JP3387533B2 - Norbornene-based copolymer hydrogenated product and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to mechanical properties, heat resistance,
Norbornene-vinylated unsaturated 6-membered ring hydrocarbon-based addition copolymer hydrogenated product with excellent optical and electrical properties,
The present invention relates to an optical material, an electrical insulating material, an electronic component processing device, and a medical device using the same.

[0002]

2. Description of the Related Art Recently, as optical materials and electrical insulating materials,
A polymer using a norbornene-based monomer is known. However, depending on the application, the ring-opening polymer of norbornene-based monomer or its hydrogenated product may have insufficient heat resistance, while the addition-type polymer of norbornene-based monomer has a glass transition temperature (hereinafter, Tg Is too high, which makes molding difficult. It is known that the glass transition temperature is lowered by addition-copolymerizing a norbornene-based monomer with ethylene or the like, but it is difficult to obtain a norbornene-based resin having an appropriate Tg because it is too low.

In order to solve such a problem, an addition type copolymer of a norbornene type monomer and a styrene type monomer has been developed (JP-A-4-45113). However, this resin has a large birefringence when the copolymerization ratio of styrene is large, the performance as an optical material becomes insufficient, and the time required for the track to the dielectric breakdown, which shows the electric insulation stability, is short. There was a problem with the performance as a material.

The use of hydrogenated polystyrene as an optical material is disclosed in JP-A-1-317728 and JP-A1-2.
It is known from Japanese Patent No. 94721, Japanese Patent Laid-Open No. 1-132603, and the like. However, Tg is about 110 ° C at most,
There is a problem that the heat resistance is insufficient depending on the purpose and application.

On the other hand, a resin obtained by copolymerizing alkylidene norbornene and terpenes using a Friedel-Crafts catalyst is also known (US Pat. No. 3,510,461).
However, this resin has a low molecular weight as used in tackifiers, does not have the strength required for optical materials, and its optical properties and electrical insulation properties have not been known.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent efforts to develop optical materials, electrical insulating materials, electronic component processing equipment, and medical equipment having higher heat resistance, and as a result, norbornene-based monomers have been developed. And vinylated unsaturated 6-membered ring hydrocarbon monomer addition type copolymer hydrogenated product, heat resistance, transparency, light deterioration resistance, low birefringence, electrical insulation, high frequency characteristics, electrical insulation stability The inventors have found that they can be used as optical materials having low elution properties of organic substances and excellent mechanical strength, electrical insulating materials, electronic component processing equipment, and medical equipment, and have completed the present invention.

[0007]

Thus, according to the present invention, a copolymer of 5 to 95% by weight of a norbornene-based monomer and 95 to 5% by weight of a vinylated unsaturated six-membered ring hydrocarbon-based monomer is used as a nuclear hydrogen. A norbornene-vinylated unsaturated 6-membered ring hydrocarbon-based addition type copolymer having an addition rate of 50% or more hydrogenated and an intrinsic viscosity [η] measured in toluene at 25 ° C. of 0.1 to 10 dl / g Provided are a polymer hydrogenated product, an optical material using the same, an electrical insulating material, an electronic component processing device, and a medical device.

(Norbornene-based Monomer) The norbornene-based monomer used in the present invention is disclosed in JP-A-2-2274.
24, JP-A-2-276842, JP-A-3-148.
82, JP-A-3-122137, and JP-A-4-638.
Nos. 07 and the like, for example, norbornene, its alkyl, alkylidene, aromatic substituted derivatives and halogens, hydroxyl groups, ester groups, alkoxy groups, cyano groups and amide groups of these substituted or unsubstituted olefins Substituted polar groups such as imide group and silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2. -Norbornene,
5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl- 5-methyl-2-norbornene and the like; cyclopentadiene multimers, derivatives and substitutions thereof similar to the above,
For example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene, 1,4: 5,8-dimethano-1,
2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7, 8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a, 6,9,9
a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene and the like; an adduct of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1, 4, 4a,
4b, 5,8,8a, 9a-octahydrofluorene,
5,8-methano-1,2,3,4,4a, 5,8,8a
-Octahydro-2,3-cyclopentadienonaphthalene and the like; and the like. In the present invention, at least one norbornene-based monomer is used.

(Vinylated unsaturated 6-membered ring hydrocarbon type monomer) Examples of the vinylated unsaturated 6-membered ring hydrocarbon type monomer used in the present invention include styrene, α-methylstyrene,
Styrene-based monomers such as p-methylstyrene, o-methylstyrene, m-methylstyrene, α-vinylnaphthalene, β-vinylnaphthalene, and p-methoxystyrene;
Examples thereof include terpene-based monomers such as d-limonene, 1-limonene, and dipentene (dl-limonene). In the present invention, one or more vinylated unsaturated 6-membered hydrocarbon hydrocarbon monomers are used.

(Norbornene-vinylated unsaturated 6-membered ring hydrocarbon type addition copolymer) The norbornene-vinylated unsaturated 6-membered hydrocarbon type addition copolymer used in the present invention is
Norbornene-based monomer 5 to 95% by weight, preferably 1
0 to 70% by weight, more preferably 20 to 60% by weight, and a vinylated unsaturated 6-membered hydrocarbon addition type copolymer 95 to 5
%, Preferably 90 to 30% by weight, more preferably 80 to 40% by weight. If the amount of the norbornene-based monomer is too small, the Tg of the desired hydrogenated product will be too low, resulting in poor heat resistance. On the other hand, if the amount of the norbornene-based monomer is too large, the Tg of the hydrogenated product is too high, which makes melting difficult and deteriorates moldability.

The addition type copolymer using a terpene type monomer as a comonomer has a low birefringence in an unhydrogenated state as compared with the addition type copolymer using a styrene type monomer as a comonomer. Therefore, when the nuclear hydrogenation rate is low,
The one in which the terpene-based monomer is used more than the styrene-based monomer has an advantage that the birefringence is low. However, the six-membered ring other than the aromatic ring having an unsaturated bond in the ring in the repeating unit is more susceptible to light resistance deterioration than the unhydrogenated aromatic ring, and the aromatic ring is unsaturated in the six-membered ring. Since hydrogen is rarely left with the bond left, when the unhydrogenated portion remains, the resin containing more styrene-based monomer is more excellent in resin stability as a result.

(Third Component Monomer) In the present invention,
During the polymerization, it is in a range that does not substantially impair the effects of the present invention, generally 50% by weight or less, preferably 30% by weight, based on all monomers.
In the range of not more than 10% by weight, more preferably not more than 10% by weight, one or more other copolymerizable olefins other than the above can be used as the third component monomer.

As the third component monomer used in the present invention, monoolefins such as ethylene, propylene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, vinylcyclohexane and isopropenylcyclohexane; cyclopentene , Cyclohexene, cycloheptene and other cyclic olefins; butadiene, cyclopentadiene, isoprene, 1,3-pentadiene,
Furan, thiophene, 4-vinylcyclohexene, 4-
Dienes such as isopropenylcyclohexene; substitution products thereof with introduction of halogen groups such as chlorine and bromine, ester groups, etc .; ethylene oxide, propylene oxide, trimethylene oxide, trioxane, dioxane, cyclohexene oxide, styrene oxide,
Cyclic ethers such as epichlorohydrin and tetrahydrofuran; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; and the like.

(Polymerization catalyst) The method of addition-polymerizing these monomers is not particularly limited, and known polymerization catalysts such as transition metal compounds and I-IV of the periodic table are used.
Examples thereof include organometallic compounds of the group, protonic acids, and the like, and two or more kinds of these may be combined.

The transition metals are IVB to V in the periodic table.
Transition metals selected from the group consisting of Group III,
Examples include titanium, zirconium, vanadium, iron, cobalt, tungsten, nickel, palladium and the like.
Examples of the transition metal compound include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium monochloride, titanium (III) chloride, titanium (IV) chloride, titanium (IV) bromide and bis (cyclo). Pentadienyl) dimethyl titanium, (cyclopentadienyl) titanium trichloride,
Titanium compounds such as dichlorotitanium bis (acetylacetonate); zirconium compounds obtained by substituting titanium of these titanium compounds with zirconium and vanadium; vanadium compounds; ferrous chloride, ferric chloride, ferrous bromide, ferrous bromide Iron compounds such as ferric iron, ferric acetate, iron (III) acetylacetonate, and ferrocene; cobalt acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt benzoate,
Cobalt chloride, cobalt bromide, cobalt (II) tetrafluoroborate, cobalt 4-cyclohexylbutyrate,
Cobalt compounds such as cobalt stearate; Tungsten compounds such as tungsten hexachloride and tungsten tetrachloride; Nickelocene, nickel acetate, nickel bromide, nickel chloride, nickel bisacetylacetonate, tetrakis (triphenylphosphine) nickel,
Nickel compounds such as dicarbonylbis (triphenylphosphine) nickel, bis (allyl) nickel, dibromobis (triphenylphosphine) nickel, allylnickel chloride, chloro (phenyl) bis (triphenylphosphine) nickel; palladium (I
I) Acetate, palladium bisacetylacetonate, palladium bromide, palladium chloride, palladium iodide, palladium oxide, monoacetonitrile tris (triphenylphosphine) palladium tetrafluoroborate, carbonyl tris (triphenylphosphine) palladium, dichlorobis (acetonitrile) Palladium compounds such as palladium, dichlorobis (benzonitrile) palladium, dichlorobis (triphenylphosphine) palladium, tetrakis (acetonitrile) palladium tetrafluoroborate and the like are exemplified.

As the organometallic compound, there are II-I of the periodic table.
Organometallic compounds up to Group V, such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum,
Tribenzyl aluminum, diethyl aluminum monochloride, di-n-propyl aluminum monochloride, diisobutyl aluminum monochloride, di-n-
Butyl aluminum monochloride, diethyl aluminum monobromide, diethyl aluminum monoiodide,
Diethyl aluminum monohydride, di-n-propyl aluminum monohydride, diisobutyl aluminum monohydride, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, isobutyl aluminum sesquichloride, ethyl aluminum dichloride,
Organoaluminum compounds such as ethylaluminum dibromide, propylaluminum dichloride, isobutylaluminum dichloride, methylaluminoxane and ethylaluminoxane; Examples of organotin compounds include tin dichloride, tin tetrachloride, tin tetrabromide and triphenylmethyltin pentachloride In addition to the organotin compound (1), trifluoroboron, trichloroboron, boron trifluoride diether etherate and the like can be used.

The catalyst may be used in combination of two or more kinds. Moreover, you may use the catalyst system which added the component which improves polymerization activity. As such a polymerization catalyst system, titanium tetrachloride / 2-methoxy-2-phenylpropane, titanium tetrachloride / t-butanol, titanium tetrachloride / 1,4-bis (2-methoxy-2-propyl) benzene, etc. And living cation catalyst system.

As the proton acid polymerization catalyst, HCl,
HF, HBr, H₂SO_Four, H₃BO₃ , HClO, CH₃
COOH, Cl₃CCOOH, CF₃SO₃H etc.
Be done.

(Polymerization Solvent) The polymerization of the norbornene-vinylated unsaturated 6-membered cyclic hydrocarbon addition type copolymer used in the present invention can be carried out without using a solvent, but it is also carried out in an inert organic solvent. be able to.

In the present invention, the polymerization solvent used for the polymerization of the norbornene-vinylated unsaturated 6-membered ring hydrocarbon type addition copolymer is an aromatic solvent such as benzene, toluene or xylene; pentane, hexane or heptane. , Hydrocarbon solvents such as octane, cyclopentane, cyclohexane, methylcyclohexane and decalin; methyl chloride, methylene chloride, 1,2-dichloroethane, 1,
Halogenated hydrocarbon solvents such as 1,1-trichloroethane, 1,1,2-trichloroethane, and 1,1,2-trichloroethylene; polar solvents such as nitromethane;
Etc., and two or more of these may be mixed and used.

(Polymerization temperature) The polymerization temperature is usually -150 to 1
It is desirable to carry out at a temperature of 00 ° C, preferably -100 ° C to 80 ° C.

(Polymerization pressure) The polymerization pressure is usually 0 to
It is preferable to select from the range of 50 kgf / cm ² .

(Hydrogenation) The hydrogenated norbornene-vinylated unsaturated six-membered ring hydrocarbon-based addition copolymer of the present invention is hydrogenated to the above-mentioned addition-type copolymer to increase the nuclear hydrogenation rate. 50% or more, preferably 80% or more, more preferably 90% or more.

The term "nuclear hydrogenation rate" as used herein means the hydrogenation reaction among the unsaturated bonds in the unsaturated 6-membered ring structure of the norbornene-vinylated unsaturated 6-membered ring hydrocarbon addition copolymer. Says the percentage of saturation.

The hydrogenation reaction of the addition type copolymer is carried out by a usual method.

(Hydrogenation catalyst) The hydrogenation catalyst can be used if it is generally used for hydrogenating an olefin compound, and examples thereof include Wilkinson's complex, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutyl. Heterogeneous catalysts such as aluminum, diatomaceous earth, magnesia, alumina, synthetic zeolite, etc., on which catalytic metals such as nickel, palladium, and platinum are supported are mentioned. Among them, pores with magnesia, activated alumina, synthetic zeolite as a carrier 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 are preferred.

When the hydrogenation reaction is carried out using a heterogeneous catalyst such as nickel, palladium or platinum, the reactivity can be enhanced by adding a small amount of alcohols such as isopropyl alcohol. The amount added was 100 parts per 100 parts of solution.
It is 5 to 5 parts, preferably 1 to 3 parts.

(Hydrogenation condition) The hydrogenation reaction is carried out in the presence of a catalyst, generally under a hydrogen pressure of 1 to 150 atm, at 0 to 25.
It is carried out at 0 ° C, preferably 20 to 220 ° C. The hydrogenation rate can be arbitrarily adjusted by changing the hydrogen pressure, reaction temperature, reaction time, catalyst concentration and the like.

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

Further, the heterogeneous catalyst which is a hydrogenation catalyst has a particle size of 0.2 μm or more, that is, a particle size of 0.
If you use a material that does not substantially contain less than 2 μm,
It is preferable since the heterogeneous catalyst can be easily removed by filtration. If the particle size is too small, it tends to leak during filtration, and it becomes difficult to remove it even by centrifugation, and the amount of transition metal atoms, which is the residue of the polymerization catalyst or hydrogenation catalyst in the thermoplastic norbornene-based resin, increases. Also, if a filter having a small pore size is used to prevent leakage, clogging easily occurs, resulting in poor work efficiency.

(Norbornene-vinylated unsaturated 6-membered ring hydrocarbon addition copolymer hydride) The hydrogenated product of the present invention has an intrinsic viscosity [η] of 0.1 measured at 25 ° C. in toluene. 10 dl / g. If [η] is too small, the mechanical strength of the molded product will be low, and if [η] is too large, the melt viscosity will be high and the moldability will be poor.

The Tg of the hydrogenated product is 100 to 350 ° C.,
The temperature is preferably 110 to 250 ° C., and the Tg value can be appropriately controlled by changing the type of monomer, the copolymerization ratio, and the hydrogenation rate.

The hydrogenated product of the present invention has a low birefringence and a retardation value of 30 nm or less, preferably 20 nm or less.

Further, the hydrogenated product of the present invention is
Excellent chemical resistance, solvent resistance, mechanical strength, heat deterioration resistance, and light deterioration resistance.

The hydrogenated product of the present invention is preferably as small as possible in the content of transition metal atoms and chlorine atoms derived from the polymerization catalyst, residues of the hydrogenation catalyst and the like. The above-mentioned pore volume, hydrogenation using a heterogeneous catalyst using a carrier having a specific surface area, or treating the hydrogenated solution with an adsorbent used as a carrier for such a heterogeneous catalyst, By repeatedly washing the hydrogenated solution with acidic water and pure water,
1 pp of transition metal atom, chlorine atom, hydrogenation catalyst residue
It can be m or less.

(Additive) If desired, various additives may be added to the hydrogenated product of the present invention. Examples of the additives used include phenol-based and phosphorus-based antioxidants, antistatic agents, ultraviolet absorbers, rubber polymers, petroleum resins, and heterogeneous thermoplastic resins. Also, moldability,
For the purpose of improving physical properties, for example, fibrous fillers such as glass fiber and carbon fiber; fine particle fillers such as silica, alumina, talc, aluminum hydroxide and calcium carbonate; tetrakis [2-
(3,5-di-t-butyl-4-hydroxyphenyl)
Ethyl propionate] Methane, antioxidants such as 2,6-di-t-butyl-4-methylphenol; and the like, as well as light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, flame retardants, pigments, Dyes, anti-blocking agents, etc. may be added. In general, in order to prevent elution from the hydrogenated norbornene-based copolymer, it is preferable that these additives have a large molecular weight, and a smaller amount is preferable.

When the sheet is formed by the solution spraying method,
A leveling agent may be added to reduce the surface roughness. As the leveling agent, for example, a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, a silicone-based leveling agent, or the like can be used as a coating leveling agent, and among them, those having good compatibility with a solvent are preferable.

When an additive is added to the hydrogenated product of the present invention, it is added within the range according to the purpose. For example, when an additive is added, the transparency generally decreases, but when molding into a chemical container, it is necessary to have a transparency that allows the amount and state of the contents to be confirmed, and therefore the required light transmission. As for the ratio, a molded plate with a thickness of 1.2 mm is used, and the wavelength range is 4
Measured in the range of 00 to 700 nm, usually 40% or more,
It is preferably at least 50%, more preferably at least 60%. Similarly, the light transmittance when used as an optical material is usually 85% or more, preferably 88% or more, more preferably 90% or more when measured at a wavelength of 400 to 830 nm. The additive also affects the electrical properties. When used as an electrically insulating material, the volume resistivity value is 10
¹⁶ Ωcm or more, preferably 5 × 10 ¹⁶ Ωcm or more, the dielectric constant is 3 or less at any frequency of 10 ² Hz, 10 ⁶ Hz, or 10 ⁹ Hz, preferably 2.5 or less, the dielectric loss tangent is 10 ² Hz, 10 ⁶ Hz, 10 ⁹ Hz as 10 ^-3 or less at any frequency, preferably 7 × 10 ^-4 or less. Further, the time required for the track showing the electric insulation stability is 100 hours or longer, preferably 150 hours or longer, more preferably 170 hours or longer.

(Use) The hydrogenated product of the present invention is useful in various fields such as optical materials and various molded products. For example, optical materials; medical equipment; electrical insulation materials; electronic component processing equipment; electronic component applications such as windows for light receiving elements; structural materials and building materials for windows, equipment parts, housings, bumpers, room mirrors, headlamp covers Automotive equipment such as tail lamp covers and instrument panels; electrical equipment such as speaker cone materials, speaker vibration elements, microwave oven containers, films, seats, helmets, etc.

(Optical Material) The hydrogenated material of the present invention is excellent in transparency, low birefringence, heat resistance and low hygroscopicity, and can be melt-molded. Therefore, for example, an optical disk, an optical lens, an optical card. , Optical fiber, optical mirror, prism,
It is useful as an optical material such as a liquid crystal display element substrate, a light guide plate, a polarizing film, and a retardation film.

(Medical Equipment) The hydrogenated product of the present invention is capable of adsorbing chemicals, particularly chemicals having polar groups such as alcohols, amines, esters, amides, ethers, carboxylic acids and amino acids. In addition, since the amount of organic substances contained in the resin as impurities is small and does not exude, it does not deteriorate even when it comes into contact with chemicals. Furthermore, the residual amount of transition metal atoms and hydrogenation catalytic metal derived from the polymerization catalyst is reduced by the above-mentioned method or a method of repeatedly washing the resin solution with acidic water and pure water, and the residual amount is reduced to 1 ppm. Since it can be made the following, it can be used as a medical device.

The medical device of the present invention is, for example, a liquid or powder such as a liquid medicine container for injection, an ampoule, a prefilled syringe, an infusion bag, a solid medicine container, an eye drop container, an instillation container, or the like. Chemical containers; Food containers; Sampling test tubes for blood tests, blood collection tubes, sample containers such as sample containers; Medical devices such as syringes;
Sterile containers for medical instruments such as scalpels, forceps, gauze and contact lenses; experimental and analytical instruments such as beakers, petri dishes, flasks, test tubes, centrifuge tubes; medical optical components such as plastic lenses for medical examinations; medical infusions Piping materials such as tubes, pipes, joints, valves; artificial dentures, artificial hearts, artificial roots and other artificial organs and parts thereof;
Are exemplified. In particular, in the case of medicine bottles, prefilled syringes, sealed medicine bags, ampoules, vials, eye drop containers, etc., which store medicines, especially liquid medicines for a long period of time, compared to conventional resin ones, transparency, In addition to physical properties, there are no impurities that elute from the resin, it has excellent chemical resistance, and since it does not adsorb chemicals, it has the favorable property that the quality of chemicals is small.

(Equipment for electronic component processing) The hydrogenated product of the present invention, particularly the one having a catalytic metal residue of 1 ppm or less, has substantially no impurities eluted from the resin and is excellent in physical properties such as heat resistance. In addition, since it has resistance to many chemicals used for processing electronic parts, particularly most strong acids except sulfuric acid, it has preferable properties as a device for processing electronic parts.

The electronic component processing equipment is (A) IC, L
Semiconductors such as SI, hybrid ICs, liquid crystal display elements,
Equipment that contacts electronic parts such as light-emitting diodes, (B)
Wafers, liquid crystal substrates, equipment that comes into contact with manufacturing intermediates such as those having a transparent electrode layer or protective layer laminated thereon, and (C) chemical liquids or super liquids used in the processing of manufacturing intermediates in the manufacturing process of electronic components. Equipment that comes into contact with processing liquid such as pure water. Examples of (A) the equipment that comes into contact with the electronic component and (B) the equipment that comes into contact with the intermediate for manufacturing the electronic component include, for example, a tank,
Containers for treating and transferring trays, carriers, cases, etc .; carrier tapes, protective materials such as separation films; and the like. (C) Examples of equipment that comes into contact with the treatment liquid include pipes, tubes, valves, sippers, flow meters, filters, pumps, and other pipes; sampling containers, resist containers, developer containers, stripping liquid containers, cleaning liquid containers, Liquid containers such as bottles, ampoules and bags; and the like.

(Electrical Insulation Material) The hydrogenated material of the present invention is
It is useful in a wide range of fields as an electrically insulating material. For example, OA for electric wire / cable coating materials, consumer / industrial electronic devices, copiers / computers / printers, etc.
General insulating materials for equipment, instruments, etc .; circuit boards such as hard printed boards, flexible printed boards, and multilayer printed wiring boards, especially high-frequency circuit boards for satellite communication equipment that require high-frequency characteristics; liquid crystal boards / optical memories・ Substrate of transparent conductive film such as surface heating element such as defroster of automobile or aircraft; Transistor, IC, LS
Semiconductor encapsulants and parts such as I / LED; Encapsulation materials for electric / electronic parts such as motors, contactors, switches and sensors; Body materials for TVs and video cameras;
It can be suitably used for a parabolic antenna, a flat antenna, a structural member of a radar dome, and the like.

[0046]

EXAMPLES The present invention will be described more specifically with reference to the following Reference Examples, Comparative Examples and Examples. Parts are based on weight unless otherwise specified. The number average molecular weight was determined by gel permeation chromatography using toluene as a solvent, and the intrinsic viscosity was 25 ° C in toluene.
According to the C method, the light transmittance was measured at a wavelength of 8 using a spectrophotometer.
At 30 nm, the retardation value was measured by the double pass method with a wavelength of 830 nm. The volume resistivity, dielectric constant and dielectric loss tangent are measured by the method of JIS K6911, the time required for the track is measured by the method of ASTM-D-2132-6T, and the bending strength is measured by the method of ASTM-D-790. Measured.

Reference Example 1 40 parts of norbornene, 120 parts of styrene, 140 parts of nitromethane, and 18 parts of toluene were placed in a reactor substituted with nitrogen.
I prepared 0 copies. Keep the temperature at 20 ℃, while stirring,
A solution prepared by dissolving 0.3 parts of [Pd (CH ₃ CN) ₄ ] (BF ₄ ) ₂ in 60 parts of toluene was added. After reacting for 1 hour, 1000 parts of methanol was added, and the precipitated copolymer was filtered and recovered. 300 parts methanol and 40 concentrated hydrochloric acid
After washing with 150 parts of a mixed solution, it was washed twice with 150 parts of methanol and dried at a temperature of 100 ° C. and a pressure of 1 mmHg for 24 hours to obtain 85 parts of a copolymer.

Comparative Example 1 The copolymer obtained in Reference Example 1 had an intrinsic viscosity [η] in toluene of 25 ° C. of 0.48 dl / g and Tg of 190 ° C. 5.6 ppm measured from ¹ H-NMR spectrum
-C = CH- derived proton peaks seen in
The peak of saturated carbon-bonded protons at 3 ppm was observed at an integration ratio of 5:12, and the copolymerization ratio of norbornene and styrene calculated based on the peak was 4: 1 by weight.
It was 7:53.

This copolymer was hot pressed to a thickness of 3 m.
m, 40 × 60 mm plate was molded, and using a long life fade meter (Suga Test Instruments, FAL-3 type), black panel temperature 63 ° C., irradiation time 100 hours, before and after irradiation with 400 nm light The light transmittance was measured. The light transmittance before irradiation was 90.3%, and the light transmittance after irradiation was 85.3%.

When this copolymer was molded into a plate having a thickness of 1.2 mm and a diameter of 65 mm by hot pressing, the retardation value was 100 nm or less.

The bending strength of this copolymer is 665 kgf /
It was cm ² . The volume resistivity is 5 × 10 ¹⁶ Ωcm or more, the dielectric constant is 2.41 in any of 10 ² Hz, 10 ⁶ Hz, and 10 ⁹ Hz, and the dielectric loss tangent is 10 ² Hz, 10 ⁶ Hz, 1
Either ^{0 9 Hz 4 × 10 - 4} , the time required for the track was 1.7 hours.

Example 1 50 parts of the copolymer obtained in Reference Example 1 was added to cyclohexane 200
Dissolved in alumina, nickel catalyst on alumina (0.35 parts by weight of nickel, 0.2 parts by weight of nickel oxide, 1 part by weight of catalyst, 0.5 cm ³ / g of pore volume, 200 m ² / g of specific surface area)
g) 3 parts was added, and the mixture was placed in an autoclave, and after stirring and mixing, the air therein was replaced with hydrogen, and the hydrogen pressure was 50 kgf / c.
The reaction was carried out at m ² and a temperature of 230 ° C. for 5 hours. After the reaction,
The resulting hydrogenated product was filtered to remove the catalyst, poured into 500 parts of acetone to coagulate, and the precipitate was collected by filtration to 1 mmH.
After drying for 24 hours, 46 parts of hydrogenated product was obtained.

The obtained hydrogenated product had an intrinsic viscosity [η] in toluene at 25 ° C. of 0.40 dl / g and a Tg of 220.
It was ℃. Further, the ¹ H-NMR chart of the copolymer of Comparative Example 1 and this hydrogenated product were compared, and the hydrogenated product had a peak of aromatic protons of about 7 ppm, 5.6 pp.
Since the proton peak derived from -C = CH- of m disappeared, it was found that the hydrogenation rate was almost 100%. In addition, as a result of atomic absorption analysis of a 10 wt% cyclohexane solution of this hydrogenated product, palladium atom in the hydrogenated product was 1.5 ppm and nickel atom was 1.2 ppm.

As a result of molding and measurement in the same manner as in Comparative Example 1, the light transmittance before irradiation was 90.3%, and the light transmittance after irradiation was 86.9%. Retardation value is 20n
It was m or less. Thus, the hydrogenated product of the present invention was excellent in performance as an optical material.

The bending strength of this hydrogenated product is 660 kgf.
Was / cm ² . The volume resistivity is 5 × 10 ¹⁶ Ω
cm or more, dielectric constant 10 ² Hz, 10 ⁶ Hz, 10 ⁹ Hz
2.32, dielectric loss tangent is 10 ² Hz, 10 ⁶ H
It was 4 × 10 ^{−4 at} any of z and 10 ⁹ Hz, and the time required for the track was 191 hours. Thus, the hydrogenated product of the present invention was also excellent as an electrical insulating material.

Reference Example 2 130 parts of α-methylstyrene instead of 120 parts of styrene
Polymerization reaction was performed in the same manner as in Reference Example 1 except that parts were used.
90 parts of a copolymer was obtained.

Comparative Example 2 The copolymer obtained in Reference Example 2 had an intrinsic viscosity of 0.54 dl / g measured in toluene at 25 ° C., and had a peak of 5.6 ppm and ^{1 to 3} ppm in ¹ H-NMR spectrum. And the copolymerization ratio of norbornene and α-methylstyrene calculated on the basis of 2:25 is 4:25 by weight.
It was 3:57.

As a result of molding and measurement in the same manner as in Comparative Example 1, the light transmittance before irradiation was 90.6%, and the light transmittance after irradiation was 85.5%. Retardation value is 100
It was less than or equal to nm. The Tg was 196 ° C.

The bending strength was 670 kgf / cm ² . The volume resistivity of this resin is 5 × 10 ¹⁶ Ωcm or more,
Dielectric constant ^{10 2 Hz, 10 6 Hz,} 10 9 Hz of either 2.38, the dielectric loss tangent ^{10 2 Hz, 10 6 Hz,} 10 9
The frequency required for the truck was 4 × 10 ^{−4 at} any frequency of 1.9 hours.

Example 2 50 parts of the resin obtained in Reference Example 2 was used in place of the copolymer obtained in Reference Example 1, and another nickel-supported alumina catalyst was used as a catalyst (0.35 parts by weight of nickel in 1 part by weight of the catalyst). Parts, nickel oxide 0.2 parts by weight, pore volume 0.8 cm ³ / g, specific surface area 300 m ² / g) except that hydrogenation reaction is performed under the same conditions as in Example 1 except that hydrogen is used. 46 parts of additive were obtained.

The intrinsic viscosity of this hydrogenated product measured in toluene at 25 ° C. was 0.55 dl / g, and Tg was 215 ° C. In addition, the copolymer of Comparative Example 2 and this hydrogenated product
Comparing the ¹ H-NMR charts, it was found that 7
It was found that the hydrogenation rate was almost 100% because the peak of the aromatic proton near ppm and the peak of the proton derived from -C = CH- at 5.6 ppm disappeared.

As a result of molding and measurement in the same manner as in Comparative Example 1, 4
The light transmittance before irradiation with 00 nm light was 90.5%, and the light transmittance after irradiation was 87.9%. The retardation value was 20 nm or less. In addition, palladium atom is less than 1 ppm (detection limit), nickel atom is 0.1 pp
It was less than m (detection limit).

The bending strength of this hydrogenated product is 670 kgf.
Was / cm ² . The volume resistivity is 5 × 10 ¹⁶ Ωcm or more, the dielectric constant is 2.27 at any of 10 ² Hz, 10 ⁶ Hz, and 10 ⁹ Hz, and the dielectric loss tangent is 10 ² Hz, 10 ⁶ Hz, 1
It was 5 × 10 ^{−4 at} any of ⁰⁹ Hz, and the time required for the track was 183 hours.

Reference Example 3 A polymerization reaction was carried out in the same manner as in Example 1 except that 60 parts of l-limonene was used instead of 120 parts of styrene to obtain 60 parts of a copolymer.

Comparative Example 3 The copolymer obtained in Reference Example 3 had an intrinsic viscosity of 0.39 dl / g measured in toluene at 25 ° C. and a Tg of 183 ° C. ¹ H-NMR spectrum of 5.6 ppm and ¹ to 3 p
The integral ratio of the pm peak was 2:39, and the copolymerization ratio of norbornene and 1-limonene calculated on the basis of it was 31:69 by weight.

As a result of molding and measurement in the same manner as in Comparative Example 1, 4
The light transmittance before irradiation with 00 nm light was 90.3%, and the light transmittance after irradiation was 78.3%. The retardation value was 35 nm or less.

Example 3 Example except that the copolymer obtained in Reference Example 3 was used in place of the copolymer obtained in Reference Example 1, and the alumina-supported nickel catalyst used in Example 2 was used. 41 parts of hydrogenated product were obtained in the same manner as in 1.

The intrinsic viscosity of this hydrogenated product measured at 25 ° C. in toluene was 0.40 dl / g and Tg was 188 ° C. In addition, the copolymer of Comparative Example 3 and this hydrogenated product
Comparing the ¹ H-NMR charts, it was found that the hydrogenation rate was almost 100% because the proton peak derived from —C═CH— at 5.6 ppm disappeared in the hydrogenated product.

As a result of molding and measurement as in Comparative Example 1, the light transmittance before irradiation was 90.3%, and the light transmittance after irradiation was 86.3%. Retardation value is 20n
It was m or less.

The bending strength of this hydrogenated product is 660 kgf.
Was / cm ² . The volume resistivity is 5 × 10 ¹⁶ Ωcm or more, the dielectric constant is 2.27 at any of 10 ² Hz, 10 ⁶ Hz, and 10 ⁹ Hz, and the dielectric loss tangent is 10 ² Hz, 10 ⁶ Hz, 1
It was 4 × 10 ^{−4 at} any of ⁰⁹ Hz, and the time required for the track was 183 hours.

Further, as a result of atomic absorption analysis of a 10 wt% cyclohexane solution of this hydrogenated substance, palladium atom in the hydrogenated substance was 1.5 ppm and nickel atom was 1.2 ppm.
It was ppm.

Reference Example 4 45 parts of a hydrogenated product was obtained in the same manner as in Example 1 except that 60 parts of dipentene was used instead of 120 parts of styrene.

Comparative Example 4 The copolymer obtained in Reference Example 4 had an intrinsic viscosity of 0.40 dl / g measured in toluene at 25 ° C. and a peak of 5.6 ppm and ^{1 to 3} ppm in ¹ H-NMR spectrum. And the copolymerization ratio of norbornene and dipenteene calculated on the basis of the integral ratio is 35:65 by weight.
Met.

As a result of molding and measurement in the same manner as in Comparative Example 1, 4
The light transmittance before irradiation with 00 nm light was 90.2%, and the light transmittance after irradiation was 78.1%. The retardation value was 35 nm or less. The Tg was 172 ° C.

Example 4 40 parts of the copolymer obtained in Reference Example 4 was used in place of 50 parts of the copolymer obtained in Reference Example 1, and the alumina-supported nickel catalyst used in Example 2 was used. Example 1 except
A hydrogenation reaction was carried out under the same conditions as in 1. to obtain 35 parts of a hydrogenated product.

The intrinsic viscosity of this hydrogenated product measured in toluene at 25 ° C. was 0.41 dl / g, and the Tg was 18
It was 5 ° C. Further, the ¹ H-NMR chart of the copolymer of Comparative Example 3 and this hydrogenated product were compared, and it was found that the proton peak derived from -C = CH- at 5.6 ppm disappeared in the hydrogenated product. It was found that the hydrogenation rate was almost 100%.

As a result of molding and measurement in the same manner as in Comparative Example 1, the light transmittance before irradiation was 90.1%, and the light transmittance after irradiation was 86.6%. Retardation value is 20n
It was m or less.

The flexural strength of this hydrogenated product is 650 kgf.
Was / cm ² . The volume resistivity is 5 × 10 ¹⁶ Ωcm or more, the dielectric constant is 2.28 at any of 10 ² Hz, 10 ⁶ Hz, and 10 ⁹ Hz, and the dielectric loss tangent is at 10 ² Hz, 10 ⁶ Hz, 1
At any frequency of ⁰⁹ Hz, 4 × 10 ⁻⁴ , and the time required for the track was 175 hours.

Example 5 800 parts of a 10 wt% cyclohexane solution of the hydrogenated product obtained in Example 1 was treated with activated alumina (Neobead D, manufactured by Mizusawa Chemical Co., Ltd., pore volume 0.8 cm ³ / g, specific surface area 300 m ² /
g) Inner diameter 10 cm, length 100 cm filled with 4.5 parts
Through the column with a residence time of 100 seconds, and
Circulate for 4 hours. The hydrogenated product was solidified by pouring into 2500 parts of isopropyl alcohol with stirring. The solidified hydrogenated product was collected by filtration, washed twice with 430 parts of isopropyl alcohol, and then dried in a rotary vacuum dryer at 5 torr and 120 ° C. for 48 hours to recover 75 parts by weight.

The palladium atom in this hydrogenated product is 1
Below ppm (detection limit), 0.1 ppm of nickel atom
(Detection limit) or less.

Example 6 Using the hydrogenated product obtained in Example 5, a mold clamping pressure of 350
t, resin temperature 330 ° C., mold temperature 150 ° C., injection molding, diameter 200 mm, height 130 mm, average thickness 3 mm
Cylindrical transparent container and 100mm x 50mm x 2.0
mm test pieces were prepared.

The test piece had a light transmittance of 90.9% and a turbidity of 0.08%.

300 ml of LB medium (1% by weight of bactotryptone, 0.5% by weight of yeast extract, 1% by weight of NaCl, and 0.1% by weight of glucose were adjusted to pH 4.5) in the prepared container, and agar was added. Put 6g, one piece of test piece, cap with aluminum foil, 121 ℃, 3
Steam sterilization was performed for 0 minutes.

After sterilization, the temperature was kept at 37 ° C. for 3 days, but no fungal growth was observed.

The appearance of the container after sterilization was good, and no turbidity, cracking, or thermal deformation was visually observed. It was measured after removing the LB medium solidified by agar from the test piece taken out from the container, but no change was observed in turbidity and light transmittance.

The test piece was treated with an aqueous sodium carbonate solution having a pH of 9,
After immersing in hydrochloric acid and ethanol of pH 4 for 48 hours, the appearance was observed, but there was no change in turbidity or light transmittance.

Further, the test piece was subjected to an eluate test according to the Japanese Pharmacopoeia 12th revision “Plastic test method for infusion”. Bubbling disappeared within 3 minutes, pH difference was -0.04,
Ultraviolet absorption was 0.007 and potassium permanganate reducing substance was 0.12 ml. From this result, the hydrogenated product of the present invention is excellent as a raw material for medical devices, and
It was found that it is also suitable for electronic parts processing equipment because it has a small amount of extractables and has excellent heat resistance and chemical resistance.

[0088]

INDUSTRIAL APPLICABILITY The norbornene-vinylated unsaturated six-membered ring hydrocarbon-based addition copolymer hydrogenated product of the present invention has heat resistance, transparency, light deterioration resistance, low birefringence, electrical insulation, and high frequency. It is excellent in properties, electrical insulation stability, low elution of organic substances, mechanical strength and the like, and can be used for optical materials, electrical insulating materials, electronic component processing equipment, medical equipment.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Io Natsuume Io 1-2-1, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Nippon Zeon Co., Ltd. Research and Development Center (56) Reference JP-A-4-80220 (JP, A) ) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (5)

(57) [Claims] 1. 5-95% by weight of norbornene-based monomer
And a vinylated unsaturated 6-membered ring hydrocarbon monomer 95 to 5% by weight of a copolymer having a nuclear hydrogenation rate of 50% or more, and an intrinsic viscosity [η] measured in toluene at 25 ° C. Is 0.1 to 10 dl / g, norbornene-vinylated unsaturated six-membered ring hydrocarbon-based addition type hydrogenated product. 2. An optical material comprising the hydrogenated norbornene-vinylated unsaturated 6-membered ring hydrocarbon addition copolymer according to claim 1. 3. An electrical insulating material comprising the norbornene-vinylated unsaturated 6-membered ring hydrocarbon-based addition-type copolymer hydrogenated product according to claim 1. 4. A device for processing electronic parts, which comprises the norbornene-vinylated unsaturated 6-membered ring hydrocarbon-based addition-type copolymer hydrogenated product according to claim 1. 5. A medical device comprising the norbornene-vinylated unsaturated 6-membered ring hydrocarbon-based addition copolymer hydrogenated product according to claim 1.