JP3087368B2 - Method for producing hydrogenated thermoplastic norbornene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogenated thermoplastic norbornene-based polymer, and more particularly to a method for hydrogenating a thermoplastic norbornene-based polymer in the presence of a solvent and a hydrogenation catalyst. The present invention relates to a method for producing a hydrogenated thermoplastic norbornene-based polymer, which comprises treating the hydrogenated thermoplastic norbornene-based polymer with an adsorbent during or after the hydrogenation reaction.

[0002]

2. Description of the Related Art In recent years, a material having a high light transmittance has been demanded as an optical material.
The wavelength is 400 to 70 when the injection molded product is 3 mm thick.
It is said that those having a light transmittance of 90% or more in the entire range of 0 nm are preferable. That is, if the light transmittance is inferior in a part of visible light, the lens is colored,
When used near a strong light source, light energy of that wavelength is absorbed and converted to heat to become a high temperature, so that even a material having a high heat resistance to some extent may cause melting.

Conventionally, polymethyl methacrylate (PMMA) and polycarbonate (PC) have been known as resins used for optical materials. Among them, PMMA is excellent in transparency, and the light transmittance of an injection molded product having a thickness of 3 mm is 90% at a wavelength of 430 nm and 9% at a wavelength of 700 nm.
Although it reached 1%, there was a problem in terms of heat resistance and moisture resistance. Further, PC has better heat resistance and moisture resistance than PMMA, but has a light transmittance at a wavelength of 430 nm of at most 86%.
And the birefringence is large.

In recent years, hydrogenated thermoplastic norbornene-based polymers have attracted attention as optical materials having excellent heat resistance, moisture resistance and low birefringence. However, when a molded article having a thickness of 3 mm is injection-molded with a hydrogenated thermoplastic norbornene-based polymer produced by a conventional method, the light transmittance at a wavelength of 700 nm is 9%.
Although it is 0% or more, the light transmittance at 430 nm is 9
Only less than 0% was obtained. Furthermore, even if an information medium optical element is produced by depositing a metal film on a substrate made of a hydrogenated thermoplastic norbornene-based polymer, the adhesiveness between the metal film and the substrate may be high, such as blisters occurring at high temperature and high humidity. May not always be sufficient, and improvement has been desired.

As will be described later, the present inventors have improved the transparency of a hydrogenated thermoplastic norbornene-based polymer and the adhesion to a metal film by reducing the concentration of a transition metal atom as a polymerization catalyst residue. I found something. However, a conventionally used method of washing a polymer with a poor solvent, a method of precipitating a polymerization catalyst in a non-solvent, or a polymerization reaction solution in the presence of a compound having a hydroxyl group is activated alumina, an adsorbent such as zeolite. Processing method (JP-A-3-66725)
Even if the polymerization catalyst is removed by the method described above, the concentration of the transition metal atom as the polymerization catalyst residue in the polymer after the treatment is about 2 ppm or more, and even in the hydrogenated product of the thermoplastic norbornene-based polymer, Of less than about 2 ppm was not obtained.

[0006]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies on the transparency of a hydrogenated thermoplastic norbornene-based polymer and the problem of adhesion to a metal film. That the transition metal atoms derived from the polymerization catalyst in trace amounts in the product adversely affect the transparency and adhesion to the metal film, and that the thermoplastic norbornene-based polymer was hydrogenated in the presence of a solvent and a hydrogenation catalyst. When producing a hydrogenated thermoplastic norbornene-based polymer, the reaction metal is treated with an adsorbent during or after the hydrogenation of the thermoplastic norbornene-based polymer, so that the transition metal Was found to be easily removed, and a hydrogenated thermoplastic norbornene polymer having good transparency and good adhesion to a metal film could be obtained.

[0007]

Thus, according to the present invention, there is provided a process for producing a hydrogenated thermoplastic norbornene polymer having a low content of transition metal atoms derived from a polymerization catalyst.

(Thermoplastic norbornene-based polymer) The thermoplastic norbornene-based polymer of the present invention contains, as an impurity, a polymerization catalyst for polymerizing a monomer. Specific examples of the polymer include a ring-opening polymer of a norbornene monomer, an addition polymer of a norbornene monomer, and an addition polymer of a norbornene monomer and an olefin.

As the norbornene-based monomer, for example,
Norbornene and its alkyl and / or alkylidene substitutes, for example, 5-methyl-2-norbornene, 5-dimethyl-2-norbornene, 5-ethyl-2
-Norbornene, 5-butyl-2-norbornene, 5-
Polar group-substituted products such as halogen such as ethylidene-2-norbornene; dicyclopentadiene, 2,3-dihydrodicyclopentadiene and the like; dimethanooctahydronaphthalene, alkyl- and / or alkylidene-substituted products thereof, halogen and the like Polar group substituents, for example, 6-
Methyl-1,4: 5,8-dimethano-1,4,4a,
5,6,7,8,8a-octahydronaltarene, 6-
Ethyl-1,4: 5,8-dimethano-1,4,4a,
5,6,7,8,8a-octahydronaphthalene, 6-
Ethylidene-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene,
6-chloro-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene,
6-cyano-1,4: 5,8-dimetano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene,
6-pyridyl-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene,
6-methoxycarbonyl-1,4: 5,8-dimethano-
1,4,4a, 5,6,7,8,8a-octahydronaphthalene and the like; adducts of cyclopentadiene with tetrahydroindene and the like; cyclopentadiene trimers and tetramers, for example, 4,9: 5,8 -Dimethano-3a, 4,4a,
5,8,8a, 9,9a-octahydro-1H-benzoindene, 4,11: 5,10: 6,9-trimethano-
3a, 4,4a, 5,5a, 6,9,9a, 10,10
a, 11,11a-dodecahydro-1H-cyclopentaanthracene;

(Polymerization Method) The ring-opening polymerization of a norbornene-based monomer is usually carried out using a catalyst consisting essentially of a transition metal compound and an organometallic compound of a Group I to IV metal of the periodic table. Examples of the transition metal compound include halides, oxyhalides, oxides, and the like of transition metals such as titanium, molybdenum, and tungsten.
Cl ₄ , TiBr ₄ , WBr ₄ , WCl ₆ , WOF ₄ , Mo
Br ₂ , MoCl ₅ , MoOF _{4 and the} like. Examples of the organometallic compound of a Group I to IV metal include an organoaluminum compound and an organotin compound.
Specific examples include trimethylaluminum, triphenylaluminum, ethylaluminum sesquichloride, tetrabutyltin, diethyltindiiodide, n-butyllithium, diethylzinc, trimethylboron, and the like.

In the case of addition-type polymerization of a norbornene-based monomer or addition-type polymerization of a norbornene-based monomer and an olefin, ring-opening polymerization may be performed by a known method using a known transition metal catalyst. Usually, a catalyst formed from a titanium compound or a vanadium compound supported on a magnesium compound and an alkylaluminum compound is used. The titanium compound or the vanadium compound supported on the magnesium compound is a complex containing at least magnesium, titanium and halogen. The production method is described in, for example, JP-A-48-16986.
JP-A-51-20297, JP-A-52-8748
No. 9 and JP-A-53-2580.
Vanadium compounds include VCl ₄ , VOBr ₂ , VO
(OCH ₃ ) ₂ Cl, VO (OC ₃ H ₇ ) ₃ , VO (OC ₄ H
₉ ) Cl _{2 and the} like and mixtures thereof are exemplified. Examples of the alkyl aluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide and the like, and mixtures thereof.

After the polymerization has progressed to the desired molecular weight, the polymerization is stopped. To stop the polymerization, the polymerization catalyst is inactivated, and then the polymerization catalyst is removed. To inactivate the polymerization catalyst, for example, a catalyst inactivating agent such as water or alcohol may be added to the polymerization reaction solution. As a result, the polymerization catalyst precipitates, but if refluxed, the precipitated polymerization catalyst becomes a hard and large lump, and thus is easily removed. In order to remove the polymerization catalyst, for example, the polymerization catalyst which has been inactivated and precipitated may be removed by centrifugation, removed by filtration, or the polymerization reaction solution in which the reaction has been stopped may be washed with a large amount of a poor solvent. Alternatively, the polymerization reaction solution may be treated with an adsorbent such as activated alumina or zeolite in the presence of a compound having a hydroxyl group. In the removal by these methods, the transition metal atom derived from the polymerization catalyst is usually 2 to 10 pp relative to the polymer.
m.

(Hydrogenation reaction) A thermoplastic norbornene-based polymer is prepared by saturating an olefinically unsaturated group in its molecule, that is, a double bond of a main chain and a double bond of an unsaturated ring. It can be a polymer hydrogenated product.

The hydrogenation catalyst can be used as long as it is generally used for hydrogenating olefin compounds. For example, Wilkinson complex, cobalt acetate /
Triethylaluminum, nickel acetylacetonate / triisobutylaluminum, diatomaceous earth, magnesia, alumina, synthetic zeolite, nickel,
Heterogeneous catalysts carrying a catalytic metal such as palladium and platinum can be used. Of these, magnesia, activated alumina, synthetic zeolite carrier and the pore volume 0.5 cm ³ / g or more, preferably 0.7 cm ³ / g or more, and preferably a specific surface area of 250 meters ² / g or more heterogeneous catalysts preferred .

The hydrogenation reaction is carried out at 0 to 280 ° C., preferably 20 to 230 ° C., under a hydrogen pressure of 1 to 150 atm, depending on the type of the hydrogenation catalyst. For example, in the case of a catalyst in which nickel is supported on activated alumina, 200 to 250
C is preferable, and 220 to 230 C is more preferable. The hydrogenation rate can be arbitrarily adjusted by changing the hydrogen pressure, reaction temperature, reaction time, catalyst concentration, and the like.

The hydrogenation reaction of the thermoplastic norbornene polymer in the present invention is usually carried out in an inert organic solvent. As the organic solvent, a hydrocarbon solvent is preferable,
Among them, a cyclic hydrocarbon-based solvent excellent in the solubility of the norbornene-based polymer to be produced is particularly preferable. Specific examples include benzene, aromatic hydrocarbons such as toluene, n-pentane, aliphatic hydrocarbons such as hexane, cyclohexane,
Examples thereof include alicyclic hydrocarbons such as decalin and halogenated hydrocarbons such as methylene dichloride and dichloroethane, and a mixture of two or more of these can be used. When a solvent is used, the amount of the solvent to 1 part by weight of the norbornene-based polymer is 1 to 20 parts by weight, preferably 1 to 20 parts by weight.
10 parts by weight.

(Removal of Catalyst) The removal of the catalyst after the completion of the hydrogenation reaction may be carried out by a conventional method such as centrifugation or filtration. The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by chemical conversion is preferred because it is simple and efficient. In the case of filtration, pressure filtration or suction filtration may be performed, and diatomaceous earth,
It is preferable to use a filter aid such as perlite. As described below, an adsorbent for transition metal atoms derived from the polymerization catalyst may be used as a filter aid.

Further, as a heterogeneous catalyst which is a hydrogenation catalyst, one having a particle size of 0.2 μm or more, that is, a particle size of 0.2 μm or more.
When a material substantially not containing less than 2 μm is used,
It is preferable because the heterogeneous catalyst can be easily removed by filtration. If the particle size is too small, it tends to leak during filtration, and it is difficult to remove even by centrifugation, and the transition metal atomic weight, which is the residue of the polymerization catalyst or hydrogenation catalyst in the hydrogenated thermoplastic norbornene polymer, is large. Become. Further, if filtration is performed using a filter having a small pore diameter so as not to leak, clogging is liable to occur, resulting in poor working efficiency.

(Adsorption Treatment) In the present invention, a polymer reaction solution is treated with an adsorbent. If the polymerization reaction solution is treated with an adsorbent before hydrogenation, the transition metal atoms derived from the polymerization catalyst can be removed, but the presence of the transition metal atoms derived from the polymerization catalyst has little effect on the hydrogenation reaction. The hydrogenation reaction is preferably performed continuously, and usually the reaction solution is treated with an adsorbent during or after the hydrogenation reaction to remove transition metal atoms derived from the polymerization catalyst.

The treatment of the reaction solution with the adsorbent means (1) adding an adsorbent to the reaction solution from the beginning of the hydrogenation reaction to carry out the reaction and simultaneously removing the hydrogenation reaction catalyst and the adsorbent; (2) hydrogenation The reaction is performed by adding an adsorbent to the reaction solution from the beginning of the reaction, and after removing the adsorbent, the hydrogenation reaction catalyst is removed.
(3) An adsorbent is added to the reaction solution during the hydrogenation reaction to carry out the reaction, and the hydrogenation reaction catalyst and the adsorbent are simultaneously removed. (4) The adsorbent is added to the reaction solution during the hydrogenation reaction. There is a method such as removing the adsorbent after removing the adsorbent and removing the hydrogenation reaction catalyst. The adsorption treatment after the hydrogenation reaction includes (5) adding the adsorbent to the reaction solution after the completion of the hydrogenation reaction and stirring. (6) Add the adsorbent to the reaction solution after the completion of the hydrogenation reaction and stir to remove the adsorbent, and then remove the hydrogenation reaction catalyst (7) Hydrogenation After the reaction is completed, the reaction solution is passed through an adsorbent column to remove the hydrogenation reaction catalyst. (8) After the hydrogenation reaction is completed, the reaction solution is passed through the adsorbent column as a method of removing the hydrogenation reaction catalyst. (9) After removing the hydrogenation catalyst, transfer the reaction solution to the adsorbent column. To (10) were added adsorbent sufficiently stirred to remove the adsorbent to the reaction solution after the hydrogenation catalyst removal, there is a method such. These may be performed in combination. As a modification of the method (8), for example, the hydrogenation catalyst may be removed using an adsorbent as a filter aid.

Among these methods, from the viewpoint of the efficiency of removing the transition metal atoms derived from the polymerization catalyst, which is the object of the present invention,
A method in which an adsorbent treatment is performed during the hydrogenation reaction of (1), (2), (3), and (4) is preferable. Furthermore, the methods (1) and (2) are preferable from the viewpoint of the length of the processing time and the safety of the operation. Among them, the method (1) has high working efficiency because the hydrogenation catalyst and the adsorbent are removed at the same time.

The adsorbent is not particularly limited as long as it can sufficiently adsorb the transition metal catalyst residue used for polymerization and hydrogenation. Examples of the adsorbent include synthetic zeolites, natural zeolites, activated alumina, activated clay, and other SiO ₂ and Al _2. O ₃ or a crystalline or amorphous mixed composition thereof is preferred. Further, the specific surface area is 50 m ₂ / g or more, preferably 100 m ₂ / g or more, more preferably 200 m ₂ / g or more, and the pore volume is 0.5 cm ³ / g or more, preferably 0.6 cm ³ / g or more. More preferably, it is at least 0.7 cm ³ / g. If the specific surface area or the pore volume is small, the adsorption capacity is inferior. The size is 0.2 μm or more, preferably 10 μm to 3 cm, more preferably 100 μm to 1 cm. If it is too small, it is difficult to remove it. If it is too large, it is not sufficiently adsorbed because the packing ratio of the column is poor or the probability of contact with the transition metal catalyst residue in the hydrogenated solution is low.

As described above, the adsorption treatment is performed by (I)
(II) a method of passing a solution through a column packed with an adsorbent, (II) a method of adding an adsorbent, stirring and removing the adsorbent by filtration or the like, (I
II) A method of adding an adsorbent during the hydrogenation reaction. As described above, the method of adding an adsorbent during the hydrogenation reaction (III) is most preferable.

(I) Method of passing a solution through a column packed with an adsorbent This corresponds to the above (7), (8) and (9).

The filling rate is ρ (g / m ³ ), and the specific surface area is S
(M ² / g) and ρS when the residence time is t (sec)
What is necessary is just to process so that t (second / m) becomes 10 ⁹ or more. Usually, S is about 100 to 1000 m ² / g and ρ is about 4 to 8 × 10 ⁵ g / m ³ , so the residence time may be set to 30 seconds or more.

In this case, if a large amount of the hydrogenated solution is treated, the adsorbing ability decreases, so that the treatment time needs to be extended, and furthermore, saturation is reached and adsorption is stopped. When the transition metal atom concentration starts to increase, it is necessary to refill a new one.

(II) Method of adding adsorbent after hydrogenation reaction This corresponds to the above (5), (6) and (10).

The specific surface area is S (m ² / g), the amount of adsorbent added is m (g), the stirring time is t (second), and the amount of the solution to be treated is V
(G), Smt / V when hydrogen solution concentration is c
c (seconds / m) is 10 ³ or more, preferably 10 ⁴ or more, more preferably 10 ⁵ or more; Sm / Vc is 1 or more, preferably 5 or more, more preferably 10 or more;
(Second) should be 100 or more, preferably 200 or more, more preferably 300 or more. Depending on the efficiency of the stirring, it is necessary to lengthen the stirring time, and it is difficult to control the efficiency of the stirring in practice. Therefore, it is preferable to stir as long as the efficiency of the entire operation allows.

Normally, S is about 100 to 1000 m ² / g, so when the concentration of the hydrogenated solution is 10%, for example, 10 g or more of the adsorbent is added to 1 kg of the solution,
The stirring may be sufficient for at least 00 seconds.

(III) A method of adding an adsorbent during the hydrogenation reaction This is the most preferred embodiment of the present invention, which corresponds to the above (1), (2), (3) and (4).

Basically, it is the same as the case (II).
However, in particular, in the case of (1) and (2) in which the adsorbent is added from the beginning of the hydrogenation reaction, the stirring time in (III) becomes the hydrogenation reaction time, which is a long time.
Only Sm / Vc needs to be considered.

(Hydrogenated thermoplastic norbornene-based polymer) The hydrogenated thermoplastic norbornene-based polymer of the present invention has the same heat resistance, heat deterioration resistance and light resistance as the conventional hydrogenated thermoplastic norbornene-based polymer. Not only is it excellent in deterioration, moisture resistance, chemical resistance and the like, but also has a low content of transition metal atoms derived from the polymerization catalyst. Therefore, the hydrogenated thermoplastic norbornene-based polymer of the present invention is more excellent in transparency than conventional ones, and, for example, in an information recording medium optical element having a metal reflection film or a metal recording film described below. Good adhesion to metal films and the like, such as swelling is unlikely to occur even under high temperature and high humidity conditions.

(Additives) If necessary, well-known additives such as antioxidants, light stabilizers, ultraviolet absorbers, lubricants, etc. may be added to the hydrogenated thermoplastic norbornene polymer of the present invention.
Plasticizers, flame retardants, antistatic agents, heat stabilizers, hydrogenated petroleum resins, dyes, pigments, inorganic and organic fillers, and the like can be blended and used as a resin composition.

(Molding) The hydrogenated thermoplastic norbornene-based polymer of the present invention can be molded into an optical element substrate according to a conventional method. The molding method is not particularly limited, and a general plastic molding method, for example, a molding method such as an injection molding method, an extrusion molding method, or a compression molding method can be applied.

By forming an information recording film layer on an optical element substrate obtained by molding, an information recording medium optical element is obtained. As the information recording film layer, usually, a metal film is used as a metal reflection film or a metal recording film, and an information recording medium element optical element, for example, an optical recording medium disk or an optical recording medium card is manufactured. The formation of the metal reflection film is performed by depositing a metal having a high reflectance, for example, nickel, aluminum, or gold, and in the case of a metal recording film,
This is performed by depositing a general Tb-Fe-Co alloy or the like as a magneto-optical recording film. The method for depositing the metal film on the optical element substrate is also not particularly limited, and a usual deposition method, for example, a vacuum deposition method, a sputtering method, or the like can be applied.

In addition, a known injection molding method, for example,
Plastic lenses can also be molded according to JP-A-141518, JP-A-60-225722, JP-A-61-144316, and the like.

In addition, an optical element such as a Fresnel lens can be manufactured by bonding an optical element pattern to an optical element substrate by a known method.

[0038]

The present invention will be described more specifically with reference to the following Reference Examples, Examples and Comparative Examples.

Reference Example 1 In a separable flask sufficiently dried and purged with nitrogen, 1 g of 27 g of 6-ethylidene-2-tetracyclododecene was added.
Hexene and toluene were 3 mmol and 120 m, respectively.
1 was added.

Further, 3.0 m of triethylaluminum
mol, 0.60 mmol of titanium tetrachloride, and 3.0 mmol of triethylamine, and a ring-opening polymerization reaction was performed at 25 ° C. for 4 hours with stirring. Distilled water was added at a rate of 140 g, and the mixture was washed by stirring for 1 hour, then, a ring-opened polymer was precipitated with a mixed solvent of equal amounts of acetone and isopropyl alcohol, filtered, and dried to obtain a ring-opened polymer. Was.

The molecular weight of this ring-opened polymer is 24,000,
Tg was 146 ° C.

10 parts by weight of the dried ring-opened polymer was dissolved in 90 parts by weight of cyclohexane, and the concentration of titanium atom as a transition metal catalyst residue was measured by atomic absorption spectrometry. 37 ppm.

Reference Example 2 Cyclohexane was added to 10 g of the ring-opened polymer obtained in Reference Example 1 at a ratio of 100 ml to dissolve it, added at a ratio of 1 g of palladium carbon, and placed in a stainless steel ampoule.
After mixing, replace the air in the ampoule with hydrogen to reduce the hydrogen pressure to 5
The pressure was adjusted to 0 kg / cm 2 G, and the mixture was kept at 10 ° C. with stirring for 30 minutes. Thereafter, the temperature was increased to 120 ° C., and the temperature was maintained for 18 hours to perform hydrogenation. Distilled water was added at a rate of 100 g, and the mixture was washed with water by stirring for 1 hour. Thereafter, the ring-opened polymer was precipitated with a mixed solvent of equal amounts of acetone and isopropyl alcohol, filtered, dried and hydrogenated with the ring-opened polymer. I got something.

The hydrogenation rate of this hydrogenated ring-opening polymer was 99.7%, and Tg was 140 ° C.

10 parts by weight of the hydrogenated product of the dried ring-opening polymer was dissolved in 90 parts by weight of cyclohexane, and the concentrations of titanium atoms and palladium atoms, which were transition metal catalyst residues, were measured by atomic absorption spectrometry. They were 9 ppm and 4 ppm, respectively, based on the hydrogenated polymer.

Example 1 1 g of cyclohexane was added to 10 g of the polymer obtained in Reference Example 1.
Palladium carbon 1
g, activated alumina (specific surface area: 320 m ² / g, pore volume: 0.8 cm ³ / g, average particle size: 15 μm, manufactured by Mizusawa Chemical Co., Neobead D powder) at a ratio of 0.3 g. After mixing, the air in the ampoule was replaced with hydrogen to adjust the hydrogen pressure to 50 kg / cm ² G, and the mixture was kept at 10 ° C for 30 minutes while stirring. Thereafter, the temperature was increased to 120 ° C., and the temperature was maintained for 18 hours to perform hydrogenation. The mixture was filtered to remove palladium carbon and activated alumina, and the ring-opened polymer was precipitated with a mixed solvent of equal amounts of acetone and isopropyl alcohol, filtered and dried to obtain a hydrogenated ring-opened polymer.

The hydrogenation rate of this hydrogenated ring-opened polymer was 99.7%, and the Tg was 140 ° C.

10 parts by weight of the hydrogenated product of the dried ring-opening polymer was dissolved in 90 parts by weight of cyclohexane, and the concentrations of titanium atoms and palladium atoms as transition metal catalyst residues were measured by atomic absorption spectrometry. Both were below the detection limit of 1 ppm with respect to the polymer hydrogenated product.

Example 2 Activated alumina having a specific surface area of 350 m ² / g, a pore volume of 0.8 cm ³ / g and a particle size of about 3 mm (manufactured by Mizusawa Chemical, Neo Bead D)
The pellets) were packed in a column having a radius of 3 cm and a height of 100 cm (filling rate: 5.0 × 10 ⁵ g / m ³ ), and the hydrogenated product 10 obtained in Reference Example 2 was set so that the residence time was 100 seconds. A solution in which 90 parts by weight of cyclohexane was dissolved was passed. Using this solution, by atomic absorption spectrometry,
When the concentrations of the titanium atom and the palladium atom, which are the transition metal catalyst residues, were measured, they were all below the detection limit of 1 ppm with respect to the hydrogenated ring-opening polymer.

Example 3 A synthetic zeolite (Mizuka Sieves-13X, manufactured by Mizusawa Chemical Co., Ltd.) having a specific surface area of 500 m ² / g, a pore volume of 1.2 cm ³ / g and a particle size of 1.8 mm was applied to a column having a radius of 3 cm and a height of 100 cm. The packed column (packing rate 8.8 × 10 ⁵ g /
m ³ ), a solution obtained by dissolving 10 parts by weight of the hydrogenated product obtained in Reference Example 2 in 90 parts by weight of cyclohexane was passed so that the residence time was 100 seconds. Using this solution, the concentration of a transition metal catalyst residue, titanium atom and palladium atom, was measured by atomic absorption spectrometry. there were.

Example 4 300 g of a solution obtained by dissolving 10 parts by weight of the hydrogenated product obtained in Reference Example 2 in 90 parts by weight of cyclohexane was mixed with 1 part of a 10 cm radius.
1g into a beaker and 6g of activated alumina used in Example 1
And a 3 cm long Teflon cylindrical stirrer tip is inserted, and a magnetic stirrer is used for 1 minute for 60 minutes.
Rotated at 00 rpm.

After the activated alumina was removed by filtration, the concentration of titanium and palladium atoms, which are transition metal catalyst residues, was measured using this solution by atomic absorption spectrometry. On the other hand, both were below the detection limit of 1 ppm.

Example 5 An injection molding machine (manufactured by Sumitomo Heavy Industries, Model DISK5-3M) was used at a mold temperature of 110.degree. C. and an injection temperature of 300.degree.
Each of the polymer hydrogenated products obtained in Steps (1) to (4) was
m, formed into an optical disk substrate having a diameter of 130 mm. Aluminum aluminum was vacuum-deposited on these substrates and subjected to a high-temperature and high-humidity test at 70 ° C. and 90% humidity for 24 hours. No abnormality such as blisters was observed in the adhesion between the metal aluminum film and the substrates.

Comparative Example 1 An optical disk substrate was molded in the same manner as in Example 5 except that the polymer hydrogenated product obtained in Reference Example 2 was used instead of the polymer hydrogenated product obtained in Example 1, and metal aluminum was used. Deposited,
A high-temperature and high-humidity test was performed, but blisters were observed between the metal aluminum film and the substrate, and there was a problem in adhesiveness.

Example 6 Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Model DISK5-3M), the polymer hydrogenated products obtained in Examples 1-4 at a mold 145 ° C. and an injection temperature of 290 ° C. were each thickened. A 3mm projection TV lens is molded, and 6 minutes after injection, 90 ° C
Cooled down. When the light transmittance was measured using a spectrophotometer, the light transmittance was 90% in the entire region of 400 to 700 nm.
As described above, at least 90.6%, 90.5%, 9
0.2% and 90.4%. In particular, the hydrogenated polymer obtained in Example 1 had the highest light transmittance in the entire range of 400 to 700 nm.

Comparative Example 2 A lens was molded in the same manner as in Example 6, except that the polymer hydrogenated product obtained in Reference Example 2 was used instead of the polymer hydrogenated product obtained in Examples 1 to 4. The light transmittance in the region of -450 nm was 90% or less, and at most 89.0%.

[0057]

The resin produced by the production method of the present invention has the same heat resistance and moisture resistance as those of the conventional thermoplastic norbornene resin, but has improved transparency and is 430 nm in an injection molded product having a thickness of 3 mm. Is suitable for a material of an optical element requiring transparency. Further, the content of the transition metal atom derived from the polymerization catalyst is 1
ppm or less, and good adhesion to a metal film or the like of the optical element.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Io Natsuume 1-2-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon Co., Ltd. Research and Development Center Examiner Satoshi Morikawa (56) References JP-A-3-66725 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 61/00-61/12

Claims (1)

(57) [Claims] When producing a hydrogenated thermoplastic norbornene-based polymer by hydrogenating a thermoplastic norbornene-based polymer in the presence of a solvent and a hydrogenation catalyst, a reaction solution is added during or after the hydrogenation reaction. A method for producing a hydrogenated thermoplastic norbornene-based polymer, wherein the hydrogenated product is treated with an adsorbent.