JP2003277460A - Optical material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical material suitable as a material for spectacle lenses or the like, having large Abbe number and high refractive index and also high heat resistance, and exhibiting such good processability as to scarcely emit unpleasant odor when undergoing machining such as grinding or cutting. <P>SOLUTION: The optical material consists of a polymer which is obtained from a sulfur-containing polymerizable compound as the monomer. The polymerizable compound has (a) at least one adamantyl group, (b) at least two polyaddition-type functional groups and (c) at least one sulfur atom, being e.g. 1,3-adamantane dithiol, 3,5-dimercaptoadamantan-1-ol, 1,3-bis(2- mercaptoethylthio)adamantane. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerizable compound having an adamantane skeleton and an optical material obtained by using the compound.

[0002]

2. Description of the Related Art Plastic materials are lighter in weight and less liable to break than glass materials, easy to dye, and have good workability such as cutting and polishing. Therefore, plastic materials have been widely used in various optical lenses, especially spectacle lenses in recent years. .

Performances required for optical materials, particularly spectacle lenses, include high refractive index, high Abbe number, high heat resistance, and high strength.

A material generally used for plastic lens applications is a resin made of poly [diethylene glycol bis (diallyl carbonate)]. This resin has various characteristics such as excellent impact resistance and good dyeability and processability. However, since the refractive index is as low as 1.50, when a lens with high power is manufactured, the center thickness and edge thickness of the lens become large, and chromatic aberration, birefringence, increase in weight and deterioration of aesthetics occur, so that the refractive index High-quality materials are required.

In order to increase the refractive index, introduction of halogen atoms such as bromine, sulfur atoms and aromatic compounds into monomer molecules has been studied. Above all, the method of introducing a sulfur atom is effective in improving the refractive index while maintaining high optical physical properties such as Abbe number and weather resistance, and therefore, vigorous research has been conducted. For example, a sulfur-containing polyurethane resin composed of polyisocyanate and polythiol is known, and JP-A-63-46213 discloses a lens composed of a polymer of a polymercapto compound and a xylidene diisocyanate compound. No. 270859, 1,2-bis ((2-mercaptoethyl (thio)-
A lens made of a polymer of 3-mercaptopropane and a polyisocyanate compound is disclosed. In addition, polythio (meth) acrylate resin (Japanese Patent Laid-Open No. 64-2661)
3, JP-A-64-31759), or a sulfur-containing poly (meth) acrylate resin, a resin containing an episulfide compound (JP-A-9-110979), and the like.

However, even now, a further refractive index,
Materials with well-balanced physical properties such as Abbe number and heat resistance are required.

Further, 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 that an odor during processing such as cutting and polishing, that is, a bad odor derived from sulfur is generated. For example, in the edge processing to match the shape of the lens to the spectacle frame, the lens is exposed to high temperatures, so part of the lens material may undergo thermal decomposition, which may cause a strange odor and a foul odor specific to sulfur. Worsening the situation. Therefore, there is a strong demand for a high-refractive-index lens that does not generate an odor during processing.

On the other hand, the adamantane derivative has a unique structure of being non-aromatic and rigid,
Has attracted attention in various fields. For example, JP-A-60-10
0537 is diallyl adamantanedicarboxylate, and in JP-A-63-307844 is adamantyl di (meth).
Acrylate derivatives are disclosed. However, although these materials show high heat resistance, they have a refractive index of 1.53 to
It is not sufficient for high-value-added plastic lens applications such as about 1.55, or it is not always sufficiently satisfactory in terms of weather resistance because it contains halogen atoms.

[0009]

The present invention has a high refractive index,
Optical material with excellent Abbe number and heat resistance, low odor,
And it aims at providing the novel polymeric compound which provides this optical material.

[0010]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies to solve the above problems. As a result, the polymer using a specific polymerizable compound having an adamantyl group as a monomer has a high refractive index, an Abbe number and heat resistance, and further has an excellent property that the odor generated during processing is significantly low. The present invention has been completed and the present invention has been completed.

That is, the present invention provides a polymerization based on a sulfur-containing polymerizable adamantane compound having (a) at least one adamantyl group (b) at least two polyaddition functional groups (c) at least one sulfur atom in one molecule. An optical material comprising a polymer containing units.

By using such a 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.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a sulfur-containing polymerization containing (a) at least one adamantyl group in one molecule, (b) at least two polyaddition functional groups, and (c) at least one sulfur atom. An optical material comprising a polymer containing polymerized units based on a polymerizable adamantane compound).

The sulfur-containing polymerizable adamantane compound (hereinafter referred to as the sulfur-containing polymerizable adamantane compound), which is a constituent unit of the polymer as the optical material of the present invention, includes (a) at least one adamantyl group in one molecule, Any compound can be used without particular limitation as long as it is a compound having all of (b) at least two polyaddition functional groups and (c) at least one sulfur atom.

The sulfur-containing polymerizable adamantane compound has (a) at least one adamantyl group (cyclic group derived from adamantane ring; hereinafter referred to as adamantane skeleton) in the molecule. When the polymerized unit based on such a compound serves as a constituent element of the polymer, the polymer has excellent heat resistance and can be made into a polymer having an extremely small odor during grinding or the like.

The sulfur-containing polymerizable adamantane compound has (b) at least two polyaddition functional groups in its molecule.

The polyaddition functional group is a functional group capable of causing an addition reaction with another polyaddition functional group to cause a polymer formation reaction by polyaddition. Most of such addition reactions include a functional group consisting of an atomic group consisting of a hetero atom such as a hydroxyl group, a mercapto group, an amino group, and a hydrosilyl group, and an active hydrogen atom bonded to the hetero atom (hereinafter referred to as an addition side group). Functional group of 1) is added to a cyclic group containing a hetero atom or a group containing a double bond (hereinafter referred to as a functional group on the side to be added). When the functional group on the side to be added is a cyclic group containing a hetero atom, it is usually converted into a functional group on the side to be added by ring-opening by an addition reaction (for example, an epoxy group. Undergoes ring-opening by the addition to change to a group having a hydroxyl group).

The polyaddition functional group of the sulfur-containing polymerizable 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. Specifically exemplifying the polyaddition functional group, as the functional group on the side to be added, a mercapto group, a hydroxyl group, an amino group, a silyl group,
A dithiocarboxyl group, a thiocarboxyl group, a carboxyl group, a carboxamide group, a dithiocarboxamide group and the like can be mentioned, and the functional group on the side to be added is a cyclic group containing a hetero atom such as an episulfide group, an epoxy group or an aziridine group. And an isocyanate group, a thioisocyanate group (hereinafter sometimes collectively referred to as a (thio) isocyanate group), a group containing a double bond such as a ketene group, an ethenyl group, and the like. As the polyaddition functional group which the sulfur-containing polymerizable adamantane compound in the present invention has, among these, from the viewpoint that a polymer having good reactivity and excellent optical properties can be easily obtained, a mercapto group, a hydroxyl group, Episulfide groups or (thio) isocyanate groups are particularly preferred.

The sulfur-containing polymerizable adamantane compound in the present invention has at least two polyaddition functional groups. Moreover, from the viewpoint of easiness of synthesis of such a compound,
The number of polyaddition functional groups is preferably 4 or less.

The polyaddition functional groups may be the same or different, but in view of easiness of synthesis of the sulfur-containing polymerizable adamantane compound and stability, a functional group on the addition side, It is preferable that only one of the functional groups on the side to be added be present, and most preferable that all polyaddition functional groups are the same.

These polyaddition functional groups may be directly bonded to the adamantane ring, or may be bonded to the adamantyl group via a hetero atom or various organic residues (hereinafter, the hetero atom And an organic residue may be collectively referred to as “organic residue, etc.” In addition, the organic residue, etc. and the polyaddition functional group bonded thereto are treated as one group,
It may be referred to as a "group having a polyaddition functional group". ), Furthermore, these coupling forms may be mixed.

When a plurality of groups having a polyaddition functional group are bonded to the adamantyl group, each group having a polyaddition functional group may be different or the same. But it is okay. Furthermore, the group having one polyaddition functional group may have a plurality of polyaddition functional groups.

The organic residue or the like is not particularly limited as long as it is an organic residue having a valence of [the number of polyaddition functional groups bonded to the organic residue + 1] and a known hetero atom or organic residue. The groups can be applied without any restrictions. As a hetero atom,
Examples are sulfur atom, oxygen atom, 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 is an ester bond, a thioester bond, an amide bond, a urethane bond, a thiourethane bond, a carbonate bond, an ether bond, a thioether bond (sulfide bond), a dithioether bond (disulfide bond), an amino bond, a sulfonyl bond. Etc. may contain a bond other than a carbon-carbon bond. A preferred specific example of the group having a medium-addition functional group having such an organic residue will be described in detail as a group represented by the general formula (2) described later.

Further, the sulfur-containing polymerizable adamantane compound in the present invention may have only one group having a polyaddition functional group bonded to the adamantyl group, but preferably, the polyaddition functional group and / or Alternatively, a compound having a plurality of groups having a polyaddition functional group bonded to an adamantyl group is preferable. By using such a compound, the obtained polymer has an adamantane skeleton (adamantyl group) in the main chain, and heat resistance, optical properties and the like can be further improved.

The position at which 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 1-position, 3-position of the adamantane skeleton, It may be on the carbon atom at the bridgehead position such as the 5th or 7th position, or on the methylene carbon at the 2nd, 4th, 6th or 8th position. When it is on a methylene carbon, two bonds (substitutions) may be formed on the same carbon.

Further, the adamantyl group has, in addition to the polyaddition functional group or the group having the polyaddition functional group, a substituent having no polyaddition functional group (hereinafter, other substituent). It doesn't matter. 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 halogen atom, which are further substituted with various known substituents. Is also good. Among these, from the viewpoint of ease of synthesis, an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an acyloxy group having 2 to 6 carbon atoms such as an acetyloxy group and a propionyloxy group; an acetylthio group, An acylthio group having 2 to 6 carbon atoms such as a propionylthio group is particularly preferable.

Such other substituents may also be bonded to any position of the adamantyl group, and in the case of the 2-position, 4-position, 6-position, 8-position, etc. of the adamantane skeleton, on the carbon atom concerned. To the above-mentioned polyaddition functional group and / or a group having a polyaddition functional group and other substituents may be bonded one by one, or two other substituents may be bonded. good.

The sulfur-containing polymerizable adamantane compound in the present invention has (c) at least one sulfur atom in the molecule. The polymer obtained by having a sulfur atom can have a high refractive index, and the polymer can be suitably used for various optical applications such as eyeglass lenses.

The number of sulfur atoms contained in the sulfur-containing polymerizable adamantane compound is not particularly limited as long as it is at least one as described above, but it is preferable that an optical material having a high refractive index can be easily obtained. , A number such that the sulfur atom content [(the number of sulfur atoms contained × 32 / the molecular weight of the sulfur-containing polymerizable adamantane compound)] is 0.15 or more, preferably 0.18 or more (generally two or more) Is preferred.

Further, the sulfur atom contained in the sulfur-containing polymerizable adamantane compound may be in any existing form, may be present as an atom constituting the polyaddition functional group, or may be a group having the polyaddition functional group. In the above, it may be present as an atom constituting an organic residue or the like, or may be present in another substituent.

When present as a polyaddition functional group,
Examples include mercapto group, thioisocyanate group, episulfide group, dithiocarboxyl group, thiocarboxyl group, and the like, which are present as atoms constituting an organic residue or when present in other substituents. Examples of the sulfide bond, disulfide bond, thioester bond, dithioester bond, thioamide bond, sulfinyl bond and sulfonyl bond are exemplified.

From the viewpoint of low odor during processing such as grinding and excellent workability, it is preferable that at least half of the sulfur atoms contained in the sulfur-containing polymerizable adamantane compound are directly bonded to the adamantyl group. More preferably, all sulfur atoms are directly bonded to the adamantyl group. Specifically, for example, when the sulfur-containing polymerizable adamantane compound has two sulfur atoms, it is preferable that at least one is directly bonded to the adamantyl group, and both are directly bonded to the adamantyl group. More preferably. Similarly, when the number of sulfur atoms is three, it is preferable that at least two are directly bonded to the adamantyl group, and it is more preferable that all three are directly bonded to the adamantyl group. This makes it extremely easy to achieve both high refractive index and low odor.

The above-mentioned sulfur-containing polymerizable adamantane compound is excellent in easiness of synthesis, refractive index, heat resistance, low odor, etc., and therefore, is represented by the following general formula (1):

[0034]

[Chemical 3]

[Wherein Z is the following general formula (2)

[0036]

[Chemical 4]

(In the formula, R ² represents a divalent hydrocarbon group which may have a substituent, R ³ represents a polyaddition functional group, s is an integer of 0 to 2, and t is 0. Is an integer from 3 to t
There the case of 2 or _{3, (- [S] s -R} 2 -) group may each be the same or different indicated by. ) Represents a group represented by, ^{R 1} represents an alkyl group having 1 to 6 carbon atoms, 2 carbon atoms
6 represents an acyloxy group or an acylthio group having 2 to 6 carbon atoms, a represents an integer of 2 to 6, b represents an integer of 0 to 6, and Z and R ¹ are the same when a plurality of them are present. Or different and at least 1 in the molecule
There are two sulfur atoms. ] The compound represented by the above is particularly preferable.

Z in the general formula (1) is the following general formula (2).

[0039]

[Chemical 5]

(In the formula, R ² represents a divalent hydrocarbon group which may have a substituent, R ³ represents a polyaddition functional group, s is an integer of 0 to 2, and t is 0. Is an integer from 3 to t
There the case of 2 or _{3, (- [S] s -R} 2 -) group may each be the same or different indicated by. And a group having a polyaddition functional group as described above.

Specific examples of the polyaddition functional group are as described above. In particular, a mercapto group, a hydroxyl group, an episulfide group, a thioisocyanate group or an isocyanate group is more preferable.

[0042] The polyaddition functional groups, when t is 1 to 3 for the adamantyl group is bonded via a group represented by _{t (- - [S] s} -R 2).

[0043] The ^{_{(- [S] s -R 2}} -) in the group represented by, s is an integer of 0-2. Specifically, when s is 1, it indicates a sulfide bond, and when s is 2, it indicates a disulfide bond.

R ² may have a substituent 2
It is a valent hydrocarbon group and is not particularly limited, but a hydrocarbon group having 1 to 20 constituent carbon atoms is preferable. The hydrocarbon group is an alkylene group having a main chain carbon number of 1 to 10 (preferably 1 to 4) such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group and a hexamethylene group; A cycloalkylene group having 5 to 10 carbon atoms constituting a ring such as a cyclohexylene group and a cyclopentylene group; an arylene group having 6 to 12 carbon atoms constituting a ring such as a phenylene group and a naphthylene group. You can

The substituent for R ² is not particularly limited as long as it does not affect the polyaddition reaction for obtaining the polymer, and various known substituents may be present. 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; a benzyl group, a phenethyl group and the like having 7 to 11 carbon atoms.
Aralkyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, etc., C1-C4 alkoxy group; acetyl group, etc., C2-C4 acyloxy group; phenyl group And aryl groups having 6 to 12 carbon atoms such as toluyl group and naphthyl group; and aromatic heterocyclic groups having 4 to 10 carbon atoms such as thienyl group, furyl group and benzothienyl group.

When the substituent has a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of the refractive index and light resistance of the cured product to be obtained, fluorine is included. It is preferably other than an atom, and particularly preferably a bromine atom.

The hydrocarbon group represented by R ² is an alkylene group having 1 to 4 carbon atoms or a carbon number from the viewpoint of easiness of synthesis of the sulfur-containing polymerizable adamantane compound, the refractive index of the resulting polymer, and heat resistance. An arylene group having 6 to 12 is preferable, an alkylene group having 1 to 4 carbon atoms is more preferable, and a methylene group and an ethylene group are particularly preferable.

In the above general formula (2), t is 0 to 3
It is an integer, and when t is 0, the polyaddition functional group is
It is shown that it is directly bonded to the ethyl group. Also, t is 2
Or in the case of 3, (-[S]_s-R²-) Group
Is {-([S]_s-R²)-([S]_s-R²)-}, {-
([S]_s-R²)-([S]_s-R²)-([S]_s-R²) −}
It means that it may be repeated like. Again this
In this case, the (-[S] _s-R²Group represented by-)
(Rank) may be the same or different, request
Physical properties of used optical materials and sulfur-containing polymerizable adamantane compounds
It may be appropriately selected depending on the difficulty of synthesizing the product.

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

(I) t = 0: same as the polyaddition functional group described above.

(Ii) When t is 1 and s is 0: a group having a mercapto group such as a mercaptomethyl group, a 2-mercaptoethyl group and a 3-mercaptopropyl group as a polyaddition functional group; thioisocyanatomethyl Group, a group having a thioisocyanate group such as a 2-thioisocyanatoethyl group and a 3-thioisocyanatopropyl group as a polyaddition functional group.

(Iii) t = 1 and s = 1: a group having a mercapto group such as a mercaptomethylthio group or a 2-mercaptoethylthio group as a polyaddition functional group; a hydroxymethylthio group or a 2-hydroxyethylthio group. A group having a hydroxyl group such as a group as a polyaddition functional group; a group having an isocyanate group such as an isocyanate methylthio group and a 2-isocyanatoethylthio group as a polyaddition functional group; a thioisocyanatomethylthio group, 2 -Groups having a thioisocyanate group such as ethylthio group as a polyaddition functional group; an episulfide group such as β-epithiopropylthio group, γ-epithiobutylthio group as a polyaddition functional group A group having; a group having a carboxyl group such as a carboxymethylthio group and a 3-carboxypropylthio group as a polyaddition functional group, aminomethyl A group having an amino group such as a thio group as a polyaddition functional group.

(Iv) t = 1 and s = 2: a group having a mercapto group such as a 2-mercaptoethyldithio group as a polyaddition functional group; a 2-thioisocyanato ethyldithio group or another thioisocyanate A group having a group as a polyaddition functional group; a group having an episulfide group such as a β-epithiopropyldithio group as a polyaddition functional group.

(V) t is 2 or more: 2- (2-mercaptoethylthio) ethylthio group, 2- (2-mercaptoethyldithio) ethylthio group, 4- (2-mercaptoethyldithio) phenyldithio group, It has a mercapto group such as a 2- [2- (4-mercaptophenyldithio) ethyldithio] ethylthio group and a 2- [2- (4-mercapto-2,6-dibromophenyldithio) ethyldithio group as a polyaddition functional group. Group: Having a hydroxyl group such as 2- (hydroxymethylthio) ethylthio group as a polyaddition functional group; Having an isocyanate group such as 2- (2-isocyanatoethylthio) methyl group as a polyaddition functional group Group;
A group having a thioisocyanate group such as a 2- (2-thioisocyanatoethylthio) methyl group as a polyaddition functional group; an amino group such as a (2-aminoethylthio) methyl group as a polyaddition functional group A group having; a group having a carboxyl group such as a 2- (carboxymethylthio) ethyl group as a polyaddition functional group.

Among these groups, t is 0 or t is 1 or 2 and s is 1 and R is R because the polymer obtained by polymerization has excellent heat resistance and a high refractive index. ^A group in which 2 is a hydrocarbon group having 1 to ² carbon atoms is particularly preferable.

A specific example of a particularly preferred group is t
Is 0, a mercapto group, a hydroxyl group, an episulfide group, a thioisocyanate group, an isocyanate group, or the like; t is 1, s is 1, and R ² has 1 to ² carbon atoms.
A group having a mercapto group such as a mercaptomethylthio group or a 2-mercaptoethylthio group as a polyaddition functional group as the hydrocarbon group of; a hydroxymethylthio group,
A group having a hydroxyl group such as a 2-hydroxyethylthio group as a polyaddition functional group; a group having an isocyanate group such as an isocyanate methylthio group and a 2-isocyanatoethylthio group as a polyaddition functional group; thioisocyanate A group having a thioisocyanate group such as a natomethylthio group or a 2-thioisocyanatoethylthio group as a polyaddition functional group; a group having an episulfide group such as a β-epithiopropylthio group as a polyaddition functional group And the like; t is 2, s is 1, and R ² is a hydrocarbon group having 1 to ² carbon atoms;
A group having a mercapto group such as a (2-mercaptoethylthio) ethylthio group as a polyaddition functional group; a group having a hydroxyl group such as a 2- (2-hydroxyethylthio) ethylthio group as a polyaddition functional group Can be mentioned.

In the general formula (1), a is an integer of 2 to 6, that is, 2 to 6 groups represented by Z are bonded to the adamantyl group. From the viewpoint of ease of synthesis, a is preferably 2-4. The groups represented by Z may be the same or different. In the case of different groups, it is preferable to have a polyaddition functional group of only one kind of the group on the side to be added or the group on the side to be added as described above.

In the compound represented by the general formula (1) of the present invention, in addition to the polyaddition functional group and / or the group having a polyaddition functional group, the compound represented by R ¹ and having 1 to 6 carbon atoms. One to six alkyl groups, C2-6 acyloxy groups and / or C2-6 acylthio groups may be bonded to the adamantane ring.

As the alkyl group having 1 to 6 carbon atoms,
Any known alkyl group may be used, but preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an n-pentyl group, an isopentyl group,
A linear or branched one such as an n-hexyl group or a 2-methylpentyl group. Specific examples of preferable acyloxy groups having 2 to 6 carbon atoms include acetyloxy group and propionyloxy group, and preferable examples of acylthio groups having 2 to 6 carbon atoms include acetylthio group and propionylthio group. To be done.

When there are a plurality of R ¹ (b is 2 to 6)
In each case), they may be the same or different.

The sulfur-containing polymerizable adamantane compound represented by the above general formula (1) contains at least one sulfur atom. The sulfur atom, a mercapto group or thioisocyanate group as described above, may be present as atoms constituting the polyaddition functional groups in the form of such episulfide ^{group, (- S-R 2 -} ), It may exist as an atom constituting (— [S] _s— R ² —) _t in the form of (—S—R ² —S—R ² —) or the like, or R ^{1 in} the form of an acylthio group or the like. It may exist as an atom constituting, or these existence forms may be mixed.

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

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

[0064]

[Chemical 6]

[0065] [In the above formulas, ^{R 1} has the same meaning as ^{R 1} in the general formula (1), the ^{R 4} is mercapto or thio isocyanate groups, a is an integer of 1 to 6, b is 0 The integer of 6, c is an integer of 0 to 4, a + c is 2 to 6, and when c is 1 to 4, R ⁴ is a mercapto group. In the general formula (3), the sulfur-containing polymerizable adamantane compound has 2 to 6 mercapto groups (and hydroxyl groups) or thioisocyanate groups as polyaddition functional groups.
Further, at least two sulfur atoms are present in the atomic group constituting the mercapto group or thioisocyanate group.

Specific examples of the sulfur-containing polymerizable adamantane compound represented by the above general formula (3) include compounds in which R ⁴ is a mercapto group, 1,3-adamantanedithiol and 2,4-dimethyladamantane- 1,3-dithiol, 1,3,5-adamantane trithiol,
1,3,6-adamantane trithiol, 1,3,5
7-adamantane tetrathiol, 1,2,3,5,7
-Adamantane pentathiol, 5-mercaptoadamantane-1,3-diol, 5,7-dimercaptoadamantane-1,3-diol, 1-acetyloxyadamantane-3,5-dithiol, 1-acetylthioadamantane-3, 5-dithiol, 1-acetylthioadamantane-3,5,7-trithiol and the like are compounds in which R ⁴ is a thioisocyanate group, 1,3-adamantane dithioisocyanate and 1,3,5-adamantane trithio. Examples thereof include isocyanate and 2,4-dipropyladamantane-1,3-dithioisocyanate.

When the sulfur-containing polymerizable adamantane compound represented by the above 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 thiocyanate, thiourea, triphenylphosphine sulfide, or thiamethylbenzothiazol-2-thione. A method of reacting with an agent, or a compound in which an adamantyl group is directly bonded to a hydroxyl group and thiocyanate, thiourea, triphenylphosphine sulfide,
It can be obtained by a method of reacting with a thiating agent such as 3-methylbenzothiazol-2-thione.

A more specific description of such a manufacturing method is as follows. (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), an adamantyl group is directly bonded to a halogen atom. The reaction conditions in the case of reacting the compound (hereinafter, simply referred to as a halogenated adamantane compound) and the thiating agent are not particularly limited, and known conditions may be appropriately selected and adopted, but general reaction conditions are It is as follows. That is, the halogenated adamantane compound is reacted with at least one equivalent of a thialating agent with respect to the halogen atom of the halogenated adamantane compound to be converted into a mercapto group. The thiation agent is as described above.

In these reactions, hydrogen halide is produced as the reaction progresses, so it is generally carried out in the presence of a basic compound for trapping this. Examples of the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; lithium methoxide, sodium methoxide, sodium ethoxide, t
Alkali metal salts of alcohols such as potassium butoxy; organic bases such as triethylamine, pyridine and quinoline.

In the above reaction, it is preferable to use a solvent because the halogenated adamantane compound and the thiating agent are usually solid. Examples of the solvent preferably used as the solvent include water; alcohol solvents such as methanol, ethanol, and isopropanol; pentane, hexane, cyclohexane, heptane, benzene, toluene,
A hydrocarbon solvent such as xylene can be used. These solvents may be appropriately selected depending on the type of halogen compound or basic compound used in the reaction, but generally, a solvent showing 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 raw material and solvent, but is generally 50 to 350 ° C.,
It is preferably 100 to 300 ° C. The reaction time also varies depending on the type of raw material, but is usually in the range of 10 minutes to 200 hours, preferably 1 hour to 60 hours. When the reaction is carried out at a temperature not lower 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) As another method for obtaining a compound having a mercapto group as a polyaddition functional group represented by the general formula (3), an adamantyl group is directly bonded to a hydroxyl group. A method of reacting the compound (hereinafter, simply referred to as adamantatyl alcohol) with a thiating agent can be mentioned. Although these reaction conditions are not particularly limited, general reaction conditions are as follows.

That is, 1 equivalent or more of a thialating agent is reacted with adamantyl alcohol and the hydroxyl group of the adamantyl alcohol to be converted into a mercapto group. The thiating agent in this case is as described above. These reactions are generally carried out in the presence of an acidic compound in order to promote generation of carbocation which is an intermediate. 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 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 adamantyl alcohol or the thiating agent is added to the acidic compound. When the solubility is low, it is preferable to use a solvent. Examples of suitable solvents include water; alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as diethyl ether, dioxane and tetrahydrofuran; pentane, hexane, cyclohexane, heptane, benzene and toluene. And a hydrocarbon solvent such as 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 above reaction varies depending on the type of raw material and solvent, but is generally 20 to 200 ° C.,
It is 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. Further, 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 reaction device such as an autoclave. Depending on the raw materials used, the reaction may be promoted by removing the water generated during the reaction. At that time, azeotropic dehydration can be carried out by a water distilling device such as Dean Stark.

By carrying out the above reaction, the adamantyl alcohol and the thiating agent form a salt. Then, the salt is decomposed by heating and stirring the reaction mixture in the presence of a basic compound to give the desired content. Sulfur-polymerizable adamantane compound. Examples of the basic compound used here include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alcohols such as lithium methoxide, sodium methoxide, sodium ethoxide and potassium t-butoxide. Alkali metal salts; organic bases such as triethylamine, pyridine, quinoline and the like can be mentioned. The basic 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 raw material and solvent, but is generally 20 to 200 ° C, and preferably 80 to 150 ° C. The reaction time also varies depending on the type of raw material, but is usually 1
It is in the range of 0 minutes to 48 hours, preferably 1 hour to 24 hours.

A compound containing both mercapto group / hydroxyl group can be obtained by controlling the amount of the thiating agent used in the reaction or the acidic compound serving as a catalyst, the reaction time, and the reaction temperature to make some of the hydroxyl groups unreacted. Can be obtained.

When the compound represented by the general formula (3) has an alkyl group as R ¹ , a halogenated adamantane compound as a raw material or a compound having the alkyl group as an adamantyl alcohol may be used. .
When it has an acyloxy group or an acylthio group,
The mercapto group or hydroxyl group of the compound having a mercapto group or hydroxyl group obtained by the above method may be acylated with various known acylating agents. As the reaction conditions in this case, known acylation conditions may be appropriately selected and employed.

(Iii) Method for Producing Compound Having Thioisocyanate Group (Production Method C) The compound having a thioisocyanate group as a polyaddition functional group represented by the general formula (3) is, for example, an adamantyl group. Starting from an amine compound directly bonded to an amino group,
It can be obtained by a method in which carbon disulfide is reacted in the presence of a base to obtain a dithiocarbamate, and then phosgene or an alkyl chloroformate is reacted to cause thermal decomposition.

As the amine compound having an adamantyl group as a raw material (hereinafter, aminated adamantane compound), a known compound is used, or a halogenated adamantane compound or adamantyl alcohol as described above is used as a raw material, and chlorine contained in the compound is used. , A halogen atom such as bromine or a hydroxyl group is converted to an amino group by reacting with ammonia. Known conditions may be appropriately adopted as the amination 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. The general reaction conditions are as follows. Is. That is, the aminated adamantane compound is reacted with 1 equivalent or more of carbon disulfide per amino group. These reactions are generally performed in the presence of a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia water; alcohols such as lithium methoxide, sodium methoxide, sodium ethoxide and potassium t-butoxide. Mention may be made of alkali metal salts.

In the above reaction, it is generally preferable to use a solvent in order to increase the solubility of the basic compound. Examples of suitable solvents include water; alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as diethyl ether, dioxane and tetrahydrofuran; pentane, hexane, cyclohexane, heptane, benzene and toluene. And a hydrocarbon solvent such as xylene. 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-mentioned reaction varies depending on the kinds of the raw materials and the solvent, but it is generally from -10 to 150 ° C, preferably from 20 ° C to the reflux temperature. 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 8 hours.

The obtained dithiocarbamate salt can be generally used for the next reaction after being purified and / or as it is in an unpurified state, but it is preferably used in an unpurified state from the viewpoint of easiness of operation.

In order to convert the dithiocarbamate into an adamantane compound having an isocyanate group,
An alkyl chloroformate or phosgene is added to the reaction solution containing the crude dithiocarbamate obtained by the above method to cause a reaction and then thermally decomposed, or thermally decomposed while reacting. Alkyl chloroformate or phosgene added at this time is 1 relative to the crude dithiocarbamate.
Use more than equivalent. As the alkyl chloroformate,
Examples thereof include methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate and the like. In the above reaction, it is not necessary to add a solvent when the crude dithiocarbamate is reacted in an unpurified state, but it is preferable to use a solvent when the crude dithiocarbamate is reacted after purification. Examples of suitable solvents include water; ether solvents such as diethyl ether, dioxane and tetrahydrofuran; pentane, hexane, cyclohexane, heptane, benzene,
A hydrocarbon solvent such as toluene or xylene can be used.

In the method of reacting a dithiocarbamate with an alkyl chloroformate or phosgene and then thermally decomposing it, first, the reaction is carried out at 20 to 70 ° C. for 1 hour.
The time is 0 minutes to 48 hours, preferably 1 hour to 8 hours. Then, water is added to the reaction mixture containing the obtained intermediate, the organic phase is separated, and subsequently dried, and then heated to 70 to 120 ° C. while containing the solvent or after distilling the solvent to obtain the desired product. You can get it.

When the method of thermally decomposing while reacting is adopted, the reaction may be carried out at a temperature of 70 to 120 ° C.

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

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

[0090]

[Chemical 7]

[In the above formula, R¹, R^TwoAnd b are either
Also in the general formula (1)¹, R ^TwoSynonymous with and b
And d is an integer of 1 to 6, and c is an integer of 0 to 4.
, D + c is an integer of 2 to 6, u is 1 or 2, v
Indicates 1 or 2. When v is 2, (-[S]
_u-R²The groups represented by-) may be the same or different.
Good, and even R¹Groups represented by and {(-[S]_u-R²
−)_vAnd when any of the groups represented by —SH} are plural,
May be the same or different. ] In the above general formula (4), sulfur-containing polymerizable adamanta
Compounds have 1 to 6 mercuric groups as polyaddition functional groups.
Have a hydroxyl group and 1 to 4 hydroxyl groups, or have a hydroxyl group
It has 2 to 6 mercapto groups. With the mercapto group
The total number of hydroxyl groups is 2 to 6. The sulfur atom is a merca
And the mercapto group and the
At least one in each of the organic residues connecting the mantyl groups
Exist each.

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

Specific examples of the sulfur-containing polymerizable adamantane compound of the present invention represented by the above 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, 1,3,3 5-
Tris [2- (2-mercaptoethylthio) ethylthio] adamantane, 1,3-bis (2-mercaptoethyldithio) adamantane, 1,3,5-tris (2-mercaptoethyldithio) adamantane, 1,3,5 , 7
-Tetrakis (2-mercaptoethyldithio) adamantane, 1,3,5-tris [4- (2-mercaptoethyl-1-dithio) phenyldithio] adamantane, 1,
3,5-Tris [2- (4-mercaptophenyldithio) ethyldithio] adamantane, 3- (2-mercaptoethylthio) -2,2-dimethyladamantane-1-
Examples include compounds such as all and 3,5-bis (2-mercaptoethylthio) adamantan-1-ol.

The sulfur-containing polymerizable adamantane compound represented by the general formula (4) is generally produced by the production method B shown in the general formula (3) using adamantyl alcohol as a starting material. Accordingly, instead of the step of (i) using a dimercapto compound instead of the thiating agent and (ii) heating and stirring the reaction mixture in the presence of a basic compound to decompose the salt, the acid used in the reaction is used. It is possible to change the point of carrying out the step of neutralizing and to carry out other conditions under the same conditions. Here, the dimercapto compound refers to a compound having two mercapto groups in the molecule, and examples thereof include ethanedithiol, bis (2-mercaptoethyl) sulfide, and propanedithiol. The dimercapto compound is preferably used in an amount of 5 equivalents or more with respect to one hydroxyl group possessed by adamantyl alcohol. Further, by controlling the amount of the dimercapto group-containing compound or the acidic compound used as a catalyst, the reaction time, the reaction temperature, and the like,
A part of the hydroxyl groups can be left unreacted and left.

The acid is neutralized by adding a hydroxide of an alkali metal or an alkaline earth metal such as sodium hydroxide, potassium hydroxide or calcium hydroxide to a solution having a pH of about 5-9. Add until you get it.

Also in this case, when R ¹ is contained, the introduction method is the same as that of the compound represented by the general formula (3).

Further, instead of adamantyl alcohol as a raw material, a compound represented by the above general formula (3) can be used, and it can be produced in the same manner as above.

As still another production method, a compound having a hydroxyl group as a polyaddition functional group of R ⁵ among the compounds represented by the general formula (5) described later is used, and the hydroxyl group is subjected to the production method B described above. The method of converting into a mercapto group according to

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

[0100]

[Chemical 8]

[In the above formula, R¹, R^TwoAnd b are either
Also in the general formula (1)¹, R ^TwoSynonymous with and b
And R⁵Is a hydroxyl group, a carboxyl group or an amino group
, D is an integer of 1 to 6, c is an integer of 0 to 4,
d + c is an integer of 2 to 6, u is 1 or 2, and v is 1
Or 2 and the product of d, u and v is 2 or more (d × u
Xv ≧ 2). When v is 2, (-[S]
_u-R²The groups represented by-) may be the same or different.
Good, and even R¹Groups represented by and {(-[S]_u-R²
−)_v-R^Five}, When there are plural groups
May be the same or different. ] In the compound represented by the above general formula (5), polyaddition
As the functional group, a hydroxyl group, a carboxyl group and / or
It has 2 to 6 mino groups. The sulfur atom is (-[S]_u-R
²−)_vThere is at least one in the group represented by
When there is one sulfur atom in, {(-[S]
_u-R^Two−)_v-R⁵} The group represented by} is at least 2
Exist.

Specific examples of the sulfur-containing polymerizable adamantane compound represented by the above general formula (5) include 1,3-bis (hydroxymethylthio) adamantane, 1,3-bis (2-hydroxyethylthio) adamantane, 1,3
-Polyaddition functionality such as bis [2- (2-hydroxyethylthio) ethylthio] adamantane, 1,3-bis (hydroxymethyldithio) adamantane, 5,7-bis (hydroxymethylthio) adamantane-1,3-diol A compound having only a hydroxyl group as a group; 1,3-bis (carboxymethylthio) adamantane, 1,3-bis (3
Compounds having a carboxyl group as a polyaddition functional group such as -carboxypropylthio) adamantane and 1,3-bis (3-carboxypropyldithio) adamantane;
1,3-bis (aminomethylthio) adamantane, 1,
3-bis (2-aminoethylthio) adamantane, 1,
Examples thereof include compounds having an amino group as a polyaddition functional group such as 3-bis (2-aminoethylthio) -5,7-dimethyladamantane and 1,3-bis (2-aminoethyldithio) adamantane. Among these, in the general formula (5), a compound in which u is 1 is preferable, and a compound in which d is 2 to 4 is 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 easiness of synthesis.

As a method for synthesizing the compound having an amino group among the compounds represented by the general formula (5), the production method B described for the compound represented by the general formula (3) is generally used. , (I) a compound having a mercapto group and an amino group or a protected amino group in place of the thiating agent (hereinafter referred to as a mercapto group-containing amino compound), and (ii) a basic compound for decomposing the salt. In the presence of the compound, in place of the step of heating and stirring the reaction mixture, (a) when using a compound having an amino group, neutralizing the acidic compound used in the reaction with a basic compound,
(b) When a compound having a protected amino group is used, the same method is used using adamantyl alcohol as a raw material, except that an amino group is produced using a deprotecting agent such as an acid or a basic compound. You can

Specific examples of the mercapto group-containing amino compound include 2-aminoethyl mercaptan and 2-aminoethyl mercaptan.
Aminopropyl mercaptan, 4-aminocyclohexyl mercaptan, 4-aminophenyl mercaptan, etc.
And the amino group of these compounds are protected in the form of an acetamido group, an N-toluenesulfonyl group, a benzyloxycarbonyl group, a phthalimido group, an amide group such as a trifluoroacetyl group, and an imide group such as a phthalimido group. A compound is illustrated.

The mercapto group-containing amino compound is usually used in an amount of 1 equivalent or more, preferably 5 equivalents or more, per one hydroxyl group of adamantyl alcohol.

As a method of synthesizing a compound having a carboxyl group among the compounds represented by the general formula (5), generally, an amino group among the compounds represented by the above general formula (5) is In the method for producing a compound having, a method of using a compound having a carboxyl group or a protected carboxyl group and a mercapto group instead of the mercapto group-containing amino compound (hereinafter, referred to as a mercapto group-containing carboxyl compound) is adopted. do it.

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 the carboxyl group contained in these compounds is methyl. Examples include compounds protected in the form of an ester such as an ester group, a benzyl ester group, and a t-butyl ester group.

Further, 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-mentioned general formula (5), instead of the mercapto group-containing amino compound, a hydroxyl group or a protected group is protected. A method using a compound having a hydroxyl group and a mercapto group (hereinafter referred to as a mercapto group-containing alcohol) may be adopted.

Examples of the mercapto group-containing alcohol include 2-mercaptoethanol, 2-mercaptopropanol, 4-mercaptocyclohexanol, 4-mercaptophenol, and the like, and the hydroxyl groups of these compounds are methyl ether group, benzyl ether group, 2-methoxyethoxymethyl ether group, allyl ether group,
Examples include compounds protected in the form of ether such as t-butyldimethylsilyl ether group.

In any of the above methods, when neutralizing the (a) acidic compound, a hydroxide of an alkali metal or alkaline earth metal such as sodium hydroxide, potassium hydroxide or calcium hydroxide is used, It may be added until the pH of the solution obtained by the reaction becomes about 5 to 9, and (b) when deprotecting a compound having a protected group, a known deprotection method may be appropriately adopted. Good. (D) Compound represented by the following general formula (6)

[0111]

[Chemical 9]

[0112] [In the above ^formulas, R ^1, are both ^R 2, a and b, ^R 1 in the general formula ^{(1), R} 2, a and b
Is synonymous with, R ⁶ is an epoxy group, an isocyanate group,
A thioisocyanate group or an episulfide group, u
Represents 1 or 2, and v represents 1 or 2. Further, v when is _{2, (- [S] u -R} 2 -) groups represented by may each be the same or different, further, a group represented by R ¹ and {(- [S] both) _v group represented by -R ^6} is, - _u -R ²
When there are two or more, they may be the same or different. In the general formula (6), the sulfur-containing polymerizable adamantane compound has 2 to 6 epoxy groups, isocyanate groups, thioisocyanate groups and / or episulfide groups as polyaddition functional groups. Further, at least one sulfur atom is present for each group connecting the polyaddition functional group and the adamantyl group.

Specific examples of the compound represented by the above general formula (6) include 1,3-bis (glycidylthio) adamantane, 1,3,5-tris (glycidylthio) adamantane and 1,3-bis [( Compounds having an epoxy group as a polyaddition functional group such as 3,4-epoxycyclohexyl) ethyldithio] adamantane; 1,3-bis (isocyanatomethylthio) adamantane, 1,3-bis (2-isocyanatoethyl) Thio) 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) adamantane, 1,3-bis (2-isocyanatomethyldithio) adamantane, 1,3-bis (2-isocyanatoethyldithio) adamantane, 1,3-bis (isocyanate) Compounds having an isocyanate group as a polyaddition functional group such as natomethyldithio) adamantane; 1,3-bis (thioisocyanatomethylthio) adamantane, 1,
3-bis (2-thioisocyanatoethylthio) adamantane, 1,3-bis (2-thioisocyanatopropylthio) adamantane, 1,3-bis (2-thioisocyanatopropylthio) -5-methyladamantane,
1,3,5-Tris (thioisocyanatomethylthio)
Adamantane, 1,3,5-tris (2-thioisocyanatoethylthio) adamantane, 1,3-bis (2-
Thioisocyanatomethyldithio) adamantane, 1,
A compound having a thioisocyanate group as a polyaddition functional group such as 3-bis (2-thioisocyanatoethyldithio) adamantane and 1,3,5-tris (thioisocyanatomethyldithio) adamantane, 1,3- Bis (β-
Epithiopropylthio) adamantane, 1,3,5-tris (β-epithiopropylthio) adamantane, 1,
An episulfide compound such as 3-bis (β-epithiopropyldithio) adamantane is exemplified.

The sulfur-containing polymerizable adamantane compound represented by the above general formula (7) can be generally produced by the following method.

In the case of a compound having an epoxy group as a polyaddition functional group, it is represented by, for example, an adamantane compound having a mercapto group represented by the general formula (3) or (4) and epichlorohydrin. It can be obtained by reacting epihalohydrin with an alkali in the presence of an alkali.

In this method, the epihalohydrin compound is preferably epichlorohydrin.
In addition, the epihalohydrin compound is one of the mercapto groups of the adamantane compound having a mercapto group.
It is preferable to use 1 equivalent or more, preferably 2 to 30 equivalents. The reaction may be carried out without a solvent or using a solvent. When using a solvent, it is desirable to use one in which either the adamantane compound having a mercapto group as a raw material or epihalohydrin is soluble. Specific examples of the solvent include water, amides, alcohols,
Examples thereof include sulfoxides, ethers, aromatic hydrocarbons, halogenated hydrocarbons and the like. The reaction easily proceeds in the presence of a stoichiometric amount of base or more. That is, 1 mol or more of the base may be used with respect to 1 mol of the epihalohydrin compound used. Examples of the base include tertiary amines such as pyridine, triethylamine and diazabicycloundecene, and hydroxides of alkali or alkaline earth metals. Preferred are hydroxides of alkali metals or alkaline earth metals. And more preferably,
Examples thereof include sodium hydroxide and potassium hydroxide. The reaction temperature is usually -10 to 100 ° C, preferably-
It is 10 to 60 ° C. The reaction time may be any time as long as the reaction is completed under the various conditions described above, but usually 10 hours or less is suitable.

As another method of producing an epoxy compound, a method of producing an unsaturated compound corresponding to the desired epoxy compound by oxidation with an organic peracid, alkylhydroperoxide, hydrogen peroxide, etc. can also be adopted. . Various conditions for producing the epoxy compound by the oxidation may be appropriately selected from known conditions and employed.

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 thiocyanate, thiourea or triphenylphosphine sulfide. ,
It can be obtained by a method of reacting with a thiating agent such as 3-methylbenzothiazol-2-thione to convert into an episulfide group.

In the method for producing an episulfide compound from a compound having an epoxy group, when thiocyanate is used as a thiating agent, a preferable thiocyanate is a salt of amine, alkali metal or alkaline earth metal. More preferable are potassium thiocyanate and sodium thiocyanate. The thiocyanate is used stoichiometrically in a 1-fold molar amount relative to the epoxy compound, but is preferably used in a 1- to 10-fold molar amount for the reaction. More preferably, 1 to 5 times the molar amount is used for the reaction. The reaction may be carried out without solvent or in a solvent, but when a solvent is used, it is desirable to use one in which any of thiocyanate, thiourea and epoxy compound is soluble.

Specific examples of the solvent include water and methanol.
Alcohols such as alcohol, ethanol and isopropanol,
Ethers such as diethyl ether, tetrahydrofuran, dioxane; methyl cellosolve, ethyl cellosolve,
Examples thereof include hydroxy ethers such as butyl cellosolve; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloroethane, chloroform and chlorobenzene. Further, adding an acid, an acid anhydride or the like as a polymerization inhibitor to the reaction solution is an effective means from the viewpoint of increasing the yield. Specific examples of the acid and acid anhydride 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, anhydrous nitric acid, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, Examples thereof include phthalic anhydride, silica gel, silica alumina, aluminum chloride and the like, and it is possible to use some of them in combination. The addition amount is usually 0.001 to 10 wt% with respect to the total amount of the reaction solution. The reaction temperature is usually 0 to 100 ° C., preferably 20.
~ 70 ° C. The reaction time may be any time as long as the reaction is completed under the above-mentioned various conditions, but usually 20 hours or less is suitable. The reaction product can be washed with an acidic aqueous solution to improve the stability of the resulting compound. 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,
Examples thereof include peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid and maleic acid. These may be used alone or in combination of two or more. Aqueous solutions of these acids usually exhibit effects at pH 6 or lower, but more effectively at pH 3 or lower.

As a method for synthesizing a compound having an isocyanate group, for example, in the sulfur-containing polymerizable adamantane compound represented by the general formula (5), the polyaddition functional group is a carboxyl group, and Hydrazinocarbonyl is obtained by reacting a compound having d of 2 or more with an alcohol under heating under reflux with a lower alcohol to obtain an alkyl ester derivative, and reacting the alkyl ester derivative with hydrazine hydrate under ice cooling. After introducing a group and further reacting with sodium nitrite in dilute hydrochloric acid, Curt in hot benzene
It can be obtained by ius rearrangement.

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 or the like can be used, and as the lower alcohol, methanol, ethanol, propanol or the like can be mentioned. The amount of the lower alcohol used is not particularly limited as long as it is 1 equivalent or more with respect to one carboxyl group, and the lower alcohol used may be used as a solvent. Moreover,
A solvent such as toluene or benzene may be used. Water produced by the reaction may be subjected to azeotropic dehydration by using a Dean-Stark apparatus with anhydrous sodium sulfate, a dehydrating agent such as molecular sieve, or toluene as a solvent. The reaction can be carried out at room temperature or above and below the boiling point of the solvent, but it is generally preferred to carry out under reflux.

Then, the obtained ester derivative is reacted with hydrazine hydrate to obtain a hydrazinocarbonyl derivative. The amount of hydrazine hydrate used at this time is not limited as long as it is 1 equivalent or more with respect to one ester group, but in general, a range of 1 to 10 equivalents is preferable. At this time, as a reaction solvent, methanol, ethanol, propanol, butanol, THF, dioxane,
A polar solvent such as water can be used, but it is preferable to use a lower alcohol in which the ester derivative as a raw material is dissolved and a product is precipitated. 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 preferably cooled to room temperature or lower.

Then, the obtained hydrazinocarbonyl derivative is reacted with nitrite in a dilute acid and then subjected to Curtius rearrangement under heating conditions to obtain the desired 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 interfere with the reaction can be used together.
The reaction temperature with nitrite is Curtius
There is no particular limitation as long as it is a reaction temperature at which a transfer reaction does not occur, but a range of 0 to 10 ° C is desirable. The obtained reaction product is
Since it usually precipitates, it is collected by filtration. Then, the filtrate is subjected to Curtius transfer by heating to be converted into a target compound having an isocyanate group. The Cu
The solvent for the rtius 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 depending on the starting material and solvent used, and is generally 30 to 120 ° C.

In the case of a compound having a thioisocyanate group as a polyaddition functional group, the thioisocyanate group is introduced by the same method as described for the compound represented by the general formula (4). It can be manufactured. In this case, the starting 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 polyaddition functional group is an isocyanate group or a thioisocyanate group in view of physical properties of the obtained optical material and easiness of polyaddition reaction. A compound having a nato group and / or an episulfide group is preferable. Further, in consideration of easiness of synthesis and the like, a compound in which u is 1 is preferable, and a compound in which d is 2 to 4 is more preferable.

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

[0128]

[Chemical 10]

[In the above formula, R ¹ , a and b are all
R ¹ in the general formula (1) has the same meaning as a and b,
R ⁷ and R ⁸ each independently have the same meaning as R ² in the general formula (1), u is 1 or 2, and w is an integer of 0 to 2. When w is 2, (-[S] _u- R
^The groups represented by 8-- may be the same or different, and further, the group represented by R ¹ and [-R ⁷ -(-[S]
_When there are a plurality of groups represented by _u —R ⁸ —) _w —SH], they may be the same or different. ]

[0130]

[Chemical 11]

[In the above formula, R ¹ , a and b are all
R ¹ in the general formula (1) has the same meaning as a and b,
R ⁷ and R ⁸ each independently have the same meaning as R ² in the general formula (1), R ⁹ is any group selected from a thioisocyanate group and an episulfide group, and u is 1 or 2. , W represents an integer of 0 to 2. Further, when w is _{2, (- [S] u -R} 8 -) groups represented by may each be the same or different, further, a group represented by R ¹ and [-R 7 ^- ( ^- [S] _u -R 8 - none) groups represented by _w -R ^9], each may be the same or different when there are a plurality of. The compound represented by the general formula (7) or (8) has at least 2 as a polyaddition functional group of a mercapto group, a thioisocyanate group or an episulfide group.
I have one. Since one sulfur atom is present in each atomic group constituting these polyaddition functional groups, the number of sulfur atoms contained in the molecule is at least two or more.

Specific examples of the compound represented by the above general formula (7) include 1,3-bis (mercaptomethyl) adamantane and 1,3,5-tris (mercaptomethyl).
Examples thereof include adamantane, 1,3-bis (2-mercaptoethylthiophenyl) adamantane, and 2,2-bis (2-mercaptoethylthiophenyl) adamantane.

The compound represented by the general formula (8) includes 1,3-bis [(2-thioisocyanatomethylthio) ethyl] adamantane and 1,3-bis (2-thioisocyanatoethylthiomethyl) adamantane. , 1,3
-Bis (2-thioisocyanatopropylthiomethyl)
Adamantane, 1,3-bis (2-thioisocyanatopropylthiomethyl) -5-methyladamantane, 1,
3-bis [4- (thioisocyanatomethylthio) phenyl)] adamantane, 1,3-bis [4- (2-thioisocyanatoethylthio) phenyl] adamantane,
A compound having a thioisocyanate group as a polyaddition functional group such as 2,2-bis [4- (2-thioisocyanatoethylthio) phenyl] adamantane; 1,3-bis (β
-Epithiopropylthiomethyl) adamantane, 1,
Compounds having an episulfide group as a polyaddition functional group such as 3,5-tris (β-epithiopropylthiomethyl) adamantane and 1,3-bis [2- (β-epithiopropyldithio) ethyl] adamantane It is specifically exemplified.

The compound represented by the general formula (7) can be produced by the method described in the general formula (4), using as a raw material a compound in which a hydroxyl group is bonded to an adamantyl group through a carbon atom or the like. Here, the compound in which the hydroxyl group is bonded to the 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 and 1,3-bis (2-hydroxyethyl) adamantane are respectively adamantane-
1,3-dicarboxylic acid or adamantane-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.

Of the compounds represented by the general formula (8), the compounds having a thioisocyanate group as a polyaddition functional group have an amino group such as the compound represented by the general formula (10) described later. It can be produced from a compound by converting an amino group into a thioisocyanate group by a method similar to that described for the compound represented by the general formula (6).

Further, among the compounds represented by the general formula (8), the compound having an episulfide as a polyaddition functional group is, for example, a compound having a mercapto group represented by the general formula (7) as a raw material, Similar to the method for producing the compound represented by the general formula (6), a method of reacting the compound with epihalohydrin to form an epoxy compound, and then converting the epoxy group of the epoxy compound into an episulfide group with a thiolizing agent Can be manufactured by

Among the compounds represented by the above general formula (7) or (8), a compound in which u is 1 is preferable from the viewpoint of physical properties when used as an optical material and easiness of synthesis, and among them, A compound in which w is 0 or 1 and a is 2 to 4 is more preferable.

(F) Compound represented by the following general formula (9) or (10)

[0139]

[Chemical 12]

[In the above formula, R ¹ , a and b are all
R ¹ in the general formula (1) has the same meaning as a and b,
R ⁷ and R ⁸ each independently have the same meaning as R ² in the general formula (1), R ¹⁰ is an epoxy group or an isocyanate group, u is 1 or 2, and x is 1 or 2. Further, when x is _{2, (- [S] u -R} 8 -) groups represented by may each be the same or different, further, a group represented by R ¹ and {-R 7 ^- ( ^{_{- [S] u -R 8 -}} ) x -R
^When there are a plurality of groups represented by ^{10 3} }, they may be the same or different. ]

[0141]

[Chemical 13]

[In the above formula, R¹, A and b are
R in the general formula (1)¹, A and b are synonymous with
R⁷And R⁸Are each independently in the general formula (1)
R^TwoIs synonymous with R¹¹Is a hydroxyl group, amino group or
A ruboxyl group, u is 1 or 2, and x is 1 or 2.
You When x is 2, (-[S]_u-R⁸-)
The groups may be the same or different, and
R¹And a group represented by {-R ⁷-(-[S]_u-R⁸−)_x
-R¹¹}, When there are plural groups,
Each may be the same or different. ] The compound represented by the general formula (9) or (10) is less
There are at least two {-R⁷-(-[S]_u-R⁸−)_x
There is one or more in each of the groups indicated by −}, and
There are at least two sulfur atoms in the molecule.

Specific examples of the compound represented by the above general formula (9) include 1,3-bis (glycidylthiomethyl) adamantane, 1,3,5-tris (glycidylthiomethyl) adamantane, 1,3- Screw {2- [2-
Compounds having an epoxy group as a polyaddition functional group such as (3,4-epoxycyclohexyl) ethyldithio] ethyl} adamantane; 1,3-bis [2- (isocyanatomethylthio) ethyl] adamantane, 1,3-bis (2
-Isocyanatoethylthiomethyl) adamantane,
1,3-bis (2-isocyanatopropylthiomethyl) adamantane, 1,3-bis (2-isocyanatopropylthiomethyl) -5-methyladamantane, 1,
3-bis [4- (isocyanatomethylthio) phenyl] adamantane, 1,3,5-tris [4- (isocyanatomethylthio) phenyl] adamantane, 2,2
Examples thereof include compounds having an isocyanate group as a polyaddition functional group such as -bis [4- (2-isocyanatoethylthio) phenyl] adamantane.

The compound represented by the general formula (10) includes 1,3-bis (aminomethylthiomethyl) adamantane, 1,3-bis [2- (2-aminoethylthio) ethyl] adamantane, 1,3 3-bis (2-aminoethylthiomethyl) -5,7-dimethyladamantane,
A compound having an amino group as a polyaddition functional group such as 1,3-bis (2-aminoethyldithiomethyl) adamantane; 1,3-bis (hydroxymethylthiomethyl) adamantane, 1,3-bis [2- ( 2-hydroxyethylthio) ethyl] adamantane, 1,3-bis (2-hydroxyethylthiomethyl) -5,7-dimethyladamantane, 1,3-bis (2-hydroxyethyldithiomethyl) adamantane, etc. Compounds having a hydroxyl group as a functional group; 1,3-bis (carboxylmethylthiomethyl) adamantane, 1,3-bis [2- (2-carboxylethylthio) ethyl] adamantane, 1,3-bis (2-carboxylethyl) Thiomethyl) -5,7-dimethyladamantane, 1,3-bis (2-carboxylethyldithiomethyl) Compounds which have a carboxyl group are exemplified as polyaddition functional group such as adamantane.

As the method for synthesizing the compound represented by the general formula (9), the same method as 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 raw material compound, and in the case of a compound having an isocyanate group, a general formula ( A compound having a carboxyl group represented by 10) can be used.

As a method for synthesizing the compound represented by the general formula (10), the same method as the method for producing the compound represented by the general formula (5) can be used. In this case, the compound in which the hydroxyl group shown in the production method of the general formula (7) is bonded to the adamantyl group via the carbon atom can be used as the raw material compound.

Further, the compounds represented by the above general formulas (3) to (10) are not limited to the above-mentioned methods, but include hydroxyl group, mercapto group, isocyanate group, thioisocyanate group, epoxy group, It can also be produced by converting an episulfide group, a carboxyl group, an amino group and the like by various known methods.

The sulfur-containing polymerizable adamantane compound produced by the various production methods as described above is used, after being isolated if necessary. As the isolation method at this time, a known method can be used without any limitation. For example, when the purification yield or the decolorization operation does not need to be performed because the reaction yield is high, the water-soluble by-products such as the hydrogen chloride and the salt of the basic compound produced may be filtered or washed with water. After removing, the solvent may be simply distilled off. Further, when the reaction yield is low or when coloring is a problem, known purification operations such as distillation, column chromatography and the like, activated carbon treatment, adsorbent treatment such as silica treatment, or water, hydrochloric acid water or water. An operation appropriately selected from known decolorization operations such as washing with an aqueous sodium oxide solution may be performed.

The structure of the produced sulfur-containing polymerizable adamantane compound can be identified and confirmed by the following means, for example.

(I) 1H-nuclear magnetic resonance spectrum (1H-
By measuring NMR), the bonding mode of hydrogen atoms existing 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 a compound having a hydroxyl group, absorption due to OH stretching vibration in the vicinity of 3500 to 3650 cm-1, and in the case of a compound having a mercapto group is 25
Weak absorption due to SH stretching vibration at 50 to 2600 cm -1, 2 in the case of a compound having a thioisocyanate group
Strong absorption due to NCS stretching vibration around 040 to 2130 cm -1, strong absorption due to C = O stretching vibration near 1700 to 1750 cm -1 when having an acylthio group or acyloxy group, and having epoxy group near Two
Strong absorption based on C = O stretching vibration near 990 to 3050 cm -1, but 570 to 7 when having a sulfide group
Strong absorption due to stretching vibration of CS is observed near 10 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) Mass spectrum analysis (MASS, E
By method I), the molecular weight of the compound can be known.

Among the sulfur-containing polymerizable adamantane compounds represented by the above general formulas (3) to (10), the general formulas (3), (in terms of easy synthesis and high polyaddition reactivity) can be obtained. The compound represented by 4) or (6) is particularly preferable.

The sulfur-containing polymerizable adamantane compound obtained by the above method is made into a polymer by a polyaddition reaction. As described above, the polyaddition reaction is a reaction in which the functional group on the addition side and the functional group on the addition side react as a set. Therefore, except for the case where the polyaddition functional group is a cyclic group containing a hetero atom, in order to obtain a polymer,
Both a compound having at least two functional groups on the addition side and a compound having at least two functional groups on the addition side are necessary. On the other hand, the polyaddition functional group is an epoxy group,
In the case of a cyclic group containing a heteroatom such as an episulfide group, the cyclic group undergoes addition to open the ring, and thereby the side group to be added (hydroxyl group, mercapto group, etc.)
Is generated, and the newly generated group on the side of addition is subsequently added to the cyclic group containing a hetero atom, and therefore polymerization is performed only with a compound having a cyclic group containing a hetero atom as a polyaddition functional group. It is possible to

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 addition side and the compound having the functional group on the addition side may be the sulfur-containing polymerizable adamantane compound in the present invention, but the polymer Considering the cost of the raw material compound, various optical physical properties such as the Abbe number and refractive index of the resulting optical material, and mechanical properties such as impact resistance, the sulfur-containing polymerizable adamantane compound in the present invention, polyaddition It is preferable to obtain a polymer by reacting with another compound having a functional group (hereinafter referred to as a comonomer). Examples of the polyaddition functional group contained in these comonomers include the same groups as the polyaddition functional group contained in the sulfur-containing polymerizable adamantane compound in 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 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 are included. Are preferred.

Specific examples of such comonomers include comonomers having a functional group on the side to be added, polyhydric alcohol compounds such as trimethylolpropane and trimethylolpropane; methanedithiol and 1,2-ethane. Dithiol, 1,1-propanedithiol, 1,2
-Propanedithiol, 1,3-propanedithiol,
2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] pepta-exo-cis-
2,3-Dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto- 1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-
Mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3 -Propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2
-Mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate),
Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4,8-bis (mercaptomethyl)- 3,6,9-Trithia-1,
Aliphatic polythiols such as 11-undecanedithiol; 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2
-Bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyleneoxy) ) Benzene, 1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,2,2 4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene, 1,2,4-
Tris (mercaptoethyleneoxy) benzene, 1,
3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,
2,3,5-Tetrakis (mercaptomethyleneoxy)
Benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 2,4-dimethylbenzene-1,3-dithiol, 4,5 -Dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol , Phenylmethane-
Aromatic polythiols such as 1,1-dithiol and 2,4-di (p-mercaptophenyl) pentane; 2-methylamino-4,6-dithiol-sym-triazine, 2
-Thiobenzeneoxy-4,6-dithiol-sym-
Polythiols containing heterocycles such as triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine, and 2,5-bis (mercaptomethyl) -1,4-dithiane; 1,2-bis (mercapto) Methylthio) 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
-Aromatic polythiols containing a sulfur atom in addition to the mercapto group such as tetrakis (mercaptoethylthio) benzene and their nuclear alkylated compounds; bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) ) 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) propane, 1,3-bis (2-mercapto Ethylthio) 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) propane, 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; hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercapto) Acetate), hydroxyethyl sulfide bis (3
-Mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithian-2,5-diolbis (2-mercaptoacetate), 1,4-dithian-2,5-diolbis (3-
Mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester),
Dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis (2-
Mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester) ), Bis (2,3,2,2-dithiopropionate)
3-dimercaptopropyl ester) and other aliphatic polythiols containing a sulfur atom in addition to the mercapto group;
4-thiophenedithiol, 2,5-dimercapto-
Heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as 1,3,4-thiadiazole; polycarboxylic acids such as maleic acid, fumaric acid, phthalic acid, trimellitic acid and pyromellitic acid; 1,2-diamino Propane, 1,3-
Diaminopropane, 1,2-diaminobutane, 1,3-
Diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-
Primary polyamines such as diaminoheptane and 1,2-bis- (3-aminopropoxy) ethane; N, N'-diethylethylenediamine, N, N'-diethyl-1,2-
Diaminopropane, N, N'-diethyl-1,3-diaminopropane, piperazine, 2-methylpiperazine,
2,5- or 2,6-dimethylpiperazine, 1,2
-Di- (4-piperidyl) ethane, 1,3-di- (4-
Specific examples thereof include secondary polyamines such as piperidyl) propane, 1,4-di- (4-piperidyl) butane, and tetramethylguanidine. These comonomers are
Each of them may be used alone, or two or more kinds may be mixed and used.

Of the above comonomers, compounds having a plurality of mercapto groups (polythiols) are preferable,
2,2-bis (mercaptomethyl) -1,3-propanedithiol, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4,8-bis (mercaptomethyl) -3,6,9 -Trithia-1,11-undecanedithiol, 1,2,4-tris (mercaptomethyl) benzene and the like are mentioned as particularly preferable compounds.

Further, as the comonomer having a functional group on the addition side, as a compound having a (thio) isocyanate group as a polyaddition functional group, o-xylylene di (thio) isocyanate, m-xylylene di ( Thio) isocyanate, p-xylylene di (thio) isocyanate,
α, α, α ', α'-tetramethyl-p-xylylene di (thio) isocyanate, α, α, α', α'-tetramethyl-m-xylylene di (thio) isocyanate,
1,3,5-Tris [(thio) isocyanatomethyl]
Aromatic (thio) isocyanates such as benzene; 4-chloro-m-xylylene di (thio) isocyanate, 4,
5-dichloro-m-xylylene di (thio) isocyanate, 2,3,5,6-tetrabromo-p-xylylene di (thio) isocyanate, 4-methyl-m-xylylene di (thio) isocyanate, 4-ethyl-m -Aromatic (thio) isocyanates substituted with chlorine, bromine or lower alkyl groups such as xylylenedi (thio) isocyanate; isophorone di (thio) isocyanate, norbornene di (thio) isocyanate, bis [(thio) isocyanatomethyl ] Norbornene, methylenebis [cyclohexyl (thio) isocyanate], bis [(thio) isocyanatomethyl] cyclohexane and other monocyclic or polycyclic (thio) isocyanates; 1,3-dithiolane-4,5-di (thio) ) (Thio) isocyanate consisting of a ring containing a sulfur atom such as isocyanate Over preparative like; 4,5-bis [(thio)
Aliphatic (thio) such as isocyanatomethyl] -1,3-dithiolane, tris [(thio) isocyanatomethylthio] methane, hexamethylenedi (thio) isocyanate
Specific examples include isocyanates. Further, oligomers such as burettes and aflots of these (thio) isocyanates can be mentioned.

As a compound having an ethenyl group as a polyaddition functional group, divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol dithio (meth) acrylate, in one molecule Examples thereof include urethane-modified (meth) acrylates containing at least two or more (meth) acryloxy groups, epoxy-modified (meth) acrylates and polyester-modified (meth) acrylates, which have both ethenyl groups and (thio) isocyanate groups. Examples of the compound include 2- (meth) acryloxyethyl (thio) isocyanate and (meth) acryloyl (thio) isocyanate. These comonomers may be used alone or in combination of two or more. Among these, compounds having a (thio) isocyanate group as a polyaddition functional group are particularly preferable.

In order to obtain a polymer from the comonomer as described above and the sulfur-containing polymerizable adamantane compound of the present invention, usually, the polyaddition functional group contained in the sulfur-containing polymerizable adamantane compound of the present invention is When the polyaddition functional group of the comonomer is added, the polyaddition functional group of the comonomer is added to the side of the polyaddition functional group of the sulfur-containing polymerizable adamantane compound. When it is a group, the polyaddition functional group of the comonomer may be appropriately selected from compounds which are groups on the side to be added, and these may be polymerized by the method described below.

As described above, these comonomers include at least two or more polyaddition groups, regardless of whether they are groups to which the polyaddition functional group they have are added or groups to which they are added. It is necessary to include a comonomer having a functional group. Considering various physical properties of the resulting polymer, as a cross-linked polymer, as at least one of the sulfur-containing polymerizable adamantane compound or comonomer,
It is more preferable to add a compound having three or more polyaddition functional groups. If necessary, a comonomer having a group of the same type as the polyaddition functional group of the sulfur-containing polymerizable adamantane compound in the present invention may be further blended,
As the sulfur-containing polymerizable adamantane compound in the present invention, a compound having a group on the addition side and a compound having a group on the addition side are used in combination, and a compound having any polyaddition functional group as a comonomer. It is also possible to use.
Further, a compound having only one polyaddition functional group may be blended.

In these sulfur-containing polyaddition adamantane compounds and comonomers, (functional group on the side to be added / functional group on the side to be added) is 0.5 to 3 (preferably 0.5 to 1.
It is preferable to appropriately select and use the polymer within the range of 5) because the polymer obtained has good optical and mechanical properties. Specifically, for example, it is used so that (the number of (thio) isocyanate groups) / (the number of hydroxyl groups + the number of mercapto groups) is 0.5 to 3.0 (preferably 0.5 to 1.5). The sulfur-containing polyaddition adamantane compound and the comonomer are preferably added.

Further, from the viewpoint of excellent polymerizability, the compound having a (thio) isocyanate group as a polyaddition functional group and the compound having a mercapto group or a hydroxyl group are combined so that It is preferable to select the sulfur-containing polyaddition adamantane compound and comonomer in the invention.

Further, in order to obtain a polymer having an excellent balance between heat resistance and impact resistance, the mass derived from the adamantane ring in the finally obtained polymer (of the substituents of the 136-adamantane ring) Number; hereinafter referred to as AD ratio)
However, it is preferable to adjust the ratio of the sulfur-containing polymerizable adamantane compound to the comonomer so as to occupy 15 to 60% of the mass of the obtained polymer. Generally, a polymer having a higher AD ratio is more excellent in heat resistance, and conversely, a lower AD ratio is more excellent in impact resistance.

In order to attain such a range, it is possible to use a compound having a molecular weight of 50 to 500 as the comonomer and polymerize the sulfur-containing polyaddition adamantane compound and the comonomer in the range of 0.5 to 3. preferable.

Further, it becomes easy to obtain a high refractive index by appropriately selecting the sulfur-containing polyaddition adamantane compound and the comonomer so that the sulfur atom content of the obtained polymer is 0.15 or more. .

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

Further, if necessary, additives such as an ultraviolet absorber, an antioxidant, a coloring preventing agent, a fluorescent dye, a light stabilizer, an oil-soluble dye, and an internal release agent for improving weather resistance are appropriately added. Good. Further, a catalyst for improving the polymerization reactivity may be appropriately used, and for example, an organic peroxide, an azo compound or a basic catalyst is effective for improving the reactivity between the mercapto group and the ethenyl group, and mercapto Groups and hydroxyl groups, (thio)
In order to improve the reactivity with the 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 in a known range,
Generally, it is usually 0.0 with respect to 1 mol of the polyaddition functional group of the sulfur-containing polyaddition adamantane compound and the comonomer.
It may be used in an amount of about 001 mol to 0.1 mol.

The method for producing a polymer from the above-described sulfur-containing polyaddition adamantane compound and comonomer, and other components optionally blended is not particularly limited, and a known polyaddition type polymer is used. The method of manufacturing the above may be appropriately adopted.

As an example, a manufacturing method in which the polymer is an optical material such as a spectacle lens will be described. The sulfur-containing polyaddition adamantane compound, the comonomer, and additives and catalysts to be blended as necessary are mixed and sufficiently defoamed to obtain a uniform raw material mixture. Then, the raw material mixture is poured into a known cast polymerization method, that is, into a mold in which a glass or metal mold and a resin gasket are combined and heated to cure. At this time, in order to facilitate the removal of the resin after molding, the mold may be subjected to a mold release treatment in advance, or a mold release agent may be mixed in the raw material mixture. The polymerization temperature is
Depending on the compound used, it is generally -20 to +1
At 50 ° C, the polymerization time is 0.5 to 72 hours. The polymerization temperature and the polymerization time vary depending on the composition of the monomer and the kind and amount of the additive, but in general, the temperature starts to be raised from 5 to 20 ° C and the temperature is increased to about 100 to 130 ° C in 8 to 30 hours. The temperature may be raised and held 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, in the case where the polyaddition functional group is a cyclic group containing a hetero atom, it is added at the same time as the group on the side to which the cyclic group containing the hetero atom is added. As a result, a ring-opening group is generated. Therefore, it is possible to polymerize only the compound containing only the cyclic group containing the hetero atom.

A cyclic group containing such a hetero atom is
It is possible to polymerize alone by heating, but it is preferable to heat using a curing catalyst. Examples of the curing catalyst include compounds known as ring-opening polymerization catalysts for epoxy groups and / or episulfide groups, such as amines, phosphines, mineral acids, Lewis acids, organic acids, silicic acids, and tetrafluoroboric acid. Can be used. Specific examples include amines such as n-propylamine, n-butylamine, benzylamine and dihexylamine;
Ammonium salts of the amines with halogens, mineral acids, Lewis acids, organic acids, silicic acid, tetrafluoroboric acid, etc .; Complexes of amines with borane and boron trifluoride: trimethylphosphine, tris (4-methyl) Phosphines such as phenyl) phosphine and diphenylcyclohexylphosphine;
Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid and their half-esters; Lewis acids represented by boron trifluoride, boron trifluoride etherate and the like; organic acids represented by carboxylic acids and these Half-esters: silicic acid, tetrafluoroboric acid, etc. These catalysts alone
You may use it in mixture of 2 or more types.

The above curing catalyst may be used usually in an amount of 0.0001 to 0.1 mol per mol of a cyclic group having a hetero atom such as an epoxy group and / or an episulfide group.

Further, the primary or secondary polyamines and polycarboxylic acids exemplified as the above-mentioned comonomers also act as a curing catalyst. In this case, the polyamines and polycarboxylic acids are incorporated into the polymer and also serve as units constituting the polymer. In such a case, the blending amount thereof may be larger than the range used as the curing catalyst.

As the compound having a cyclic group having a hetero atom, the sulfur-containing polymerizable adamantane compound in the present invention may be used alone, but if necessary,
You may use together the other compound which has the cyclic group which has a hetero atom. As such a compound, various known epoxy compounds and episulfide compounds may be used.

Further, the sulfur-containing polymerizable adamantane compound or comonomer of the present invention having a polyaddition functional group other than the cyclic group having a hetero atom as described above can be used in combination.

Also in these cases, the mass derived from the adamantane ring in the obtained polymer (the number of substituents on the 136-adamantane ring) accounts for 15 to 60% of the mass of the obtained polymer, Further, it is preferable to adjust the compounding ratio of each component so that the sulfur atom content is 15% or more.

Further, also in this case, if necessary, an ultraviolet absorber, an antioxidant, a coloring preventing agent for improving weather resistance,
Additives such as fluorescent dyes, light stabilizers, oil-soluble dyes, and internal release agents may be added as appropriate.

A polymer is produced from the sulfur-containing polymerizable adamantane compound of the present invention having the above-described cyclic group having a hetero atom as a polyaddition functional group, and other components optionally blended. The method to do is not particularly limited,
A known method for producing a polyaddition type polymer may be appropriately adopted.

As an example, the sulfur-containing polymerizable adamantane compound of the present invention having a heteroatom-containing cyclic group as a polyaddition functional group, the above-mentioned various curing catalysts, and other components to be blended as necessary are added. Mixing, sufficient degassing to obtain a uniform raw material mixture, then using the raw material mixture,
Optical materials such as spectacle lenses can be manufactured by the same method as described above.

The optical material made of the polymer obtained by the above-mentioned method is, if necessary, antireflection, imparts high hardness,
Improved wear resistance, improved chemical resistance, anti-fog property, or
To improve the fashionability, surface polishing,
Antistatic treatment, hard coat treatment, anti-reflection coat treatment,
Physical or chemical treatment such as dyeing treatment and light control treatment can be performed. Further, the optical material obtained in the present invention,
Dyeing can be easily carried out in water or a solvent using an ordinary disperse dye. At the time of dyeing, a carrier which is a dyeing aid may be added to the dyeing bath to further facilitate dyeing.

The optical material made of the polymer of the present invention thus obtained has extremely low dispersion, high refractive index, excellent heat resistance, is colorless and transparent, is lightweight, has weather resistance and impact resistance. In addition to excellent optical properties, low water absorption, and excellent surface hardness, it can be used not only as optical element materials for eyeglass lenses, camera lenses, LCD substrates, etc., but also as materials for glazing materials, paints, and adhesives. It is suitable. Furthermore, it is also a material with excellent processability because it also has the characteristic that it has little odor during molding.

Further, not only the optical material but also the other materials requiring high heat resistance and low odor during processing can be used.

[0189]

EXAMPLES The present invention will be described below 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: The refractive index ( _nd ) and Abbe number at 20 ° C. were measured using an Abbe refractometer manufactured by Atago Co., Ltd. Bromonaphthalene 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: Using TMA (manufactured by Seiko Epson), 5 g of the test piece was weighted and heated at 5 ° C / min, and the thermal deformation starting temperature was measured. -Weather resistance: The sample was placed in a long life xenon fade meter manufactured by Suga Test Instruments Co., Ltd., and exposed to xenon light for 100 hours, and then the hue was compared and evaluated with a plastic lens before the test. (○): Almost no change in hue was observed. (X): The hue turned yellow. Odor: The odor during cutting with a diamond cutter or during polishing with a ball scraper was evaluated according to the following criteria. (A): No odor is felt. (○): A substance that has a slight odor but does not bother you for a long time. (△): It has an odor, but it is not noticeable in a short time. (▲): Something that causes a slight unpleasant odor. (X): Those with a bad odor. Things that offend you. -Impact resistance The impact resistance is measured by measuring a flat test piece with a thickness of 2 mm with a weight of 16.
Evaluation was performed by dropping 3 g of a hard sphere from a height of 127 cm.

The sulfur-containing polymerizable adamantane compound used as the raw material was synthesized by the following method.

Production Example 1 17 g (0.1 mol) of 1,3-adamantanediol
And 152 g of thiourea (2.0 mol, 20 molar equivalents relative to the adamantane compound) were added with 500 g of concentrated hydrochloric acid (500 g per 0.1 mol of the adamantane compound),
The mixture was heated and stirred at 100 ° C. for 10 hours. After cooling to room temperature, 600 g of 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 a precipitated white solid was isolated.
Table 1 shows the elemental analysis, MASS, 1 H-NMR and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 3-mercaptoadamantan-1-ol (Compound A).

Production Example 2 3-mercaptoadamantan-1-ol 10 g (0.
After adding 250 g of concentrated hydrochloric acid to 054 mol) and 76 g (1.0 mol) of thiourea, the mixture was heated and stirred at 100 ° C. for 15 hours. After cooling to room temperature, 300 g of 50% sodium hydroxide aqueous solution was added, and then the mixture was heated and stirred at 10 ° C. for 2 hours. The white solid deposited by cooling to room temperature was recrystallized from water / methanol (weight ratio 1: 8) to isolate 8.2 g of a white solid. Table 1 shows the elemental analysis, MASS, 1 H-NMR, 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 9.2 g (0.0) of 1,3,5-adamantanetriol
(5 mol) was used for mercapto formation and subsequent post-treatment under the same charging ratio and reaction conditions as in Production Example 1 to isolate 4.7 g of a white solid. Table 1 shows the elemental analysis, MASS, 1H-NMR, and IR spectrum of the obtained white solid.
Shown in. From these analysis results, it was confirmed that the isolated compound was 5-mercaptoadamantane-1,3-diol (Compound C).

Production Example 4 5-Mercaptoadamantane-1,3-diol 8.0
Using g (0.04 mol), the same preparation ratio and reaction conditions as in Production Example 2 were used to carry out mercapto formation and subsequent post-treatment to isolate 5.4 g of a white solid. Table 1 shows the elemental analysis, MASS, 1 H-NMR, and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 3,5-dimercaptoadamantan-1-ol (Compound D).

Production Example 5 3,5-dimercaptoadamantan-1-ol 10.
Using 8 g (0.04 mol) of the same preparation ratio and reaction conditions as in Production Example 2, mercapto formation and subsequent post-treatment were carried out to isolate 5.5 g of a white solid. Table 1 shows the elemental analysis, MASS, 1 H-NMR, and IR spectrum of the obtained white solid. From these analysis results, the isolated compound was 1,3,5-adamantane trithiol (Compound E).
Was confirmed.

Production Example 6 10 g of 1,3,5,7-adamantane tetraol
(0.05 mol) and thiourea (380 g, 5 mol) were added with concentrated hydrochloric acid (410 g), and then the pressure was applied to 120 ° C.
The mixture was heated and stirred for 60 hours. After cooling to room temperature,
After adding 500 g of 50% sodium hydroxide aqueous solution, the mixture was heated and stirred 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, MASS, 1 H-NMR, and IR spectrum of the obtained white solid. From these analysis results, it was confirmed that the isolated compound was 1,3,5,7-adamantane tetrathiol (Compound F).

Production Example 7 25 g (0.15 mo) of 1,3-adamantanediol
l) and 280 g of 1,2-ethanedithiol (3.0 mo
6 g (0.03 mol) of p-toluenesulfonic acid in 1)
After adding, 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, and then 5% sodium hydrogen carbonate solution 200
After washing with 200 ml of water and then with 200 ml of water and distilling off 1,2-ethanedithiol under reduced pressure, distillation under reduced pressure (boiling point 28
(0 ° C./0.5 mmHg) to obtain 16 g of a colorless oily substance.
Elemental analysis of the obtained colorless oil, MASS, 1H-NMR, I
The R spectrum is shown in Table 2. 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 2
6 g of p-toluenesulfonic acid in 80 g (3.0 mol)
After adding (0.03 mol), the mixture was heated and stirred at 140 ° C. for 15 hours. After cooling to room temperature, p-
After the toluenesulfonic acid was filtered off, it was washed with 200 ml of a 5% sodium hydrogen carbonate solution and then 200 ml of water,
After the bis (2-mercaptoethyl) sulfide was distilled off under reduced pressure, the residue was distilled under reduced pressure (boiling point 320 ° C./0.5 mmHg) to obtain 24 g of the desired product as a colorless oil. The elemental analysis, MASS, 1H-NMR, and IR spectrum of the obtained colorless oil are shown in Table 2.
Shown in. From these analysis results, the isolated compounds were 1, 3, 5
-Tris [2- (2-mercaptoethylthio) ethylthio] adamantane (Compound H) was confirmed.

Production Example 9 17 g (0.1 mol) of 1,3-adamantanediol
And 1,2-ethanedithiol 280 g (3.0 mol)
After adding 2 g (0.01 mol) of p-toluenesulfonic acid to the above, 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 150 ml of water, and 1,2-ethanedithiol was distilled off under reduced pressure, followed by vacuum distillation ( Boiling point 220 ° C / 0.5
mmHg), and 13 g of a colorless oily substance was obtained. Table 2 shows the elemental analysis, MASS, 1H-NMR, and IR spectrum of the obtained colorless oil. From these analysis results, the isolated compound was 3-
It was confirmed to be (2-mercaptoethylthio) adamantan-1-ol (Compound I).

Production Example 10 2,3-Adamantanedicarboxylic acid 22.4 g (0.1
0 mol), 6 g of p-toluenesulfonic acid (0.03 m)
ol) was added with 200 g of ethanol, and then heated and refluxed for 10 hours while distilling off water using a Dean-Stark dehydrator. After cooling to room temperature, the solvent was distilled off, chloroform and water were added, and the mixture was neutralized with a 1N sodium hydrogen carbonate aqueous solution. After the organic layer was dried and concentrated, the residue was 24.4.
g was obtained. It was confirmed from 1 H-NMR that the main product was ethyl 1,3-adamantanedicarboxylate. 19.6 g of the obtained ester body was added to dry tetrahydrofuran 3
It was dissolved in 00 ml 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 adding 500 ml of chloroform to the reaction solution, the organic phase is separated, followed by concentration and drying to obtain 13.6 g of a white solid.
Obtained. From 1H-NMR, it was confirmed that the main product was 1,3-bis (hydroxymethyl) adamantane.
Using the obtained alcohol derivative (9.8 g), the same preparation ratio and reaction conditions as in Production Example 2 were used to carry out mercapto formation and subsequent post-treatment to isolate 7.8 g of a white solid. Elemental analysis of the obtained white solid, MASS, 1H-NMR,
The IR spectrum is shown in Table 2. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (mercaptomethyl) adamantane (Compound J).

Production Example 11 23.2 g of 1,3,5-adamantane trithiol
(0.10 mol) and 9.0 g of pyridine were added to 200 ml of toluene and then cooled to 0 ° C., and acetyl chloride was added to 7.
After 9 g (0.10 mol) was gradually added dropwise, the mixture was heated with stirring at 70 ° C. for 2 hours. The mixture was allowed to cool, chloroform and water were added, the organic layer was neutralized with diluted hydrochloric acid, and the organic layer was separated and concentrated. Purification was performed by column chromatography to obtain a white solid 7.
2 g was isolated. Elemental analysis of the obtained white solid, MAS
Table 2 shows the S, 1H-NMR and IR spectra. From these analysis results, it was confirmed that the isolated compound was 5-acetylthio-1,3-dimercaptoadamantane (Compound K).

Production Example 12 3,5-dimercaptoadamantan-1-ol 21.
6 g (0.10 mol) and acetic acid 23 g (0.20 mo
1) was added to 200 ml of toluene, 1 g of p-toluenesulfonic acid monohydrate was further added, and the mixture was heated with stirring while distilling water using a Dean-Stark dehydrator. After 4 hours, the mixture was allowed to cool, chloroform and water were added, the organic layer was neutralized with sodium carbonate, and then the organic layer was separated and concentrated. Purification was performed by column chromatography, and 9.4 g of a white solid was isolated. Elemental analysis of the obtained white solid, MASS, 1H-NMR,
The IR spectrum is shown in Table 3. From these analysis results, it was confirmed that the isolated compound was 5-acetyloxy-1,3-dimercaptoadamantane (Compound L).

Production Example 13 42 g (0.24 mo) of 1,3-adamantanediol
l) and 100 g of ethyl thioglycolate (0.8 mo
8 g (0.04 mol) of p-toluenesulfonic acid in 1)
After adding, the mixture was heated and stirred at 130 ° C. for 6 hours.
After cooling to room temperature and filtering off the precipitated p-toluenesulfonic acid, 200 ml of 5% sodium hydrogen carbonate solution,
Then, it was washed with 200 ml of water, and ethyl thioglycolate was further distilled off under reduced pressure, followed by vacuum distillation (boiling point 280 ° C. /
0.5 mmHg) to obtain 44 g of a colorless oily substance. 1H-NMR
From 1,3-bis (ethoxycarbonylmethylthio)
I confirmed it was Adamantane.

Subsequently, 37 g of this 1,3-bis (ethoxycarbonylmethylthio) adamantane was added to ethanol 10
The solution was dissolved in 0 ml, and 12.4 g of hydrazine monohydrate was added dropwise while maintaining the temperature at 5 ° C. After 2 hours, the resulting solid of 1,3-bis (hydrazinocarbonylmethylthio) adamantane was collected by filtration. 2 ml of this with 20 ml of cold ethanol
Washed twice. 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. Furthermore, a solution prepared by dissolving 4.4 g of sodium nitrite in 12 ml of water was added dropwise. 1
After hours, 60 ml of benzene was added and the temperature was raised to room temperature with stirring. The organic phase was separated, dried over anhydrous magnesium sulfate, and then slowly added dropwise to 200 ml of benzene at 60 ° C. After reacting for 2 hours as it was, it was cooled to room temperature, and benzene was distilled off under reduced pressure. The obtained pale yellow oily substance was distilled under reduced pressure (boiling point 270 ° C./0.5 mmHg) to obtain 27 g of the desired product as a colorless oily substance. Table 3 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 (isocyanatomethylthio) adamantane (Compound M).

Production Example 14 A white solid was obtained by carrying out the reaction in the same manner as in Production Example 13 except that ethyl thiopropionate was used instead of ethyl thioglycolate. Table 3 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 (2-isocyanatoethylthio) adamantane (Compound N).

Production Example 15 76 g (1.0 mol) of carbon disulfide, 52 g of water, 50% N
In a mixed solution of 81.8 g (1.0 mol) of an aOH aqueous solution,
83 g (0.5 mol) of 1,3-adamantanediamine was added dropwise at 20 to 30 ° C. over 2 hours, and after completion of the addition, heating was performed at 70 to 80 ° C. for 1 hour. To this reaction liquid, water 10
After adding 0 ml and 200 ml of toluene, 100 g (1.05 mol) of methyl chloroformate was added at 40 to 50 ° C.
Over 1 hour at 40 ° C after the addition is complete.
Held for 1 hour. The lower aqueous layer was separated and discarded, and the obtained organic layer was dried and then kept at 90 to 100 ° C. for 3 hours to complete the decomposition. The obtained reaction solution was desolvated under reduced pressure and distilled under reduced pressure (230 ° C./0.5 mmHg) to obtain 42 g of a white solid. Elemental analysis of the obtained white solid, MAS
Table 3 shows the S, 1 H-NMR and IR spectra. From these analysis results, it was confirmed that the isolated compound was 1,3-adamantane dithioisocyanate (Compound O).

Production Example 16 100 g of 1,3-adamantanedithiol (0.5 mo
1) and epichlorohydrin 93 g (1.0 mol)
Cool to 0 ° C. and add 5 mmol of sodium hydroxide (0.2
An aqueous solution prepared by dissolving g) in 5 ml of water was added, and 1 was added at this temperature.
Stir for hours. Then, the solution was stirred for 3 hours while maintaining the liquid temperature at around 40 to 45 ° C. After returning to room temperature, an aqueous solution obtained by dissolving 40 g (1 mol) of sodium hydroxide in 60 ml of water was added,
The solution was added dropwise while maintaining the liquid temperature at around 40 to 45 ° C., and then stirred for 2 hours while maintaining the liquid temperature as it was. 100 ml of water was added to the reaction mixture, extracted with 200 ml of toluene, and then washed with water. After drying the toluene layer, the solvent was distilled off to obtain 95.0 g of a white solid. Table 3 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 (glycidylthio) adamantane (Compound P).

Production Example 17 1,3-Bis (glycidylthio) adamantane 93.6
(0.3 mol) and 40 ml of ethanol were added to an aqueous solution prepared by dissolving 87.5 g (0.9 mol) of potassium thiocyanate in 60 ml of water, and the liquid temperature was raised to 45 ° C over 1 hour, and the reaction was carried out at this temperature for 5 hours. Let 500 ml of water was added to the reaction mixture, extraction was performed with 500 ml of toluene, and the toluene layer was washed 3 times with 500 ml of water. The toluene layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain a white solid. Elemental analysis of the obtained white solid, MASS, 1H
-NMR and IR spectra are shown in Table 3. From these analysis results, it was confirmed that the isolated compound was 1,3-bis (β-epithiopropylthio) adamantane (Compound Q).

[0210]

[Table 1]

[0211]

[Table 2]

[0212]

[Table 3]

The compounds of the present invention produced in Production Examples 1 to 17 are all at least 2 at the 1 to 7 positions of the adamantyl group.
A compound having a polyaddition functional group and / or a group having a polyaddition functional group at a position. Table 4 collectively shows the substituents of these produced compounds.

[0214]

[Table 4]

The abbreviations of the polymerizable compounds (comonomer) other than the sulfur-containing polymerizable adamantane compound used in the present invention used in Examples and Comparative Examples are shown below.

PETP: Pentaerythritol tetrakis (3-mercaptopropionate) DDOL: 1,10-decanediol XDI: m-xylylenediisocyanate H6-XDI: 1,3-bis (isocyanatomethyl)
Cyclohexane NBDI: Norbornane diisocyanate (Note: 2,5
Mixture of-and 2,6-norbornane diisocyanate) XDTI: m-xylylene dithioisocyanate MEI: 2-methacryloxyethyl isocyanate DMMD: 2,5-bis (mercaptomethyl) -1,4
-Dithiane METM: 1,2-bis (2-mercaptoethyl-1-
Thio) -3-mercaptopropane DDTL: 1,10-decanedithiol ADSH: 1-adamantanethiol ADDL: 1,3-adamantanediol Examples 1 to 20 The polymerizable mercapto compounds of the present invention produced in Production Examples 1 to 17 above. , A polymerizable isocyanate compound, a polymerizable thioisocyanate compound, or two or more kinds thereof were used and comonomers were added to prepare curable compositions having the monomer compositions shown in Tables 5 and 6.

Polymerization was carried out as follows. That is, the sulfur-containing polymerizable adamantane compound of the present invention, a comonomer, and dibutyltin dilaurate (DBT) as a polymerization catalyst.
(DL) 1 × 10 ⁻⁵ mol was mixed to form a uniform solution, which was sufficiently defoamed and then poured into a lens mold made of a glass mold and a gasket that had been subjected to a mold release treatment. 50 ° C
For 10 hours, at 60 ° C. for 5 hours, and at 120 ° C. for 3 hours to obtain a lens-shaped polymer. After the completion of the polymerization, the lens was gradually cooled and the lens was taken out from the mold. Physical properties of the obtained polymer are shown in Tables 5 and 6. The AD ratio of the polymer is also shown in the table.

[0218]

[Table 5]

[0219]

[Table 6]

As shown in Tables 5 and 6, the polymers of Examples 1 to 20 containing the sulfur-containing polymerizable adamantane compound of the present invention as polymerized units were colorless and transparent,
The refractive index ( _nd ) is very high, the Abbe number (ν) is also high,
It can be seen that it has optical properties suitable for applications such as eyeglass lenses. It also has excellent heat resistance and has very little odor,
The weather resistance was also good. Particularly, regarding the odor, the more the sulfur atom in the polymer is directly bonded to the adamantyl group, the more excellent it is.If all the sulfur atoms are directly bonded to the adamantyl group, the odor is completely eliminated during the work. I couldn't feel it.

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

Comparative Examples 1 to 5 Polymers were obtained by polymerizing each compound shown in Table 7 in the same manner as in Examples without blending the sulfur-containing polymerizable adamantane compound in the present invention. The physical properties of the obtained polymer are shown in Table 7.

[0223]

[Table 7]

Comparative Example 1 shows the results when the polymer obtained has no adamantane ring. 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, a remarkably unpleasant odor was generated, and there was a problem in workability.

The polymer in Comparative Example 4 has the same AD ratio and sulfur atom content as in Example 20. In this case, in contrast to Example 20 in which the sulfur atom was directly bonded to the adamantane ring, in Comparative Example 4 in which all the sulfur atoms were not directly bonded to the adamantane ring, the odor was remarkable and the sulfur atom contained in the polymer It can be understood that is derived from a sulfur-containing polymerizable adamantane compound.

Further, Comparative Example 5 is an example of using an adamantane compound having only one polyaddition functional group, but in this case, a cured product could not be obtained.

Example 21 1 part of tripropylamine was added to 100 parts by weight of compound P, which is an epoxy-based sulfur-containing polymerizable adamantane compound.
Parts by weight were mixed and poured into a mold composed of two glass plates and polymerized and cured at 90 ° C. for 8 hours to obtain a polymer.
The material obtained had a refractive index of 1.60, an Abbe number of 38, a heat resistance of 155 ° C., and good weather resistance. Also,
There was almost no odor during polishing, and the level was (⊚).

Example 22 1 part by weight of tripropylamine was added to 100 parts by weight of a compound Q which is an episulfide-based sulfur-containing polymerizable adamantane compound, and the mixture was poured into a mold composed of two glass plates. Then, the mixture was polymerized and cured at 90 ° C. for 8 hours to obtain a polymer. Refractive index of the obtained material is 1.64, Abbe number is 34
The heat resistance was 150 ° C. and the weather resistance was good. Further, there was almost no odor during polishing, and the level was (⊚).

Comparative Example 6 1,3-bis (glycidyloxy) adamantane 100
1 part by weight of tripropylamine was mixed in parts by weight, and the mixture was poured into a mold composed of two glass plates and polymerized and cured at 90 ° C. for 8 hours to obtain a polymer. The material obtained had a refractive index of 1.54, an Abbe number of 46, and a heat resistance of 129 ° C. The refractive index was significantly lower than the polymers obtained from the sulfur-containing polymerizable adamantane compound of the present invention in Examples 21 and 22.

Example 23 When an impact resistance test was conducted on optical materials molded using the compound G of Example 7 and Example 14, no crack was observed in any case.

[0231]

The cured product obtained from the sulfur-containing polymerizable adamantane compound of the present invention as a raw material 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. Is. Further, the polymer has a characteristic that the workability of polishing and the like is very good because it has little bad odor during polishing and molding.

Therefore, the cured product obtained by homopolymerizing the sulfur-containing polymerizable adamantane compound in the present invention or copolymerizing it with a comonomer is useful as an optical material,
For example, it is most suitable as an optical lens such as a spectacle lens and an optical device lens, and can be suitably used for applications such as a prism, an optical disc substrate, an optical fiber, and an LCD substrate.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 BA02 CA01 CA04 CA31 CA32                       CA34 CC23 CC26 CC54 CD08                       HA01 HA07 HB02 HB03 RA13                       SA02

Claims (5)

[Claims] 1. A polymerized unit based on a sulfur-containing polymerizable adamantane compound having (a) at least one adamantyl group (b) at least two polyaddition functional groups (c) at least one sulfur atom in one molecule. An optical material comprising a polymer containing. 2. The optical material according to claim 1, wherein at least half of the sulfur atoms contained in the sulfur-containing polymerizable adamantane compound in claim 1 are sulfur atoms directly bonded to an adamantyl group. 3. The optical material according to claim 1 or 2, wherein the polyaddition functional group contained in the sulfur-containing polymerizable adamantane compound is a mercapto group, a hydroxyl group, an episulfide group, a thioisocyanate group or an isocyanate group. 4. The sulfur-containing polymerizable adamantane compound has the following general formula (1): [Wherein Z is the following general formula (2): (In the formula, R ² represents a divalent hydrocarbon group which may have a substituent, R ³ represents a polyaddition functional group, and s represents 0 to 2
Integer, t is an integer of 0 to 3, when t is 2 or _{3, (- [S] s -R} 2 -) group may each be the same or different indicated by. ), R 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 is 2
To b, b represents an integer of 0 to 6, Z and R ¹ may be the same or different when a plurality of Z and R ¹ are present, and at least one sulfur atom is present in the molecule. To do. ] The optical material of Claims 1-3 which is a compound shown by these. 5. A polymerized unit based on a sulfur-containing polymerizable adamantane compound having (a) at least one adamantyl group (b) at least two polyaddition functional groups (c) at least one sulfur atom in one molecule. Including polymers.