JP2002047310A - Hydrogenated cyclic conjugated diene polymer and optical disk substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly purified resin with high thermostability, plasticity and mechanical properties. SOLUTION: A hydrogenated cyclic conjugated diene polymer containing transition metals and aluminium in total 10 ppm or less is obtained from a cyclic conjugated diene polymer consisting of x wt.% unit derived from a cyclic conjugated diene monomer, y wt.% unit derived from a styrene monomer and z wt.% unit derived from a conjugated diene monomer (x, y and z satisfy following relation; 1<=x<=100, 0<=y<=99, 0<=z<=99 and x+y+z=100) by hydrogenating reaction using a hydrogenation catalyst. The polymer is hydrogenated at carbon - carbon double bonds and aromatic rings. An optical disc substrate mainly comprised of the polymer is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a purified hydrogenated cyclic conjugated diene polymer and an optical disk substrate. More specifically, a hydrogenated cyclic conjugated diene polymer having excellent heat resistance, moldability, transparency, optical isotropy, dimensional stability (low water absorption) and / or mechanical properties, and low metal content, and a polymer thereof. And an optical disc substrate mainly composed of

[0002]

2. Description of the Related Art In addition to transparency, plastics used for optical disks are required to have various properties such as optical isotropy (low birefringence), dimensional stability, light resistance, weather resistance, and thermal stability. You. Currently, polycarbonate is exclusively used as an optical disk substrate, but recently, a magneto-optical recording disk (M
OD), the development of digital versatile discs (DVDs), and the development of high recording density represented by the development of blue lasers. There is a growing concern about warpage and heat resistance.

[0003] Specifically, there are concerns regarding the heat resistance of the optical disk, such as the production process and the heat load during use. For example, in the production process, in particular, a write-once type optical disk exclusively for recording and reproduction, and an erasable type optical disk for recording-reproduction-erasing / re-recording, etc., have several layers of films such as metal oxides and alloy compounds on the substrate. It is necessary to perform sputtering under a high temperature and a high vacuum, and with a resin having low heat resistance, the entire substrate may be deformed.

In addition, recording, reproducing, erasing,
At the time of an operation such as re-recording, the recording film reaches 200 ° C. or higher due to the irradiation of the high-energy laser, and it is expected that the substrate locally becomes considerably high temperature, and pits, lands, and grooves may be deformed. Further, when an optical disk is used for in-vehicle use, the optical disk may be left at about 100 ° C. for a long time, so that the entire substrate or pits, lands,
The groove may be deformed. Such heat load is expected to become more severe with the recent increase in recording density, and development of a resin having high heat resistance has been desired.

[0005] Recently, 1,3 has been used as a high heat-resistant resin.
-Cyclic conjugated diene polymers such as cyclohexadiene have been proposed. JP-A-7-247321 discloses a cyclic conjugated diene homopolymer and JP-A-7-24.
No. 7323 discloses a copolymer of a cyclic conjugated diene and various monomers. In addition, Japanese Patent Application Laid-Open
JP-A-258362 and JP-A-8-225616 disclose hydrogenated cyclic conjugated diene-based polymers. Also, JP-A-10-152512 and JP-A-1
In JP-A-152529, an initiator for synthesizing a cyclic conjugated diene-based polymer is disclosed.

However, there is no detailed description of applying these resins to optical discs. In general, resins used for optical applications such as optical discs have transparency, weather resistance, light resistance, optical isotropy (low birefringence), dimensional stability, and thermal stability. The balance between moldability, heat resistance (heat deformation temperature) and mechanical properties (particularly toughness) must be satisfied, and a high degree of structural optimization is required. Therefore, there is no optical disk substrate that can be used so far, and its development has been desired.

By the way, the resin used for the optical disk must maintain transparency, heat resistance, weather resistance and light resistance for a long period of time, and for that purpose, it is necessary to minimize the amount of metal contained in the resin. In particular, it is difficult to remove metals derived from a homogeneous hydrogenation catalyst used for the hydrogenation catalyst. Regarding a method for purifying a cyclic conjugated diene polymer, for example, JP-A-7-258362 discloses that a solution containing a catalyst after a hydrogenation reaction of a cyclic conjugated diene polymer is poured into ethanol to recover the resin. A method is disclosed. Japanese Patent Application Laid-Open No. 9-291119 discloses a method for removing a nitrogen-containing compound using a supercritical fluid. However, in any case, a method for highly removing metals has not been disclosed, and its development has been desired.

[0008]

As is apparent from the prior art, an object of the present invention is to provide a highly purified resin having high heat resistance, excellent moldability and mechanical properties, and high purity. .

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have introduced a cyclic conjugated diene polymer,
By optimizing the structure of the polymer and at the same time developing a resin with a highly reduced metal content, we believe that it is possible to provide a material suitable for optical applications, and as a result of extensive research, completed the present invention. Reached.

That is, in the present invention, a unit x weight% derived from a cyclic conjugated diene monomer and a unit y derived from a styrene monomer are used.
% By weight, unit z% by weight derived from a chain conjugated diene monomer
(Where x, y, and z are 1 ≦ x ≦ 100, 0 ≦ y
≤99, 0≤z≤99, x + y + z = 100. ) Is obtained by subjecting a cyclic conjugated diene-based polymer to a hydrogenation reaction in the presence of a hydrogenation catalyst, and hydrogenating the carbon-carbon double bond and the aromatic ring contained in the polymer.
Transition metal and aluminum content of 1
It is a hydrogenated cyclic conjugated diene polymer having a content of 0 ppm or less. Further, the present invention is an optical disc substrate mainly comprising the hydrogenated cyclic conjugated diene polymer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Cyclic conjugated diene-based polymer) The cyclic conjugated diene-based polymer in the present invention is a unit derived from a cyclic conjugated diene-based monomer and, if necessary, a unit derived from a styrene-based monomer and / or a chain conjugated diene-based unit. It is a polymer containing a unit derived from a monomer. The cyclic conjugated diene monomer is a cyclic hydrocarbon having a conjugated diene structure, and specifically, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3- Cyclooctadiene and derivatives thereof can be mentioned. Of these, 1,3-cyclohexadiene is preferred from the viewpoint of reactivity and polymer properties. These may be used alone or in combination of two or more.

The styrene monomer is an aromatic hydrocarbon substituted with a vinyl derivative, specifically, styrene,
Examples thereof include o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, and vinylnaphthalene. Of these, styrene is preferred from the viewpoint of availability and polymer properties. These may be used alone or in combination of two or more. By introducing a unit derived from a styrene monomer, there is an advantage that the heat distortion temperature can be adjusted to some extent. In addition, since it is generally cheaper than the cyclic conjugated diene, it contributes to reduction of the raw material cost, which is preferable.

The chain conjugated diene monomer includes 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-diene.
Butadiene and the like can be mentioned. Of these, 1,3-butadiene or isoprene is particularly preferred in terms of availability and reactivity. These may be used alone,
Two or more types may be used in combination. By introducing a unit derived from a chain conjugated diene monomer, the heat deformation temperature can be adjusted to some extent, and the toughness can be improved, which is preferable.

Regarding the quantitative relationship of the units derived from each monomer in the cyclic conjugated diene-based copolymer in the present invention, the unit x weight% derived from the cyclic conjugated diene-based monomer and the unit derived from the styrene-based monomer When the unit y weight% and the unit z weight% derived from the chain conjugated diene monomer are satisfied, the following formula is satisfied, but can be appropriately set within this range according to the target optical disc. Further, in the present invention, in order to set the heat deformation temperature of the obtained cyclic conjugated diene copolymer to 110 ° C. or higher,
It is also preferable to appropriately adjust the units derived from the monomers within the range of the following formula. 1 ≦ x ≦ 100 0 ≦ y ≦ 99 0 ≦ z ≦ 99 x + y + z = 100

The bonding structure of the unit derived from the monomer in the cyclic conjugated diene polymer containing a styrene monomer and / or a chain conjugated diene monomer is not particularly limited. Structural units such as (1) Structural units in which units derived from cyclic conjugated diene-based monomers and styrene-based monomers and / or chain conjugated diene-based monomers are completely randomly bonded, structural units tapered, and block-type Linked structural units, (2) units derived from cyclic conjugated diene-based monomers and styrene-based monomers bonded randomly or in a tapered form, (3) units and chains derived from cyclic conjugated diene-based monomers (4) Structural units in which units derived from a cyclic conjugated diene-based monomer are bonded in a random or tapered manner, (4) structural units in which units derived from a cyclic conjugated diene-based monomer are bonded in a block form, (5) styrene-based monomer (6) a structural unit in which a unit derived from a body is bonded in a block form, and (6) a structural unit in which a unit derived from a chain conjugated diene monomer is bonded in a block form.

These structural units are present in one molecule of the copolymer.
It may be repeated about 10 times. In order to distinguish these structural units such as random, tapered, and block types, a ¹ H-NMR spectrum (270 MHz) of the styrene-based copolymer in deuterated chloroform at room temperature was measured, and the units derived from the cyclic conjugated diene were measured. It can be easily discriminated by examining the signal shape of the carbon-carbon double bond part of the unit derived from the chain conjugated diene. That is, in the case of the random type, the signal is widened so that the microstructure of the signal cannot be analyzed, and the shape of the widened signal is a gentle peak or a double peak. In the case of the tapered type, the signal is widened so that the microstructure of the signal cannot be analyzed, and the signal has a shape in which the low magnetic field side is high and the high magnetic field side is low. In the case of the block type, a sharp signal is given so that the microstructure can be analyzed.

The structure of the cyclic conjugated diene polymer is preferably a chain or star-shaped branched structure. In particular, a star-shaped branched structure is preferable because the fluidity is improved as compared with the chain structure in comparison with the molecular weight, and the moldability is improved. The molecular weight is preferably set to an appropriate value depending on the application to be used, but it is 10,000 as a value in terms of polystyrene (number average molecular weight) measured by GPC (gel permeation chromatography).
~ 1,000,000, preferably 20,000 ~ 80
0000, more preferably 30,000 to 700,0
It is preferably in the range of 00. If the molecular weight is too small, the moldability is improved, but the toughness is not preferred because the toughness is reduced, and if the molecular weight is too large, the toughness is improved,
It is not preferable because the moldability decreases. As the cyclic conjugated diene-based polymer, a single monomer composition may be used alone, or a mixture of different monomer compositions or different molecular weights may be used.

(Production of Cyclic Conjugated Diene Polymer) The cyclic conjugated diene polymer can be obtained by anionic polymerization, radical polymerization,
Although it can be produced by a conventionally known method such as cationic polymerization or coordination polymerization, it is preferable to use an anionic polymerization technique from the viewpoint that the structure can be easily controlled.

Examples of the initiator for the polymerization using the anionic polymerization technique include metals of Groups 1 and 2 of the periodic table and their organometallic compounds. In particular,
Lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, strontium, barium, radium, methyl lithium, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, iso-butyl lithium, sec- Butyl lithium, cyclopentadienyl lithium, phenyl lithium, cyclohexyl lithium, methyl sodium, ethyl sodium, n-propyl sodium, iso-propyl sodium, n-butyl sodium, cyclopentadienyl sodium, dimethylmagnesium, bis (cyclopentadiene Enyl) magnesium, dimethyl calcium, bis (cyclopentadienyl) calcium, and the like. Of these, organolithium compounds are preferred in terms of availability and operability, and n-butyllithium and sec-butyllithium are particularly preferred. These may be used alone,
Two or more types may be combined.

In conducting anionic polymerization, an electron-donating compound may be added for the purpose of further activating the above-mentioned initiator and improving the reaction rate, increasing the molecular weight and preventing the anion from being deactivated. The electron donating compound is a compound that can donate electrons to the metal of the initiator without impairing the function of the initiator, and is a compound containing an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specifically, ethers such as furan, tetrahydrofuran, diethyl ether, anisole, diphenyl ether, methyl-t-butyl ether, dioxane, dioxolan, dimethoxyethane, diethoxyethane, trimethylamine, triethylamine, tributylamine, tetramethylmethylenediamine, tetramethyl Ethylenediamine, tetraethylmethylenediamine, tetraethylethylenediamine, tetramethyl1,
Tertiary amines such as 3-propanediamine, tetramethylphenylenediamine, diazabicyclo [2,2,2] octane, thioethers such as dimethylsulfide, thiophene and tetrahydrothiophene, trimethylphosphine, triethylphosphine, tri-n-butylphosphine; Tertiary phosphines such as triphenylphosphine, dimethylphosphinomethane, dimethylphosphinoethane, dimethylphosphinopropane, diphenylphosphinomethane, diphenylphosphinoethane, and diphenylphosphinopropane can be exemplified. Of these, particularly preferred are tetrahydrofuran, dimethoxyethane, tetramethylethylenediamine, and diazabicyclo [2,2,2] octane. These may be used alone or in combination of two or more.

The amount of the electron-donating compound depends on the type of the initiator and the electron-donating compound.
0.1 to 100 mol, preferably 0.2 to 100 mol
It is 50 mol, more preferably 0.3 to 10 mol. If the amount is too small, the activating effect cannot be obtained, and if the amount is too large, the activating effect does not increase, and the electron donating compound is wasted.
However, this does not apply when an electron donating compound is used as a solvent.

The cyclic conjugated diene polymer in the present invention can be synthesized by a solution polymerization or bulk polymerization technique. The solvent used for the synthesis by solution polymerization is not particularly limited as long as the solvent dissolves the polymer and does not deactivate the active terminal at the time of polymerization.
C4-12 aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane and n-heptane; cyclobutane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, decalin and the like C4-12 alicyclic hydrocarbons; C6-12 aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, cumene, tetralin, and naphthalene; diethyl ether, tetrahydrofuran, methyl-t-butyl ether and the like C4-12 ethers can be mentioned. In the present invention, since the copolymer after polymerization is subjected to a hydrogenation reaction, in the case of solution polymerization, the solution used is preferably used as it is for the hydrogenation reaction. From such a viewpoint, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferable, and cyclohexane, methylcyclohexane, and methyl-
t-Butyl ether is particularly preferred.

The reaction conditions at the time of polymerization vary depending on the polymerization method and the like, and are not particularly limited. However, the reaction is usually carried out at a temperature in the range of -20 to 200 ° C, preferably 0 to 150 ° C, more preferably 10 to 100 ° C. Will be The reaction time is usually 5 minutes to 20 hours, preferably 10 minutes.
Minutes to 15 hours, more preferably 30 minutes to 10 hours. In addition, since the active end may be very sensitive to water, oxygen, etc. during the polymerization reaction, the reaction is carried out under an inert atmosphere such as nitrogen or argon, and in an environment where reagents, solvents, and inert gases are sufficiently dehydrated. Is preferred.

Specific examples of the method for polymerizing a cyclic conjugated diene polymer containing a unit derived from a styrene monomer and / or a chain conjugated diene monomer include the following methods. A method comprising a step of mixing and polymerizing a cyclic conjugated diene monomer, a styrene monomer and / or a chain conjugated diene monomer. According to this method, a copolymer containing a portion in which units derived from a cyclic conjugated diene monomer and a styrene monomer and / or a chain conjugated diene monomer are randomly or tapered is synthesized. Can be. A method comprising a step of independently adding a cyclic conjugated diene-based monomer, a styrene-based monomer, and a chain conjugated diene-based monomer to a reaction system and polymerizing the same. By this method, a copolymer containing a portion in which units derived from the respective monomers are bonded in a block form can be synthesized.

A method comprising the step of adding a coupling agent to the copolymer obtained by the above method. By this method, it is possible to synthesize a copolymer in which the copolymer is linked in a chain or star-shaped branch. Examples of the coupling agent used herein include halogenated silanes such as dimethyldichlorosilane, methyltrichlorosilane, tetrachlorosilane and tetrabromosilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, bis (trimethoxysilyl) methane, Alkoxysilanes such as bis (trimethoxysilyl) ethane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, and tetraphenoxysilane;
Aryloxysilanes, α, α'-dichloroxylene,
halides such as α, α'-dibromoxylene, tetrakis (chloromethyl) benzene and tetrakis (bromolomethyl) benzene; esters such as dimethyl oxalate, dimethyl succinate, dimethyl glutarate, dimethyl phthalate and dimethyl terephthalate; Can be mentioned.

(Hydrogenated cyclic conjugated diene-based polymer) In the present invention, the cyclic conjugated diene-based polymer is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst, and the carbon-carbon double polymer contained in the polymer is subjected to a hydrogenation reaction. The bond and the aromatic ring are hydrogenated to obtain a hydrogenated styrenic copolymer. The hydrogenation catalyst in the present invention is not particularly limited as long as it can hydrogenate a carbon-carbon double bond and an aromatic ring contained in the polymer, but it is mainly a heterogeneous hydrogenation catalyst and a homogeneous hydrogenation catalyst. Can be mentioned.

Specific examples of the heterogeneous hydrogenation catalyst include noble metals such as nickel, palladium, platinum, cobalt, ruthenium and rhodium or carbons such as oxides, salts and complexes thereof, alumina, silica, silica alumina and diatomaceous earth. A catalyst supported on a porous carrier can be used. Among them, those in which nickel, palladium, platinum, and ruthenium are supported on alumina, silica, silica alumina, and diatomaceous earth have high reactivity and are preferably used. Such a hydrogenation catalyst is preferably used in the range of 0.5 to 40% by weight based on the copolymer, depending on its catalytic activity.

Examples of the homogeneous hydrogenation catalyst include halides of transition metals such as vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, acetylacetonate complex, carboxylate complex, naphthate complex, and tritium complex. Fluoroacetate complex,
And stearate complexes. Specifically, transition metals such as triethyl vanadate, tris (acetylacetonate) chromium, tris (acetylacetonate) manganese, cobalt acetate, tris (acetylacetonate) cobalt, cobalt octenoate, and bis (acetylacetonate) nickel Compounds can be mentioned. Of these, cobalt and nickel compounds are preferred from the viewpoint of catalytic activity, and tris (acetylacetonate) cobalt and bis (acetylacetonate) nickel are particularly preferred.

In the case of a homogeneous hydrogenation catalyst, it is necessary to combine these transition metal compounds with an organoaluminum compound in order to exhibit the hydrogenation catalytic activity. The organic aluminum compound is a compound having at least one aluminum-carbon bond in the molecule, and specifically, a trialkylaluminum compound such as triethylaluminum and triisobutylaluminum, diethylaluminum ethoxide, diisobutylaluminum butoxide, ethyl Organic aluminum alkoxide compounds such as aluminum sesquiethoxide, organic aluminum oxy compounds such as methylaluminoxane and ethylaluminoxane, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like Organic aluminum halide compounds and the like can be mentioned. Of these, trialkylaluminum compounds such as triethylaluminum and triisobutylaluminum are preferred.

The transition metal compound is preferably used in the range of 0.01 to 5% by weight based on the polymer, depending on the catalytic activity. The quantitative relationship between the transition metal compound and the organoaluminum compound is as follows:
Mol, preferably 2 to 10 mol.

[0031] The hydrogenation reaction is usually carried out in the presence of a solvent. The hydrogenation reaction may be performed after once isolating the polymer after the polymerization reaction.However, when the polymerization is performed using a solution polymerization method, the polymerization solution is used as it is, or a necessary solvent is added. It is possible from the viewpoint of economy. Such a solvent is preferably selected in consideration of the hydrogenation catalytic activity, the presence or absence of side reactions such as molecular chain scission, the solubility of the polymer before and after the hydrogenation reaction, and the like. Specifically, n-butane, n- C4-12 aliphatic hydrocarbons such as pentane, n-hexane and n-heptane; cyclobutane;
C4-12 alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane and decalin; C4-C12 ethers such as diethyl ether, tetrahydrofuran and methyl-t-butyl ether; Can be mentioned. Of these, although depending on the type of catalyst, cyclohexane, methylcyclohexane, methyl-
t-Butyl ether is particularly preferred. In addition, polar solvents such as esters and alcohols are added to the above-mentioned solvents within a range not hindering the solubility of the polymer, for the purpose of increasing the activity of the reaction, or suppressing the molecular weight reduction due to molecular chain breakage due to hydrogenolysis. You may.

In the present invention, it is preferable to carry out the hydrogenation reaction in the above solvent system at a concentration of the cyclic conjugated diene polymer of 3 to 50% by weight. If the concentration of the polymer is less than 3% by weight, it is not preferable from the viewpoint of productivity and economy, and if it exceeds 50% by weight, the solution viscosity becomes too high, which is not preferable from the viewpoint of handling and reactivity.

The hydrogenation reaction conditions depend on the catalyst used, but are usually hydrogen pressure of 1 to 25 MPa and reaction temperature of 70 to 250.
It is performed within the range of ° C. If the reaction temperature is too low, the reaction hardly proceeds, and if the reaction temperature is too high, the molecular weight is likely to be reduced by hydrogenolysis, which is not preferable. In order to prevent a decrease in molecular weight due to molecular chain breakage and to promote the reaction smoothly, hydrogen is applied at an appropriate temperature and hydrogen pressure appropriately determined according to the type and concentration of the catalyst used, the concentration of the copolymer solution, the molecular weight, and the like. It is preferable to carry out a chemical reaction.

The degree of hydrogenation of the hydrogenated cyclic conjugated diene polymer and the hydrogenated cyclic conjugated diene-based polymer thus obtained is determined by the hydrogenation rate = [1-｛(aroma contained per mole of polymer after hydrogenation). Sum of moles of aromatic ring and moles of carbon-carbon double bond) / (sum of moles of aromatic ring and moles of carbon-carbon double bond per mole of polymer before hydrogenation) 間] X1
When expressed using an index of 00 (%) (calculated using ¹ H-NMR spectrum), the hydrogenation rate of the hydrogenated styrene copolymer used in the present invention is 90 to 100%,
Preferably 95 to 100%, more preferably 99 to 10
It is preferably 0%. If the hydrogenation rate is too low, the transparency and the physical heat resistance of the copolymer decrease, which is not preferable.

After the completion of the hydrogenation reaction, the catalyst can be removed by a known post-treatment method such as centrifugation or filtration. However, when a homogeneous hydrogenation catalyst is used, the catalyst after the hydrogenation reaction is removed. It is preferable to add an active hydrogen-containing compound to decompose and deactivate the catalyst, and at the same time, to precipitate the catalytic metal component. The active hydrogen-containing compound includes α-oxyacid, β-
It is at least one compound selected from the group consisting of oxyacids and derivatives in which hydroxyl groups are substituted with alkoxyl groups. Specific examples include glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 2-hydroxy-2-methylpropionic acid, and 2-hydroxy-
2-methylbutyric acid, 2-hydroxy-3-methylbutyric acid, 3
-Hydroxy-2,2-dimethyl lactic acid, mandelic acid, diphenyl glycolic acid, tropic acid, 3-hydroxy-3
-Phenylpropionic acid, methoxyacetic acid, 2-methoxypropionic acid, 3-methoxypropionic acid, and α-methoxyphenylacetic acid.

Of these, glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 2-hydroxy-2-methylpropionic acid, methoxyacetic acid,
-Methoxypropionic acid, 3-methoxypropionic acid is preferred, glycolic acid, lactic acid, 2-hydroxybutyric acid,
2-Hydroxy-2-methylpropionic acid is particularly preferred. These compounds are used in an amount of 0.1 to 100 with respect to 1 equivalent of the total number of moles of the transition metal compound and the organoaluminum compound.
It may be added in moles.

It is also preferable to add a compound selected from the group consisting of water and alcohol in addition to the active hydrogen-containing compound. These compounds may be added in an amount of 0.1 to 100 mol per 1 equivalent of the total number of moles of the transition metal compound and the organoaluminum compound. The reaction time when the active hydrogen-containing compound is added is 1 minute to 10 hours, preferably 5 minutes to 5 hours. The reaction temperature is 0 to 200 ° C,
Preferably it is 20 to 180 degreeC.

The active hydrogen-containing compound binds to the metal contained in the homogeneous hydrogenation catalyst component, insolubilizes it, and precipitates out of the solution. After the precipitation, the precipitated metal component can be removed by a known post-treatment method such as centrifugation or filtration. In the present invention, in order to remove the catalytic metal residue more highly and efficiently, the reaction solution may be treated by contacting it with an adsorbent. The adsorbent is not particularly limited, but acid clay, activated clay, activated carbon, diatomaceous earth, silica gel, alumina, silica alumina, zeolite and the like are preferably used. Examples of the treatment method include a method of adding an adsorbent to a polymer solution, mixing and stirring, and then removing the mixture by filtration or the like, and a method of flowing the polymer solution through a packed bed (packed column) of the adsorbent.

In the present invention used for an optical disk, it is necessary to reduce the residual catalytic metal component in the resin as much as possible.
The amount of the residual metal catalyst is preferably 10 ppm or less, more preferably 1 ppm or less, and even more preferably 500 ppm or less.
pb or less. From the polymer solution from which the hydrogenation catalyst has been removed, the desired hydrogenated cyclic conjugated diene-based polymer can be obtained by a method such as evaporation of the solvent, stripping, or reprecipitation. The hydrogenated cyclic conjugated diene-based polymer obtained in the present invention may be used as a blend of the polymers having different molecular weights or a composition with another polymer according to the purpose.

The hydrogenated cyclic conjugated diene-based polymer of the present invention contains Irganox 101 in order to improve thermochemical stability during melt molding or to prevent autoxidation.
0, 1076 (manufactured by Ciba-Geigy), hindered phenol stabilizers such as Irgafos 168 (manufactured by Ciba-Geigy), or addition-type stabilizers such as Sumilizer GM and Sumilizer GS (manufactured by Sumitomo Chemical). Is preferably added. If necessary, release agents such as long-chain aliphatic alcohols and long-chain aliphatic esters, and other additives such as lubricants, plasticizers, ultraviolet absorbers, and antistatic agents can be added.

The optical disk of the present invention can be formed by a known method such as injection molding, injection compression molding, extrusion molding, and solution casting. In particular, it can be suitably used for production by injection molding or injection compression molding. In molding such an optical disk, the resin temperature is 250 to 380 ° C, preferably 270 to 350 ° C, and more preferably 280 to 34 ° C.
A range of 0 ° C is used, and the mold temperature is 40 to 200 ° C, preferably 60 to 190 ° C, more preferably 70 to 18 ° C.
A range of 0 ° C. is used.

[0042]

According to the present invention, a cyclic conjugated diene-based polymer obtained by polymerizing a cyclic conjugated diene-based monomer, a styrene-based monomer unit and / or a chain conjugated diene-based monomer can be used. An optical disk mainly comprising a hydrogenated cyclic conjugated diene-based polymer obtained by hydrogenating a cyclic conjugated diene-based polymer containing units is provided. This polymer has excellent physical heat resistance, is highly purified, and has excellent mechanical properties and transparency, so that it can be suitably used as an optical disk substrate.

[0043]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples. (Reagents and Solvents) Styrene, 1,3-cyclohexadiene and isoprene were purified by distillation from calcium hydride, and 4A molecular sieves were added thereto, followed by sufficient drying. As cyclohexane and methyl-t-butyl ether, dehydrated grades were purchased, and 4A molecular sieves were further added thereto, and those sufficiently dried were used.

Diazabicyclo [2,2,2] octane (DABCO) was used by dissolving it in cyclohexane, adding 4A molecular sieve and drying it sufficiently. n-
Butyllithium and sec-butyllithium were commercially available cyclohexane solutions as they were. Nickel / silica alumina (65% nickel loading) is Aldric
h and used as is. Lactic acid used a commercial product as it was.

(Measurement of physical properties) Number average molecular weight: gel permeation chromatography (GP manufactured by Showa Denko KK)
C, using Syodex System-11) using tetrahydrofuran as a solvent to determine the molecular weight in terms of polystyrene.

Hydrogenation rate: JEOL JNR-EX270
Hydrogenation rate = [1- 型 (1 mol of aromatic ring and mol of carbon-carbon double bond contained in 1 mol of copolymer after hydrogenation) by ¹ H-NMR measurement using Sum of numbers)
/ (Sum of the number of moles of the aromatic ring and the number of moles of the carbon-carbon double bond contained in 1 mole of the copolymer before hydrogenation)}] × 100
(%) Was determined.

Residual metal content in resin: Quantified by ICP emission spectrometry. Glass transition temperature (Tg): TA Instrument
The measurement was performed at 20 ° C./min using a 2920 type DSC manufactured by s company. Heat distortion temperature: Measured according to JIS7206.

Example 1 501 g of 1,3-cyclohexadiene, 2000 g of cyclohexane, 600 mg of diazabicyclo [2,2,2] octane (DABCO) were placed in a stainless steel autoclave which had been sufficiently dried and purged with nitrogen.
Was charged. After heating the solution to 40 ° C., 1.6 Mn
-Butyl lithium-hexane solution (3.3 mL) was added, and 5
Allowed to react for hours. After the completion of the reaction, isopropanol 0.4
g was added to obtain a cyclohexadiene polymer. GPC
And the number average molecular weight was 180,000.

In this solution, 4.3 g of tris (acetylacetonate) cobalt and 1 g of triisobutylaluminum were added.
2.5 g was added, and the hydrogen pressure was 5 MPa and the temperature was 130 ° C.
The hydrogenation reaction was performed for hours. Add 20g of lactic acid to this solution
Was added and the reaction was carried out at a temperature of 130 ° C. for 2 hours. The solution was taken out of the autoclave, filtered under pressure using a filter having a pore size of 5 μm, and 100 g of basic alumina was added, followed by stirring at room temperature for 1 hour. The basic alumina was removed from the solution to obtain a colorless and transparent solution.

The solution was added as a stabilizer to Sumilizer GS.
Was added to the polymer in an amount of 0.3% by weight, and the mixture was concentrated under reduced pressure and flushed to distill off the solvent to obtain a massive colorless and transparent hydrogenated cyclohexadiene polymer. ^The degree of hydrogenation determined from ¹ H-NMR was 99.8%. The amount of residual catalytic metal in the resin by ICP emission spectroscopy was 3 p for Co.
pm and Al were 4 ppm. The glass transition temperature measured by DSC was 235 ° C., and the heat distortion temperature was 1
It was 85 ° C.

Example 2 406 g of styrene, 1, 1 in a sufficiently dried and nitrogen-purged stainless steel autoclave.
51 g of 3-cyclohexadiene, 200 of cyclohexane
0 g, diazabicyclo [2,2,2] octane (DAB
(CO) 680 mg. After heating the solution to 40 ° C., a 1.6 Mn-butyllithium-hexane solution 3.
8 mL was added and reacted for 2 hours. Then isoprene 2
4 g was added as a cyclohexane solution, and the mixture was further reacted for 2 hours. After completion of the reaction, 0.4 g of isopropanol was added to obtain a styrene-cyclohexadiene-isoprene copolymer. The number average molecular weight determined by GPC is 11,000
It was 0. The weight ratio of styrene / cyclohexadiene / isoprene determined from ¹ H-NMR was 86/10/4. From the form of the ¹ H-NMR spectrum, it was found that the bond between styrene and cyclohexadiene was a taper type, and the bond between isoprene was a block type.

To this solution were added 1300 g of cyclohexane, 700 g of methyl-t-butyl ether and 80 g of nickel / silica alumina, and a hydrogen pressure of 10 MPa and a temperature of 180 ° C.
For 10 hours. The solution was taken out of the autoclave and subjected to pressure filtration using a membrane filter having a pore size of 0.1 μm, whereby a colorless and transparent solution was obtained. To this solution was added 0.3% by weight of Sumilizer GS as a stabilizer with respect to the polymer, followed by concentration under reduced pressure and flashing to remove the solvent, and a block of colorless and transparent hydrogenated styrene-cyclohexadiene-isoprene copolymer. A coalescence was obtained. ^The degree of hydrogenation determined from ¹ H-NMR was 99.8%. According to ICP emission spectroscopy analysis, the amount of residual catalyst metal in the resin was 0.7 ppm for Ni, 0.5 ppm for Al,
i was 0.3 ppm and all were 1 ppm or less. The glass transition temperature measured by DSC was 148 ° C, and the heat distortion temperature of the molded product was 114 ° C.

Example 3 A polymer obtained in the same manner as in Example 1 was prepared at a cylinder temperature of 320 ° C. and a thickness of 0.6.
mm discs. This disk was heated at 100 ° C. for 8 hours, and the groove depth of the disk was measured. As a result, it was found that the groove depth was exactly the same as that before heating, and the depth was maintained.

Example 4 A polymer obtained by the same method as in Example 2 was molded into a disk by the same method as in Example 3. This disk was heated at 100 ° C. for 8 hours, and the groove depth of the disk was measured. As a result, it was found that the groove depth was 99% of the groove depth before heating, and the depth was maintained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/00 CER C08J 5/00 CER G11B 7/24 526 G11B 7/24 526N F-term (Reference) 4F071 AA12X AA21X AA22X AA75 AA76 AA78 AH19 BB02 BB03 BB05 BB06 BC03 BC10 4J026 HA13 HA20 HA26 HA29 HA32 HA35 HA39 HA49 HB05 HB06 HB26 HB32 HB35 HB39 HB45 HB48 HC14 HC15 HC16 HC26 HC39 HC45 HE04 AB03 AB100 AS03 AB00 BC04H CA04 CA05 CA25 CA31 DA01 HA03 HB02 HB16 HB17 HB29 HB38 HC27 HC84 HD04 HE14 HE32 HE35 JA36 5D029 KA13 KC13

Claims (3)

[Claims] 1. A unit x weight% derived from a cyclic conjugated diene-based monomer, a unit y weight% derived from a styrene-based monomer, and a unit z weight% derived from a chain conjugated diene-based monomer (where x, y and z are 1 ≦ x ≦ 100, 0 ≦ y ≦ 99, 0 ≦ z ≦ 9
9, x + y + z = 100 is satisfied. ) Is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst to obtain a transition metal and a transition metal obtained by hydrogenating a carbon-carbon double bond and an aromatic ring contained in the polymer. A hydrogenated cyclic conjugated diene-based polymer having a total aluminum content of 10 ppm or less. 2. An optical disk substrate mainly comprising the hydrogenated cyclic conjugated diene-based polymer according to claim 1. 3. The optical disk substrate according to claim 2, wherein the heat distortion temperature is 110 ° C. or higher.