Polymerizable composition and resin obtained by polymerizing and curing same

Abstract

The present invention makes it possible to provide a polymerizable composition comprising a compound (a) that is represented by formula (1). (In the formula, n represents an integer of 0-3, p represents an integer of 0-2, q represents an integer of 1-3, and p+q=3. Each R1 is the same or different and represents a C1-6 alkylene group. Each R2 is the same or different and represents a hydrogen atom or a methyl group. Each Z is the same or different and represents a hydrogen atom or a vinyl group.)

Description

Polymerizable composition and resin obtained by polymerizing and curing the same

[0001] The present invention relates to a polymerizable composition and a resin obtained by polymerizing and curing the same, which are suitable for use in optical materials such as filters, plastic lenses, prisms, and optical fibers as transparent members that need to block radiation, particularly filters and plastic lenses.

[0002] Generally, radiation shielding materials can easily shield against alpha rays by using thin materials such as paper, and against beta rays by using thin metal plates such as aluminum, but they can weaken gamma rays and X-rays by using thick plates such as lead or iron as shielding materials.However, these materials are not transparent, so it is not possible to visualize the other side of the shielding material.

[0003] In such circumstances, at advanced medical facilities where CT (computed tomography) and PET (positron emission tomography) devices are used for diagnosis and treatment, and at nuclear power plants, it is necessary to transmit images visually or via camera to check the situation at the site where radiation is being used while also providing sufficient shielding from radiation. This requires materials that are transparent to visible light while providing sufficient shielding from radiation.

[0004] In response to such demands, lead-containing glass is generally known as a material that is transparent and capable of shielding radiation (Patent Documents 1 and 2). However, unlike plastics, lead-containing glass is inferior in processability and moldability, and its high specific gravity makes it disadvantageous for applications requiring light weight.

[0005] On the other hand, rubber sheets filled with heavy metals such as barium sulfate, cerium oxide, and barium oxide are commonly known as radiation-shielding plastics (Patent Document 3). However, these rubber sheets are opaque, making it impossible to check the location where radiation is being used.

[0006] For these reasons, there is a demand for plastic materials that are easy to process, lightweight, and have radiation shielding properties.

[0007] JP 2016-008146 JP 2014-062863 JP 2015-224967

[0008] An object of the present invention is to solve at least one of the problems in the prior art described above. Another object of the present invention is to provide a polymerizable composition that can be cured by heat or light and can provide a transparent resin or optical material having radiation-shielding ability.

[0009] In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved by using a bismuth-containing compound having a specific structure. Specifically, the present invention includes the following aspects.

[0010] <1> A polymerizable composition containing a compound (a) represented by the following formula (1): (In the formula, n represents an integer of 0 to 3, p represents an integer of 0 to 2, q represents an integer of 1 to 3, and p+q=3. In addition, R １ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ２ are the same or different and represent a hydrogen atom or a methyl group, and Z are the same or different and represent a hydrogen atom or a vinyl group.) <2> The polymerizable composition according to <1> above, further comprising (b) a compound having two or more thiol groups in one molecule. <3> The polymerizable composition according to <1> above, further comprising (c) a compound having at least one group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group. <4> The polymerizable composition according to <1> above, wherein the compound (a) is a compound represented by the following formula (2): (In the formula, p represents an integer of 0 to 2, q represents an integer of 1 to 3, and p+q=3. In addition, R ２are the same or different and represent a hydrogen atom or a methyl group, and Z are the same or different and represent a hydrogen atom or a vinyl group.) <5> The polymerizable composition according to <2> above, wherein the (b) compound having two or more thiol groups in one molecule is one or more selected from the group consisting of bis(2-mercaptoethyl)sulfide, pentaerythritol tetrakis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, and 1,3-bis(mercaptomethyl)benzene. <6> The compound (c) having at least one group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group is selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, ...methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate, methyl (meth)acrylate The polymerizable composition according to <3> above, wherein the compound is one or more compounds selected from the group consisting of diol di(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, an ethylene oxide adduct of bisphenol A di(meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, dimethyl (meth)acrylamide, phenyl vinyl sulfide, phenyl vinyl sulfoxide, 4-methyl-5-vinylimidazole, and 1-vinylimidazole. <7> A resin obtained by polymerizing and curing the polymerizable composition according to any one of <1> to <6> above.<8> An optical material containing the resin according to the above item <7>. <9> A color tone changing material containing the resin according to the above item <7>.

[0011] By using the polymerizable composition according to a preferred embodiment of the present invention, it is possible to provide transparent resins and optical materials having radiation shielding properties.

[0012] 1 is a graph showing the transmission spectra of the polymer films of Examples 1 to 4 and Reference Example 1. 2 is a graph showing the relationship between the charge ratio of each component and the refractive index in the polymer films of Examples 1 to 5 and Reference Example 1.

[0013] Hereinafter, the present invention will be described in detail by way of examples and working examples, but the present invention is not limited to the illustrated examples and working examples, and can be modified in any manner as long as it does not significantly deviate from the content of the present invention. In one embodiment of the present invention, a polymerizable composition is provided that contains a compound (a) represented by the following formula (1). The polymerizable composition of the present invention encompasses both an embodiment that contains only the compound (a) represented by the following formula (1) and an embodiment that contains the compound (a) represented by the following formula (1) and other components. In the formula, n represents an integer of 0 to 3, p represents an integer of 0 to 2, q represents an integer of 1 to 3, and p+q=3. １ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ２ are the same or different and each represents a hydrogen atom or a methyl group, and Z are the same or different and each represents a hydrogen atom or a vinyl group.

[0014] Each component will be described below. Compound (a) represented by the above formula (1) (hereinafter also referred to as "(a) compound") includes all compounds that satisfy the above conditions. These may be used alone or in combination of two or more. The (a) compound used in the present invention has the advantage of not having the odor of sulfur compounds.

[0015] A more preferred compound is a compound represented by the following formula (2): In the formula, p represents an integer of 0 to 2, q represents an integer of 1 to 3, and p+q=3. ２are the same or different and each represents a hydrogen atom or a methyl group, and Z are the same or different and each represents a hydrogen atom or a vinyl group.

[0016] The compound (a) can be obtained by reacting a triphenylbismuthine compound with a carboxylic acid compound as shown below.

[0017] In the formula, n represents an integer of 0 to 3, p represents an integer of 0 to 2, q represents an integer of 1 to 3, and p+q=3. １ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ２ are the same or different and each represents a hydrogen atom or a methyl group, and Z are the same or different and each represents a hydrogen atom or a vinyl group.

[0018] The polymerizable composition containing the compound (a) may further contain (b) a compound having two or more thiol groups in one molecule, and / or (c) a compound having at least one group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group.

[0019] (b) Compounds having two or more thiol groups in one molecule (hereinafter also referred to as "(b) compounds") include all compounds that satisfy this condition.

[0020] Examples of the (b) compound include o-dimercaptobenzene, m-dimercaptobenzene, p-dimercaptobenzene, 1,3,5-trimercaptobenzene, methanedithiol, 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis(2-mercaptoethyl)sulfide, 1,2-bis(2-mercaptoethylthio)ethane, 1,5-dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2- Dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptopropane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,1,1-tris(mercaptomethyl)propane, tetrakis(mercaptomethyl)methane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-Tetrakis(mercaptomethylthio)propane, 1,2,6,7-tetramercapto-4-thiapentane, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(2-mercaptoacetate), 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane Examples of the mercaptocyclohexane include, but are not limited to, hexane, 1,4-dimercaptocyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, 2,5-bis(mercaptomethyl)-1,4-dithiane, 2,5-bis(mercaptoethyl)-1,4-dithiane, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, bis(4-mercaptophenyl)sulfide, bis(4-mercaptophenyl)ether, 2,2-bis(4-mercaptophenyl)propane, bis(4-mercaptomethylphenyl)sulfide, bis(4-mercaptomethylphenyl)ether, and 2,2-bis(4-mercaptomethylphenyl)propane. These mercaptocyclohexanes may be used alone or in combination of two or more.

[0021] Preferred compounds as the (b) compound include bis(2-mercaptoethyl)sulfide, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,2,6,7-tetramercapto-4-thiapentane, 4,8-dimercapto Examples of preferred compounds include methyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,3-bis(mercaptomethyl)benzene, and 1,4-bis(mercaptomethyl)benzene. Specific examples of more preferred compounds include bis(2-mercaptoethyl)sulfide, pentaerythritol tetrakis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, and 1,3-bis(mercaptomethyl)benzene.

[0022] The ratio of the (a) compound to the (b) compound may be any ratio, but a preferred range of the composition is a ratio of the number of double bonds in the (a) compound to the number of SH groups in the (b) compound of 0.5 to 10.0, more preferably 0.8 to 5.0, and most preferably 0.9 to 1.2. If the ratio is less than 0.5 or exceeds 10.0, polymerization may not be sufficient, resulting in a decrease in heat resistance.

[0023] (c) Compounds having at least one group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group (hereinafter also referred to as "(c) compounds") include all compounds that satisfy this condition.

[0024] Examples of the (c) compound include methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate. Examples of the (c) compound include, but are not limited to, glycerin di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide adduct di(meth)acrylate of bisphenol A, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, dimethyl (meth)acrylamide, phenyl vinyl sulfide, phenyl vinyl sulfoxide, 4-methyl-5-vinylimidazole, and 1-vinylimidazole. Preferred examples of the (c) compound include 2-hydroxyethyl (meth)acrylate, dimethyl (meth)acrylamide, and 2-carboxyethyl (meth)acrylate. These compounds may be used alone or in combination of two or more.

[0025] The ratio of the (a) compound to the (c) compound is arbitrary. By mixing the (c) compound, the viscosity of the polymerizable composition can be adjusted to a range that is easy to handle, the uniformity of the solution can be improved, and a homogeneous cured product can be produced after curing. Phthalic acid methacrylate type monomers are highly compatible with (meth)acrylic acid, glycidyl (meth)acrylate, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, dimethyl (meth)acrylamide, etc., and mixing improves handling. Furthermore, mixing can adjust the mechanical strength, refractive index, and other optical properties of the cured resin.

[0026] The ratio of the (a) compound, the (b) compound, and the (c) compound may be any ratio. A preferred range of the composition is a ratio of (the number of double bonds in the (a) compound + the number of double bonds in the (c) compound) / the number of SH groups in the (b) compound of 0.5 to 10.0, more preferably 0.8 to 5.0, and most preferably 0.9 to 1.2. If the ratio is less than 0.5 or exceeds 10.0, polymerization may not be sufficient, resulting in reduced heat resistance.

[0027] In another embodiment of the present invention, there is provided a resin obtained by polymerizing and curing a polymerizable composition containing the compound (a).

[0028] The polymerizable composition containing the compound (a) of the present invention has a polymerizable group containing an unsaturated double bond, and therefore is cured by a polymerization reaction to obtain a resin. Examples of the polymerization reaction include a photopolymerization curing reaction and a heat polymerization curing reaction. In a preferred embodiment of the present invention, a photopolymerization curing reaction, which allows polymerization in a short time, is preferred. In another embodiment of the present invention, a thermal polymerization curing reaction may be selected. In an embodiment of the present invention, a thermal curing reaction and a photocuring reaction may be combined.

[0029] The polymerization and curing reaction of the polymerizable composition containing the compound (a) of the present invention can be carried out in the presence or absence of a polymerization catalyst. When polymerizing the polymerizable composition containing the compound (a) of the present invention to obtain a resin, it is preferable to polymerize and curing in the presence of a polymerization catalyst to promote the polymerization reaction. Therefore, in one embodiment of the present invention, a resin obtained by polymerizing and curing the polymerizable composition of the present invention in the presence of a polymerization catalyst, as well as an optical material obtained from the resin, are provided. The resin and optical material thus obtained are preferably transparent. In another embodiment of the present invention, a method for producing a cured product, preferably an optical material, is provided, characterized by curing the polymerizable composition of the present invention by irradiation with ultraviolet or visible light in the presence of a polymerization catalyst.

[0030] In the case of a photopolymerization reaction, a polymerizable composition containing the compound (a) of the present invention is cured by irradiation with light rays (active energy rays), to produce a resin as a cured product. The light rays are not particularly limited as long as they can cure the polymerizable composition, but typically include ultraviolet light, visible light, radiation, and electron beams. Preferred are ultraviolet light or visible light, and more preferred is ultraviolet light because of its fast polymerization rate. The irradiation intensity of the light rays is not particularly limited, but is typically 10 to 100,000 mW / cm. ２ The irradiation time is not particularly limited, but is usually from 1 minute to several hours, preferably from 1 to 60 minutes. The irradiation temperature is not particularly limited, and polymerization is possible at around room temperature. When the polymerizable composition containing the compound (a) of the present invention is solid at room temperature, photocuring may be carried out while heating it to a temperature equal to or higher than the melting point.

[0031] The polymerization catalyst is not particularly limited and may be appropriately selected depending on the type of reactant, polymerization conditions, etc. In the case of photopolymerization, a compound that generates radicals upon irradiation with light (preferably active energy rays) (photodecomposition-type radical polymerization initiator) is preferred, and specific examples include, but are not limited to, benzoin derivatives, benzyl derivatives, benzophenone derivatives, and acetophenone derivatives. Among these, commercially available products such as hydroxycyclohexyl-phenyl ketone (trade name Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals), 2,2-dimethoxy-2-phenylacetophenone (Irgacure (registered trademark) 651), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure (registered trademark) 2959), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Irgacure (registered trademark) TPO) are preferably used.

[0032] Alternatively, it is also preferable to use a compound (redox polymerization initiator) that generates radicals in the coexistence of an oxidizing agent and a reducing agent as a polymerization catalyst for the photopolymerization reaction. Specific examples include a system that combines an oxide selected from persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, and peroxides such as hydrogen peroxide, t-butyl peroxide, and methyl ethyl ketone peroxide with a reducing compound selected from L-ascorbic acid, sodium hydrogen sulfite, and the like.

[0033] Alternatively, a photoredox catalyst that generates radicals upon irradiation with light such as visible light is also preferably used as a polymerization catalyst for the photopolymerization reaction. Specific examples include ruthenium (II) polypyridyl complexes (e.g., Ru(bpz) ３ - (PF ６ ) ２ catalysts), and transition metal complexes such as iridium(III) phenylpyridyl complexes.

[0034] In the case of a thermal polymerization reaction, a polymerizable composition containing the compound (a) of the present invention is polymerized (cured) by heating to produce a resin as a cured product.

[0035] The polymerization catalyst used in the thermal polymerization reaction is preferably a compound that generates radicals upon heating (thermal decomposition type radical polymerization initiator). Specific examples include persulfates such as sodium persulfate, ammonium persulfate, and potassium persulfate; hydrogen peroxide; organic peroxides such as t-butyl hydroperoxide; and azo compounds such as 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-2(-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionitrile), and 2,2'-azobis(isobutyronitrile) (AIBN).

[0036] The polymerization catalyst may be one or more compounds selected from the group consisting of peroxides, azo compounds, redox polymerization initiators, and transition metal complexes. The polymerization catalysts may be used alone or in combination.

[0037] The amount of polymerization catalyst added cannot be determined in general because it varies depending on the components, mixing ratio, and polymerization / curing method of the polymerizable composition containing the compound (a) of the present invention. However, it is typically 0.0001% by mass to 10% by mass, preferably 0.001% by mass to 5% by mass, more preferably 0.01% by mass to 1% by mass, and most preferably 0.01% by mass to 0.5% by mass, relative to 100% by mass of the total polymerizable composition. If the amount added is more than 10% by mass, rapid polymerization may occur. If the amount added is less than 0.0001% by mass, the resulting composition may not be sufficiently cured, resulting in poor heat resistance. Therefore, in a preferred embodiment of the present invention, the resin production method includes the step of adding a polymerization catalyst in an amount of 0.0001 to 10% by mass relative to the total amount of the polymerizable composition, and polymerizing and curing the composition.

[0038] Polymerization (curing) of the polymerizable composition containing the compound (a) of the present invention by heating is usually carried out as follows. That is, the curing time is usually 1 to 100 hours, and the curing temperature is usually -10°C to 140°C. The polymerization is carried out by a step of maintaining the polymerizable composition at a predetermined polymerization temperature for a predetermined time, a step of increasing the temperature at a rate of 0.1°C to 100°C / h, and a step of decreasing the temperature at a rate of 0.1°C to 100°C / h, or a combination of these steps. The curing time refers to the polymerization and curing time including the temperature increase process, and includes the step of maintaining the polymerizable composition at the predetermined polymerization (curing) temperature as well as the step of increasing the temperature and cooling the temperature to the predetermined polymerization (curing) temperature.

[0039] The polymerization and curing process (photopolymerization and thermal polymerization) is not particularly limited, but is preferably a curing process using a metal, ceramic, glass, resin, or other mold. Specifically, the components of the polymerizable composition containing the compound (a) of the present invention and a polymerization catalyst are mixed together. These may be mixed simultaneously in the same container under stirring, or the raw materials may be added and mixed stepwise, or several components may be mixed separately and then remixed in the same container. Furthermore, the raw materials and auxiliary materials may be mixed in any order. The set temperature and time required for mixing are essentially any conditions that ensure sufficient mixing of the components. The polymerizable composition thus obtained is poured into a mold or other form, and the polymerization and curing reaction is carried out by heating or irradiation with ultraviolet light or other light, and then the mixture is removed from the mold. In this way, a resin is obtained by curing the polymerizable composition containing the compound (a) of the present invention. The polymerization reaction (curing process) can be carried out in air, in an inert gas atmosphere such as nitrogen, or under reduced pressure or pressure.

[0040] After curing, the resulting resin is preferably annealed for about 10 minutes to 5 hours at a temperature of 50 to 150° C. to remove distortion. Furthermore, the resulting resin may be subjected to surface treatment such as hard coating or anti-reflection, as needed.

[0041] When producing the resin of the present invention, additives such as ultraviolet absorbers, antioxidants, adhesion improvers, and mold release agents may be added to the polymerizable composition to further improve the practical utility of the resulting resin.

[0042] As described above, the polymerizable composition containing the compound (a) of the present invention can provide a resin excellent in at least one property such as a high refractive index, photopolymerization curability, thermal polymerization curability, etc. Thus, a resin (cured product) obtained by curing the polymerizable composition also represents one embodiment of the present invention.

[0043] One embodiment of the present invention is a molded article produced using a resin obtained by polymerizing and curing a polymerizable composition containing the compound (a) of the present invention. The molded article is useful, for example, in advanced medical settings where diagnostics are performed using CT (computed tomography) or PET (positron emission tomography) devices, and in nuclear power plants. It can be used as a radiation shielding plate or shielding filter, or it can be used directly as an optical material (component). For example, its use in a camera lens can protect the camera sensor from radiation damage and transmit images with radiation noise removed. These applications include optical materials (components), machine component materials, electrical and electronic component materials, automotive component materials, civil engineering and construction materials, molding materials, and various other applications, including paints and adhesives. Among these, preferred are optical materials for optical applications such as spectacle lenses, (digital) camera imaging lenses, light beam focusing lenses, light diffusing lenses, and other lenses, LED sealants, optical adhesives, optical transmission bonding materials, prisms, filters, diffraction gratings, watch glasses, and transparent glass and cover glass for display devices; display device applications such as substrates for display elements such as LCDs, organic ELs, and PDPs, color filter substrates, touch panel substrates, display backlights, light guide plates, display protective films, anti-reflection films, and anti-fogging films; optical memories, recording media such as electronic paper, sensor materials for UV checkers, light-adjusting materials for window glass, sunglasses, and automotive window glass; textiles, cosmetic materials, photochromic materials, and other color-changing materials for printing materials. Optical adhesives, prisms, and coating agents are particularly preferred as optical materials.

[0044] The present invention will be specifically explained with reference to the following examples, but the present invention is not limited to these examples.

[0045] Example 1 Triphenylbismuthine (0.192 g, 0.437 mmol) represented by the following structural formula (hereinafter referred to as "BiPh") was placed in a recovery flask. ３ ") and commercially available mono(2-methacryloyloxyethyl)phthalate (1.22 g, 4.37 mmol) (hereinafter sometimes referred to as "MOEP") represented by the following structural formula were mixed and reacted at 40°C for 24 hours. After the reaction, the mixture was placed under reduced pressure to remove the benzene. A monomer solution was prepared by adding the polymerization initiator IRGACURE (registered trademark) 651 (1.12 mg, 1 mol% relative to the vinyl group) to the resulting monomer. The monomer solution was sandwiched between two PVA / PET sheets (SO sheets manufactured by Aicello Co., Ltd.) with a 250 μm spacer in between, and irradiated with 365 nm UV for 5 minutes to produce a polymer film.

[0046] Examples 2 to 5 Polymer films of Examples 2 to 5 were produced in the same manner as in Example 1, except that the amounts of ingredients were changed to those shown in Table 1 below.

[0047] Below, [BiPh ３ The NMR spectra of the monomers prepared with the molar ratios of [BiPh]:[MOEP] of 1:10, 1:3, and 1:2 are shown. The NMR was measured using an ECX-400 manufactured by JEOL Ltd. ３ ]:[MOEP]=1:10 １ H NMR (400MHz, CDCl ３ , δin ppm): 1.70-2.05 (br, 3H, CH ２ =C-CH ３ ), 4.19-4.64 (br, 4H, O-CH ２ -CH ２ -O), 5.00-6.70 (br, COOH), 5.33-5.77 (br, 1H, C=CHH), 5.87-6.35 (br, 1H, C=CHH), 6.85-8.30 (br, 4+0.014×5H, Ph and -C ６ H ４ -)

[0048] [BiPh３ ]:[MOEP]=1:3 １ H NMR (400MHz, CDCl ３ , δin ppm): 1.70-2.05 (br, 3H, CH ２ =C-CH ３ ), 3.20-5.10 (br, COOH+H ２ O), 4.19-4.64 (br, 4H, O-CH ２ -CH ２ -O), 5.33-5.77 (br, 1H, C=CHH), 5.87-6.35 (br, 1H, C=CHH), 6.85-8.30 (br, 4+0.04×5H, Ph and -C ６ H ４ -)

[0049] [BiPh ３ ]:[MOEP]=1:2 １ H NMR (400MHz, CDCl ３ , δin ppm): 1.70-2.05 (br, 3H, CH ２ =C-CH ３ ), 3.20-5.10 (br, COOH+H ２ O), 4.19-4.64 (br, 4H, O-CH ２ -CH ２ -O), 5.33-5.77 (br, 1H, C=CHH), 5.87-6.35 (br, 1H, C=CHH), 6.85-8.30 (br, 4+0.43×5H, Ph and -C ６ H ４ -), 8.66 (d, 0.1 x 2H, Ph (ortho position))

[0050] The polymer films of Examples 1 to 5 obtained above and BiPh ３The transmittance, refractive index, and X-ray transmittance at 589 nm were measured for the polymer film of Reference Example 1, in which the MOEP ratio was 0:10 (however, in Example 5, only the refractive index and X-ray transmittance were measured). The measurement results are shown in Table 2 below. FIG. 1 shows a graph illustrating the transmission spectra of the polymer films of Examples 1 to 4 and Reference Example 1. FIG. 2 shows a graph illustrating the relationship between the component ratio and refractive index for the polymer films of Examples 1 to 5 and Reference Example 1. The transmittance at 589 nm was measured at room temperature in air using a UV-visible spectrophotometer (Shimadzu Corporation, UV-2600i, equipped with an ISR-2600Plus integrating sphere unit). The refractive index was measured using a multi-wavelength Abbe refractometer (Atago Co., Ltd., DR-M4). A 589 nm interference filter was used, and 1-bromonaphthalene was used as the intermediate solution. The X-ray transmittance was measured using a small-angle X-ray scattering device (SAXS: NANO-Viewer manufactured by Rigaku Corporation) as the X-ray source (detector). The measurement conditions were as follows: X-ray source: CuKα 1.54 angstroms (8.048 keV) Tube voltage (accelerating voltage): 40 kV

[0051]

[0052] Next, for the polymer films of Examples 1 to 5 and the polymer film of Reference Example 1, the thicknesses of the polymer films were changed as shown in Table 3 below, and the X-ray transmittance was measured in the same manner as above. The results are shown in Table 3.

[0053]

[0054] (Example 6) Triphenylbismuthine (0.292 g, 0.664 mmol), mono(2-methacryloyloxyethyl)phthalate (0.554 g, 1.99 mmol) obtained by purifying a commercially available product by silica gel column chromatography, and benzyl methacrylate (0.351 g, 1.99 mmol) represented by the following structural formula were mixed in a recovery flask and reacted at 40°C for 24 hours. After the reaction, the mixture was placed under reduced pressure to remove benzene. Lauroyl peroxide (1.59 mg, 3.98 × 10 －２A monomer solution containing 1 mmol of vinyl groups was prepared, and the monomer solution was placed on a PVA / PET sheet (SO sheet manufactured by Aicello Co., Ltd.) with a 250 μm spacer interposed therebetween, and the sheet was uniformly spread using a glass plate. The resulting mixture was then thermally cured in an oven at 60°C under reduced pressure for 24 hours to produce a polymer film.

[0055] Example 7 Triphenylbismuthine (0.696 g, 1.58 mmol), mono(2-methacryloyloxyethyl)phthalate (1.32 g, 4.74 mmol), a commercially available product purified by silica gel column chromatography, and methyl methacrylate (0.475 g, 4.74 mmol) represented by the following structural formula were mixed in a recovery flask and reacted at 40°C for 24 hours. After the reaction, the mixture was placed under reduced pressure to remove the benzene. A monomer solution was prepared by adding lauroyl peroxide (0.475 g, 4.74 mmol, 1 mol% relative to the vinyl group) to the resulting monomer. The monomer solution was placed on a PVA / PET sheet (SO sheet manufactured by Aicello Co., Ltd.) with a 250 μm spacer between them, and the resulting mixture was uniformly spread using a glass plate. The mixture was then thermally cured in an oven at 60°C for 24 hours under reduced pressure to produce a polymer film.

Claims

1. A polymerizable composition comprising a compound (a) represented by the following formula (1): (In the formula, n represents an integer of 0 to 3, p represents an integer of 0 to 2, q represents an integer of 1 to 3, and p+q=3. １ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ２ are the same or different and each represents a hydrogen atom or a methyl group, and Z are the same or different and each represents a hydrogen atom or a vinyl group.

2. The polymerizable composition according to claim 1, further comprising (b) a compound having two or more thiol groups in one molecule.

3. The polymerizable composition according to claim 1, further comprising (c) a compound having at least one group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group.

4. The polymerizable composition according to claim 1, wherein the compound (a) is a compound represented by the following formula (2): (In the formula, p represents an integer of 0 to 2, q represents an integer of 1 to 3, and p+q=3. ２ are the same or different and each represents a hydrogen atom or a methyl group, and Z are the same or different and each represents a hydrogen atom or a vinyl group.

5. The polymerizable composition according to claim 2, wherein the (b) compound having two or more thiol groups in one molecule is one or more selected from the group consisting of bis(2-mercaptoethyl)sulfide, pentaerythritol tetrakis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, and 1,3-bis(mercaptomethyl)benzene.

6. The compound (c) having at least one group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group is selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, The polymerizable composition according to claim 3, which is one or more compounds selected from the group consisting of nandiol di(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide adduct di(meth)acrylate of bisphenol A, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, dimethyl (meth)acrylamide, phenyl vinyl sulfide, phenyl vinyl sulfoxide, 4-methyl-5-vinylimidazole, and 1-vinylimidazole.

7. A resin obtained by polymerizing and curing the polymerizable composition according to any one of claims 1 to 6.

8. An optical material comprising the resin according to claim 7.

9. A color-changing material comprising the resin according to claim 7.

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