JP3360335B2 - Molding material composed of vinylated cyclic hydrocarbon polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material comprising a vinylated saturated cyclic hydrocarbon polymer and its use, and more particularly to a vinylated saturated cyclic hydrocarbon polymer having a low molecular weight content and a low transition metal atomic weight. The present invention relates to a molding material comprising: a medical device which does not degrade a contacting agent; an electrical insulating material having excellent electrical insulation and high-frequency characteristics; and a device for processing electronic components having excellent heat resistance and chemical resistance.

[0002]

2. Description of the Related Art Medical devices have recently been replaced with disposable devices in order to prevent secondary infection with viruses due to repeated use. Also, injections, etc.
In the past, pre-filled syringes, which had previously inhaled the injection drug in the syringe, were circulated, and the syringe after the injection was discarded. It became so.

[0003] Medical drug containers require a certain degree of transparency so that the contents can be easily viewed. Therefore, glass, polyethylene, polypropylene, polyvinyl chloride, and the like have been conventionally used. However, the glass may be broken, heavy, and alkali ions and the like are easily eluted, the shards are dangerous, and it is difficult to burn. Therefore, it is difficult to dispose the glass. Also, from polyethylene, polypropylene, etc.,
In some cases, low-molecular-weight organic components were eluted, and chlorine was eluted from polyvinyl chloride, and the contents were sometimes altered.

As an electrical insulating material, polyolefin resins such as polyvinyl chloride, polyethylene, and polystyrene have been widely used. These have excellent electrical properties such as high insulation resistance, high dielectric breakdown voltage, low dielectric constant, low water absorption, chemical resistance, etc., but have insufficient heat resistance, and under severe conditions I can not use it. In addition, polystyrene is inferior in arc resistance and tracking resistance, and furthermore, the difference between the melting point and the pyrolysis onset temperature is small. was there.

[0005] Polyethylene terephthalate is widely used as an electrical insulating material having excellent electrical properties, mechanical strength, transparency and the like. There is a problem such as large.

Further, as insulating materials used for composite materials such as printed boards, laminated boards, and conductive films, resins, epoxy resins, and polyimides having excellent heat resistance, such as polysulfone and polyethersulfone, have been used. However, these are all water-absorbing, in applications that need to go through processes such as vacuum evaporation and sputtering when combined with a conductive layer, in those processes, due to moisture in the resin, There is a problem that it takes a long time to raise the degree of vacuum to the required degree of vacuum and productivity is deteriorated. In addition, epoxy resin and polyimide are not suitable for use in high frequency applications because their dielectric constant and dielectric loss are too large.

Metals such as brass and fluororesins such as polypropylene, polytetrafluoroethylene and perfluoroalkoxy fluororesins are used in equipment for processing electronic components such as wafer carriers. However, those made of metal are too heavy, and have no resistance to acids used for processing electronic components.Polypropylene has poor dimensional accuracy, and polytetrafluoroethylene cannot be injection-molded and has poor productivity because it is machined out. , Poor dimensional accuracy,
The perfluoroalkoxy fluororesin has a large molding shrinkage, poor dimensional accuracy, and difficulty in synthesizing the resin.

Recently, it has been disclosed in Japanese Patent Application Laid-Open No. 63-4391 that vinylcyclohexane-based polymers can be used as optical materials.
No. 0, JP-A-1-132603 and the like. However, chemical resistance, low elution, electrical insulation, high frequency characteristics, and the like of vinylated cyclic hydrocarbon-based polymers including vinylcyclohexane-based polymers have not been known.

[0009]

The inventors of the present invention have conducted intensive studies and found that a vinylated cyclic hydrocarbon-based polymer or a hydrogenated product thereof has excellent chemical resistance and high-frequency electrical insulation, and has a high degree of impurity elution. The inventors have found that there is no adsorption of drug components, and have completed the present invention.

[0010]

According to the present invention, the intrinsic viscosity [η] measured in toluene at 25 ° C. is 0.1 to 20 dl / g, and the content of the resin component having a molecular weight of 2000 or less is 1% by weight. Hereinafter, 0.2 parts by weight is added to 99.8 parts by weight of a vinylated cyclic hydrocarbon-based polymer or a hydrogenated product thereof in which the residual amount of transition metal atoms derived from the polymerization catalyst is 1 ppm or less.
The present invention provides a molding material to which a rubbery polymer is added in the range of not more than 3 parts by weight.

(Vinylated Cyclic Hydrocarbon Polymer) The resin used in the present invention is a vinyl cyclic hydrocarbon polymer comprising a repeating unit represented by the following general formula 1, general formula 2, or general formula 3. is there.

General formula 1:

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General formula 2:

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General formula 3:

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The above general formula 1, general formula 2, general formula 3
In the formula, R ^{1 to} R ⁴² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ^{4 to} R ¹² , R ^{16 to} R ²⁶ ,
R ^{30 to} R ⁴² represent adjacent carbon atoms forming a ring and may form a double bond.

Examples of the vinylated cyclic hydrocarbon-based monomer used for obtaining the vinylated cyclic hydrocarbon-based polymer of the present invention include vinylcyclopentane-based monomers such as vinylcyclopentane and isopropenylcyclopentane. A vinylated five-membered hydrocarbon monomer such as a vinylcyclopentene monomer such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene;
Styrene, α-methylstyrene, 4-methylstyrene,
Styrene monomers such as 2-methylstyrene and 4-phenylstyrene, vinylcyclohexane monomers such as vinylcyclohexane and 3-methylisopropenylcyclohexane, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl- Vinylcyclohexene monomers such as 4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenylcyclohexene, d-terpenes, 1-terpenes,
Vinylated 6-membered ring hydrocarbon monomers such as terpene monomers such as diterpenes; vinylcycloheptane monomers such as vinylcycloheptane and isopropenylcycloheptane; 4-vinylcycloheptene; 4-iso Vinylated hydrocarbon monomers such as vinylcycloheptene monomers such as propenylcycloheptene; and the like. Among them, a six-membered ring hydrocarbon monomer is preferable. However, as described below, a monomer containing no aromatic ring is preferable, and when a styrene-based monomer containing an aromatic ring is used, it is preferable that the aromatic ring is not substantially left by a hydrogenation reaction. preferable.

In the present invention, a monomer other than the vinylated cyclic hydrocarbon-based monomer may be copolymerized within a range in which the repeating unit in the polymer is less than 10% by weight. Examples of copolymerizable monomers include ethylene, propylene, isobutene, 2-methyl-1-butene, and 2-methyl-1-
Α-olefin-based monomers such as pentene and 4-methyl-1-pentene; cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-
Cyclopentadiene monomers such as ethylcyclopentadiene, 5-methylcyclopentadiene, and 5,5-dimethylcyclopentadiene; cyclic olefin monomers such as cyclobutene, cyclopentene, cyclohexene and dicyclopentadiene; butadiene, isoprene;
1,3-pentadiene, furan, thiophene, 1,3-
Conjugated diene monomers such as cyclohexene; ethylene oxide, propylene oxide, trimethylene oxide, trioxane, dioxane, cyclohexene oxide, styrene oxide, epichlorohydrin,
Cyclic ether monomers such as tetrahydrofuran; heterocyclic-containing vinyl compound monomers such as methyl vinyl ether, N-vinylcarbazole and N-vinyl-2-pyrrolidone; Generally, when the content of the repeating unit derived from a monomer other than the vinylated cyclic hydrocarbon-based monomer increases, the transparency of the vinylated cyclic hydrocarbon-based polymer of the present invention decreases.

In the present invention, the catalyst used for the polymerization is
There is no particular limitation, and known cationic polymerization catalysts, living cationic polymerization catalysts, Ziegler catalysts, Kaminsky catalysts, and the like can be used. As the cationic polymerization catalyst, AlCl
₃ , AlBr ₃ , BF ₃ , BCl ₃ , BF ₃ OEt ₂ , Ti
Cl ₄ , TiBr ₄ , FeCl ₃ , FeCl ₂ , SnC
l ₄ , SnCl ₂ , TiCl ₄ / Cl ₃ CCOOH, SnC
metal halides such as l ₄ / Cl ₃ CCOOH, WCl ₆ , MoCl ₅ ; Pd (CH ₃ CN) ₂ Cl ₂ , Pd (C ₆ H
_{5 CN) 2 Cl 2, Pd} (CH 3 CN) 4 (BF 4) Pd catalyst, such as _{2; HCl, HF, H 2} SO 4, H 3 BO 3, HC
Hydrogen acids such as 10 ₄ , CF ₃ COOH, CCl ₃ COOH; and the like. Living cation polymerization catalysts using a Lewis acid and an initiator compound in combination include TiCl ₄ /
2-methoxy-2-phenylpropane, TiCl ₄ / t
- butanol, TiCl ₄ / 1,4-bis (2-methoxy-2-propyl) benzene, TiCl _{4/2-phenyl-2-propanol} and the like, as Ziegler _{catalysts, TiCl 4 -Et 3 Al, TiCl} 3 -Et ₃ Al
OEt, TiCl ₃ —Bu ₃ Al _{2 and the} like. Examples of the Kaminsky catalyst include dicyclopentadienyl diconium (IV) dichloride-methylaluminoxane, cyclopentadienyl titanium (III) dichloride-methylaluminoxane, (isopropyl Riden-9-fluorenyl-cyclopentadienyl) zirconium (IV)
Dichloride-methylaluminoxane, dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium (IV) dichloride-methylaluminoxane and the like.

The polymerization catalyst is used in a molar ratio of 0.000001 to 1 times, preferably 0.000 times, to the monomer.
The range is 1 to 0.5 times.

In the present invention, the polymerization of the monomer is usually carried out by
This is performed using a solvent. Examples of the solvent include aromatic solvents such as benzene, toluene, and xylene; hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, and decalin; methyl chloride, methylene chloride, and 1,2- Dichloroethane, 1,1,1-trichloroethane, 1,
Halogenated hydrocarbon solvents such as 1,2-trichloroethane and 1,1,2-trichloroethylene; and the like. Usually, hydrocarbon solvents, especially cyclopentane, cyclohexane, methylcyclohexane, decalin and the like are preferred because of their excellent polymer solubility.

In the present invention, the polymerization is usually carried out at -100 to
The reaction is performed at 100 ° C, preferably in the range of -50 to 50 ° C.

The vinylated cyclic hydrocarbon-based polymer used in the present invention may be hydrogenated in order to enhance the light resistance, heat resistance, oxidation resistance and the like. When hydrogenating, preferably 50% or more, more preferably 70% or more.
%, Particularly preferably 90% or more. In particular, when a large amount of an aromatic ring structure derived from a styrene-based monomer is contained, the thermal decomposition temperature is low, and it is difficult to control the resin temperature during melt molding. Preferably, the structure is saturated. When a combination catalyst of a transition metal compound and an alkyl metal compound is selected and used in the hydrogenation reaction described below, the aromatic ring structure derived from the styrene monomer remains without being selectively hydrogenated. When a monomer is used, it is preferable to use another hydrogenation catalyst.

In the present invention, the hydrogenation catalyst for hydrogenating a vinylated cyclic hydrocarbon polymer having an unsaturated bond is not particularly limited, and those used for hydrogenating olefin compounds can be used. For example, catalytic metals such as nickel, palladium and platinum; Wilkinson complexes;
Ziegler catalysts such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum; heterogeneous catalysts in which diatomaceous earth, magnesia, alumina, synthetic zeolite, and the like carry a catalytic metal such as nickel, palladium, and platinum; is, inter alia, magnesia, activated alumina, synthetic zeolite carrier and the pore volume 0.5 cm ³ / g or more, preferably 0.7 cm ³ / g or more, and preferably a specific surface area 2
Heterogeneous catalysts of 50 m ² / g or more are preferred. These carriers adsorb transition metals and chlorine atoms derived from the polymerization catalyst.
Further, when a heterogeneous catalyst having a particle size of 0.2 μm or more, that is, a catalyst substantially not containing a particle size of less than 0.2 μm is used, it is easy to remove the heterogeneous catalyst by filtration. Is preferred. If the particle size is too small, it is likely to leak during filtration, and it will be difficult to remove even by centrifugation,
The transition metal atomic weight, which is a residue of the polymerization catalyst or hydrogenation catalyst in the vinylated cyclic hydrocarbon-based polymer, increases. Further, if filtration is performed using a filter having a small pore diameter so as not to leak, clogging is liable to occur, resulting in poor working efficiency.

When a hydrogenation reaction is carried out, a small amount of alcohol such as isopropyl alcohol can be added to increase the reactivity. In this case, the amount of the alcohol added is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight per 100 parts by weight of the solution.

The hydrogenation reaction of the vinylated cyclic hydrocarbon polymer used in the present invention is usually carried out in an inert organic solvent. Since the vinylated cyclic hydrocarbon-based polymer of the present invention does not substantially contain a gel, it is soluble in a suitable inert organic solvent and is easily hydrogenated. As the organic solvent, a hydrocarbon-based solvent is preferable, and among them, a cyclic hydrocarbon-based solvent having excellent solubility of a vinylated cyclic hydrocarbon polymer to be produced is particularly preferable. Specific examples include benzene,
Aromatic hydrocarbons such as toluene, n-pentane, aliphatic hydrocarbons such as hexane, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, methylene dichloride, halogenated hydrocarbons such as dichloroethane, and the like; And two or more of these may be used in combination. Usually, it may be the same as the polymerization reaction solvent, and the polymerization reaction solution may be reacted as it is by adding a hydrogenation catalyst or the like. When a solvent is used, the amount of the solvent to be used is 1 part by weight of the vinylated cyclic hydrocarbon-based polymer is from 0.8 to 20%.
Parts by weight, preferably 1 to 10 parts by weight.

The hydrogen pressure in the hydrogenation reaction of the vinylated cyclic hydrocarbon polymer is not particularly limited, but is usually from 10 to 20.
0 kg / cm ² , preferably 20-150 kg / cm ² ,
More preferably, it is 30 to 100 kg / cm ² . The reaction pressure and the reaction time are adjusted so that the hydrogenation rate is 80% or more, preferably 85% or more, more preferably 90% or more.

After the completion of the hydrogenation reaction, the catalyst is removed by centrifugation,
It may be performed according to a conventional method such as filtration. The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by filtration is preferred because it is simple and efficient. In the case of filtration, pressure filtration or suction filtration may be used. From the viewpoint of efficiency, it is preferable to use a filter aid such as diatomaceous earth and perlite. An adsorbent for the transition metal atoms derived from the polymerization catalyst, such as the above-mentioned carrier for the hydrogenation catalyst, may be used as a filter aid.

The intrinsic viscosity [η] of the vinylated cyclic hydrocarbon-based polymer or its hydrogenated product used in the present invention, measured in toluene at 25 ° C., is determined by the polymerization time or the monomer concentration in the reaction solution. Varies from 0.1 to 20 dl /
g, preferably 0.2 to 10 dl / g, more preferably 0.3 to 8 dl / g. If the intrinsic viscosity is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor. This resin has a polystyrene equivalent molecular weight of 2, as determined by high performance liquid chromatography analysis using toluene as a solvent.
The component content of 000 or less is preferably 1% by weight or less, and particularly preferably 0.5% by weight or less.
If the low molecular weight component content is more than that, a method of injecting the resin solution into a mixed solvent of a good solvent and a poor solvent of the resin to solidify the resin, gradually adding the poor solvent to the resin solution to solidify the resin A method, a method of pouring a resin solution into a poor solvent to perform coagulation, or the like may be performed one or more times to lower the concentration. If the low molecular weight component is large, the medical equipment may be eluted by contact with a living body or a medicine. The resin used in the present invention has a glass transition temperature (hereinafter, referred to as Tg) of about 100 ° C to 200 ° C.

The polymer used in the present invention may be crystalline or amorphous. In the case of crystallinity, the heat deformation temperature is high and the heat resistance is excellent, which is advantageous for steam sterilization treatment for medical use and soldering treatment for electric insulation materials, but tends to cause molding distortion, and precision molding is required. Have difficulty. In the case of amorphous, the heat distortion temperature is Tg or lower and the heat resistance is inferior, but precision injection molding is possible, and it is suitable for use as an electronic component processing equipment, particularly a wafer carrier.

(Additives) If desired, various additives may be added to the polymer of the present invention or its hydrogenated product. Examples of the additive used include an ultraviolet absorber, a rubbery polymer, a petroleum resin, and a different thermoplastic resin. Further, for the purpose of improving moldability, physical properties, etc., for example, fibrous fillers such as glass fiber and carbon fiber; silica, alumina, talc, glass beads,
Fine particle fillers such as aluminum hydroxide and calcium carbonate; tetrakis [2- (3,5-di-t-butyl-
4-hydroxyphenyl) ethyl propionate] Phenolic and phosphorus-based antioxidants such as methane and 2,6-di-t-butyl-4-methylphenol; carbon, graphite, alcohol compounds and polyhydric alcohols A conductivity imparting agent such as a partial ester, or an antistatic agent; and the like may be added, and a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a pigment, a dye, an antiblocking agent, and the like may be added. Generally, in order to avoid elution from the polymer, these additives are preferably as large as possible in molecular weight and as small as possible. In addition,
Transparency tends to be lost when an inorganic filler such as glass fiber or silica fine particles is blended in the resin used in the present invention, but especially in the case of a crystalline resin, the heat deformation temperature increases,
It is preferable because the heat resistance is improved. The amount of the inorganic filler is preferably 1 to 200 parts by weight based on 100 parts by weight of the resin.
Parts by weight, more preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight.

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

When an additive is added to the polymer or hydrogenated product of the present invention, it is added in a range according to the purpose.
For example, when an additive is added, the transparency generally decreases. However, in the case of molding into a chemical container, the transparency is necessary to confirm the amount and the state of the contents, and thus the necessary light transmission is required. The total light transmittance when a molded plate having a thickness of 2 mm is used is usually 20% or more, preferably 30%.
%, More preferably 50% or more. As the electronic component processing equipment, those having excellent transparency are preferable. Additives also affect electrical properties. When used as an electrical insulating material, the volume resistivity is 10 ¹⁵ Ωcm or more, and the dielectric constant is 3 or less, preferably 2.5 or less at any of 10 ² Hz, 10 ⁶ Hz and 10 ⁹ Hz frequencies.
The dielectric loss tangent is 10 ⁻³ or less, preferably 7 × 10 ⁻⁴ at any of the frequencies of 10 ² Hz, 10 ⁶ Hz and 10 ⁹ Hz.
It is as follows.

(Molding) The method for molding the polymer of the present invention or a hydrogenated product thereof is not particularly limited. The molding method may be selected according to the melting point and Tg of the polymer, the purpose of use, the shape to be used, and the like. For example, an injection molding method, a press molding method, a solution casting method, a blow molding method, an inflation molding method, an extrusion molding method, or the like can be used.

(Medical Instrument) The medical instrument of the present invention comprises the vinylated cyclic hydrocarbon-based polymer obtained as described above or a hydrogenated product thereof. The polymer used in the present invention or a hydrogenated product thereof has low adsorption of chemicals, particularly chemicals having polar groups such as alcohols, amines, esters, amides, ethers, carboxylic acids, and amino acids, and In addition, since organic substances and the like contained as impurities in the resin are less likely to ooze out, the resin does not deteriorate even when it comes into contact with chemicals. Further, the pore volume is 0.5 cm ³ / g.
Above, preferably 0.7 cm ³ / g or more, and preferably 250 m ² / g or more, treated with an adsorbent such as magnesia, activated alumina, or synthetic zeolite, or the resin solution is treated with acidic water and pure water. By repeatedly washing, the residual amount of transition metal atoms and the like derived from the polymerization catalyst can be reduced and the residual amount can be reduced to 1 ppm or less, so that it can be used as medical equipment.

The medical equipment of the present invention includes, for example, liquid or powder, solid, such as liquid medicine containers for injection, ampules, prefilled syringes, infusion bags, solid medicine containers, ophthalmic containers, and infusion containers. Drug containers; Food containers; Sampling test tubes for blood tests, blood collection tubes, sample containers such as sample containers; Medical instruments such as syringes;
Sterilization containers used for sterilization of medical instruments such as scalpels, forceps, gauze, contact lenses, etc. that come into contact with living bodies; experiments on beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.
Analytical instruments; medical optical components such as plastic lenses for medical examinations; medical infusion tubes, piping materials such as pipes, fittings, valves; artificial organs such as denture bases, artificial hearts, artificial roots and their parts; You. In particular,
For a long time, medicine bottles, especially liquid medicines, prefilled syringes, sealed medicine bags, ampules, vials, ophthalmic containers, etc., are more transparent and physical compared to those made of conventional resin. In addition to its properties, there are no impurities eluted from the resin, and it has excellent chemical resistance.
Since it does not adsorb a drug, it has a preferable property that the quality of the drug is small.

The electric insulating material of the present invention comprises the vinylated cyclic hydrocarbon-based polymer obtained as described above or a hydrogenated product thereof. The polymer or its hydrogenated product used in the present invention is useful in a wide range of fields as an electric insulating material. For example, coating materials for electric wires and cables,
General insulating materials such as industrial electronic equipment, office automation equipment such as copiers, computers, and printers, and instruments; circuit boards such as rigid printed boards, flexible printed boards, and multilayer printed wiring boards, especially sanitary products that require high-frequency characteristics High-frequency circuit boards for communication equipment; Transparent conductive film base materials such as liquid crystal substrates, optical memories, surface heating elements such as automobile and aircraft defrosters; Transistors and ICs
・ Encapsulation materials and parts for semiconductors such as LSIs and LEDs; Encapsulation materials for electric and electronic parts such as motors, connectors, switches, and sensors; Body materials for televisions and video cameras; Parabolic antennas, flat antennas, and radar dome structures It can be suitably used for members.

The equipment for treating electronic parts of the present invention comprises the vinylated cyclic hydrocarbon-based polymer obtained as described above or a hydrogenated product thereof. The polymer used in the present invention or a hydrogenated product thereof, particularly those in which the transition metal residue is reduced to 1 ppm or less by the method described above, have substantially no impurities or the like eluted from the resin and have poor physical properties such as heat resistance. It has excellent properties and is resistant to many chemicals used for processing electronic components, particularly to most strong acids except sulfuric acid.

The electronic parts processing equipment is (A) IC, L
Semiconductors such as SI, hybrid ICs, liquid crystal display elements,
Equipment that comes into contact with electronic components such as light-emitting diodes, (B)
Equipment that comes into contact with a production intermediate such as a wafer, a liquid crystal substrate, a laminate of a transparent electrode layer and a protective layer, etc., and (C) a chemical solution or a super liquid used in the processing of the production intermediate in the electronic component production process. Equipment that comes into contact with processing liquid such as pure water. (A) equipment that comes into contact with the electronic component, and (B) equipment that comes into contact with the production intermediate of the electronic component include, for example, a tank,
Containers for processing and transporting trays, carriers, cases and the like; protective materials such as carrier tapes and separation films; and the like. (C) Examples of equipment that comes into contact with the processing liquid include pipes such as pipes, tubes, valves, shippers, flow meters, filters, and pumps; sampling vessels, resist vessels, developer vessels, stripper vessels, cleaning fluid vessels, Liquid containers such as bottles, ampoules and bags; and the like.

[0039]

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

Reference Example 1 A reaction vessel in which 120 parts by weight of styrene, 120 parts by weight of toluene, and 0.01 part by weight of azoisobutyronitrile polymerization catalyst were purged with nitrogen was heated to 80 ° C. while stirring to obtain 5 parts by weight. Allowed to react for hours. The reaction solution was added to a large amount of methanol to precipitate a polymer, which was separated by filtration, dried under reduced pressure of 1 mmHg for 24 hours, and dried to obtain 105 parts by weight of polystyrene. The intrinsic viscosity measured in toluene at 25 ° C. was 0.55 dl / g, and the Tg was 99 ° C.

100 parts by weight of the obtained polystyrene was dissolved in a mixed solvent of 300 parts by weight of tetrahydrofuran and 300 parts by weight of cyclohexane, and 10 parts by weight of a diatomaceous earth-supported nickel catalyst (35% nickel supported) was added. The reaction was performed at a 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 added to 1000 parts of methanol with stirring to precipitate a polymer. The polymer was separated by filtration, kept at 60 ° C. under a reduced pressure of 5 torr or less for 24 hours, and dried. Thus, 94 parts of a hydrogenated product of polystyrene was obtained.

The hydrogenated polystyrene had an intrinsic viscosity of 0.55 dl / g, a hydrogenation rate of the aromatic hydrocarbon ring measured by ¹ H-NMR of 91%, and a Tg of 1%.
30 ° C. In addition, 10 of hydrogenated polystyrene
As a result of atomic absorption analysis of the cyclohexane solution by weight, the nickel atomic weight was 1.6 ppm and the aluminum atomic weight was 2.22 ppm.

Example 1 800 parts by weight of a cyclohexane solution containing 97 parts by weight of a polystyrene hydrogenated product obtained in Reference Example 1 was filled with 4.5 parts by weight of activated alumina (manufactured by Mizusawa Chemical Co., Ltd., Neo Bead D), and had an inner diameter of 10 cm and a length of 10 cm. Residence time of 10 cm column
Passed to 0 seconds and circulated for 24 hours. The mixture was poured into 2500 parts by weight of isopropyl alcohol with stirring to solidify the hydrogenated polystyrene. The coagulated polystyrene hydrogenated product was collected by filtration, washed twice with 430 parts by weight of isopropyl alcohol, and dried in a rotary vacuum dryer at 5 torr and 100 ° C. for 48 hours,
8 parts by weight were recovered.

The hydrogenated polystyrene has an intrinsic viscosity,
Although Tg was not different from that of Reference Example 1, the thermal decomposition temperature (5% weight phenomenon temperature) by thermogravimetric analysis in nitrogen (heating rate 10 ° C./min) was 405 ° C., and the nickel atomic weight Was 0.1 ppm (detection limit) or less, the aluminum atomic weight was 0.21 ppm, and the resin component having a molecular weight of 2000 or less was 0.1%.

Example 2 99.8 parts by weight of the hydrogenated polystyrene obtained in Example 1 was added to a rubbery polymer (Toughtec H11052 manufactured by Asahi Kasei Corporation,
Glass transition temperature: 0 ° C. or less) 0.2 parts by weight, antioxidant (Irganox 1010 manufactured by Ciba-Geigy) 0.05
Parts by weight and a twin-screw kneader (TEM-3 manufactured by Toshiba Machine Co., Ltd.)
5B, screw diameter 37 mm, L / D = 32, screw rotation speed 250 rpm, resin temperature 240 ° C., feed rate 10 kg / hour), and extruded into pellets.

Example 3 Using the pellets obtained in Example 2, injection molding (mold clamping pressure 350 tons, resin temperature 260 ° C., mold temperature 100 ° C.)
And diameter 200mm, height 130mm, average thickness 3mm
Transparent container having a cylindrical side surface and one bottom surface, and 10
25 test pieces A of 0 mm × 50 mm × 2.0 mm, outer diameter 18 mm, inner diameter 14 mm, length 110 mm, inner capacity 10
Three syringe cylinders for ml were prepared.

When the total light transmittance of the test piece A was measured, the transparency was good at 90.5%. The turbidity was measured and found to be 0.1%. In the molded container,
LB medium (Bactotryptone 1% by weight, yeast extract 0.5% by weight, NaCl 1% by weight, glucose 0.1% by weight aqueous solution adjusted to pH 7.5) 300 m
1, 6 g of agar, and one piece of test piece A were capped with aluminum foil, and sterilized in an autoclave at 121 ° C. for 30 minutes.

After the treatment, the mixture was kept at 37 ° C. for 3 days, but no growth of fungi was observed.

The appearance of the transparent container after the treatment was good, and no white turbidity, cracking, or deformation due to heat was visually observed. LB solidified by agar from test piece A taken out of container
The turbidity measured after removing the medium is 0.28%,
The total light transmittance was 90.0%.

In addition, ethanol was added to each of the test pieces A one by one.
70% nitric acid, phosphoric acid, hydrofluoric acid (hydrofluoric acid 7% by weight, nitric acid 4
2% by weight, water 51%), 37% hydrochloric acid, 30% diluted sulfuric acid, concentrated sulfuric acid, 30% aqueous hydrogen peroxide, saturated aqueous potassium hydroxide, 29% aqueous ammonia, acetone, isopropyl alcohol, trichloroethylene, 2.38 weight % Aqueous solution of tetramethylammonium hydroxide and an etching solution for aluminum (80% by weight of concentrated phosphoric acid, 5% by weight of nitric acid, 5% by weight of glacial acetic acid, 10% by weight of water) for 5 minutes. Swelling was observed in the test piece immersed in trichlorethylene, and the surface was carbonized in the test piece immersed in concentrated sulfuric acid, but the effect of other chemicals was not observed. Further 37
48% aqueous hydrochloric acid, saturated aqueous solution of potassium hydroxide, ethanol
After soaking for an hour, no effect was observed.

A hard glass flask was charged with 200 g of distilled water, covered with a hard glass lid, and autoclaved to 121 g.
C., steam sterilized for 1 hour, cooled to room temperature, and allowed to stand for 24 hours to recover distilled water.

Further, the test piece A was ultrasonically washed in distilled water for 20 minutes, and then dried at 40 ° C. for 10 hours. This test piece A was cut into 10 mm width, 20 g was put into a hard glass flask, 200 g of distilled water was added, the hard glass lid was put, the autoclave was steam sterilized at 121 ° C. for 1 hour, and cooled to room temperature. After that, the mixture was allowed to stand for 24 hours to recover distilled water.

From the difference between the results of the two types of distilled water, such as atomic absorption spectrometry, ion chromatography, and combustion-non-dispersive infrared gas analysis, the amount of nickel eluted from the test piece was determined. 0.01 ppm (detection limit) or less, aluminum atom elution amount is 0.01 ppm
(Detection limit) Below, total organic carbon amount 2 ppm (detection limit)
It was below.

The test piece A was subjected to an elution test according to the Japanese Pharmacopoeia, 12th Edition, "Plastic Test Method for Infusion". Bubbles disappear within 3 minutes, the pH difference is -0.04,
The ultraviolet absorption was 0.006 and the potassium permanganate reducing substance was 0.13 ml.

The syringe cylinder was ultrasonically washed in distilled water for 20 minutes and then dried at 40 ° C. for 10 hours. The distal ends of the three syringe cylinders are closed with a Teflon stopper, and the distal ends are held downward in holders.
10 ml of 0 ppm vitamin B ₂ aqueous solution, 300 ppm methamphetamine hydrochloride aqueous solution, and 1000 ppm tranexamic acid aqueous solution were added, and the rear end was sealed with a Teflon stopper. After standing at room temperature for 30 days in a dark place, as a result of high performance liquid chromatography analysis, the vitamin B ₂ concentration was about 790 ppm and the methamphetamine hydrochloride concentration was about 290 p.
pm, tranexamic acid concentration was about 980 ppm.

From the above, the pellets are used for medical equipment,
It turns out that it is an excellent molding material as an equipment for processing electronic parts.

Example 4 Using the pellets obtained in Example 1, injection molding (mold clamping pressure 350 tons, resin temperature 260 ° C., mold temperature 100 ° C.)
And 10 disks 100 mm in diameter and 1.2 mm in thickness,
Twenty test pieces B of 27 mm × 12.7 mm × 4.0 mm were prepared.

The disc having a diameter of 100 mm is subjected to JI
The volume resistivity, the dielectric constant, and the dielectric loss tangent of the test piece B obtained in Example 1 were measured using the ASTM-
The bending strength was measured by the method of D-790. Flexural strength is 410 kgf / cm ² , volume resistivity is 5 × 10 ¹⁶ Ωc
m, the dielectric constant is 2.37 at any of the frequencies of 10 ² Hz, 10 ⁶ Hz and 10 ⁹ Hz, and the dielectric loss tangent is 10 ² Hz.
Hz, 10 ⁶ Hz, and 10 ⁹ Hz, the frequency was 5 × 10 ⁻⁴ .

This indicates that these pellets are excellent molding materials as electric insulating materials.

Example 5 A 0.1 wt% toluene solution of (isopropylidene-9-fluorenyl-cyclopentadienyl) zirconium (IV) dichloride was placed in a reaction vessel in which 400 parts by weight of toluene had been purged with nitrogen, and stirred. 20 parts by weight of a toluene solution of methylaluminoxane (methyl group: A1 = 1.7: 1) 40 at 5.25% by weight in terms of A1 atom
Parts by weight were added. After stirring at 25 ° C for 20 minutes, 25 ° C
, 100 parts by weight of 4-vinylcyclohexene were continuously added over a period of 30 minutes, and the mixture was further reacted for 5 hours.

After adding 5 parts by weight of isopropyl alcohol and 2 parts by weight of water to the reaction solution, the mixture was stirred at 60 ° C. for 2 hours. After cooling to 25 ° C., 5 parts by weight of anhydrous calcium sulfate powder was added with stirring, and the mixture was reacted for 2 hours with stirring. Insolubles in the reaction solution were removed by filtration with a pressure filter using diatomaceous earth as a filtration bed to obtain a transparent reaction solution.
The reaction solution was poured into 1500 parts by weight of methanol with vigorous stirring to precipitate a polymer, which was separated by filtration and 5 torr.
Drying at 80 ° C. for 24 hours under reduced pressure of r or less gave 64 parts by weight of poly-4-vinylcyclohexene.

This poly-4-vinylcyclohexene 64
Parts by weight were dissolved in 600 parts by weight of cyclohexane, and the same column treatment as in Example 1 was performed. The mixture was poured into 1800 parts by weight of isopropyl alcohol while stirring to precipitate a polymer. The precipitated polymer was collected by filtration and collected for 5 to
It was dried at 100 ° C. for 48 hours under reduced pressure of not more than rr to obtain 55 parts by weight.

This poly-4-vinylcyclohexene has an intrinsic viscosity of 0.61 dl / g, a Tg of 135 ° C. and a melting point of 26
The thermal decomposition temperature (5% weight loss temperature) was 420C, the zirconium atomic weight was 0.1 ppm (detection limit) or less, the aluminum atom was 0.45 ppm, and the resin component having a molecular weight of 2000 or less was 0.1% or less. Was.

Example 6 The same rubbery polymer 0.1 as used in Example 2 was added to 50 parts by weight of poly-4-vinylcyclohexene obtained in Example 5.
Parts by weight, 0.2 parts by weight of an antioxidant (Irganockle 1010, manufactured by Ciba Geigy) and an average diameter of 20 μm and an average length of 6 mm surface-treated with methyltrimethoxysilane
Of glass fiber was added, and the screw rotation speed was 200 r with the same twin-screw kneader used in Example 2.
pm, the resin temperature was 280 ° C., and the feed rate was 10 kg / hour.

Example 7 The pellets obtained in Example 6 were subjected to injection molding (mold clamping pressure 350 t, resin temperature 300 ° C., mold temperature 100 ° C.)
A container and a test piece similar to those in Example 3 were prepared and subjected to the same treatment. The total light transmittance of the test piece A was 30.5%.

No growth, deformation, cracking, etc. of the bacteria were observed after steam sterilization, and the total light transmittance of the test piece A was 30.1%.
%Met.

In addition, when immersed in a chemical, swelling was observed in the test piece immersed in trichlorethylene, and the surface was carbonized in the test piece immersed in concentrated sulfuric acid, but no effect was observed by other chemicals. Further immersion in 37% hydrochloric acid, a saturated aqueous solution of potassium hydroxide, and ethanol for 48 hours, no effect was observed.

The amount of eluted from 20 g of the test piece A after steam sterilization and standing for 24 hours was 0.0 zirconium atom.
2 ppm (detection limit) or less, aluminum atom elution amount 0.01 ppm (detection limit) or less, total organic carbon amount 2 pp
m (detection limit).

In the eluate test, bubbling disappeared within 3 minutes, pH difference was -0.05, and ultraviolet absorption was 0.00.
7, 0.09 ml of potassium permanganate-based reducing substance.

From this, the pellets are used for medical equipment,
It turns out that it is an excellent molding material as an equipment for processing electronic parts.

Example 8 A disk and a test piece B were prepared using the pellets of Example 6 in the same manner as in Example 4, and the volume resistivity, dielectric constant, and dielectric loss tangent were measured according to the method of ASTM-D-790. The bending strength was measured. Flexural strength: 430 kgf / cm ² , volume resistivity: 5 × 10 ¹⁶ Ωcm or more, dielectric constant: 10 ² Hz, 10 ⁶ H
z, 10 ⁹ Hz, respectively at a frequency of, 2.93,2.8
1, 2.80, dielectric loss tangent is 10 ² Hz, 10 ⁶ Hz, 10
^At a frequency of ⁹ Hz, 0.004, 0.001,
It was 0.001.

The test piece A obtained in Example 7 was heated at 240 ° C.
No change was observed even after contact with the solder for 10 seconds.

From this, it can be seen that this pellet is an excellent molding material as an electric insulating material.

[0074]

The medical device comprising the vinylated cyclic hydrocarbon-based polymer of the present invention or a hydrogenated product thereof does not deteriorate the contacting agent, and the electrical insulating material has excellent electrical insulating properties and high frequency characteristics. Equipment for processing electronic components is excellent in heat resistance, chemical resistance, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Io Natsuume 1-2-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon Co., Ltd. Research and Development Center (56) References JP-A-1-178505 (JP) , A) JP-A-1-132603 (JP, A) JP-A-63-43910 (JP, A) Yoshito Raft, New Polymer One Point 20 Medical Polymer Material, Japan, Kyoritsu Shuppan Co., Ltd., 1989 February 20, 3-9, 55 edited by The Society of Polymer Science, Fumihiko Sato et al., New high molecular weight material One Point-7 Heat-resistant and insulating material, Japan, Kyoritsu Shuppan Co., Ltd., January 20, 1988, 16- 17,81 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 10/00-10/14 C08F 8/00-8/50 C08L 1/00-101/16

Claims (4)

(57) [Claims] 1. An intrinsic viscosity [η] measured in toluene at 25 ° C. of 0.1 to 20 dl / g, a content of a resin component having a molecular weight of 2,000 or less of 1% by weight or less, and a residual amount of transition metal atoms derived from a polymerization catalyst . Is at most 1 ppm, or 99.8 parts by weight of a hydrogenated cyclic hydrocarbon-based polymer or a hydrogenated product thereof ,
A molding material comprising a rubbery polymer in an amount of 0.2 parts by weight or less . 2. An intrinsic viscosity [η] measured in toluene at 25 ° C. of 0.1 to 20 dl / g, a content of a resin component having a molecular weight of 2,000 or less of 1% by weight or less, and a residual amount of transition metal atoms derived from a polymerization catalyst . Is at most 1 ppm, or 99.8 parts by weight of a hydrogenated cyclic hydrocarbon-based polymer or a hydrogenated product thereof ,
Medical equipment comprising a rubbery polymer in an amount of 0.2 parts by weight or less . 3. An intrinsic viscosity [η] measured in toluene at 25 ° C. of 0.1 to 20 dl / g, a content of a resin component having a molecular weight of 2,000 or less of 1% by weight or less, and a residual amount of transition metal atoms derived from a polymerization catalyst . Is at most 1 ppm, or 99.8 parts by weight of a hydrogenated cyclic hydrocarbon-based polymer or a hydrogenated product thereof ,
An electrically insulating material obtained by adding a rubbery polymer in a range of 0.2 parts by weight or less . 4. An intrinsic viscosity [η] measured in toluene at 25 ° C. of 0.1 to 20 dl / g, a content of a resin component having a molecular weight of 2,000 or less of 1% by weight or less, and a residual amount of transition metal atoms derived from a polymerization catalyst . Is at most 1 ppm, or 99.8 parts by weight of a hydrogenated cyclic hydrocarbon-based polymer or a hydrogenated product thereof ,
(A) equipment which comes into contact with an electronic component, (B) equipment which comes into contact with an intermediate for the production of an electronic component, and (C) which is obtained by adding a rubbery polymer in a range of 0.2 parts by weight or less . At least one electronic component processing equipment selected from equipment that comes into contact with the processing solution used for processing.