WO2019177084A1 - ビスマス化合物、硬化性組成物、および硬化体 - Google Patents

ビスマス化合物、硬化性組成物、および硬化体 Download PDF

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WO2019177084A1
WO2019177084A1 PCT/JP2019/010471 JP2019010471W WO2019177084A1 WO 2019177084 A1 WO2019177084 A1 WO 2019177084A1 JP 2019010471 W JP2019010471 W JP 2019010471W WO 2019177084 A1 WO2019177084 A1 WO 2019177084A1
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Prior art keywords
bismuth
meth
compound
acrylate
phosphate ester
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PCT/JP2019/010471
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English (en)
French (fr)
Japanese (ja)
Inventor
川崎　剛美
百田　潤二
智宏 河村
真由美 岸
道人 中谷
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Tokuyama Corp
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Tokuyama Corp
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Priority to SG11202008887YA priority Critical patent/SG11202008887YA/en
Priority to EP19768656.1A priority patent/EP3766892A4/en
Priority to JP2020506636A priority patent/JP7271504B2/ja
Priority to CA3093895A priority patent/CA3093895A1/en
Priority to CN201980019616.4A priority patent/CN111886239B/zh
Priority to RU2020133808A priority patent/RU2791556C2/ru
Priority to US16/980,466 priority patent/US11186600B2/en
Priority to KR1020207026260A priority patent/KR102679412B1/ko
Priority to MX2020009557A priority patent/MX2020009557A/es
Publication of WO2019177084A1 publication Critical patent/WO2019177084A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C07F9/092—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl substituted by B, Si or a metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/90—Antimony compounds
    • C07F9/92—Aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids

Definitions

  • the present invention relates to a novel bismuth compound, a novel curable composition containing the bismuth compound, and a novel cured product obtained by curing the curable composition.
  • Bismuth has high X-ray blocking performance compared to compounds containing barium, antimony, tin and the like, and is an atom suitable for lead replacement.
  • a material using bismuth a method in which bismuth or a bismuth compound is directly kneaded with a resin material is known (see Patent Document 1). According to this method, bismuth or a bismuth compound can be blended with various materials.
  • this method is based on direct kneading, there is room for improvement in that bismuth cannot be sufficiently dispersed in the material unless highly kneaded.
  • Patent Document 2 a compound in which an organic group is coordinated to bismuth is known (see Patent Document 2, Non-Patent Document 1, and Non-Patent Document 2).
  • the familiarity with the organic material is improved, and it is possible to easily disperse in the material as compared with the method of kneading directly with the resin.
  • the organic group is an alkyl group, an aryl group (see Patent Document 2), or a polyethylene glycol chain (see Non-Patent Documents 1 and 2).
  • a material in which bismuth is dispersed in an organic material for example, a polymerizable radical polymerizable monomer and a bismuth compound are mixed to obtain a curable composition, and the curing is performed. It is preferable to employ a method of polymerizing the conductive composition into a cured product.
  • the compound in which an organic group is coordinated to bismuth obtained by the above method does not have a polymerizable group capable of participating in the polymerization of a radical polymerizable monomer, when these compounds are used, In some cases, the curable composition was not sufficiently polymerized and a cured product could not be obtained.
  • Non-Patent Document 3 dimethyl sulfoxide (DMSO) is coordinated in addition to (meth) acrylic acid, and it is known that the solubility is improved.
  • DMSO dimethyl sulfoxide
  • Non-Patent Document 3 only shows copolymerization with methyl methacrylate in dimethylformamide (DMF), and is polymerized in a solution. It was difficult to contain bismuth in a high concentration.
  • DMF dimethylformamide
  • the compound described in Patent Document 3 salicylic acid is bonded in addition to (meth) acrylic acid, and according to the study by the present inventors, the compound has solubility in other monomers such as a crosslinking agent. It was not sufficient, and as a result, it was found that it was difficult to contain bismuth in the cured product at a high concentration.
  • an object of the present invention is to provide a novel bismuth compound having high solubility in organic substances, particularly radical polymerizable monomers.
  • Another object of the present invention is to provide a bismuth component in a cured product obtained from a curable composition that can be copolymerized with the radical polymerizable monomer and is combined with the radical polymerizable monomer.
  • It is an object of the present invention to provide a novel bismuth compound that can be dispersed in a cured product and can reduce coloring of a cured product.
  • Still another object of the present invention is to provide a method for producing the bismuth compound. Still other objects and advantages of the present invention will become apparent from the following description.
  • the present invention (1) A bismuth compound in which a phosphate ester having a (meth) acryl group is bonded to bismuth.
  • the present invention can take the following aspects.
  • the phosphoric acid ester having a (meth) acryl group is derived from 2-((meth) acryloyloxy) ethyl dihydrogen phosphate and bis [2-((meth) acryloxyoxy) ethyl hydrogen phosphate].
  • the bismuth compound of (1) or (2) which is at least one selected.
  • a curable composition comprising the bismuth compound according to any one of (1) to (3) and another radical polymerizable monomer different from the bismuth compound.
  • the method for producing a bismuth compound according to (1) characterized in that bismuth (meth) acrylate or bismuth subsalicylate is reacted with a phosphate ester having a (meth) acryl group to dehydrate.
  • (8) When producing the bismuth compound The method according to (7) above, wherein a phosphoric acid ester having 0.3 to 10 mol of (meth) acrylic acid is used per 1 mol of bismuth (meth) acrylate or bismuth subsalicylate.
  • the present invention provides a bismuth compound that is easily dissolved in an organic substance and that is particularly highly soluble in a radical polymerizable monomer. Furthermore, the bismuth compound of the present invention can be radically polymerized, and a cured product in which a bismuth component is highly dispersed in a cured product obtained by copolymerizing with a radical polymerizable monomer different from the bismuth compound. Can be obtained. Moreover, coloring of the cured body can be reduced. As a result, by using the bismuth compound of the present invention, it is possible to produce a cured product that is safe, excellent in blocking effect such as X-rays, little colored, and high in transmittance. Therefore, the obtained cured body can be suitably used for eyeglass lenses for medical use.
  • FIG. 1 is a photograph of the bismuth portion observed with a field emission transmission electron microscope (STEM) of the bismuth compound produced in Example 1.
  • FIG. FIG. 2 is a photograph of the bismuth portion observed with a field emission transmission electron combined mirror (STEM) of the bismuth compound produced in Production Example 2.
  • the present invention relates to a bismuth compound in which a phosphate ester having a (meth) acryl group is bonded to bismuth.
  • (meth) acryl refers to methacryl and / or acryl.
  • the bismuth compound exhibits an excellent effect because it is a phosphate ester having a (meth) acryl group that is bonded to bismuth.
  • a phosphoric acid ester having a (meth) acryl group is bonded to bismuth.
  • the production is preferably performed by a method in which a bismuth (meth) acrylate or bismuth subsalicylate is bonded to a phosphate ester having a (meth) acryl group to obtain the bismuth compound of the present invention.
  • a bismuth (meth) acrylate or bismuth subsalicylate known ones can be used.
  • bismuth (meth) acrylate or bismuth subsalicylate will be described.
  • bismuth (meth) acrylate includes a compound in which (meth) acrylic acid is bonded to bismuth.
  • the bismuth (meth) acrylate includes a compound in which bismuth oxide forms a composite with (meth) acrylic acid (hereinafter simply referred to as “ (Also referred to as “a compound derived from bismuth (meth) acrylate”).
  • compound derived from bismuth (meth) acrylate is not clear, the hydroxyl group formed on the surface of bismuth oxide and (meth) acrylic acid are condensed. It is considered that the compound is bound.
  • the inclusion of a compound derived from (meth) acrylic acid bismuth oxide can be estimated by its production conditions (raw material balance) or, for example, infrared spectroscopic analysis (IR) and elemental analysis of the product.
  • IR infrared spectroscopic analysis
  • the compound derived from bismuth (meth) acrylate is very difficult to separate from bismuth (meth) acrylate, the effect of the present invention is not greatly impaired by the mixture.
  • the bismuth (meth) acrylate of the present invention is represented by the following formula (1).
  • R is a hydrogen atom or a methyl group.
  • the bismuth (meth) acrylate is a compound in which (meth) acrylic acid is bonded to bismuth (Bi 3+ ), and the bismuth component can be confirmed by a field emission transmission electron microscope (STEM). That is, the dispersion state of bismuth in the bismuth (meth) acrylate can be observed with a field emission transmission electron microscope. Observation conditions with a field emission transmission electron microscope are as shown in the following examples. When measured under the following conditions, the bismuth component is observed in white.
  • the bismuth (meth) acrylate is aggregated due to its high associative property or low solubility in a solvent. Therefore, when the bismuth component is observed with STEM, it is observed as aggregated particles.
  • the aggregated particles preferably have a longest diameter (hereinafter sometimes simply referred to as “long diameter”) in the range of 0.1 to 30 nm, preferably in the range of 0.1 to 20 nm. Is more preferable, and a range of 0.5 to 10 nm is further preferable.
  • the bismuth (meth) acrylate represented by the formula (1) preferably has a major axis (size) of aggregated particles observed by STEM in the range of 0.1 to 30 nm.
  • the major axis is in the range of 0.1 to 30 nm, even in the bismuth compound described later, the aggregated particles satisfy the same major axis range, and at the same time, the solubility and dispersion in the radical polymerizable monomer, etc. It is thought that the nature becomes high.
  • the conventional bismuth compound into which an organic group is introduced becomes an aggregated particle having a major axis exceeding 30 nm.
  • bismuth subsalicylate includes a compound in which salicylic acid is bonded to bismuth.
  • the bismuth component can be confirmed by the same method as the above-described bismuth (meth) acrylate.
  • the bismuth subsalicylate of the present invention is represented by the following formula (2).
  • the production method of the bismuth (meth) acrylate or bismuth subsalicylate is not particularly limited, and can be produced by a known method. Commercially available bismuth (meth) acrylate or bismuth subsalicylate can also be used. Below, an example of a manufacturing method is shown for bismuth (meth) acrylate as an example.
  • Bismuth (meth) acrylate is produced by mixing bismuth nitrate and (meth) acrylic acid in the presence of an acid, and then neutralizing with a base. At this time, an excess of (meth) acrylic acid, for example, 5 to 10 mol of (meth) acrylic acid is used with respect to 1 mol of bismuth nitrate. In the following, description will be given in order.
  • ⁇ Acid> In producing the bismuth (meth) acrylate of the present invention, preferred examples of the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. Of these, nitric acid is preferably used to reduce impurities. These acids can be present in the reaction system in the form of an aqueous solution. Therefore, in the manufacturing method of bismuth (meth) acrylate, it is preferable that water is included as a solvent. When used in the form of an aqueous solution, a commercially available acid of 0.01 to 16N can be used. The amount of acid used is preferably 0.1 to 1 mol per mol of bismuth nitrate (for example, in the case of nitric acid, 0.1 to 1 mol of HNO 3 ).
  • (meth) acrylic acid used for producing the bismuth (meth) acrylate can be used. And in this invention, when manufacturing the said (meth) acrylic-acid bismuth, it is preferable that the usage-amount of (meth) acrylic acid shall be 5 mol or more and 10 mol or less per mol of bismuth nitrate.
  • the bismuth (meth) acrylate having a bismuth component having a major axis of 0.1 to 30 nm can be easily produced. Further, it can be obtained as bismuth (meth) acrylate with little coloring.
  • the amount of (meth) acrylic acid used is 3 to 20 mol per mol of bismuth nitrate. More preferred is 5 to 10 mol.
  • the base is used to neutralize the (meth) acrylic acid as a raw material and the acid, and known bases can be used.
  • specific examples include inorganic bases such as alkali hydroxides and organic amines such as amine compounds.
  • inorganic bases such as alkali hydroxides
  • organic amines such as amine compounds.
  • the base is used to neutralize an excessively present acid component after reacting bismuth nitrate with (meth) acrylic acid in the presence of an acid.
  • the amount used is an excessive amount of (meth) acrylic acid (when 3 mol of (meth) acrylic acid is used per 1 mol of bismuth nitrate), and approximately the same mole as the total number of moles of the acid.
  • a number is preferred. For example, when 0.5 mol of acid and 5 mol of (meth) acrylic acid are used per 1 mol of bismuth nitrate, it is preferable to use approximately 5.5 mol of base.
  • ⁇ Reaction conditions> In the method for producing bismuth (meth) acrylate, production conditions other than the above will be described.
  • a method of stirring and mixing acid, bismuth nitrate and (meth) acrylic acid in the reaction system can be employed.
  • the solvent include water, methanol, ethanol, acetone, and THF. Among these, it is preferable to use water.
  • the amount of the solvent used is preferably such that each component can be sufficiently mixed.
  • the solvent is preferably 3 to 50 ml, more preferably 5 to 20 ml, more preferably 7.5 to 15 ml per gram of bismuth nitrate. Is more preferable.
  • each component into the reaction system for example, an acid diluted with the solvent as necessary, bismuth nitrate diluted with the solvent as necessary, (meth) acrylic diluted with the solvent as necessary
  • acids are added together in the reaction system and stirred and mixed.
  • a solvent is introduced into the reaction system in advance, and an acid diluted with the solvent as necessary, bismuth nitrate diluted with the solvent as necessary, and diluted with the solvent as needed (meta )
  • a method of adding acrylic acid together and stirring and mixing may be employed.
  • two components are introduced into the reaction system in advance and the other one component is introduced into the reaction system, or one component is introduced into the reaction system in advance and the other two components are combined together.
  • bismuth nitrate added with water and nitric acid (if necessary, diluted dilute nitric acid is used). It is preferable to employ a method in which a polymerization inhibitor such as dibutylhydroxytoluene (BHT), hydroquinone, 4-tert-butylpyrocatechol is added to the obtained mixed solution, and finally (meth) acrylic acid is mixed.
  • BHT dibutylhydroxytoluene
  • 4-tert-butylpyrocatechol is added to the obtained mixed solution
  • (meth) acrylic acid is mixed.
  • bismuth nitrate may be precipitated as a solid, but the reaction proceeds smoothly by carrying out the reaction at a composition ratio that dissolves uniformly at a temperature of about 60 ° C. ,desirable.
  • reaction temperature The temperature (reaction temperature) at which each component is stirred is preferably 30 to 80 ° C., for example, and more preferably 50 to 70 ° C. Moreover, reaction time may be normally 20 minutes or more and 1 hour or less, for example.
  • the atmosphere during the reaction may be any atmosphere under atmospheric pressure, reduced pressure, or increased pressure. In consideration of operability, stirring and mixing (reaction) of each component is performed under atmospheric pressure. It is preferable. Moreover, it may be any of an air atmosphere, an inert gas atmosphere, and a dry air atmosphere. In consideration of operability, it is preferably carried out in an air atmosphere.
  • the reaction system By performing the reaction under the above conditions, the reaction system once becomes a uniform state (solution is transparent). Next, when the reaction is continued by stirring, the inside of the reaction system starts to be suspended. Before the suspension becomes high, the desired amount of the base is added to the reaction system to neutralize it. At this time, if the temperature rises due to the heat of neutralization and exceeds the boiling point of the solvent, the precipitate generated by neutralization foams. Therefore, it is desirable to carry out neutralization at a rate at which the temperature rise during neutralization does not exceed the boiling point.
  • the treatment after adding the base the following method is preferably employed. First, in the obtained reaction solution, there may be a case where a yellow colored component, which is considered to be a partially colored yellow bismuth oxide component, is once confirmed.
  • reaction solution When this yellow colored component is present, it is preferable to continue to heat and stir the reaction solution, whereby the component is redispersed and the reaction solution becomes colorless. This state is desirably the end point of the reaction. On the other hand, when the obtained reaction solution is colorless, the reaction solution may be in an end point.
  • the bismuth compound of the present invention includes a compound in which a phosphate ester having a (meth) acrylic group (hereinafter sometimes referred to simply as “phosphate ester”) is bonded to bismuth.
  • phosphate ester a phosphate ester having a (meth) acrylic group
  • solubility, particularly solubility in a solution-like radical polymerizable monomer is improved.
  • a cured product obtained by curing the curable composition containing the compound and the radical polymerizable monomer has excellent physical properties and can contain a high concentration of bismuth component.
  • This bismuth compound can improve the solubility in the radical polymerizable monomer as compared with the bismuth (meth) acrylate or bismuth subsalicylate.
  • bonding form of bismuth and the phosphate ester which has a (meth) acryl group is not specifically limited, Any of an ionic bond and a coordinate bond may be sufficient.
  • the bismuth compound is a compound in which bismuth oxide forms a complex with the phosphate ester and, if necessary, (meth) acrylic acid or salicylic acid.
  • compound derived from bismuth oxide a compound derived from bismuth oxide
  • the structure of the compound forming this composite is not clear, a hydroxyl group formed on the surface of bismuth oxide, a phosphate ester, and (meth) acrylic acid or It is considered that the carboxyl group of salicylic acid is condensed and bound. This bismuth oxide-derived compound is very difficult to separate from the bismuth compound.
  • a compound derived from bismuth oxide when by-produced, it is preferably used in a state containing a compound derived from bismuth oxide.
  • the bismuth oxide-derived compound is produced as a by-product, it is desirable to adjust the production conditions and the like so that the amount does not deteriorate the solubility of bismuth (meth) acrylate or bismuth subsalicylate.
  • the inclusion of a compound derived from bismuth oxide can be comprehensively determined by the production conditions or methods such as IR, NMR, and X-ray photoelectron spectroscopy (XPS).
  • a phosphate ester bonded or forming a composite is a phosphate ester having one (meth) acryl group (phosphate mono (di) ester), for example, One formed from 2- (methacryloyloxy) ethyl dihydrogen phosphate, phenyl-2- (methacryloyloxy) ethyl hydrogen phosphate, or a phosphate ester having two (meth) acryl groups (phosphate diester), For example, it is preferably formed from bis [2- (methacryloxyoxy) ethyl] hydrogen phosphate.
  • the phosphate ester may be formed only from any one of a phosphate ester having one (meth) acryl group and a phosphate ester having two (meth) acryl groups. It may be formed from both in proportion. In particular, in order to obtain a bismuth compound with little coloration or the like, only a phosphate ester (phosphate monoester) having one (meth) acryl group may be bonded.
  • the phosphate ester is formed from one having one (meth) acrylic group and one having two (meth) acrylic groups, the solubility in the radical polymerizable monomer is improved, And in order to suppress aggregation of a bismuth component, it is preferable to set it as the following ratios. Specifically, 1 mol of a phosphate ester derived from one having a (meth) acrylic group and 0.05 to 3 mol of a phosphate ester derived from one having two (meth) acrylic groups Preferably, it consists of 0.1 to 2 mol, more preferably 0.15 to 1 mol.
  • the advantage of including both one having (meth) acrylic groups and two having (meth) acrylic groups is that bismuth has one (meth) acrylic group (a divalent phosphate group). And those having two (meth) acrylic groups (those having a monovalent phosphate group) are bonded to each other, and the bonded preferable site is a (meth) acrylic group. This is considered to be due to the presence of a phosphate ester derived from one having two (meth) acrylic groups in an amount of 0.05 to 3 mol with respect to 1 mol of the phosphate ester derived from one having one of the above. .
  • the presence of two (meth) acrylic groups in the above ratio tends to decrease the bismuth concentration, but on the other hand, the solubility in the radical polymerizable monomer is improved. As a result, there is an advantage that the bismuth component can be present in the cured body at a high concentration in a balanced manner.
  • the bismuth compound may be bonded with other compounds as long as the phosphate ester is bonded.
  • salicylic acid or (meth) acrylic acid may be further bonded.
  • the ratio of the phosphate ester to the salicylic acid or (meth) acrylic acid is preferably 0.1 to 10 moles of salicylic acid or (meth) acrylic acid per mole of the phosphate ester, The amount is more preferably 5 mol, further preferably 0.1 to 1 mol, and particularly preferably 0.1 to 0.5 mol.
  • the above range is based on the total number of moles of phosphate esters.
  • the bismuth compound is a compound in which at least a phosphate ester having a (meth) acrylic group is bonded to bismuth, but its production method, IR, NMR (nuclear magnetic resonance spectroscopy), and energy dispersive X It can be confirmed that the phosphate ester having a (meth) acrylic group is bound by elemental analysis or the like using a line spectrometer (EDS). Moreover, the number of bonds of salicylic acid or (meth) acrylic acid and each phosphate ester can be determined by these methods.
  • Suitable bismuth compounds of the present invention include those represented by the following formulas (3) to (5).
  • each R is independently a hydrogen atom or a methyl group.
  • 2n + u + v + w 3 and u, v, w, and n are 2-((meth) acryloyloxy) ethyl (u) hydrogen phosphate residues, phenyl-2-(( The number of moles of (meth) acryloyloxy) ethyl (v) residue, bis [2-((meth) acryloxyoxy) ethyl] (w) residue, and salicylic acid (n) residue is shown.
  • the bismuth compounds of the formulas (3) to (5) may be a mixture of a plurality of compounds instead of a single compound.
  • the number of moles of each residue represents the number of moles of the entire mixture.
  • x: y: z 1: 0.05 to 3: 0.5
  • n 0, it is the same as that obtained by replacing x with u, y with v, and z with w in the above definition.
  • the bismuth compound of the present invention forms a particulate aggregate due to its high cohesiveness or low solubility.
  • the major axis of the aggregated particles is preferably in the range of 0.1 to 30 nm when observed with a field emission transmission electron microscope.
  • the agglomerated particles have a major axis in the range of 0.1 to 30 nm, it is considered that the solubility in organic substances, particularly radical polymerizable monomers, is increased, and the dispersibility in the obtained cured product is increased.
  • the long diameter of the aggregated particles exceeds 30 nm, the solubility is lowered, and the dispersibility in the obtained cured product tends to be lowered.
  • the agglomerated particles have a major axis of less than 0.1 nm, it is difficult to produce or becomes close to a complex in which three (meth) acrylic acids are bonded to bismuth, and the concentration of bismuth decreases and solubility in organic matter is reduced. Decreases and the dispersion state in the obtained cured product tends to deteriorate.
  • the major axis is preferably 0.5 to 20 nm in view of the productivity of itself, the solubility in organic substances, and the dispersibility in the obtained cured product, and preferably 0.5 to More preferably, it is 10 nm.
  • the bismuth compound a particulate aggregate is formed.
  • Phosphate ester, and if necessary, a compound in which salicylic acid or (meth) acrylic acid is bonded to bismuth, and optionally bismuth oxide contained therein are phosphoric ester, and if necessary, salicylic acid or (meta )
  • the bismuth component in the compound (compound derived from bismuth oxide) that forms a composite with acrylic acid can be confirmed by a field emission transmission electron microscope (STEM).
  • STEM field emission transmission electron microscope
  • the major axis of the observed bismuth component agglomerated particles is preferably in the range of 0.1 to 30 nm. Next, the suitable manufacturing method of this bismuth compound is demonstrated.
  • the bismuth compound is preferably produced by reacting the bismuth (meth) acrylate or bismuth subsalicylate with a phosphate ester having a (meth) acryl group. Specifically, in an aliphatic hydrocarbon solvent or an aromatic solvent, a polymerization inhibitor is added as necessary, and the bismuth (meth) acrylate or bismuth subsalicylate and a phosphate ester having a methacryl group are added. It is preferable to produce the bismuth compound of the present invention by reacting and dehydrating.
  • the phosphate ester may be a phosphate ester having one (meth) acryl group, a phosphate ester having two (meth) acryl groups, and a mixture thereof.
  • Examples of the phosphate ester having one (meth) acryl group include 2- (methacryloyloxy) ethyl dihydrogen phosphate, phenyl-hydrogen phosphate- 2- (methacryloyloxy) ethyl is mentioned.
  • phosphate ester having two (meth) acryl groups examples include, for example, bis [2- (methacryloxyoxy) hydrogen phosphate. Ethyl].
  • bifunctional phosphate phosphate examples include, for example, bis [2- (methacryloxyoxy) hydrogen phosphate. Ethyl].
  • a mixture of these monofunctional phosphate esters and bifunctional phosphate esters may be used for the reaction. What is necessary is just to determine the usage-amount of phosphate ester so that the desired bismuth compound may be obtained.
  • the amount of phosphate ester used is preferably in the range of 0.3 to 10 with respect to 1 mol of bismuth (meth) acrylate or bismuth subsalicylate.
  • a phosphate ester having a (meth) acryl group diphenyl-2-methacryloyloxyethyl phosphate, phenylbis [2- (methacryloyloxy) is used to improve compatibility with other monomers.
  • a phosphate triester such as ethyl)] phosphate and tris [2- (methacryloyloxyethyl)] phosphate may be further added.
  • the compounding amount of the phosphoric acid triester is 0.1 to 20 mol per mol of the phosphoric acid ester having one (meth) acrylic group and / or the phosphoric acid ester having two (meth) acrylic groups. 0.2 to 5 mol is more preferable.
  • ⁇ Aliphatic hydrocarbon solvent or aromatic solvent> it is preferable that the bismuth (meth) acrylate or bismuth subsalicylate and the phosphate ester are mixed and reacted in an aliphatic hydrocarbon solvent or an aromatic solvent.
  • an aliphatic hydrocarbon solvent or an aromatic solvent having a high boiling point, specifically, a boiling point of 100 ° C. or higher.
  • An aliphatic hydrocarbon solvent or an aromatic solvent can also be used as a mixed solution.
  • Examples of the aliphatic hydrocarbon solvent or aromatic solvent include hexane, heptane, nonane, decane, undecane, dodecane, xylene, dimethoxybenzene, and isomers thereof, benzene, toluene, chlorobenzene, bromobenzene, anisole, or Examples include petroleum ether, petroleum benzine, and benzoin.
  • the amount of the aliphatic hydrocarbon solvent or aromatic solvent is not particularly limited as long as it is an amount that can sufficiently mix the bismuth (meth) acrylate or bismuth subsalicylate and the phosphate ester. .
  • an aliphatic hydrocarbon solvent or an aromatic solvent in a ratio of 10 to 100 ml per 1 g of bismuth (meth) acrylate or bismuth subsalicylate.
  • the method of introducing the bismuth (meth) acrylate or bismuth subsalicylate and the phosphate ester into the reaction system is not particularly limited.
  • the bismuth (meth) acrylate or bismuth subsalicylate diluted with the aliphatic hydrocarbon solvent or aromatic solvent as necessary, and the diluted with the aliphatic hydrocarbon solvent or aromatic solvent as necessary It is possible to employ a method in which phosphate esters are added together in the reaction system and stirred and mixed.
  • the (meth) acrylic acid diluted with the aliphatic hydrocarbon solvent or the aromatic solvent if necessary, by introducing an aliphatic hydrocarbon solvent or an aromatic solvent into the reaction system in advance.
  • a method of adding bismuth or bismuth subsalicylate and the phosphate ester diluted with the aliphatic hydrocarbon solvent or the aromatic solvent as necessary together and stirring and mixing can also be employed.
  • bismuth (meth) acrylate or bismuth subsalicylate is made uniform in an aliphatic hydrocarbon solvent or an aromatic solvent.
  • bismuth (meth) acrylate or bismuth subsalicylate may not dissolve, but in this case, an ultrasonic device or the like is used so that there is no lump of bismuth (meth) acrylate or bismuth subsalicylate. It is preferable to pulverize the lump. Thereafter, it is preferable to employ a method in which phosphoric acid ester is added to a cloudy solution in which bismuth (meth) acrylate or bismuth subsalicylate is dispersed and stirring and heating are started.
  • the temperature at the time of stirring each component may be the reflux temperature of the aliphatic hydrocarbon solvent or aromatic solvent, but in order to reduce coloring of the resulting bismuth compound, It is desirable to carry out at a temperature of 30 to 110 ° C., more preferably 40 to 100 ° C., further preferably 45 to 90 ° C.
  • the reaction temperature is 30 to 110 ° C.
  • This dehydration can be performed while mixing the bismuth (meth) acrylate or bismuth subsalicylate and the phosphate ester, or can be performed after mixing both. However, considering the efficiency of the reaction, it is preferable to dehydrate while mixing.
  • reaction time is not particularly limited, and may usually be 20 minutes or longer and 2 hours or shorter.
  • the atmosphere for performing the reaction may be any of an air atmosphere, an inert gas atmosphere, and a dry air atmosphere in consideration of operability. In consideration of operability, the reaction may be performed in an air atmosphere. preferable.
  • the obtained bismuth compound is preferably concentrated by distilling off the solvent, and if there is an insoluble turbid component, it is preferably separated by filtration or centrifugation. Further, the concentrated reaction solution obtained by this treatment is purified by reprecipitation by adding a solvent that is soluble in the reaction solvent used and does not dissolve the bismuth compound. When the high boiling point solvent remains, the above decantation operation is repeated to replace the solvent. Thereafter, the remaining solvent is distilled off, followed by vacuum drying, whereby the bismuth compound can be purified and taken out.
  • the obtained bismuth compound can be polymerized and cured by itself to produce a cured product. Especially, in order to make the obtained hardening body more useful, it is preferable to set it as the curable composition combined with the other radically polymerizable monomer.
  • the present invention also provides a curable composition comprising the bismuth compound and a radical polymerizable monomer other than the bismuth compound (sometimes simply referred to as “radical polymerizable monomer”).
  • an ordinary known monomer can be used as the radical polymerizable monomer.
  • various commercially available monofunctional or functional groups such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, vinyl pyridine, vinyl pyrrolidone, acrylonitrile, phenyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, etc.
  • a polyfunctional acrylic acid, methacrylic acid ester, or a vinyl compound can be mentioned.
  • a styrene compound can be used.
  • styrene compound examples include styrene, methylstyrene and its structural isomer, methylstyrene dimer, chlorostyrene, bromostyrene, divinylbenzene and the like.
  • the said radically polymerizable monomer may be used independently and may be used in mixture of multiple.
  • the blending ratio of the bismuth compound and the radical polymerizable monomer other than the bismuth compound is appropriately determined according to the use of the obtained cured product.
  • the bismuth compound it is possible to use 1 to 500 parts by mass of a radical polymerizable monomer per 100 parts by mass of the bismuth compound in consideration of X-ray blocking effect, dispersibility, coloring reduction effect and the like.
  • the amount is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass.
  • the curable composition of the present invention may contain a known compounding agent that is blended in the radical polymerizable curable composition. Specifically, a radical polymerization initiator, an antioxidant, a release agent for increasing the release property from the mold, a dye for adjusting the color tone of the cured product, a chain transfer agent for controlling the polymerization property, etc. Can be blended. These compounding agents can be blended within a range not impairing the effects of the present invention.
  • Each compounding agent is preferably compounded in an amount of 0 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, more preferably 0.02 parts per 100 parts by mass in total of the bismuth compound and the radical polymerizable monomer. It is more preferable to add up to 15 parts by mass.
  • These curable compositions can be produced by mixing the bismuth compound, the radical polymerizable monomer, and various compounding agents blended as necessary.
  • a well-known method is employable as a method of hardening
  • photopolymerization, thermal polymerization, or both polymerization methods can be employed.
  • a suitable polymerization method is determined by a radical polymerization initiator to be blended as necessary.
  • the curable composition of the present invention can be made into a cured product having high permeability and low coloring while containing a bismuth component having a high X-ray blocking ability.
  • the cured product obtained from the curable composition of the present invention has, for example, a thickness of 2 mm, a transmittance at a wavelength of 560 nm of 80% or more, an X-ray blocking ability equivalent to a lead foil equivalent to 0.02 mm or more, and a yellowness of 40 or less.
  • the bismuth component contained in the cured product can be 5 to 40% by mass when the total mass of the cured product is 100% by mass.
  • the cured product obtained by the present invention has a radiation blocking function despite being visible light transmissive, it can be used as a transparent radiation shielding material.
  • ⁇ Measurement of major axis of bismuth component of bismuth compound For observation of the bismuth compound (observation of the major axis of the bismuth component), a field emission transmission electron microscope (STEM) was used (Tecnai (registered trademark) F20, manufactured by FEI). Morphological observation and element mapping (bismuth component mapping) were performed in the HAADF-STEM mode at an acceleration voltage of 200 kV. The sample was dropped on a copper mesh covered with a collodion film, and the excess solution was sucked on a filter paper laid down, air-dried and then vacuum-dried, and subjected to a field emission transmission electron microscope.
  • STEM field emission transmission electron microscope
  • ⁇ Method of analyzing bismuth compound> For IR measurement, a Fourier transform infrared spectrophotometer was used (Perkin Elmer, Spectrum One). The measurement was performed by the ATR method of single reflection and four times of integration. For the TG-DTA measurement, a differential thermothermal gravimetric simultaneous measurement apparatus (manufactured by Rigaku, TG8120) was used. Scanning was performed from room temperature to 500 ° C. at a heating rate of 10 ° C./min under an air stream.
  • a microscopic Raman spectroscope manufactured by JASCO Corporation, NRS-7100 was used, and for the sample excitation, a 532 nm laser, an objective lens 100 times, a 600 line / mm grating, and apertures of ⁇ 25 ⁇ m and ⁇ 4000 ⁇ m were used, respectively. The time was measured at 20 seconds ⁇ 2.
  • a nuclear magnetic resonance apparatus manufactured by JEOL RESONANCE, JNM-ECA400II
  • Heavy acetone was used as a solvent, and measurement was performed at a sample concentration of 1 wt%.
  • An X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, ESCA5701ci / MC) was used for the XPS measurement.
  • As the X-ray source monochromated Al-K ⁇ (14 kV-330 W) was used.
  • the aperture diameter was ⁇ 800 ⁇ m, the photoelectron extraction angle was 45 °.
  • the sample was pulverized in an agate mortar, and the obtained powder was fixed to a substrate with carbon tape, introduced into a measurement chamber, and measured.
  • a curable composition containing the bismuth compound, a radical polymerizable monomer, and a thermal polymerization initiator blended as necessary was thermally polymerized to prepare a 2 mm thick cured body (plate).
  • the light transmittance of 560 nm of the obtained cured product was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-2550). Further, the yellowness of the cured product (plate) was measured using S & M COLOR COMPUTER SM-T manufactured by SUGA TEST INSTRUMENTS. Further, the X-ray blocking ability of the obtained cured product was measured by using the shielding rate of 59.5 eV ⁇ rays emitted from 241 Am as the thickness equivalent of the lead plate.
  • Production Example 1 (Production of bismuth methacrylate) 55.9 g (115 mmol) of bismuth nitrate pentahydrate was placed in a 1000 ml three-necked flask containing a stirring bar, and 500 ml of deionized water was added. To this was added 5.4 g of concentrated nitric acid (HNO 3 ; 71 mmol) and stirred gently. To this, 1.9 g of BHT and 75 ml (885 mmol) of methacrylic acid were added.
  • HNO 3 concentrated nitric acid
  • the flask was equipped with a thermometer, a Dimroth condenser, and a dropping funnel containing a solution of 37.4 g (935 mmol) of sodium hydroxide dissolved in 60 ml of deionized water.
  • the contents in the flask were placed in an oil bath.
  • the mixture was heated with stirring, and the temperature was raised from room temperature to 65 ° C. in 20 minutes.
  • BHT was slightly dissolved as a solid.
  • the aqueous sodium hydroxide solution in the dropping funnel was added at a time. A slightly yellowed precipitate was formed, and the reaction system became uneven.
  • the temperature in the flask was about 85 ° C.
  • the contents were stirred for 1 hour while heating the temperature in the flask to 95 ° C. The reaction was considered complete when the yellow color of the precipitate disappeared and became colorless.
  • Example 1 10.6 g of bismuth methacrylate obtained in Production Example 1 (22.8 mmol in terms of bismuth) and phosphoric acid ester (2-methacryloyloxyethyl acid phosphate; MR-200 manufactured by Daihachi Chemical Industry (phosphoric monoester and diester) 1000 ml eggplant-shaped flask of about 1: 1 mixture of 2-hydrogen 2-hydrogen phosphate (methacryloyloxy) ethyl 30.3 mmol, hydrogen phosphate bis [2- (methacryloxyoxy) ethyl] 29.1 mmol)) And 300 ml of toluene was added. This was ultrasonically dispersed with a bath-type sonicator.
  • the resulting cloudy solution was transferred to a 1000 ml four-necked flask equipped with a Dean-Stark trap, and the reaction was carried out with stirring in an oil bath at 120 ° C., and the produced water was removed from the system. The end point of reaction was defined as the point at which no water was produced. A homogeneous dispersion solution was obtained.
  • Production Example 2 In Production Example 1, the reaction was performed under the same conditions as Production Example 1 except that 30 ml of methacrylic acid was used. The obtained sample was dissolved in chloroform, and STEM observation was performed on the slightly dissolved solution (FIG. 2). In FIG. 2, it was confirmed that the plate-like bodies having a diameter of 50 nm or more were further aggregated. Since this compound was hardly dissolved in the monomer, the cured product was not evaluated.
  • Example 2 In Example 1, a 500 ml eggplant type flask was used as a reaction layer, which was connected to an evaporator and synthesized under the same conditions except that the reaction was performed at 50 ° C. under reduced pressure. The reaction was carried out while distilling off toluene under reduced pressure. When the remaining gel-like solution reached about 50 ml, 300 ml of toluene was added again and dispersed uniformly. A solution with higher transparency than the original solution was obtained. This was again heated to 50 ° C. and the solvent was distilled off under reduced pressure. After concentration, 400 ml of toluene was further added to obtain a uniformly dispersed solution. The same measurement as in Example 1 was performed to identify the compound.
  • Example 2 as a result of the measurement, methacrylic acid was hardly bonded, and 2.5 mol of phosphorus was contained per mol of bismuth by EDS analysis and 2.6 mol of XPS analysis. I understood. From 31 P-NMR analysis, only the phosphate monoester was observed as a clear peak. That is, a bismuth compound in which only a phosphoric acid monoester was bonded was produced.
  • Example 3 8.2 g of the bismuth compound obtained in Example 1 was dissolved in 6.2 g of a mixed monomer having a mass ratio of 1: 1 of styrene and benzyl methacrylate. To this, 0.03 g of azobisisobutyronitrile (AIBN) was further added and completely dissolved. This monomer solution was placed under reduced pressure by a vacuum pump to remove dissolved oxygen. This monomer solution was poured into a 2 mm thick glass mold and polymerized at a maximum temperature of 90 ° C. for 2 hours to obtain a cured product. The obtained cured product was measured for yellowness, 560 nm transmittance, and X-ray shielding ability according to the method described above. The results are shown in Table 1.
  • Example 4 A cured product was obtained in the same manner as in Example 3 except that 3.1 g of the bismuth compound obtained in Example 2 and 3.1 g of the mixed monomer used in Example 3 were used. The obtained cured product was measured for yellowness, 560 nm transmittance, and X-ray shielding ability according to the method described above. The results are shown in Table 1.
  • This solution was centrifuged at 20,000 ⁇ g for 30 minutes, and the supernatant was pressure filtered through a 0.2 ⁇ m membrane filter to obtain a light scattering light yellow solution.
  • the solution was concentrated to 50 ml with an evaporator, and 400 ml of hexane was added. A viscous white precipitate formed.
  • the mixture was dispersed with a bath sonicator and allowed to stand. The supernatant hexane was removed by decantation. This washing with hexane was repeated three times. To the obtained white viscous body, 2.54 g of BHT was added and dispersed in 100 ml of acetone.
  • the organic solvent was distilled off by an evaporator, and acetone was added and dissolved again so that the whole became 100 ml, whereby a strongly scattering light yellow solution was obtained.
  • This solution was centrifuged at 20,000 ⁇ g for 30 minutes, and the supernatant was pressure-filtered through a 0.2 ⁇ m membrane filter to obtain a light scattering light yellow solution.
  • the organic solvent was removed with an evaporator and dried in vacuum. 55.04 g of a bismuth compound which is a scattering light yellow viscous liquid was obtained.
  • Example 6 0.12 g of 2,2′-azobis (2,4-dimethylvaleronitrile (V-65)) was added to 16.28 g of the bismuth compound obtained in Example 5 and completely dissolved. The monomer solution was poured into a 2 mm thick glass mold and polymerized at a maximum temperature of 90 ° C. for 3 hours to obtain a cured product. According to the above method, yellowness, 560 nm transmittance, and X-ray shielding ability were measured, and the results are shown in Table 1. As a result of analyzing the obtained cured product, it was found from XPS measurement that 2.29 mol of phosphorus was contained with respect to 1 mol of bismuth.
  • Example 7 Next, 37.59 g of bismuth (III) salicylate (manufactured by Sigma-Aldrich, 103.81 mmol in terms of bismuth), 16.72 g of phosphate diester bis [(2-methacryloyloxyethyl)] phosphate (manufactured by Sigma-Aldrich, 51. 89 mmol), phosphoric acid triester diphenyl-2-methacryloyloxyethyl phosphate 18.81 g (manufactured by Daihachi Chemical Industry Co., Ltd.
  • Example 8 2.47 g of styrene was added to 15.04 g of the bismuth compound obtained in Example 7 and dissolved uniformly. Further, 0.12 g of 2,2′-azobis (2,4-dimethylvaleronitrile (V-65)) was added and completely dissolved. This monomer solution was placed under reduced pressure by a vacuum pump to remove dissolved oxygen. This monomer solution was poured into a glass mold having a thickness of 2 mm and polymerized at a maximum temperature of 90 ° C. for 3 hours to obtain a cured product, which had a yellowness of 560 nm according to the above method. The X-ray shielding ability was measured, and the results are shown in Table 1. As a result of analyzing the obtained cured product, it was found from XFR analysis that 0.54 mol of phosphorus was contained with respect to 1 mol of bismuth.
  • Comparative Example 1 A cured product was obtained in the same manner as in Example 3 except that 7.1 g of the bismuth oxide solubilized product obtained in Production Example 3 and 1.0 g of the mixed monomer used in Example 3 were used. The obtained cured product was measured for yellowness, 560 nm transmittance, and X-ray shielding ability according to the method described above. The results are shown in Table 1.
  • Table 1 summarizes the yellowness, 560 nm transmittance, and X-ray shielding ability of the plates obtained in Examples 3, 4, 6, 8 and Comparative Example 1.
  • Comparative Example 1 has a high X-ray blocking ability due to the amount of bismuth oxide, but is highly colored and hardly transmits light.
  • Examples 3, 4, 6, and 8 had shielding ability according to the amount of bismuth, had transparency that could be used as an optical material, and had acceptable yellowness.

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EP4183579A4 (en) * 2020-07-17 2024-09-11 Tokuyama Corporation Curable composition and cured body of same
WO2022014591A1 (ja) * 2020-07-17 2022-01-20 株式会社トクヤマ 硬化性組成物及びその硬化体
JPWO2022014591A1 (https=) * 2020-07-17 2022-01-20
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JP7676807B2 (ja) 2021-02-24 2025-05-15 三菱瓦斯化学株式会社 重合性組成物及びそれを重合硬化してなる樹脂
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KR20250143308A (ko) 2023-01-31 2025-10-01 가부시끼가이샤 도꾸야마 수지 조성물, 경화성 조성물, 경화체, 광학 물품, 러버 시트, 눈용 보호구 및 항균·항바이러스제
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WO2025089145A1 (ja) * 2023-10-26 2025-05-01 三菱瓦斯化学株式会社 重合性組成物及びそれを重合硬化してなる樹脂
WO2025134806A1 (ja) * 2023-12-20 2025-06-26 株式会社トクヤマ 硬化性組成物、硬化体、光学物品、レンズ、ラバーシート、眼用保護具、抗菌・抗ウイルス剤、及び樹脂組成物

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