WO2003081295A1 - Optical material and polymerizable sulfur-containing adamantane compounds - Google Patents

Abstract

The invention relates to an optical material suitable for lenses of eyeglasses and so on, which exhibits a high refractive index, a high Abbe number, and excellent heat resistance and is excellent in workability to generate little uncomfortable odor in machining such as grinding or polishing. The optical material is characterized by consisting of a polymer comprising units derived from a polymerizable sulfur-containing adamantane compound bearing in the molecule (a) at least one adamantyl group, (b) at least one polymerizable functional group, and (c) at least one sulfur atom.

Description

 Description Optical materials and polymerizable sulfur-containing adamantane compounds

 The present invention relates to an optical material and a novel polymerizable sulfur-containing adamantane compound particularly suitable for producing the optical material. Background art

 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.

 As a material generally used for plastic lens applications, there is a resin made of poly [jeti-lendarycolbis (diaryl carbonate)]. This resin has various characteristics such as excellent impact resistance, good dyeability and good workability. However, since 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.

In order to increase the refractive index, introduction of halogen atoms such as bromine, sulfur atoms, and aromatic compounds into monomer molecules is being studied. Above all, the method of introducing a sulfur atom is effective in terms of improving the refractive index while maintaining high optical properties such as Abbe number and weather resistance, and has been vigorously studied. For example, poly A sulfur-containing polyurethane resin comprising isocyanate and polythiol is known. JP-A-63_46213 discloses a lens comprising a polymer of a polymercapto compound and a xylidenediisocyanate compound. A lens made of a polymer of 1,2-bis ((2-mercaptoethyl (thio) -13-mercaptopropane and a polyisocyanate compound), and a polythio (methacrylate) resin (JP 64-26613, JP-B 64-3-1759), or a sulfur-containing poly (meth) acrylate resin, a resin composed of a sulfide compound (Japanese Patent Application Laid-Open No. 9-110979), and the like have also been proposed.

 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.

 Further, 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. Furthermore, in order to achieve a high refractive index, it is necessary to use a polymercapto compound having a high sulfur content. However, 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. For example, in Koburi processing to match the shape of the lens to the spectacle frame, 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.

 On the other hand, adamantane derivatives have attracted attention in various fields because of their unique structures of being non-aromatic and rigid. For example, Japanese Patent Application Laid-Open No. 63-1000 377 discloses diaryl adamantane dicarboxylate, and Japanese Patent Application Laid-Open No. 63-078444 discloses adamantyl di (meth) atalylate derivative. However, 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. As a result, 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

 (b) at least one polymerizable functional group

 (c) at least one sulfur atom

And a polymer containing polymerized units based on a polymerizable sulfur-containing adamantane compound having the following formula:

 By using such a polymerizable sulfur-containing adamantane compound as a monomer, 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. BEST MODE FOR CARRYING OUT THE INVENTION

 As described above, 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. When 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.

Furthermore, in order to obtain a polymer having an excellent balance between heat resistance and impact resistance, 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 Δ / ヽ. Further, 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. In the case of a polyaddition functional group, it is preferable that the polymerizable sulfur-containing adamantane compound contains two or more polyaddition functional groups. In the case of a radical polymerizable functional group, the number may be one or plural.

 As the polyaddition functional group, 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.

 As the radical polymerizable functional group, for example, an atalyloyl group or a methacryloyl group is particularly preferably used.

 Further, the polymerizable sulfur-containing adamantane compound has at least (C) in its molecule.

It has one sulfur atom. The sulfur atom may be directly bonded to the adamantane skeleton, or may be included in a part of the substituent. In particular, it is preferable that at least half of the sulfur atoms contained in the polymerizable sulfur-containing adamantane compound are directly bonded to the adamantyl group, because the odor is low during the processing such as grinding and the workability is excellent. More preferably, all the sulfur atoms are directly bonded to the adamantyl group. Specifically, for example, when 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.

 Further, 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.In particular, from the viewpoints of high refractive index, high Abbe number, high heat resistance, low odor, etc. It is desirable to use a novel polyaddition-containing sulfur-containing adamantane compound or a polymer containing a polymerized unit based on a radical-polymerizable sulfur-containing adamantane compound.

 Hereinafter, the novel polyaddition-containing sulfur-containing adamantane compound and its polymerization, and the novel radically polymerizable sulfur-containing adamantane compound and its polymerization will be described in more detail.

Polyadditive 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"). Functional group on the side to be added. This is caused by addition to a cyclic group containing a hetero atom or a group containing a double bond (hereinafter referred to as a functional group to be added). The functional group on the side to be added is a cyclic group containing a hetero atom. In the case of the group (1), 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. And 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. Among the polyaddition functional groups of the polymerizable sulfur-containing adamantane compound in the present invention, mercapto is preferred because of its good reactivity, and a polymer having excellent optical properties can be easily obtained. Particularly preferred are a group, a hydroxyl group, an episulfide group, an epoxy group, or a (thio) isocyanate group.

 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.

These 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”). Below, the hetero atom and the organic residue may be collectively referred to as “organic residue”. In addition, the 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.

 When a plurality of groups having a polyaddition functional group are bonded to the adamantyl group, 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. Examples of 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).

Further, 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. By using such a compound, the obtained polymer has an adamantane skeleton (adamantyl group) in the main chain, and thus, heat resistance, optical properties and the like can be further improved. 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.

 Further, 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. Absent. Examples of the other 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. Among them, from the viewpoint of easiness of synthesis, 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. By having a sulfur atom, 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.

 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. When it is present or when it is present in another substituent, 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)

(Where Z is the following general formula (2)

(Wherein, 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, and s represents 0 or 1, t is an integer of 0 to 3, and when t is 2 or 3, the groups represented by (-[X] _s -R2--) may be the same or different.)

Wherein 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.

As described above, Z is a group represented by the following general formula (2) and a group having a polyaddition functional group R ³ .

 Specific examples of the polyaddition functional group are 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.

In the case of t force S 1 to 3, the polyaddition functional group is bonded to the adamantyl group via a group represented by (1- [X] _s —R ² —) _t .

In the group represented by (([X] _s —R ² —)), 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. Examples of 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. Is an alkylene group having 1 to 6 (preferably 1 to 4); a cycloanolylene group having 4 to 12 carbon atoms constituting a ring such as a cyclohexylene group or a cyclopentylene group; a phenylene group, Examples thereof include arylene groups having 6 to 12 carbon atoms, which constitute a ring such as a methylphenylene group and a naphthylene group.

In addition, 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. Groups; 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; and aromatic heterocyclic groups having 4 to 10 carbon atoms, such as a phenyl group, a furyl group, and a benzothienyl group. When a halogen atom is used as a substituent, 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. And 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.

In the above general formula (2), 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}. In this case, 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.

Specific examples of preferred groups Z represented by the general formula (2) are as follows. It is as follows.

 (i) When t is 0: Same as the polyaddition functional group described above.

 (ii) 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.

 (iii-1) t force where S 1 and s are 1 and X is a sulfur atom: a group having a mercapto group as a polyaddition functional group such as a mercaptomethylthio group or a 2-mercaptoethylthio group; a hydroxymethylthio group A group having a hydroxyl group such as 1,2-hydroxyethylthio group as a polyaddition functional group; and a polyaddition functional group having an isocyanate group such as isocyanatomethylthio group and 2-isocyanatomethylthio group. A group having a thioisocyanato group as a polyaddition functional group such as a thioisocyanatomethylthio group or a 2-thioisocyanatomethylthio group; a β-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; And a group having a Amino groups, such as thioether group as polyaddition functional groups.

(iii-2) When t force is 1, s is 1 and 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. Group having an ebisulphide group such as β-epitipropyloxy group, γ-epipityptyloxy group as a polyaddition functional group; Groups having a carboxyl group as a polyaddition functional group, such as a propyloxymethyloxy group or a 3-carboxypropyloxy group, groups having an amino group, such as an aminomethyloxy group, as a polyaddition functional group, etc. .

 (iv) When t is 2 or more: 2- (2-mercaptoethylthio) ethylthio group, 4- (2-mercaptoethylthio) phenylthio group, 2- [2- (4-menoleptophenylphenylthio) A) a group having a mercapto group as a polyaddition functional group, such as an ethylthio group, an ethylthio group, a 2- [2- (4mercapto-2,6-dibromophenylthio) ethylthio group, or a 2- (2mercaptoethylthio) ethyloxy group; A group having a hydroxyl group as a polyaddition functional group such as a 2- (hydroxymethylthio) ethylthio group or a 2- (hydroxyethyloxy) ethylthio group; an isocyanate such as a 2- (2-isocyanatoethylthio) methyl group; A group having a thioisocyanate group such as a 2_ (2-thioisocyanatoethylthio) methyl group as a polyaddition functional group; (2-aminoethyl) And a group having a carboxyl group such as 2 _ (carboxymethyl thio) Echiru group as polyaddition functional group; e) having a amino group as polyaddition functional groups groups such as a methyl group.

Among these groups, 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.

Specific examples of 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 β-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. .

In the general formula (1), a is an integer of 2 to 4, that is, 2 to 4 groups represented by Z are bonded to the adamantyl group. When a is 2 to 4, the synthesis becomes easy. 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 η-pentyl group, an isopentyl group. Linear or branched such as a group, η-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.

When there are a plurality of R ¹ (when b is 2 to 4), they may be the same or different. The polymerizable sulfur-containing adamantane compound represented by the general formula (1) contains at least one sulfur atom. As described above, 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. even if it exists as an atom that constitutes (1 [X] _s —R ² —) _t (when X is a sulfur atom) Or it may be present as an atom constituting R ¹ in the form of an acylthio group or the like, and these existing forms may be mixed.

 Among the polymerizable sulfur-containing adamantane compounds represented by the general formula (1), particularly preferable compounds are shown below in view of easiness of synthesis and obtained optical properties.

 (A) A compound represented by the following general formula (3).

[Wherein, 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, and b is 0 to 4 Where c is an integer between 0 and 3, c + d is between 2 and 4, and c :! In the case of 33, R ⁴ is a mercapto group. ]

 In the above general formula (3), 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. Among the compounds represented by the above formula (3), compounds having d of 2 to 4 are more preferable.

Specific examples of the 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 thioisocyanate group, 1,3-adamantane dithioisocyanate, 1,3,5-adamantane trithioisocyanate, 2,4-di- Propyl adamantane 1, 3 One DOO such dithio isocyanurate Na and the like.

 When 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. Or 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. Can be obtained.

 The following is a more specific description of such a manufacturing method.

 (i) Production method from compound having halogen atom (Production method A)

—As a method for obtaining 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.

 In these reactions, hydrogen halide is generated with the progress of the reaction, and therefore, the reaction is generally performed in the presence of a basic compound that captures the hydrogen halide. Examples of 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.

 In the above reaction, since the halogenated adamantane compound and the thiocyanating agent are usually solid, it is preferable to use a solvent. Preferred examples of 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. When the reaction is performed at a temperature equal to or higher than the boiling point of the solvent, it is preferable to use a pressure reactor such as an autoclave. (ii) Production method from compound having hydroxyl group (Production method B)

 Other methods for obtaining a compound having a mercapto group as a polyaddition functional group represented by the general formula (3) include 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. These reaction conditions are not particularly limited, but general reaction conditions are as follows.

 That is, one or more equivalents of a thiation agent are reacted with adamantyl alcohol and a hydroxyl group of the adamantyl alcohol which is to be converted into a mercapto group. In this case, 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. Examples of 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.

 In the above reaction, when the adamantyl alcohol or the thiating agent is a solid and the acidic compound used is also a solid, or even when the acidic compound is a liquid, the acidic compound of the adamantyl alcohol or the thiating agent is used. When the solubility in is low, it is preferable to use a solvent. Preferred examples of the 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. And hydrocarbon solvents such as benzene, toluene and xylene. These solvents may be appropriately selected depending on the type of alcohol compound or acidic compound used in the reaction.

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. When the reaction is carried out at a temperature equal to or higher than the boiling point of the solvent, it is preferable to use a pressure reactor such as an autoclave. In addition, depending on the raw materials used, 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.

 By performing the above reaction, the adamantyl alcohol and the thiocyanating agent form a salt. Subsequently, by heating and stirring the reaction mixture in the presence of a basic compound, the salt is decomposed to give the desired compound. It is a polymerizable sulfur-containing adamantane compound. Examples of 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. Alkali metal salts of alcohols; organic bases such as triethylamine, pyridine and quinoline. 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.

 Also, by controlling the amount of the thialating agent used in the reaction and the amount of the acidic compound serving as a catalyst, the reaction time, and the reaction temperature, a part of the hydroxyl groups is made unreacted, thereby obtaining a compound containing both a mercapto group and a hydroxyl group. I can do it.

When 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. When 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.

 (iii) Method for producing a compound having a thioisocyanate group (Production method C) 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 (hereinafter, aminated adamantane compound) 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. Examples of 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.

In the above reaction, it is generally preferable to use a solvent in order to increase the solubility of the basic compound. Examples of 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. be able to. These solvents may be appropriately selected depending on the type of aminated adamantane compound or basic compound used in the reaction.

 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.

 In general, it is preferable to use the obtained dithiorbamate in an unpurified state because it can be used in the next reaction without purification or unpurified after purification.

In order to convert dithiocarbamate to an adamantane compound having an isocyanate group, 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. Examples of the alkynole chloroformate include, for example, methyl chloroformate, ethynolechlorohonolemate, propinolechlorofosolemate, isopropinolechloroformate, butyl chloroformate and the like. In the above reaction, when the crude dithiocarbamate is reacted without purification, it is not particularly necessary to add a solvent. However, when the crude dithiocarbamate is reacted after purification, it is preferable to use a solvent. Preferred examples of 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.

 In the method of reacting dithiol rubbamate with an alkyl chloroformate or phosgene and then thermally decomposing the reaction, first, 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.

 When employing a method of performing thermal decomposition while reacting, the reaction may be performed at a temperature of 70 to 120 ° C.

When the polymerizable sulfur-containing adamantane compound having a thioisocyanate group has R ¹ as a substituent, the method of introducing the same is the same as that for a compound having a mercapto group.

 (B) A conjugated product represented by the following general formula (4).

[In the above formulas, neither RR ^2, b and X, RR ² in the general formula (1), b, have the same meanings as X, d is:! Represents an integer of 44, c represents an integer of 0、3, d + c is an integer of 2〜4, u represents 1 and V represents 1 or 2. When V is 2, the groups represented by (-[X] _u —R ² —) may be the same or different, and the group represented by R ¹ and {(— [X ] _u — R2—) _v — SH} Each of them may be the same or different when there are a plurality of them. ]

 In the above general formula (4), 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. In addition, 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.

 Among the compounds represented by the general formula (4), a compound in which V is 1 is more preferable from the viewpoint of ease of synthesis.

Specific examples of the 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-mercaptoethylthio) l-l-l-l-ol; 3-bis (2-mercaptoethyloxy) Compounds where X is all oxygen atoms, such as damantane, 1,3,5-tris (2-mercaptoethyloxy) adamantane, 1,3,5,7-tetrakis (2-mercaptoethyloxy) adamantane; 1 , 3-bis [2-((2-mercaptoethyloxy) ethylthio] adamantane, 1,3,5-tris [2- (2- (2-mercaptoethyloxy) ethylthio] ethylthio] adamantane, 1,3,5-tris [2- (2-Mercaptoethyloxy) ethylthio] adamantane, 3- (2-mercaptoethyloxy) 1,2,2-dimethinoreaadamantane, 1,1-ol, 1,3-bis [2- (2-mercaptoethyloxy) ethyloxy] adamantane, 1,3,5 —Tris [2- (2-mercaptoethyloxy) ethylamoxy] adamantane, 1,3,5-tris [2- (2-mercaptoethyloxy) ethylamoxy] X such as adamantane is an oxygen atom and a sulfur atom in both directions. And the like.

 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. Here, 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. Further, in place of the dimercapto compound in the above (ii), 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.

Also in this case, when R ¹ is present, the method of introducing R ¹ is represented by general formula (3). Same as for compounds.

 In addition, 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.

Still other fabrication methods, as polyaddition functional group of the general formula (5) Chi sac compound represented by R ⁵ described below, using a compound having a hydroxyl group, according to the hydroxyl groups on the production method B And converting to a mercapto group.

 (C) A compound represented by the following general formula (5).

[Wherein, RR ² , b and X have the same meanings as RRX in the general formula (1), R ⁵ represents a hydroxyl group, a carboxyl group or an amino group, and 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, and the product of d and V is 2 or more (dXv≥2 ). When V is 2, the groups represented by (-[X] _u — R ² —) may be the same or different, and the group represented by R ¹ and {(— [X] _When there are a plurality of groups represented by _u — R ^2- ) vR ⁵ }, 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 .

Specific examples of the polymerizable sulfur-containing adamantane compound represented by the above general formula (5) 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. Compound having only a hydroxyl group as a polyaddition functional group; having a carboxyl group as a polyaddition functional group such as 1,3-bis (carboxymethylthio) adamantane and 1,3-bis (3-carboxypropylthio) adamantane. 1,3-bis (aminomethylthio) adamantane, 1,3-bis (2-aminoethylthio) adamantane, 1,3-bis (2-aminoethylthio) 1.5,7-dimethyladamantane Compounds having an amino group as a polyaddition functional group are exemplified. Among these, compounds in which d is 2 to 4 in the general formula (5) are more preferable. Further, a compound having only a hydroxyl group as a polyaddition functional group is preferable from the viewpoint of physical properties as an optical material and ease of synthesis.

 As a method of synthesizing a compound having an amino group among the compounds represented by the general formula (5), generally, in the production method B described for the compound represented by the general formula (3), (i) ) A compound having a mercapto group and an amino group or a protected amino group (hereinafter, referred to as a mercapto group-containing amino compound) instead of the thiazide, and (ii) a basic disulfide compound for salt decomposition. (A) When a compound having an amino group is used, neutralize the acidic compound used in the reaction with a basic compound instead of heating and stirring the reaction mixture in the presence of a compound. (B) When a compound having a protected amino group is used, adamantyl alcohol is used as a raw material except that the amino group is generated using a deprotecting agent such as an acid or a base compound. Used as well Method can be used.

Specific examples of the mercapto group-containing amino compound 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. Are exemplified. 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.

 As 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) In the production method of the present invention, 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.

 In the case of a compound having a hydroxyl group, in the method for producing a compound having an amino group among the compounds represented by the above general formula (5), a hydroxyl group or a protected hydroxyl group is used in place of the amino compound having a mercapto group. And a mercapto group-containing compound (hereinafter, referred to as a mercapto group-containing alcohol) or a diolic compound having a thioether bond.

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.

 In any of the above methods, (a) when the acidic compound is neutralized, 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. (b) When deprotecting a compound having a protected group, a known deprotection method may be used. May be appropriately adopted.

 (D) a compound represented by the following general formula (6)

[In the above formula, all of ¹ , R ² , a, b and X have the same meanings as RR ² , a, b and X in the general formula (1), and R ⁶ is an epoxy group or an isocyanate. Represents a thioisocyanate group, a thioisocyanate group or a no or episulfide group, u represents 1 and V represents 1 or 2. When V is 2, the groups represented by (-[X] _u — R ² —) may be the same or different, and the group represented by R ¹ and {(— [X] _u — R 2

-) In the case where there are a plurality of groups represented by v-R ⁶ }, they may be the same or different, and have at least two sulfur atoms in the molecule. ]

 In the above general formula (6), the polymerizable sulfur-containing adamantane compound has an epoxy group, an isocyanate group, a thioisocyanate group and a

It has 2 to 4 Z or ebisulphide groups. 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.

 Specific examples of 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) isocyanate group as a polyaddition functional group such as adamantan 1,3-bis (thioisocyanatomethylthio) adamantane, 1,3-bis (2-thioisocyanatoethylthio) adamantane, 1,3-bis (2-thioisocyanatopropylthio) adamantane, 1,3 —Bis (2-thioisocyanatopropylthio) 1-5-methyladamantane, 1,3,5-tris (thioisocyanatomethylthio) adamantane, 1,3,5-tris (2-thioisocyanatoethylthio) adamantane Compounds having a thioisocyanate group as an additional functional group, 1,3-bis (] 3-epitipropylpropyl) adamantane, 1,3,5-tris (] 3-epitipropylthio) adamantane, etc. Are exemplified.

 The polymerizable sulfur-containing adamantane compound represented by the general formula (6) can be generally produced by the following method.

In the case of a conjugate having an epoxy group as a polyaddition functional group, examples thereof include an adamantane compound having a mercapto group represented by the general formula (3) or (4) and epichlorohydrin. Epiha mouth hydrin in the presence of al force It is obtained by reacting.

 In the method, 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. Examples of 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.

 Further, as another method for producing an epoxy compound, 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.

In addition, in the case of a compound having an episulfide group as a polyaddition functional group, 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.

 When a thiocyanate is used as a thiocyanate in the above method for producing an episulfide compound from a compound having an epoxy 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.

Specific examples of 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. In addition, 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. Specific examples of 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. Some of these can be used in combination. 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. Specific examples of 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.

 As a method for synthesizing a compound having an isocyanate group, for example, among the polymerizable sulfur-containing adamantane compounds represented by the general formula (5), the polyaddition functional group is a carboxyl group. , And 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. Thus, 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.

First, 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. As the 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. 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.

 Next, the obtained ester derivative is reacted with hydrazine hydrate to obtain a hydrazinocarbonyl derivative. 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. At this time, as 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.

 Next, 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. As the 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. Next, 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.

In the case of a compound having a thioisocyanate group as a heavy functional group, the thioisocyanate group is introduced in the same manner as described for the compound represented by the general formula (4). Can be manufactured. In this case, 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).

 Among the compounds represented by the above general formula (6), 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. And / or compounds having an episulphide group are preferred.

 (E) a compound represented by the following general formula (7) or (8)

[Wherein, 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 ⁸ ) ~ R ⁹ } _a (8)

[Wherein, 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. Compounds having a thioisocyanate group as a polyaddition functional group; 1,3-bis (; 3-epitipropylthiomethyl) adamantane, 1,3,5-to Scan compounds having a E pin Surufi de group as polyaddition functional group such as (over E Pichi O propyl thio methyl) Adamantan are specifically exemplified.

In the compound represented by the above general formula (7), 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). Here, 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. For example, 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.

 Further, among the compounds represented by the general formula (8), 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).

 Further, among the compounds represented by the general formula (8), 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, In the same manner as in the method for producing the compound represented by the general formula (6), 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.

 Among the compounds represented by the above general formulas (7) and (8), compounds having w of 0 or 1 are more preferable from the viewpoint of physical properties when used as an optical material and ease of synthesis.

(F) a compound represented by the following general formula (9) or (10) 0)

[In the above formula,! ^, 3, b and X have the same meanings as R a and b in the general formula (1), and R ⁷ and R ⁸ each independently have the same meaning as R ² in the general formula (1). R ^1D represents an epoxy group or an isocyanate group, u represents 1, X represents 1 or 2. Also, when X is 2, (an ^{_{[X] u - R 8 -}} ) group may each be the same or different as indicated by the further and groups represented by R ¹ {- R ⁷ - ( one [X] _U -R ⁸ -) 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. ]

[In the above formula,! ^, 3, b and X have the same meanings as R ¹ a and b in the general formula (1), and R ⁷ and R ⁸ each independently have the same meaning as R ² in the general formula (1). R ¹¹ represents a hydroxyl group, an amino group or a carboxyl group, u represents 1, and X represents 1 or 2. Also, when X is 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.

 Specific examples of 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] adamantane, 1,3,5-tris [4-1 (isocyanatomethyl) Examples of the polyaddition functional group having an isocyanate group as a polyaddition functional group, such as ruthio) pheninole] adamantane and 2,2-bis [4-1 (2-isocyanate-tetinorethio) phenyl] adamantane, are exemplified. .

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. Compound having an amino group as a 1 "biofunctional group; 1,3-bis (hydroxymethylthiomethyl) adamantane, 1,3-bis [2- (2-hydroxydecynolethio) ech / re] adamantane, 1,3-bis (2-hydroxyethynolethio) Hydroxyl group as a polyaddition functional group such as 1,7-dimethinorea adamantane, 1,3-bis (2-hide mouth chelethyldithiomethyl) adamantane 1,3-bis (carboxylmethylthiomethyl) adamantane, 1,3-bis [2- (2-carboxylethylthio) ethyl] adamantane, 1,3-bis (2-carboxylethylthiomethyl) Examples thereof include compounds having a carboxyl group as a polyaddition functional group such as 1,5,7-dimethyladamantane and 1,3-bis (2-carboxylethyldithiomethyl) adamantane. 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. In this case, 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.

 As 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. In this case, 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.

Further, 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. For example, when a purification operation or a decolorization operation does not need to be performed because the reaction yield is high, 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.

 (i) By measuring the 1H-nuclear magnetic resonance spectrum (1H-NMR), the bonding mode of hydrogen atoms present in the compound can be known.

(ii) The characteristic absorption of each compound can be observed by measuring the infrared absorption spectrum (IR). For example in general, in the case of compounds having a hydroxyl group, absorption based on OH stretching vibration in the vicinity of 3,500-3,650 cm- ^1, in the case of compounds having a mercapto group rather based on SH stretching vibration 2550~ 2600 c π ¹ Weak absorption, 2040-21 30 cm for compounds with thioisocyanate group-Strong absorption based on NCS stretching vibration in the vicinity of ^1, 1700-1750 cm for a compound with an acylthio or acyloxy group - ¹ near the C = 0 stretching vibration strong absorption based on dynamic, strong absorption based on C = 0 stretching vibration near 2990~ 3050 cm one ¹ if having an epoxy group, 5 70 in the case of having a sulfide group Strong absorption based on the stretching vibration of CS is observed around 710 cm- ¹ .

 (iii) By elemental analysis, each weight% of carbon, hydrogen, sulfur, and other elements (nitrogen, halogen) can be determined, and the composition formula of the monomer can be determined.

 (iv) The molecular weight of a compound can be determined by mass spectrometry (MAS S, EI method).

The polymerization represented by the above general formulas (3) to (10)! "Among the raw sulfur-containing adamantane compounds, compounds represented by the general formulas (3), (4) and (6) are particularly preferable in that they are easy to synthesize and can obtain a powerful polyaddition reactivity. Polyaddition reaction of polyadditive sulfur-containing adamantane compound

 The polymerizable sulfur-containing adamantane compound obtained by the above method is converted into a polymer by a polyaddition reaction. In the polyaddition reaction, as described above, 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. On the other hand, when 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.) are generated, and 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.

 First, the case where the polyaddition functional group is a group other than a cyclic group containing a hetero atom will be described.

In this case, 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. Considering the cost of the compound to be a coalescing raw material, various optical properties such as Abbe number and refractive index of the obtained optical material, and mechanical properties such as impact resistance, 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). Examples of the 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. As the comonomer, known compounds having a polyaddition functional group as described above can be used without limitation.

 Considering various optical physical properties such as the Abbe number and refractive index of the obtained optical material, and mechanical physical properties such as impact resistance, the total carbon number is 1 to 30 and 2 to 6 polyaddition functional groups. Comonomers having a group are preferred.

Specific examples of such comonomers include 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 ester), 2,3-dimercaptocoha Acid (2-mercaptoethyl ester), 2,3-dimercapto-11-propanol (2-mercaptoacetate), 2,3-dimercapto-11-propanol (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate) 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) 1,3-bis (1,2-dimercaptopropyl) methyl ether, bis (2-mercaptopropyl) (Tinole) ether, ethylene glycol monolevis (2-menolecaptoacetate), ethylene glycolonelevis (3-menolecaptopropionate), trimethylolpropanebis (2-mercaptoacetate), trimethylolpropanebis (3 —Mercaptopropionate), Suritol Tetrakis (2-mercaptoacetate), Pentaeryth Litoltetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -1,3-mercaptopropane, 4,8-bis (mercaptomethyl) 13,6,9-trithia-1 1 Aliphatic polythiols such as 1,1,1-decanedithiol; 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimenolecaptobenzene, 1,2-bis (mercaptomethinole) Benzene, 1,3-bis (menolecaptomethinole) Benzene, 1,4-bis (menolecaptomethinole) benzene, 1,2-bis (menolecaptoethylenole) benzene, 1,4-bis (mercaptoethylene) Xi) Benzene, 1,2,3-trimercaptobenzene, 1,2,4-trime / lecaptobenzene, 1,3,5-trimenolecaptobenzene, 1,2,3-tris (mel Captomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,2,4 tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-to Lis (menolecaptoethyleneoxy) benzene, 1,2,4 Tris (menolecaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 1, 2, 3, 4 -Tetramercaptobenzene, 1,2,3,5-tetrakis (menolecaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (menolecaptomethyleneoxy) benzene, 1,2,3 4-tetrakis (mercaptoethyleneoxy) benzene, 2,4-dimethinolebenzene-1,1,3-dithiole, 4,5 dimethinolebenzene-1,1,3-dithiol, 9,10-anne Hexadimethanethiol, 1,3-di (p-methoxyphenole) Propane 1,2,2-dithiol, 1,3-diphenylenopropane 2,2-dithiole, feninolemethane 1,1,1 Aromatic polythiols such as dithio-mono, 2,4-di (p-mercaptophenyl) pentane; 2-methylamino-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-1,4,6 —Dithiophenol s vm—Triazine, 2-Thiptinoleoxy 4,6 Dithiono ls ym-triazine, 2,5-bis (mercaptomethyl) polythiols containing heterocycles such as 1,1,4-dithiane; 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) Benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis ( Mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis ( Aromatic polythiols containing sulfur atoms in addition to mercapto groups such as mercaptoethylthio) benzene and their alkylated nuclei; (Captomethinole) sulfide, bis (mercaptoethyl) sulfide, bis (menolecaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) Methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, 1,3-bis (mercaptomethylthio) ethane ) Propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) propane, 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) Bread, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5 —Dimercapto-1,4-dithiane, etc., and their esters of thioglycolic acid and mercaptopropionic acid; hydroxymethylsulfidobis (2-mercaptoacetate), hydroxy Methyl sulfidobis (3-mercaptopropionate), hydroxyxetyl sulfidobis (2-mercaptoacetate), hydroxyxethylsulfone sulfide (3-mercaptopropionate), hydroxypropyl sulfidobis (2-me (Captoacetate), hydroxypropylsulfidobis (3-mercaptopropionate), 2-mercaptoethyl etherolevis (2-methylolcaptoacetate), 21-mercaptoethyl ether terbis (3- Mercaptopropionate), 1,4-dithiane-1,2,5-diolbis (2-mercaptoacetate), 1,4-dithiane-1,2,5-diolbis (3-mercaptopropionate), bis-thioglycolate (2-mercapto) Ethyl ester), bis thiodipropionate (2-meth Captoethyl ester), bis 4-thiodibutyrate (2-mercaptoethyl ester), bis dithiodiglycolate (2-mercaptoethyl ester), bis dithiodipropionate (2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolate bis (2,3-dimercaptopropyl ester), bis-thiodipropionate bis (2,3-dimercaptopropyl ester), Aliphatic polythiols containing a sulfur atom in addition to a mercapto group, such as bis (2,3-dimercaptopropyl ester) dithioglycolate and bis (2,3-dimercaptopropyl ester) dithiodipropionate; Thiophenedithiol, 2,5-dimercapto-11,3,4-mercapto groups such as thiadiazole Heterocyclic compounds containing an external sulfur atom; polycarboxylic acids such as maleic acid, fumaric acid, phthalic acid, trimellitic acid, and pyromellitic acid; 1,2-diaminoprop, 1,3-diaminopropane, 2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,2-bis (3-aminopropoxy) ethane Primary polyamines such as ；, Ν, ジ ェ -ethylethylenedi N, N '—Jetyl_1,2-Diaminopropane, N, N'—Jethyl 1,3-Diaminopropane, Piperazine, 2-Methylbiperazine, 2,5—or 2,6-Dimethylpiperazine, 1 Secondary polyamines such as, 2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidinole) propane, 1,4-di (4-piperidyl) butane, tetramethyldanidine And the like. These comonomers may be used alone or in combination of two or more.

 Among the above comonomers, compounds having a plurality of mercapto groups (each polythiols) are preferable, and 2,2-bis (mercaptomethyl) -1,1,3-propanedithiol and 1,2-bis (2-mercaptoethyl) are preferred. Ruthio) 1-3-mercaptopropane, 4,8-bis (mercaptomethyl) 1,3,6,9-trithia1-1,11-onedecanedithiol, 1,2,4-tris (mercaptomethyl) benzene Particularly preferred compounds of the formula

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). ) Isocyanate, p-xylylene di (thio) isocyanate, a, a, a ', a-tetramethyl-p-xylylene di (thio) isocyanate, a, a, α', a'-tetramethylolene m-xysilylene (Cho) isocyanate, 1,3,5-tris [(thio) isocyanatomethyl] 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-ethyl-m-xylylene di (thio) isocyanate; isophorone Di (thio) isocyanate, norbornene di (thio) isocyanate, bis [(thio) isocyanatomethyl] norbornene, methylenebis [cyclohexyl (thio) isocyanato], bis [(thio) isocyanatomethyl] Monocyclic or polycyclic (thio) isocyanate such as cyclohexane; a sulfur-containing ring such as 1,3-dithiolane 1,4,5-di (thio) isocyanate (thio) isocyanates 4,5-bis [(thio) isocyanato-methyl] 1,1,3-dithiolane, tris [(thio) isocyanato-methylthio] methane, aliphatic (thio) isocyanate such as hexamethylenedi (thio) isocyanate And the like. Further, oligomers such as a buret form and an afloat form of these (thio) isocyanates may be mentioned.

 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.

In order to obtain a polymer from the comonomer as described above and the polymerizable sulfur-containing adamantane compound of the present invention, usually, the side to which the polyaddition functional group of the polymerizable sulfur-containing adamantane compound of the present invention is added. Group, the polyaddition functional group of the comonomer is the group to be added, and conversely, the polymerizable sulfur-containing adamantane compound. In the case where 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.

 As described above, 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. Further, if necessary, 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.

 These 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.

In addition, in view of particularly excellent polymerizability, 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.

 Further, as described above, in order to obtain a polymer having an excellent balance between heat resistance and impact resistance, 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%. In general, the higher the AD ratio, the higher the heat resistance, and the lower the AD ratio, the more excellent the impact resistance. To achieve such a range, 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.

It is preferable to polymerize in the range of 5 to 3.

 Furthermore, 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.

 Further, in addition to the sulfur-containing polyadditive adamantane compound and the comonomer, various monomers polymerized by other polymerization methods may be appropriately blended.

Further, if necessary, 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. Further, a catalyst for improving the polymerization reactivity may be used as appropriate.For example, organic peroxides, azo compounds and basic catalysts are effective for improving the reactivity between the mercapto group and the ether group. 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 may be added within a known range. Generally, 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.

As an example, a manufacturing method when the polymer is an optical material such as an eyeglass lens will be described. 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. Then 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 In order to facilitate removal of the mold, 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.

 Next, the case where the polyaddition functional group is a cyclic group containing a hetero atom will be described.

 As described above, when 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. Examples of 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. Specific examples include n-propynoleamine, n-butylamine, benzylamine, dihexylamine 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. In this case, the polyamines / polycarboxylic acids are incorporated into the polymer and also serve as a unit constituting the polymer. In such a case, the compounding amount may be larger than the range used as the curing catalyst.

 Further, as the compound having a cyclic group having a hetero atom, 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. As such a compound, various known epoxy compounds and episulfide compounds may be used.

 Furthermore, the 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.

Also in these cases, 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.

 In this case, if necessary, 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.

 Producing a polymer from the polymerizable sulfur-containing adamantane compound of the present invention having a cyclic group having a hetero atom as described above as a polyaddition functional group, and other components which are combined as required. The method for producing the polymer is not particularly limited, and a known method for producing a polyaddition-type polymer may be appropriately employed.

 As an example, 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).

{Wherein, R ¹ represents an alkyl group having 1 to 6 carbon atoms, and Z ¹ represents the following formula (Π)

One (X ¹ ) _e — (R ² — X ² ) _f — Υ ¹ (Π) (Wherein, 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 (ΙΠ)

One (X ³ ) _g- (R ³ -X ⁴ ) _h — Υ ² (ΙΠ)

(Wherein, 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, and 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, and in the case of h force S 2 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)

― (X ⁵ ) “(R ⁴ — X ⁶ )” H (IV)

(Wherein, 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 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.)

Wherein a is an integer of 1 to 4, b is an integer of 0 to 3, c is an integer of 0 to 3 (伹, a + b + c is 1 to 4), d represents an integer of 0 to 4, RZ ¹及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 (タ ン)

-(X ¹ ) _e- (R ² -X ² ) fY ¹ (Π)

(Wherein, 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, and when f is 2 to 6, (R ² — The groups represented by X ² ) may be the same or different, and e + f is 1 or more. )

Having ¹ to 4 substituents Z ¹ having a (meth) acryloyl group (a is 1 to 4). The (meth) atalyloyl group Y ¹ of the substituent Z ¹ is a radically polymerizable group, whereby the compound becomes a radically polymerizable compound. R ² in the above formula (Π) 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. And 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. An aromatic heterocyclic group having 4 to 10 carbon atoms, such as a phenyl group, a furyl group or a benzophenyl group; a hydroxyl group; a nitro group; a cyano group.

 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.

Among these 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.

In the above formula (Π), 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. You. That is, since at least one of e and f is not 0, 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.

On the other hand, when f is an integer of 1 to 6, 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 — When f is 2 to 6, the groups represented by (R ² — X ² ) may be the same or different. For each repeating (R ² — X ² ) unit, 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.

In the Z ^1, in that the resulting high refractive index is preferably X ¹ and X ² are both sulfur atom. In addition, 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. Further, e is preferably 1 in terms of easiness of synthesis and stability.

Although 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.

Radically polymerizable Adamantan compounds of the present invention, in addition to the group having a (meth) Atariroiru group represented by Z ^1, represented by Z ^2, Z ³ and R ^1, have a (meth) § click acryloyl group Unsubstituted groups may be attached to the adamantane skeleton.

z ² is the following formula (m)

One (X ³ ) _g- (R ³ -X ⁴ ) _h -Υ ² (ΙΠ)

(Wherein, 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, and Y ² represents a carbon atom other than a (meth) atalyloyl group) Represents an acyl group having a prime number of 2 to 7, g is 0 or 1, h is an integer of 0 to 6, and when h is 2 to 6, the groups represented by (R ³ — X ⁴ ) are the same or different And g + h is 1 or more.)

Is a group represented by

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. Further, 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.

Z ³ is the following formula (IV)

One (X ⁵ ) “(R ⁴ -X ⁶ ) j—H (IV)

(Wherein, 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.

In the above formula, R ⁴ is a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms.Specifically, 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.

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 -} υ - (R ⁴ - O) One H.

In the Z ^3, for ease of synthesis,; i is laid preferred that 0-4, more preferably 0-2, particularly preferably 0.

These Z 2 ²及Pi sigma ³ is 1 to four in total present in the molecule.

Furthermore, (in Zeta ^3, ends unless become main mercapto group) Χ ¹ ~Χ Both ^Θ 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. In this case, for example, when there are a plurality of atoms represented by X ² (when f is 2 to 6, when a is 2 to 4, etc.), 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.

In the general formula (I), 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.

In the radically polymerizable adamantane compound of the present invention, 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.

Further, considering the ease of synthesis, the heat resistance of the obtained polymer, the Abbe number, etc., among the compounds represented by the general formula (I), the following formula (V)

(Wherein, 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, and 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).

Are preferred.

In the above formula, 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 .

There are 2 to 4 groups represented by {(X ¹ ) _e — (R ⁷ —S) _m — Y ¹ } in the compound (o is 2 to 4), and these may be the same or different However, in consideration of the ease of synthesis, all groups are the same, or R ⁷ , Y \ e and m are the same, and only X ¹ is different (only when e is 1). Is preferred. Incidentally m is an integer from 0 to 2, when m is 2, one ^{_{{(X e - (R 7}} -S) 2 one Y ^1} 2 single R ⁷ present in the well at each same It may be different. In the above formula (V), 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 η are the same. , X ³ are preferably different (but only when g is 1).

Further, the group represented by {(X ¹ ) _e — (R ⁷ — S) m—Y ¹ } and {(X ³ ) _g —

(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.

Considering the ease of synthesis, the refractive index of the obtained polymer, the Abbe number, and the heat resistance, 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.

Although 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. In some cases, it may be simply referred to as 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. At this time, 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. . In a compound having both a hydroxyl group and a mercapto group, since the mercapto group is substituted first, 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.

 The 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. Instead of the acid halide, a known ester synthesis method such as acylation with an acid anhydride or a transesterification reaction using an acid ester can also be employed.

 When an acid halide is used, hydrogen halide is generated with the progress of the reaction. Therefore, the reaction is generally performed in the presence of a basic compound that captures the hydrogen halide. Examples of 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.

In the reaction, it is generally preferable to use a solvent. As the solvent Examples of 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. In addition, stirring is preferably performed during the reaction.

Further, in order to prevent polymerization of the reaction product, it is desirable to carry out the reaction by adding a polymerization inhibitor. As 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 (π), 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. As an isolation method at this time, 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. When the 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.

At this time, 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. Examples of 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.

 It is preferable to use a solvent in order to carry out the reaction in a homogeneous system. Examples of 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. Also, use 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. In addition, depending on the raw materials used, 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.

 When a salt is formed as an intermediate with the thiocyanating agent by this reaction, the salt is decomposed by heating and stirring the reaction mixture in the presence of the basic compound. An adamantane compound having a mercapto group represented by the formula: 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.

 In addition, by controlling the amount of the thiazide or the acid conjugate used as a catalyst used in the reaction, the reaction time, and the reaction temperature, only a part of the hydroxyl groups is converted to a mercapto group, and both the mercapto group and the hydroxyl group are converted. It is also possible to obtain compounds containing.

 After completion of the reaction, the solvent may be removed from the product solution, and if necessary, purified by a known method.

When 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.

Examples of the dio compound include ethylene glycol, propylene dalicol, diethylene glycol, triethylene glycol, and the like. Examples of the dimercaptoid conjugate 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.

 As the acidic compound, 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.

In this case, 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. Bye, Also, 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.

 In the above-mentioned method, 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. Polymerization of Radicanole-Polymerizable Sulfur-Containing Adamantane Compound

 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. When the radical polymerizable sulfur-containing adamantane compound of the present invention is used for such applications, 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. And other unsaturated monomers that can be copolymerized (hereinafter, also referred to as comonomers) can be used in combination to form a copolymer.

 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,

Benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) ately Rate, tetraethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, bisphenol A di (meth) acrylate, 2,2-bis (4-1 (meth) ataryloy / reoxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-14- (meth) atalyloyloxyethoxyphenyl) (meth) acrylate compounds such as propane; methylthio (meth) acrylate, phenylthio (meth) atari Rate, benzylthio (meta) Acrylate, ethanedithioldithio (meth) atarylate, benzenedithio monoresitia (meta) acrylate, xylylenedithioldithio (meth) acrylate, or other thio (meth) acrylic acid ester compound; dia Ryl phthalate, diaryl terephthalate, diaryl isophthalate, diaryl tartrate, diaryl tartrate diepoxysuccinate, diaryl malate, aryl cinnamate, arylinoisocyanurate, dichloryl chlorendate, diaryl hexaphthalate, diaryl carbonate, aryl diglycolate, etc. Aryl compounds: styrene, di-vinylinolebenzene, chlorostyrene, bromostyrene, dibutene styrene, vinylinolephthalene, isopropylinolenaphthalene, α-methinolestyrene, α-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. In addition, during polymerization, 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, α-rays, rays, γ-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.

 In this method, 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.

Among the polymerization conditions, 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.

 Since 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. In this case, 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 can be mentioned. 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

 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. Alternatively, in order to improve the fashionability or the like, 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. Further, the optical material obtained in the present invention can be easily dyed in water or a solvent using a usual disperse dye. At the time of dyeing, a carrier as a dyeing assistant may be added to the dyeing bath to further facilitate the dyeing.

The thus obtained 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.

 In addition to optical materials, it is of course possible to use it for other applications that require high heat resistance and low odor during processing. Example

 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

 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.

 'Heat resistance: 5 g of a test piece was weighted using TMA (manufactured by Seiko Epson), heated at 5 ° C for Z minutes, and the thermal deformation onset temperature was measured.

 'Weather resistance: A sample was set in a long life xenon fade meter manufactured by Suga Test Instruments Co., Ltd., and after exposure to xenon light for 100 hours, the plastic lens and the hue before the test were compared and evaluated.

 (A): Little change in hue was observed.

 (F): Hue turned yellow.

• 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.

 (B): The power to feel the odor faintly.

 (C): A substance that has an odor but does not matter in a short time.

 (D): Those with a little unpleasant odor.

 (F): Those with a bad odor. Offensive.

 Production Example 1

 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 2

 To 10 g (0.054 monole) of 3-menolecaptoadamantane and 76 g (1.0 mol) of thiourea are added 250 g of concentrated hydrochloric acid, followed by heating and stirring at 100 ° C for 15 hours. Was performed. After cooling to room temperature, 300 g of a 50% aqueous sodium hydroxide solution was added, followed by heating and stirring at 10 ° C for 2 hours. After allowing to cool to room temperature, the precipitated white solid was recrystallized from water-z methanol (weight ratio 1: 8), and 8.2 g of a white solid was isolated. Table 1 shows the elemental analysis, MAS S, 1H-NME, and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 1,3-adamantanedithiol (compound B).

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).

 Production Example 4

 5-Menolecaptoadamantane 1,1,3-Diozure 8.0 g (0.04 monole) of mercapto, followed by post-treatment at the same charge ratio and reaction conditions as in Production Example 2 As a result, 5.4 g of a white solid was isolated. Table 1 shows the elemental analysis, MASS, 1H-NMR, and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 3,5-dimercaptoadamantan-111-ol (Compound D).

 Production Example 5

 Using 10.8 g (0.04 monole) of 3,5-dimercaptoadamantane 1-one-nore at the same charge ratio and reaction conditions as in Production Example 2, mercapto-formation followed by post-treatment 5.5 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. The results of these analyzes confirmed that the isolated compound was 1,3,5-adamantanetrithiol (Compound E).

 Production Example 6

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).

 Production Example 7

 To 25 g (0.15 mol / l) of 1,3-adamantanediol and 280 g (3.0 mol) of 1,2-ethanedithiol were added 6 g (0.0 mol) of p-tonorenesnolefonic acid. (0.3 mol) was added, and the mixture was heated and stirred at 140 ° C. for 12 hours. After cooling to room temperature, the precipitated p-toluenesulfonic acid was filtered off, washed with 5% sodium bicarbonate solution 20 Om1, then with water 20 Om1, and 1,2-ethanedithiol was further reduced in pressure. After distilling off, the residue was distilled under reduced pressure (boiling point: 280 ° C., 0.5 mmHg) to obtain 16 g of a colorless oil. Table 2 shows the elemental analysis, MASS, 1H-NMR, and IR spectrum of the obtained colorless oil. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (2-mercaptoethylthio) adamantane (Compound G).

 Production Example 8

 1,3,5-Adamantanetriol 25 g (0.15 mol) and bis (2-mercaptoethyl) sulfide 280 g (3.0 mol) to p-toluenesulfonate 6 g (0.03 mol), and the mixture was heated and stirred at 140 ° C. for 15 hours. After cooling to room temperature, the precipitated p-toluenesulfonic acid was filtered off,

After washing with 5% sodium hydrogen carbonate solution (200 ml) and then with water (200 ml), bis (2-mercaptoethyl) sulfide was distilled off under reduced pressure, followed by distillation under reduced pressure (boiling point: 320 ° C / 0. 5 mmHg) to give 24 g of the desired product as a colorless oil. Table 2 shows the elemental analysis, MAS S, 1H-NMR, and IR spectrum of the obtained colorless oil. Based on the results of these analyses, the isolated compound was identified as 1,3,5-tris [2- (2-mercapto Ethylthio) ethylthio] adamantane (compound H). Production Example 9

 To 17 g (0.1 monole) of 1,3-adamantandiole and 280 g (3.0 monole) of 1,2-ethanedithionole, add 2 g (0.01 monole) of p- / reensenolephonic acid After the addition, the mixture was heated and stirred at 120 ° C for 2 hours. After cooling to room temperature, the precipitated P-toluenesulfonic acid was filtered off, washed with 150 ml of a 5% sodium hydrogencarbonate solution and then with 15 Om 1 of water, and 1,2-ethanedithiol was distilled off under reduced pressure. The residue was distilled under reduced pressure (boiling point: 22 ° C / 0.5 mmHg) to obtain 13 g of a colorless oily substance. Table 2 shows the elemental analysis, MAS S, 1H-NMR, and IR spectra of the obtained colorless oil. From the results of these analyses, it was confirmed that the isolated conjugate was 3- (2-mercaptoethylthio) adamantan-11-ol (compound I). Production Example 10

200 g of ethanol was added to 22.4 g (0.10 mol) of 1,3-adamantanedicarboxylic acid and 6 g (0.03 mol) of p-tonolenesulfonic acid, and the mixture was dean-dewatered using a Dean-Stark dehydrator. The mixture was heated under reflux for 10 hours while distilling off water. After cooling to room temperature, the solvent was distilled off, and chloroform and water were added, followed by neutralization with a 1N aqueous solution of sodium hydrogen carbonate. After drying and concentrating the organic layer, 24.4 g of a residue was obtained. 1 H-NMR confirmed that the main product was ethyl 1,3-adamantanedicarboxylate. 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. 7.8 g of a white solid was isolated by mercapto formation and subsequent post-treatment under the same reaction conditions. Table 2 shows the elemental analysis, MASS, 1H-NMR, and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (mercaptomethyl) adamantane (compound). Production Example 11

 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).

 Production Example 12

 3,5-Dimenolecaptoadamantane-1-oneole 21-6 g (0.10 monole) and acetic acid 23 g (0.20 mol) were added to toluene 20 Om 1 and p-toluenesulfonic acid was added. 1 g of monohydrate was weighed and heated and stirred while distilling off water using a Dean-Stark dehydrator. After 4 hours, the mixture was allowed to cool, and then added to a form and water, and the organic layer was neutralized with sodium carbonate. Purification was performed by column chromatography, and 9.4 g of a white solid was isolated. Table 3 shows the elemental analysis, MAS S, 1H-NMR, and IR spectra of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 5-acetyloxy-1,1,3-dimercaptoadamantane (compound).

 Production Example 13

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. (Boiling point 280 ° C / 0.5 mmHg) to obtain 44 g of a colorless oil. From 1H-NMR, it was confirmed to be 1,3-bis (ethoxycarbonylmethylthio) adamantane.

Subsequently, 37 _g of this 1,3-bis (ethoxycarbonylmethylthio) adamantane was dissolved in 100 _ml of ethanol, and 12.4 _g of hydrazine monohydrate was added dropwise while maintaining the temperature at 5 ° C. Two hours later, the resulting solid of 1,3-bis (hydrazinocarbonmethylthio) adamantane was collected by filtration. This was washed twice with 20 ml of cold ethanol. After drying, it was dissolved in about 30 ml of water, cooled to 5 ° C, and 7 g of concentrated hydrochloric acid was added dropwise. Further, a solution of 4.4 g of sodium nitrite dissolved in 12 ml of water was added dropwise. One hour later, 60 ml of benzene was added, and the temperature was raised to room temperature with stirring. After separating the organic phase and drying over anhydrous magnesium sulfate, the organic phase was slowly dropped into 200 ml of benzene at 60 ° C. After the reaction as it was for 2 hours, the mixture was cooled to room temperature, and benzene was distilled off under reduced pressure. The obtained pale yellow oil was distilled under reduced pressure (boiling point: 270; C / 0.5 mmHg) to obtain 27 g of the desired product as a colorless oil. Table 3 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-bis (isocyanatomethylthio) adamantane (Compound M).

 Production Example 14

The reaction was carried out in the same manner as in Production Example 13 except that ethyl thiopropionate was used instead of ethyl thioglycolate to obtain a white solid. Table 3 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 1,3-bis (2-isocyanatoethylthio) adamantane (compound N).

 Production Example 15

 To a mixture of 76 g (1.0 mol) of carbon disulfide, 52 g of water and 81.8 g (1.0 mol) of a 50% aqueous solution of NaOH, 83 g of 1,3-adamantandiamine (0. (5 mol) was added dropwise at 20 to 30 ° C over 2 hours, and after completion of the addition, the mixture was heated at 70 to 80 for 1 hour. After 100 ml of water and 200 ml of toluene are added to the reaction solution, 100 g (1.05 mol) of methyl chloroformate is added dropwise at 40 to 50 ° C over 1 hour. It was kept at 50 ° C for 1 hour. The lower aqueous layer was separated and discarded. The obtained organic layer was dried and kept at 90 to 100 ° C for 3 hours to complete the decomposition. The resulting reaction solution is desolvated under reduced pressure, and distilled under reduced pressure (2

30 ° C / 0.5 mmHg) to obtain 42 g of a white solid. Table 3 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 1,3-adamantanedithioisocyanate (compound O).

 Production Example 16

 Cool 100 g (0.5 monole) of 1,3-adamantandithiol and 93 g (1.0 mol) of epichronorehydrin to 10 ° C and add 5 mmol (0.2 g) of sodium hydroxide. An aqueous solution dissolved in 5 ml of water was added, and the mixture was stirred at this temperature for 1 hour. Thereafter, the mixture was stirred for 3 hours while maintaining the liquid temperature at about 40 to 45 ° C. After returning to room temperature, an aqueous solution prepared by dissolving 40 g (1 mol) of sodium hydroxide in 60 ml of water was added.

The solution was added dropwise while maintaining the temperature at around 40 to 45 ° C, and then stirred for 2 hours while maintaining the solution temperature. The reaction mixture was added with 100 ml of water, extracted with 200 ml of toluene, and washed with water. After drying the toluene layer, the solvent was distilled off to obtain 95.0 g of a white solid. Elemental analysis, MASS, 1H-NMR, IR spectrum of the obtained white solid Are shown in Table 3. From the results of these analyses, it was confirmed that the isolated compound was 1,3-bis (glycidinolethio) adamantane (compound P).

 Production Example 1 7

1,3-Bis (glycidylthio) adamantane 93.6 (0.3 mol) and ethanol 4 Om 1 in an aqueous solution of 87.5 g (0.9 mol) of potassium thiocyanate dissolved in 60 ml of water In addition, 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 (β-epipop-piruthio) -damantane (compound Q). The analysis results of Compounds A to Q are shown in Tables 1 to 3 below.

Production example Elemental analysis MASS 1 H- MR I R

N o. (E I) (ppm) (cm-1)

(Compound No)

 Straight

 C Η Ν S C Η Ν S

1 65.33 8.97 17.11 65.16 8.77 17.39 184 δ 1.4.25 ppm (15 H) around 3620 cm-1 (A) (M ⁺ ) (adamantane reduction, (OH stretching vibration) proton of mezorecapto group) 2560 c Around m-1 δ 4.4 ppm (1 H) (SH stretching vibration)

(Proton of hydroxy group)

 2 59.87 8.01 32.14 59.94 8.06 32.00 200 δ 1.5.4 ppm (16H) around 2560 cm-1

(Β) ( ⁺ ) (proton of adamantane ring and menolecapto (SH stretching vibration) group)

3 60.13 8.11 15.95 59.95 8.07 16.00 200 δ 1,42.5 ppm (14H) around 3620 cm-1 (C) (M ⁺ ) ((OH stretching vibration) proton of adamantane ring and menolecapto group) 2560 cm- Around 1 δ 4, 5 ppm (2H) (SH stretching vibration) (hydroxyl group proton)

4 55.38 7.52 29.81 55.50 7.47 29.63 216 δ 1.42.5 ppm (15 H) around 3620 cm-1 (D) (M ⁺ ) (adamantane ring, (OH stretching vibration) proton of mercapto group) 2560 cm Around -1 δ 4.4 ppm (1 H) (SH stretching vibration)

(Proton of hydroxyl group)

5 45.54 6.15 48.44 51.67 6.95 41.38 232 δ 1.32.4 ppm (16H) Around 2560 cm-1 (Ε) (M ⁺ ) (proton based on adamantane ring mercapto (SH stretching vibration) group)

6 45.54 6.15 48.44 45.41 6.11 48.48 264 51, 32.5 ppm (16 H) Around 2560 cm-1 (F) (M ⁺ ) (proton based on adamantane ring and mercapto (shrinking vibration of SH)) ·

Table 2

 Production example Elemental analysis MASS 1 H-NMR I R

N (E I) (ppm) (cm-l) (Compound

 No) Direct calculation

 C Η Ν S C Η Ν S

 7 52.65 7.61 39.88 52.44 7.56 40.00 320 δ 1, 5-2.3 ppm (16H) around 2560 cm-1 (G) (M +) ((SH stretching vibration) proton of adamantane ring and mercapto group)

 δ 2.6 to 2.9 ppm (8H)

(SCH ₂ protons)

 8 49.21 7.41 i 43.56 49.04 7.33 43.63 440 δ 1.5 to 2.4 ppm (16H) around 2560 cm-1 (H) (M +) (proton of adamantane ring and mercapto (SH stretching vibration) group)

 δ 2.6 to 2.9 ppm (24H)

(SCH ₂ protons)

9 59.16 8.32 26.15 58.96 8,26 26.23 244 δ1.4 ~ 2,3 ppm (15H) Around 3620 cm-l (I) (M ⁺ ) (Adamantane ring, (OH stretching vibration) proton of mercapto group) Around 2560 cm-1 2.6 to 2.9 ppm (.

 Ά) (S 伸 extension irfgUS movement)

(SCH ₂ protons)

 δ 4.2 pm (1H)

 (Proton of hydroxyl group)

 10 63.17 8.89 28.14 63.10 8.83 28.08 228 δ 1.4 to 2.6 ppm (2 OH) 2550 cm-1

(J) (M +) (adamantane ring, mercapto group, (stretching vibration of SH)

SCH ₂ protons)

 11 52.60 6.71 35.25 52.51 6.62 35.04 274 δ 1, 4 to 2.3 ppm (15H) Around 2560 cm-l

(κ). (M ⁺ ) ((SH stretching vibration) proton of adamantane ring and mercapto group) Around 1710 cm-l δ 2.1 ppm (3 H) (c = o stretching vibration)

(Proton of acetyl group)

Table 3

 Production example Elemental analysis MASS 1 H-NMR I R

 Ν ο, ϋ ί ノ (ppm)

 (Compound

 No) Experimental value Calculated value

 C H N S C H N S

C 1 t ςj T-J) ij J55.58 7.00 24.97 55.77 _ 7.04 24.81 9 ς Η S i 4 ~ 9

C 1 t ςj TJ) ij J

(L) (Μ ⁺ ) (adamantane 璟, (SH stretching vibration of proton) of mercapto group) with 1740 m-1; loaf δ 2.2 ppm (6H) (c = o stretching vibration) (acetyl group Proton)

tj 53.97 5.71 9.11 20.64 54.16 5.86 9.03 20.65 3 1 0 iS 1 ~ 2 5ηητη f 1 Η) 9 9 70 With cm-1; Loaf (M) ( ⁺ ) (Proton of adamantane ring) (NCO stretching vibration )

 δ 4.5 ppm (1 4H)

(SCH ₂ protons)

1 4 56.94 6.63 8.10 18.70 56.76 6.56 8.28 18,94 3 3 8 δ 1, 42.5 ppm (14 H) 2 2 Around 70 cm-l (N) (Μ ⁺ ) (Adamantane ring proton) (N CO stretching vibration)

 5 3.5 to 3.9 ppm (4 H)

( ₂ SCH, 0 CNC protons)

1 5 57.67 5.70 11.30 25.82 57.56 5.65 11.19 25.61 25 0 δ 1.4 2.3 ppm (14H) 20 600 cm-1 (O) (Μ ⁺ ) (Adamantane ring proton) (NC S stretching vibration)

1 6 61.67 7.92 20.40 61.49 7.76 20.52 3 1 2 δ 1, 44.5 ppm (24H) 3 0 20 cm-1 (P) (Μ ⁺ ) (Adamantane ring, epoxy group Vibration) Mouth Ton)

1 7 55.89 7.06 37.44 55.76 7.03 37.21 344 δ 1.4 2.3 ppm (16 H) 6 20 cm-1 (Q) (Μ ⁺ ) (Adamantane ring, Episulfide (Ebisulphide ring extension) Proton) Shrinking vibration)

3 2.6.3 lppm (8H)

 (Ebisulfide and SCE

T)

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.

 Table 4

 Note) In the table, when the adamantyl group is substituted with a hydrogen atom, it is indicated as "one". Abbreviations of polymerizable compounds (comonomer) other than the polymerizable sulfur-containing adamantane compound of the present invention used in Examples and Comparative Examples are shown below.

PETP: Pentaerythritol tetrakis (3-mercaptopropionate) DDOL: 1,10—decanediol

 XD I: m-xylylene diisocyanate

 H6-XD I: 1,3-bis (isocyanatomethyl) cyclohexane NBD I: Norbornane diisocyanate (Note: Mixture of 2,5- and 2,6-norbornane diisocyanate)

 XDT I: m-xylylene dithioisocyanate

 ME I: 2-Methacryloxyshethyl isocyanate

 DMMD: 2,5-bis (mercaptomethyl) -1,4-dithiane METM: 1,2-bis (2-mercaptoethyl-1-1-thio) -1,3-mer'ronokun

 DDTL: 1, 10_decanedithiol

 ADSH: 1—Adamantanethiol

 ADDL: 1,3—adamantandiole ~ 20

 Production Example 1 to: Using any one or more of the polymerizable mercapto compound, polymerizable isocyanate compound, and polymerizable thioisocyanate compound of the present invention produced in L7, Curable compositions having the monomer compositions shown in Tables 5 and 6 were prepared.

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.

Table 5

Example Active hydrogen compound [Sulfur content] / m (thio) Isocyanate compound AD Refractive index Abbe number Heat resistance

 Appearance Weather resistance Odor

No. o 1 [Sulfur content] No 1 ratio (n _d ) (v) (° C)

 1

 Compound A / 0.10 XD I / O. 10 0.36 1.58 42 Transparent colorless 131 A A

Two

 Compound BZO. 10 XD I / O. 10 0.35 1.63 38 Colorless and transparent 139 A A

Three

 Compound C / 0.06 XD I /0.09 0.28 1.57 42 Colorless and transparent 143 A A

Four

 Compound 06 XD I /0.09 0.27 1.61 41 Colorless and transparent 145 A A

Five

 Compound E / 0.06 XD I / O. 09 0.26 1.63 40 Colorless and transparent 142 A A

6

 Compound FZ0.05 XD I / O. 10 0.21 1.60 43 Colorless and transparent 134 A A

7

 Compound GZ0.10 XD I / O. 10 0.26 1.68 35 Colorless and transparent 125 A B

8

 Compound H / 0.06 XD I / O. 09 0.15 1.64 38 Colorless and transparent 118 A C

9

 Compound I / 0.10 XD I / O. 10 0.29 1.60 41 Colorless and transparent 123 A B

Ten

 Compound J / 0.10 XD I / 0.10 0.32 1.63 40 Colorless and transparent 132 A C

11

 Compound K / 0.06 XD I / O. 09 0.21 1.62 42 Colorless and transparent 115 A A

12

Compound L 0.06 XD I /0.09 0.22 1.59 43 Colorless and transparent 117 AA

Table 6

Example Active hydrogen compound [Sulfur content] / m (thio) Isocyanate compound AD Refractive index Abbe number Heat resistance

 Appearance Weather resistance Odor

No. 01 [containing sulfur] / mo 1 ratio (n _d ) (V) (.C)

 Compound B / 0.06

 13 XD I / O. 10 0.20 1.62 39 Colorless and transparent 126 A C

 PETP / 0.02

 H6-XD I / O. 05

 14 Compound G / 0.10 0.26 1.62 41 Colorless and transparent 135 A B

 NBD I / 0. 05

 Fifteen

 Compound GZ0.10 XDT I / O. 10 0.25 1.68 34 Colorless and transparent 125 A C

16

 Compound G / 0.10 Compound MZ 0.10 0.43 1.63 40 Colorless and transparent 162 A B

17

 Compound G / 0.10 Compound N / 0.10 0.41 1.63 40 Colorless and transparent 160 A B

18

 Compound GZ 0.10 Compound 0 0.10 '0.47 1.64 37 Colorless and transparent 167 A B

 ME I / O. 05

 19 compounds GZ0.10 0.27 1.62 40 Colorless and transparent 138 A B

 XD I / O. 05

 Compound BZ0. 05

 20 XD I / O. 10 0.18 1.57 46 Colorless and transparent 102 A A

DDOL / 0. 05

As shown in Tables 5 and 6, 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. In addition, the heat resistance was excellent, the odor was very low, and the weather resistance was good. In particular, regarding 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 couldn't feel it at all.

 Also, from the comparison of Examples 2, 7, and 10, when the number of the polyaddition functional groups of the comonomer and the polymerizable sulfur-containing adamantane compound used is the same, the higher the AD ratio, the more the heat resistance. It turns out that it is excellent.

 Comparative Examples 1 to 5

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.

Table 7

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. In this case, in contrast to Example 20 in which a sulfur atom is directly bonded to an adamantane ring, 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.

 Example 2 1

 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

 One part by weight of 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.

 Comparative Example 6

100 parts by weight of 1,3-bis (glycidyloxy) adamantane is mixed with 1 part by weight of trifluoroamine and injected into a mold composed of two glass plates And 90. Polymerization and curing were performed with C for 8 hours to obtain a polymer. The refractive index of the obtained material was 1.54, the number was 46, and the heat resistance was 129 ° C. Compared with the polymer obtained from the polymerizable sulfur-containing adamantane compound of the present invention in Examples 21 and 22, the refractive index was significantly lower.

 Example 23

 When an optical material molded using the compound G of Example 7 and Example 14 was subjected to an impact resistance test, no crack was observed in any case.

 Example 24

 Synthesis of 1,3-bis (2-methacryloylthioethylthio) adamantane a) Starting compound: Synthesis of 1,3-bis (2-mercaptoethylthio) adamantane

 Compound G (1,3-bis (2-mercaptoethylthio) adamantane) was obtained in the same manner as in Production Example 7.

 b) Synthesis of 1,3-bis (2-methacryloylthioethylthio) adamantane ''

To 32.1 g (0.10 mol) of 1,3-bis (2-mercaptoethylthio) adamantane obtained according to the above method, 19.0 g (0.24 mol) of pyridine and p-methoxy were added. 64 mg of phenol and 300 ml of black form were added, and the mixture was cooled to 0 ° C. To this, 25.1 g (0.24 mol) of methacrylic acid chloride was gradually added dropwise, and the mixture was stirred at 0 ° C for 3 hours and at 20 ° C overnight. After the reaction, the pyridine hydrochloride of pyridine was filtered off, and the reaction solution was washed with 1N hydrochloric acid, a 5% aqueous sodium hydroxide solution and a 20% aqueous sodium chloride solution in this order, and then the solvent was distilled off. The residue was purified by column chromatography using silica gel to obtain 20.5 g of a colorless transparent oil. 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-bis (2-methacryloylthioethylthio) adamantane. 1, 3-bis (2-mercaptoethylthio) ada ' The yield from tan was 45%.

 Example 25

 Synthesis of 1,3,5-tris (2-methacryloylthioethylthio) adamantane

 a) Starting compound: Synthesis of 1,3,5-tris (2-mercaptoethylthio) adamantane

 Compound H (1,3,5-tris (2-mercaptoethylthio) adamantane) was obtained in the same manner as in Production Example 8.

 b) Synthesis of 1,3,5-tris (2-methacryloylthioethylthio) adamantane

 1,3,5-Tris (2-mercaptoethylthio) adamantane 41.3 g (0.10 monole) obtained according to the above method, pyridine 28.5 g (0.36 mol), p-methoxy Using 83 mg of phenol and 37.6 g (0.36 mol) of methacrylic acid chloride, the reaction was carried out in the same manner as in b) of Example 24 to obtain 24.7 g of a colorless transparent oil.

 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%.

 Example 26

 Synthesis of 1,3,5-tris (methacryloylthio) adamantane

 a) Starting compound: Synthesis of 1,3,5-trimercaptoadamantane Compound E (1,3,5-trimercapto.adamantane) as in Preparation Example 5.

b) Synthesis of 1,3,5-tris (methacryloylthio) adamantane 4.6 g of 1,3,5-trimercaptoadamantane obtained according to the above method (0.02 mol), 5.7 g (0.072 monole) of pyridine, 9 mg of p-methoxyphenol, and 7.5 g (0.072 mol) of methacrylic acid chloride, Example 24b) The reaction was carried out in the same manner as in the above to give 3.1 g of a colorless transparent oil.

 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%.

 Example 2 7

 Synthesis of 1,3,5,7-tetrakis (methacryloylthio) adamantane a) Starting compound: Synthesis of 1,3,5,7-tetramercaptoadamantane Compound F (1,3,3) 5,7-tetramercaptoadamantane).

 b) Synthesis of 1,3,5,7-tetrakis (methacryloylthio) adamantane

 2.6 g (0.01 mol) of 1,3,5,7-tetramercaptoadamantane obtained according to the above method, 3.8 g (0.048 mol) of pyridine, 5 mg of p-methoxyphenol Using 5.0 g (0.048 monole) of methacrylic acid chloride, the reaction was carried out in the same manner as in b) of Example 24 to obtain 1.2 g of a colorless transparent oil.

 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%.

 Example 2 8

 Synthesis of 1,3-bis (methacryloylthiomethyl) adamantane

a) Starting compound: Synthesis of 1,3-bis (mercaptomethyl) adamantane Compound J (1,3-bis (mercaptomethyl) adamantane) was obtained in the same manner as in Production Example 10.

 b) Synthesis of 1,3-bis (methacryloylthiomethyl) adamantane

4.6 g (0.02 mol) of 1,3-bis (mercaptomethyl) adamantane, 3.8 g (0.048 mol) of pyridine, 9 mg of p-methoxyphenol, 5.0 mg of methacrylic acid chloride g (0.048 mol), and the reaction was carried out in the same manner as in Example 24 b) to obtain 3.2 g of a colorless transparent oil.

 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%.

 Example 2 9

 Synthesis of 1,3-bis (2-methacryloylthioethylthio) -5,7-dimethyl / rare damantane

 a) Starting compound: Synthesis of 1,3-bis (2-mercaptoethylthio) -1,5,7-dimethyladamantane

 The reaction was carried out in the same manner as in a) of Example 24, using 2,9.4 g (0.15 mol) of 5,7-dimethyladamantane-1,3-dione. 4 g were obtained.

 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%.

b) 1,3-bis (2-methacryloylthioethylthio) -1,5,7-dimethyl 1,3-bis (2-mercaptoethylthio) 1.5,7-dimethyladamantane 7.0 g (0.02 mol) obtained according to the above method, pyridine 3.8 g (0.048 mol), The same reaction as in b) of Example 24 was carried out using 14 mg of p-methoxyphenol and 5.0 g (0.048 mol) of methacryloyl chloride to obtain 4.6 g of a colorless transparent oil.

 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%. Example 30

 Synthesis of 3,5-bis (methacryloylthio) adamantan-111-ol Compound D (3,5-dimercaptoadamantan-l-ol) was obtained in the same manner as in Production Example 4. 3,5-dimercaptoadamantan-1-ol 4.3 g (0.02 mol), pyridine 3.8 g (0.048 mol), p-methoxyphenol 9 mg, methacrylic acid chloride 5. Using 0 g (0.048 mol), the reaction was carried out in the same manner as in b) of Example 24 to obtain 2.2 g of a colorless transparent oil.

 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%.

 Example 3 1

Synthesis of 3,5-bis (methacryloylthio) 1-1-acetyladamantane To 3.5 g (0.01 monole) of 3,5-bis (methacryloylthio) adamantane obtained in Example 30 was obtained. Add 7 mg of p-methoxyphenol and 10 Om1 of tonoleene, and add acetyl chloride 1. Og (0.012 mol) at room temperature. Was slowly added dropwise, followed by stirring at 100 ° C for 2 hours. After the reaction, the mixture was washed with a 10% aqueous sodium hydrogencarbonate solution and a 20% aqueous sodium chloride solution, and the solvent was distilled off. The residue was purified by column chromatography using silica gel to obtain 0.91 g of a colorless transparent oil.

 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%.

 Example 32

 Synthesis of 1,3,5-tris (acryloylthio) adamantane

 Compound E (1,3,5_trimercaptoadamantane) was obtained in the same manner as in Production Example 5. 1, 3, 5-trimercaptoadamantane 2.3 g (0.01 mol), pyridine 2.8 g (0.036 mol), p-methoxyphenol 5 mg, acrylic acid chloride 3.3 Using g (0.036 mol), the reaction was carried out in the same manner as in b) of Example 24 to obtain 1.1 g of a colorless transparent oil.

 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%.

 Example 33

 Synthesis of 1,3-bis (2-acryloyloxhetylthio) adamantane a) Starting compound: Synthesis of 1,3-bis (2-hydroxyxethylthio) adamantane

Using 25.2 g (0.15 mol) of 1,3-adamantanediol and 234 g (3.0 mol) of 2-mercaptoethanol, react in the same manner as in Example 24 a). Was carried out to obtain 3.9 g of a colorless transparent oily substance.

 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

 1,3-bis (2-hydroxyschithio) obtained according to the above method, 2.9 g (0.01 m / re) of damantane, 6 mg of p-methoxyphenol, 100 ml of tonolen After 1.9 g (0.024 mol) of methacrylic chloride was gradually added dropwise at room temperature, the mixture was stirred at 100 ° C for 2 hours. After the reaction, the reaction mixture was washed with a 10% aqueous sodium hydrogencarbonate solution and a 20% aqueous sodium chloride solution, and the solvent was distilled off. The residue was purified by column chromatography using silica gel to obtain 2.0 g of a colorless transparent oil.

 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

co Table 9

MC: Methacrylic acid chloride

Table 10

AC: Acrylic acid chloride, MC: Methacrylic acid chloride

Examples Elemental analysis MASS 1 H-NMR

 Experimental value m direct (E I) vppm)

 C H— N S C H N S

 24 Rashi "Kal 57.71 7.01 28.28 57.85 7.06 28.08 456 δ 1.5 to 2.5 ppm (20H) 1710 cm-1 Polymerization (M +) (adamantane skeleton, methacryl (carbonyl group) Methyl contained in sulfur-containing group Group) around 1635 cm-1 Data "Mantane 52. 5-3. O pm (8H) (unsaturated hydrocarbon group) Compound (methylene carbon adjacent to sulfur)

 δ 5.0-7.Oppm (4H)

 (* Unsaturated hydrocarbon)

 25 Rashi'kar 54.40 6.48 31.30 54.51 6.53 31.18 617 61.5-2.5 pm (22H) 1710 cm-1 Around polymerizable (M +) (adamantane skeleton, methacrylic (carbonyl) methyl contained in sulfur-containing group Group) around 1635 cm-1 ata'mantan δ 2.5 to 3.0 ppm (12H) (unsaturated hydrocarbon group) Compound (methylene carbon adjacent to sulfur)

 85.0 to 7.Oppm (6H)

 (Unsaturated hydrocarbon group)

26 Rashi'ka ^ 60.23 6.48 22.12 60.51 6.46 22.03 436 δ 1.5-2.5 ppm (22H) 1710 cm-1 Around polymerizable (M ⁺ ) (adamantane skeleton, methacrylic (carbo group)) Included methyl group) around 1635 cm-1 Mata "mantan δ 5.0 ~ 7. Oppm (6H) (unsaturated hydrocarbon group) Compound (unsaturated hydrocarbon group)

27 Rashi'cal 58.08 5.96 24.00 58.18 6.01 23.89 536 δ 1.5 to 2.5 ppm (24H) 1710 cm-1 Around Polymerizable (M ⁺ ) (including adantan skeleton, methacrylic (carboyl group)) Methyl group contained in sulfur group) Around 1635 cm-1 Attached "mantan δ 5.0-7. Oppm (8H) (unsaturated hydrocarbon group) Compound (unsaturated hydrocarbon group)

¾ Table 1 2

Example. Elemental analysis MASS 1 H-NMR

 Experimental value Calculated value (E I) (ppm)

 C H N S C H N S

 28 Rush 'force 65.64 7.55 17.58 65.89 7.74 17.59 364 δ 1.5.5 ppm (2 OH) 1 71 0 cm-1 Around polymerizable WL) Coumanotano Xiao, Gkulinole (carbonyl group) Methyl contained in sulfur-containing group Group) around 1 635 cm-1 amantane δ 2.5 3. Oppm (4H) (unsaturated hydrocarbon group) Compound (methylene carbon adjacent to sulfur)

 δ 5.0 7.0 (4Η)

 (Unsaturated hydrocarbon group)

 29 Starting compound 55.01 8.00 36.71 55.12 8.09 36.79 348 ■ δ1.5.2.3 ppm (20H) Around 2550 cm-1

し L ノレ 、 ノレ (M +) Tan skeleton, adamanta (mercapto group)

And L Nore, Nore

 Capto group)

 δ 2. "6—2.9 pm (8 H)

 (Methylene carbon adjacent to sulfur)

Rashi * Cal 59.66 7.55 26.58 59.46 7.48 26.46 484 S 1., 32.5 ppin (24H) 1710 cm-1 Around polymerizable (M ⁺ ) (adamantane skeleton, adamanta (canoleboninole group)) Na-^! Tinoreta around 1635 cm-1 Mata "Methyl group contained in mantane cryl group) (Unsaturated hydrocarbon group) Compound δ 2.5 3. Oppm (8H)

 (Methylene carbon adjacent to sulfur)

 δ 5.0 7.0 (4Η)

 (Unsaturated hydrocarbon group)

30 lash * force; ^ 61.29 7.01 18.31 61.33 6.86 18.19 352 δ1.5.2.5 pm (19H) 1 around 710 cm-1 Polymerizable (M ⁺ ) (adamantane skeleton, methacrylic (carbonyl group) Sulfur-containing group Around 1 635 cm-1 Mata "mantan 54.2 (1 H) (hydroxyl group) (unsaturated hydrocarbon group) Compound δ 5.0 ~ 7. O pm (4H) 3620 cm-1 near

(Unsaturated hydrocarbon group) (hydroxyl group)

Table 13

Example Elemental analysis 1 l J JVLK

 Experimental value Calculated value (E I) (ppm)

 C H N S C H N S

 31 Physical 63.55 6.92 16.87 63.46 6.92 16.94 378 δ 1.52.5 ppm (22 H) Around 1710 cm-1 Polymerizable (M +) (adamantane skeleton, methacrylic Acetinole contained canoleboninole ata 'mantan group)

 Compound 8 5, 0 7.Oppm (4H) around 1700 cm-1

 (Unsaturated hydrocarbon group) (carbonyl group included in acetyl group) Around 1635 cm-1 (unsaturated hydrocarbon group)

32 Rash'cal 57.79 5.82 ― 24.08 57.84 5.62 ― 24.38 394 δ 1.5 2,5 ppm (13H) around 1710 cm-1 Polymerizable (M ⁺ ) (adamantane skeleton) (carbonyl group) Sulfur-containing 55.0 ~ 7. O pm (9H) around 1635 cm-1 Attached “mantan (unsaturated hydrocarbon group) (unsaturated hydrocarbon group) compound

 33 Raw material 68.20 8.21 22.20 58.29 8.39 22.23 288 δ1.5.2.3 ppm (14H) around 3620 cm-1 Compound (M (adamanotano skeleton) (hydroxyl group)

 δ 2.6-3.7 ppm (10H)

 (Methyle adjacent to sulfur and oxygen

 Carbon, hydroxyl)

 W calc 62.13 7.82 15.17 62.23 7,60 15.10 424 δ 1.52.5 pm (2 OH) around 1710 cm-1 ) Around 1635 cm-1 'atamantane 52.5.4.2 ppm (8H) (unsaturated hydrocarbon group) Compound (methylene adjacent to sulfur and oxygen)

 Carbon).

 δ 5.0 7. Oppm (4H)

 (Unsaturated hydrocarbon group)

^ Example 3 4 to 4 5

 Using the radically polymerizable sulfur-containing adamantane compound of the present invention produced in the above Examples 24 to 33, the comonomer shown as the following component B or C is added, if necessary, to add Table 14 to Table 15 Was prepared and polymerized and cured to obtain a cured product.

 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

10 When the mantan compound was solid, it was heated until it became liquid, or it was made liquid by adding an appropriate comonomer. This mixed solution was injected into a cylindrical shape composed of a glass plate and a gasket made of ethylene monoacetate butyl copolymer, and casting polymerization was performed. In the polymerization, the temperature was gradually raised from 33 to 90 ° C over 17 hours using an air furnace, and the temperature was maintained at 90 ° C for 5 hours. After the polymerization was completed, the mold was taken out of the air oven, allowed to cool, and the cured product was removed from the glass of the mold. Each abbreviation in Tables 14 to 15 means the following compounds.

 [Component A] The radically polymerizable sulfur-containing adamantane compound of the present invention produced in each of the examples having the corresponding numbers.

 [B component]

 20 GMA: Glycidyl methacrylate

 3 G: Triethylene glycol dimethacrylate

 [C component]

 M S: α-methinolestyrene

 Β ζ ΜΑ: Benzyl methacrylate

 twenty five

Various physical properties of each of the thus-obtained hard Eich bodies were measured by the test methods described above. The results are shown in Tables 14 to 15. Comparative Examples 7 to 9

 As the A component, the following compounds are used in place of the radically polymerizable sulfur-containing adamantane compound of the present invention.

(Mouth:

レ、）

Les,)

The curable compositions shown in Table 15 were prepared using, and cured products were obtained in the same manner as in Example 34. Physical properties of the obtained cured product were measured in the same manner as in the examples. Table 15 also shows the results.

Table 14

 Monomer composition Physical properties of cured product

Example Refractive index Abbe number Heat resistance

 A B c AD

Weather resistance Odor Appearance ratio (n _d ) (V)

 34 24

 0.129 1.645 41 145 ° C A A-B Colorless and transparent (100)

 35 25

 0.22 1.654 40 154 = C A A-B Colorless and transparent (100)

 , 26

 36 0.31 1.635 42 168 A A-B Colorless and transparent

 (100)

 27

 37 0.25 1.643 41 172 ° C A A-B Colorless and transparent

 (100)

 28

 38 0.37 1.630 42 150. C A A-B colorless and transparent

 (100)

 29

 39 0.27 1.654 40 143 "C A A-B colorless and transparent

 (100)

 30

 40 0.38 1.602 44 134V, A A-B colorless and transparent

 (100)

 31

 41 0.35 1.592 44 152. C A A-B colorless and transparent

(100)

o

 Table 15

 Monomer, Sosei Physical properties of hardened body

 Example AD refractive index Abbe number Heat resistance

ABC Weather resistance Odor Appearance ratio (n _d ) (v)

 32

 42 0. 34 1.640 41 1 6 IX: A A—B Colorless and transparent

 (100)

 33

 43 0.32 1. 591 44 149 A A-B colorless and transparent

 (100)

 24 GMA

 44 0.26 1.631 42 142 A A-B colorless and transparent

 (90) (10)

 24 3 G MS

 45 0.25 1.633 40 145V A A-B Colorless and transparent

 (85) (5) (10)

Comparative Example 7 0 1.630 39 129V A F Colorless and transparent

 Π B zMA

Comparative Example 8 0 1.658 26 1 10 F A-B Colorless and transparent

 (80) (20)

 No

Comparative Example 9 0.29 1.577 42 1 57 F A-B

(100) colorless and transparent

Comparison of each example with 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. In addition, as compared with 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. Furthermore, as compared with Comparative Example 9, it can be seen that Examples of the present invention have a refractive index and are excellent in weather resistance. As described above, it can be seen that 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.

 For this reason, 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.

Claims

The scope of the claims 1. In one molecule,  (a) at least one adamantyl group  (b) at least one polymerizable functional group  (c) at least one sulfur atom An optical material comprising a polymer containing a polymerized unit based on a polymerizable sulfur-containing adamantane compound having the following formula: 2. The polymerizable sulfur-containing adamantane compound has two or more polymerizable functional groups 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. The optical material according to claim 1, which has an optical material. 3. The polymerizable sulfur-containing adamantane compound has the following general formula (1)

 [In the formula, Z is the following general formula (2) -ff-x -R ² rR ³ } (2) (Wherein, 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, and s represents 0 or 1 and are integers from 0 to 3, and when t is 2 or 3, the groups represented by (one [X] _s —R2—) may be the same or different.) Wherein 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, a represents an integer of 2 to 4, b represents an integer of 0 to 4, both Z and R ¹ are each in a case there are a plurality of which may be the same as or different from each other, and it exists at least one sulfur atom in the molecule. ] 3. The optical material according to claim 1, which is a compound represented by the formula: 4. The optical material according to claim 1, wherein the polymerizable sulfur-containing adamantane compound has at least one polymerizable functional group selected from the group consisting of an atariloyl group and a methacryloyl group. 5. The polymerizable sulfur-containing adamantane compound has the following general formula (I)

{Wherein, R ¹ represents an alkyl group having 1 to 6 carbon atoms, and Z ¹ represents the following formula (Π) One (X ¹ ) _e- (R ² — X ² ) _f — Υ ¹ (Π) (Wherein 1 ² is a substituted or unsubstituted hydrocarbon group having 1 to 1 5 carbon atoms, the X ^1, X ² each independently represent an oxygen atom or a sulfur atom, Y ¹ represents a (meth) Atariroiru 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.) And z ² is a group represented by the following formula (m) One (x ³ ) _g- (R ³ -x ⁴ ) _h -Y ² (m) (Wherein, 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, and Y ² represents a carbon atom other than a (meth) atalyloyl group) Represents an acyl group having a prime number of 2 to 7, g is 0 or 1, h is an integer of 0 to 6, and when h is 2 to 6, the groups represented by (R ³ — X ⁴ ) are the same or different And g + h is 1 or more.) Z ³ is a group represented by the following formula (IV) One (X ^{5) "(R 4 - X 6) jH} (IV) (Wherein, 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,; i is Is an integer of 0 to 6, and 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; A is an integer of 1 to 4, b is an integer of 0 to 3, c is an integer of 0 to 3 (however, a + b + c is:! ~ 4), d represents an integer of 0 to 4, and each of RZ ¹ and Z ² may be the same or different when there are a plurality of them, and each of RZ ¹ and Z ² represents an atom represented by X ^{J to} X ⁶ At least one of them is a sulfur atom. ) 5. The optical material according to claim 4, which is a compound represented by the formula: 6. A polymerizable sulfur-containing adamantane compound represented by the following general formula (1):

In the formula, Z is the following general formula (2) ² ir R ³ } (2) (Wherein, 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, and s represents 0 or 1, t is an integer of 0 to 3, and when t is 2 or 3, the groups represented by (— [X] _s —R2—) may be the same or different.) R ¹ represents an alkyl group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms or an azylthio group having 2 to 6 carbon atoms, and a represents an integer of 2 to 4. And b represents an integer of 0 to 4. When there are a plurality of Z and R ¹ , each may be the same or different, and at least one sulfur atom is present in the molecule. 7. Polymerizable sulfur-containing adamantane compound represented by the following general formula (I)

In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, and Z ¹ represents the following formula (Π) One (X ¹ ) _e- (R ² -X ² ) _f -Υ ¹ (Π) (Wherein, Shaku 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) acryloyl 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.) And z ² is a group represented by the following formula (m) One (x ³ ) _g- (R ³ -x ⁴ ) _h _Y ² (m) (Wherein, 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, and 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, and when h is 2 to 6, the group represented by (R ³ — X ⁴ ) is the same May be different, and g + h is 1 or more.) Z ³ is a group represented by the following formula (IV) One (X ⁵ ); one (R ⁴ — X ⁶ ) j— H (IV) (Wherein, 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 Is an integer of 0 to 6, and 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; A is an integer of 1 to 4, b is an integer of 0 to 3, c is an integer of 0 to 3 (where a + b + c is 1 to 4) in a), d is an integer of 0 to 4, both R \ Z ¹ and Z ² may each be the same or different when there are a plurality of, and of the atoms represented by E ^1-6 At least one is a sulfur atom. 8. A polymerizable composition comprising the polymerizable sulfur-containing adamantane compound according to claim 6 or 7.