JP2000038414A - Molding material comprising hydrogenated alpha-olefin- cyclopentadiene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molding material excellent in transparency, heat resistance, chemical resistance, electric insulation and high frequency property useful for medical care and medicine or insulating material for electric and electronic parts by including a specific copolymer. SOLUTION: This composition comprises (A) to (B). (A) is a copolymer comprising 0 to 39 mole % of a compound of formula I (R1 is H, a 1 to 16C saturated aliphatic hydrocarbon) and 61 to 100% of a compound of formula II (R2 is the same as R1). (B) is a copolymer including the repeating unit of formulas I to III (n and p are each 0 or 1; m is an integer; R3 to R22 are each H, a halogen or aromatic or aliphatic hydrocarbon group), and the repeating unit of formula IV (q is 2 to 8), in the molar ratio of (I+II)/(III+IV)=95 to 99.9/0.1 to 5, I/II=0 to 39/61 to 100, IV/III=0 to 95/5 to 100. The above described copolymers have reduced viscosity ηsp/c of 0.25 to 3 dL/g observed in 0.5 g/dL toluene solution at 30 deg.C, and the amount of the remaining metallic components is 10 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a molding material of a hydrogenated α-olefin-dicyclopentadiene copolymer. More specifically, the present invention relates to a molding material for medical use and medicine excellent in transparency, heat resistance and chemical resistance, and an insulating material for electric and electronic parts excellent in electric insulation, high frequency characteristics and heat resistance.

[0002]

2. Description of the Related Art As materials for medical devices such as syringes and medicine containers and medicine containers, a certain degree of transparency is required to identify the contents, and glass has been used for a long time.
There has been a concern that the glass may be heavy and break, and that the alkali component may be eluted. As resin materials, polyethylene, polypropylene,
Polyvinyl chloride or the like is used. However, these resins have a drawback that impurities such as residual metal components, residual monomers, and low molecular weight components in the resin may be eluted, and furthermore, they are inferior in heat resistance and thus difficult to sterilize with hot water or steam. .

[0003] Electricity of circuit boards, sealants, connectors, etc.
As insulating materials for electronic components, polyolefin resins such as polyethylene, polypropylene, and polystyrene, polyvinyl chloride, polyethylene terephthalate, polysulfone, polyether sulfone, epoxy resins, and polyimides are used. However, polyolefin resins such as polyethylene, polypropylene, and polystyrene, and polyvinyl chloride are excellent in electrical insulation, low moisture absorption, chemical resistance, etc., but heat resistance is not satisfactory and the range of use is limited. I have. Polyethylene terephthalate, polysulfone, polyethersulfone, epoxy resin, and polyimide have the disadvantage of high hygroscopicity, and have a large dielectric loss tangent in the high-frequency band of the microwave region, which has been rapidly expanding in recent years in communications and the like. Therefore, the loss is large and it is not suitable for a circuit board, a connector, a capacitor film, etc. used in a high frequency range.

[0004] In recent years, cyclic olefin polymers have been actively developed. These cyclic olefin-based polymers are expected to be applied to optical materials such as optical disc substrates, optical lenses, and optical sheets as thermoplastic resins having high transparency and heat resistance and low birefringence. The present inventors have previously proposed hydrogenated products of α-olefin-dicyclopentadiene-based copolymers as novel cyclic olefin-based copolymers (Japanese Patent Application Nos. 9-18491 and 9-516).
No. 38). This hydrogenated α-olefin-dicyclopentadiene copolymer has excellent chemical homogeneity and has the advantage that it can be produced at low cost.

[0005]

The present invention relates to the above hydrogenated α
-Molding materials comprising olefin-dicyclopentadiene copolymers, especially molding materials for medical and pharmaceutical use or electric and
The present invention relates to an insulating material for electronic components. An object of the present invention is to provide a molding material having excellent properties such as transparency, heat resistance, moisture absorption, chemical resistance, electrical insulation, and high frequency characteristics.

[0006]

The present inventors have proposed that the hydrogenated α-olefin-dicyclopentadiene copolymer proposed above not only has excellent transparency and heat resistance but also has chemical resistance and electric insulation. The present invention has been found to be excellent in properties and high-frequency properties and suitable for molding materials for medical and pharmaceutical use or insulating materials for electric and electronic parts.

That is, the present invention provides the following copolymer [X]
Or a molding material comprising an α-olefin-dicyclopentadiene-based copolymer represented by [Y].

Copolymer [X]: 0-39 mol% of a repeating unit of the following formula (A) and 61-100 mol% of a repeating unit of the following formula (B), in a toluene solution having a concentration of 0.5 g / dL, The reduced viscosity η _sp / c measured at 30 ° C. is 0.25 to 3
dL / g, and the content of the residual metal component is 10 p.
pm or less.

[0009]

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[In the formula (A), R ¹ is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. ]

[0011]

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[In the formula (B), R ² is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. Copolymer [Y]: represented by a repeating unit of the following formulas (A), (B), (C) and (D):

[0013]

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[In the formula (A), R ¹ is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. ]

[0015]

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[In the formula (B), R ² is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. ]

[0017]

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[In the formula (C), n is 0 or 1, m
Is 0 or a positive integer, p is 0 or 1, R
³ to R ²² are the same or different, a hydrogen atom, a halogen atom, an aromatic hydrocarbon group or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, 6 to 10 carbon atoms, also, R ¹⁹ And R ²⁰ or R ²¹ and R ²² may form an alkylidene group, or R ¹⁹ or R ²⁰ and R ²¹ or R ²² may form a ring,
Further, the ring may have a double bond or an aromatic ring. ]

[0019]

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[In the formula (D), q is an integer of 2 to 8.] ]

The mol% of the repeating unit represented by the formulas (A), (B), (C) and (D) is represented by [A],
Assuming that [B], [C], and [D], the composition ratio is ([A] + [B]) / ([C] + [D]) = 95-9.
9.9 / 0.1-5, [A] / [B] = 0-39 / 6
1 to 100 and [D] / [C] = 0 to 95/5 to 10
0, and the reduced viscosity η _sp / c measured at 30 ° C. in a toluene solution having a concentration of 0.5 g / dL is 0.25 to 3
dL / g, and the content of the residual metal component is 10 p.
pm or less.

Among such molding materials, it is preferable that the use thereof is a molding material for medical / medical use or an insulating material for electric / electronic parts.

Hereinafter, the present invention will be described in detail. The hydrogenated α-olefin-dicyclopentadiene-based copolymer used in the present invention is a copolymer having a structural formula represented by the following [X] or [Y]. That is, the copolymer [X] is 0 to 3
It is composed of 9 mol% of the following formula (A) and 61 to 100 mol% of the repeating units represented by the following formula (B).

[0024]

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Here, R ¹ in the formula (A) is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. Examples of the saturated aliphatic hydrocarbon group include an alkyl group having 1 to 16 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.

[0026]

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Here, R ² in the formula (B) is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. Examples of the saturated aliphatic hydrocarbon group include an alkyl group having 1 to 16 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.

The repeating unit represented by the formula (A) accounts for 0 to 39 mol%, preferably 1 to 38 mol%, and more preferably 5 to 35 mol%, of all the repeating units. Formula (B)
Is a proportion of 61 to 100 mol%, preferably 62 to 99 mol%, and more preferably 6 to 100 mol%.
5 to 95 mol%.

The copolymer [Y] is represented by the following formula (A):
It consists of repeating units represented by (B), (C) and (D).

[0030]

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Here, R ¹ in the formula (A) is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. Examples of the saturated aliphatic hydrocarbon group include an alkyl group having 1 to 16 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.

[0032]

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Here, R ² in the formula (B) is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. Examples of the saturated aliphatic hydrocarbon group include an alkyl group having 1 to 16 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.

[0034]

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In the formula (C), n is 0 or 1. m is 0 or a positive integer of 1 to 3, and 0 or 1 is preferable. p is 0 or 1. R ^{3 to} R ²² are the same or different and are a hydrogen atom, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as a phenyl group and a naphthyl group.
May be substituted with an alkyl group. Carbon number 1-12
Examples of the saturated aliphatic hydrocarbon group include an alkyl group such as a methyl group and an ethyl group, and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Examples of the unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms include an alkenyl group such as a vinyl group and a propenyl group.

[0036] Here, in the R ¹⁹ and R ^20, or a methylidene group and R ²¹ and R ^22, may form an alkylidene group such as ethylidene group, and the R ¹⁹ or R ^20, R
²¹ or R ²² may form a ring, and the ring may have a double bond or an aromatic ring.

[0037]

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In the formula (D), q is an integer of 2 to 8,
2, 3, and 4 are preferred.

In the copolymer [Y], the compound represented by the formula (A):
When the mol% of the repeating unit represented by (B), (C) and (D) is [A], [B], [C], and [D], respectively, the composition ratio is as follows. .

That is, ([A] + [B]) / ([C]
+ [D]) is 95 to 99.9 / 0.1 to 5, preferably 95 to 98/2 to 5. [A] / [B] is 0 to 39/61 to 100, preferably 1 to 38/62 to
99. [D] / [C] is 0 to 95/5 to 10
0, preferably 0 to 80/20 to 100.

These copolymers are prepared by copolymerizing dicyclopentadiene and α-olefin with another copolymerization monomer as required and using a metallocene catalyst to obtain α-olefin-dicyclopentadiene. It can be synthesized by hydrogenating a system copolymer using a hydrogenation catalyst. This is a metallocene catalyzed polymerization,
It is obtained by making good use of the phenomenon that a chain of dicyclopentadiene components is hardly generated, and has a high alternating copolymerizability between a cyclic olefin component and an α-olefin component, that is, a copolymer having high chemical homogeneity. It is a feature and advantage of being a polymer. Further, since the most inexpensive cyclic olefin called dicyclopentadiene is used, it is possible to synthesize with extremely low raw material cost.

The α-olefin used is preferably ethylene or propylene, particularly preferably ethylene, in view of the polymerization activity, the molecular weight of the obtained copolymer, the raw material cost, and the like. That is, in the present invention, the most preferably used is a hydrogenated ethylene-dicyclopentadiene copolymer.

The molecular weight of the hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention depends on the mechanical properties and mechanical strength required for the intended molding material, and the resin flow required for molding. Although it is determined in consideration of the properties, the reduced viscosity η _sp / c measured at 30 ° C. in a toluene solution having a concentration of 0.5 g / dL is 0.25 to 3
dL / g, preferably from 0.3 to
It is 2 dL / g. If it is smaller than 0.25 dL / g, it becomes a brittle molded product having low mechanical strength, which is not preferable.
If it is larger, the mechanical properties of the molded product are high, but the melt viscosity or solution viscosity of the resin becomes too high and molding is difficult, which is not preferable.

The molecular weight of the hydrogenated α-olefin-dicyclopentadiene copolymer is determined by supplying a certain amount of a molecular weight regulator such as hydrogen or 1-hexene to the polymerization reaction system, changing the concentration of the metallocene catalyst, It can be controlled by a method such as changing the feed rates of dicyclopentadiene and α-olefin to the system.

The glass transition temperature of the hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention is 120.
~ 180 ° C.

The residual metal component contained in the molding material is not preferable because there is a fear that the metal component may be eluted and there is a fear that the contacting chemicals and chemicals may be deteriorated. Hydrogenated α-olefin of the present invention
In the molding material comprising a dicyclopentadiene copolymer, the content of the residual metal component is preferably 10 ppm or less, more preferably 5 ppm or less.
Note that the numerical values described here indicate values obtained by summing the contents of all residual metal components.

Most of the residual metal contained in the molding material is derived from the catalytic metal in the production of the resin. Various methods are conceivable for removing the catalytic metal, but a metallocene catalyst is used as a polymerization catalyst, and a combination of tris (acetylacetonato) cobalt or bis (acetylacetonato) nickel with an alkylaluminum compound is used as a hydrogenation catalyst. We have already found and proposed an effective method for removing the catalyst efficiently using a homogeneous catalyst such as a Ziegler-type hydrogenation catalyst (Japanese Patent Application Nos. 9-283489 and 9-283489). No. 10-81590).
According to them, a mixture of an oxycarboxylic acid represented by glycolic acid and lactic acid and water, and, if necessary, a mixture of an active hydrogen-containing compound represented by an alcohol, are used in the solution after hydrogenation, and the amount of catalyst used is , A catalytic metal component is precipitated by adding a certain amount of the catalyst metal, and then separated and removed by filtration. Generally, in polymerization with a metallocene catalyst, it is necessary to use a large amount of alkylaluminum as a metallocene alkylating agent with respect to the metallocene as a metallocene alkylating agent when methylaluminoxane (MAO) used as a cocatalyst or an ionic boron compound is used as a cocatalyst. Therefore, removal of aluminum is a problem, but according to such a purification method, the aluminum content can be suppressed to an extremely low value of 10 ppm or less.

When a metallocene catalyst is used as a polymerization catalyst and a heterogeneous catalyst in which a metal such as palladium, rhodium, nickel or the like is supported on a carrier such as carbon, alumina or silica / alumina is used as a hydrogenation catalyst, the following is used. Purification methods may be mentioned. To the solution after polymerization, a mixture of oxycarboxylic acid represented by glycolic acid and lactic acid and water, and further, if necessary, a mixture of active hydrogen-containing compounds represented by alcohols are added in a certain amount according to the amount of catalyst used, The metal component derived from the polymerization catalyst is precipitated and separated and removed by filtration.
Next, a heterogeneous hydrogenation catalyst is added to the filtrate, hydrogenation is performed, and then the mixture is filtered again to remove the heterogeneous catalyst.

Examples of the residual metal component contained in the molding material comprising the hydrogenated α-olefin-dicyclopentadiene copolymer of the present invention include those derived from a polymerization catalyst such as zirconium, hafnium, titanium, boron and aluminum. Nickel, cobalt, iron, palladium, rhodium,
Examples thereof include those derived from a hydrogenation catalyst such as ruthenium, platinum, manganese, copper, vanadium, magnesium, molybdenum, chromium, and zinc.

In the hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention, the content of the gel component contained in the resin is preferably 1% by weight or less,
More preferably, it is 0.1% by weight or less. Here, the gel means that the resin is converted into a 5% by weight toluene solution, and then the solution is subjected to a microfilter (pore size: 1.0 μm).
Refers to the residue remaining on the filter when filtered. By measuring the weight of the residue after drying, the gel content in the resin can be easily measured.

When the content of the gel component is 1% by weight or more, in a melt molding typified by injection molding or extrusion molding, even if the molding conditions are devised, a linear mark called a silver streak or a fish eye is formed on the molded product. It is unavoidable that mottled fogging called "mottled" occurs. Also, transparency in film casting by solution casting method,
The surface smoothness decreases, which is not preferable.

Gels produced in the production of hydrogenated α-olefin-dicyclopentadiene copolymer can be roughly classified into the following three types. (1) Those generated in the polymerization step, which are derived from a poly-α-olefin represented by polyethylene in which only the α-olefin component is polymerized, or a copolymer containing an extremely large amount of α-olefin component. (2) A double bond portion remaining in the dicyclopentadiene component of the α-olefin-dicyclopentadiene copolymer before hydrogenation is crosslinked and gelled before hydrogenation. (3) Gelled by heating and melting in a solvent removing step or a pelletizing step.

To minimize these gels,
For example, the following method can be mentioned. The gel of (1) is generated in the polymerization step, but when polymerization is carried out while maintaining the amount of dicyclopentadiene relative to the α-olefin, this type of gel is hardly generated. However, during the polymerization, if the metallocene catalyst is deactivated by impurities such as water and oxygen in the polymerization system, this type of gel may be generated. It is necessary to pay attention to replacement with gas.

It is also necessary to pay attention to the method of adding the metallocene catalyst to the polymerization system. Metallocene catalysts consist of a powdered metal complex called a metallocene and an aluminum compound such as methylaluminoxane (MAO) or triisobutylaluminum, or a cocatalyst such as an ionic boron compound. However, these are usually supplied to the polymerization reaction system through a pipe in a solution state. At this time, when a catalyst solution having a polymerization activity in which the metallocene and the cocatalyst are reacted in advance is sent, polymerization of a gaseous α-olefin component, for example, only ethylene gas, occurs on a small amount of catalyst attached to the inner wall of the pipe, It may drop into the polymerization solution and mix with the copolymer to remain as a gel. In order to prevent this, a solvent is further allowed to flow after the catalyst solution is flown to wash the inside of the pipe, and more preferably, a method of supplying the metallocene solution and the cocatalyst solution to the polymerization system through separate pipes is exemplified. .

The gel of the type (2) can be generated in both the polymerization step and the hydrogenation step. It is considered that the crosslinking of the double bond remaining in the dicyclopentadiene component of the α-olefin-dicyclopentadiene copolymer is caused by a cationic polymerization mechanism, not by coordination polymerization such as olefin polymerization using a metallocene catalyst. Therefore, as in the case of (1), it is necessary to remove the impurities such as water and oxygen in the polymerization system as much as possible and to suppress the deactivation of the metallocene catalyst so as not to generate active species for cationic polymerization. It also leads to suppression.

Further, α-olefin-
Without isolating the dicyclopentadiene copolymer
Performing a hydrogenation reaction with the polymerization solution is included.
If the copolymer before hydrogenation is isolated and exposed to air, gelation tends to occur. When the solution after polymerization is exposed to the atmosphere from an inert gas atmosphere, gelation gradually starts to occur. Therefore, it is preferable to immediately send the solution after polymerization to an autoclave while maintaining the solution under an inert gas atmosphere, and to add a hydrogenation catalyst to perform a hydrogenation reaction. 48 after completion of polymerization
The hydrogenation is preferably performed within an hour, more preferably within 24 hours.

The gel of (3) is generated in the post-treatment step. The amount of the residual catalyst metal is reduced, an antioxidant described later is applied, and the post-treatment step is performed in a nitrogen atmosphere. Can be suppressed.

If a small amount of gel remains in the resin even when the above-mentioned method is used, it can be removed by filtration. In the gels of (1) and (2), solution filtration
The gel of (3) can be removed by melt filtration.

If a large amount of low-molecular-weight organic substances are present as impurities in the resin, their dissolution and bleeding may cause problems, which is not preferable as a molding material used for medical / medical applications or precision electronic parts. The hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention is obtained by performing polymerization while maintaining an excess of dicyclopentadiene with respect to α-olefin, such as low molecular weight polyethylene. Low molecular weight poly-α-olefins have the advantage of being difficult to produce.

Other low molecular weight organic substances include those derived from solvents and those derived from monomers. Hydrogenated α-
The olefin-dicyclopentadiene-based copolymer is usually synthesized using a hydrocarbon-based solvent, and specific examples of low-molecular-weight organic substances derived from the solvent include aliphatic hydrocarbons such as pentane, hexane, octane, and decane. Hydrogen, alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane, and aromatic hydrocarbons such as benzene, toluene and xylene are exemplified. Of these, aromatic hydrocarbons, especially toluene, are used.

As a low molecular weight organic substance derived from a monomer,
And tetrahydrodicyclopentadiene. Tetrahydrodicyclopentadiene is a product obtained by hydrogenating dicyclopentadiene as a monomer. Hydrogenated α-
Synthesis of an olefin-dicyclopentadiene-based copolymer requires two-step reactions of polymerization and hydrogenation. However, from the viewpoint of economy and suppression of gelation of the obtained copolymer, a solution is prepared after polymerization. Without isolating the polymer from
It is desirable to continuously hydrogenate. According to the polymerization method we have found that keeps the monomer ratio between dicyclopentadiene and α-olefin above a certain value, a considerable amount of dicyclopentadiene is still present in the polymerization system even at the end of the polymerization reaction. Therefore, if hydrogenation is performed continuously from the polymerization,
The remaining dicyclopentadiene is also hydrogenated at the same time to form tetrahydrodicyclopentadiene.

In the molding material of the present invention, the content of such a low molecular weight organic substance is preferably 0.1% by weight or less, more preferably 0.01% by weight or less.
If the content is 0.1% by weight or more, its dissolution and bleeding may cause a problem, which is not preferable. In order to suppress the low molecular weight organic matter to 0.1% by weight or less, the catalyst component is removed from the solution after hydrogenation by filtration in the same manner as described above,
Subsequently, a method (flushing) of distilling off the solvent and tetrahydrodicyclopentadiene at a high temperature and under reduced pressure can be mentioned. Tetrahydrodicyclopentadiene has a boiling point of 19
It is important to note that the temperature is as high as 4 ° C and the ignition point is as low as 235 ° C. Recently, however, we have used high-boiling solvents such as tetrahydronaphthalene, 1-methylnaphthalene and 2-methylnaphthalene with a boiling point of 195 ° C or more. Then, they found that tetrahydrodicyclopentadiene and the high-boiling-point solvent could be efficiently distilled off, and separately proposed (Japanese Patent Application No. 10-161968).

Various additives may be used in the hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention, if necessary. An example of the additive used is an antioxidant. Since a cyclic olefin resin has a large amount of tertiary carbon in its structure, when it comes in contact with oxygen at high temperature, it undergoes so-called oxidative degradation to produce gels and decomposition products,
Coloring, burning and silver streaks of the molded product are liable to occur, but these can be effectively suppressed by adding an antioxidant represented by a phenol compound or a phosphorus compound.

As such an antioxidant, generally known general-purpose agents such as Irganox 1010 and Irganox 1076 (trade name, manufactured by Ciba Geigy) can be used. Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butylphenol, 4-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4′-bis (2,6-di-t-butylphenol), 2,2 ′ -Methylene-bis (4-methyl-6-t
-Butylphenol), 4,4'-methylene-bis (2,6-di-t-butylphenol), 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, Tetrakis [2- (3,5-di-
t-butyl-4-hydroxyphenyl) ethyl propionate] methane, pentaerythrityl-tetrakis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,
4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris (4-tert-butyl) -3-hydroxy-2,6-dimethylbenzyl) isocyanurate, octadecyl-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,2'-thio-bis- (4-methyl-6-t-butylphenol), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] and the like.

Examples of the phosphorus-based antioxidants include tris (2,4-di-t-butylphenyl) phosphite and bis- (2,6-di-t-butyl-4-methylphenyl).
-Pentaerythritol diphosphite, tris (nonylphenyl) phosphite, 3,5-di-t-butyl-
4-hydroxybenzyl phosphonate diethyl ester and the like.

These may be used alone or in combination of two or more. Further, a phosphorus-based antioxidant may be mixed with a phenol-based antioxidant and used. The amount is usually added in the range of 0.01 to 3% by weight, preferably 0.01 to 1% by weight based on the resin.

In the purification method of removing these catalyst components by filtration and then distilling off the solvent, these antioxidants are added at the time of solution after filtration, and then the solvent is distilled off at a high temperature. In this case, the gelation and deterioration of the resin can be suppressed.

Additives other than the above-mentioned antioxidants include an ultraviolet absorber, a bluing agent for making the yellowness of a molded product inconspicuous, a release agent, a flame retardant, a pigment, a dye, an antistatic agent, carbon and the like. Examples thereof include a conductivity-imparting agent such as graphite, a leveling agent represented by a fluorine-based or silicon-based surfactant, a wax, a rubbery polymer, and an inorganic filler such as glass fiber and silica fine particles. It is preferable that these additives have as large a molecular weight as possible to prevent elution from the resin, and it is preferable that the amount of these additives be as small as possible to prevent a decrease in transparency.

The method for molding the molding material of the present invention is not particularly limited. An optimal method may be selected according to the application and purpose. Specific examples include injection molding, extrusion molding, blow molding, inflation, T-die, press molding, and solution casting.

The medical / pharmaceutical molding material of the present invention comprises:
Since it has a high glass transition temperature and excellent heat resistance and does not cause hydrolysis, it has a preferable property that it can be sterilized with hot water or steam. Even if such treatment is performed, the transparency is hardly reduced, and the appearance and the mechanical properties are hardly changed. This is because the hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention has high chemical homogeneity, more specifically α-olefin
The fact that the alternating copolymerizability of the olefin component and the dicyclopentadiene component is extremely high and that there is almost no α-olefin block component also contributes effectively. Medical treatment of the present invention
Pharmaceutical molding materials withstand radiation sterilization such as γ-rays,
Such sterilization may be further performed as necessary.

The hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention has high chemical resistance and solvent resistance and is not attacked by polar solvents such as alcohols and ketones. It can withstand most acids and alkalis other than concentrated sulfuric acid. In addition, the content of the residual metal component in the resin is 1
Since it is as low as 0 ppm or less and the amount of low molecular weight organic substances is extremely small, there are almost no impurities eluted from the resin, and the chemicals in contact therewith are not deteriorated. Furthermore, it has the property of extremely low water absorption and low water vapor permeability, and can be suitably used as a molding material for medical and pharmaceutical applications in a wide range of applications.

Specific examples of the molding material for medical and pharmaceutical use of the present invention include a medical device, a pharmaceutical container, a pharmaceutical package, and the like. For example, a syringe, a liquid pharmaceutical container, an ampule, a vial, a prefilled syringe, a bag for infusion. Packaging materials for medicines, eye drops containers, drops containers, sampling test tubes for blood tests, blood collection tubes, medical tubes, sterile containers used for sterilization of medical materials such as scalpels and gauze, beakers, petri dishes, etc. Experiments, analytical instruments, various piping materials for infusion, and the like.

The hydrogenated α-olefin-dicyclopentadiene copolymer used in the present invention has high heat resistance, is excellent in moldability, dimensional stability, weather resistance, and has good electric insulation. It is also preferable as an insulating material for electric / electronic parts, and can be used in a wide range. Both the dielectric constant and the dielectric loss tangent are small and their frequency dependence and temperature dependence are small, so that a stable insulating material can be obtained. In particular, it has an advantage that the dielectric loss tangent is low even in a high frequency band such as a GHz band, and further, there is almost no fluctuation due to a temperature change. The dielectric loss tangent of the hydrogenated α-olefin-dicyclopentadiene copolymer in the range of 1 KHz to 20 GHz is 0.001 or less. In recent years, the use of high frequencies has been rapidly expanding in the field of communications and computers such as mobile phones and wireless devices, and such advantages are as an insulating material that has little loss and is stable against temperature changes such as heat generation of elements.
It is suitable for various high-precision electric and electronic parts for high frequencies.

Specific insulating materials for electric / electronic parts in the present invention include, for example, electric cables, covering materials for electric wires, structural members and housings used for electronic devices such as computers, televisions, telephones, printed wiring boards, and the like. General circuit board such as multilayer printed wiring board, transistor, IC, L
Examples include semiconductor sealing materials used for SI and the like, insulating materials for electronic components such as LCD substrates, motors, and capacitors. Of these, insulating materials suitable for high frequencies in the GHz band are preferable, and examples thereof include high frequency circuit boards, films used for high frequency film capacitors, and high frequency compatible connectors.

[0075]

According to the present invention, hydrogenated α-olefin-
A molding material comprising a dicyclopentadiene copolymer is provided. This molding material not only has excellent transparency and heat resistance, but also has chemical resistance, low elution of impurities, electrical insulation,
It has excellent high frequency characteristics and can be suitably used as a molding material for medical and pharmaceutical applications and as an insulating material for electric and electronic devices.

[0076]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples.

The toluene (solvent) and dicyclopentadiene used were all purified by distillation and dried sufficiently. As the metallocene, isopropylene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride was purchased from Boulder Scientific and used as it was.
The ionic boron compound is trityl-tetrakis (pentafluorophenyl) borate manufactured by Tosoh Akzo Co., Ltd.
Purchased and used as is. Triisobutylaluminum was purchased from Tosoh Akzo Co., Ltd. at a concentration of 2 M in toluene and used as it was. Tris (acetylacetonate) cobalt was purchased from Wako Pure Chemical Industries, Ltd. and used as it was.

The items measured in the examples were measured by the following methods. Glass transition temperature (Tg): TA Instruments
The temperature was raised at a rate of 20 ° C./min using Model 2920 DSC. Molecular weight: 30 ° C. of a 0.5 g / dL toluene solution
The reduced viscosity η _sp / c at was measured. Hydrogenation rate: Quantified by ¹ H-NMR using a JEOL JNM-A-400 type nuclear magnetic resonance absorption apparatus. Residual metal content in resin: quantified by ICP emission spectrometry. Content of low molecular weight organic substance in resin: Resin was dissolved in xylene, and the solution was quantified by gas chromatography using a gas chromatograph GC-9A manufactured by Shimadzu Corporation. Total light transmittance: UV-visible spectrometer (U, manufactured by Shimadzu Corporation)
V-240) was used. Coloring degree of molded product: The b value was measured with a Minolta colorimeter CR-200, and the difference Δ from a white calibration plate (b = + 2.62) was measured.
It evaluated with b. Dielectric constant and dielectric loss: HP made LCR meter (HP 4
284A) or HP network analyzer (H
P 8510C).

Reference Example 1 The inside of a 3 L stainless steel polymerization reaction vessel was purged with nitrogen, and dicyclopentadiene 18 was added.
1 g, 1150 g of toluene and 3.4 g of triisobutylaluminum were added. After replacing the inside of the container with ethylene under normal pressure, 122 mg of isopropylene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride was used.
And triisobutylaluminum 0.2 g in toluene 85
g), and 267 mg of trityl-tetrakis (pentafluorophenyl) borate
Was dissolved in 85 g of toluene, and added to the polymerization system at 20 ° C. in three divided portions of 1/3 each, and polymerization was carried out at 30 ° C. During the polymerization, ethylene at normal pressure was constantly supplied, and 157 g of dicyclopentadiene was added at such a rate that the ratio of the addition rate of dicyclopentadiene to the consumption rate of ethylene became 42:58. When the consumption of ethylene reached 90% of the molar amount corresponding to the total amount of added dicyclopentadiene of 338 g (110 minutes after the initial addition of the catalyst solution), the supply of ethylene was stopped, and the reaction was terminated.

The obtained polymerization reaction solution was immediately added to a volume of 5
Under an atmosphere of nitrogen, and tris (acetylacetonato) cobalt was added to the solution beforehand.
A hydrogenation catalyst solution prepared by reacting 0 g with 4.8 g of triisobutylaluminum in 20 mL of toluene at room temperature under a nitrogen atmosphere for 5 minutes was added. Then, hydrogen pressure 3
A hydrogenation reaction was performed at 0 atm and a temperature of 110 ° C. for 150 minutes.

After cooling the solution after the hydrogenation reaction to 95 ° C., an aqueous lactic acid solution containing 20.5 g of lactic acid and 2.7 g of water was added dropwise over 10 minutes while stirring under a nitrogen atmosphere.
The reaction was performed at 5 ° C. for 2 hours. The reaction turned from a dark brown to a cloudy pink slurry. The slurry was subsequently filtered. A filter (Naslon NF-05) having a pore size of 5 μm was set in a cylindrical filter having a diameter of 11 cm, and celite was placed on the filter with 5 cm, and a woven fabric of flannel was further placed on the filter to perform pressure filtration. Filtration proceeded smoothly. The obtained filtrate was subjected to an adsorption treatment using basic alumina to obtain a colorless and transparent resin solution.

To this solution, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] was added in an amount of 0.2% by weight based on the hydrogenated copolymer. , And then the solvent and tetrahydrodicyclopentadiene were distilled off. At first, toluene was distilled off at normal pressure, and the temperature was gradually increased.
The temperature was raised to 80 ° C., and distillation was continued under reduced pressure until no volatile components were observed. Next, the molten resin was passed through an extruder under a nitrogen atmosphere to obtain colorless and transparent pellets. When the pellets were examined, the reduced viscosity η _sp / c at 30 ° C. of a toluene solution having a concentration of 0.5 g / dL was 0.40 d
L / g, glass transition temperature is 147 ° C., hydrogenation rate is 99.9.
% (A signal of a double bond was not observed in ¹ H-NMR measurement). When the amount of residual metal was quantified by ICP emission spectrometry, Zr: 0.1 ppm or less, B:
0.1 ppm or less, Co: 0.7 ppm and Al:
It was an extremely low value of 1.8 ppm. A 5% by weight toluene solution obtained by re-dissolving the pellets in toluene was added to a 1 μm pore size.
When the gel component in the pellet was examined by passing through a micro filter of m, the gel component was 0.01% by weight or less. Further, when the content of low molecular weight organic substances in the pellets was examined by gas chromatography (GC), toluene and tetrahydrodicyclopentadiene were not observed, and it was found that low molecular weight organic substances were almost completely distilled off.

[Reference Example 2] The metallocene solution and the cocatalyst solution at the time of polymerization were added to the polymerization reaction system in 1/5 increments every 5 minutes in 5 batches.
Reference Example 1 except that the polymerization reaction was terminated after 80 minutes.
In the same manner as in the above, pellets of a hydrogenated ethylene-dicyclopentadiene copolymer were obtained. When the pellets were examined in the same manner as in Reference Example 1, the reduced viscosity η _sp / c was 0.55 d.
L / g (0.5 g / dL toluene solution, 30 ° C.), glass transition temperature is 145 ° C., hydrogenation rate is 99.9% or more ( ¹
No signal of a double bond was observed by 1 H-NMR measurement). Further, the residual metal amount is Zr: 0.1 ppm or less,
B: 0.1 ppm or less, Co: 0.6 ppm and A
l: extremely low value of 1.6 ppm. The gel component in the pellet was 0.01% by weight or less. From the GC, it was found that toluene and tetrahydrodicyclopentadiene were not observed in the pellet, and that low-molecular-weight organic substances were almost completely distilled off.

Example 1 Using the pellets of the hydrogenated ethylene-dicyclopentadiene copolymer obtained in Reference Example 1, injection molding was performed using an injection molding machine. At a melting temperature of the resin in the cylinder of 280 ° C. and a mold temperature of 80 ° C., a square plate of 88 mm × 50 mm × 2 mm was formed. The obtained square plate has a total light transmittance of 90% and a Δb value of 0.30.
And less coloring and high transparency. No silver streaks were observed in appearance, and no distortion was observed.

This square plate was autoclaved at 121 ° C. and 3
After performing steam treatment for 0 minutes and cooling to room temperature, the transparency was examined. The total light transmittance was 90%, and the Δb value was 0.3.
0, the same as before the treatment, and no decrease in transparency was observed. No change in appearance was observed.

Example 2 A square plate obtained by molding in the same manner as in Example 1 was washed with water and distilled water for injection and dried. This was cut to a width of 10 mm, 15 g thereof was placed in a hard glass flask, impregnated with 300 mL of sterile physiological saline, and heated at 121 ° C. for 1 hour in an autoclave. After cooling to room temperature, the test piece was taken out and physiological saline was collected. Separately, the same treatment was performed without inserting a square plate test piece, and using this as a blank, the amount of elution from the test piece was determined from the difference between the results of analysis by atomic absorption spectrometry. As a result, zirconium, boron, cobalt, and aluminum were all 0.1 ppm or less (less than the detection limit), and almost no metal components were eluted. Further, when the amount of the eluted organic substance was examined by gas chromatography analysis, it was 1 ppm or less, and the elution of the organic substance was hardly observed. The pH difference between the physiological saline solution containing the test piece and heat-treated and the blank heat-treated without the test piece was 0.05.

In this dissolution test, 300 mL of sterile physiological saline to be impregnated into the test piece was replaced with 300 mL of ethanol, and heat treatment was performed at 70 ° C. for 24 hours, and the amount of dissolution from the test piece was examined in the same manner. Boron, cobalt and aluminum were all 0.1 ppm or less (below the detection limit), and almost no metal components were eluted. Further, the elution amount of organic substances was 1 ppm or less, and almost no elution of organic substances was observed.

[Example 3] A square plate obtained by molding in the same manner as in Example 1 was subjected to methanol, ethanol, acetone, isopropanol, soapy water, 10% hydrochloric acid, 36% hydrochloric acid, 10% sulfuric acid, 50% Nitric acid, glacial acetic acid, 10% aqueous sodium carbonate solution, 30% aqueous ammonia, 50% caustic soda, 40% aqueous formaldehyde solution, and 30% aqueous hydrogen peroxide were each separately immersed for 10 minutes. No change was observed in the appearance of any of the square plates. The ethanol, 10% hydrochloric acid, and 10% sodium carbonate aqueous solution were further immersed for 48 hours, but no change was observed in appearance.

Example 4 Injection molding was performed using the pellets of the hydrogenated ethylene-dicyclopentadiene copolymer obtained in Reference Example 1 to form a cylindrical molded product having a diameter of 10 mmΦ, which was then processed. Thus, a cylindrical molded product having an outer diameter of 7.00 mmΦ × an inner diameter of 3.04 mmΦ × 10 mm was obtained. Using this as a test sample, a frequency of 50 MHz to 2 using an HP network analyzer (HP 8510C).
The dielectric constant and the dielectric loss tangent in the range of 0 GHz were measured. Apart from this, the hydrogenated ethylene-
A 93 μm-thick cast film having a high surface smoothness was prepared from a toluene solution of dicyclopentadiene copolymer pellets by a solution casting film forming method, and the frequency was 20 Hz to 1 MH using an HP LCR meter (HP 4284A).
The dielectric constant and the dielectric tangent in the range of z were measured. In these measurement results, 100 Hz, 10 KHz, 1 MH
z, temperature 25 ° C. at frequencies of 1 GHz and 10 GHz
In each case, the dielectric constant was almost constant at 2.30, and there was almost no fluctuation with frequency. Further, the dielectric loss tangent was an extremely low value of 0.001 or less at any frequency. Even when the measurement temperature was raised to 50 ° C. or 80 ° C., the dielectric constant was 2.30 and the dielectric loss tangent was 0.001.
The results were as follows, and almost no fluctuation due to temperature was observed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 45/00 C08L 45/00 (72) Inventor Masaki Takeuchi 4-2-2 Asahioka, Hino-shi, Tokyo Teijin Inside the Tokyo Research Center Co., Ltd. (72) Inventor Kiyonari Hashizume 4-2-2 Asahigaoka, Hino-shi, Tokyo Teijin Inside the Tokyo Research Center Co., Ltd. (72) Kaoru Iwata 4-2-2 Asahigaoka, Hino-shi, Tokyo Teijin Tokyo Research Center F-term (reference) 4J002 BK001 EJ026 EJ036 EJ046 EJ066 EU196 EV076 EW066 EW086 EW126 FD076 GB01 GQ01 4J100 AA02Q AA03Q AR03S AR21R AR22P CA04 CA06 CA31 DA09 HA04 HC88 HC90 HC91 JA44 JA51

Claims (3)

[Claims] 1. A molding material comprising a hydrogenated α-olefin-dicyclopentadiene copolymer represented by the following copolymer [X] or [Y]. Copolymer [X]: 0 to 39 mol% of the following formulas (A) and 6
The reduced viscosity η _sp / c measured at 30 ° C. in a toluene solution having a concentration of 0.5 g / dL is in the range of 0.25 to 3 dL / g. A copolymer having a residual metal component content of 10 ppm or less. Embedded image [In the formula (A), R ¹ is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. ] [In the formula (B), R ² is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. ] Copolymer [Y]: represented by a repeating unit of the following formulas (A), (B), (C) and (D): [In the formula (A), R ¹ is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. ] [In the formula (B), R ² is a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms. ] [In the formula (C), n is 0 or 1, m is 0 or a positive integer, p is 0 or 1, R ^{3 to} R ²² are the same or different, and represent a hydrogen atom, a halogen atom, a carbon atom, Number 6 ~
An aromatic hydrocarbon group of 10 or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and an alkylidene group formed by R ¹⁹ and R ²⁰ or by R ²¹ and R ²² ; R ¹⁹ or R ²⁰ and R ²¹ or R ²² may form a ring, and the ring may have a double bond or an aromatic ring. ] [In the formula (D), q is an integer of 2 to 8. ] [A], [B], [B],
[C] and [D], the composition ratio of which is ([A] +
[B]) / ([C] + [D]) = 95-99.9 / 0.
[A] / [B] = 0 to 39/61 to 100 and [D] / [C] = 0 to 95/5 to 100, in a toluene solution having a concentration of 0.5 g / dL. , A copolymer having a reduced viscosity η _sp / c measured at 30 ° C. in the range of 0.25 to 3 dL / g and a residual metal component content of 10 ppm or less. 2. The molding material according to claim 1, wherein the molding material is a molding material for medical or pharmaceutical use. 3. The molding material according to claim 1, wherein said molding material is an insulating material for electric / electronic parts.