound are present.
• the primary phosphate is added to the cloudy solution in which the bismuth(II) compound is dispersed, and stirring and heating are commenced.
• the temperature (reaction temperature) at which each component is stirred may be the reflux temperature of the aliphatic hydrocarbon solvent or aromatic solvent, but in order to minimize coloration of the resulting first bismuth compound, it is preferable to carry out the reaction at an oil bath temperature of 30 to 150°C, more preferably at a temperature of 40 to 140°C, and even more preferably at a temperature of 45 to 120°C.
• the reaction temperature is 30 to 110°C
• the dehydration can be carried out while mixing the secondary bismuth compound and the primary phosphate ester, or the two can be mixed and then dehydrated.
• the reaction time is not particularly limited, but is usually from 1 hour to 6 hours.
• the reaction may be carried out in an air atmosphere, an inert gas atmosphere, or a dry air atmosphere, and in consideration of operability, it is preferable to carry out the reaction in an air atmosphere.
• the resulting bismuth compound is concentrated by distilling off the solvent, and if there are any insoluble turbid components, it is desirable to separate them by filtration or centrifugation. Furthermore, a solvent that is soluble in the reaction solvent used but does not dissolve the bismuth compound is added to the concentrated reaction solution obtained by this process to perform reprecipitation and purification. If any high-boiling point solvent remains, the above decantation operation is repeated to replace the solvent. The remaining solvent is then distilled off and vacuum dried to extract the bismuth compound.
• the content of the first bismuth compound is, for example, 10% by mass or more and 65% by mass or less. If the content of the first bismuth compound is high, the radiation shielding ability of the cured body tends to be enhanced.
• the content of the first bismuth compound is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more. On the other hand, if the content of the first bismuth compound is excessively high, the moldability of the cured body may decrease.
• the content of the first bismuth compound is preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.
• the curable composition according to the present embodiment contains a monofunctional acrylate as a polymerizable compound.
• a monofunctional acrylate By containing a monofunctional acrylate, a cured product with high moldability can be realized.
• the curable composition may contain at least one radical polymerizable compound selected from the group consisting of a monofunctional methacrylate, a polyfunctional (meth)acrylate, a polymerizable compound having a vinyl group, and a polymerizable compound having an allyl group. It is preferable that the curable composition further contains a polyfunctional (meth)acrylate. Note that the first bismuth compound described above is not included in the polymerizable compound.
• the boiling point of these polymerizable compounds at 1 atmosphere is preferably 90°C or higher.
• the boiling point of the polymerizable compound is preferably 100°C or higher, more preferably 140°C or higher, and even more preferably 180°C or higher.
• There is no particular upper limit to the boiling point of the polymerizable compound but in one example, it is 200°C or lower, and in another example, it is 300°C or lower.
• the boiling point of the polymerizable compound can be measured, for example, by thermogravimetry (TG) analysis.
• TG thermogravimetry
• TG8120 a differential thermal and thermogravimetry simultaneous measurement device
• the content of the polymerizable compound in the curable composition according to this embodiment is, for example, 10% by mass or more and 80% by mass or less. This content can be measured, for example, by 1 H NMR.
• the ratio M11/M12 of the mass M11 of the methacrylate to the mass M12 of the acrylate is preferably 0.01 or more and 10 or less.
• the ratio M11/M12 is more preferably 0.02 or more and 5 or less, and even more preferably 0.05 or more and 3 or less.
• the monofunctional acrylate is a compound having one acryloyl group in one molecule.
• R 1 represents an alkylene group having 1 to 5 carbon atoms.
• R 1 is preferably a methylene group, an ethylene group, or an isopropylene group.
• R2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R2 may form a tetrahydrofurfuryl group together with the adjacent oxygen atom. R2 is preferably a methyl group or an ethyl group, or forms a tetrahydrofurfuryl group together with the adjacent oxygen atom.
• n1 is an integer between 0 and 30. n1 may be 7 or more, 10 or more, or 15 or more.
• monofunctional acrylates include acrylic acid, acrylamide, phenyl acrylate, benzyl acrylate, isobutyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, isocyanatoethyl acrylate, acryloxymethyltrimethoxysilane, methoxypolyethylene glycol acrylate, phenoxydiethylene glycol acrylate, ethoxylated-O-phenylphenol acrylate, etc.
• the monofunctional acrylate preferably includes tetrahydrofurfuryl acrylate.
• the content of the monofunctional acrylate is preferably 10% by mass or more and 80% by mass or less.
• the content of the monofunctional acrylate is more preferably 15% by mass or more and 60% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less.
• the ratio M1/M6 of the mass M1 of the first bismuth compound to the mass M6 of the monofunctional acrylate is preferably 0.25 or more and 5.5 or less. If this ratio is large, the radiation shielding performance of the cured body tends to improve. If this ratio is small, the compatibility of the first bismuth compound tends to increase and moldability also tends to improve. It is more preferable that this ratio is 1 or more and 3 or less.
• the monofunctional methacrylate is a compound having one methacryloyl group in one molecule.
• R 11 is a hydroxy group, a linear or branched alkyl group having from 1 to 10 carbon atoms, a linear or branched alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 4 to 10 carbon atoms, a heterocycloalkyl group having from 3 to 10 carbon atoms and from 1 to 3 heteroatoms, an aryl group having from 4 to 10 carbon atoms, or a heteroaryl group having from 3 to 10 carbon atoms and from 1 to 3 heteroatoms.
• R 11 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 even more preferably a methoxy group or a tetrahydrofuryl group.
• R 12 is a linear or branched alkylene group having from 1 to 10 carbon atoms, or an alkylene oxide group having from 1 to 10 carbon atoms.
• R 12 is preferably a linear or branched alkylene group having from 1 to 10 carbon atoms, and more preferably a methylene group or an ethylene group.
• a is 0 or 1. a is preferably 1.
• Examples of monofunctional methacrylates include methacrylic acid, methacrylamide, phenyl methacrylate, benzyl methacrylate, isobutyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, methacryloxymethyltrimethoxysilane, etc.
• the content of the monofunctional methacrylate is 20% by mass or less. If the content of the monofunctional methacrylate is high, the hardness of the cured body tends to increase and the flexibility tends to decrease.
• the content of the monofunctional methacrylate is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, and may be 0% by mass.
• the content of the monofunctional methacrylate may be 10% by mass or more and 20% by mass or less, or may be 12% by mass or more and 16% by mass or less.
• the ratio M6/M7 of the mass M6 of the monofunctional acrylate to the mass M7 of the monofunctional methacrylate may be 0.1 or more and 10 or less.
• the ratio M6/M7 may be 0.5 or more and 5 or less, or 1 or more and 3 or less.
• the ratio M1/M7 of the mass M1 of the first bismuth compound to the mass M7 of the monofunctional methacrylate may be 1 or more and 10 or less. If this ratio is large, the radiation shielding ability of the cured body tends to be enhanced. If this ratio is small, the compatibility of the first bismuth compound tends to be enhanced. This ratio may be 2 or more and 5 or less.
• the polyfunctional (meth)acrylate is a compound having two or more acryloyl groups, two or more methacryloyl groups, or one or more acryloyl groups and one or more methacryloyl groups in one molecule.
• the mechanical properties, such as impact resistance, of the cured product of the curable composition tend to be further improved.
• a di(meth)acrylate represented by the following formula (II) is preferably used.
• R3 and R4 each independently represent a hydrogen atom or a methyl group.
• R5 is a linear or branched alkylene group having a carbon number of 1 to 10.
• R5 is preferably a methylene group, an ethylene group, or an isopropylene group.
• n2 is an integer between 1 and 50. n2 may be 7 or more, 10 or more, 15 or more, or 20 or more.
• di(meth)acrylate represented by the above formula (II) examples include polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, polytetramethylene glycol dimethacrylate, polytetramethylene glycol diacrylate, ethoxylated glycerin diacrylate, pentaerythritol diacrylate, ethoxylated glycerin dimethacrylate, pentaerythritol dimethacrylate, etc.
• the content of the polyfunctional (meth)acrylate is preferably 5% by mass or more and 35% by mass or less.
• the content of the polyfunctional (meth)acrylate is high, the impact resistance of the cured body tends to be increased.
• the content of the polyfunctional (meth)acrylate is low, the compatibility of the first bismuth compound tends to be increased.
• the content of the polyfunctional (meth)acrylate is more preferably 10% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 25% by mass or less, and may be 21% by mass or less.
• This content can be measured, for example, by NMR.
• the NMR measurement conditions are the same as above.
• the ratio M1/M3 of the mass M1 of the first bismuth compound to the mass M3 of the polyfunctional (meth)acrylate is preferably 1 or more and 10 or less. If this ratio is large, the radiation shielding ability of the cured body tends to be enhanced. If this ratio is small, the impact resistance of the cured body tends to be enhanced. It is more preferable that this ratio is 1.5 or more and 5 or less.
• polymerizable compounds include polymerizable compounds having a vinyl group and polymerizable compounds having an allyl group.
• polymerizable compounds having a vinyl group examples include vinylpyridine, vinylpyrrolidone; styrene derivatives such as methylstyrene and its structural isomers, methoxystyrene and its structural isomers, methylstyrene dimer, chlorostyrene, bromostyrene, and divinylbenzene; and the like.
• polymerizable compounds having an allyl group examples include allyl methyl carbonate, allyl phenyl ether, 4-allyloxytoluene, allyloxytrimethylsilane, allyl benzoate, allyl methacrylate, and allyl glycidyl ether.
• the curable composition according to the present embodiment may contain 10% by mass or less of the nitrile compound.
• the content of the nitrile compound in the curable composition is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. If the content of the nitrile compound is low, the odor level of the cured product tends to decrease.
• the lower limit of the content of the nitrile compound is 100 ppm by mass or more, and in another example, it is 0% by mass. This content can be measured, for example, by 1 H NMR. The measurement conditions of NMR are the same as above.
• nitrile compounds include acrylonitrile, methacrylonitrile, crotononitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, allyl cyanide, allyl cyanoacetate, fumaronitrile, and 5-norbornene-2-carbonitrile.
• the curable composition according to the present embodiment may contain a polymerizable compound having a boiling point of less than 90° C. (hereinafter, also referred to as the "second polymerizable compound").
• the content of the second polymerizable compound in the curable composition is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. If the content of the second polymerizable compound is low, the odor level of the cured body tends to decrease.
• the lower limit of the content of the second polymerizable compound is, for example, 1% by mass or more, and in another example, 0% by mass. This content can be measured, for example, by 1 H NMR.
• the curable composition according to the present embodiment may contain, in addition to the first bismuth compound and the polymerizable compound, known compounding agents, coordinating organic compounds, terpenes, and the like.
• compounding agents include radical polymerization initiators, antioxidants, release agents for improving releasability from a mold, dyes for adjusting the color tone of the cured product, chain transfer agents for controlling polymerization, plasticizers for imparting plasticity, heat resistance, or cold resistance to the cured product, antioxidants for improving durability, and antiaging agents.
• each compounding agent may be within a range that does not impair the effects of the present invention.
• each compounding agent is preferably mixed in an amount of 0 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, and even more preferably 0.02 to 15 parts by mass, per 100 parts by mass of the first bismuth compound and the polymerizable compound combined.
• the coordinating organic compound is an organic compound that can be coordinated to bismuth and can function as an odor suppressant and a viscosity adjuster for the cured product.
• the acid dissociation constant pKa of the coordinating organic compound is 2.0 or more and 15 or less. It is preferable that the acid dissociation constant pKa is 0.0 or less. When a coordinating organic compound having an acid dissociation constant pKa within this range is used, a cured product with low yellowness and odor tends to be obtained.
• the dissociation constant pKa may be 3 or more, 4 or more, or 6 or more.
• the acid dissociation constant pKa of the coordinating organic compound may be 14 or less, or 11 or less.
• the acid dissociation constant pKa means the acid dissociation constant in water.
• the acid dissociation constant pKa can be experimentally determined by titration or by measuring the state of the acid. Specifically, the calculation results obtained by ACD/Lab's software V11.02 described in SciFinder-n can be used. Although this value is assumed to be in water, it is used as a unified physical property index for each compound.
• the molecular weight (relative molecular mass) of the coordinating organic compound is preferably 17 or more and 400 or less. Coordinating organic compounds with molecular weights within this range are considered to be more likely to coordinate with bismuth.
• the molecular weight of the coordinating organic compound is more preferably 18 or more and 300 or less, and even more preferably 28 or more and 200 or less.
• the boiling point of the coordinating organic compound at 1 atmosphere is preferably 20°C or higher and 500°C or lower. Using a coordinating organic compound with a boiling point within this range tends to further reduce the odor of the cured body.
• the boiling point of the coordinating organic compound is more preferably 30°C or higher and 400°C or lower, and even more preferably 120°C or higher and 360°C or lower.
• the ratio M1/M2 of the mass M1 of the first bismuth compound to the mass M2 of the coordinating organic compound is preferably 10 or more and 700 or less.
• this ratio M1/M2 is more preferably 15 or more and 300 or less, and even more preferably 20 or more and 100 or less. This ratio can be measured, for example, by 1 H NMR.
• the content of the coordinating organic compound is high, the odor of the cured body tends to be reduced.
• the content of the coordinating organic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more.
• the content of the coordinating organic compound is excessively high, there is a risk that the radiation shielding ability of the cured body will decrease.
• the content of the coordinating organic compound is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
• Examples of the coordinating organic compound include compounds having an imidazole skeleton, compounds having a pyrazole skeleton, compounds having a triazole skeleton, compounds having a tetrazole skeleton, compounds having at least one heteroatom selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and an unsaturated bond, unsaturated dicarboxylic acids, unsaturated carboxylic acid esters, and unsaturated carboxylic acid anhydrides. Note that even if the coordinating organic compound has a radical polymerizable group such as a (meth)acryloyl group, the coordinating organic compound is not included in the above-mentioned polymerizable compounds.
• the coordinating organic compound preferably contains at least one selected from the group consisting of compounds having an imidazole skeleton, compounds having a pyrazole skeleton, compounds having a triazole skeleton, and compounds having a tetrazole skeleton.
• the compound having an imidazole skeleton has a skeleton represented by the following formula (a).
• Examples of compounds having an imidazole skeleton include 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-vinyl
• Examples of the compound having an imidazole skeleton include imidazole, 2-ethylimidazole, 2-propylimidazole, 2-chloroimidazole, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole, 4-fluoroimidazole, 2-formylimidazole, 2-ethyl-4-imidazole,
• the compound having an imidazole skeleton preferably contains 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 contains imidazole.
• the compound having a pyrazole skeleton has a skeleton represented by the following formula (b).
• Examples of compounds having a pyrazole skeleton include 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, and 5-hydroxypyrazole.
• Compounds having a triazole skeleton include compounds having a 1,2,3-triazole skeleton and compounds having a 1,2,4-triazole skeleton.
• the compound having a 1,2,3-triazole skeleton has a skeleton represented by the following formula (c).
• Examples of compounds having a 1,2,3-triazole skeleton include 1,2,3-triazole, 1H-benzotriazole, and 2H-benzotriazole. It is preferable that the compound having a 1,2,3-triazole skeleton contains 1,2,3-triazole.
• the compound having a 1,2,4-triazole skeleton has a skeleton represented by the following formula (d).
• Examples of compounds 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, and 1,2,4-triazole-3-methyl carboxylate.
• the compound having a 1,2,4-triazole skeleton preferably contains 1,2,4-triazole.
• the compound having a tetrazole skeleton has a skeleton represented by the following formula (e).
• Examples of compounds having a tetrazole skeleton include tetrazole, 1-methyl-1H-tetrazole, 5-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, and 5-(2-pyridyl)-1H-tetrazole.
• the compound having a tetrazole skeleton preferably contains tetrazole.
• the coordinating organic compound includes, for example, a compound having at least one heteroatom selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and an unsaturated bond.
• the number of heteroatoms is, for example, 1 to 5, and preferably 1 or 2.
• such compounds include allyl isonicotinate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, indole, carbazole, 1,2-benzisothiazol-3(2H)-one, heliotropine, allyl cyanurate, triallyl isocyanurate, triallylamine, 2-(tert-butylamino)ethyl acrylate, and 2-(tert-butylamino)ethyl methacrylate.
• the coordinating organic compound includes, for example, an unsaturated dicarboxylic acid.
• unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentenedioic acid, methylenesuccinic acid, allylmalonic acid, isopropylidenesuccinic acid, 2,4-hexadienedioic acid, and acetylenedicarboxylic acid. It is preferable that the unsaturated dicarboxylic acid includes maleic acid.
• the coordinating organic compound includes, for example, an unsaturated carboxylate ester.
• unsaturated carboxylate ester examples include 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, and diallyl maleate. It is preferable that the unsaturated carboxylate ester includes at least one compound selected from the group consisting of 2-dimethylaminoethyl acrylate and 2-dimethylaminoethyl methacrylate.
• the coordinating organic compound includes, for example, an unsaturated carboxylic acid anhydride.
• unsaturated carboxylic acid anhydride include acrylic acid anhydride, methacrylic acid anhydride, and maleic acid anhydride.
• coordinating organic compounds include 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-benzisothiazolyl, and the like.
• the coordinating organic compound preferably contains 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.
• Carboxylic acid anhydrides can be used as carboxylic acid precursors.
• the acid dissociation constant pKa is the value of the corresponding carboxylic acid.
• the coordinating organic compound preferably contains a first coordinating organic compound and a second coordinating organic compound of a different type from the first coordinating organic compound.
• the odor can be further reduced due to the synergistic effect of these.
• 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 acid anhydride, and a compound having an imidazole skeleton.
• the curable composition contains a compound having an imidazole skeleton, the viscosity of the curable composition tends to decrease and the handleability tends to increase.
• the proportion of compounds having an imidazole skeleton is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. In one example, the proportion of compounds having an imidazole skeleton is 90% by mass or less, and in another example, 60% by mass or less.
• 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 an unsaturated carboxylic acid anhydride.
• an unsaturated carboxylic acid anhydride When an unsaturated carboxylic acid anhydride is contained, water absorption tends to be enhanced.
• the proportion of unsaturated carboxylic acid anhydrides is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. In one example, the proportion of unsaturated carboxylic acid anhydrides is 90% by mass or less, and in another example, 60% by mass or less.
• the coordinating organic compound preferably contains both a compound having an imidazole skeleton and an unsaturated carboxylic acid anhydride.
• the coordinating organic compound may contain only a compound having an imidazole skeleton and an unsaturated carboxylic acid anhydride, or may contain other compounds.
• Terpenes are hydrocarbons whose structural unit is isoprene, and can function as odor suppressants for the cured product. Terpenes include terpenes and their derivatives.
• the terpenes include, for example, at least one compound selected from the group consisting of semiterpenes, semiterpene derivatives, monoterpenes, monoterpene derivatives, sesquiterpenes, and sesquiterpene derivatives.
• the 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.
• the various derivatives may have functional groups such as hydroxyl groups and carbonyl groups.
• the terpenes preferably contain at least one compound selected from the group consisting of monocyclic monoterpenes, monocyclic monoterpene derivatives, polycyclic monoterpenes, and polycyclic monoterpene derivatives. When these monoterpenes are contained, the odor of the cured body tends to be further reduced.
• Terpenes include, for example, (-)- ⁇ -pinene, (-)- ⁇ -pinene, ( ⁇ )-camphene, ⁇ -terpinene, limonene, phenetole, p-cymene, terpinolene, 1,8-cineole, linalool, (+)-camphor, l-menthol, d-menthol, 1,4-cineol, nopinene, ⁇ -phellandrene, fenchone, borneol, and citronellol.
• the terpenes preferably include at least one selected from the group consisting of (-)- ⁇ -pinene, (-)- ⁇ -pinene, ( ⁇ )-camphene, ⁇ -methylstyrene, ⁇ -terpinene, limonene, phenetole, p-cymene, terpinolene, 1,8-cineole, linalool, (+)-camphor, and l-menthol, and more preferably include at least one selected from the group consisting of (-)- ⁇ -pinene, (-)- ⁇ -pinene, ( ⁇ )-camphene, ⁇ -methylstyrene, limonene, phenetole, p-cymene, linalool, and (+)-camphor.
• the boiling point of terpenes at 1 atmosphere is preferably 95°C or higher and 250°C or lower. Using terpenes with a boiling point within this range tends to further reduce the odor of the cured body.
• the boiling point of terpenes is more preferably 100°C or higher and 220°C or lower, and even more preferably 150°C or higher and 210°C or lower.
• the boiling point of terpenes can be measured, for example, using a boiling point measuring device.
• the ratio M1/M2 of the mass M1 of the first bismuth compound to the mass M2 of the terpenes is preferably 10 or more and 700 or less. If this ratio M1/M2 is large, the radiation shielding ability of the cured body tends to be enhanced. If this ratio M1/M2 is small, the odor of the cured body tends to be reduced. This ratio M1/M2 is more preferably 15 or more and 300 or less, and even more preferably 20 or more and 100 or less.
• the content of terpenes when the content of terpenes is high, the odor of the cured body tends to be reduced.
• the content of terpenes is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more.
• the content of terpenes when the content of terpenes is excessively high, the radiation shielding ability of the cured body may be reduced.
• the content of terpenes is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. These contents can be measured, for example, by 1 H NMR.
• the curable composition according to the present embodiment can be prepared by mixing the first bismuth compound, the polymerizable compound, and other components that are blended as necessary.
• the resin composition according to the present embodiment includes bismuth and a (meth)acrylic resin.
• the resin composition is, for example, a cured product of the curable composition according to the present embodiment described above.
• the bismuth content is preferably 20% by mass or more and 50% by mass or less.
• the bismuth content can be measured by inductively coupled plasma (ICP) emission spectrometry.
• the bismuth content may be 25% by mass or more and 40% by mass or less.
• the remainder of the resin composition may be a (meth)acrylic resin.
• the resin composition according to the present embodiment may have a peak at 1670 to 1700 cm ⁇ 1 in infrared spectroscopy (IR) analysis.
• a resin composition having this peak means that it contains a compound in which bismuth and a phosphate ester are bonded. This peak is considered to be a characteristic peak of the stretching vibration of Bi—O—P.
• the Shore D hardness of the resin composition according to this embodiment is 70 or less.
• a resin composition having a Shore D hardness of 70 or less may have rubber-like elasticity.
• the Shore D hardness may be 60 or less, 55 or less, 50 or less, or 40 or less.
• the lower limit of the Shore D hardness is not particularly limited, but in one example, it is 10 or more, and in another example, it is 20 or more.
• the Shore D hardness of the resin composition according to this embodiment is measured by a method conforming to JIS K 7215.
• the size of the test piece is 50 mm in length, 50 mm in width, and 5.7 mm in thickness.
• the test is performed by stacking two test pieces.
• the elastic modulus of the resin composition according to this embodiment is, for example, 5 MPa or more and 50 MPa or less.
• the elastic modulus may be 40 MPa or less, 30 MPa or less, or 20 MPa or less.
• the maximum point elongation of the resin composition according to this embodiment is, for example, 1% or more and 50% or less.
• the maximum point elongation may be 10% or more, 15% or more, or 20% or more.
• the maximum point stress of the resin composition according to this embodiment is, for example, 0.1 MPa or more and 5.0 MPa or less.
• the maximum point stress may be 1.0 MPa or more, 1.5 MPa or more, or 2.0 MPa or more.
• the maximum point test force of the resin composition according to this embodiment is, for example, 50 N or more.
• the maximum point test force may be 80 N or more, 100 N or more, or 150 N or more.
• the maximum point stroke of the resin composition according to this embodiment is, for example, 1 mm or more.
• the maximum point stroke may be 5 mm or more, 10 mm or more, or 15 mm or more.
• the elastic modulus, maximum point elongation, maximum point stress, maximum point test force, and maximum point stroke of the resin composition according to this embodiment are determined from the stress-strain curve (SS curve) obtained by a tensile tester.
• the size of the test piece is 20 mm wide, 100 mm long, and 5.7 mm thick.
• the tensile speed is 10 mm/min.
• the cured product according to the present embodiment is obtained by curing the above-mentioned curable composition according to the present embodiment.
• a known method can be adopted as a method for producing the cured product. Specifically, photopolymerization, thermal polymerization, or both of these polymerization methods can be adopted.
• a suitable polymerization method is determined by a radical polymerization initiator that is blended as necessary.
• the cured body according to the present embodiment contains a high concentration of bismuth, which has a high ability to block radiation such as X-rays, and yet has high transparency, flexibility, and little coloring.
• the cured body may have a thickness of 2 mm, a transmittance of 80% or more at a wavelength of 560 nm, an X-ray shielding ability equivalent to 0.02 mm or more of lead foil, and a yellowness index of 40 or less, for example.
• the amount of bismuth contained in the hardened body can be 5 to 40 mass % when the total mass of the hardened body is 100 mass %.
• the cured product according to the present embodiment is lightly colored and transparent, and therefore can be used as an optical article. Furthermore, since it has radiation shielding ability despite being transparent to visible light, it can be used as a transparent radiation shielding material. In addition, since a large-area, flexible sheet can be obtained, it can be easily shaped to suit the purpose or object.
• Optical articles containing the cured product according to this embodiment can be used as radiation shielding window materials, radiation shielding lenses, radiation protection curtains, and other sheets.
• a lens or sheet containing the cured product according to this embodiment can be used as radiation shielding glasses, radiation shielding shields, etc.
• the hardened product according to this embodiment has antibacterial and antiviral properties, and can therefore be used in applications where high hygiene is required.
• the TG-DTA measurements were performed using a simultaneous differential thermal and thermogravimetric analyzer (TG8120, manufactured by Rigaku Corporation). The temperature was scanned from room temperature to 500°C at a heating rate of 10°C/min under air flow.
• TG8120 simultaneous differential thermal and thermogravimetric analyzer
• a microscopic Raman spectrometer (NRS-7100, manufactured by JASCO Corporation) was used, and a 532 nm laser, 100x objective lens, 600 line/mm grating, ⁇ 25 ⁇ m and ⁇ 4000 ⁇ m apertures were used for sample excitation, with an exposure time of 20 seconds x 2.
• An X-ray photoelectron spectrometer (ULVAC-PHI, Inc., ESCA5701ci/MC) was used for the XPS measurements.
• Monochromatic Al-K ⁇ (14 kV-330 W) was used as the X-ray source, with an aperture diameter of ⁇ 800 ⁇ m and a photoelectron take-off angle of 45 degrees.
• the sample was crushed in an agate mortar, and the resulting powder was fixed to a substrate with carbon tape and introduced into the measurement chamber for measurement.
• the resulting cloudy solution was transferred to a 1000 mL four-neck flask equipped with a Dean-Stark trap, and the reaction was carried out while heating and stirring at 130°C in an oil bath, and the water produced was removed from the system. The reaction was terminated when no more water was produced. A pale yellow scattered solution with a slight amount of pale yellow precipitate was obtained.
• This solution was concentrated to 250 mL using a vacuum evaporator. 8 g of alumina powder was added and left to stand overnight, then suction filtered using 5B filter paper. 3 g of activated carbon (Norit, Darco G60) was added to the resulting light yellow scattered filtrate and centrifuged at 23,830 x g for 8 hours. The centrifugal supernatant was pressure filtered using a membrane filter with a pore size of 0.2 ⁇ m to obtain a light yellow transparent filtrate. The solvent was removed from this solution using a vacuum evaporator and redissolved in 250 mL of acetone.
• Example 1 To the phosphate-bonded bismuth-containing composition (referred to as "Bi compound” in the table) (40 parts by mass) obtained in Production Example 1, methoxyethyl methacrylate (MEMA) (14.9 parts by mass), tetrahydrofurfuryl acrylate (THFAA) (21.4 parts by mass), and nonaethylene glycol dimethacrylate (9G) (22.2 parts by mass) were added as polymerizable compounds. To this, imidazole (0.9 parts by mass) was added as a coordinating organic compound. Furthermore, methylstyrene dimer (MSD) (0.6 parts by mass) and KF-353A (0.01 parts by mass) were added as other compounding agents and dissolved uniformly to obtain a curable composition.
• MEMA methoxyethyl methacrylate
• TFAA tetrahydrofurfuryl acrylate
• 9G nonaethylene glycol dimethacrylate
• V-59 2,2'-azobis(2-methylbutyronitrile) (V-59) (0.9 parts by mass) and 1,1'-azobis(cyclohexane-1-carbonitrile) (V-40) (0.05 parts by mass) were further added to this curable composition and completely dissolved.
• the curable composition is placed under reduced pressure by a vacuum pump to remove dissolved oxygen.Then, the curable composition is poured into two glass plates (110 mm x 300 mm) fixed with a 3 mm square cord made of silicone resin so as to keep a gap of 3 mm, heated to a maximum temperature of 90°C over 15 hours, and maintained at 90°C for 2 hours to polymerize, thereby obtaining a pale yellow transparent cured product.
• Examples 2 to 5 and Comparative Examples 1 to 5 A pale yellow transparent cured product was obtained in the same manner as in Example 1, except that the components other than 2,2'-azobis(2-methylbutyronitrile) (V-59) and 1,1'-azobis(cyclohexane-1-carbonitrile) (V-40) were changed as shown in Table 1 below.
• Shore D hardness The Shore D hardness of the cured products obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was measured in accordance with JIS K 7215.
• the equipment used was a digital durometer (DD4, manufactured by Kobunshi Keiki Co., Ltd.) attached to a motor-driven constant pressure load device (CLE-150, manufactured by Kobunshi Keiki Co., Ltd.), and the needle was lowered at a descending speed of 1 cm/sec to read the value. The measurement was carried out three times, and the average value was regarded as the Shore D hardness of the cured product.
• MEMA Methoxyethyl methacrylate
• THFAA Tetrahydrofurfuryl acrylate
• 9G Nonethylene glycol dimethacrylate
• MMA Methyl methacrylate
• MSD Methylstyrene dimer
• KF-353A Silicone release agent
• the curable compositions of Examples 1 to 5 which contain a first bismuth compound and a monofunctional acrylate and have a monofunctional methacrylate content of 20 mass% or less, were able to produce cured bodies that were low in hardness and flexible.
• Example 6 to 30> A pale yellow transparent cured product was obtained in the same manner as in Example 1, except that the components other than 2,2'-azobis(2-methylbutyronitrile) (V-59) and 1,1'-azobis(cyclohexane-1-carbonitrile) (V-40) were changed as shown in Table 2 below.

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