WO2024228342A1 - Polymerizable composition, resin obtained by polymerizing and curing same, and optical material comprising said resin - Google Patents

Abstract

According to the present invention, it is possible to provide a polymerizable composition comprising a compound (a) represented by formula (1). (In formula (1), X₁-X₃ are the same as or different from each other, and represent a structure represented by formula (2) or a phenyl group, and at least one among X₁-X₃ represents a structure represented by formula (2). When the bismuth atom in formula (1) is bonded to the structure represented by formula (2), the bismuth atom is bonded to the oxygen atom in formula (2). The oxygen atom in formula (2) is bonded to the same bismuth atom to form a cyclic structure or is bonded to another bismuth atom to form a chain structure.) (In formula (2), Z represents a hydrocarbon group.)

Description

Polymerizable composition, resin obtained by polymerizing and curing the composition, and optical material containing the resin

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

Radiation shielding materials generally can easily block alpha rays using thin materials such as paper, and beta rays using thin metal plates such as aluminum, but gamma rays and X-rays can be weakened by using thick plates of lead or iron as shielding materials. However, these materials are not transparent, making it impossible to visualize the other side of the shielding material.

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

Amid such demands, lead-containing glass is commonly known as a material that is transparent to visible light and can block radiation (Patent Documents 1 and 2). However, unlike plastics, lead-containing glass is poorly processable and moldable, making it unsuitable for complex shapes, and its high specific gravity makes it disadvantageous for applications requiring light weight.

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 to visible light, so it is not possible to visually or camera-visually confirm the location where radiation is being used.

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

Patent Publication 2016-008146 Patent Publication 2014-062863 Patent Publication 2015-224967

The present invention aims to solve at least one of the problems in the above-mentioned conventional techniques. Furthermore, the present invention aims to provide a polymerizable composition that is solvent-soluble and thermoplastic, can be easily processed, and can be cured by heat or light, and can provide a transparent resin or optical material that has radiation shielding capabilities.

In view of the above circumstances, the present inventors 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.

（式（１）中、Ｘ_１～Ｘ_３は同一または異なって、下記式（２）で表される構造またはフェニル基を表し、Ｘ_１～Ｘ_３の少なくとも１つは式（２）で表される構造を表す。式（１）のビスマス原子について、式（２）で表される構造と結合している場合は、式（２）の酸素原子と結合する。式（２）の酸素原子は同一のビスマス原子と結合して環状構造を形成するか、あるいは他のビスマス原子と結合して鎖状構造を形成する。）

（式（２）中、Ｚは炭化水素基を表す）。
＜２＞　前記式（２）で表される構造が、下記式（３）で表される構造を表す、上記＜１＞に記載の重合性組成物である。

（式（３）中、ｎは０～１０の整数を表す。Ｒ_１は水素原子または炭化水素基を表す。）
＜３＞　式（３）におけるＲ_１が、下記式（４）で表される置換基を表す、上記＜１＞または＜２＞に記載の重合性組成物である。

（式（４）中、ｍは０～３の整数を表す。Ｒ_２は炭素数１～１０の炭化水素基を表す。）
＜４＞　さらに、（ｂ）アクリロイル基、メタクリロイル基、アリル基、及びビニル基からなる群より選択される少なくとも１つの基を有する化合物を含有する、上記＜１＞～＜３＞のいずれかに記載の重合性組成物である。
＜５＞　さらに、（ｃ）チオール基を１分子中に２個以上有する化合物を含有する、上記＜１＞～＜４＞のいずれかに記載の重合性組成物である。
＜６＞　前記式（３）で表される構造が、下記式（５）または式（６）で表される構造の少なくとも一つである、上記＜２＞に記載の重合性組成物である。

（式（５）中、Ｒ_２は炭素数１～１０の炭化水素基を表す。）

＜７＞　前記（ｂ）アクリロイル基、メタクリロイル基、アリル基、及びビニル基からなる群より選択される少なくとも１つの基を有する化合物が、メチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、グリシジル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ノナンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ビスフェノールＡのエチレンオキサイド付加物ジ（メタ）アクリレート、イソボニル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、アリル（メタ）アクリレート、２－カルボキシエチル（メタ）アクリレート、ジメチル（メタ）アクリルアミド、フェニルビニルスルフィド、フェニルビニルスルホキシド、４－メチル－５－ビニルイミダゾール、及び１－ビニルイミダゾールからなる群より選ばれる１種以上の化合物である、上記＜４＞に記載の重合性組成物である。
＜８＞　上記＜１＞～＜７＞のいずれかに記載の重合性組成物を重合硬化してなる樹脂である。
＜９＞　上記＜８＞に記載の樹脂を含む光学材料である。
＜１０＞　上記＜８＞に記載の樹脂を含む色調変化材料である。 <1> A polymerizable composition containing a compound (a) represented by the following formula (1):

(In formula (1), X ₁ to X ₃ are the same or different and represent a structure represented by formula (2) below or a phenyl group, and at least one of X ₁ to X ₃ represents a structure represented by formula (2). When a bismuth atom in formula (1) is bonded to a structure represented by formula (2), it is bonded to an oxygen atom in formula (2). The oxygen atom in formula (2) is bonded to the same bismuth atom to form a cyclic structure, or is bonded to another bismuth atom to form a chain structure.)

(In formula (2), Z represents a hydrocarbon group).
<2> The polymerizable composition according to <1> above, wherein the structure represented by formula (2) represents a structure represented by formula (3):

(In formula (3), n represents an integer of 0 to 10. R ₁ represents a hydrogen atom or a hydrocarbon group.)
<3> The polymerizable composition according to <1> or <2> above, wherein R ₁ in formula (3) represents a substituent represented by the following formula (4):

(In formula (4), m represents an integer of 0 to 3. _R2 represents a hydrocarbon group having 1 to 10 carbon atoms.)
<4> The polymerizable composition according to any one of <1> to <3> above, further comprising (b) 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.
<5> The polymerizable composition according to any one of <1> to <4> above, further comprising (c) a compound having two or more thiol groups in one molecule.
<6> The polymerizable composition according to the above item <2>, wherein the structure represented by formula (3) is at least one of structures represented by the following formula (5) or formula (6):

(In formula (5), _R2 represents a hydrocarbon group having 1 to 10 carbon atoms.)

<7> The compound (b) 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( ... The polymerizable composition according to <4> 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.
<8> A resin obtained by polymerizing and curing the polymerizable composition according to any one of <1> to <7> above.
<9> An optical material containing the resin according to <8> above.
<10> A color tone changing material containing the resin according to <8> above.

The present invention provides a polymerizable composition that is solvent-soluble and thermoplastic, can be easily processed, and can be cured by heat or light, providing a transparent resin or optical material with radiation shielding capabilities.

Fig. 1 is a diagram showing the measurement results of the ¹ H-NMR (400 MHz, CDCl ₃ ) spectrum of the polycondensate obtained in Example 1. Note that the structure bonded to the bismuth element in Fig. 1 is a phenyl group or a carboxylic acid group represented by formula (2). Fig. 2 is a diagram showing the measurement results of the ^13C -NMR (100 MHz, _CDCl3 ) spectrum of the polycondensate obtained in Example 1. Note that the structure bonded to the bismuth element in Fig. 2 is a phenyl group or a carboxylic acid group represented by formula (2). FIG. 3 is a diagram showing the measurement results of the IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 1. Fig. 4 is a diagram showing the measurement results of the ¹ H-NMR (400 MHz, CDCl ₃ ) spectrum of the polycondensate obtained in Example 5. Note that the structure bonded to the bismuth element in Fig. 4 is a phenyl group or a carboxylic acid group represented by formula (2). FIG. 5 is a diagram showing the measurement results of the IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 5. FIG. 6 is a diagram showing the measurement results of the IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 6. FIG. 7 is a diagram showing the measurement results of the IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 7. Fig. 8 is a diagram showing the measurement results of the ¹ H-NMR (400 MHz, CDCl ₃ ) spectrum of the polycondensate obtained in Example 9. Note that the structure bonded to the bismuth element in Fig. 8 is a phenyl group or a carboxylic acid group represented by formula (2).

（式（１）中、Ｘ_１～Ｘ_３は同一または異なって、下記式（２）で表される構造またはフェニル基を表し、Ｘ_１～Ｘ_３の少なくとも１つは式（２）で表される構造を表す。式（１）のビスマス原子について、式（２）で表される構造と結合している場合は、式（２）の酸素原子と結合する。式（２）の酸素原子は同一のビスマス原子と結合して環状構造を形成するか、あるいは他のビスマス原子と結合して鎖状構造を形成する。）

（式（２）中、Ｚは炭化水素基を表す）。 Hereinafter, the present invention will be described in detail by way of examples and working examples. However, the present invention is not limited to the illustrated examples and working examples, and can be modified in any manner without departing from the scope of the present invention.
In one embodiment of the present invention, there is provided a polymerizable composition comprising a compound (a) represented by the following formula (1). The polymerizable composition of the present invention encompasses both an embodiment comprising only the compound (a) represented by the following formula (1) and an embodiment comprising the compound (a) represented by the following formula (1) and other components.

(In formula (1), X ₁ to X ₃ are the same or different and represent a structure represented by formula (2) below or a phenyl group, and at least one of X ₁ to X ₃ represents a structure represented by formula (2). When a bismuth atom in formula (1) is bonded to a structure represented by formula (2), it is bonded to an oxygen atom in formula (2). The oxygen atom in formula (2) is bonded to the same bismuth atom to form a cyclic structure, or is bonded to another bismuth atom to form a chain structure.)

(In formula (2), Z represents a hydrocarbon group).

Each component will be described below.
The 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 being odorless, unlike sulfur compounds.

（式（３）中、ｎは０～１０の整数を表す。Ｒ_１は水素原子または炭化水素基を表す。）
　さらに式（３）におけるＲ_１が、下記式（４）で表される置換基を表すことが好ましい。

（式（４）中、ｍは０～３の整数を表す。Ｒ_２は炭素数１～１０の炭化水素基を表す。） A preferred embodiment of the present invention preferably includes a structure represented by the following formula (3).

(In formula (3), n represents an integer of 0 to 10. R ₁ represents a hydrogen atom or a hydrocarbon group.)
Furthermore, R ₁ in formula (3) preferably represents a substituent represented by the following formula (4).

(In formula (4), m represents an integer of 0 to 3. _R2 represents a hydrocarbon group having 1 to 10 carbon atoms.)

（式（５）中、Ｒ_２は炭素数１～１０の炭化水素基を表す。）

In another preferred embodiment of the present invention, the structure represented by formula (3) is at least one of structures represented by the following formula (5) or formula (6).

(In formula (5), _R2 represents a hydrocarbon group having 1 to 10 carbon atoms.)

The compound (a) can be obtained by reacting a triphenylbismuthine compound with a precursor dicarboxylic acid compound as shown below.
The precursor dicarboxylic acid compound used in the present invention can be used without any particular limitation, but preferably used are 2-octenylsuccinic acid, itaconic acid, phenylsuccinic acid, suberic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, allylsuccinic acid, 4-cyclohexene-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, oxa-5-norbornene-2,3-dicarboxylic acid, and the like.

（式中、ｎは０又は１を表す。Ｒ_１は少なくともエン構造を有する置換基を表す。）

(In the formula, n represents 0 or 1. _R1 represents a substituent having at least an ene structure.)

The molar ratio of the triphenylbismuthine compound to the precursor dicarboxylic acid compound is preferably triphenylbismuthine compound/precursor dicarboxylic acid compound = 1/3 to 3/3. More preferably, triphenylbismuthine compound/precursor dicarboxylic acid compound = 1.5/3 to 2.5 to 3, and even more preferably, 1.8/3 to 2.2/3. The closer the ratio is to triphenylbismuthine compound/precursor dicarboxylic acid compound = 2/3, where the numbers of phenyl groups and carboxylic acid groups are the same, the fewer the unreacted phenyl groups and carboxylic acid groups will be, and the more stable the resin network structure will be, and the higher the heat resistance, etc., can be expected to be.

　Solvents that can be used during the reaction include aliphatic hydrocarbon compounds such as hexane, heptane, and octane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as diethyl ether, tetrahydrofuran, and methylcyclopentyl ether; ester compounds such as ethyl acetate and butyl acetate; and halogen compounds such as dichloromethane, chloroform, and dichloroethane. Among these, tetrahydrofuran and methyl ethyl ketone are preferred.

After the reaction, the reaction solution is mixed with a solvent in which the resin has low solubility to cause reprecipitation, and the solvent is separated by a common method such as filtration or centrifugation to obtain the target compound (a) represented by formula (1). Examples of the solvent for reprecipitation include aliphatic hydrocarbon compounds such as hexane, heptane, and octane, and alcohol compounds such as methanol, among which aliphatic hydrocarbon compounds such as hexane, heptane, and octane are preferred. The reprecipitation solvent may be mixed in advance during the reaction, and the solvent that dissolves compound (a) represented by formula (1) may be distilled off first after the reaction to cause reprecipitation.

The compound (a) represented by formula (1) can have multiple structures, not just a single one. For example, since the bismuth atom has three substitution sites, two of the substitution sites may form an intramolecular cyclic structure with the precursor dicarboxylic acid compound, and the remaining substitution site may bond to another bismuth atom via the precursor dicarboxylic acid compound. Therefore, the compound (a) can have structures as exemplified by the following formulas (7) to (10). However, the compound (a) represented by formula (1) is not limited to these.

The polymerizable composition containing the compound (a) may further contain (b) 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, and/or (c) a compound having two or more thiol groups in one molecule.

(b) 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 "(b) compounds") include all compounds that satisfy this condition.

Examples of the (b) 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, nonanediol di(meth)acrylate, Examples of the acrylates 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.
These may be used alone or in combination of two or more.

The ratio of compound (a) to compound (b) can be any ratio. It is possible to adjust the viscosity of the polymerizable composition to a range that is easy to handle, improve the uniformity of the solution, and produce a homogeneous cured product after curing. By mixing, it is also possible to adjust the mechanical strength of the cured resin and optical properties such as the refractive index. Compound (b) can also be used as a solvent.

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

Examples of the (c) 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-dimercaptoethane, 1,5-dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 1,5-dimercaptomethyl-2-mercaptoethane ... mercaptopropane, 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, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 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, 2,2-bis(4-mercaptomethylphenyl)propane, and the like can be mentioned, but are not limited thereto.
These may be used alone or in combination of two or more.

(c) Preferred compounds as the compound are 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 bis(2-mercaptoethyl)sulfide, pentaerythritol tetrakis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, and 1,3-bis(mercaptomethyl)benzene.

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 (number of SH groups in the (c) compound)/(number of double bonds in the (a) compound + number of double bonds in the (b) compound) of 10.0 or less, more preferably 5.0 or less, and most preferably 1.2 or less. If the above ratio exceeds 10.0, polymerization may not be sufficient, resulting in reduced heat resistance.

In another embodiment of the present invention, the polymerizable composition containing the compound (a) is provided as it is as a thermoplastic resin. Also, a resin obtained by polymerizing and curing the polymerizable composition containing the compound (a) is provided.

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

The reaction of polymerizing and curing 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 cure in the presence of a polymerization catalyst to promote the polymerization reaction. Therefore, in one embodiment of the present invention, there is provided 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. The resin and optical material thus obtained are preferably transparent. In one embodiment of the present invention, there is also provided a method for producing a cured product, preferably an optical material, characterized in that the polymerizable composition of the present invention is cured by irradiation with ultraviolet light or visible light in the presence of a polymerization catalyst.

In the case of photopolymerization reaction, a polymerizable composition containing the compound (a) of the present invention is cured by irradiation with light (active energy rays) to produce a resin as a cured product. The light is not particularly limited as long as it can cure the polymerizable composition, but typically includes ultraviolet light, visible light, radiation, electron beam, etc., preferably ultraviolet light or visible light, and more preferably ultraviolet light because of its fast polymerization rate.
The irradiation intensity of the light beam is not particularly limited, but is usually 10 to 100,000 mW/ ^cm2 . The irradiation time is not particularly limited, but is usually 1 minute to several hours, preferably 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 performed while heating to a temperature equal to or higher than the melting point.

There are no particular limitations on the polymerization catalyst, and it may be selected appropriately depending on the type of reactant, polymerization conditions, etc. In the case of photopolymerization, a compound that generates radicals when irradiated 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, acetophenone derivatives, etc. 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.

Alternatively, it is also preferable to use a compound (redox-type polymerization initiator) that generates radicals (free 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; peroxides such as hydrogen peroxide, t-butyl peroxide, and methyl ethyl ketone peroxide, and a reducing compound selected from L-ascorbic acid, sodium hydrogen sulfite, etc.

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

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 cured resin.

The polymerization catalyst used in the thermal polymerization reaction is preferably a compound that generates radicals when heated (thermolyzable 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).

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. A single type of polymerization catalyst may be used alone, or multiple types may be used in combination.

The amount of polymerization catalyst added varies depending on the components of the polymerizable composition containing the compound (a) of the present invention, the mixing ratio, and the polymerization and curing method, and cannot be determined in general, but is usually 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 composition may not be sufficiently cured, resulting in poor heat resistance. Therefore, in a preferred embodiment of the present invention, the method for producing a resin includes a step of adding 0.0001 to 10% by mass of a polymerization catalyst relative to the total amount of the polymerizable composition, and polymerizing and curing the composition.

The 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 process of holding the polymerizing temperature at a predetermined temperature for a predetermined time, a process of raising the temperature at a rate of 0.1°C to 100°C/h, and a process of lowering the temperature at a rate of 0.1°C to 100°C/h, or a combination of these processes. Note that the curing time refers to the polymerization and curing time including the temperature rise process, and includes the process of raising the temperature to the predetermined polymerization (curing) temperature and cooling it down in addition to the process of holding the polymerizing (curing) temperature at the predetermined polymerization (curing) temperature.

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 the polymerization catalyst, etc. are mixed. These may all be mixed simultaneously in the same container under stirring, each raw material may be added and mixed in stages, or several components may be mixed separately and then remixed in the same container. In addition, each raw material and auxiliary raw material may be mixed in any order. In mixing, the set temperature, the time required, etc. may basically be conditions that allow each component to be sufficiently mixed. The polymerizable composition obtained in this way is poured into a mold or other form, and the polymerization and curing reaction is advanced by heating or irradiation with light such as ultraviolet rays, and then the composition 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.

After curing is complete, it is preferable to anneal the resulting resin at a temperature of 50 to 150°C for about 10 minutes to 5 hours in order to remove distortion. If necessary, the resulting resin may also be subjected to surface treatments such as hard coating and anti-reflection.

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

The polymerizable composition containing the compound (a) of the present invention can provide a resin having at least one excellent property, such as a high refractive index, photopolymerization curability, or thermal polymerization curability, as described above. In this manner, the resin (cured product) obtained by curing the polymerizable composition is also one embodiment of the present invention.

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 CT (Computed Tomography) and PET (Positron Emission Tomography) devices are used for diagnosis and treatment, and in nuclear power plants. It can be used as a radiation shielding plate or shielding filter, and can also be used directly as an optical material (component). For example, by using it in a camera lens, it is possible to protect the camera sensor from damage caused by radiation, and it is also possible to transmit images with noise caused by radiation removed. These applications include optical materials (components), machine part materials, electrical and electronic part materials, automotive part materials, civil engineering and construction materials, molding materials, etc., as well as various other applications such as paint and adhesive materials. Among them, optical materials, for example, lenses such as eyeglass lenses, (digital) camera imaging lenses, light beam condensing lenses, and light diffusing 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, substrates for color filters, substrates for touch panels, display backlights, light guide plates, display protective films, anti-reflection films, anti-fogging films, and other coating agents (coating films); optical memories, recording media such as electronic paper, sensor materials such as UV checkers, light control materials such as window glass, sunglasses, and automotive window glass, textile products, cosmetic materials, photochromic materials, and other color tone changing materials such as print materials are particularly suitable. As the optical materials, optical adhesives, prisms, and coating agents are particularly suitable.

The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto. The obtained monomers and cured products were evaluated by the following methods.
NMR: Measurement was performed using an ECX-400 manufactured by JEOL Ltd.
IR: Measurement was performed using Jasco FT-IR460Plus manufactured by JASCO Corporation.

Example 1
Polycondensation of triphenylbismuthine (BiPh ₃ ) and 2-octenylsuccinic acid (cis, trans mixture) (Bi-OSA:1-1) (typical example)
Triphenylbismuthine (220 mg, 0.500 mmol) represented by the structural formula below and 2-octenylsuccinic acid (cis, trans mixture) (OSA) (114 mg, 0.500 mmol) represented by the structural formula below were added to a two-necked test tube, and dehydrated THF (1.00 mL) was added under a nitrogen atmosphere, and the reaction was carried out under reflux conditions for 24 hours. After completion of the reaction, the solution was subjected to precipitation purification with about 30 to 50 times the amount of hexane, and centrifuged to obtain a white solid with a yield of 84.2% (390 mg). An example of the structure of the white solid obtained in Example 1 is shown in the following formula (11).
The measurement result of the ¹ H-NMR (400 MHz, CDCl ₃ ) spectrum of the polycondensate obtained in Example 1 is shown in FIG.
The ¹³ C-NMR (100 MHz, CDCl ₃ ) spectrum of the polycondensate obtained in Example 1 is shown in FIG.
The IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 1 is shown in FIG.

(Examples 2 to 4)
Polymerization was carried out in the same manner as in Example 1, except that the compounding ratio of triphenylbismuthine and 2-octenylsuccinic acid and the solvent were changed as shown in the following Table 1. The obtained results are shown in the following Table 1.

Example 5
Polycondensation of triphenylbismuthine (BiPh ₃ ), 2-octenylsuccinic acid (cis, trans mixture), and itaconic acid [Bi(OSA-IA:9-1)] Triphenylbismuthine (220 mg, 0.500 mmol), 2-octenylsuccinic acid (cis, trans mixture) (103 mg, 0.450 mmol), and itaconic acid (6.50 mg, 0.0500 mmol) represented by the following structural formula were added to a two-necked test tube, and dehydrated THF (1.00 mL) was added under a nitrogen atmosphere, and the reaction was carried out under reflux conditions for 24 hours. After the reaction was completed, the solution was subjected to precipitation purification with about 30 to 50 times the amount of hexane, and the product was centrifuged to obtain a white solid with a yield of 78.0% (193 mg). An example of the structure of the white solid obtained in Example 5 is shown in the following formula (12).
The ¹ H-NMR (400 MHz, CDCl ₃ ) spectrum of the polycondensate obtained in Example 5 is shown in FIG.
The IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 5 is shown in FIG.

Example 6
Polycondensation of triphenylbismuthine (BiPh ₃ ), 2-octenylsuccinic acid (cis, trans mixture), and phenylsuccinic acid [Bi(OSA-PSA:5-5)] Triphenylbismuthine (220 mg, 0.500 mmol), 2-octenylsuccinic acid (cis, trans mixture) (57.1 mg, 0.250 mmol), and phenylsuccinic acid (48.5 mg, 0.250 mmol) represented by the following structural formula were added to a two-necked test tube, and dehydrated THF (1 mL) was added under a nitrogen atmosphere, and the reaction was carried out under reflux conditions for 24 hours. After completion of the reaction, isolation and purification were carried out, and a yield of 77.6% (230 mg) was obtained as a white solid. An example of the structure of the white solid obtained in Example 6 is shown in the following formula (13).
The IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 6 is shown in FIG.

(Example 7)
Polycondensation of triphenylbismuthine (BiPh ₃ ), 2-octenylsuccinic acid (cis, trans mixture), and methacrylic acid [Bi(OSA-MA:5-5)] Triphenylbismuthine (220 mg, 0.500 mmol), 2-octenylsuccinic acid (cis, trans mixture) (114 mg, 0.500 mmol), and methacrylic acid (43.0 mg, 0.500 mmol) were added to a two-necked test tube, and dehydrated THF (1.5 mL) was added under a nitrogen atmosphere, and the reaction was carried out under reflux conditions for 24 hours. After the reaction was completed, 251 mg of a white solid was obtained. An example of the structure of the white solid obtained in Example 7 is shown in the following formula (14).
The IR spectrum (KBr, cm ⁻¹ ) of the polycondensate obtained in Example 7 is shown in FIG.

(Example 8)
Polycondensation of triphenylbismuthine (BiPh ₃ ), 2-octenylsuccinic acid (cis, trans mixture), and methacrylic acid [Bi(OSA-MA:5-5)] Triphenylbismuthine (220 mg, 0.500 mmol), 2-octenylsuccinic acid (cis, trans mixture) (114 mg, 0.500 mmol), and methacrylic acid (43.0 mg, 0.500 mmol) were added to a two-necked test tube, and dehydrated THF (1.5 mL) was added under a nitrogen atmosphere, and the reaction was carried out under reflux conditions for 24 hours. After the reaction was completed, 251 mg of a white solid was obtained.

(Example 9)
Polycondensation of BiPh ₃ , 2-octenylsuccinic acid (cis, trans mixture), and suberic acid [Bi(OSA-SA:7-3)] Triphenylbismuthine (220 mg, 0.500 mmol), 2-octenylsuccinic acid (cis, trans mixture) (79.9 mg, 0.350 mmol), and suberic acid (26.1 mg, 0.15 mmol) represented by the following structural formula were added to a two-necked test tube, and dehydrated THF (1 mL) was added under a nitrogen atmosphere, and the reaction was carried out under reflux conditions for 24 hours. After the reaction was completed, the solution was subjected to precipitation purification with about 30 to 50 times the amount of hexane, and the solution was centrifuged to obtain a white solid with a yield of 72.4% (144 mg). An example of the structure of the white solid obtained in Example 9 is shown in the following formula (15).
The ¹ H-NMR (400 MHz, CDCl ₃ ) spectrum of the polycondensate obtained in Example 9 is shown in FIG.

(Example 10)
The Bi -OSA :1-1 (250 mg) obtained in Example 1 was sandwiched between two polyimide films and pressed for 1 minute at 150° C. under a pressure of 15 kN in an Imoto Seisakusho press (IMC-1A45). After this, it was gradually cooled to room temperature to obtain a film with a transmittance of 50%.

The X-ray shielding property of the bismuth-containing film was evaluated using a small angle X-ray scattering device (SAXS: NANO-Viewer manufactured by Rigaku Corporation) as an X-ray source (detector). The evaluation of the X-ray transmittance was calculated using the following formula.
X-ray source: CuKα 1.54 angstroms (8.048 keV)
Tube voltage (accelerating voltage): 40 kV
X-ray transmittance (Tr) = Σ transmitted light intensity of sample [counts] / Σ direct intensity (transmitted light intensity without sample) [counts]
The X-ray transmittance of the Bi-OSA:1-1 film obtained above was 0.012% at a thickness of 449 μm (0.0449 cm) and 0.001% or less at a thickness of 947 μm (0.0947 cm). The results are shown in Table 2.

(Comparative Example 1)
X-ray shielding property of Poly(BiMA-co-DMAA) film (BiMA content 40 wt%) Poly(BiMA-co-DMAA) with the maximum BiMA content of 40 wt%, as described in JP-A 2022-128911, was produced. The X-ray shielding property of a 450 μm thick Poly(BiMA-co-DMAA) film measured under the same conditions was 5%. This result was inferior to that of Example 10.

Claims (10)

A polymerizable composition comprising a compound (a) represented by the following formula (1):

(In formula (1), X ₁ to X ₃ are the same or different and represent a structure represented by formula (2) below or a phenyl group, and at least one of X ₁ to X ₃ represents a structure represented by formula (2). When a bismuth atom in formula (1) is bonded to a structure represented by formula (2), it is bonded to an oxygen atom in formula (2). The oxygen atom in formula (2) is bonded to the same bismuth atom to form a cyclic structure, or is bonded to another bismuth atom to form a chain structure.)

(In formula (2), Z represents a hydrocarbon group). The polymerizable composition according to claim 1 , wherein the structure represented by formula (2) represents a structure represented by the following formula (3):

(In formula (3), n represents an integer of 0 to 10. R ₁ represents a hydrogen atom or a hydrocarbon group.) The polymerizable composition according to claim 1 or 2, wherein R ₁ in formula (3) represents a substituent represented by the following formula (4):

(In formula (4), m represents an integer of 0 to 3. _R2 represents a hydrocarbon group having 1 to 10 carbon atoms.) The polymerizable composition according to any one of claims 1 to 3, further comprising (b) 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. The polymerizable composition according to any one of claims 1 to 4, further comprising (c) a compound having two or more thiol groups in one molecule. The polymerizable composition according to claim 2 , wherein the structure represented by formula (3) is at least one of structures represented by the following formula (5) or formula (6):

(In formula (5), _R2 represents a hydrocarbon group having 1 to 10 carbon atoms.)

The compound (b) 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 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 4, which is one or more compounds selected from the group consisting of nonanediol 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. A resin obtained by polymerizing and curing the polymerizable composition according to any one of claims 1 to 7. An optical material comprising the resin according to claim 8. A color-changing material comprising the resin according to claim 8.

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