JPH06136057A - Hydrogenated cyclopentadiene resin, its production and optical material, medical material, electrical insulation material and electronic part treating material made from the resin - Google Patents

Abstract

PURPOSE:To obtain a resin free from cross-linked gelatinous component and having high transparency, low birefringence and excellent light-resistance, moisture resistance, moldability, electrical characteristics and mechanical strength. CONSTITUTION:The resin having an intrinsic viscosity [eta] of 0.1-10dl/g in toluene at 25 deg.C is produced by subjecting monomers composed mainly of a cyclopentadiene compound to linear addition polymerization and hydrogenating at least 90% of the recurring unit originated from the cyclopentadiene compound. The resin is useful as an optical material, medical material, electrical insulation material and material for treating electronic part.

Description

Detailed Description of the Invention

[0001]

The present invention relates to transparency, low birefringence,
Hydrogenated cyclopentadiene resin excellent in light resistance, moisture resistance, low dielectric constant, low dielectric loss, chemical resistance, etc., its manufacturing method, optical material consisting of it, medical material, electrical insulation material, electronic component processing equipment Regarding

[0002]

2. Description of the Related Art Conventionally, polymethylmethacrylate or polycarbonate has been used as a polymer material for optics, but the former has a problem that the water absorption is large and the latter has a large birefringence of an injection molded product. As a result, it is becoming difficult to meet the demand for increasingly sophisticated optical polymer materials.

As a polymer material for improving these drawbacks, for example, a thermoplastic saturated norbornene-based polymer such as a hydrogenated product of a ring-opening polymer of a norbornene-based monomer or an addition type copolymer of a norbornene-based monomer and ethylene is used. It is known to have excellent characteristics as an optical material such as an optical disk substrate (JP-A-60-26024,
JP-A-64-24826, JP-A-60-168708
No. 61-115912 and 61-120.
No. 816).

However, in these conventional techniques, polycyclic monomers such as tetracyclododecenes are used as the norbornene-based monomers. Polycyclic monomers are not always easy to manufacture. Usually, polycyclic monomers are norbornenes and dicyclopentadiene (hereinafter referred to as DCP).
And) are subjected to an addition reaction with heating to synthesize them. However, since they contain many by-products such as cyclopentadiene (hereinafter referred to as CPD) multimers, they need to be purified and separated by distillation or the like. Have difficulty. Therefore, polycyclic monomers, especially tetracyclododecene derivatives, are very expensive and are not industrially advantageous. Also, the types of monomers available are limited.

On the other hand, CPD is easily available as a C ₅ fraction in the petrochemical industry, and normally, what is stored as DCP is decomposed by heating to 180 ° C. or higher to obtain CPD with high purity. . A linear polymer is obtained from CPD by a method such as cationic polymerization and is used as a tackifier (Ann., 447 , 110, 1).
926; Ind. Eng. Chem. , 18 , 38
1, 1926; Polymer Chemistry, 19 , 734, 196
2; Polymer Chemistry, 23 , 56, 1966;
5-65220). However, these polymers are
In general, it has a small molecular weight and contains a large amount of unsaturated bonds, so that it is extremely susceptible to air oxidation, resulting in deterioration in strength and difficulty in melting, and it cannot be used as a molding material.

It is also known that this polymer can be partially hydrogenated to improve the resistance to oxidative deterioration (Polymer Chemistry, 19 , 734, 1962). It is not easy to add, and the intrinsic viscosity [η]
It is known that even with a low molecular weight of about 0.06 dl / g, the hydrogenation rate is about 73%, and for example, the stability required for optical materials is excellent. The polymer was unknown.

On the other hand, medical devices have recently been replaced with disposable devices in order to prevent the secondary infection of viruses by repeated use. Conventionally, injection drugs were also used by suctioning them with a syringe from a sterilized ampoule at the time of injection, but recently, pre-filled syringes in which the injection drug has been previously inhaled have been distributed and Later syringes were discarded.

[0008] Medical drug containers, including prefilled syringes, require a certain level of transparency so that the contents can be easily viewed. Therefore, glass, polyethylene, polypropylene, polyvinyl chloride, etc. have been conventionally used. However, the glass may be broken, heavy, and alkali ions may elute, which makes it difficult to burn, and it may be difficult to dispose of the pieces, such as the danger of handling broken pieces. there were. In addition, low molecular weight organic components may be eluted from polyethylene, polypropylene, etc., and chlorine may be eluted from polyvinyl chloride, which may deteriorate the contents.

Polyolefin resins such as polyvinyl chloride, polyethylene and polystyrene have been widely used as electrical insulating materials. These have excellent electrical properties such as high insulation resistance, high breakdown voltage, and low dielectric constant, as well as low water absorption, chemical resistance, etc., but their heat resistance is insufficient, and under severe conditions I can not use it. Further, polystyrene has problems such as poor arc resistance and tracking resistance.

Polyethylene terephthalate is a widely used electrical insulating material that has excellent electrical characteristics, mechanical strength, transparency, etc., but it is hydrolyzed by hot water or alkali, or has a poor water absorption property. There are problems such as big.

Further, as an insulating material used for a composite material such as a printed board, a laminated board and a conductive film,
Polysulfone, polyether sulfone, and other resins with excellent heat resistance and transparency, and epoxy resins, especially polyimides are used for applications requiring heat resistance, but all of these have large water absorption and conductive layers. In applications where it is necessary to go through steps such as vacuum deposition or sputtering when compounding with, it takes a long time to raise to the required degree of vacuum due to water in the resin in those steps. There is a problem that productivity becomes poor. Further, epoxy resin and polyimide are not suitable for use in high frequencies because their dielectric constant and dielectric loss are too large.

As a resin having excellent high-frequency characteristics, heat resistance, and low water absorption, a polycyclic norbornene such as a hydrogenated product of a ring-opening polymer of a norbornene-based monomer or an addition-type polymerization of a norbornene-based monomer and ethylene is used. It has been proposed to use a polymer using a monomer as an electrical insulating material (Japanese Patent Laid-Open No. 61-120816). However, as described above, the polycyclic monomer has a problem in industrial use.

As described above, each of the electrically insulating materials has advantages and disadvantages, has excellent performance in all aspects, and is not known to be easily available.

[0014]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of diligent efforts toward the development of a new resin that can be used as an optical material, a medical device, an electric insulating material, etc., the present inventors did not include a crosslinked gelled substance. Has succeeded in developing a hydrogenated CPD resin having excellent transparency, low birefringence, light resistance, moisture resistance, molding processability, mechanical strength, chemical resistance, etc., and completed the present invention. It was

[0015]

Thus, according to the present invention, at least 90% or more of the repeating units of the polymer whose main component is the linear addition polymerization repeating unit of CPDs is hydrogenated, Hydrogenated C having an intrinsic viscosity [η] of 0.1 to 10 dl / g measured in toluene at 25 ° C
Provided are a PD-based resin, a method for producing the same, an optical material made of the same, a medical instrument, an electrical insulating material, and an electronic component treating instrument.

(CPDs) The CPDs used in the present invention refer to CPD and its alkyl-substituted compounds, and specific examples thereof include:
CPD, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5
-Methylcyclopentadiene, 5,5-dimethylcyclopentadiene, and the like.

(Monomer composition) The monomer composition used in the present invention contains one or more CPDs, and the resulting polymer has heat resistance, flexibility and molding processability. ,
In addition to the CPDs, a monomer copolymerizable with the CPDs may be contained within a range where properties such as mechanical strength are not substantially impaired or improved. Monomers copolymerizable with CPDs include ethylene, propylene, isobutene, dipentene, limonene, vinylcyclohexene, and 2
-Methyl-1-butene, 2-methyl-1-pentene, 4
Α-olefins such as -methyl-1-pentene; butadiene, isoprene, 1,3-pentadiene, furan,
Conjugated dienes such as thiophene; Vinyl aromatic compounds such as styrene, α-methylstyrene and vinylnaphthalene; Ethylene oxide, propylene oxide, trimethylene oxide, trioxane, dioxane, cyclohexene oxide, styrene oxide, epichlorohydrin, cyclic ethers such as tetrahydrofuran Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; heterocyclic ring-containing vinyl compounds such as vinyl pyridine, N-vinyl carbazole and N-vinyl-2-pyrrolidone; norbornene, dicyclopentadiene, tetracyclododecene, cyclopentene, cyclohexene , Norbornadiene, cyclic olefins such as 1,3-cyclohexadiene and substituted products thereof; and the like.

C, which can be copolymerized with CPDs in the monomer composition, depending on the use of the hydrogenated CPD resin of the present invention.
The types and proportions of monomers other than PDs are determined. Generally, when the monomer other than CPDs copolymerizable with CPDs is other than cyclic olefin, the transparency of the hydrogenated CPD-based resin of the present invention increases as the content of the monomer increases.
Colorlessness and low birefringence decrease. From that viewpoint, the monomer composition used for the polymerization reaction of the CPD resin used in the present invention contains 50% by weight or more, preferably 60% by weight, of CPDs.
The above content is more preferably 70% by weight or more, particularly preferably 80% by weight or more, and particularly preferably 90% by weight or more. On the other hand, in applications where heat resistance is required, it is preferable to copolymerize a monomer such as styrene or norbornene that has a high glass transition temperature with CPDs by copolymerization. The content is preferably 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 30% by weight or more.

(Polymerization catalyst) As the polymerization catalyst, known substances can be used.
As a specific example, AlCl₃, AlBr₃, BF₃,
BCl₃, BF₃・ OEt₂, TiCl_Four, TiBr_Four, F
eCl₃, FeCl₂ , SnCl₂, SnCl_Four, TiCl
_Four/ Cl₃CCOOH, SnCl_Four/ Cl₃CCOOH, W
Cl₆, MoCl_FiveHalogenated metal such as Pd (CH
₃CN)₂Cl₂, Pd (C₆H_FiveCN)₂Cl₂, Pd (C
H₃CN)_Four(BF_Four)₂Pd catalysts such as: HCl, H
F, HBr, H₂SO_Four, H₃BO₃, HClO_Four, CH₃C
OOH, Cl₃Hydrogen acids such as CCOOH; TiCl_Four−
Et₃Ziegler catalyst such as Al; TiCl_Four/ 2-me
Toxy-2-phenylpropane, TiCl_Four/ T-pig
Nol, TiCl_Four/ 1,4-bis (2-methoxy-2)
-Propyl) benzene, 2-phenyl-2-propano
, A living acid that uses a Lewis acid and an initiator compound in combination.
Thione polymerization catalyst; and the like.

The polymerization catalyst is used in a molar ratio of 0.000001 to 1 times, preferably 0.1.
It is in the range of 0001 to 0.5 times.

(Polymerization Reaction Solvent) Polymerization is usually carried out using a solvent. Solvents include benzene, toluene,
Aromatic solvents such as xylene; pentane, hexane,
Hydrocarbon solvents such as heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, decalin; methyl chloride, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-
Halogenated hydrocarbon solvents such as trichloroethane and 1,1,2-trichloroethylene; and the like. Usually, hydrocarbon solvents, especially cyclopentane, cyclohexane, methylcyclohexane, and decalin are excellent in solubility of the polymerized polymer. ,preferable.

(Polymerization temperature) The polymerization temperature is usually -150.
~ 100 ° C, preferably in the range of -100 to 50 ° C.

(Polymer) Polymers of CPDs used in the present invention are represented by the general formula 1

[Chemical 1] (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each represent a hydrogen atom or an alkyl group), and a linear addition-type polymerized repeating unit of CPDs. As the main component, Aso, C.I. , Et al. , J. Po
lymer Sci. , PartB4,701 (1
If calculated based on the Aso method described in 966), C
The repeating unit represented by Chemical Formula 1 in the linear addition type repeating units of PDs is 20% by weight or more, preferably 3
0 wt% or more, more preferably 40 wt% or more,
The intrinsic viscosity [η] measured in toluene at 25 ° C is 0.1.
-10 dl / g, preferably 0.2-5 dl / g, and more preferably 0.3-2 dl / g. CPD
The proportion of the repeating unit represented by the chemical formula 1 in the linear addition type repeating unit of the class is determined by the polymerization catalyst, the polymerization solvent, etc. and is not affected by the presence of the comonomer or the polymerization temperature. When the intrinsic viscosity is low, the mechanical strength of the molded product of the hydrogenated product of the polymer is low, and when the intrinsic viscosity is high, the hydrogenation reaction of the polymer is difficult to proceed smoothly.
The CPD polymers used in the present invention are substantially gel-free and soluble in a suitable solvent. Those containing gel are not preferable because the hydrogenation reaction cannot be carried out smoothly.

(Hydrogenation catalyst) The hydrogenation catalyst is olefin
Which are commonly used in the hydrogenation of
It can be used if there is, for example, Wilkinson complex,
Cobalt acetate / triethylaluminum, nickel acetate
Cylacetonate / triisobutylaluminum, etc.
Or diatomaceous earth, magnesia, alumina, synthetic Zeoli
Support catalytic metals such as nickel, palladium, platinum, etc.
Heterogeneous catalysts that have been retained include magnesia,
Pore volume with activated alumina and synthetic zeolite as carrier
0.5 cm³/ G or more, preferably 0.7 cm³/ G or less
Above, preferably a specific surface area of 250 m² / G or more disproportionate
One catalyst is preferred. These carriers are derived from polymerization catalysts.
Adsorbs metal transfer and chlorine atoms. Furthermore, with a heterogeneous catalyst
And the particle size is 0.2 μm or more, that is, the particle size is 0.2
If a substance substantially less than μm is used,
It is preferable because it is easy to remove the heterogeneous catalyst due to excess
Yes. If the particle size is too small, it will easily leak during filtration, and
It becomes difficult to remove even after centrifugation, and hydrogenated CPD resin
Atoms that are residues of polymerization catalysts and hydrogenation catalysts
The amount increases. Also, the hole diameter is small so that it will not leak.
Clogged easily when filtered with a filter
Work efficiency is poor.

When the hydrogenation reaction is carried out using a supported catalyst such as nickel, palladium or platinum, the reactivity can be increased 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 reaction solvent) CP used in the present invention
The hydrogenation reaction of the D-based polymer is usually carried out in an inert organic solvent. As the organic solvent, a hydrocarbon solvent is preferable, and among them, a cyclic hydrocarbon solvent excellent in solubility of the CPD resin produced is particularly preferable. Specific examples include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as n-pentane and hexane, cyclohexane,
Examples thereof include alicyclic hydrocarbons such as decalin, halogenated hydrocarbons such as methylene dichloride, dichloroethane, and the like, and two or more kinds of these may be mixed and used. When a solvent is used, the amount of the solvent used is 0.8 to 20 parts by weight, preferably 1 to 1 part by weight based on 1 part by weight of the CPD polymer.
0 parts by weight.

Usually, it may be the same as the polymerization reaction solvent, and the reaction may be carried out by adding a hydrogenation catalyst or the like to the polymerization reaction solution as it is.

(Hydrogenation Reaction Temperature) In the present invention,
The temperature of the hydrogenation reaction is 100 ° C. or higher, preferably 12
The temperature is 0 to 300 ° C, more preferably 140 to 250 ° C. If the temperature is too low, the hydrogenation reaction will not proceed easily and the hydrogenation rate will not be sufficiently high. If the temperature is too high, C
Polymers of PDs are deteriorated by heat and are difficult to operate.

(Hydrogen pressure) The hydrogen pressure in the hydrogenation reaction is not particularly limited, but is usually 10 to 200 kg / cm ² , preferably 20 to 150 kg / cm ² , and more preferably 30 to 100 kg / cm ² .

(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. An adsorbent for a transition metal atom derived from the polymerization catalyst, such as a carrier of the hydrogenation catalyst described above, may be used as a filter aid.

(Hydrogenated CPD-based resin) The hydrogenation rate of the hydrogenated CPD-based resin of the present invention, that is, the hydrogenated CP with respect to the linear addition type repeating unit of all CPDs.
The proportion of the linear addition type repeating unit of group D can be arbitrarily adjusted by changing the hydrogen pressure, reaction temperature, reaction time, catalyst concentration and the like. The hydrogenation rate is 90% or more, preferably 95% or more, more preferably 99% or more. When the hydrogenation rate is low, the stability against air oxidation is not sufficient, and it is difficult to maintain the colorless transparency required for optical materials. However, as compared with a resin having a linear addition type repeating unit of DCPs instead of CPDs, the double bond at a position close to the main chain is saturated by hydrogenation, and thus the effect of hydrogenation is large.

Usually, the repeating units derived from the amount of monomers other than CPDs are hydrogenated in the same proportion as the linear addition type repeating units of CPDs. However, if a phenyl group is present, it can be selectively left unhydrogenated. Therefore, the hydrogenation rate of only the phenyl group does not necessarily match the above hydrogenation rate.

The molecular weight range of the hydrogenated CPD resin of the present invention is such that the intrinsic viscosity [η] measured in toluene at 25 ° C. is 0.1 to 10 dl / g, preferably 0.2 to 5 dl / g.
g, and more preferably 0.3 to 2 dl / g. If the intrinsic viscosity is too small, the mechanical strength of the molded product will decrease,
If the intrinsic viscosity is too large, the melt viscosity will be high and molding will be difficult.

The hydrogenated CPD resin of the present invention is excellent in amorphousness, transparency, low birefringence and electric insulation, and is usually 7
It has a glass transition temperature (hereinafter referred to as Tg) of 0 ° C. or higher, low hygroscopicity, and mechanical toughness.

(Molding) The hydrogenated CPD resin of the present invention is prepared by a known method such as injection molding, extrusion molding, or the like.
It can be molded by compression molding, cast molding, inflation molding, blow molding, and the like.

(Additives) If desired, various additives may be added to the hydrogenated CPD-based polymer 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. For the purpose of improving moldability and 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) ethylpropionate] methane, 2,6-
In addition to antioxidants such as di-t-butyl-4-methylphenol; and others, light stabilizers, ultraviolet absorbers, antistatic agents,
Lubricants, flame retardants, pigments, dyes, antiblocking agents and the like may be added. In general, in order to avoid elution from the CPD-based addition-type polymer hydrogenated product, it is preferable that these additives have a large molecular weight, and a smaller addition amount is more 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, and the like can be used as a coating leveling agent, and among them, those having good compatibility with a solvent are preferable.

When the additive is added to the thermoplastic resin 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 2 mm is used, and
It is usually 40% or more, preferably 50% or more, more preferably 60% or more when measured in the range of 0 to 700 nm. Similarly, the light transmittance when used as an optical material is usually 80% or more, preferably 85% or more, and 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.

(Use) The hydrogenated CPD resin 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, device parts, housings, bumpers, room mirrors,
It can be used for various applications such as headlamp covers, tail lamp covers, instrument panels and other automotive equipment; speaker cone materials, speaker vibration elements, microwave oven containers and other electrical equipment materials, films, sheets, helmets and the like.

(Optical Material) The hydrogenated CPD resin of the present invention has transparency, low birefringence, a glass transition temperature of 70 ° C. or higher (hereinafter referred to as Tg), low hygroscopicity, and mechanical toughness. Since it also has properties, it is useful as an optical material such as an optical disk, an optical lens, an optical card, an optical fiber, an optical mirror, a liquid crystal display element substrate, a light guide plate, a polarizing film, and a retardation film.

(Medical Equipment) The hydrogenated CPD resin of the present invention is a chemical, particularly a chemical having a polar group such as alcohols, amines, esters, amides, ethers, carboxylic acids and amino acids. Since it is less adsorbed and the organic substances contained as impurities in the resin rarely 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 instruments such as syringes; Sterile containers such as medical instruments such as scalpels, forceps, gauze and contact lenses; Beakers, Experimental / analytical instruments such as petri dishes, flasks, test tubes, and centrifuge tubes; medical optical components such as plastic lenses for medical examinations; medical infusion tubes, piping, joints, valves, and other piping materials; denture bases, artificial hearts, artificial constructions Artificial organs such as tooth roots and parts thereof;
Are exemplified. In particular, in the case of drug bottles, prefilled syringes, sealed drug bags, eye drop containers, ampoules, vials, eye drop containers, etc. for storing drugs, especially liquid drugs for a long period of time, compared to conventional resin products. In addition to transparency, physical properties, etc., there are no impurities, etc. eluting from the resin, excellent chemical resistance, and since it does not adsorb chemicals, it has the favorable properties of little deterioration of chemicals.

(Equipment for electronic component processing) The CPD polymer hydrogenated product of the present invention is substantially free of impurities eluted from the resin in addition to physical properties, and is used for electronic component processing. Since it has resistance to many of the chemicals used, especially most of strong acids except sulfuric acid, it has preferable properties as a device for treating 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, bottles, ampoules, bags, and other liquid containers; Can be mentioned.

(Electrical Insulation Material) The CPD polymer hydrogenated product of the present invention is useful in a wide variety of fields as an electrical insulation material. For example, coating materials for electric wires / cables, general-purpose insulating materials for consumer / industrial electronic devices, copiers / computers / printers, office automation equipment, instruments, etc .; rigid printed boards, flexible printed boards, multilayer printed wiring boards, etc. Circuit board, especially high frequency circuit board for satellite communication equipment that requires high frequency characteristics; transparent conductive film substrate for liquid crystal substrate, optical memory, surface heating element such as defroster of automobiles and aircraft, transistor, etc. IC encapsulation materials such as LSI, LED, and parts;
Encapsulation materials for electric and electronic parts such as motors, contactors, switches and sensors; body materials for TVs and video cameras; parabolic antennas, flat antennas, etc.
It can be preferably used as a structural member of a radar dome.

[0046]

EXAMPLES The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. In the examples, the number average molecular weight was determined by gel permeation chromatography using toluene as a solvent, and the intrinsic viscosity was 25 ° C.
The glass transition temperature in toluene of
The retardation value was measured by the double pass method with a wavelength of 830 nm. The proportion of the repeating unit represented by the general formula 1 in the addition-type polymerization repeating unit of CPDs is As.
o, C.I. , Et al. , J. Polymer S
ci. , Part B4, 701 (1966).

Reference Example 1 CPD (10 parts) and toluene (90 parts) were placed in a nitrogen-purged glass reaction container and cooled to 0 ° C. While stirring, 1 part by weight of a 20% by weight boron trifluoride diethyl ether complex toluene solution was added, and the mixture was allowed to react at 0 ° C. for 5 hours. The reaction solution was added to 500 parts by weight of isopropyl alcohol while stirring, and the precipitated polymerization mixture was collected, and 1 to
After drying for 24 hours under a reduced pressure of rr or less, 65 parts by weight of a colorless resin was obtained. The intrinsic viscosity of this resin is 0.52 dl / g
Met. In addition, from the infrared spectrum, it has the same skeletal structure as a known CPD polymer (polymer chemistry, 19 , 734, 1962) with an intrinsic viscosity [η] of 0.06 dl / g, and the linear CPD It was found to be a polymer composed of addition-type polymerization repeating units. In addition, in the infrared spectroscopy spectrum, at 3040 cm ⁻¹ , H—C = bond, 75
Strong absorption based on C = C bond was observed at 0 cm ^{-1, 1}
H-NMR (chloroform-d ₁ in 30 ° C.) 5.
Absorption based on an unsaturated carbon-bonded proton of the —HC═CH— group at 6 ppm and a saturated carbon-bonded proton at 1-3 ppm was observed at an intensity ratio of 2: 4. Also, 1.
3 to 1.8 ppm, 1.8 to 2.2 ppm, 2.2
The absorption at 3.0 ppm was 31.9: 18.8: 49.3, and the ratio of the repeating unit represented by the general formula 1 in the linear addition-type polymerization repeating unit of CPDs was 57% by weight. It was

Example 1 30 parts by weight of the resin obtained in Reference Example 1 was added to 70 parts by weight of cyclohexane.
Dissolve in a certain amount
0.35 parts by weight of nickel in 1 part by weight, nickel oxide
0.2 parts by weight, pore volume 0.8 cm³/ G, specific surface area 3
00m²/ G) 1 part by weight and isopropyl alcohol double
Add parts by weight, and in an autoclave, 230 ℃, hydrogen pressure 50
kg / cm²And reacted for 5 hours. After the reaction is complete, filter
Therefore, the nickel catalyst was removed and the reaction solution was added to 500 parts by weight.
Add to isopropyl alcohol with stirring to precipitate
The polymer was collected by filtration, and the polymer was removed under reduced pressure below 1 torr for 24 hours.
After drying for 27 hours, 27 parts by weight of a colorless resin was obtained. Infrared spectroscopy
3040 cm in the spectrum^-1 , 750cm^-1Absorption of
Completely disappeared,¹H-NMR peak at 5.6 ppm
Disappears completely and the hydrogenation rate is almost 100%
It was confirmed. Intrinsic viscosity is 0.52dl / g, glass transition
The temperature was 79 ° C.

This resin was press-molded at 180 ° C. to prepare a flat plate having a thickness of 2 mm and a diameter of 86 mm. The plate is colorless and transparent, and the light transmittance is 90.90 at a wavelength of 400 to 830 nm.
It was 2% or more and the retardation value was 20 nm or less.
Also, this resin is press-molded at 180 ° C. to obtain a thickness of 1.2.
A disk having a diameter of 12.5 cm and a diameter of 12.5 cm was prepared. When measured using this disc, the volume resistivity of the resin is 5 × 1.
0 ¹⁶ Ωcm or more, 10 ² Hz, 10 ⁶ Hz, 10 ⁹
The dielectric constant and the dielectric loss tangent were 2.34 and 5 × 10 ⁻⁴ at each frequency of Hz.

Reference Example 2 Boron trifluoride diethyl ether complex 20 wt% Tungsten hexachloride 1 wt% instead of 1 part by weight toluene solution
A colorless resin (85 parts by weight) was obtained in the same manner as in Reference Example 1 except that 5 parts by weight of the toluene solution was used. Intrinsic viscosity is 0.78
dl / g, the infrared spectrum, H-C = bond to 3040cm ^-1, strong absorption was observed based on the C = C bond to 750 cm ^-1, in ¹ H-NMR (chloroform -d _1,
At 30 ° C., absorption based on a proton bonded to unsaturated carbon of —HC═CH— group at 5.6 ppm and a proton bonded to saturated carbon at 1 to 3 ppm was observed at an intensity ratio of 2: 4. In addition, 1.3 to 1.8 ppm, 1.8 to 2.2 p
pm, the absorption at 2.2 to 3.0 ppm is 26.6: 23.
It was 8: 49.6, and the repeating unit represented by the general formula 1 in the linear addition polymerization repeating unit of CPDs was 53% by weight.

Example 2 25 parts by weight of a colorless resin was obtained in the same manner as in Example 1 except that the resin obtained in Reference Example 2 was used instead of the resin obtained in Reference Example 1. In the infrared spectrum, absorptions at 3040 cm ^-1 and 750 cm ^-1 disappeared completely, and ¹ H-NMR
Also in the spectrum, it was confirmed that the absorption at 5.6 ppm disappeared completely and the hydrogenation rate was almost 100%. The intrinsic viscosity was 0.76 dl / g and the glass transition temperature was 81 ° C.

Furthermore, the hydrogenated CPD resin 10% by weight cyclohexane solution was analyzed by atomic absorption spectrometry. As a result, the atomic weight of tungsten in the resin was 0.05 ppm.
Below the detection limit, the atomic weight of nickel is 0.01 ppm
(Detection limit) or less. Also, this hydrogenated CPD
Burn 100mg of resin with a Dorman burner for 5m
As a result of absorption in 1 l of pure water and analysis by ion chromatography, the amount of chlorine atoms was 0.02 ppm (detection limit) or less.

0.008 parts by weight of an antioxidant (Irganox 1010, manufactured by Ciba-Geigy) was added to 17 parts by weight of this hydrogenated CPD resin, and a twin-screw extruder (TEM-35B, manufactured by Toshiba Machine Co., screw diameter) was added. 37 mm, L / D
= 32, screw rotation speed 250 rpm, resin temperature 21
It was extruded at 5 ° C. and a feed rate of 10 kg / hour) to obtain pellets.

Injection molding (molding pressure 350 tons, resin temperature 225 ° C., mold temperature 70 ° C.) using these pellets
, Diameter 200mm, height 130mm, average thickness 3mm
A cylindrical transparent container and a test piece having a thickness of 2 mm and a diameter of 86 mm were prepared.

The test piece having a thickness of 2 mm was colorless and transparent, and had a light transmittance of 90.3% or more at a wavelength of 400 to 830 nm,
The retardation value was 20 nm or less, and the turbidity was 0.1%.

2% by weight of agar was added to LB medium (1% by weight of bactotryptone, 0.5% by weight of yeast extract, 1% by weight of NaCl, 0.1% by weight of glucose was adjusted to pH 7.5). Sterilize by steam sterilization at 121 ° C for 30 minutes to gel it,
After putting ml into a molded container and leaving it at room temperature for 6 hours,
It was capped with aluminum foil and sterilized by irradiating with γ rays at 25 kGy. After the treatment, the temperature was kept at 37 ° C for 3 days, but no fungal growth was observed. Moreover, the appearance of the transparent container after the treatment was good, and no cloudiness, cracking, or deformation was visually confirmed.

Further, the test piece was immersed in a sodium carbonate aqueous solution having a pH of 9, a hydrochloric acid having a pH of 4 and ethanol for 48 hours and then the appearance was observed, but no change was observed, and neither turbidity nor light transmittance was changed.

This test piece was cut into a width of 10 mm, 20 g was ultrasonically washed in distilled water for 20 minutes, and then dried at 40 ° C. for 10 hours. This 20-g test piece was put into a hard glass flask, and 200 g of distilled water was added. A lid made of hard glass was placed and the mixture was allowed to stand at 50 ° C. for 24 hours to collect distilled water.

As a control, 200 g of distilled water was put into a hard glass flask, and a lid made of hard glass was added.
It was left still at 24 ° C for 24 hours.

The elution amount from the test piece was obtained from the difference in the analysis results by the atomic absorption method of these two kinds of distilled water, the ion chromatography, the combustion-non-dispersive infrared gas analysis method, etc., and the tungsten atom elution amount was obtained. Is 0.05 ppm
Below the detection limit, the elution amount of nickel atoms is 0.01 pp
m (detection limit) or less, chlorine atom elution amount is 0.02 ppm
Below the (detection limit), the total amount of organic carbon was below 2 ppm (detection limit).

The test pieces were subjected to an eluate test according to the 12th revision of the Japanese Pharmacopoeia “Plastic Test Method for Infusion Solution”. Effervescence disappears within 3 minutes, pH difference is -0.02, UV absorption is 0.005, potassium permanganate reducing substance 0.13 ml, and it has suitable properties for medical use. Do you get it.

Reference Example 3 90 parts by weight of CPD, 10 parts by weight of α-methylstyrene, 300 parts by weight of toluene and 100 parts by weight of nitromethane were placed in a reactor purged with nitrogen and cooled to 0 ° C. While stirring, Pd (CH ₃ CN) ₄ (BF ₄ ) ₂ with a concentration of 1.0% by weight
64 parts by weight of a nitromethane solution of
The reaction was carried out for 2 hours while maintaining the temperature at ℃. The reaction solution was poured into 1500 parts by weight of methanol mixed with 50 parts by weight of concentrated hydrochloric acid while stirring, and the precipitated polymer was collected by filtration, washed with 300 parts by weight of methanol, and then dried at 50 ° C. under reduced pressure of 1 torr or less. After drying for 24 hours, 68 parts by weight of a colorless polymer was obtained.

The intrinsic viscosity of this polymer is 0.47 dl /
It was g. H-C = bond to 3040cm ^-1 in infrared spectrum, -C to 750 cm ^-1 = C-bond, 695
The absorption based on the phenyl group was observed at cm ⁻¹ , and ¹ H—N
In the MR spectrum, the absorption ratio based on the proton of the phenyl group at 6.4 to 7.1 ppm, the proton bound to the unsaturated carbon at 5.6 ppm, and the proton bound to the saturated carbon at 1 to 3 ppm has an intensity ratio of 4:30:66. Was observed in. ¹ H
From the NMR intensity ratio, the composition ratio of CPD and α-methylstyrene was calculated to be 95: 5 in terms of molar ratio. Also, 1.3-
1.8 ppm, 1.8 to 2.2 ppm, 2.2 to 3.0
The ppm absorption is 23.5: 13.7: 62.8,
The repeating unit represented by the general formula 1 in the linear addition polymerization repeating unit of CPDs was 47% by weight.

Example 3 60 parts by weight of the polymer obtained in Reference Example 3 was added to cyclohexane 54
Dissolved in 0 parts by weight, and further supported palladium catalyst on alumina (E4L1, manufactured by JGC Chemical Co., palladium loading 3% by weight)
3 parts by weight and 10 parts by weight of isopropyl alcohol were added, and the mixture was autoclaved at 140 ° C. and hydrogen pressure was 50 kg / c.
The reaction was carried out at m ² for 5 hours. After completion of the reaction, the palladium catalyst was removed by filtration, the reaction solution was poured into 1900 parts by weight of methanol with stirring, and the precipitated polymer was filtered and collected. 24 at 50 ° C under reduced pressure of 1 Torr or less
After drying for 55 hours, 55 parts by weight of a colorless polymer was obtained.

The intrinsic viscosity was 0.47 dl / g and the glass transition temperature was 89 ° C. 304 in the infrared spectrum
0 cm ^-1, the absorption of 750 cm ^-1 and 695cm ^-1 disappeared completely, even in the ¹ H-NMR spectrum from 6.4 to 7.
Absorption at 1 ppm and 5.6 ppm disappeared completely, and both the phenyl group and the unsaturated group of the cyclopentene ring were almost 1
It was confirmed that it was hydrogenated with 100%.

This polymer was press-molded at 200 ° C. to prepare a flat plate having a thickness of 2 mm and a diameter of 86 mm, and a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. A flat plate having a thickness of 2 mm is colorless and transparent and has a toughness, and has a light transmittance of 400 to 830.
nm is 90.4% or more, retardation value is 20 nm
It was below. The volume resistivity of this resin measured using a 1.2 mm thick disk is 5 × 10 ¹⁶ Ωcm or more, and the dielectric constant is 10 ² Hz, 10 ⁶ Hz, or 10 ⁹ Hz at any frequency. 2.33, dielectric loss tangent is also 10 ² H
It was 5 × 10 ⁻⁴ at any frequency of z, 10 ⁶ Hz, and 10 ⁹ Hz.

Example 4 78 parts by weight of a polymer was obtained in the same manner as in Example 3 except that 60 parts by weight of CPD and 40 parts by weight of styrene were used instead of 90 parts by weight of CPD and 10 parts by weight of α-methylstyrene.

The intrinsic viscosity of this polymer is 0.55 dl /
It was g. -C on H-C = bond and 750 cm ^-1 to 3040cm ^-1 in infrared spectrum = C- bond, 6
Absorption based on a phenyl group is observed at 95cm ^{-1, 1} H
-In the NMR spectrum, the absorption based on the proton of the phenyl group at 6.4 to 7.1 ppm, the proton bound to the unsaturated carbon at 5.6 ppm, and the proton bound to the saturated carbon at 1 to 3 ppm has an intensity of 26:20:54. The ratio was observed. ^{From the 1} H-NMR intensity ratio, the composition ratio of CPD and styrene was calculated to be 65:35 in terms of molar ratio.

70 parts by weight of this polymer was added to cyclohexane 6
It was dissolved in 30 parts by weight, 3.5 parts by weight of the alumina-supported nickel catalyst used in Example 1 and 10 parts by weight of isopropyl alcohol were further added, and 230 parts in an autoclave were added.
The reaction was carried out at 50 ° C. and hydrogen pressure of 50 kg / cm ² for 5 hours. After completion of the reaction, the nickel catalyst was removed by filtration, and the reaction solution was poured into 2200 parts by weight of methanol while stirring,
The precipitated polymer was filtered and collected. 1 torr at 50 ° C
It was dried under reduced pressure for 24 hours to obtain 64 parts by weight of a colorless polymer.

The intrinsic viscosity was 0.54 dl / g and the glass transition temperature was 98 ° C. 304 in the infrared spectrum
0 cm ^-1, the absorption of 760 cm ^-1 and 695cm ^-1 disappeared completely, even in the ¹ H-NMR spectrum from 6.4 to 7.
Absorption at 1 ppm and 5.6 ppm disappeared completely, and both the phenyl group and the unsaturated group of the cyclopentene ring were almost 1
It was confirmed that it was hydrogenated with 100%.

This polymer was press-molded at 200 ° C. to prepare a flat plate having a thickness of 2 mm and a diameter of 86 mm and a disk having a thickness of 1.2 mm and a diameter of 12.5 cm. A flat plate with a thickness of 2 mm is colorless and transparent and has a strong light transmittance of 400 to 830 nm.
Was 90.3% or more and the retardation value was 20 nm or less. The volume resistivity value of this resin measured using a 1.2 mm thick disk is 5 × 10 ¹⁶ Ωcm or more,
The dielectric constant is 2.31 at any frequency of 10 ² Hz, 10 ⁶ Hz, and 10 ⁹ Hz, and the dielectric loss tangent is 10 ² Hz, 1
4 × 1 at any frequency of 0 ⁶ Hz and 10 ⁹ Hz
It was ^0-4 .

Example 5 Example 3 was repeated except that 50 parts by weight of CPD, 20 parts by weight of a 50% by weight solution of isobutylene in toluene and 40 parts by weight of styrene were used instead of 90 parts by weight of CPD and 10 parts by weight of α-methylstyrene. In the same manner, 69 parts of a polymer was obtained.

The intrinsic viscosity of this polymer is 0.53 dl /
It was g. -C on H-C = bond and 750 cm ^-1 to 3040cm ^-1 in infrared spectrum = C- bond, 6
Absorption based on a phenyl group is observed at 95cm ^{-1, 1} H
-In the NMR spectrum, the absorption based on the proton of the phenyl group at 6.4 to 7.1 ppm, the proton bound to the unsaturated carbon at 5.6 ppm and the proton bound to the saturated carbon at 1 to 3 ppm has an intensity of 20:17:63. The ratio was observed. ^{From the 1} H-NMR intensity ratio, the molar ratio of CPD to isobutylene and styrene was calculated to be 57:15:27.

60 parts by weight of this polymer was added to cyclohexane 5
After dissolving in 40 parts by weight, 3.0 parts by weight of the alumina-supported nickel catalyst used in Example 1 and 10 parts by weight of isopropyl alcohol were added, and hydrogenated in the same manner as in Example 4 to obtain 56 parts by weight of a polymer. .

The intrinsic viscosity was 0.51 dl / g and the glass transition temperature was 84 ° C. 304 in the infrared spectrum
0 cm ^-1, the absorption of 760 cm ^-1 and 695cm ^-1 disappeared completely, even in the ¹ H-NMR spectrum from 6.4 to 7.
Absorption at 1 ppm and 5.6 ppm disappeared completely, and both the phenyl group and the unsaturated group of the cyclopentene ring were almost 1
It was confirmed that it was hydrogenated with 100%.

This polymer was press-molded at 200 ° C. to prepare a flat plate having a thickness of 2 mm and a diameter of 86 mm. The plate is colorless and transparent and tough, and has a light transmittance of 400 to 830 nm of 9
It was 0.5% or more and the retardation value was 20 nm or less.

Example 6 54 parts by weight of a polymer was obtained in the same manner as in Example 3 except that 90 parts by weight of CPD and 10 parts by weight of α-methylstyrene were used instead of 90 parts by weight of CPD and 10 parts by weight of dipentene.

The intrinsic viscosity of this polymer is 0.31 dl /
It was g. The infrared spectrum based on -C = C-bond to the H-C = bond and 750 cm ^-1 to 3040cm ^-1 absorption was observed, 5 in ¹ H-NMR spectrum.
Proton bound to unsaturated carbon at 6 ppm, 1-3 pp
The absorption based on the proton bound to the saturated carbon at m is 29:
An intensity ratio of 71 was observed. ^{From the 1} H-NMR intensity ratio, the composition ratio of CPD and dipentene was calculated to be 95: 5 in molar ratio.

50 parts by weight of this polymer was added to cyclohexane 5
It was dissolved in 40 parts by weight, 3.0 parts by weight of the alumina-supported nickel catalyst used in Example 1 and 10 parts by weight of isopropyl alcohol were added, and hydrogenated in the same manner as in Example 4 to obtain 43 parts by weight of a polymer. .

The intrinsic viscosity was 0.31 dl / g and the glass transition temperature was 87 ° C. 304 in the infrared spectrum
Absorption of 0 cm ^-1 and 760 cm ^-1 had completely disappeared, ¹
Also in the 1 H-NMR spectrum, the absorption at 5.6 ppm disappeared completely, and it was confirmed that almost 100% of both the unsaturated group of the cyclopentene ring and the unsaturated group of the cyclohexene ring were hydrogenated.

This polymer was press-molded at 200 ° C. to prepare a flat plate having a thickness of 2 mm and a diameter of 86 mm. The plate is colorless and transparent and tough, and the light transmittance is 400 to 830 nm.
90.5% or more and the retardation value was 20 nm or less.

Example 7 Polymer 69 was used in the same manner as in Example 3 except that 50 parts by weight of CPD and 50 parts by weight of norbornene were used instead of 90 parts by weight of CPD and 10 parts by weight of α-methylstyrene.
A polymerized part was obtained.

The intrinsic viscosity of this polymer is 0.46 dl /
It was g. The infrared spectrum based on -C = C-bond to the H-C = bond and 750 cm ^-1 to 3040cm ^-1 absorption was observed, 5 in ¹ H-NMR spectrum.
Proton bound to unsaturated carbon at 6 ppm, 1-3 pp
Absorption based on protons bound to saturated carbon at m is 18:
An intensity ratio of 82 was observed. ^{From the 1} H-NMR intensity ratio, the composition ratio of CPD and dipentene was calculated to be 66:34 in molar ratio.

60 parts by weight of this polymer was added to cyclohexane 5
After dissolving in 40 parts by weight, 3.0 parts by weight of the alumina-supported nickel catalyst used in Example 1 and 10 parts by weight of isopropyl alcohol were added, and hydrogenated in the same manner as in Example 4 to obtain 56 parts by weight of a polymer. .

The intrinsic viscosity was 0.46 dl / g and the glass transition temperature was 165 ° C. 30 in the infrared spectrum
The absorption at 40 cm ^-1 and 760 cm ^-1 has completely disappeared,
^{Also in 1} H-NMR spectrum, the absorption at 5.6 ppm disappeared completely, and the unsaturated group in the cyclopentene ring was almost 100%.
It was confirmed that hydrogen was added.

This polymer was press-molded at 200 ° C. to prepare a flat plate having a thickness of 2 mm and a diameter of 86 mm and a disc having a thickness of 1.2 mm and a diameter of 12.5 cm. A flat plate having a thickness of 2 mm is colorless and transparent and has a toughness, and has a light transmittance of 400 to 830.
90.5% or more in nm, retardation value is 20 nm
It was below. The volume resistivity of this resin measured using a 1.2 mm thick disk is 5 × 10 ¹⁶ Ωcm or more, and the dielectric constant is 10 ² Hz, 10 ⁶ Hz, or 10 ⁹ Hz at any frequency. 2.33, dielectric loss tangent is also 10 ² H
It was 4 × 10 ⁻⁴ at any frequency of z, 10 ⁶ Hz, and 10 ⁹ Hz.

Example 8 60 parts by weight of CPD and α were placed in a glass reaction vessel replaced with nitrogen.
-Methylstyrene 40 parts by weight and toluene 900 parts by weight were charged and cooled to -78 ° C. While stirring, 10 parts by weight of a 20% by weight toluene solution of boron trifluoride diethyl ether complex was added, and the reaction was allowed to proceed at −75 ° C. or lower for 5 hours. The reaction solution was added to 5000 parts by weight of isopropyl alcohol with stirring, the precipitated polymer was collected by filtration, dried under reduced pressure of 1 mmHg or less for 24 hours, and 83 parts by weight of a colorless CPD linear addition polymer. Got

The intrinsic viscosity of this polymer measured at 25 ° C. in toluene was 0.37 dl / g. In the infrared spectrum, H—C = bond at 3040 cm ⁻¹ , and 75
0 cm ^-1 to -C = C-bond, absorption based on a phenyl group was observed in 695cm ^{-1. In the 1} H-NMR spectrum, the proton of the phenyl group is present at 6.4 to 7.1 ppm.
Proton bound to unsaturated carbon at 5.6 ppm, 1-3
A peak based on protons bound to saturated carbon at ppm was observed at an intensity ratio of 28:14:57. 1H-NMR
From the intensity ratio of the spectrum, the composition ratio of CPD and styrene was calculated to be 65:35 in terms of molar ratio.

Hydrogenation was carried out in the same manner as in Example 1 except that this polymer was used instead of the polymer obtained in Reference Example 1 to obtain 29 parts by weight of a colorless hydrogenated product.

3040 cm of infrared spectrum^-1,
750 cm^-1, And 695 cm^-1 Absorption of 1H-N
6.4 to 7.1 ppm and 5.6 in the MR spectrum
Since the ppm peak has completely disappeared, this water
Confirm that the hydrogenation rate of the elementary additive is 100%
It was Intrinsic viscosity measured in toluene at 25 ° C is 0.38
The dl / g and Tg were 122 ° C.

When the hydrogenated product of the CPD-based addition polymer was dissolved in cyclohexane and analyzed, the boron atomic weight was 0.5 ppm (detection limit) or less, the nickel atomic weight was 0.01 ppm (detection limit) or less, The chlorine atom amount was 0.02 ppm (detection limit) or less.

The CPD-based addition type polymer hydrogenated product was
Pelletization was performed in the same manner as in Reference Example 3 except that the resin temperature was 260 ° C.

Injection molding (molding pressure 350 tons, resin temperature 265 ° C., mold temperature 100 ° C.) using these pellets
However, as in Example 2, a cylindrical transparent container and a thickness of 2 m
A test piece having a diameter of m and a diameter of 86 mm was prepared.

When the light transmittance of the test piece was measured, the transparency was good at a wavelength of 400 to 830 nm of 90.7% or more. The turbidity was measured and found to be 0.08%.

As in Example 1, 300 ml of LB medium containing 2% by weight of agar was placed in a molded container, one test piece was further placed therein, and then capped with aluminum foil.
Steam sterilization was performed at 30 ° C. for 30 minutes.

After the treatment, the temperature was kept at 37 ° C. for 3 days, but no fungal growth was observed. The appearance of the transparent container after the treatment was good, and no turbidity, cracking, or deformation due to heat was visually confirmed.

The turbidity measured after removing the LB medium solidified with agar from the test piece taken out from the container was 0.1.
%, And the total light transmittance was 89.8%.

Further, even after the test piece was immersed in a sodium carbonate aqueous solution having a pH of 9, a hydrochloric acid having a pH of 4, and ethanol for 48 hours, there was no change in the appearance, and there was no change in the turbidity and the light transmittance.

A test piece was cut into a 10 mm width, 20 g of which was ultrasonically washed in distilled water for 20 minutes and then dried at 40 ° C. for 10 hours. This 20-g test piece was put into a hard glass flask, and 200 g of distilled water was added. A hard glass lid was used, steam sterilization was performed at 120 ° C. for 1 hour, the mixture was cooled to room temperature, and then allowed to stand for 24 hours to collect distilled water.

As a control, 200 g of distilled water was placed in a hard glass flask, and a hard glass lid was placed on the flask.
It was sterilized by steam at 0 ° C for 1 hour, cooled to room temperature, and allowed to stand for 24 hours to collect distilled water.

The amount of elution from the test piece was determined from the difference between the analytical results of these two kinds of distilled water. As a result, the amount of boron atom elution was 0.5 ppm (detection limit) or less, and the amount of nickel atom elution was 0.01 ppm ( Detection limit) or less, chlorine atom elution amount is 0.02 ppm (detection limit) or less, total organic carbon amount is 2 p
It was below pm (detection limit).

In the same manner as in Example 1, an eluate test was conducted according to the Japanese Pharmacopoeia. Effervescence disappeared within 3 minutes, pH difference was -0.03, ultraviolet absorption was 0.006, and potassium permanganate reducing substance was 0.13 ml.

Comparative Example 1 60 parts by weight of the CPD polymer obtained in the same manner as in Reference Example 1 was dissolved in 540 parts by weight of cyclohexane, 6 parts by weight of the same palladium catalyst as used in Example 3 was added, and 90 ° C.
The reaction was carried out at a hydrogen pressure of 50 kg / cm ² for 15 hours. The hydrogenated polymer was recovered in the same manner as in Example 3 to obtain 53 parts by weight of the polymer.

The intrinsic viscosity was 0.53 dl / g and the glass transition temperature was 80 ° C. 3040 in infrared spectroscopy
absorption of cm ^-1 and 760 cm ^-1 are not lost but are strength reduction, 5.6 ppm in ¹ H-NMR spectrum
Absorption of 5.6ppm and 1-3p
The absorption intensity ratio of pm was observed at an intensity ratio of 5:95, and the hydrogenation rate was 81%.

This hydrogenated CPD resin was attempted to be pelletized in the same manner as in Example 2, but the coloring and burning were severe,
Could not be pelletized.

This polymer was press-molded at 180 ° C. to prepare a flat plate having a thickness of 2 mm and a diameter of 86 mm. Although the plate was tough, it was colored yellow and the outer periphery was strongly colored. The light transmittance of the relatively light-colored portion on the inner circumference is 89.
0% and the retardation value was 28 nm or less. When this molded plate was left to stand at room temperature in the air for 3 weeks, its toughness decreased and it became brittle.

Comparative Example 2 Chloroform 9 was used instead of 90 parts by weight of toluene of Reference Example 1.
0 parts by weight, boron trifluoride diethyl ether complex 20% by weight Toluene solution 1 part by weight Instead of titanium tetrachloride 10 parts
7.1 parts by weight of a CPD polymer was obtained in the same manner as in Reference Example 1 except that 2.5 parts by weight of a wt% toluene solution was used. The intrinsic viscosity of this polymer was 0.07 dl / g. The infrared spectrum observed H-C = bond and -C to 750 cm ^-1 = C-based binding absorbed 3040cm ^-1, the proton in the ¹ H-NMR spectrum attached to an unsaturated carbon in 5.6 ppm, Absorption based on protons bound to saturated carbon at 1-3 ppm was observed at an intensity ratio of 2: 4.

Hydrogenation was carried out in the same manner as in Example 1 except that this polymer was used instead of the polymer obtained in Reference Example 1.
7 parts by weight of hydrogenated polymer was obtained.

The intrinsic viscosity was 0.07 dl / g and the glass transition temperature was 78 ° C. 3040 in infrared spectroscopy
absorption of cm ^-1 and 760 cm ^-1 had completely disappeared, ¹ H
-In the NMR spectrum as well, the absorption at 5.6 ppm was completely disappeared, and it was confirmed that the unsaturated group of the cyclopentene ring was almost 100% hydrogenated. 180 this polymer
Attempting to form a flat plate having a thickness of 2 mm and a diameter of 86 mm by press molding at ℃, it was very brittle and it was difficult to make a plate.

[0110]

EFFECTS OF THE INVENTION The hydrogenated CPD resin of the present invention does not contain a cross-linked gelled product, and has transparency, low birefringence, light resistance, moisture resistance, chemical resistance, molding processability, electrical insulation, It has excellent mechanical strength and is suitable for optical materials, electrical insulation materials, electronic component processing equipment, and medical equipment.

Claims (6)

[Claims] 1. A polymer mainly composed of linear addition type repeating units of cyclopentadiene obtained by hydrogenating at least 90% or more of the repeating units at 25 ° C.,
Intrinsic viscosity [η] measured in toluene is 0.1-10d
A hydrogenated cyclopentadiene-based copolymer resin, which is 1 / g. 2. A hydrogenated cyclopentadiene-based resin according to claim 1, wherein a polymer containing a linear addition-type polymerization repeating unit of cyclopentadiene as a main component is subjected to a hydrogenation reaction at 100 ° C. or higher. Method. 3. An optical material comprising the hydrogenated cyclopentadiene-based resin according to claim 1. 4. A medical device comprising the hydrogenated cyclopentadiene resin according to claim 1. 5. An electrical insulating material comprising the hydrogenated cyclopentadiene resin according to claim 1. 6. A device for processing electronic parts, which comprises the hydrogenated cyclopentadiene-based resin according to claim 1.