JP2005042041A - Deuterated alicyclic group-bearing unsaturated ester, method for producing the same, polymer therefrom and optical part including the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound useful as optical parts, particularly useful as a material for a plastic optical fiber and provide a safe and efficient method for producing the same. <P>SOLUTION: This compound is represented by general formula (1) (wherein R<SP>1</SP>through R<SP>3</SP>are each H, D, a halogen atom, CH<SB>3</SB>, CD<SB>3</SB>or CF<SB>3</SB>; R<SP>4</SP>and R<SP>5</SP>are each H, D or a substituent and they may link to each other to form a cyclic skeleton; where the hydrogen atoms on the alicyclic group are deuterated more than 55 %). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a deuterated unsaturated ester having a cycloaliphatic group and a method for producing the same, and further relates to a polymer using the compound as a raw material and application to an optical component.

A polymer produced from an unsaturated ester having a cycloaliphatic group has a high glass transition point (Tg) compared to a polymer produced from a corresponding unsaturated methyl ester, etc., has low moisture absorption, etc. It has various features and is applied to plastic lenses and the like (see, for example, Patent Document 1).
On the other hand, in the field of optical materials, it is known that new optical characteristics can be exhibited by changing H atoms in a polymer material to deuterium atoms (D). For example, in a plastic optical fiber, it is often effective to convert H atoms in a polymer to D atoms in order to reduce light loss during transmission due to material loss due to C—H vibration at a certain light source wavelength. It is known (for example, refer nonpatent literature 1). Accordingly, a compound obtained by deuterating unsaturated esters having a cycloaliphatic group is expected to provide an attractive optical material.

It is known that cyclopentadiene that can be a raw material for unsaturated esters having a cycloaliphatic group can be HD-exchanged with heavy water and a base (see, for example, Non-Patent Document 2 and Non-Patent Document 3). According to these methods, a deuterated cyclopentadiene having a high D conversion rate can be obtained, but the method in which metallic sodium is poured into heavy water is adopted, and the liquid separation is performed until a high D conversion rate is reached. Since the operation was repeated many times (3 to 6 times), the synthesis method was extremely difficult to apply to mass synthesis from the viewpoint of safety and cost. That is, there remains room for improvement in the method of HD exchange of cyclopentadiene. Furthermore, no examples have been reported so far of synthesizing deuterated unsaturated esters having a cycloaliphatic group from the deuterated cyclopentadiene synthesized as described above.
POF Consortium “Plastic Optical Fiber” Kyoritsu Shuppan, 1997, pages 41-53 J. Org.Chem., 1987,52,4772 Tetrahedron, 1992,48,9649 USP 4,591,626 (1986)

  In view of these problems of the prior art, the present invention provides unsaturated esters, polymers and polymerizable compositions having deuterated cycloaliphatic groups useful as materials for optical components, particularly plastic optical fibers. The issue is to provide goods. Moreover, this invention makes it a subject to provide the method of manufacturing the compound which has deuterated cyclopentadiene as a partial structure safely and efficiently. Furthermore, an object of the present invention is to provide a novel optical component utilizing unsaturated esters having a deuterated cycloaliphatic group, a polymer and a polymerizable composition.

  As a result of intensive studies, the present inventors have succeeded in synthesizing a compound represented by the following formula (1) (hereinafter sometimes referred to as “unsaturated ester having a deuterated cyclic aliphatic group”). At the same time, a production method suitable for mass synthesis of the compound was developed, and further, application to a polymer material and an optical material using the method was studied, and the present invention was completed.

Means for solving the above problems are as follows.
[1] A compound represented by the following general formula (1).

(In the formula (1), R ^{1 to} R ³ each independently represent H, D, a halogen atom, CH ₃ , CD ₃ or CF ₃ , and R ⁴ and R ⁵ each independently represent H, D, or a substituent. R ⁴ and R ⁵ may be linked to form a cyclic skeleton, provided that 55% or more of the hydrogen atoms in the cyclic aliphatic group in the formula are deuterium atoms (D). .)

[2] The compound according to [1], wherein 60% or more of the hydrogen atoms in the cycloaliphatic group are deuterium atoms (D).
[3] The compound according to [1], wherein 80% or more of the hydrogen atoms in the cycloaliphatic group are deuterium atoms (D).
[4] The compound according to [1], which is the following compound A or the following compound B.

[5] A method for producing the compound represented by the general formula (1), wherein the cyclopentadiene represented by the formula (1-1) is HD-exchanged in heavy water in the presence of a base to obtain the formula (1- A production method comprising a step of producing the compound of 2).

(In the formula, X represents H or D, and at least one of X is D.)

[6] The production method according to [5], wherein 50% or more of hydrogen atoms on cyclopentadiene are converted to deuterium atoms (D) in the HD exchange step.
[7] Subsequent to the step, a step of generating a compound of formula (1-4) by a Diels-Alder reaction of a compound of formula (1-2) and a compound of formula (1-3), ) Of the compound of formula (1-5) by the hydration reaction of the compound of formula (1) and the esterification reaction of the compound of formula (1-5) with the compound of formula (1-6) The production method according to [5] or [6], comprising a step of producing a compound.

In the formula, each of R ^{1 to} R ⁵ is the same as the substituents R ^{1 to} R ^{5 in} the formula (1) of claim 1, and X ¹ represents Cl, Br, OH, or OD. In the formula (1), the bond between the carboxyl group and the cycloaliphatic group means the bond to the 8th or 9th position of the cycloaliphatic group.

  [8] A polymer containing at least a repeating unit represented by the following general formula (3).

Wherein R ^{1 to} R ³ each independently represents H, D, a halogen atom, CH ₃ , CD ₃ or CF ₃ , and R ⁴ and R ⁵ each independently represent H, D or a substituent. R ⁴ and R ⁵ may be linked to form a cyclic skeleton, provided that 55% or more of the hydrogen atoms in the cyclic aliphatic group in the formula are deuterium (D).

[9] The polymer according to [8] represented by the following general formula (3-A).

(In the formula, R ^{1 to} R ³ , R ⁴ and R ⁵ have the same meanings as in the general formula (3), and 55% or more of the hydrogen atoms in the cyclic aliphatic group in the formula are deuterium. (D) where A is a repeating unit derived from an unsaturated ethylenic monomer, m and n are the mole% of each repeating unit, and m + n = 100, 0 <m ≦ 100 and 0 ≦ n <. 100 is satisfied.)

[10] A polymer produced by subjecting the compound according to any one of [1] to [4] to a polymerization reaction alone or together with another polymerizable monomer.
[11] A polymerizable composition containing at least one compound according to any one of [1] to [4].
[12] An optical component comprising the polymer according to any one of [8] to [10].
[13] An optical component having a region obtained by polymerizing the polymerizable composition according to [11].
[14] The compound according to any one of [1] to [4], which is a material for optical components.
[15] The polymer according to any one of [8] to [10], which is a material for optical components.
[16] The polymerizable composition according to [11], which is a material for optical components.
[17] An optical material containing the compound according to any one of [1] to [4].
[18] An optical material containing the polymer according to any one of [8] to [10].

  According to the present invention, it is possible to provide unsaturated esters, polymers and polymerizable compositions having a deuterated cycloaliphatic group that are useful as materials for optical components, particularly plastic optical fibers. Moreover, according to this invention, the method of manufacturing the compound which has a deuterated cyclopentadiene as a partial structure safely and efficiently can be provided. Furthermore, according to the present invention, it is possible to provide a novel optical component utilizing unsaturated esters having a deuterated cycloaliphatic group, a polymer and a polymerizable composition. In particular, a plastic optical fiber produced by using the compound of the present invention has a small transmission loss and has excellent transmission ability and heat resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, the present invention will be described in detail. In the present specification, “to” means a range including numerical values described before and after the minimum and maximum values. Further, in this specification, the ratio of D atoms contained in a group is defined as an average value of {(number of D atoms) / (number of H atoms + number of D atoms)} as a deuteration rate (D conversion rate). Define.

  First, the compound represented by Formula (1) of this invention is demonstrated in detail.

In the formula (1), R ^{1 to} R ³ each independently represent H, D, a halogen atom (F, Cl, Br, I), CH ₃ , CD ₃ or CF ₃ . R ^{1 to} R ³ are preferably H, D, F, Cl, CH ₃ , CD ₃ or CF ₃ , and more preferably D, F or CD ₃ . The combination of R ^{1 to} R ³ is preferably the case where R ¹ and R ² are H or D and R ³ is H, D, CH ₃ or CD ₃ , and particularly preferably both R ¹ and R ² are D and R ³ is CD ₃ .

In the formula (1), R ⁴ and R ⁵ each independently represent H, D or a substituent. Examples of substituents include alkyl groups (including cycloalkyl groups), alkenyl groups (including cycloalkenyl groups), alkynyl groups, aryl groups, halogen atoms (F, Cl, Br, I), heterocyclic groups, cyano groups Group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group) ), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoy Group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphine group Examples include a ruoxy group, a phosphinylamino group, and a silyl group. When the substituent contains a hydrogen atom, it may be an H atom or a D atom, but is preferably a D atom. These substituents may be further substituted with these substituents.

When R ⁴ and R ⁵ are substituents, there are two conformations, and four diastereomeric isomers are possible depending on which conformation is adopted. In the compound, any isomer or isomer mixture may be used.

R ⁴ and R ⁵ may be bonded to each other to further form a cyclic skeleton. The cyclic skeleton formed by combining R ⁴ and R ⁵ is composed of at least one atom selected from carbon, nitrogen, oxygen, sulfur and phosphorus atoms, and means a non-aromatic ring structure. In the case of forming a ring, a 5- to 8-membered ring is preferable. The atoms in the ring may further have a substituent, and specific examples thereof include the same examples as the substituents which R ⁴ or R ⁵ may have. The cyclic structure is preferably a 5-membered or 6-membered hydrocarbon ring consisting only of C, H and D; a 5-membered or 6-membered saturated hydrocarbon ring consisting only of C, H and D is preferred; R ⁴ and R ⁵ is a trimethylene group (—CH ₂ —CH ₂ —CH ₂ —, wherein a part or all of H may be D), that is, the cycloaliphatic group is a tricyclodecanyl group. Some cases are particularly preferred.

R ⁴ and R ⁵ are H, D, an alkyl group (including a cycloalkyl group), an alkenyl group, F, Cl, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, an aryloxycarbonyl group or It is preferably an alkoxycarbonyl group or linked to form a cyclic skeleton; preferably H, D, an alkyl group or an alkoxy group, or linked to form a cyclic skeleton; R ⁴ and R ^It is particularly preferred that both ⁵ are D, or a cyclic skeleton is formed with a trimethylene group (—CH ₂ —CH ₂ —CH ₂ —, where H may be part or all of D).

Most preferably as a combination of R ^{1 to} R ⁵ , R ¹ and R ² are D, R ³ is CD ₃ and both R ⁴ and R ⁵ are H or D, or a trimethylene group (—CH ₂ — CH ₂ —CH ₂ —, provided that a part or all of H may be D) to form a cyclic skeleton. That is, among the compounds represented by the following general formula (1), deuterated norbornyl methacrylate (Compound A) and deuterated tricyclodecanyl methacrylate (Compound B) are most preferable.

55% or more of the hydrogen atoms in the cyclic aliphatic group (including R ⁴ and R ⁵ ) in the general formula (1) are D atoms as an average value regardless of the position. The D conversion rate of the cycloaliphatic group is preferably 60% or more, and more preferably 80% or more.

  Although the preferable specific example of a compound represented by following General formula (1) below is given, this invention is not limited to the following specific examples. In addition, although the hydrogen atom and deuterium atom in a cycloaliphatic group were abbreviate | omitted, D conversion rate is 55% or more. Also in the following exemplary compounds, the D conversion ratio in the cyclic aliphatic group is more preferably 60% or more, and further preferably 80% or more.

Next, the manufacturing method of this invention is demonstrated.
The purpose of D conversion will be described in detail as follows. The absorption wavelength corresponding to the fundamental mode of stretching vibration of C—H bond is 3390 nm, and the absorption wavelengths corresponding to 4, 5, 6 and 7th harmonic are 901, 736, 627 and 549 nm, respectively. These wavelengths belong to the wavelength region used for optical communication. It is described that a material in which C—H bonds are converted to C—D or C—F bonds is preferable for communication applications because the absorption wavelength region shifts to the long wave side (International Publication WO 93/08488). . As an improved method for transmission loss due to C—H bond, conversion to C—D bond and conversion to C—F are generally known. However, conversion to C—D bond is safer for reaction. No special equipment is required for ensuring safety and processing of by-products, which is advantageous in terms of safety and cost.

  The production method of the present invention is a method for producing unsaturated esters having a deuterated cycloaliphatic group represented by the general formula (1), wherein cyclopentadiene is dissolved in heavy water in the presence of a base, It is a manufacturing method of the deuterated unsaturated ester compound including the following process to HD exchange. That is, it is a manufacturing method including the process of producing | generating the compound of a following formula (b) by HD exchange reaction of the compound of a following formula (a).

  In the formula, X represents H or D, and at least one of X is D.

  In this step, the reaction is allowed to proceed in heavy water in the presence of a base. The reaction solvent is preferably stirred during the reaction. In the above step, the base extracts H from cyclopentadiene to generate a cyclopentadienyl anion, and the cyclopentadienyl anion abstracts D in heavy water, so that HD exchange proceeds.

Although the usage-amount of heavy water is not limited, It is preferable to add about 2 to 10 times by mass with respect to cyclopentadiene. As the base, an ionic compound having a heavy hydroxide ion (OD ⁻ ) or a compound that reacts with D ₂ O to give OD ⁻ can be used. Specific examples include NaOD, KOD, metallic sodium, sodium methoxide (NaOCH ₃ ), sodium t-butoxide (NaOt-Bu), potassium methoxide (KOCH ₃ ), potassium t-butoxide (KOt-Bu) and the like. . It is advantageous from the viewpoint of cost that a base such as NaOCH ₃ or KOt-Bu that does not contain a D atom and is mild in reaction with heavy water can be used. Although the usage-amount of a base is not limited, It is preferable to use 0.5%-10% by molar ratio with respect to heavy water, More preferably, it is 1.0-3.0%.

  Cyclopentadiene can be obtained by cracking commercially available dicyclopentadiene. Since cyclopentadiene has the property of being easily dimerized and returned to dicyclopentadiene, the HD exchange step is preferably performed at room temperature or lower. More preferably, it is carried out at −10 to 10 ° C., more preferably 0 to 5 ° C. The reaction time is not limited, but as a guide, it is about 2 to 4 hours when carried out at 0 to 5 ° C.

  In this step, since the water-insoluble cyclopentadiene is reacted in heavy water, the reaction solution is separated into two phases. Although the H-D exchange is possible even when the two phases are kept separated, it is preferable to add a compatible liquid or an interlayer transfer catalyst in order to improve the reaction rate. Specifically, it is preferable to add dimethyl sulfoxide (DMSO), deuterated methanol, tetrahydrofuran, 1,4-dioxane, quaternary ammonium salts, quaternary phosphonium salts and the like to the reaction system. It is particularly preferable to add DMSO about 0.5 to 1.5 times by mass with respect to heavy water.

The D conversion rate of cyclopentadiene can be measured by an integral value of ¹ H-NMR. Specifically, deuterated cyclopentadiene and a standard substance (eg, benzene, toluene, etc.) are mixed in a certain amount (eg, equimolar amounts) and NMR is measured, and the integrated value of the peak derived from cyclopentadiene and the standard substance are derived. It can be calculated by comparing the integrated values of the peaks. Furthermore, there is a derivatization method as a method for reliably calculating the D conversion rate. Specifically, deuterated cyclopentadiene is derivatized with an olefin having an electron-withdrawing group that has not been deuterated by the Diels-Alder reaction, and the integrated value of ¹ H-NMR of the resulting addition product. It is a method of calculating by comparing. This derivatization method will be described in detail in Examples.

  Deuterated cyclopentadiene can be isolated and purified by distillation (boiling point 41-43 ° C./normal pressure). Further, when synthesizing a compound having dicyclopentadiene obtained by dimerizing cyclopentadiene (for example, Exemplified Compound I-1) as an intermediate, without isolating as cyclopentadiene, for example, stirring at room temperature or under heating. It is also possible to guide to dicyclopentadiene as it is in one pot.

Next, the steps required to synthesize the compound represented by the general formula (1) from deuterated cyclopentadiene will be described.
The method of synthesizing the compound represented by the general formula (1) using deuterated cyclopentadiene as a raw material is not particularly limited, and any route and method capable of synthesizing using deuterated cyclopentadiene as a raw material should be adopted. Is possible. An example reaction scheme is shown below, but is not limited to this route. In the following reaction formula, a hydrogen atom is omitted, but it may be H or D. In the following formula (1), the bond between the carboxyl group and the cycloaliphatic group means the bond to the 8th or 9th position of the cycloaliphatic group.

In the synthetic route, first, Step 1 is a Diels-Alder reaction, which is a step of obtaining a compound of formula (1-4) from a compound of formula (1-2) and a compound of formula (1-3). . When R ⁴ and R ^{5 in} formula (1-3) are substituents, there are a plurality of stereoisomers, and any of these reagents may be used, or a mixture may be used. Step 2 is a water addition reaction, which is a step of obtaining a compound of formula (1-5) from a compound of formula (1-4). Any reagent and method capable of adding water to the double bond can be selected, and examples thereof include a method of heating in dilute sulfuric acid. Here, it is also possible to use heavy water in place of normal water, thereby leading to a compound having a high D conversion rate. Step 3 is a step of obtaining the compound of formula (1) by esterification reaction of the compound of formula (1-5) and the compound of formula (1-6). Any esterification reagent (eg, X ¹ = Cl or acid chloride, X ¹ = OH or carboxylic acid) and method selection is possible, for example, heating the corresponding carboxylic acid and alcohol in the presence of concentrated sulfuric acid The method of doing is mentioned.

In addition, other reaction may be contained between each process, for example, the functional group conversion process etc. of the substituent represented by R < ⁴ > or R < ⁵ > may be contained. In the synthesis of the exemplary compound (I-1) described later as an example, the step of catalytic hydrogenation with H ₂ or D ₂ corresponds to this functional group conversion.

  Next, the polymer of the present invention will be described. The polymer of the present invention is a polymer containing at least a repeating unit represented by the following general formula (3).

In the formula, R ^{1 to} R ³ , R ⁴ and R ⁵ have the same meanings as those in the general formula (1), and the preferred ranges are also the same, and 55% of the hydrogen atoms in the cyclic aliphatic group The above is deuterium (D), and the preferable range of the D conversion rate is the same as that of the compound represented by the general formula (1).

  The polymer of the present invention may be a homopolymer consisting only of the repeating unit of the formula (3) or a copolymer containing other repeating units. When the polymer of the present invention is used for an optical material, particularly when used for a plastic optical fiber matrix, a polymer represented by the following general formula (3-A) is preferable.

  A is a repeating unit derived from an unsaturated ethylenic monomer. Examples of unsaturated ethylenic monomers include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyl esters, vinyl ketones, allyl compounds, olefinic acids, vinyl ethers, N-vinyl amides, vinyl phenomenes. Examples include ring compounds, maleic acid esters, itaconic acid esters, fumaric acid esters, and crotonic acid esters. Of these, (meth) acrylic acid esters are particularly preferred.

  Specific examples include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate. , Hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, norbornyl acrylate, isobornyl acrylate, adamantyl acrylate , Tricyclodecyl acrylate, dicyclopentanyl acrylate, 2-acetoxyethyl acrylate Dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3- Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2 -Butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (added mole number n = 9), 1-bromine Mo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3 3,3-pentafluoropropyl acrylate, 1-trifluoromethyl-2,2,2-trifluoroethyl acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, 2,2 3,3,4,4-hexafluorobutyl acrylate and the like.

  Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, norborn Nyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, tricyclodecyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3 Phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, Dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate , 2- (2-Methoxyeth B) Ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate 2,2,3,3,3-pentafluoropropyl methacrylate, 1-trifluoromethyl-2,2,2-trifluoroethyl methacrylate, 2,2,3,3,4,4,5,5-octa Fluoropentyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl methacrylate and the like, and the C—H bond in these repeating units is particularly preferably a CD bond. .

  m and n are mol% of each repeating unit, and satisfy m + n = 100, 0 <m ≦ 100 and 0 ≦ n <100. m is preferably 1 to 75 mol%, and more preferably 1 to 50 mol%.

  The polymer of the present invention can be polymerized alone or in combination with other monomers using the compound of the general formula (1) as a monomer by using a homopolymerization or copolymerization method of an unsaturated ester, which is usually used. It can be produced by polymerization. Further, without using the compound of the general formula (1) as a monomer, for example, after polymerizing or copolymerizing a corresponding poly (meth) acrylic acid, a cyclic aliphatic group is formed by a polymer reaction (esterification). It can also be introduced. When the copolymer represented by the general formula (3-A) is produced, an unsaturated ester monomer having a deuterated cyclic aliphatic group and an unsaturated ethylenic monomer corresponding to A are copolymerized. It is preferable to produce by polymerization.

  Although the specific example of the polymer containing the repeating unit of General formula (3) below is given, of course, the polymer of this invention is not limited to these.

Next, an embodiment in which the compound and polymer of the present invention are used as an optical material used for production of an optical component will be described.
The compounds and polymers of the present invention include lenses for general cameras, video cameras, laser pickup lenses, fθ lenses for laser printers, Fresnel lenses, lenses for liquid crystal projectors, lenses for glasses, optical fibers, Molecular) It can be used for the production of optical components such as optical waveguides. Among these, it can be suitably used as a material for optical fibers (SI-POF, MSI-POF, GI-POF, etc.) and polymer optical waveguides.

  When the polymer of the present invention is used as a material for optical components, a refractive index control agent (hereinafter sometimes referred to as “dopant”) may be added to the polymer of the present invention in order to obtain desired optical properties. In such a case, there are an embodiment in which the dopant is uniformly dispersed in the polymer of the present invention and an embodiment in which there is a concentration distribution. In an embodiment having a dopant concentration distribution, the refractive index is distributed based on the concentration distribution, and application to an array lens used in a GI POF or a copying machine is preferable.

  The optical component of the present invention uses a known molding method such as an injection molding method, a compression molding method, a micromold method, a floating mold method, a low link method, a casting method, etc., for the composition containing the polymer of the present invention. And it can manufacture by shape | molding in a desired shape. Furthermore, moisture resistance, optical properties, chemical resistance, abrasion resistance, anti-fogging, etc. may be improved by applying various coatings to the surface of the molded product obtained by the molding method as described above.

Hereinafter, the aspect of GI-POF manufactured using the polymeric composition containing the compound represented by Formula (1) of this invention is demonstrated in detail. GI-POF consists of a clad part and a core part. First, the core part will be described.
The core part is formed by polymerizing a polymerizable composition. The polymerizable composition contains one or more polymerizable monomers as essential components, and may further contain additives such as a polymerization initiator, a chain transfer agent, or a refractive index control agent. The polymerizable monomer is preferably a compound represented by the formula (1), and more preferably selected from exemplary compounds of the compound represented by the formula (1). An ethylenically unsaturated monomer copolymerizable with the compound may be used together with the compound represented by the formula (1). As the monomer, (meth) acrylic acid esters are preferable, and deuterated. More preferred are (meth) acrylic acid esters.

  The polymerization initiator can be appropriately selected according to the monomer used and the polymerization method, and includes benzoyl peroxide (BPO), t-butylperoxy-2-ethylhexanate (PBO), and di-t-butyl. Peroxide compounds such as peroxide (PBD), t-butyl peroxyisopropyl carbonate (PBI), n-butyl 4,4, bis (t-butylperoxy) valerate (PHV), or 2,2′-azo Bisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylpropane), 2 , 2′-azobis (2-methylbutane), 2,2′-azobis (2-methylpentane), 2,2′-azobis (2,3-dimethyl) Butane), 2,2′-azobis (2-methylhexane), 2,2′-azobis (2,4-dimethylpentane), 2,2′-azobis (2,3,3-trimethylbutane), 2, 2'-azobis (2,4,4-trimethylpentane), 3,3'-azobis (3-methylpentane), 3,3'-azobis (3-methylhexane), 3,3'-azobis (3 4-dimethylpentane), 3,3′-azobis (3-ethylpentane), dimethyl-2,2′-azobis (2-methylpropionate), diethyl-2,2′-azobis (2-methylpropio) And azo compounds such as di-t-butyl-2,2′-azobis (2-methylpropionate). Two or more kinds of polymerization initiators may be used in combination.

  The polymerizable composition for forming the core part preferably contains a chain transfer agent. The chain transfer agent is mainly used for adjusting the molecular weight of the polymer. When the polymerizable composition contains a chain transfer agent, the polymerization rate and degree of polymerization of the polymerizable monomer can be more controlled by the chain transfer agent, and the molecular weight of the polymer can be adjusted to a desired molecular weight. it can. For example, when a preform having a region corresponding to each of the core part and the clad part is prepared, and then the preform is drawn by stretching to form an optical transmission body, the molecular weight is adjusted to adjust the stretching. The mechanical characteristics in can be set within a desired range, which contributes to improvement of productivity. About the said chain transfer agent, according to the kind of polymerizable monomer used together, a kind and addition amount can be selected suitably. The chain transfer constant of the chain transfer agent for each monomer can be referred to, for example, Polymer Handbook 3rd edition (edited by J. BRANDRUP and EH IMMERGUT, published by JOHN WILEY & SON). The chain transfer constant can also be obtained by experiment with reference to Takayuki Otsu and Masaaki Kinoshita "Experimental Method for Polymer Synthesis", Kagaku Dojin, published in 1972.

  Examples of chain transfer agents include alkyl mercaptans (n-butyl mercaptan, n-pentyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, t-dodecyl mercaptan, etc.), thiophenols (thiophenol, m-bromothiophenol, p-bromothiophenol, m-toluenethiol, p-toluenethiol, etc.) are preferably used, and among them, alkyl mercaptans such as n-octyl mercaptan, n-lauryl mercaptan, and t-dodecyl mercaptan are preferably used. A chain transfer agent in which a hydrogen atom of a C—H bond is substituted with a deuterium atom or a fluorine atom can also be used. In addition, the said chain transfer agent may use 2 or more types together.

  In the present invention, the polymerizable composition for the core part may contain a refractive index adjusting component. In that case, a refractive index distribution type plastic optical fiber can be produced by providing a gradient in the concentration of the refractive index adjusting component along the direction of polymerization during polymerization. The refractive index adjusting component means a component different from the refractive index of the polymerizable monomer used together, and may be a low molecular compound or a high molecular compound. The refractive index difference is preferably 0.005 or more. As the refractive index adjusting component, it is preferable to use a component having a property of increasing the refractive index as compared with a polymer containing no additive. Further, the refractive index adjusting component may be a polymerizable compound, and when the polymerizable compound is a refractive index adjusting component, the copolymer containing this as a copolymerizing component is compared with a polymer not containing this, It is preferable to use one having a property of increasing the refractive index. Refractive index adjusting component having the above properties, capable of stably coexisting with the polymer, and stable under the polymerization conditions (polymerization conditions such as heating and pressurization) of the polymerizable monomer as the raw material described above Can be used as For example, the refractive index adjusting component is contained in the core portion-forming polymerizable composition, the progress of polymerization is controlled by the interfacial gel polymerization method in the step of forming the core portion, and the concentration of the refractive index adjusting component is given a gradient. It is preferable to form a refractive index distribution structure based on the concentration distribution of the refractive index adjusting component in the core part (hereinafter, the core part having a refractive index distribution may be referred to as a “refractive index distribution type core part”). By forming the gradient index core portion, the obtained optical member becomes a gradient index plastic optical member having a wide transmission band.

  Examples of the refractive index adjusting component include low molecular weight compounds such as benzyl benzoate (BEN), diphenyl sulfide (DPS), triphenyl phosphate (TPP), benzyl n-butyl phthalate (BBP), diphenyl phthalate ( DPP), biphenyl (DP), diphenylmethane (DPM), tricresyl phosphate (TCP), diphenyl sulfoxide (DPSO), sulfurized diphenyl derivatives, dithian derivatives and the like. The sulfurized diphenyl derivative and dithiane derivative are appropriately selected from the compounds specifically shown below. Among them, BEN, DPS, TPP, DPSO, sulfurized diphenyl derivatives, and dithian derivatives are preferable. In addition, the compound which substituted the hydrogen atom which exists in these compounds with the deuterium atom can also be used in order to improve the transparency in a wide wavelength range. Examples of the polymerizable compound include tribromophenyl methacrylate. When a polymerizable compound is used as the refractive index adjusting component, it is more difficult to control various properties (particularly optical properties) because the polymerizable monomer and the polymerizable refractive index adjusting component are copolymerized when forming the matrix. However, it may be advantageous in terms of heat resistance.

  By adjusting the concentration and distribution of the refractive index adjusting agent, the refractive index of the core portion can be changed to a desired value. The addition amount is appropriately selected according to the application. A plurality of types of refractive index adjusting agents may be added.

  When heat and / or light is supplied to the polymerizable composition containing the monomer represented by the formula (1), for example, a radical or the like is generated from the polymerization initiator, and is represented by the formula (3). Homopolymerization or copolymerization starts. In the case where a refractive index adjusting component is included in addition to the polymerizable monomer, for example, as in the later-described interfacial gel polymerization method, the polymerization progress direction is controlled so that the concentration of the refractive index adjusting component is inclined. Therefore, even when the refractive index adjusting component is not included, the refractive index distribution structure can be formed by giving a gradient to the copolymerization ratio of the polymerizable monomer. In particular, in the present invention, since the compound represented by the above formula (1) is used as the polymerizable monomer, the optical transmission loss of the produced optical member can be greatly reduced. Furthermore, an increase in optical transmission loss due to moisture absorption can be significantly reduced. Further, the polymerization rate and degree of polymerization of the polymerizable monomer can be controlled by a polymerization initiator and a chain transfer agent added as required, and the molecular weight of the polymer can be adjusted to a desired molecular weight. For example, when the obtained polymer is drawn by drawing to obtain an optical fiber, the molecular weight of the polymer produced by the chain transfer agent (preferably 10,000 to 1,000,000, more preferably 30,000 to 500,000) If is adjusted, the mechanical properties at the time of stretching can be in a desired range, which contributes to the improvement of productivity.

  Next, the cladding part will be described. The cladding part, which is another important element constituting the GI-POF, is preferably made of a transparent polymer having a refractive index that is at least 3% smaller than that of the core part. When the refractive index is less than 3%, the ratio of light reflected by the clad portion is reduced and the light guide loss is increased. From the viewpoint of the numerical aperture, the clad portion is preferably a fluororesin. Preferred fluororesins include, for example, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropene, trifluoromethyl trifluorovinyl ether, perfluoropropyl trifluorovinyl ether, perfluoro-t-butyl methacrylate. And fluorine-containing polymers such as polymethyl methacrylate, polyethyl methacrylate, and copolymers thereof. Among these fluorine-containing polymers, vinylidene fluoride-tetrafluoroethylene copolymer, trifluoroethylene-vinylidene fluoride copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropene copolymer are particularly preferable. And methacrylic acid perfluoro-t-butyl polymer. Specifically, the clad part has a refractive index of 1.42 or less, is not crystalline but is amorphous, and has an adhesive property with a polymer of (meth) acrylic acid esters which is a matrix of the core part. A good one is desirable.

  Hereinafter, an embodiment in which the compound represented by the formula (1) of the present invention is used in the production of a gradient index plastic optical member having a core part and a clad part will be described. Although there are mainly two types of this embodiment, it is not limited to the following embodiments.

In the first embodiment, the first step of polymerizing the polymerizable composition for the cladding part to produce a cylindrical tube that becomes the cladding part, and the polymerizable composition for forming the core part in the hollow part of the cylindrical tube are interfaced. A second step of forming a region to be a core portion by gel polymerization and producing a preform having regions corresponding to the core portion and the cladding portion, and a step of processing the obtained preform into a desired form 3 is a method for producing a plastic optical member.
In the second embodiment, the outer core polymerizable composition is polymerized by rotation polymerization in a hollow portion of a cylindrical pipe made of a fluorine-containing resin such as polyvinylidene fluoride resin, which corresponds to the clad portion, and two layers are formed. Forming a region to be an inner core part by interfacial gel polymerization of a polymerizable composition for forming an inner core part in a further hollow part of the first step of producing a concentric cylindrical pipe comprising: A plastic optical including a second step of manufacturing a preform composed of regions corresponding to the cladding portion, the outer core portion, and the inner core portion, and a third step of processing the obtained preform into a desired shape. It is a manufacturing method of a member. In the latter embodiment, when producing a two-layer concentric cylindrical pipe, it is not stepwise as described above, but one step of the melt coextrusion method of the polymer of the fluororesin and the polymer composition for the outer core. You may produce by.

  The polymerizable composition for forming the clad part or the outer core part contains a polymerizable monomer and, if desired, a polymerization initiator and a chain transfer agent for initiating polymerization of the polymerizable monomer. The polymerizable composition for forming the core part or inner core part includes a polymerizable monomer represented by the general formula (1), and a polymerization initiator that initiates polymerization of the polymerizable monomer, if desired, a chain transfer agent, And a refractive index adjusting agent. In the first embodiment, the polymerizable monomers used in the polymerizable composition for forming the cladding part / core part and in the second embodiment for forming the outer core part / inner core part are equal to each other. (However, the composition ratio may not be the same, and the subcomponents may not be equal.) By using the same type of polymerizable monomer, it is possible to improve light transmittance and adhesiveness at the cladding / core or outer core / inner core interface.

  In the second embodiment, by forming the outer core portion between the cladding portion and the core portion, it is possible to reduce a decrease in adhesiveness and a decrease in productivity due to a difference in material between the cladding portion and the core portion. Yes. As a result, the range of selection of materials used for the cladding part and the core part can be expanded. In the present embodiment, it is preferable to use a fluorine-containing resin having high hydrophobicity for the clad part and capable of increasing the difference in refractive index from the core part. Specifically, polyvinylidene fluoride resin or the like is preferable. The cylindrical tube corresponding to the clad portion can be produced by, for example, molding a commercially available fluororesin into a pipe having a desired diameter and thickness by melt extrusion. Furthermore, the above-mentioned polymerizable composition can be rotationally polymerized in the hollow portion of the obtained pipe to form an outer core layer on the inner wall thereof. In addition, a similar structure can be produced by co-extrusion of a polymer comprising the fluororesin and the polymerizable composition.

  In the polymerizable composition for forming the cladding part, the outer core part, and the core part, the preferred range of the content ratio of each component differs depending on the type and cannot be determined unconditionally, but in general, a polymerization initiator Is preferably from 0.005 to 0.5 mass%, more preferably from 0.01 to 0.5 mass%, based on the polymerizable monomer. The chain transfer agent is preferably 0.10 to 0.40 mass%, more preferably 0.15 to 0.30 mass%, based on the polymerizable monomer. Moreover, in the polymerizable composition for forming a core part, the refractive index adjusting component is preferably 1 to 30% by mass, and more preferably 1 to 25% by mass with respect to the polymerizable monomer.

  The molecular weight of the polymer component obtained by polymerizing the polymerizable composition for forming the cladding part, outer core part, and core part is in the range of 10,000 to 1,000,000 in terms of weight average molecular weight because of the relationship of stretching the preform. It is preferably 30,000 to 500,000, and more preferably 30,000 to 500,000. Further, the molecular weight distribution (MWD: weight average molecular weight / number average molecular weight) is also influenced from the viewpoint of stretchability. If the MWD becomes large, even if there are very few components having an extremely high molecular weight, the stretchability deteriorates, and in some cases, stretching may not be possible. Therefore, as a preferable range, MWD is preferably 4 or less, and more preferably 3 or less.

  Other additives can be added to the clad part, the outer core part, and the polymerizable composition for forming the core part, as long as the reactivity during polymerization and the optical transmission performance are not deteriorated. For example, for the purpose of improving weather resistance, durability, and the like, stabilizers such as an oxidation resistance agent and a light resistance agent can be added. Further, for the purpose of improving optical transmission performance, a stimulated emission functional compound for optical signal amplification can be added. By adding the compound, it becomes possible to amplify the attenuated signal light with the excitation light and improve the transmission distance, so that it can be used as a fiber amplifier in a part of the optical transmission link.

Next, each process of said 1st and 2nd form (especially said 1st embodiment) is demonstrated in detail.
In the first step, a single-layer hollow tube (for example, a cylindrical shape) corresponding to the cladding portion or two layers corresponding to the cladding portion and the outer core portion is manufactured. Examples of a method for producing a hollow cylindrical tube include a production method as described in International Publication WO 93/08488. Specifically, the polymer composition for forming the cladding part is placed in a cylindrical polymerization container, or the polymerizable composition for forming the outer core part is made of a fluororesin pipe (further placed in a cylindrical container on the outside) ) And polymerizing the polymerizable monomer while rotating the polymerization vessel (preferably while maintaining the axis of the cylinder in a horizontal state), thereby allowing one layer (single) or two layers (double) ) A structure composed of a cylindrical polymer can be produced. It is preferable to remove dust contained in the composition by filtering with a filter before pouring into the polymerization vessel. Although the polymerization temperature and the polymerization time vary depending on the monomer and polymerization initiator used, in general, the polymerization temperature is preferably 60 to 150 ° C., and the polymerization time is preferably 5 to 24 hours. At this time, as described in JP-A-8-110419, the raw material may be prepolymerized to increase the raw material viscosity. In addition, if the container used for polymerization is deformed by rotation, the resulting cylindrical tube is distorted. Therefore, it is desirable to use a metal tube / glass tube having sufficient rigidity.

  The structure composed of the single- or double-cylindrical polymer has a core portion (in the second embodiment, an inner core portion. Hereinafter, the term “core portion” also means “inner core portion”. It is preferable to have a bottom so that a polymerizable composition as a raw material can be injected. The bottom is preferably made of a material that is rich in adhesion and adhesion to the polymer constituting the cylindrical tube. Further, the bottom can be made of the same polymer as the cylindrical tube. For example, before or after polymerization is performed by rotating the polymerization vessel (hereinafter sometimes referred to as “rotational polymerization”), the bottom portion made of the polymer is placed in the polymerization vessel with a small amount in the polymerization vessel. It can be formed by injecting a polymerizable monomer and polymerizing.

  After the rotational polymerization, the structure obtained at a temperature higher than the polymerization temperature of the rotational polymerization may be subjected to heat treatment for the purpose of completely reacting the remaining monomer and polymerization initiator, and the desired hollow After the tube is obtained, the unpolymerized composition may be removed.

  In the first step, once the polymerizable composition is polymerized to produce a polymer, a desired shape (single cylindrical shape in the present embodiment) is obtained using a molding technique such as extrusion molding. Alternatively, a double (concentric cylindrical) structure composed of a fluororesin and the polymerizable composition polymer can be obtained.

  In the second step, the polymerizable composition for core portion formation is injected into the hollow portion of the single- or double-cylindrical structure produced in the first step, and the polymerizable monomer in the composition is added. Polymerize. It is preferable to remove dust contained in the composition by filtering with a filter. The polymerization method is particularly preferably an interfacial gel polymerization method that does not use a solvent or the like from the viewpoint of residues after polymerization. By using this interfacial gel polymerization method, the polymerization of the polymerizable monomer proceeds from the inner wall surface having increased viscosity toward the radial direction and the center of the cross section due to the gel effect of the cylindrical tube. When the refractive index adjusting component is added to the polymerizable monomer and polymerized, a monomer having a high affinity for the polymer constituting the cylindrical tube is unevenly distributed on the inner wall surface of the cylindrical tube and polymerized on the outer side. A polymer having a low refractive index adjusting component concentration is formed. The ratio of the refractive index adjusting component in the formed polymer increases toward the center. In this way, a concentration distribution of the refractive index adjusting component is generated in the region to be the core portion, and a continuous refractive index distribution is introduced based on this concentration distribution.

  As described above, in the second step, the refractive index distribution is introduced into the region to be the core portion to be formed. However, since the thermal behavior is different between the portions having different refractive indexes, the polymerization is performed at a constant temperature. If done in, due to the difference in thermal behavior, the volume shrinkage responsiveness to the polymerization reaction changes in the core region, bubbles are mixed inside the preform, or micro voids are generated, When the obtained preform is heated and stretched, a large number of bubbles may be generated. When the polymerization temperature is too low, the polymerization efficiency is lowered, and it takes time to complete the reaction, so that productivity is remarkably impaired. Further, the polymerization is incomplete, the light transmittance is lowered, and the optical transmission capability of the manufactured optical fiber is impaired. On the other hand, if the initial polymerization temperature is too high, the response to the shrinkage of the region that becomes the core portion cannot be relaxed, and the tendency of bubble generation is remarkable. Therefore, the polymerization temperature and the post-treatment temperature are adjusted while taking into consideration the boiling point of the monomer and the glass transition temperature (Tg) of the polymer to be produced. However, the post-treatment temperature is selected so as to be equal to or higher than the glass transition temperature of the polymer. For example, when a typical methacrylate monomer is used, the polymerization temperature is preferably 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C. It is also preferable to perform polymerization in a pressurized inert gas in order to increase the responsiveness to polymerization shrinkage. Furthermore, the generation of bubbles can be further reduced by dehydrating and degassing the monomer before polymerization in a reduced-pressure atmosphere.

  Although the polymerization temperature and the polymerization time vary depending on the monomer used, in general, the polymerization temperature is preferably 60 to 150 ° C., and the polymerization time is preferably 5 to 72 hours. Specifically, when methyl methacrylate is used as the polymerizable monomer and 2,2′-azobis (2,4,4-trimethylpentane) is used as the polymerization initiator, the initial polymerization temperature is set to 100 to 110 ° C. 48 It is preferably maintained for 72 hours, then heated to 120-160 ° C. and polymerized for 24-48 hours. When di-t-butyl peroxide is used as the polymerization initiator, the initial polymerization temperature is 90-110. It is preferable that the temperature is maintained at 4 ° C. for 4 to 48 hours, the temperature is raised to 120 to 160 ° C., and polymerization is performed for 24 to 48 hours. In addition, although temperature rise may be performed in steps or continuously, it is better that the time required for temperature increase is short.

  The polymerization is preferably performed under pressure (hereinafter, polymerization performed under pressure is referred to as “pressure polymerization”). When performing pressure polymerization, the single- or double-cylindrical structure into which the polymerizable composition is injected is inserted into the hollow portion of the jig, and polymerization is performed while being supported by the jig. preferable. The jig preferably has a hollow shape into which the structure can be inserted, and the hollow portion preferably has a shape similar to that of the structure. In the present embodiment, since the structure serving as the cladding portion is a cylindrical tube, the jig is also preferably cylindrical. The jig suppresses the cylindrical tube from being deformed during the pressure polymerization and supports the shrinkage of the region that becomes the core portion as the pressure polymerization progresses. Therefore, it is preferable that the hollow portion of the jig has a diameter larger than the outer diameter of the single- or double-cylindrical structure and supports the cylindrical tube serving as the cladding portion in a non-contact state. The hollow portion of the jig preferably has a diameter that is larger by 0.1% to 40% than the outer diameter of the single- or double-cylindrical structure, and has a diameter that is larger by 10 to 20%. It is more preferable to have.

  The single- or double-cylindrical structure can be placed in the polymerization vessel in a state of being inserted into the hollow portion of the jig. In the polymerization vessel, the single- or double-cylindrical structure is preferably arranged with the height direction of the cylinder vertical. After the cylindrical tube is arranged in the polymerization vessel while being supported by the jig, the inside of the polymerization vessel can be pressurized. It is preferable to pressurize the inside of the polymerization vessel with an inert gas such as nitrogen and to proceed with the pressure polymerization in an inert gas atmosphere. The preferred range of pressure during polymerization varies depending on the monomer used, but the pressure during polymerization is generally preferably about 0.05 to 1.0 MPa.

  Through the above steps, a preform for the optical member can be obtained. In the second embodiment, a method for producing a cylindrical preform having an outer core portion of one layer has been described. However, the outer core portion may have two or more layers. Moreover, after the outer core part is formed into various forms by processing (for example, the form of an optical fiber by stretching), the outer core part may be integrated with the inner core part so that both cannot be identified.

  In the third step, the produced preform is processed to obtain an optical member having a desired form. For example, if the preform is sliced perpendicular to the axial direction, a disk-shaped or columnar lens having a non-concave surface can be obtained. Further, it is stretched to obtain a plastic optical fiber. The optical fiber can be produced by heating and stretching the preform in the third step, and the heating temperature can be appropriately determined according to the material of the preform. In general, it is preferably performed in an atmosphere at 180 to 250 ° C. The stretching conditions (stretching temperature and the like) can be appropriately determined in consideration of the diameter of the obtained preform, the diameter of the desired plastic optical fiber, the material used, and the like. For example, as described in Japanese Patent Application Laid-Open No. 7-234322, the drawing tension is set to 10 g or more in order to orient the molten plastic, or as described in Japanese Patent Application Laid-Open No. 7-234324. In order not to leave distortion after melt drawing, it is preferable to be 100 g or less. Further, as described in JP-A-8-106015, a method of providing preheating at the time of stretching can be used. With respect to the fiber obtained by the above method, the bending and lateral pressure characteristics of the fiber can be improved by defining the breaking elongation and hardness of the obtained wire as described in JP-A-7-244220.

  The plastic optical fiber manufactured by the above-described method can be used for various purposes as it is. In addition, for the purpose of protection and reinforcement, the present invention can be used for various applications in a form having a coating layer on the outside, a form having a fiber layer, and / or a state in which a plurality of fibers are bundled. The coating process is performed, for example, by passing the fiber strands through opposed dies having holes through which the fiber strands pass, filling the molten coating resin between the opposed dies, and moving the fiber strands between the dies. Fiber can be obtained. In order to protect the coating layer from stress to the internal fiber when it is flexible, it is desirable that the coating layer is not fused with the fiber. Further, at this time, since the fiber strand is thermally damaged by being in contact with the molten resin, it is desirable to select a resin that can be melted at a moving speed or low temperature that suppresses damage as much as possible. At this time, the thickness of the coating layer depends on the melting temperature of the coating material, the wire drawing speed, and the cooling temperature of the coating layer. In addition, a method of polymerizing a monomer applied to the optical member, a method of winding a sheet, a method of passing the optical member through an extruded hollow tube, and the like are known.

  By coating the strand, a plastic optical fiber cable can be manufactured. At that time, as a form of the coating, a contact type coating in which the interface between the coating material and the plastic optical fiber is in contact with the entire circumference, and a loose having a gap at the interface between the coating material and the plastic optical fiber There is a mold coating. In the loose type coating, for example, when the coating layer is peeled off at the connection portion with the connector or the like, moisture may enter from the gaps at the end face and diffuse in the longitudinal direction. However, in the case of a loose-type coating, since the coating and the strands are not in close contact, most of the damage such as stress and heat applied to the cable can be mitigated by the coating layer, and the damage to the strands can be reduced. Since it can be reduced, it can be preferably used depending on the purpose of use. As for the propagation of moisture, by filling the voids with fluid semi-solid or powdery particles, moisture propagation from the end face can be prevented, and heat and A coating with higher performance can be formed by having functions different from moisture propagation prevention such as improvement of mechanical functions. In order to produce a loose type coating, the void layer can be formed by adjusting the position of the extrusion nipple of the crosshead die and adjusting the pressure reducing device. The thickness of the gap layer can be adjusted by pressurizing / depressurizing the nipple thickness and the gap layer.

  Furthermore, you may provide a coating layer (secondary coating layer) further in the outer periphery of a coating layer (primary coating layer) as needed. Flame retardants, UV absorbers, antioxidants, radical scavengers, photosensitizers, lubricants, etc. may be introduced into the secondary coating layer, and as long as moisture permeation resistance is satisfied, Introduction is possible. In addition, some flame retardants contain halogen-containing resins such as bromine, additives, and phosphorous. However, metal hydroxides are becoming mainstream as flame retardants in terms of safety such as reduction of toxic gases. . Since the metal hydroxide has moisture as crystal water inside, and the attached water cannot be completely removed during the manufacturing process, the flame retardant coating by the metal hydroxide is the moisture-permeable coating of the present invention. It is desirable to provide as an outer layer coating (secondary coating layer) of (primary coating layer).

  Moreover, in order to provide a plurality of functions, coatings having various functions may be laminated. For example, in addition to flame retardancy as in the present invention, a barrier layer for suppressing moisture absorption of the wire and a moisture absorbing material for removing moisture, such as a moisture absorbing tape or moisture absorbing gel, are provided in the coating layer or between the coating layers. In addition, a flexible material layer for relaxing stress at the time of flexibility, a cushioning material such as a foam layer, a reinforcing layer for increasing rigidity, and the like can be selected and provided depending on the application. In addition to the resin, if the thermoplastic resin contains a fiber having a high elastic modulus (so-called tensile fiber) and / or a highly rigid metal wire, the mechanical strength of the resulting cable can be reinforced. It is preferable because it is possible. Examples of the tensile strength fiber include aramid fiber, polyester fiber, and polyamide fiber. Examples of the metal wire include stainless steel wire, zinc alloy wire, copper wire and the like. None of these are limited to those described above. In addition, a metal tube exterior for protection, an aerial support line, and a mechanism for improving workability during wiring can be incorporated.

  In addition, depending on the type of use, the cable shape is a collective cable in which the strands are concentrically arranged, an aspect called a tape core wire arranged in a row, and a collective cable in which they are gathered together with a presser roll or wrap sheath The form can be selected according to the situation.

  In addition, the cable using the optical fiber of the present invention has a higher tolerance than the conventional optical fiber with respect to the axis deviation, so it can be used for joining by butt, but an optical connector for connection is used at the end. It is preferable to securely fix the connecting portion. As the connector, various commercially available connectors such as PN type, SMA type, and SMI type that are generally known can be used.

  An optical fiber as an optical member of the present invention and a system for transmitting an optical signal using an optical fiber cable include various light emitting elements, light receiving elements, optical switches, optical isolators, optical integrated circuits, optical transceiver modules, and the like. It is composed of an optical signal processing device including components. Moreover, you may combine with another optical fiber etc. as needed. Any known technique can be applied as a technique related to them. For example, the basic and actual of plastic optical fiber (published by NTS Corporation), Nikkei Electronics 2001.1.2.3, pp. 110-127 “Printed Wiring You can refer to "This time, optical components are mounted on the board." Combined with various technologies described in the above documents, internal wiring in computers and various digital devices, internal wiring in vehicles and ships, optical terminals and digital devices, optical links between digital devices, general households and housing complexes・ Suitable for optical transmission systems suitable for short distances such as high-speed, large-capacity data communications and control applications that are not affected by electromagnetic waves, including optical LANs in factories, offices, hospitals, schools, etc. Can be used.

  Furthermore, IEICE TRANS. ELECTRON., VOL. E84-C, No.3, MARCH 2001, p.339-344 “High-Uniformity Star Coupler Using Diffused Light Transmission”, Journal of Japan Institute of Electronics Packaging Vol.3, No.6, 2000 pp. 476 to 480, “Light-Bus Bath Technology Interconnection”, and Japanese Patent Application Laid-Open No. 2003-152284, etc .; Optical buses described in JP-A-2002-90571, JP-A-2001-290055, etc .; JP-A-2001-74971, JP-A-2000-329962, JP-A-2001-74966, JP-A-2001-74968 Optical branching and coupling devices described in JP-A-2001-318263, JP-A-2001-31840, and the like; and optical stars described in JP-A-2000-241655, etc. Couplers: Optical signal transmission devices and optical data bus systems described in JP 2002-62457, JP 2002-101044, JP 2001-305395, and the like; Optical described in JP 2002-23011, etc. Signal processing apparatus; optical signal cross-connect system described in Japanese Patent Application Laid-Open No. 2001-86537; optical transmission system described in Japanese Patent Application Laid-Open No. 2002-26815; each of Japanese Patent Application Laid-Open Nos. 2001-339554 and 2001-339555 Multi-function system described in the official gazette; and various optical waveguides, optical splitters, optical couplers, optical multiplexers, optical demultiplexers, etc., combined with transmission / reception that is multiplexed, etc. A system can be constructed. In addition to the above optical transmission applications, it can also be used in the fields of illumination, energy transmission, illumination, and sensors.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing contents, processing means, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
The synthesis example of exemplary compound (I-1) is demonstrated in detail below. According to this example, exemplary compound (I-1) in which the D conversion rate of the cycloaliphatic group is about 83% can be obtained. It is possible to synthesize a tricyclodecanyl ester having a high D conversion rate using D ₂ O which is the cheapest deuterium source, and shows the usefulness of the production method of the present invention.

  Exemplified compound (I-1) was synthesized by the synthesis route of reaction formula (5) shown below.

Synthesis of cyclopentadiene (A-2):
325 g (2.5 mol) of dicyclopentadiene (A-1) was placed in a 500 ml eggplant-shaped flask equipped with a distillation apparatus and cracked by heating at 160 ° C. for 8 hours under normal pressure to obtain a colorless and transparent liquid cyclopentadiene ( A-2) 230g (yield about 71%) was obtained. The ¹ H NMR data of the compound (A-2) is shown below.
¹ H NMR (300 MHz, CDCl ₃ ): δ 3.0 (m, 2H), 6.5 (m, 2H), 6.6 (m, 2H)

Synthesis of deuterated cyclopentadiene (A-3):
To a 2 L three-necked flask, 100 g (NaOD / D ₂ O) 30 wt% sodium heavy hydroxide aqueous solution (0.73 mol as NaOD) and 820 g (41 mol) heavy water were added and cooled to 5 ° C. with stirring. . To this solution, 500 ml of dimethyl sulfoxide and 132 g (2.0 mol) of (A-2) were added while keeping the temperature of the reaction solution at 10 ° C. or lower, and 3 times while cooling with ice (maintaining the internal temperature at 0 to 10 ° C.). Stir for hours. The reaction solution was transferred to a separatory funnel and allowed to stand, the aqueous layer was discarded, and the organic layer was returned to the flask. For 3 hours. 400 ml of cymene (isopropyltoluene) was added for liquid separation, the aqueous layer was discarded, and then distilled at normal pressure to obtain 43 g (yield: about 30%) of (A-3). The D conversion rate was calculated to be 96% by the method shown below.

(A-3) Deuteration rate determination method (D rate conversion measurement):
The D conversion rate was determined using a derivatization technique. Specifically, 410 mg (2.2 mmol) of p-tolylmaleimide was added to a solution of 158 mg (2.2 mmol) of (A-3) in 0.5 ml of ethyl acetate, and the mixture was stirred at room temperature for 1 hour. The Diels-Alder adduct (A-7) was isolated by thin layer silica gel chromatography, and the D conversion rate was calculated from the integral value of ¹ H NMR.
The ¹ H NMR data of the Diels-Alder product (A-7) (showing the non-deuterated product) is shown below.
¹ H NMR (300 MHz, CDCl ₃ ): δ 1.61 (s, 2H), 2.33 (s, 3H), 3.33 (m, 2H), 3.48 (m, 2H), 6.23 ( s, 2H), 6.98 (d, 2H), 7.24 (d, 2H)
The scheme of the Diels-Alder reaction is shown below.

Synthesis of deuterated dicyclopentadiene (A-4):
57 g (0.79 mol) of (A-3) having a D conversion rate of 96% was heated to reflux (external temperature 60 ° C.) for 5 hours. The remaining (A-3) was distilled off under reduced pressure to obtain 51 g (yield: about 89%) of a colorless transparent liquid (A-4).

Synthesis of (A-5):
(A-4) To 51 g (0.35 mol), 84 g (4.2 mol) of heavy water and 36 g (0.37 mol) of concentrated sulfuric acid (H ₂ SO ₄ ) were added and heated under reflux for 6 hours (external temperature 120 ° C.). After cooling to room temperature, the reaction mixture was poured into ice water and extracted with toluene. The organic layer was washed twice with saturated brine and dried over anhydrous sodium sulfate. Toluene was distilled off under reduced pressure, followed by distillation under reduced pressure (70 to 80 ° C./3 to 4 mmHg), and 37 g (yield: about 63%) of a synthetic intermediate (A-5) of an oily and colorless transparent liquid as a regioisomer mixture. Obtained.

Synthesis of deuterated tricyclodecanyl alcohol (A-6):
In an autoclave, a solution of 34 g (0.21 mol) of (A-5) in 150 ml of ethanol and 0.34 g of hydrogenated catalyst 5% Pd / C were added and charged with hydrogen gas (H ₂ ) to 5.0 MPa. After stirring at room temperature for 4 hours, the catalyst was filtered through celite and ethanol was distilled off under reduced pressure to obtain 31 g (yield: about 90%) of an oily, colorless and transparent synthetic intermediate (A-6).

Synthesis of deuterated tricyclodecanyl methacrylate (I-1):
To a three-necked eggplant-shaped flask, 28 g (0.17 mol) of (A-6), 19.2 g (0.21 mol) of methacrylic acid-d ₅ , 0.3 ml of concentrated sulfuric acid and 30 mg of polymerization inhibitor Irganox were added, and a nitrogen atmosphere Below, the mixture was heated and stirred for 5 hours at an external temperature of around 120 degrees. After cooling to room temperature, the reaction mixture was poured into ice water and extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography (developing solution: ethyl acetate: hexane = 1: 10), and 21 g (yield: about 52%) of (I-1) was obtained as an oil. Obtained as a colorless transparent liquid.

Identification of deuterium compounds (A-5, A-6 and I-1):
A non-deuterated product (hereinafter referred to as H form) of each compound was synthesized with the same formulation as the above method (except that a deuterium compound was used), and the structure was identified by ¹ H-NMR. Furthermore, it was confirmed by gas chromatography that the retention time was almost the same as that of the H form and that the purity was 98% or more.
The ¹ H-NMR (300 MHz, CDCl ₃ ) data of the H form is shown below.
Form A of (A-5) (however, a mixture of positional isomers): δ1.2-2.1 (m, 9H), 2.4-2.8 (m, 2H), 3.7-3.9 (M, 1H), 5.42-5.47 (m, 1H), 5.67-5.70 (m, 1H)
H form of (A-6): δ 0.9-1.1 (m, 2H), 1.2-2.1 (m, 13H), 3.71-3.74 (m, 1H)
H form of (I-1): δ 0.9-1.1 (m, 2H), 1.1-2.1 (m, 15H), 4.62 (m, 1H), 5.51 (s, 1H), 6.06 (s, 1H)

Although the deuteration rate of the final product (I-1) is not directly measured, the deuteration rate of (A-3) is 96% (D number of A-4: 0.96 × 12), The ratio of D in the dilute sulfuric acid used in the water addition step is 92% (D number introduced in the water addition step: 0.92 × 1), and H ₂ is used in the hydrogenation step. (D number introduced by the hydrogenation step: 0 × 2), the D conversion rate of the cycloaliphatic group of (I-1) (total of D number and H number: 15) is about 83 from the following formula: % Can be estimated.
(0.96 × 12 + 0.92 × 1 + 0 × 2) /15=0.83

[Example 2]
In the synthesis route of the above reaction formula (5), desulfuric acid (D ₂ SO ₄ ) is used in the water addition reaction step (A-4 → A-5), and deuterium gas (D ₂ ) is used in the catalytic hydrogenation step. By using this, (I-1) having a higher D conversion rate can be produced. A synthesis example of (I-1) having a D conversion rate of 96% or more is shown below. Hereinafter, in Example 2, the synthetic intermediate and (I-1) synthesized in this example are described as “high D ratio”.

Synthesis of high D ratio (A-5):
To 74 g (0.52 mol) of (A-4) having a conversion rate of 96% synthesized by the method shown in Example 1, 118 g (5.9 mol) of heavy water and 36 g of heavy concentrated sulfuric acid (D ₂ SO ₄ ) 36 mol) was added and heated to reflux for 6 hours (external temperature 120 ° C.). After cooling to room temperature, the mixture was poured into ice water and extracted with toluene. The organic layer was washed twice with saturated brine and dried over anhydrous sodium sulfate. Toluene was distilled off under reduced pressure and distilled under reduced pressure (70 to 80 ° C./3 to 4 mmHg), and 53 g (yield about 63%) of a synthetic intermediate (A-5) of an oily, colorless and transparent liquid was obtained as a regioisomer mixture. Obtained.

Synthesis of high D ratio (A-6):
To the autoclave was added a 125 g ethanol solution of 49 g (0.30 mol) of (A-5) with a high D ratio synthesized by the above method and 0.50 g of hydrogenated catalyst 5% Pd / C, and deuterium gas (D ₂ ) was added. Filled to 5.2 MPa. After stirring at room temperature for 7 hours, the catalyst was filtered through Celite and ethanol was distilled off under reduced pressure to obtain 43 g (yield: about 86%) of an oily, colorless and transparent synthetic intermediate (A-6).

Synthesis of high D ratio (I-1):
(A-6) 31.2 g (0.19 mol), methacrylic acid-d ₅ 21.1 g (0.23 mol), concentrated sulfuric acid 0.3 ml, and polymerization inhibitor Irganox synthesized by the above method Using 30 mg, 24 g (yield: about 54%) of (I-1) was obtained as an oily colorless transparent liquid by the same method as described in Example 1.

  Although the actual deuteration rate of (I-1) having a high D conversion rate is not directly measured, the deuteration rate of (A-3) is 96%, and in the reagents used thereafter Since all the hydrogen atoms contained in (I-1) among the hydrogen atoms are deuterium atoms, the D conversion rate of these compounds does not fall below 96%.

[Example 3]
The embodiment shown in the embodiment 1 can be further simplified and reduced in cost. In the examples shown below, in the process of (A-2) → (A-4), NaOD is changed to NaOCH ₃ which is cheap and easily available, and the liquid separation operation in the middle is omitted. In this example, compound (I-1) was synthesized using ordinary water instead of heavy water in (A-4) → (A-5). is there. The D conversion rate of (I-1) synthesized in this way is lower than that shown in Example 1, but still has a D conversion rate of 70%.

Synthesis of (A-4):
To a 2 L three-necked flask, 21 g (0.39 mol) of NaOCH ₃ and 400 g (20 mol) of heavy water were added and cooled to 5 ° C. with stirring. To this solution, 400 ml of dimethyl sulfoxide and 66 g (1.0 mol) of (A-2) synthesized by the method described in Example 1 were added while keeping the temperature of the reaction solution at 10 ° C. or lower, and ice-cooled (internal temperature was reduced). The mixture was stirred for 3 hours. Let stand for several minutes and extract a small amount (about 0.2 ml) of cyclopentadiene as a supernatant, and convert into D by the method of derivatization with Diels-Alder reaction with p-tolylmaleimide in the same manner as described in Example 1. The rate was measured. The conversion to D was 87%. A cooling tube was attached to the reaction solution, and the mixture was stirred at 40 ° C. for 7 hours. After cooling to room temperature, the reaction solution was transferred to a separatory funnel and extracted with 500 ml of ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After distilling off the solvent and the remaining cyclopentadiene under reduced pressure, the residue was isolated by distillation to obtain 37 g (yield: about 52%) of deuterated dicyclopentadiene (A-4).

Synthesis of (A-5):
80 g of 30% sulfuric acid (adjusted from H ₂ SO ₄ and H ₂ O) was added to 35 g (0.25 mol) of (A-4) synthesized in this way, and the mixture was heated to reflux (external temperature 120 ° C.) for 6 hours. The treatment was performed in the same manner as described in Example 1 to obtain 28 g (yield: about 70%) of (A-5) as a regioisomer mixture.

Synthesis of (A-6) and (I-1):
Using 26 g (0.16 mol) of (A-5) synthesized as described above, catalytic hydrogenation using H ₂ was performed in the same manner as described in Example 1, and 22 g of (A-6) was obtained. (Yield about 84%). Using 20 g (0.12 mol) of this (A-6), 14.6 g (0.16 mol) of methacrylic acid-d ₅ , 0.2 ml of concentrated sulfuric acid, and 20 mg of polymerization inhibitor Irganox, Example 1 16 g (yield: about 55%) was obtained in the same manner as described in 1.

Although the deuteration rate of the final product (I-1) was not directly measured, the deuteration rate of the intermediate (A-3) was 87%, and the sulfuric acid containing no D atom in the water addition step Since H ₂ is used in the hydrogenation step, D is not introduced in the subsequent step, and the D conversion rate of the cycloaliphatic group of (I-1) is about 70% from the following formula: Can be estimated.
(0.87 × 12) /15=0.70

[Example 4]
Next, production of GI-POF synthesized from the above Examples 1 to 3 using (I-1) having a high D conversion rate as a raw material will be described.
Deuterated methyl deuteride as a polymerizable monomer on a vinylidene fluoride resin pipe (inner diameter: 22 mm, length: 600 mm, bottom is also made of KF-850) produced by extrusion using KF-850 manufactured by Kureha Chemical A predetermined amount of a mixture of 8/2 (mass ratio) of methacrylate (MMA-d ₈ : water removed to 1000 ppm or less) and compound (I-1) (total deuteration rate 83%) was injected. As a polymerization initiator, dimethyl-2,2′-azobis (2-methylpropionate) is 0.5% by mass with respect to the monomer mixed solution, and n-lauryl mercaptan as a chain transfer agent is 0% with respect to the monomer mixed solution. .62% by mass was blended. The polymerization vessel into which the monomer mixed solution had been poured was placed in a 60 ° C. hot water bath, and prepolymerization was performed for 2 hours with shaking. Thereafter, the polymerization vessel was kept in a horizontal state at 65 ° C. (a state in which the height direction of the cylinder was horizontal) and polymerized by heating for 3 hours while rotating at 3000 rpm. Then, it heat-processed for 24 hours at 90 degreeC, and obtained the cylindrical tube which consists of the said copolymer.

  Next, in the hollow part of the cylindrical tube, a polymerizable monomer (deuterated methyl methacrylate (MMA-d8) (with water removed to 1000 ppm or less)) and compound I-1 (TCDMA: total A deuteration rate of 87.3% is a mixture of 8/2 by mass ratio, and a solution in which deuterated bromobenzene as a refractive index adjusting component is mixed by 10% by mass with respect to the monomer mixture solution has an accuracy of 0.2 μm. The filtrate was directly injected while filtering through a membrane filter made of ethylene tetrafluoride, 0.016% by mass of di-t-butyl peroxide as a polymerization initiator with respect to the monomer mixture solution, and n-lauryl mercaptan as a chain transfer agent. 0.27% by mass with respect to the monomer mixed solution The cylindrical tube into which this mixed solution or the like was injected was placed in a glass tube having an inner diameter that was 9% wider than the outer diameter of the cylindrical tube. In the inserted state, it was allowed to stand vertically in a pressure polymerization vessel, and then the inside of the pressure polymerization vessel was replaced with a nitrogen atmosphere, and then the pressure was increased to 0.1 Mpa, followed by heat polymerization at 100 ° C. for 48 hours. A preform was obtained by pressurizing to 0.4 Mpa, heating and polymerizing for 24 hours at 120 ° C. The preform had a weight average molecular weight of 116,000. The glass transition temperature (Tg) is 117 ° C., which is higher than the Tg of PMMA-d8, which is 105 ° C., indicating that it can withstand use at higher temperatures.

  The resulting preform did not contain bubbles due to volume shrinkage upon completion of polymerization. The preform was drawn by heat drawing at 230 ° C. to produce a plastic optical fiber having a diameter of about 300 μm. In the stretching process, no bubbles were observed in the preform. When the transmission loss value of the obtained fiber was measured, it was 98 dB / km at a wavelength of 650 nm, 100 dB / km at a wavelength of 780 nm, and 150 dB / km at a wavelength of 850 nm. When the bandwidth of this fiber was measured, it was 1 GHz · 100 m.

[Examples 5-6, Comparative Examples 1-2]
Monomer in the polymerization composition for the core part, the monomer composition (MMA-d ₈ / TCDMA (8/2)) is the same, and only the total deuteration rate of compound I-1 (TCDMA) is as shown in Table 1. Otherwise, the same operation as in Example 4 was performed to obtain a fiber, and the same evaluation as in Example 4 was performed. The results are also shown in Table 1.

Claims (11)

A compound represented by the following general formula (1).

(In the formula (1), R ^{1 to} R ³ each independently represent H, D, a halogen atom, CH ₃ , CD ₃ or CF ₃ , and R ⁴ and R ⁵ each independently represent H, D, or a substituent. R ⁴ and R ⁵ may be linked to form a cyclic skeleton, provided that 55% or more of the hydrogen atoms in the cyclic aliphatic group in the formula are deuterium atoms (D). .) The compound according to claim 1, wherein 60% or more of the hydrogen atoms in the cycloaliphatic group are deuterium atoms (D). The compound according to claim 1, wherein 80% or more of the hydrogen atoms in the cycloaliphatic group are deuterium atoms (D). The compound according to claim 1, which is the following compound A or the following compound B.

(However, 50% or more of the hydrogen atoms in the cyclic aliphatic group contained in each of the compounds A and B are deuterium atoms.) It is a manufacturing method of the compound represented by General formula (1) in Claim 1, Comprising: The cyclopentadiene of Formula (1-1) is HD-exchanged in heavy water in presence of a base, Formula (1) -2) The manufacturing method including the process of producing | generating the compound.

(In the formula, X represents H or D, and at least one of X is D.) Following the step, a step of producing a compound of formula (1-4) by a Diels-Alder reaction of a compound of formula (1-2) and a compound of formula (1-3), a compound of formula (1-4) A compound of formula (1-5) by a step of producing a compound of formula (1-5) by a hydration reaction of and an esterification reaction of a compound of formula (1-5) and a compound of formula (1-6) The manufacturing method of Claim 5 including the process to do.

(In the formula, each of R ^{1 to} R ⁵ is the same as the substituents R ^{1 to} R ^{5 in} the formula (1) of claim 1, and X ¹ represents Cl, Br, OH, or OD.) A polymer containing at least a repeating unit represented by the following general formula (3).

Wherein R ^{1 to} R ³ each independently represents H, D, a halogen atom, CH ₃ , CD ₃ or CF ₃ , and R ⁴ and R ⁵ each independently represent H, D or a substituent. R ⁴ and R ⁵ may be linked to form a cyclic skeleton, provided that 55% or more of the hydrogen atoms in the cyclic aliphatic group in the formula are deuterium (D). A polymer produced by polymerizing the compound according to any one of claims 1 to 4 alone or together with another polymerizable monomer. The polymeric composition containing at least 1 sort (s) of the compound of any one of Claims 1-4. An optical component having a region containing the polymer according to claim 7 or 8. An optical component having a region formed by polymerizing the polymerizable composition according to claim 9.