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WO2003081295A1 - Materiau optique et composes d'adamantane soufres polymerisables - Google Patents

Materiau optique et composes d'adamantane soufres polymerisables Download PDF

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Publication number
WO2003081295A1
WO2003081295A1 PCT/JP2003/003588 JP0303588W WO03081295A1 WO 2003081295 A1 WO2003081295 A1 WO 2003081295A1 JP 0303588 W JP0303588 W JP 0303588W WO 03081295 A1 WO03081295 A1 WO 03081295A1
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Prior art keywords
group
compound
adamantane
sulfur
represented
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English (en)
Japanese (ja)
Inventor
Hiromasa Yamamoto
Junji Takenaka
Masakazu Sai
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Tokuyama Corp
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Tokuyama Corp
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Priority claimed from JP2002083229A external-priority patent/JP4204242B2/ja
Priority claimed from JP2002221788A external-priority patent/JP3981602B2/ja
Application filed by Tokuyama Corp filed Critical Tokuyama Corp
Publication of WO2003081295A1 publication Critical patent/WO2003081295A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to an optical material and a novel polymerizable sulfur-containing adamantane compound particularly suitable for producing the optical material.
  • Plastic materials are lighter and harder to break than glass materials, are easier to dye, and have better workability such as cutting and polishing.
  • the performance required for optical materials, especially for spectacle lenses, includes high refractive index and high Abbe number, high resistance to i ", high strength, and the like.
  • This resin has various characteristics such as excellent impact resistance, good dyeability and good workability.
  • the refractive index is as low as 1.5, when a lens with a high power is manufactured, the center thickness of the lens divided by the edge becomes large, causing chromatic aberration, birefringence, an increase in weight, and a decrease in aesthetics. Materials with a high rate are required.
  • JP-A-63_46213 discloses a lens comprising a polymer of a polymercapto compound and a xylidenediisocyanate compound.
  • JP-A-63-162671 and JP-A-63-188660 disclose a thio (meth) acrylate polymerizable monomer having a sulfide structure.
  • Japanese Patent Application Laid-Open No. 4-161141 discloses a polymer obtained by polymerizing and curing a thio (meth) acrylate polymerizable monomer having a dithiane ring.
  • the cured product obtained by polymerizing and curing these polymerizable monomers has an index of refraction of about 1.58 to 1.63, which is improved compared to conventional cured products, but further improvement is required. I have. Further, the heat resistance of these cured products is not sufficiently satisfactory, and since they contain sulfur atoms, the odor at the time of molding is severe.
  • JP-A-2-258819 discloses dithiomethacrylate of 4,4'-dimercaptodiphenyl sulfide.
  • the cured product obtained by polymerizing this compound has a very high refractive index of 1.68 and a small odor during molding.However, the Abbe number is extremely small and the weather resistance is extremely poor. is there.
  • Japanese Patent Application Laid-Open No. 8-12669 discloses an aromatic vinyl compound having a dithiane ring.
  • the rigid body obtained by polymerizing and curing this compound has a high refractive index of 1.66, but a low Abbe number of 31, and is desired to have an improved Abbe number.
  • a polymercapto compound having a high sulfur content it is necessary to use.
  • such a lens has a problem in that it emits an odor during machining such as cutting and polishing, that is, an odor derived from sulfur.
  • the lens is exposed to high temperatures, and some of the lens material may be thermally decomposed, producing a sulfur-specific odor and odor, and the working environment Mimicking the worse. For this reason, there is a strong demand for high refractive lenses that do not generate odor during processing.
  • adamantane derivatives have attracted attention in various fields because of their unique structures of being non-aromatic and rigid.
  • Japanese Patent Application Laid-Open No. 63-1000 377 discloses diaryl adamantane dicarboxylate
  • Japanese Patent Application Laid-Open No. 63-078444 discloses adamantyl di (meth) atalylate derivative.
  • these materials exhibit high heat resistance, but have a refractive index of about 1.53 to 1.55, which is insufficient for high value-added plastic lens applications, or weather resistance due to the inclusion of halogen atoms. It is not always satisfactory in terms of sex and so on.
  • the present invention has been made in view of the prior art as described above, and is an optical material having a high refractive index, a high Abbe number and excellent heat resistance, a low odor, and a novel optical material. It is an object of the present invention to provide a polymerizable compound. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above problems.
  • a polymer using a specific polymerizable compound having an adamantyl group as a monomer has a high refractive index, a high Abbe number, and heat resistance, and furthermore, the odor generated during processing is remarkably low.
  • the present invention has been found to have excellent characteristics such as low profile, and the present invention has been completed. That is, the optical material according to the present invention has (a) at least one adamantyl group
  • the resulting polymer can be used as an optical material having excellent physical properties such as high refractive index, high heat resistance, and low odor. it can.
  • the optical material according to the present invention comprises a polymerizable material containing (a) at least one adamantyl group, (b) at least one polymerizable functional group, and (c) at least one sulfur atom in one molecule. It is composed of a polymer containing a polymerization unit based on a sulfur-containing adamantane compound.
  • Examples of the polymerizable sulfur-containing adamantane compound include: (a) a compound having at least one adamantyl group, (b) at least one polymerizable functional group, and (c) at least one sulfur atom in one molecule. It can be used without any particular restrictions.
  • the polymerizable sulfur-containing adamantane compound has (a) at least one adamantyl group (a cyclic group derived from an adamantane ring; hereinafter, it may be referred to as an adamantane skeleton) in its molecule.
  • an adamantane skeleton a cyclic group derived from an adamantane ring; hereinafter, it may be referred to as an adamantane skeleton.
  • the polymerized unit based on such a compound is used as a constituent element of the polymer, the polymer has excellent heat resistance, and can be a polymer having extremely low odor during grinding and the like.
  • the mass derived from the adamantane ring (136-adadamant) in the finally obtained polymer is required.
  • Number of substituents on the mantan ring; hereinafter referred to as AD ratio) 1 Adjust the ratio of polymerizable sulfur-containing adamantane compound to comonomer to account for 15 to 60% of the mass of the polymer obtained. Les, prefer to do. Generally, the higher the AD ratio, the better the heat resistance, and the lower the AD ratio!
  • the polymer having excellent impact resistance can be obtained as the value of ⁇ / ⁇ .
  • the polymerizable sulfur-containing adamantane compound has (b) at least one polymerizable functional group in the molecule.
  • the polymerizable functional group may be a polyaddition functional group or a radical polymerizable functional group.
  • a polyaddition functional group it is preferable that the polymerizable sulfur-containing adamantane compound contains two or more polyaddition functional groups.
  • a radical polymerizable functional group the number may be one or plural.
  • a polyaddition functional group selected from the group consisting of a mercapto group, a hydroxyl group, an episulfide group, an epoxy group, a thioisocyanate group and an isocyanate group is particularly preferably used.
  • radical polymerizable functional group for example, an atalyloyl group or a methacryloyl group is particularly preferably used.
  • the polymerizable sulfur-containing adamantane compound has at least (C) in its molecule.
  • the sulfur atom may be directly bonded to the adamantane skeleton, or may be included in a part of the substituent.
  • the number of sulfur atoms in the polymerizable sulfur-containing adamantane compound is two, it is preferable that at least one is directly bonded to the adamantyl group, and both are directly bonded to the adamantyl group. Is more preferable. Also, if the number of sulfur atoms is three, at least two Is preferably directly bonded to an adamantyl group, and more preferably all three are directly bonded to an adamantyl group. This makes it extremely easy to achieve both high refractive index and low odor.
  • the number of sulfur atoms in the polymerizable sulfur-containing adamantane compound is not particularly limited as long as it is at least one as described above, but preferably from the viewpoint that an optical material having a high refractive index is easily obtained.
  • a number such that the sulfur atom content [(the number of sulfur atoms contained in 32 X) the molecular weight of the non-polymerizable sulfur-containing adamantane compound] is 0.15 or more, preferably 0.18 or more (generally, (Two or more).
  • the optical material of the present invention comprises a polymer containing a polymerization unit based on the above polymerizable sulfur-containing adamantane compound.
  • a polymerization unit based on the above polymerizable sulfur-containing adamantane compound.
  • the polyaddition functional group contained in the polyaddition sulfur-containing adamantane compound is a functional group capable of causing an addition reaction with another polyaddition functional group and causing a polymer formation reaction by polyaddition.
  • Many of such addition reactions involve a functional group consisting of an atomic group consisting of a helium atom such as a hydroxyl group, a mercapto group, an amino group, or a hydrosilyl group, and an active hydrogen atom bonded to the helium atom (hereinafter, referred to as a "group").
  • group an active hydrogen atom bonded to the helium atom
  • a functional group to be added is a cyclic group containing a hetero atom.
  • the ring is usually opened by an addition reaction to change to a functional group on the side to be added (for example, the ring is opened by receiving an epoxy group on an epoxy group to form a hydroxyl group). To a group having).
  • the polyaddition functional group of the polymerizable sulfur-containing adamantane compound in the present invention may be a functional group on the side to be added or a functional group on the side to be added.
  • Specific examples of the functional group to be added include a mercapto group, a hydroxyl group, an amino group, a silyl group, a dithiocarboxyl group, a thiocarboxyl group, a carboxyl group, and a carboxyamide group.
  • Functional groups on the side to be added include cyclic groups containing heteroatoms such as episulphide groups, epoxy groups, and aziridine groups, and isocyanate groups.
  • a group containing a double bond such as a thioisocyanate group (hereinafter, these may be collectively referred to as a (thio) isocyanate group), a ketene group, and an ether group.
  • a (thio) isocyanate group a group containing a double bond
  • a ketene group a group containing a double bond
  • an ether group a group containing
  • the polymerizable sulfur-containing adamantane compound of the present invention has at least two polyaddition functional groups. Further, from the viewpoint of the ease of synthesis of such a compound, the number of the polyaddition functional groups is preferably four or less.
  • the polyaddition functional groups may be the same or different, but from the viewpoint of the ease of synthesis of the polymerizable sulfur-containing adamantane compound and stability, the functional group on the side to be added may be added. It is preferable that only one of the functional groups on the other side be used, and it is most preferable that all the polyaddition functional groups are the same.
  • polyaddition functional groups may be directly bonded to the adamantan ring, or may be bonded to the adamantyl group via a heteroatom or various organic residues (hereinafter, referred to as “additive”).
  • organic residue the hetero atom and the organic residue may be collectively referred to as “organic residue”.
  • organic residue and the like and the polyaddition functional group bonded thereto may be referred to as a “group having a polyaddition functional group” as one group. ), And further, these bonding forms may be mixed.
  • the groups may be different or the same for each group having a polyaddition functional group. Further, one group having a polyaddition functional group may have a plurality of polyaddition functional groups.
  • the organic residue and the like are not particularly limited as long as they are [number of polyaddition functional groups bonded to the organic residue + 1] valent organic residue, and include known heteroatoms and organic residues. Can be applied without any restrictions.
  • the hetero atom include a sulfur atom, an oxygen atom, a nitrogen atom and the like.
  • the organic residue is preferably a divalent organic residue having 1 to 60 carbon atoms, and more preferably a divalent organic residue having 1 to 20 carbon atoms.
  • the organic residue includes an ester bond, a thioester bond, an amide bond, a urethane bond, a thiourethane bond, a carbonate bond, an ether bond, a thioether bond (a sulfide bond), a dithioether bond (a disulfide bond), and an amino bond. And a bond other than a carbon-carbon bond such as a sulfonyl bond.
  • Preferred specific examples of such a group having a polyaddition functional group having an organic residue and the like will be described in detail as a group represented by the following general formula (2).
  • the polymerizable sulfur-containing adamantane compound in the present invention may be one in which only one group having a polyaddition functional group is bonded to an adamantyl group, but preferably a polyaddition functional group and / or a polyaddition
  • the compound is preferably a compound having a plurality of groups having an acidic functional group bonded to an adamantyl group.
  • the position where the polyaddition functional group and / or the group having the polyaddition functional group is bonded to the adamantyl group may be any position of the adamantyl group, for example, the first, third, fifth, and fifth positions of the adamantan skeleton. It may be on the carbon atom at the bridgehead such as the 7th position, or on the methylene carbon at the 2nd, 4th, 6th and 8th position. When it is on a methylene carbon, two bonds (substitution) may be on the same carbon.
  • the adamantyl group may have a substituent having no polyaddition functional group (hereinafter, other substituents) in addition to the polyaddition functional group or the group having the polyaddition functional group.
  • substituents include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aralkyl group, an acyloxy group, an acylthio group, and a nitrogen atom. These are further substituted with various known substituents. It may be.
  • alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group
  • acetylyl groups having 2 to 6 carbon atoms such as acetyloxy group and propionyloxy group
  • acetylthio group an acylthio group having 2 to 6 carbon atoms such as a propionylthio group is particularly preferred.
  • Such other substituents may be bonded to any position of the adamantyl group, and when the adamantane skeleton is at the 2-, 4-, 6-, 8-position, etc.
  • Each of the polyaddition functional group and the group having the polyaddition functional group and the other substituent may be bonded one by one, or two of the other substituents may be bonded.
  • the polymerizable sulfur-containing adamantane compound of the present invention has (C) at least one sulfur atom in the molecule.
  • a polymer obtained can have a high refractive index, and the polymer can be suitably used for various optical applications such as eyeglass lenses.
  • the sulfur atom contained in the polymerizable sulfur-containing adamantane compound may be in any existing form, and may be present as an atom constituting a polyaddition functional group. In the group having the polyaddition functional group, it may be present as an atom constituting an organic residue or the like, or may be present in another substituent. However, as described above, it is preferable that at least half of the sulfur atoms be directly bonded to the adamantane skeleton.
  • a polyaddition functional group When it is present as a polyaddition functional group, it may be in the form of a mercapto group, thioisocyanate group, episulfide group, dithiocarboxyl group, thiocarboxyl group, etc.
  • examples of such a form include a sulfide bond, a disulfide bond, a thioester bond, a dithioester bond, a thioamide bond, a sulfiel bond, and a sulfonyl bond.
  • the polymerizable sulfur-containing adamantane compound as described above is excellent in terms of ease of synthesis, refractive index, heat resistance, low odor, etc., and therefore has the following general formula (1)
  • R 2 represents a divalent hydrocarbon group which may have a substituent
  • X represents an oxygen atom or a sulfur atom
  • R 3 represents a polyaddition functional group
  • s represents 0 or 1
  • t is an integer of 0 to 3
  • the groups represented by (-[X] s -R2--) may be the same or different.
  • 1 ⁇ represents an alkyl group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms or an acylthio group having 2 to 6 carbon atoms, and a represents an integer of 2 to 4, b represents an integer of 0 to 4, and both Z and R 1 are the same when there is more than one Or different, and there is at least one sulfur atom in the molecule.
  • the compound represented by is particularly preferable.
  • Z is a group represented by the following general formula (2) and a group having a polyaddition functional group R 3 .
  • polyaddition functional group examples include as described above. Particularly, a mercapto group, a hydroxyl group, an episulfide group, an epoxy group, a thioisocyanate group or an isocyanate group is more preferred.
  • the polyaddition functional group is bonded to the adamantyl group via a group represented by (1- [X] s —R 2 —) t .
  • s is 0 or 1. Specifically, when X is an oxygen atom and s is 0, one [X] s — indicates a single bond, and when s is 1, it indicates an ether bond (one O—). When X is sulfur-sulfur and s is 0, one [X] s — indicates a single bond, and when s is 1, it indicates a sulfide bond (one S—).
  • R 2 is a divalent hydrocarbon group which may have a substituent, and is not particularly limited, but is preferably a hydrocarbon group having 1 to 15 carbon atoms.
  • the hydrocarbon group include a methylene group, an ethylene group, a trimethylene group, a propylene group, a 1,4-butylene group, a 1,3-butylene group, a 1,2-butylene group, and a hexamethylene group.
  • the substituent in R 2 has an effect on the polyaddition reaction to obtain a polymer.
  • the group is not particularly limited as long as it is not present, and may have various known substituents. Specifically, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group; an aralkyl having a carbon number of 7 to 11 such as a benzyl group and a phenethyl group.
  • alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxyloxy group, butoxy group, t-butoxy group
  • alkenyl groups having 2 to 4 carbon atoms such as acetyl group
  • phenyl group And aryl groups having 6 to 12 carbon atoms such as a tolyl group and a naphthyl group
  • aromatic heterocyclic groups having 4 to 10 carbon atoms, such as a phenyl group, a furyl group, and a benzothienyl group.
  • the nitrogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom from the viewpoint of the refractive index of the obtained cured product and light resistance.
  • a bromine atom is particularly preferred.
  • the hydrocarbon group represented by R 2 is an alkylene group having 1 to 4 carbon atoms or 6 to 1 carbon atoms from the viewpoint of ease of synthesis of the polymerizable sulfur-containing adamantane compound, the refractive index of the obtained polymer, and heat resistance.
  • An arylene group of 2 is preferred, and the number of carbon atoms:!
  • Alkylene groups of 4 to 4 are more preferred, and methylene groups and ethylene groups are particularly preferred.
  • t is an integer of 0 to 3, and when t is 0, it indicates that the polyaddition functional group is directly bonded to the adamantyl group. Further, when t is 2 or 3, (one [X] s - R 2 - ) groups represented by the, ⁇ - ([X] s - R 2) - ([X] s one R2) - ⁇ , ⁇ ((X) S — R2)-([X] s -R2) one ([X] s -R2) one ⁇ .
  • the groups (units) represented by (_ [X] S — R 2 —) may be the same or different, and the physical properties of the required optical material and polymerizable sulfur-containing Depending on the difficulty of synthesizing the adamantane compound, it may be appropriately selected.
  • Those having t forces of 1 and s of 0 a group having a mercapto group such as a mercaptomethyl group, a 2-mercaptoethyl group, or a 3-mercaptopropyl group as a polyaddition functional group; a thioisocyanatomethyl group; LT thioisocyanato group such as thioisocyanatoethyl group and 3-thioisocyanatopropyl group as a polyaddition functional group.
  • a group having a mercapto group such as a mercaptomethyl group, a 2-mercaptoethyl group, or a 3-mercaptopropyl group as a polyaddition functional group
  • a thioisocyanatomethyl group such as thioisocyanatoethyl group and 3-thioisocyanatopropyl group as a polyaddition functional group.
  • a group having a thioisocyanato group as a polyaddition functional group such as a thioisocyanatomethylthio group or a 2-thioisocyanatomethylthio group; a ⁇ -epitipropylpropyl group, a y-epitiobutylthio group, etc.
  • a group having a carboxyl group such as a carboxymethylthio group or a 3-carboxypropylthio group as a polyaddition functional group;
  • a group having a Amino groups, such as thioether group as polyaddition functional groups such as a thioether group as polyaddition functional groups.
  • X is an oxygen atom: a group having a mercapto group as a polyaddition functional group such as a mercaptomethyloxy group or a 2-mercaptoethyloxy group; isocyana A group having an isocyanate group such as monomethyloxy group or 2-isocyanatoethyloxy group as a polyaddition functional group; or a thioisocyanate group such as thioisocyanatomethyloxy group or 2-thioisocyanatoethyloxy group.
  • the polymerized polymer since the polymerized polymer has excellent heat resistance and a high refractive index, the group in which t is 0 or X is a sulfur atom and the t force S 1 or 2, s And a group in which R 2 is a hydrocarbon group having 1 to 2 carbon atoms.
  • particularly preferable groups include, when t is 0, a mercapto group, a hydroxyl group, an episulfide group, a thioisocyanate group or an isocyanato group; t-force S l, s- force SI, and A group having a mercapto group as a polyaddition functional group such as a mercaptomethylthio group or a 2-mercaptoethylthio group as a group in which R 2 is a hydrocarbon group having 1 to 2 carbon atoms; a hydroxymethylthio group; —A group having a hydroxyl group such as a hydroxyethylthio group as a polyaddition functional group; isocyanate group such as an isocyanatomethylthio group or a 2-isocyanatoethylthio group.
  • a group having a thioisocyanato group such as a thioisocyanatomethylthio group or a 2-thioisocyanatomethylthio group as a polyaddition functional group; and a episosulfide group such as a ⁇ -epitipropylpropylthio group.
  • Examples of the group having an additional functional group include: t-force 2, s-force Si, and R 2 is a hydrocarbon group having 1 to 2 carbon atoms, and 2— (2-mercaptoethylthio) A) a group having a mercapto group as a polyaddition functional group such as an ethylthio group; and a group having a hydroxyl group as a polyaddition functional group such as a 2- (2-hydroxyshethylthio) ethylthio group. .
  • a is an integer of 2 to 4, that is, 2 to 4 groups represented by Z are bonded to the adamantyl group.
  • the groups represented by Z may be the same or different. In the case of a different group, it preferably has a polyaddition functional group of only one of the group on the side to be added and the group on the side to be added as described above.
  • the compound represented by the general formula (1) of the present invention includes, in addition to the polyaddition functional group and the group having Z or the polyaddition functional group, an alkyl group having 1 to 6 carbon atoms represented by R 1. And 0 to 4 C 2 to C 6 acyloxy groups and Z or C 2 to C 6 acyloxy groups may be bonded to the adamantane ring.
  • the alkyl group having 1 to 6 carbon atoms may be any known alkyl group, but is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a ⁇ -pentyl group, an isopentyl group. Linear or branched such as a group, ⁇ -hexyl group, 2-methylpentyl group and the like. Further, the acetyloxy group, propionyloxy group and the like as the C 2-6 acyloxy group are preferable, and the acetyl- and propionylthio groups and the like as the C2-C6 acylthio group are preferable. Is exemplified.
  • the polymerizable sulfur-containing adamantane compound represented by the general formula (1) contains at least one sulfur atom.
  • the sulfur atom may be present as an atom constituting a polyaddition functional group in the form of a mercapto group, a thioisocyanate group, an episulfide group, or the like, or (1-S—R 2—) , (1 S—R 2 — S—R 2 1) etc.
  • R 1 has the same meaning as R 1 in the general formula (1)
  • R 4 represents a mercapto group or a thioisocyanate group
  • d is an integer of 1 to 4
  • b is 0 to 4
  • c is an integer between 0 and 3
  • c + d is between 2 and 4
  • R 4 is a mercapto group.
  • the polymerizable sulfur-containing adamantane compound has 2 to 4 mercapto groups (and hydroxyl groups) or thioisocyanate groups as weighted carophilic functional groups. Further, at least one sulfur atom is present in the atomic group constituting the mercapto group or the thioisocyanate group.
  • compounds having d of 2 to 4 are more preferable.
  • polymerizable sulfur-containing adamantane compound represented by the general formula (3) As a compound in which R 4 is a mercapto group, 1,3-adamantane dithionole, 2,4-dimethy / readamantane-1,1,3-dithiol, 1,3,5-adamantane trithionole, 1 , 3,6-adamantane trithionole, 1,3,5,7-adamantanetetrathiol, 5-mercaptoadamantane 1,1,3-diol, 5,7-dimercaptoadamantane 1,3-diol, 1-acetinoleoxyadamantane 1,3,5-dithio-mono-1,1-acetylthioadamantane 3,5-dithio-one, 1-aceti / rethioadamantane 1-3 , 5,7-trithiol and the like, as compounds in which R 4 is a thio group,
  • the polymerizable sulfur-containing adamantane compound represented by the general formula (3) is a compound having a mercapto group, it can be generally obtained by the following production method.
  • the compound is, for example, a compound in which a halogen atom such as chlorine or bromine is directly bonded to an adamantane skeleton and a thiocyanate such as thiocyanate, thiourea, triphenylphosphine sulfide, or 3-methylbenzothiazole-2-thione.
  • a compound in which an adamantyl group is directly bonded to a hydroxyl group and a thiocyanate such as thiocyanate, thiourea, triphenylphosphine sulfide, or 3-methylbenzothiazole-2-thione.
  • a compound in which an adamantyl group is directly bonded to a hydroxyl group and a thiocyanate such as thiocyanate, thiourea, triphenylphosphine sulfide, or 3-methylbenzothiazole-2-thione.
  • a compound having a mercapto group as a polyaddition functional group represented by the general formula (3) a compound in which an adamantyl group is directly bonded to a halogen atom (hereinafter referred to as a compound).
  • the reaction conditions for reacting the adamantane compound with the thiazide are not particularly limited, and known conditions may be appropriately selected and employed, but the general reaction conditions are as follows. It is as follows. That is, a halogenated adamantane compound is allowed to react with one or more equivalents of a thiamide compound to a halogen atom of the adamantane compound to be converted into a mercapto group.
  • the thiating agent is as described above.
  • the reaction is generally performed in the presence of a basic compound that captures the hydrogen halide.
  • the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and hydroxide hydroxide; alkali metals of alcohols such as lithium methoxide, sodium methoxide, sodium methoxide and potassium t-toxide. Salts; examples include organic bases such as triethylamine, pyridine, and quinoline.
  • a solvent since the halogenated adamantane compound and the thiocyanating agent are usually solid, it is preferable to use a solvent.
  • the solvent include water; alcohol solvents such as methanol, ethanol and isopropanol; and carbonized solvents such as pentane, hexane, cyclohexane, heptane, benzene, toluene and xylene.
  • Hydrogen solvents can be mentioned. These solvents may be appropriately selected depending on the type of the halogen compound or the basic compound used in the reaction, but generally, a solvent having a high dielectric constant is preferably used in order to shorten the reaction time.
  • the temperature in the above reaction varies depending on the type of the raw material and the solvent, but is generally 50 to 350 ° C, preferably 100 to 300 ° C.
  • the reaction time also varies depending on the type of the raw material, but is usually in the range of 10 minutes to 200 hours, preferably 1 hour to 60 hours.
  • a pressure reactor such as an autoclave.
  • adamantatyl alcohol a compound in which an adamantyl group is directly bonded to a hydroxyl group (hereinafter, simply referred to as adamantatyl alcohol).
  • a method of reacting with a thialating agent may be mentioned.
  • reaction conditions are not particularly limited, but general reaction conditions are as follows.
  • a thiation agent is reacted with adamantyl alcohol and a hydroxyl group of the adamantyl alcohol which is to be converted into a mercapto group.
  • the chewy pill is as described above.
  • These reactions are generally performed in the presence of an acidic compound to promote the generation of an intermediate carbocation.
  • the acidic compound include mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, and nitric acid, and organic acids such as acetic acid, acetic acid, acetic acid, trifluoroacetic acid, and methanesulfonic acid.
  • the acidic compound of the adamantyl alcohol or the thiating agent is used.
  • a solvent include water; alcohol solvents such as methanol, ethanol and isopropanol; ethenol solvents such as getyl ether, dioxane and tetrahydrofuran; pentane, hexane, cyclohexane and heptane.
  • hydrocarbon solvents such as benzene, toluene and xylene.
  • the temperature in the reaction varies depending on the type of the raw material and the solvent, but is generally from 20 to 200 ° C, preferably from 80 to 150 ° C.
  • Reaction time also depends on the type of raw material Depending on the type, it usually ranges from 10 minutes to 48 hours, preferably from 1 hour to 24 hours.
  • a pressure reactor such as an autoclave.
  • the reaction may be promoted by removing water generated during the reaction. In this case, azeotropic dehydration can be performed using a water distillation apparatus such as Dean Stark.
  • the adamantyl alcohol and the thiocyanating agent form a salt.
  • the salt is decomposed to give the desired compound.
  • It is a polymerizable sulfur-containing adamantane compound.
  • the basic compound used herein include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and hydroxide hydroxide; lithium methoxide, sodium methoxide, sodium ethoxide, potassium t-butoxide, and the like.
  • the basic aldehyde compound can be added alone or dissolved in a soluble solvent such as water.
  • the temperature in this reaction varies depending on the type of the raw material and the solvent, and is generally 20 to 200 ° C, preferably 80 to 150 ° C.
  • the reaction time also varies depending on the type of the raw material, but is usually in the range of 10 minutes to 48 hours, preferably 1 hour to 24 hours.
  • the compound represented by the general formula (3) has an alkyl group as R 1
  • the halogenated adamantane compound or the adamantyl alcohol having the alkyl group as the adamantyl alcohol is used as a raw material. Things may be used.
  • the compound has an acyloxy group or a thiol group
  • the mercapto group or the hydroxyl group of the compound having a mercapto group or a hydroxyl group obtained by the above-mentioned method is oxidized with various known acylating agents. It's good! ,.
  • the reaction conditions in this case may be appropriately selected from known acylation conditions and employed.
  • a compound having a thioisocyanate group as a polyaddition functional group represented by the general formula (3) may be, for example, a adamantyl group directly having an amino group. Can be obtained by reacting carbon disulfide in the presence of a base with an amine compound bound to thiophene to obtain dithiolbamate, and then reacting with phosgene or alkyl chloroformate to thermally decompose.
  • a known amide compound having an adamantyl group may be used as a raw material, or may be a halogenated adamantane compound or adamantyl alcohol as a raw material. It can be obtained by converting a halogen atom such as chlorine or bromine or a hydroxyl group to an amino group by reacting with ammonia.
  • Known amination conditions may be appropriately selected from known conditions.
  • the reaction for obtaining the dithiocarbamate by reacting the aminated adamantane compound with carbon disulfide is not particularly limited, and known conditions may be appropriately selected.
  • General reaction conditions are as follows. . That is, an aminated adamantane compound is reacted with one or more equivalents of carbon disulfide per amino group. These reactions are generally performed in the presence of a basic compound.
  • the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and hydroxide hydroxide; ammonia water; lithium methoxide, sodium methoxide, sodium ethoxide, t-butoxide.
  • Alkali metal salts of alcohols such as potassium can be mentioned.
  • a solvent in order to increase the solubility of the basic compound.
  • the solvent preferably used include: water; Alcohol solvents such as ethanol, ethanol, and isopropanol; ether solvents such as getyl ether, dioxane, and tetrahydrofuran; and hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, benzene, toluene, and xylene.
  • Alcohol solvents such as ethanol, ethanol, and isopropanol
  • ether solvents such as getyl ether, dioxane, and tetrahydrofuran
  • hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, benzene, toluene, and xylene.
  • the temperature in the above reaction varies depending on the type of the raw material and the solvent, but in general,
  • the temperature is from 10 to 150 ° C., preferably from 20 ° C. to a reflux temperature.
  • the reaction time also varies depending on the type of the raw material, but is usually in the range of 10 minutes to 48 hours, preferably 1 hour to 8 hours.
  • the obtained dithiorbamate in an unpurified state because it can be used in the next reaction without purification or unpurified after purification.
  • an alkyl chloroformate or phosgene is added to the reaction solution containing the crude dithiocaproluvate obtained by the above method, and the reaction is carried out. Thermal decomposition or thermal decomposition while reacting.
  • the alkyl chloroformate or phosgene added at this time is used in an amount of 1 equivalent or more based on the crude dithiol rubbamate.
  • alkynole chloroformate examples include, for example, methyl chloroformate, ethynolechlorohonolemate, propinolechlorofosolemate, isopropinolechloroformate, butyl chloroformate and the like.
  • the solvent include water; ether solvents such as ethyl ether, dioxane, and tetrahydrofuran; and charcoal such as pentane, hexane, cyclohexane, heptane, benzene, tonolene, and xylene. Hydrogenated solvents can be mentioned.
  • the reaction is carried out at 20 to 70 ° C for 10 minutes to 48 hours, preferably Perform for 1 to 8 hours. Then, water is added to the reaction mixture containing the obtained intermediate, and the organic phase is separated. After drying, the mixture is heated to 70 to 120 ° C. with or without solvent after drying. By doing so, the desired product can be obtained.
  • the reaction may be performed at a temperature of 70 to 120 ° C.
  • the method of introducing the same is the same as that for a compound having a mercapto group.
  • the polymerizable sulfur-containing adamantane compound has a weight of 1 to 3 mercapto groups and 1 to 3 hydroxyl groups or a hydroxyl group without a hydroxyl group, It has four mercapto groups.
  • the number of the mercapto groups and the hydroxyl groups is 2 to 4 in total.
  • at least one sulfur atom may be present in the atomic group constituting the mercapto group, and may be present as X in an organic residue connecting the mercapto group and the adamantyl group.
  • polymerizable sulfur-containing adamantane compound of the present invention represented by the general formula (4) include 1,3-bis (2-mercaptoethylthio) adamantane, 1,3,5-tris (2-mercaptoethylthio) adamantane, 1,3,5,7-tetrakis (2-mercaptoethylthio) adamantane, 1,3-bis [2- (2-mercaptoethylthio) ethylthio] adamantane, 1 , 3,5-tris [2- (2-mercaptoethylthio) ethylthio] adamantane, 1,3,5-tris [2- (2-mercaptoethylthio) ethylthio] adamantane, 3- (2- Compounds in which X is a sulfur atom, such as 1,2,2-dimethyladamantan-l-l-ol, 3,5-bis (2-mercaptoeth
  • the production of the polymerizable sulfur-containing adamantane compound represented by the general formula (4) is generally carried out by the production method B shown in the production method of the general formula (3) using adamantyl alcohol as a starting material. Accordingly, instead of (i) using a dimercapto compound in place of the thiation agent, and (ii) heating and stirring the reaction mixture in the presence of a basic compound for salt decomposition, The point where the step of neutralizing the acid used is changed, and other conditions can be performed under the same conditions.
  • the dimercapto compound refers to a compound having two mercapto groups in the molecule, and includes, for example, ethanedithiol, bis (2-mercaptoethyl) sulfide, propanedithiol, and the like.
  • the dimercapto compound is preferably used in an amount of 5 equivalents or more based on one hydroxyl group of adamantyl alcohol. Further, by controlling the amount of the dimercapto group-containing compound used and the amount of the acid'1 ⁇ raw compound serving as a catalyst, the reaction time, the reaction temperature, and the like, some of the hydroxyl groups can be left unreacted.
  • a diol compound is used, and a hydroxyl group of the obtained compound is converted to a mercapto group by a thiocyanating agent in the same manner as described above.
  • Compounds having the same can also be produced.
  • the neutralization of the acid is carried out by reacting a solution obtained by the reaction with a hydroxide of alkali metal or alkaline earth metal such as sodium oxide, hydroxide hydroxide or calcium hydroxide. Add it until you reach ⁇ 9.
  • a compound represented by the above general formula (3) can be used as a raw material in place of adamantyl alcohol, and can be produced in the same manner as described above.
  • R 5 represents a hydroxyl group, a carboxyl group or an amino group
  • d represents an integer of 1 to 4.
  • C is an integer of 0 to 3
  • d + c is an integer of 2 to 4
  • u is 1
  • V is 1 or 2
  • the product of d and V is 2 or more (dXv ⁇ 2 ).
  • the groups represented by (-[X] u — R 2 —) may be the same or different, and the group represented by R 1 and ⁇ (— [X]
  • each may be the same or different, and at least two of X are sulfur atoms.
  • the compound represented by the general formula (5) has 2 to 4 hydroxyl groups, carboxyl groups, and amino or amino groups as polyaddition functional groups. There are at least two sulfur atoms in the group represented by (-[X] u -R2-) v .
  • polymerizable sulfur-containing adamantane compound represented by the above general formula (5) examples include 1,3-bis (hydroxymethylthio) adamantane and 1,3-bis (2-hydroxyxenoretio) Adamantane, 1, 3-bis [2- Droxitytilthio) etinorethio] adamantane, 1,3-bis [2- (2-hydroxyethynoleoxy) etinorethio] adamantane, 5,7_bis (hydroxymethylthio) adamantane 1,1,3-diol, etc.
  • the mercapto group-containing amino compound examples include 2-aminoethylmercaptan, 2-aminopropylmercaptan, 4-aminocyclohexylmercaptan, 4-aminophenylmercaptan, and the like.
  • the protected amino group is protected in the form of an acetoamide group, an N-toluenesulfonyl group, a benzyloxycarbonyl group, a phthalimid group, an amide group such as trifluoroacetyl group, and an imido group such as a phthalimid group.
  • the mercapto group-containing amino compound is generally used in an amount of 1 equivalent or more, preferably 5 equivalents or more, per one hydroxyl group of adamantyl alcohol.
  • a method for synthesizing a compound having a carboxyl group among the compounds represented by the general formula (5) generally, a compound having an amino group among the compounds represented by the above general formula (5)
  • a method using a compound having a carboxyl group or a protected carboxyl group and a mercapto group (hereinafter, referred to as a mercapto group-containing carboxyl compound) instead of the mercapto group-containing amino compound may be adopted. I just need.
  • Examples of the mercapto group-containing carboxyl compound include 2-mercaptopropionic acid, 2-mercaptovaleric acid, 4-mercaptocyclohexanecarboxylic acid, 4-mercaptobenzoic acid, and the like, and carboxyl groups and methyl esters of these compounds.
  • Compounds protected in the form of an ester such as a group, a benzyl ester group and a t-butyl ester group are exemplified.
  • a hydroxyl group or a protected hydroxyl group is used in place of the amino compound having a mercapto group.
  • a mercapto group-containing compound hereinafter, referred to as a mercapto group-containing alcohol
  • a diolic compound having a thioether bond hereinafter, referred to as a mercapto group-containing alcohol
  • Examples of the mercapto group-containing alcohol include 2-mercaptoethanol, 21-mercaptopropanol, 41-mercaptocyclohexanol, 4-mercaptophenol, 2- (2-mercaptoethylthio) ethanol, and the like.
  • the hydroxyl group of the compound of the formula is a methyl ether group, a benzyl ether group, Examples include compounds protected in the form of ethers such as methoxetoxymethyl ether group, aryl ether group and t-butyl dimethinolesilyl ether group.
  • Examples of the diol compound having a thioether bond include 2- (2-hydroxy ether). Tilthio) Ethanol and the like.
  • a hydroxide of an alkali metal or alkaline earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. May be added until the pH of the solution obtained by the reaction becomes about 5 to 9.
  • a known deprotection method may be used. May be appropriately adopted.
  • the polymerizable sulfur-containing adamantane compound has an epoxy group, an isocyanate group, a thioisocyanate group and a
  • the sulfur atom is represented as X in the group connecting the polyaddition functional group and the adamantyl group, or as an episulfide group or a thiol group. There are at least two isocyanate groups.
  • the compound represented by the above general formula (6) include 1,3-bis (glycidylthio) adamantane, 1,3,5-tris (glycidylthio) adamantane, 1,3-bis [(3, 4-epoxycyclohexyl) ethynolethio] a compound having an epoxy group as a polyaddition functional group such as adamantane; 1,3-bis (isocyanatomethylthio) adamantane, 1,3-bis (2 —Isocyanatoethylthio) adamantane, 1,3-bis (2-isocyanatopropylthio) adamantane, 1,3-bis (2-isocyanatopropylthio) _5-methyladamantane, 1,3,5-tris (Isocyanatomethylthio) adamantane, 1,3,5-tris (2-isocyanatoethylthio) iso
  • the polymerizable sulfur-containing adamantane compound represented by the general formula (6) can be generally produced by the following method.
  • examples thereof include an adamantane compound having a mercapto group represented by the general formula (3) or (4) and epichlorohydrin.
  • an epihalohydrin compound is preferably epichlorohydrin.
  • the ephalohydrin compound is used in an amount of 1 equivalent or more, preferably 2 to 30 equivalents, per one of the mercapto groups of the adamantane compound having a mercapto group.
  • the reaction may be carried out without solvent or in the presence of a solvent. If a solvent is used, use a solution in which either the adamantane compound having a mercapto group or the ephalohydrin as the raw material is soluble. It is desirable.
  • Specific examples of the solvent include water, amides, alcohols, sulfoxides, ethers, aromatic hydrocarbons, halogenated hydrocarbons, and the like.
  • the reaction proceeds easily in the presence of a stoichiometric or more base. That is, 1 mol or more of the base may be used per 1 mol of the epihalohydrin compound used.
  • the base include tertiary amines such as pyridine, triethylamine, diazavicine pendene and the like, hydroxides of alkaline earth metals and alkaline earth metals, and preferred are alkali metals or alkaline earth metals.
  • a metal hydroxide is more preferable, and sodium hydroxide, potassium hydroxide and the like are more preferable.
  • the reaction is usually carried out at a temperature of 110 to 110 ° C, preferably 110 to 60 ° C.
  • the reaction time is not particularly limited as long as the reaction is completed under the above-mentioned various conditions, but is usually 10 hours or less.
  • an unsaturated compound corresponding to a target epoxy compound is produced by oxidizing with an organic peracid, alkyl hydroperoxide, hydrogen peroxide or the like.
  • a method can also be adopted.
  • Various conditions for producing the epoxy compound by the oxidation may be appropriately selected and used from known conditions.
  • the epoxy group of the compound having an epoxy group produced by the above method is replaced with thiocyanic acid. It can be obtained by a method of reacting with a thiating agent such as a salt, thiourea, triphenylphosphine sulfide, or 3-methylbenzothiazole-12-thione to convert it into an episulfide group.
  • a thiating agent such as a salt, thiourea, triphenylphosphine sulfide, or 3-methylbenzothiazole-12-thione to convert it into an episulfide group.
  • a preferred thiocyanate is a salt of an amine, an alkali metal or an alkaline earth metal. More preferred are potassium thiocyanate and sodium thiocyanate.
  • the thiocyanate is used stoichiometrically in a molar amount of 1-fold the epoxy compound, but is preferably used in an amount of 1 to 10-fold molar. More preferably, the reaction is performed using 1 to 5 moles. The reaction may be carried out without a solvent or in a solvent. When a solvent is used, it is preferable to use a solvent in which either a thiocyanate, a thiourea or an epoxy compound is soluble.
  • the solvent include water, alcohols such as methanol, ethanol, and isopropanol; ethers such as getyl ether, tetrahydrofuran, and dioxane; and hydroxy acids such as methylcellosolve, ethylse / resonolev, and butylcelloso / rebu. Ters; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as dichloroethane, chloroform, and chlorobenzene.
  • adding an acid or an acid anhydride to the reaction solution as a polymerization inhibitor is an effective means from the viewpoint of increasing the yield.
  • acids and acid anhydrides include nitric acid, hydrochloric acid, sulfuric acid, fuming sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid , Maleic acid, benzoic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride Phthalic anhydride, silica gel, silica alumina, aluminum chloride and the like.
  • the addition amount is usually 0.01 to 10 wt% based on the total amount of the reaction solution.
  • the reaction is usually carried out at a temperature of 0 to 100 ° C, preferably 20 to 70 ° C.
  • the reaction time is not particularly limited as long as the reaction is completed under the above-mentioned various conditions, but is preferably 2 hours or less.
  • the stability of the resulting compound can be improved by washing the reaction product with an acidic aqueous solution.
  • the acid used in the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, and maleic acid. . These may be used alone or as a mixture of two or more. Aqueous solutions of these acids usually work well below pH 6, but more effectively below pH 3.
  • the polyaddition functional group is a carboxyl group.
  • d is 2 or more, reacted with a lower alcohol under heating and reflux under an acid catalyst to obtain an alkyl ester derivative, and the alkyl ester derivative is reacted with hydrazine hydrate under ice cooling.
  • the compound can be obtained by introducing a hydrazinocarbonyl group, further reacting with sodium nitrite in dilute hydrochloric acid, and then performing Curtius rearrangement in hot benzene.
  • a carboxylic acid compound having an adamantyl group is reacted with a lower alcohol in the presence of a suitable acid catalyst to convert it into an alkyl ester derivative.
  • a suitable acid catalyst sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like can be used, and as the lower alcohol, methanol, ethanol, propanol and the like can be mentioned.
  • the amount of the lower alcohol used is not particularly limited as long as it is at least 1 equivalent to one carboxyl group, and the lower alcohol used may be used as a solvent. Further, a solvent such as toluene or benzene may be used.
  • Water generated by the reaction may be subjected to azeotropic dehydration using a dehydrating agent such as anhydrous sodium sulfate or molecular sieve, or a Dean-Stark apparatus using toluene as a solvent.
  • a dehydrating agent such as anhydrous sodium sulfate or molecular sieve, or a Dean-Stark apparatus using toluene as a solvent.
  • the reaction can be carried out at room temperature or higher and below the boiling point of the solvent, but it is generally preferable to carry out the reaction under reflux.
  • the amount of hydrazine hydrate to be used at this time is not limited as long as it is at least 1 equivalent to one ester group, but generally it is preferably in the range of 1 to 10 equivalents.
  • a reaction solvent a polar solvent such as methanol, ethanol, propanol, butanol, THF, dioxane, or water can be used, but a lower alcohol that dissolves the ester derivative as a raw material and precipitates a product can be used. It is desirable to use.
  • the reaction can be carried out at a reaction temperature of 0 ° C. or higher and the boiling point of the solvent or lower, but it is preferable to carry out the reaction after cooling to room temperature or lower.
  • the obtained hydrazinocarbonyl derivative is reacted with nitrite in a dilute acid, and then subjected to a Curt-to-us transition under a heating condition to obtain a target isocyanate compound.
  • a dilute acid a dilute hydrochloric acid aqueous solution, a dilute sulfuric acid aqueous solution, or the like can be used, and if necessary, various organic solvents that do not hinder the reaction can be used in combination.
  • the reaction temperature with nitrite is not particularly limited as long as the reaction temperature does not cause the subsequent Curtius rearrangement reaction, but is preferably in the range of 0 to 1 ° C.
  • the obtained reaction product usually precipitates and is collected by filtration.
  • the filtrate is subjected to a Curtius transition by heating to be converted into a target compound having an isocyanate group.
  • the solvent at the time of the Curtius transition is not particularly limited as long as it does not react with the product, but benzene, toluene and the like are preferable.
  • the reaction temperature may be appropriately selected and carried out according to the raw materials and the solvent used, and is generally 30 to 120.
  • the thioisocyanate group is introduced in the same manner as described for the compound represented by the general formula (4). Can be manufactured.
  • the raw material The compound having an amino group can be synthesized by the method shown in the method for producing the compound represented by the general formula (5).
  • the isocyanate group and the thioisocyanate group as the polyaddition functional groups in terms of the physical properties of the obtained optical material and the easiness of the polyaddition reaction.
  • / or compounds having an episulphide group are preferred.
  • R a, b and X have the same meanings as R a, b and X in the general formula (1), and R 7 and R 8 each independently represent a group represented by the general formula (1). It has the same meaning as R 2 that put, u is a 1, w is an integer of 0-2. Further, in the case of w 2 (an [X] u - R 8 - ) groups represented by may each be the same or different, further, a group represented by R 1 and [one R 7 - When there are a plurality of groups represented by (one [X] u — R 8 —) w — SH], each may be the same or different. ]
  • R 1 a, b and X have the same meanings as those of the length 1 , a, b and X in the general formula (1), and R 7 and R 8 each independently represent the general formula ( It has the same meaning as R 2 in 1), R 9 is any group selected from a thioisocyanate group and an episulfide group, u represents 1 and w represents an integer of 0 to 2. Also, w In the case of 2 (one [X] u - R 8 - ) groups represented by may each be the same or different, further, groups and [one R 7 represented by R 1 - (an [X] u — R 8 —) w — R 9 ] are the same or different when there are a plurality of groups.
  • the compound represented by the above general formula (7) or (8) has at least two mercapto groups, thioisocyanato groups or episulphide groups as polyaddition functional groups. Further, since one sulfur atom exists in each of the atomic groups constituting the polyaddition functional group, the number of sulfur atoms in the molecule is at least two or more.
  • Specific examples of the compound represented by the general formula (7) include 1,3-bis (mercaptomethyl) adamantane, 1,3,5-tris (mercaptomethyl) adamantane, and 1,3-bis (2- Menolecaptoethylthiophenyl) adamantane, 2,2-bis (2-mercaptoethylthiophenyl) adamantane and the like are exemplified.
  • Compounds represented by the general formula (8) include 1,3-bis [(2-thioisocyanato-methylthio) ethyl] adamantane, 1,3-bis (2-thioisocyanato-ethylthiomethyl) adamantane, 3-bis (2-thioisocyanatopropylthiomethyl) adamantane, 1,3-bis (2-thioisocyanatopropynolethiomethyl) -1,5-methyladamantane, 1,3-bis [4-1 (thioisocyanate) Tomidothio) phenyl)] adamantane, 1,3-bis [4- (2-thioisocyanato-ethylthio) phenyl] adamantane, 2,2-bis [4- (2-thioisocyanato-ethylthio) phenyl] adamantane, etc.
  • the hydroxyl group is bonded to a carbon atom through a carbon atom or the like.
  • a compound bonded to an ethylene group can be used as a raw material, and the others can be produced by the method described in the general formula (4).
  • the compound in which a hydroxyl group is bonded to an adamantyl group via a carbon atom or the like can be produced, for example, using a compound having an adamantyl group and a carboxyl group as a raw material.
  • 1,3-bis (hydroxymethyl) adamantane 1,3-bis (2-hydroxyshethyl) adamantane is, respectively, adamantane 1,1,3-dicarboxylic acid or adamantane 1,1,3- It can be obtained by esterifying diacetic acid with a lower alcohol in the presence of an acid catalyst, followed by treatment with a reducing agent such as lithium aluminum hydride.
  • compounds having a thioisocyanate group as a polyaddition functional group include compounds having an amino group such as a compound represented by the following general formula (10). From an amino group to a thioisocyanate group in the same manner as described for the compound represented by the general formula (6).
  • those having an episulfide as a polyaddition functional group include, for example, a compound having a mercapto group represented by the general formula (7) as a raw material,
  • the compound is reacted with ephalohydrin to form an epoxy compound, and then the epoxy group of the epoxy compound is converted to an epipulphide group by a thiolating agent. It can be manufactured by the following method.
  • R 1D represents an epoxy group or an isocyanate group
  • u represents 1
  • X represents 1 or 2.
  • R 1 ⁇ - R 7 - any group is represented by X -R 10 ⁇ , may each be the same or different when there is more than, have at least two sulfur atoms in Chikaratsu molecule You. ]
  • R 11 represents a hydroxyl group, an amino group or a carboxyl group
  • u represents 1
  • X represents 1 or 2.
  • (an [S] u - R 8 - ) group may each be the same or different as indicated by the further and groups represented by R 1 ⁇ - R 7 - ( - [X] u -R 8 - ) any group is represented by x -R 11 ⁇ , may each be the same or different when there are a plurality of, and in the molecule to have at least two sulfur atoms . ]
  • the compound represented by the general formula (9) or (10) has at least two sulfur atoms. That is, in the group represented by ⁇ — R 7 — (1- [X] u — R 8 —) — ⁇ At least one of X is a sulfur atom, or at least one group represented by ⁇ —R 7 —S—R 8 —S—R 8 — ⁇ is present You.
  • the compound represented by the above general formula (9) include 1,3-bis (glycidiothiomethinole) adamantan, 1,3,5-tris (glycidinolethiomethyl) adamantane, and 1,3-bis ⁇ 21- [2- (3,4-epoxycyclohexyl) ethyldithio] ethyl ⁇ Compounds having an epoxy group as a polyaddition functional group such as adamantane; 1,3-bis [2- (isocyanatomethylthio) ) Ethyl adamantan, 1,3-bis (2-isocyanatoethylthiomethyl) adamantan, 1,3-bis (2-isocyanatopropylthiomethyl) adamantan, 1,3-bis (2-isocyanate) Natopropylthiomethyl) 1-5-methyladamantane, 1,3-bis [4-1 (isocyanatomethylthio) phenyl]
  • the compounds represented by the general formula (10) include 1,3-bis (aminomethylthiomethyl) adamantane, 1,3-bis [2- (2-aminoethylthio) ethyl] adamantane, and 1,3-bis ( Polyaddition such as 2-aminoethylthiomethyl) 1,5,7-dimethyladamantane, 1,3-bis (2-aminoethyldithiomethy ⁇ /) adamantane, etc.
  • the compound represented by the general formula (9) As a method for synthesizing the compound represented by the general formula (9), a method similar to the method for producing the compound represented by the general formula (6) can be used.
  • the compound represented by the general formula (7) in the case of a compound having an epoxy group, the compound represented by the general formula (7) can be used as a starting compound, and in the case of a compound having an isocyanate group, the starting compound As the compound, a compound having a carboxyl group represented by the general formula (10) can be used.
  • a method for synthesizing the compound represented by the general formula (10) a method similar to the method for producing the compound represented by the general formula (5) can be used.
  • a compound in which a hydroxyl group shown in the production method of the general formula (7) is bonded to an adamantyl group via a carbon atom can be used as a raw material compound.
  • the compounds represented by the above general formulas (3) to (10) are not limited to the above-mentioned methods, and may be a hydroxyl group, a mercapto group, an isocyanate group, a thioisocyanate group, an epoxy group, an episulfate. It can also be produced by converting a carboxylic acid group, a carboxyl group, an amino group and the like by various known methods. The polymerizable sulfur-containing adamantane compound produced by such various production methods is used if necessary after isolation. As an isolation method at this time, a known method can be used without any limitation.
  • a water-soluble by-product such as a salt of a generated hydrogen chloride and a basic compound is filtered or washed with water. After removal, the solvent may simply be distilled off. Also, if the reaction yield is low or coloring is a problem If necessary, a known purification operation such as distillation or column chromatography, and an adsorbent treatment such as activated carbon treatment or silica treatment, or a known decolorization such as washing with water, hydrochloric acid solution or aqueous sodium hydroxide solution The operation selected as appropriate from the operation may be performed.
  • the structure of the produced polymerizable sulfur-containing adamantane compound can be identified and confirmed by, for example, the following means.
  • the characteristic absorption of each compound can be observed by measuring the infrared absorption spectrum (IR).
  • IR infrared absorption spectrum
  • each weight% of carbon, hydrogen, sulfur, and other elements can be determined, and the composition formula of the monomer can be determined.
  • the molecular weight of a compound can be determined by mass spectrometry (MAS S, EI method).
  • the polymerizable sulfur-containing adamantane compound obtained by the above method is converted into a polymer by a polyaddition reaction.
  • the functional group on the side to be added and the functional group on the side to be added are paired and reacted. Therefore, except for the case where the polyaddition functional group is a cyclic group containing a heteroatom, in order to obtain a polymer, a polymer having at least two functional groups on the side to be added is added to the polymer. And a compound having at least two functional groups on the other side.
  • the polyaddition functional group is a cyclic group containing a hetero atom such as an epoxy group or an episulfide group
  • the ring is opened by receiving the cyclic group, and thereby the ring on the side to be added is added.
  • Groups hydroxyl groups, mercapto groups, etc.
  • the newly generated groups to be added continue to be added to the cyclic groups containing heteroatoms. It is possible to polymerize only with a compound having a group.
  • the polyaddition functional group is a group other than a cyclic group containing a hetero atom.
  • both the compound having the functional group on the side to be added and the compound having the functional group on the side to be added may be the polymerizable sulfur-containing adamantane compound of the present invention.
  • the polymerizable sulfur-containing adamantane compound of the present invention is It is preferable to form a polymer by reacting with another compound having an additional functional group (hereinafter, referred to as a comonomer).
  • polyaddition functional groups of these comonomers include the same groups as the polyaddition functional groups of the polymerizable sulfur-containing adamantane compound of the present invention.
  • known compounds having a polyaddition functional group as described above can be used without limitation.
  • the total carbon number is 1 to 30 and 2 to 6 polyaddition functional groups. Comonomers having a group are preferred.
  • comonomers having a functional group on the side to be added include polyhydric alcohol compounds such as trimethylolpropane and triethylolpropane; methanedithiol, 1′2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiole, 1,2,3-propanetrithiole, 1, , 1-six-mouth hexanedithiol, 1,2-cyclohexanedithiol, 2-methylcyclohexane-1,2,3-dithiol, bicyclo [2,2,1] pepter e Xo—cis—2, 3 _dithio 1 / re, 1,1-bis (mercaptomethyl) cyclohexane, thiomalate bis (2-mercaptoethyl
  • compounds having a plurality of mercapto groups are preferable, and 2,2-bis (mercaptomethyl) -1,1,3-propanedithiol and 1,2-bis (2-mercaptoethyl) are preferred.
  • Examples of the comonomer having the functional group on the side to which the force P is applied include compounds having a (thio) isocyanate group as a polyaddition functional group, such as O-xylylene di (thio) isocyanate and m-xylylene di (thio).
  • Aromatic (thio) isocyanates such as benzene; 4-chloro-1 m-xylylene di (thio) isocyanate, 4,5- Dichloro-1-m-xylylenedi (thio) isocyanate, 2,3,5,6-tetrabromo-1-p-xylylenedi (thio) isocyanate, 4-methylene-xylylene Aromatic (thio) isocyanates substituted with chlorine, bromine or lower alkyl group such as di (iso) isocyanate, 4-eth
  • Compounds having an ethenyl group as a polyaddition functional group include divinyl benzene, ethylene dariko resin (meth) acrylate, trimethylolpropan ter (meth) acrylate, and ethylene daricol dithio (meth) acrylate. And urethane-modified (meth) acrylates containing at least two or more (meth) acryloxy groups in one molecule, epoxy-modified (meth) acrylates and polyester-modified (meth) acrylates, and the like.
  • Examples of the compound having both the (thio) isocyanate group include 2- (meth) ataliloxityl (thio) isocyanate, (meth) atariloyl (thio) isocyanate, and the like. These comonomers may be used alone or in combination of two or more. Of these, compounds having a (thio) isocyanate group as a polyaddition / functional group are particularly preferred.
  • the side to which the polyaddition functional group of the polymerizable sulfur-containing adamantane compound of the present invention is added.
  • the polyaddition functional group of the comonomer is the group to be added, and conversely, the polymerizable sulfur-containing adamantane compound.
  • the polyaddition functional group of the product is a group to which the polyaddition functional group is added
  • a compound in which the polyaddition functional group of the comonomer is the group to be added is appropriately selected, and these will be described later.
  • the polymerization may be performed by any suitable method.
  • these comonomers include at least two or more polyaddition functional groups regardless of whether the polyaddition functional group of the comonomer is a group to be added or a group to be added. It must contain comonomer. Taking into account the various physical properties of the obtained polymer, a compound having three or more weight-added citrus functional groups as at least one of the polymerizable sulfur-containing adamantane compound and the comonomer so as to be a crosslinked polymer. Is more preferable.
  • a comonomer having a group of the same kind as the polyadditive functional group of the polymerizable sulfur-containing adamantane compound of the present invention may be further blended, or as the polymerizable sulfur-containing adamantane compound of the present invention. It is also possible to use a compound having a group on the side to be added and a compound having a group on the side to be added in combination, and to use a compound having any polyaddition functional group as a comonomer. Furthermore, a compound having only one polyaddition functional group may be blended.
  • sulfur-containing polyadditive adamantane compounds and comonomers are arranged so that (the functional group on the side to be added and the functional group on the side to be added) are in the range of 0.5 to 3 (preferably 0.5 to 1.5). It is preferable to appropriately select and use it because the resulting polymer has good optical and mechanical properties. Specifically, for example, (number of (thio) isocyanate groups) Z (the number of hydroxyl groups + mercapto groups) is 0.5 to 3.0 (preferably 0.5 to 1.5). It is advisable to blend the sulfur-containing polyadditive adamantane compound and comonomer used.
  • a combination of a compound having a (thio) isocyanate group as a polyaddition functional group and a compound having a mercapto group or a hydroxyl group is considered.
  • Sulfur-containing polyadditive adamantane compound and co It is preferred to select a monomer.
  • the AD ratio in the finally obtained polymer is 15 to 6 in the mass of the obtained polymer. It is preferable to adjust the ratio of the polymerizable sulfur-containing adamantane compound to the comonomer so as to account for 0%.
  • a compound having a molecular weight of 50 to 500 is used as the comonomer, and the molar ratio of the sulfur-containing polyadditive adamantane compound to the comonomer is 0.1.
  • a high refractive index can be easily obtained by appropriately selecting a sulfur-containing polyadditive adamantane compound and a comonomer so that the obtained polymer has a sulfur atom content of 0.15 or more.
  • additives such as an ultraviolet absorber, an antioxidant, an anti-coloring agent, a fluorescent dye, a light stabilizer, an oil-soluble dye, and an internal release agent for improving weather resistance may be appropriately added.
  • a catalyst for improving the polymerization reactivity may be used as appropriate.
  • organic peroxides, azo compounds and basic catalysts are effective for improving the reactivity between the mercapto group and the ether group.
  • organic peroxides, azo compounds and basic catalysts are effective for improving the reactivity between the mercapto group and the ether group.
  • organic peroxides, azo compounds and basic catalysts are effective for improving the reactivity between the mercapto group and the ether group.
  • organic tin compound, an amine compound or the like In order to improve the reactivity between the mercapto group or the hydroxyl group and the (thio) isocyanate group, it is effective to add an organic tin compound, an amine compound or the like.
  • the amount of these catalysts
  • the amount of the catalyst is usually 0.0001 to 0.1 mol per mol of the polyadditive functional group of the sulfur-containing polyadditive adamantane compound and the comonomer. Use about 1 mole.
  • the method for producing a polymer from the sulfur-containing polyadditive adamantane compound and comonomer as described above, and other components blended as necessary is particularly limited. Instead, a known method for producing a polyaddition-type polymer may be appropriately employed.
  • the polymer is an optical material such as an eyeglass lens
  • the sulfur-containing polyadditive adamantane compound, comonomer, and additives and catalysts, if necessary, are mixed and sufficiently defoamed to obtain a uniform raw material mixture.
  • raw material mixture known casting polymerization method that is injected into a mold in combination with glass or metallic Mo one field and a resin gasket, c when the curing heat to the resin after molding
  • the mold may be subjected to a mold release treatment in advance, or a mold release agent may be mixed into the raw material mixture.
  • the polymerization temperature varies depending on the compound used, but is generally from 120 to 115 ° C., and the polymerization time is from 0.5 to 72 hours.
  • the polymerization temperature and polymerization time vary depending on the composition of the monomer and the type and amount of additives, but generally, the temperature is raised from 5 to 20 ° C, and the temperature is raised from 100 to 130 ° C. The temperature may be raised to about C in 8 to 30 hours, and maintained for about 1 to 10 hours.
  • the polyaddition functional group is a cyclic group containing a hetero atom.
  • the cyclic group containing the hetero atom is a group to which the cyclic group containing the heteroatom is added, and at the same time, it is opened by being added. Ringing results in the group to be added. Therefore, it is possible to polymerize only with the compound containing only the cyclic group containing the hetero atom.
  • Such a cyclic group containing a hetero atom can be polymerized alone by heating, but is preferably heated using a curing catalyst.
  • the curing catalyst include compounds known as a ring-opening polymerization catalyst for an epoxy group and a Z or episulfide group, for example, amines, phosphines, mineral acids, Lewis acids, organic acids, carboxylic acids, and tetrafluoroboric acid. Can be used.
  • Ammonium salts of the amines with halogens, mineral acids, Lewis acids, organic acids, carboxylic acids, and tetrafluoroboric acid complexes of the amines with borane and boron trifluoride: trimethylphosphine; Phosphines such as tris (4-methylphenyl) phosphine and diphenylcyclohexylphosphine; mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid; and their half esters; boron trifluoride, boron trifluoride etherate, etc.
  • Typical examples are Lewis acids; organic acids such as carboxylic acids and their half esters; and caustic acid and tetrafluoroboric acid. These catalysts may be used alone or as a mixture of two or more! / ,.
  • the above curing catalyst may be used in an amount of usually about 0.0001 to 0.1 mol per 1 mol of a heterocyclic atom-containing cyclic group such as an epoxy group and a Z or episulfide group.
  • the primary or secondary polyamines and polycarboxylic acids exemplified as the comonomer also act as a curing catalyst.
  • the polyamines / polycarboxylic acids are incorporated into the polymer and also serve as a unit constituting the polymer.
  • the compounding amount may be larger than the range used as the curing catalyst.
  • the polymerizable sulfur-containing adamantane compound of the present invention may be used alone, and if necessary, other compounds having a cyclic group having a hetero atom may be used. May be used in combination.
  • various known epoxy compounds and episulfide compounds may be used.
  • polymerizable sulfur-containing adamantane compound comonomer of the present invention having a polyaddition functional group other than the above-described cyclic group having a hetero atom can also be used in combination.
  • the AD ratio in the obtained polymer is It is preferable to adjust the compounding ratio of each component so that it occupies 15 to 60% of the mass and the sulfur atom content is 15% or more.
  • additives such as an ultraviolet absorber, an antioxidant, an anti-coloring agent, a fluorescent dye, a light stabilizer, an oil-soluble dye, and an internal mold release agent for improving weather resistance are appropriately added. You may squeeze.
  • the method for producing the polymer is not particularly limited, and a known method for producing a polyaddition-type polymer may be appropriately employed.
  • the polymerizable sulfur-containing adamantane compound of the present invention having a cyclic group having a hetero atom as a polyaddition functional group, the above-described various curing catalysts, and other components blended as necessary may be mixed and sufficiently mixed.
  • An optical material such as a spectacle lens can be manufactured using the raw material mixture by the same method as described above. Radical polymerizable sulfur-containing adamantane compound
  • the radically polymerizable sulfur-containing adamantane compound of the present invention is represented by the following general formula (I).
  • R 1 represents an alkyl group having 1 to 6 carbon atoms
  • Z 1 represents the following formula ( ⁇ )
  • R 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, X 1 and X 2 each independently represent an oxygen atom or a sulfur atom, and Y 1 represents a (meth) atalyloyl group; e is 0 or 1, f is an integer of 0 to 6, and when f is 2 to 6, the groups represented by (R 2 — X 2 ) may be the same or different, and e + f Is 1 or more.
  • Z 2 is a group represented by the following formula ( ⁇ )
  • R 3 represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms
  • X 3 and X 4 each independently represent an oxygen atom or a sulfur atom
  • Y 2 represents a group other than a (meth) atalyloyl group Represents an acyl group having 2 to 7 carbon atoms
  • g is 0 or 1
  • h is an integer of 0 to 6
  • the group represented by (R 3 — X 4 ) is the same But may be different, and g + h is 1 or more.
  • Z 3 is a group represented by the following formula (IV)
  • R 4 represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms
  • X 5 and X 6 each independently represent an oxygen atom or a sulfur atom, i is 0 or 1, j is 0
  • the groups represented by (R 4 — X 6 ) may be the same or different, i + j is 1 or more, and the terminal is always a hydroxyl group. Is.
  • a is an integer of 1 to 4
  • b is an integer of 0 to 3
  • c is an integer of 0 to 3
  • ⁇ , a + b + c is 1 to 4
  • d represents an integer of 0 to 4
  • RZ 1 ⁇ Pi Z 2 Les deviation also may each be the same or different when there are a plurality of, and of the atoms represented by Chi ⁇ kai 6 least One is a sulfur atom.
  • the compound has the following formula ( ⁇ ⁇ )
  • R 2 represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms
  • X 1 , X 2 are Each independently represents an oxygen atom or a sulfur atom
  • Y 1 represents a (meth) atalyloyl group
  • e is 0 or 1
  • f is an integer of 0 to 6
  • R 2 — The groups represented by X 2 ) may be the same or different, and e + f is 1 or more.
  • R 2 in the above formula ( ⁇ ) is a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms.
  • the hydrocarbon group may be any known group, specifically, a methylene group, an ethylene group, a propylene group, a trimethylene group, a 1,4-butylene group, a 1,3-butylene group, a 1,2-butylene group.
  • alkylene groups having 1 to 6 carbon atoms such as hexylene group; arylene groups having 6 to 12 carbon atoms such as phenylene group, methylphenylene group and naphthylene group; cyclopentylene group, cyclohexylene group and the like. Examples thereof include a cycloalkylene group having 4 to 12 carbon atoms.
  • the substituent in the case of a substituted hydrocarbon group is not particularly limited, and may have various known substituents. Specific examples include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a t-butoxy group; and an alkoxy group having 2 to 4 carbon atoms such as an acetyl group.
  • halogen atom When a halogen atom is used as a substituent, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And a bromine atom is particularly preferred.
  • hydrocarbon groups a high Abbe number can be obtained. It is preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably a methylene group or an ethylene group, since raw materials for synthesizing the radically polymerizable adamantane compound are easily available.
  • X 1 and X 2 each independently represent an oxygen atom or a sulfur atom, e is 0 or 1, f is an integer of 0 to 6, and e + f is at least 1 or more.
  • the (meth) acryloyl group represented as Y 1 is always bonded to an oxygen atom or a sulfur atom, and accordingly, a (meth) acryloyloxy group or ( (Meta) Atariloylthio group is formed. Therefore, when f is 0, the structure is such that the (meth) atalyloyloxy group or the (meth) acryloylthio group is directly connected to the adamantane skeleton.
  • the (meth) atalyloyloxy group or the (meth) acryloylthio group has one (X 1 ) e — (R 2 — X 2 ) ( 2— bonded to the adamantane skeleton through the group represented by —
  • the groups represented by (R 2 — X 2 ) may be the same or different.
  • R 2 and X 2 may be different. Considering the ease of synthesis, even when each R 2 is different, X 2 is Preferably they are identical.
  • the resulting high refractive index is preferably X 1 and X 2 are both sulfur atom.
  • f is more preferably 0 to 4 in consideration of ease of synthesis and low odor during processing, and particularly preferably 0 to 2 in consideration of heat resistance.
  • e is preferably 1 in terms of easiness of synthesis and stability.
  • the Z 1 may be attached one 1-4 to Adamantan skeleton as described above, even in each same they if (when a is 2 to 4) which Z 1 is present 2-4 It may be different. That is, each Z 1, the type and X 1, X 2 and R 2, The values of e and f may be different. Considering the ease of synthesis, it is preferable that only the forces X 1 in which all Z 1 are the same are different and that R 2 , X 2 , Y e and f are the same. In consideration of the heat resistance of the obtained polymer, a is preferably 2 to 4.
  • R 3 represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms
  • X 3 and X 4 each independently represent an oxygen atom or a sulfur atom
  • Y 2 represents a carbon atom other than a (meth) atalyloyl group
  • the Z 2 is its terminal (meth) Atariroiru ⁇ Shi Le group 2-7 carbon atoms other than groups.
  • the acetyl group having 2 to 7 carbon atoms is not particularly limited and may be any known one, and may be an aliphatic acetyl group such as an acetyl group, a propioyl group, a butyryl group, an isobutyryl group, or an aromatic group such as a benzoyl group. Specific examples include a system acyl group. In order to obtain a high Abbe number, an aliphatic acyl group is preferable, and an aliphatic acyl group having 2 to 4 carbon atoms is more preferable.
  • 1 3 is a substituted or unsubstituted hydrocarbon group having 1 to 1 5 carbon atoms, specifically exemplified are the same as the previous SL R 2, the preferred type is the same as R 2.
  • X 3 and X 4 are each independently an oxygen atom or a sulfur atom, g is 0 or 1, h is an integer of 0 to 6, and when h is 2 to 6, (R 3 — X 4 )
  • the group represented by — Or may be different, and g + h is 1 or more.
  • Z 2 is also Z 1 and the like, each may be the same or different when there are multiple. Preferred types and numerical ranges regarding these is similar to those described (X 1 and X 3, X 2 and X 4, e and g, f and h are each corresponding) with respect to Z 1.
  • the Z 2 does not need to be present in the molecule, and if present, is at most three. In consideration of easiness of synthesis, heat resistance of the obtained polymer, Abbe number, etc., it is preferable that Z 2 does not exist, that is, b is 0.
  • R 4 represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms
  • X 5 and X 6 each independently represent an oxygen atom or a sulfur atom, i is 0 or 1, j is 0 to When j is 2 to 6, the groups represented by (R 4 — X 6 ) may be the same or different, i + j is 1 or more, and the terminal is always a hydroxyl group. is there.
  • Is a group represented by The Z 3 may not be present in the molecule, if present is three or less.
  • R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms.
  • R 2 the same as the above R 2 are exemplified, and the preferred types thereof are also the same as R 2 is there.
  • X 5 and X 6 are each independently an oxygen atom or a sulfur atom; i is 0 or 1, j is an integer of 0 to 6; when i is 2 to 6, (R 4 — X 6 ) May be the same or different, and i + j is 1 or more.
  • the terminal When the terminal is a mercapto group, the mercapto group reacts with the (meth) acryloyl group, resulting in extremely poor storage stability. Therefore, the terminal must be a hydroxyl group. That is, when j is 0, X 5 is always an oxygen atom; and when i is 1 to 6, Z 3 is one (X 5 ) i— (R 4 — X 6 ) (j - ⁇ - (R 4 - O) One H.
  • Both ⁇ represents an oxygen atom or a sulfur atom is a at least one of the atoms represented in this xix 6 sulfur Is an atom. That is, the radically polymerizable adamantane compound of the present invention has at least one sulfur atom in the molecule. Thereby, a high refractive index can be obtained when used as an optical material.
  • at least one of the plurality of X 2 is It does not matter if it is a sulfur atom. More preferably, it is a compound in which at least two of the atoms represented by xix 6 are sulfur atoms.
  • R 1 is an alkyl group having 1 to 6 carbon atoms. Specific examples include a methynole group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like.
  • d shows the integer of 0-4. When d is 2 to 4, they may be the same or different.
  • ZZZ 3 and R 1 may be bonded (substituted) at any position on the adamantane skeleton, but from the viewpoint of ease of synthesis, Z 2 Preferably, Z 3 is bonded to the bridgehead of the adamantane skeleton.
  • R 1 is an alkyl group having 1 to 6 carbon atoms
  • R 7 and R 8 are each an alkylene group having 1 to 6 carbon atoms
  • X 1 and X 3 each represent an oxygen atom or a sulfur atom
  • Y 1 Represents a (meth) atalyloyl group
  • Y 2 represents an acyl group having 2 to 7 carbon atoms other than the (meth) atalyloyl group
  • c is an integer of 0 to 3
  • d is an integer of 0 to 4
  • e and g Are each 0 or 1, m and n are each an integer of 0-2, o is an integer of 2-4, p is an integer of 0-2, and c + o + p is 2-4, e + m is 1 to 3, g + n is:! ⁇ a 3, further m, when n are both 0, at least one atom represented by X 1 or X 3 is always a sulfur atom).
  • R 1 X 1 , X 3 , Y ⁇ Y 2 , c, d, e, and g are the same as those described for the compound of the general formula (I).
  • the alkylene group having 1 to 6 carbon atoms represented by R 7 and R 8 is the same as the alkylene group having 1 to 6 carbon atoms described as R 2 .
  • the group represented by ⁇ (X 3 ) g — (R 8 -S) n -Y 2 ⁇ may be absent, or one or two groups may be present. When two groups are present, they may be the same or different.However, considering the ease of synthesis, these two groups are the same or R 8 , Y 2 , g and ⁇ are the same. , X 3 are preferably different (but only when g is 1).
  • (R 8 -S) n — Y 2 ⁇ and the group represented by (R 7 — S) m and (R 8 — S) n have the same group, which facilitates synthesis. It is particularly preferred in terms of the point. It is more preferable that X 1 and X 3 are all sulfur atoms in that a higher refractive index can be obtained.
  • the most preferred compound is a compound in which X 1 is a sulfur atom and c and p are 0 in the above formula (V). It is.
  • the radically polymerizable sulfur-containing adamantane compound of the present invention can be obtained by elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum as described for the polyaddition sulfur-containing adamantane compound.
  • the structure can be identified and confirmed.
  • In the infrared absorption spectrum (IR) observe the absorption based on the unsaturated hydrocarbon group at the terminal in the vicinity of 1600 to 1650 cm- 1 and the strong absorption based on the carbonyl group in the vicinity of 1700 to 1750 cm- 1. Can be.
  • the method for producing the radically polymerizable sulfur-containing adamantane compound of the present invention is not particularly limited, it can be generally produced by the method described below. That is, in the general formula (I), a compound having a hydrogen atom bonded instead of Y 1 in Z 1 (and Y 2 in Z 2 if present), that is, a compound having a hydroxyl group or a mercapto group.
  • Adamantane compound as a raw material compound which is used as a (meth) acrylic acid halide ⁇ and, if necessary, other than a (meth) acrylic acid halide having 2 to 7 carbon atoms. (Hereinafter simply referred to as an acyl halide having 2 to 7 carbon atoms.
  • an acid halide together with (meth) acrylic acid halide) ⁇ in the presence of a basic compound. It can be produced by a known acylation (esterification) method.
  • various target compounds can be synthesized by adjusting the equivalent number of the acid halide to the hydroxyl group and mercapto group of the raw material. For example, in a raw material compound having only a mercapto group, by using one or more equivalents of an acid halide with respect to one mercapto group, an acylated target compound can be obtained according to the amount of the acid halide used. .
  • the target compound in which both the hydroxyl group and the mercapto group are substituted or the hydroxyl group remains depending on the equivalent number of the acid halide.
  • the desired compound can be obtained.
  • reaction conditions for the reaction of the adamantane compound having a hydroxyl group or a mercapto group with an acid halide may be appropriately selected from known conditions as necessary.
  • a known ester synthesis method such as acylation with an acid anhydride or a transesterification reaction using an acid ester can also be employed.
  • the reaction is generally performed in the presence of a basic compound that captures the hydrogen halide.
  • the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and hydroxide hydroxide; and alcohols such as lithium methoxide, sodium methoxide, sodium ethoxide, and t-butoxy potassium.
  • Alkali metal salts organic bases such as triethylamine, pyridine and quinoline.
  • the amount of the basic aldehyde compound used may be within a known range, and is generally about 1.0 to 50 equivalents to the acid halide.
  • a solvent In the reaction, it is generally preferable to use a solvent.
  • suitable solvents include: water; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as getyl ether, tetrahydrofuran, and dioxane; dichloromethane, chloroform, tetrachloroethylene, and chloroform.
  • Halogen solvents such as benzene, o-dichlorobenzene and the like; and hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, benzene, tonolene and xylene. These solvents may be appropriately selected as needed.
  • the amount of the solvent used is not particularly limited, and generally, the concentration of the raw material compound should be about 0.1 to 50% by weight!
  • the reaction temperature varies depending on the type of the raw material and the solvent, but is generally from 120 to 100 ° C, preferably from 110 to 60 ° C.
  • the reaction time also varies depending on the type of the raw material, but is usually in the range of 10 minutes to 48 hours, preferably 1 hour to 24 hours.
  • stirring is preferably performed during the reaction.
  • a polymerization inhibitor in order to prevent polymerization of the reaction product, it is desirable to carry out the reaction by adding a polymerization inhibitor.
  • the polymerization inhibitor known compounds can be used without any limitation. Specific examples include hydroquinone, p-methoxyphenol, 2,6-di-t-butynole 4-methinolephenol, phenolic polymerization inhibitors such as t-butynole force; phenolic polymerization inhibitors such as phenothiazine, copper chloride ( ⁇ ), and shiridani (m); Among these, p-methoxyphenol and p-t-butyl catechol are preferred in consideration of the ability to inhibit polymerization, coloring of the product, and removal from the reaction product after the reaction.
  • the amount of the polymerization inhibitor depends on the type of the inhibitor and the reaction temperature, but is generally 0.01 to 10 parts by weight based on 100 parts by weight of the adamantane compound as a raw material. And preferably 0.1 to 5 parts by weight.
  • the radically polymerizable sulfur-containing adamantane compound of the present invention produced by such a production method is used if necessary after isolation.
  • a known method is used without any limitation. For example, high reaction yield If purification and decoloring operations are not necessary, simply remove the salt between the generated hydrogen chloride and the basic compound by filtration or washing, and then distill off the solvent. But it doesn't matter.
  • reaction yield is low or coloring is a problem
  • known purification operations such as distillation and column chromatography, and adsorbent treatments such as activated carbon treatment and silica treatment, or water, hydrochloric acid water or water
  • An operation appropriately selected from known decolorizing operations such as washing with an aqueous sodium oxide solution may be performed.
  • the adamantane compound to be used as a starting material in the above reaction can be produced by various methods.
  • a typical production method is, for example, a method in which a hydroxyl group-containing adamantane compound is reacted with a thiourea or other thiaminating agent under acidic conditions to give a mercapto group-containing adamantane compound, or And a method of reacting an adamantane compound having a thiol group or a mercapto group with various diol compounds and dithiol compounds. Further, in the compounds described for the polyaddition-containing sulfur-containing adamantane compound, an adamantane compound having a hydroxyl group or a mercapto group may be used as a starting compound.
  • the conditions for reacting an adamantane compound having a hydroxyl group with a thiation agent to form an adamantane compound having a mercapto group are not particularly limited, and a known method may be employed. Generally, it is possible by adopting the following method. That is, an alcohol in which a hydroxyl group such as 1-adamantanol is directly bonded to the adamantane skeleton, or a hydroxyl group such as 11- (hydroxymethyl) adamantane is bonded to the adamantane skeleton through a hydrocarbon group having 1 to 15 carbon atoms.
  • the above compound or the like may be used as a raw material, and a hydroxyl group to be converted into a mercapto group may be reacted with at least 1 equivalent, preferably 1.0 to 50 equivalents of a thiazide.
  • the alcohol in which the hydroxyl group as the raw material is directly bonded to the adamantane skeleton includes 1-adamantanol, 1,3-adamantanediol, 1,3,5-adamantanetriol, 1,3,5,7 —Adamantanetetraol, 3— Methinole 1-adamantane, 5,7-dimethanole 1,3-adamantanediol, etc. can be used.
  • Examples of alcohols in which a hydroxyl group is bonded to an adamantane skeleton via a hydrocarbon group include: Hydroxymethyl) adamantane, 1,3-bis (hydroxymethinole) adamantane, 1,3-bis (hydroxyxethyl) adamantane and the like can be used.
  • As the thialating agent thiocyanate, thiourea, triphenylphosphine sulfide, 3-methylbenzothiazole-2-thione, or the like may be used.
  • This reaction is generally performed in the presence of an acid compound to promote the generation of an intermediate carbocation.
  • the acidic compound include mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, and nitric acid, and organic acids such as acetic acid, chloroacetic acid, trifluoroacetic acid, methanesulfonic acid, and p-toluenesulfonic acid.
  • the amount of the acid compound to be used may be in a known range, and is generally 1 equivalent or more, preferably 1.0 to 50 equivalents, per hydroxyl group to be converted into a mercapto group.
  • a solvent in order to carry out the reaction in a homogeneous system.
  • the solvent include water; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as getyl ether, dioxane, and tetrahydrofuran; And the like. These solvents may be appropriately selected depending on the types of alcohol compounds and acidic compounds used in the reaction.
  • the amount of the general solvent used is such that the concentration of the adamantane compound as a raw material is 1.0 to 50% by weight.
  • the reaction temperature at this time varies depending on the types of raw materials and solvents used, but is generally 20 to 200 ° C, preferably 80 to 150 ° C.
  • the reaction time also varies depending on the type of raw material, but is usually in the range of 10 minutes to 48 hours, preferably 1 hour to 24 hours.
  • a pressurized reactor such as an autoclave. It is also possible to carry out the reaction at a temperature higher than the boiling point of the solvent.
  • the reaction may be promoted by removing water generated during the reaction. In this case, azeotropic dehydration can be performed using a water distillation apparatus such as Dean-Stark.
  • Examples of the basic conjugate used herein include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and hydrating hydride; lithium methoxide, sodium methoxide, sodium ethoxide, t-butoxide.
  • Alkali metal salts of alcohols such as potassium; and organic bases such as triethylamine, pyridine and quinoline.
  • the basic compound can be added alone or dissolved in a solvent such as water.
  • the temperature in this reaction is a force that varies depending on the type of the raw material and the solvent, generally 20 to 200 ° C, and preferably 80 to 150 ° C.
  • the reaction time also varies depending on the type of the raw material, but is usually in the range of 10 minutes to 48 hours, preferably 1 hour to 24 hours.
  • the solvent may be removed from the product solution, and if necessary, purified by a known method.
  • the starting compound having a portion corresponding to (R 2 —X 2 ) f is a compound that is difficult to obtain, for example, an adamantane compound having a hydroxyl group or a compound obtained by the above method may be used.
  • Diamantane compound having a mercapto group and the corresponding structure eg, HX 2 — R 2 — X 2 H, HX 2 — R 2 — X 2 — R 2 — X 2 H
  • the compound can be obtained by reacting the compound with a dithiol compound under acidic conditions.
  • dio compound examples include ethylene glycol, propylene dalicol, diethylene glycol, triethylene glycol, and the like.
  • dimercaptoid conjugate examples include ethanedithiol, bis (2-mercaptoethyl) sulfide, propanedithiol, and the like. You. If necessary, both a diol compound and a dithiol compound can be used in combination. The amount of these diol compounds and dithiol compounds to be used is generally 1.0 to 50 equivalents to one portion corresponding to (R 2 —X 2 ) f to be introduced.
  • the same compounds as those used for the reaction between the adamantane compound having a hydroxyl group and the thiazing agent can be used.
  • the amount of the acidic compound used may be in a known range, and is generally at least 1 equivalent, preferably 1.0 to 50 equivalents per hydroxyl group or mercapto group.
  • an adamantane compound having a hydroxyl group or a mercapto group, a diol compound, or a dithiol compound used as a raw material may be appropriately selected according to the structure of the adamantane compound to be obtained, in consideration of availability of the raw material and the like.
  • the number of (R 2 — X 2 ) f groups (etc.) to be introduced is controlled by controlling the amount of diol compound / dithiol compound used, the amount of acidic compound used as a catalyst, the reaction time, the reaction temperature, etc. can do.
  • the target compound can be obtained by neutralizing (neutralizing) the acid used after completion of the reaction and performing, for example, distillation under reduced pressure.
  • the sulfur-containing adamantane compound obtained in this manner is reacted with (meth) acrylic acid halide (and, if necessary, C 2-7 acyl halide) by the above-mentioned method.
  • the radical polymerizable sulfur-containing adamantane compound of the present invention can be obtained.
  • the radical polymerizable sulfur-containing adamantane compound of the present invention is polymerized and cured as a polymer monomer to obtain a cured product having a high refractive index, a high Abbe number, excellent heat resistance, and low odor during molding. give.
  • the radically polymerizable sulfur-containing adamantane compound of the present invention can be suitably used as a raw material of an optical material, particularly a lens material, by utilizing the above-mentioned properties obtained when homopolymerized.
  • the radical polymerizable sulfur-containing adamantane compound of the present invention is also taken into consideration in consideration of other physical properties such as the refractive index, Abbe number, and heat resistance.
  • other unsaturated monomers that can be copolymerized hereinafter, also referred to as comonomers
  • comonomers unsaturated monomers that can be copolymerized
  • the comonomer is not particularly limited as long as it is a polymerizable monomer copolymerizable with the radically polymerizable sulfur-containing adamantane compound of the present invention, and is appropriately selected from those which give necessary physical properties according to the intended use. You can use it.
  • Specific examples of comonomers suitable for use as an optical material include methyl (meth) acrylate,
  • Aryl compounds styrene, di-vinylinolebenzene, chlorostyrene, bromostyrene, dibutene styrene, vinylinolephthalene, isopropylinolenaphthalene, ⁇ -methinolestyrene, ⁇ -methino Aromatic Bulle compounds such as styrene dimer; (meth) urethane (meth) Atari rate or epoxy (meth) Atari rate or the like having on or more Atari rate based 2 Tsu the like. These comonomers can be used alone or in combination of two or more.
  • the copolymerization composition in the case of copolymerization may be appropriately determined according to the purpose, but the radical polymerizable sulfur-containing adamantane compound of the present invention is 10 to 98% by weight based on the total weight of all polymerizable monomers. %, Especially 20 to 95% by weight (the remainder is the amount of comonomer).
  • the polymerization method of polymerizing and curing the radically polymerizable sulfur-containing adamantane compound of the present invention or a mixture thereof with a comonomer to obtain a cured product is not particularly limited, and a known polymerization method can be employed.
  • various types of stabilizers such as mold release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, photochromic compounds, etc. Agents and carotenoids can be mixed and used as necessary.
  • the polymerization can be initiated by using a radical polymerization initiator such as various peroxide azo compounds, or by irradiating ultraviolet rays, ⁇ -rays, rays, ⁇ -rays or the like, or a combination of both.
  • a radical polymerization initiator such as various peroxide azo compounds, or by irradiating ultraviolet rays, ⁇ -rays, rays, ⁇ -rays or the like, or a combination of both.
  • the radical polymerization initiator is not particularly limited, and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoic acid peroxide, decanolyl peroxide, and lauroyl. Peroxide, Acecilha.
  • Acyl peroxysides such as oxosides; peroxysides such as t-butylinoleoxy-12-ethylhexanoate, t-butylperoxydicarbonate, cuminolepa-hydroxyneodecanate, and t-butylperoxybenzoate Esters; dicarbonate such as diisopropylpropyl peroxydicarbonate, di-2-ethylhexyl peroxy dicarbonate, di sec-butyl / reoxycarbonate; 2, 2'-azobisisoprop Tazonitrile, 2,2'-azobis (4-dimethylpareronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1 1-carbonitrile), etc. And the like.
  • the amount of the radical polymerization initiator used depends on the polymerization conditions, the type of the initiator, and the type and composition of the polymerizable composition of the present invention, and cannot be limited unconditionally. It is preferable to use 0.01 to 10 parts by weight with respect to 0 parts by weight.
  • the polymerization method is not particularly limited. However, when the use as an optical material such as a lens is considered, it is preferable to perform casting polymerization. Hereinafter, a typical casting polymerization method will be described in more detail.
  • a polymerizable composition of the present invention to which a radical polymerization initiator has been added is injected between molds held by an elastomer gasket or a spacer, and heated in an air furnace to polymerize and cure. After that, it is done by taking out.
  • the temperature particularly affects the properties of the obtained cured product.
  • This temperature condition is affected by the type and amount of the initiator and the type of the monomer, and thus cannot be unconditionally limited.However, in general, the polymerization is started at a relatively low temperature and the temperature is gradually increased. Raise It is preferable to perform a so-called tapered two-stage polymerization in which the polymerization is cured at a high temperature at the end of the polymerization.
  • the polymerization time also varies depending on various factors like the temperature, it is preferable to determine the optimal time in advance according to these conditions, but in general, the conditions are such that the polymerization is completed in 2 to 40 hours. It is preferred to choose
  • Casting polymerization can also be carried out by known photopolymerization using ultraviolet rays.
  • benzoin benzoin methyl ether ⁇ ⁇ benzoin petit / lethenole
  • benzophenolene acetofenone
  • 4,4'-neck mouth benzophenone diethoxyacetophenone
  • 2- Hydroxy-1-methyl-1-phenylpropane-1-one benzylmethylketal
  • 1- (4-isopropylphenyl) 1-2-hydroxy-1-methylpropane-1-one 1-hi Droxycyclohexylpheninole ketone, 2-isopropylthioxanthone and the like
  • These photopolymerization initiators are generally used in the range of 0.001 to 5 parts by weight based on 100 parts by weight of all monomers.
  • Optical materials are generally used in the range of 0.001 to 5 parts by weight based on 100 parts by weight of all monomers.
  • Optical materials made of the above-mentioned polyaddition or radical polymerizable sulfur-containing adamantane compound polymer may be provided with anti-reflection, high hardness, improved wear resistance, improved chemical resistance, and improved anti-fog properties, if necessary.
  • physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, and light control treatment can be performed.
  • the optical material obtained in the present invention can be easily dyed in water or a solvent using a usual disperse dye.
  • a carrier as a dyeing assistant may be added to the dyeing bath to further facilitate the dyeing.
  • optical material comprising the polymer of the present invention has extremely low dispersion. It has high refractive index, excellent heat resistance, and is colorless and transparent, lightweight, excellent in weather resistance and impact resistance, and has low water absorption and excellent surface hardness. It is suitable not only for optical element materials such as spectacle lenses, camera lenses, and LCD substrates, but also for glazing materials, paints, and adhesives. In addition, it has the characteristic of low odor during molding, and is a material with excellent workability.
  • the performance test of the obtained lens was evaluated by the following test methods.
  • Refractive index and Abbe number 20 using an Abbe refractometer manufactured by Atago Co., Ltd.
  • the refractive index ( nd ) and Abbe number at C were measured.
  • Bromophthalene or methylene iodide was used as the contact liquid. It is preferable that both the refractive index and the Abbe number are high.
  • 'Appearance Coloring and transparency were visually observed.
  • Odor Odor during cutting with a diamond cutter or polishing with a rubbing machine was evaluated according to the following criteria. (A): No odor is felt.
  • 1,3-Adamantanediol 17 g (0.1 monole) and thiourea 152 g (2.0 mol, 20 mol equivalent to adamantane compound) are mixed with concentrated hydrochloric acid 500 g (adamantane compound 0.1 mol). 500 g), and the mixture was heated and stirred at 100 ° C for 10 hours. After cooling to room temperature, 600 g of a 50% sodium hydroxide aqueous solution was added, and the mixture was heated and stirred at 110 ° C for 2 hours. After allowing to cool to room temperature, 12.1 g of the precipitated white solid was isolated. Table 1 shows the elemental analysis, MAS S, 1H-NMR, and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 3-mercaptoadamantan-111-ol (Compound A).
  • Production Example 3 Using 9.2 g (0.05 mol) of 1,3,5-adamantane triolate, mercapto-formation and subsequent post-treatment are carried out under the same charge ratio and reaction conditions as in Production Example 1. As a result, 4.7 g of a white solid was isolated. Table 1 shows the elemental analysis, MAS S, 1H-NMR, and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 5-mercaptoadamantane-1,3-diol (compound C).
  • 1,3,5,7-adamantanetetraol (10 g, 0.05 mol) and thiourea (380 g, 5 mol) are added with concentrated hydrochloric acid (410 g). For 60 hours. After cooling to room temperature, 5 0 g of a 50% aqueous sodium hydroxide solution was added, and the mixture was heated with stirring at 110 ° C for 2 hours. After cooling to room temperature, 0.7 g of the precipitated white solid was isolated. Table 1 shows the elemental analysis, MAS S, 1H-NMR, and IR spectrum of the obtained white solid. From the results of these analyses, it was confirmed that the isolated compound was 1,3,5,7-adamantanetetrathiol (diamide F).
  • the obtained ester (19.6 g) was dissolved in dry tetrahydrofuran furan (30 Om1), and 2.7 g of lithium aluminum hydride was gradually added under ice-cooling. After stirring for 3 hours, the reaction solution was slowly added to 500 ml of ice-cooled 1N hydrochloric acid. After addition of 50 Oml of black-mouthed form to the reaction solution, the organic phase was separated, concentrated and dried to obtain 13.6 g of a white solid. 1H-NMR confirmed that the main product was 1,3-bis (hydroxymethyl) adamantane. Using 9.8 g of the obtained alcohol, the same charging ratio as in Production Example 2 was used.
  • 1,3'5-Adamantanetrithiol 23-2 g (0.10 mol) and pyridine 9.0 g were added to toluene 20 Om1, cooled to 0 ° C, and acetyl chloride 7.9 g (0.10 mol) was gradually added dropwise, followed by 70 for 2 hours.
  • the mixture was heated and stirred with a solid solution. The mixture was allowed to cool, and the form and water were added thereto. The organic layer was neutralized with dilute hydrochloric acid, and the organic layer was separated and concentrated.
  • the elemental analysis, MASS, 1H NMR, and IR spectrum of the obtained white solid are shown in Table 2. From these analysis results, the isolated compound was 5-acetylthio-1,3-dimercaptoa. It was confirmed to be damantane (compound).
  • 1,3-Adamantanediol 42 g (0.24 mol) and thioglycolic acid After adding 8 g (0.04 monole) of p-toluene snolefonic acid to 100 g of ethyl (0.8 mol), the mixture was heated and stirred at 130 ° C. for 6 hours. After cooling to room temperature, the precipitated p-toluenesulfonic acid was filtered off, washed with 200 ml of 5% sodium hydrogencarbonate solution and then with 200 ml of water, and ethyl thioglycolate was distilled off under reduced pressure.
  • the liquid temperature was raised to 45 ° C over 1 hour, and the reaction was performed at this temperature for 5 hours.
  • 50 Oml of water was added to the reaction mixture, extracted with 50 Oml of Tonolen, and the toluene layer was washed three times with 50 Om1 of water.
  • the toluene layer was dried with anhydrous sodium sulfate, and the solvent was distilled off to obtain a white solid.
  • Table 3 shows the elemental analysis, MASS, 1H-NMR, and IR spectrum of the obtained white solid. From the results of these analyses, it was confirmed that the isolated compound was 1,3-bis ( ⁇ -epipop-piruthio) -damantane (compound Q). The analysis results of Compounds A to Q are shown in Tables 1 to 3 below.
  • Each of the compounds of the present invention produced in Production Examples 1 to 17 has a polyaddition functional group and a group having Z or a polyaddition functional group at at least two positions 1 to 7 of the adamantyl group. It is a compound, and Table 4 summarizes the substituents of these manufactured compounds.
  • PETP Pentaerythritol tetrakis (3-mercaptopropionate)
  • DDOL 1,10—decanediol
  • H6-XD I 1,3-bis (isocyanatomethyl) cyclohexane
  • NBD I Norbornane diisocyanate (Note: Mixture of 2,5- and 2,6-norbornane diisocyanate)
  • DMMD 2,5-bis (mercaptomethyl) -1,4-dithiane
  • METM 1,2-bis (2-mercaptoethyl-1-1-thio) -1,3-mer'ronokun
  • ADSH 1—Adamantanethiol
  • ADDL 1,3—adamantandiole ⁇ 20
  • the polymerization was carried out as follows. That is, the polymerized sulfur-containing adamantane compound of the present invention, a comonomer, and 1 ⁇ 10 15 mol of dibutyltin dilaurate (DBTDL) as a polymerization catalyst were mixed to form a uniform liquid, and after sufficient defoaming, demolding treatment was performed. It was injected into the lens mold consisting of the applied glass mold and gasket. Heat polymerization was performed at 50 at 10 hours, then at 60 at 5 hours, and further at 120 ° C for 3 hours to obtain a lens-shaped polymer. After completion of the polymerization, the mixture was gradually cooled, and the lens was taken out of the mold. Tables 5 and 6 show the physical properties of the obtained polymer. You. The AD ratio of the polymer is also shown in the table.
  • the polymers of Examples 1 to 20 containing the polymerizable sulfur-containing adamantane compound according to the present invention as polymerized units are colorless and transparent, and have a refractive index (n d ). It is very high and has a high Abbe number (V), indicating that it has optical properties suitable for applications such as eyeglass lenses.
  • V Abbe number
  • the heat resistance was excellent, the odor was very low, and the weather resistance was good.
  • the odor the higher the proportion of the sulfur atom in the polymer directly bonded to the adamantyl group, the better the odor is.If all the sulfur atoms are directly bonded to the adamantyl group, the odor is reduced during the work. I could't feel it at all.
  • a polymer was obtained by polymerizing each of the compounds shown in Table 7 in the same manner as in the examples without blending the polymerizable sulfur-containing adamantane compound in the present invention.
  • the physical properties of the obtained polymer are shown in Table II.
  • Comparative Example 1 shows the results when no adamantane ring was present in the obtained polymer. In these cases, the Abbe number was low and the heat resistance was poor. Further, as shown in Comparative Examples 2 and 3, when the sulfur content was increased to obtain a high refractive index, an extremely unpleasant odor was generated, and there was a problem in workability.
  • the polymer in Comparative Example 4 was a polymer having the same AD ratio and sulfur atom content as in Example 20.
  • Comparative Example 4 in which all sulfur atoms are not directly bonded to an adamantane ring, has a pronounced odor and has a polymer. It can be understood that it is important that the sulfur atom is derived from the polymerizable sulfur-containing adamantane compound.
  • Comparative Example 5 is an example in which an adamantane compound having only one polyaddition functional group was used. In this case, no cured product was obtained.
  • Compound P which is an epoxy-based polymerizable sulfur-containing adamantane compound, was mixed with 100 parts by weight of 1 part by weight of tripropylamine, and injected into a mold composed of two glass plates. Polymerization and curing were performed at 0 ° C for 8 hours to obtain a polymer. The obtained material had a refractive index of 1.60 and an Abbe number of 38, and a heat resistance of 15.5 ° (: excellent in weather resistance. In addition, there was almost no odor during polishing. (A) level Example 2 2
  • tripropylamine was added to 100 parts by weight of compound Q, which is a polymerizable sulfur-containing adamantane compound of episulphide type, and this was injected into a mold composed of two glass plates. Polymerization and curing were performed at 0 ° C for 8 hours to obtain a polymer.
  • the obtained material had a refractive index of 1.64 and an Abbe number of 34, and had heat resistance of 150 ° C. and good weather resistance. In addition, there was almost no odor during polishing, and it turned out at (A) level.
  • Table 11 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3,5-tris (2-methacryloylthioethylthio) adamantane. The yield from 1,3,5-tris (2-mercaptoechinorecho) adamantane was 40%.
  • Table 11 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3,5-tris (methacryloylthio) adamantane. The yield from 1,3,5-trimercaptoadamantane was 36%.
  • Table 11 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3,5,7-tetrakis (methacryloylthio) adamantane. The yield from 1,3,5,7-tetramercaptoadamantane was 22%.
  • Table 12 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (methacryloylthiomethyl) adamantane. The yield from 1,3-bis (mercaptomethyl) adamantane was 44%.
  • Table 12 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (2-mercaptoethylthio) -1,5,7-dimethyladamantane. The yield from 5,7-dimethyladamantane-1,3-diol was 37%.
  • Table 12 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (2-methacryloylthioethylthio) -1,5,7-dimethyladamantane. The yield from 1,3-bis (2-mercaptoethylthio) -1,5,7-dimethyladamantane was 47%.
  • Table 12 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 3,5-dimethacryloylthioadamantan-111-ol. The yield from 3,5-dimercaptoadamantan-1-ol was 31%.
  • Table 13 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 3,5-dimethacryloylthio-11-acetyladamantane. The yield from 3,5-bis (methacryloylthio) adamantan-1-ol was 24%.
  • Table 13 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3,5-tris (atalyloylthio) adamantane. The yield from 1,3,5-trimercaptoadamantane was 28%.
  • Table 13 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (2-hydroxyxylthio) adamantane. The yield from 1,3-adamantanediol was 9%. b) Synthesis of 1,3-bis (2-acryloyloxyshetylthio) adamantane
  • Table 13 shows the elemental analysis, mass spectrum, proton nuclear magnetic resonance spectrum, and infrared absorption spectrum of the obtained colorless and transparent oily substance. From the results of these analyses, it was confirmed that the isolated compound was 1,3-bis (2-atalyloyloxhetylthio) adamantane. The yield from 1,3-bis (2-hydroxyethylthio) adamantane was 48%.
  • Tables 8 to 10 show the structures of the radically polymerizable sulfur-containing adamantane compounds described in Examples 24 to 33 and the starting compounds. Table 8
  • the polymerization was carried out as follows. That is, with respect to 100 parts by weight of the curable composition, 0.5 parts by weight of t-butylperoxyneodecanate and 1,1,3,3-tetramethylbutylperoxide were used as a radical polymerization initiator. 4 parts by weight of xy-2-ethylhexanate were added and mixed well. Radical polymerizable sulfur-containing ada
  • the following compounds are used in place of the radically polymerizable sulfur-containing adamantane compound of the present invention.
  • Comparative Example 7 shows that the polymer of the radically polymerizable sulfur-containing adamantane compound of the present invention has excellent heat resistance and low odor.
  • Comparative Example 8 it can be seen that the Example of the present invention has a higher Abbe number and is excellent in heat resistance and weather resistance.
  • Comparative Example 9 it can be seen that Examples of the present invention have a refractive index and are excellent in weather resistance.
  • the cured product containing the radically polymerizable sulfur-containing adamantane compound of the present invention as a monomer has an excellent balance of various physical properties and can be suitably used as an optical material such as an eyeglass lens. The invention's effect
  • the cured product obtained from the polyadditive or radically polymerizable sulfur-containing adamantane compound of the present invention has a high refractive index and a high Abbe number, and is useful as a monomer that gives a cured product excellent in heat resistance and weather resistance. It is. Further, the polymer has a characteristic that the operability such as polishing is very low since the polymer has little odor during polishing and molding.
  • the cured product obtained by homopolymerizing the polymerizable sulfur-containing adamantane compound or copolymerizing with the comonomer in the present invention is useful as an optical material, for example, an optical lens such as an eyeglass lens or an optical instrument lens. It can be suitably used for applications such as prisms, optical disc substrates, optical fibers, and LCD substrates.

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Abstract

La présente invention a trait à un matériau optique approprié pour verres de lunettes et autres, présentant un indice de réfraction élevé, un nombre Abbe élevé, et une excellente résistance thermique et une excellente aptitude au façonnage dégageant très peu d'odeur désagréable en cours d'usinage tel que le doucissage et le polissage. Le matériau optique est caractérisé en ce qu'il est constitué d'un polymère comprenant des unités dérivées d'un composé d'adamantane soufré polymérisable porteur dans la molécule (a) d'au moins un groupe adamantyle, (b) d'au moins un groupe fonctionnel polymérisable, et (c) d'au moins un atome de soufre.
PCT/JP2003/003588 2002-03-25 2003-03-25 Materiau optique et composes d'adamantane soufres polymerisables Ceased WO2003081295A1 (fr)

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* Cited by examiner, † Cited by third party
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CN114106345A (zh) * 2021-10-19 2022-03-01 西北工业大学宁波研究院 一种发光铜-硫醇聚合物单晶及其制备方法
US11807596B2 (en) 2017-10-26 2023-11-07 Shikoku Chemicals Corporation Thiol compounds, synthesis method therefor, and utilization of said thiol compounds

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JP2001042534A (ja) * 1999-07-26 2001-02-16 Fuji Photo Film Co Ltd 遠紫外線露光用ポジ型フォトレジスト組成物
EP1099721A1 (fr) * 1999-11-09 2001-05-16 Mitsubishi Gas Chemical Company, Inc. Composition pour la production de résines
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11807596B2 (en) 2017-10-26 2023-11-07 Shikoku Chemicals Corporation Thiol compounds, synthesis method therefor, and utilization of said thiol compounds
JP2019085402A (ja) * 2017-11-02 2019-06-06 四国化成工業株式会社 チオール化合物、その合成方法および該チオール化合物の利用
JP7106426B2 (ja) 2017-11-02 2022-07-26 四国化成工業株式会社 チオール化合物、その合成方法および該チオール化合物の利用
CN114106345A (zh) * 2021-10-19 2022-03-01 西北工业大学宁波研究院 一种发光铜-硫醇聚合物单晶及其制备方法

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