JP2017179001A - Resin molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin molded body excellent in water vapor barrier property and impact resistance and hardly absorbing proteins.SOLUTION: There is provided a resin molded body having norbornene-based ring-opened polymer hydride or a resin composition containing the norbornene-based ring-opened polymer hydride as a molding material, the norbornene-based ring-opened polymer hydride is an amorphous polymer having a repeating unit derived from 2-norbornene and a repeating unit derived from a substituent-containing norbornene-based monomer and the molding material and the resin molded body have specific physical values.SELECTED DRAWING: None

Description

  The present invention relates to a resin molded article that is excellent in water vapor barrier properties and impact resistance and hardly adsorbs protein.

  In recent years, cyclic olefin resins are widely used as molding materials for resin moldings such as pharmaceutical containers and medical instruments because they are excellent in transparency, low moisture absorption, heat resistance, chemical resistance, and the like. Yes.

  For example, Patent Document 1 discloses a norbornene-based ring-opening polymer hydrogen obtained using a norbornene-based monomer capable of giving a crystalline polymer and a norbornene-based monomer capable of giving an amorphous polymer. The compounds are described. This document also describes that the norbornene-based ring-opening polymer hydride is excellent in water vapor barrier properties, heat resistance, oil resistance, mechanical properties, transparency, workability, and the like.

JP 2012-140541 A

The norbornene-based ring-opening polymer hydride described in Patent Document 1 has both a crystalline property and an amorphous property, and such a polymer is excellent in various properties as described above.
However, even when this norbornene-based ring-opening polymer hydride is used as a molding material, a resin molded article having excellent impact resistance may not be obtained.
In general, if the monomer used is changed or additives are used in order to improve the impact resistance of the resin, the resulting molded resin has a reduced water vapor barrier property or protein adsorption. Sometimes it was easier to do.

In a pharmaceutical container, it is important to have excellent impact resistance, excellent water vapor barrier properties, and difficulty in adsorbing proteins. However, as described above, the actual situation is that it is difficult to obtain a resin molded body that sufficiently satisfies all these characteristics.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a resin molded article that is excellent in water vapor barrier properties and impact resistance and hardly adsorbs proteins.

  In order to solve the above-mentioned problems, the present inventors diligently studied a resin molded body obtained by molding a cyclic olefin resin. As a result, the resin molded body having a retardation value in a specific range obtained using a specific molding material is found to be excellent in water vapor barrier properties and impact resistance, and difficult to adsorb proteins, The present invention has been completed.

Thus, according to the present invention, the following resin moldings [1] to [3] are provided.
[1] A resin molded body using a hydride of norbornene ring-opening polymer or a resin composition containing a hydride of norbornene ring-opening polymer as a molding material, wherein the hydride of norbornene ring-opening polymer is 2 -An amorphous polymer having a repeating unit derived from norbornene and a repeating unit derived from a substituent-containing norbornene-based monomer, formed by molding the molding material into a sheet, and cutting out the resulting resin sheet When the tensile test was performed on the B-shaped test piece based on ISO 527, the tensile elongation was 100 to 200%, and the retardation value was measured when the retardation was measured using at least a part of the resin molded body as the test piece. Is a resin molded product characterized by being 10 to 100 nm.
[2] The total amount of the repeating unit derived from 2-norbornene and the repeating unit derived from the substituent-containing norbornene monomer in the hydride of norbornene-based ring-opening polymer is 90 to The resin molded product according to [1], which is 100 mol%.
[3] Ratio of repeating unit derived from 2-norbornene and repeating unit derived from substituent-containing norbornene-based monomer in the hydride of norbornene-based ring-opening polymer (repeating unit derived from 2-norbornene: substituent-containing norbornene) [1] or [2], wherein the molar ratio of the repeating units derived from the monomer is 20:80 to 80:20.

  ADVANTAGE OF THE INVENTION According to this invention, the resin molded object which is excellent in water vapor | steam barrier property and impact resistance, and is hard to adsorb | suck protein is provided.

It is a figure explaining the retardation measurement in an Example.

  The resin molded body of the present invention is a resin molded body using a norbornene ring-opening polymer hydride or a resin composition containing a norbornene ring-opening polymer hydride as a molding material, the norbornene ring-opening polymer. The hydride is an amorphous polymer having a repeating unit derived from 2-norbornene and a repeating unit derived from a substituent-containing norbornene monomer, and the resin obtained by molding the molding material into a sheet shape When a tensile test was performed based on ISO 527 for the B-shaped test piece prepared by cutting out the sheet, the tensile elongation was 100 to 200%, and the retardation was measured using at least a part of the resin molded body as the test piece. Sometimes, the retardation value is 10 to 100 nm.

[Molding material]
In the resin molded product of the present invention, a hydride of norbornene ring-opening polymer (hereinafter referred to as “heavy”) having a repeating unit derived from 2-norbornene and a repeating unit derived from a substituent-containing norbornene monomer as a molding material. Or a resin composition containing the polymer (α).

The norbornene ring-opening polymer hydride is a polymer obtained by subjecting a norbornene ring-opening polymer to a hydrogenation reaction. The norbornene-based ring-opening polymer is a polymer obtained by subjecting a norbornene-based monomer to a ring-opening polymerization reaction.
The “norbornene monomer” refers to a monomer having a norbornene ring structure in the molecule.

2-Norbornene used for producing the polymer (α) is a known compound. 2-norbornene is obtained, for example, by reaction of cyclopentadiene with ethylene.
Since the polymer (α) has a repeating unit derived from 2-norbornene, the resin molded product obtained by molding the polymer (α) or the resin composition containing the polymer (α) is heat resistant. Excellent water vapor barrier properties as well.

The substituent-containing norbornene monomer used for producing the polymer (α) is a norbornene monomer having a substituent. The “substituent-containing norbornene-based monomer” includes those having a newly formed ring structure in which two or more substituents are bonded.
Since the polymer (α) has a repeating unit derived from a substituent-containing norbornene-based monomer, a resin molded product obtained by molding a polymer (α) or a resin composition containing the polymer (α) Is excellent in impact resistance.

  Examples of the substituent-containing norbornene-based monomer include a substituent-containing norbornene-based monomer that does not have a ring condensed with the norbornene ring in the molecule and a polycyclic norbornene-based monomer having three or more rings.

  Specific examples of the substituent-containing norbornene-based monomer having no ring condensed with the norbornene ring in the molecule include 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, and 5-decyl. Norbornenes having an alkyl group or a cycloalkyl group such as norbornene, 5-cyclohexylnorbornene, 5-cyclopentylnorbornene; 5-vinylnorbornene, 5-ethylidenenorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene, 5-cyclopentenylnorbornene Norbornenes having an alkenyl group or cycloalkenyl group such as: norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnor Lunene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, 5,6-di It has a polar group containing an oxygen atom such as (hydroxymethyl) norbornene, 5,5-di (hydroxymethyl) norbornene, 5-hydroxyisopropylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene Norbornenes; norbornenes having a polar group containing a nitrogen atom such as 5-cyanonorbornene;

  The tricyclic or more polycyclic norbornene monomer is a norbornene monomer having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. Specific examples thereof include monomers represented by the following formula (1) or formula (2).

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

Examples of the monomer represented by the formula (1) include aromatic rings such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene. monomers having no; tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 ^{2 , 11} . Monomer having an aromatic ring such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene) ;

  Examples of the monomer represented by the formula (2) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.

  Specific examples of tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene. Tetracyclododecenes having a substituted or alkyl group; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl-8- Toxicarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride, etc. Tetracyclododecenes having substituents containing oxygen atoms; tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic imide A tetracyclododecene having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; a tetracyclododecene having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; Can be mentioned.

Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes having a substituted or alkyl group; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc .; Heterocyclic rings such as 12-phenylhexacycloheptadecene Sacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12 , 13-dicarboxylic acid, hexacycloheptadecene 12,13-dicarboxylic anhydride, etc., hexacycloheptadecenes having a substituent containing an oxygen atom; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13- Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic acid imide; Hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Hexa cycloheptanone decene and the like having a substituent containing a Le hexa cycloheptanone de silicon atoms Sen and the like.
These substituent-containing norbornene monomers can be used singly or in combination of two or more.

  As the substituent-containing norbornene-based monomer, a substituent-containing norbornene-based monomer having no ring condensed with the norbornene ring in the molecule is preferable, norbornene having an alkyl group or a cycloalkyl group, or an alkenyl group or Norbornenes having a cycloalkenyl group are more preferable, and norbornenes having an alkenyl group are more preferable.

When producing the polymer (α), in addition to the above-described 2-norbornene and substituent-containing norbornene monomers, other monomers capable of ring-opening copolymerization with these monomers may be used. it can.
Other monomers capable of ring-opening copolymerization with 2-norbornene and / or substituent-containing norbornene-based monomers include monocyclic olefins such as cyclohexene, cycloheptene, cyclooctene and their derivatives; cyclohexadiene, cyclohepta Cyclic dienes such as dienes and derivatives thereof; and the like.

The polymer (α) can be produced according to a known method using a metathesis polymerization catalyst.
Examples of the metathesis polymerization catalyst to be used include Japanese Patent Publication No. 41-20111, Japanese Patent Publication No. 46-14910, Japanese Patent Publication No. 57-17883, Japanese Patent Publication No. 57-61044, Japanese Patent Publication No. 54-86600. A general metathesis polymerization catalyst essentially described in (a) a transition metal compound catalyst component and (b) a metal compound promoter component, as described in JP-A-58-127728, JP-A-1-240517, etc. A Schrock type polymerization catalyst (Japanese Patent Laid-Open No. 7-179575, Schrock et al., J. Am. Chem. Soc., 1990, Vol. 112, p. 3875) and a Grubbs type polymerization catalyst (Fu et al., J. Am. Chem. Soc., 1993, 115, 9856-; Nguyen et al., J. Am. . .Soc, 1992 year, the first 114, pp. 3974, pp ~;. Grubbs et al, living ring-opening metathesis catalyst of WO 98/21214 pamphlet, etc.) and the like; and the like.

  Among these, in view of the molecular weight distribution of the resulting polymer, a metathesis polymerization catalyst comprising (a) a transition metal compound catalyst component and (b) a metal compound promoter component is preferred.

The (a) transition metal compound catalyst component is a compound of a transition metal belonging to Group IVB, VB, VIB, VIIB, or VIII of the Deming periodic table. For example, halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives of these, or derivatives of these transition metals. A complexed product of a complexing agent such as P (C ₆ H ₅ ) ₅ may be mentioned.

Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , WBr ₃ , WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₄ , WO ₂ and H ₂ WO ₄ . Of these, W, Mo, Ti, or V is preferable from the viewpoint of polymerization activity and the like, and these halides, oxyhalides, and alkoxy halides are particularly preferable.

  The (b) metal compound co-catalyst component is a compound of Group IA, IIA, IIIA, IVA, IIB, IIIB metal of the Deming periodic table and has at least one metal element-carbon bond or metal element-hydrogen bond. Is. Examples thereof include organic compounds such as Al, Sn, Li, Na, Mg, Zn, Cd, and B.

  Specific examples of the (b) metal compound promoter component include organoaluminum compounds such as trimethylaluminum, triisobutylaluminum, diethylaluminum monochloride, methylaluminum sesquichloride, ethylaluminum dichloride; tetramethyltin, diethyldimethyltin, tetra Organotin compounds such as butyltin and tetraphenyltin; organolithium compounds such as n-butyllithium; organic sodium compounds such as n-pentylsodium; organomagnesium compounds such as methylmagnesium iodide; organozinc compounds such as diethylzinc; Organic cadmium compounds such as cadmium; organic boron compounds such as trimethylboron; and the like. Of these, Group IIIB metal compounds are preferred, and Al organic compounds are particularly preferred.

  In addition to the components (a) and (b), a metathesis polymerization activity can be increased by adding a third component. As the third component to be used, aliphatic tertiary amine, aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound , Halogen-containing compounds, and other Lewis acids.

  The compounding ratio of these components is in the range of 1: 1 to 1: 100, preferably 1: 2 to 1:10 in terms of the molar ratio of the component (a): component (b) to the metal element. Moreover, (a) component: 3rd component is 1: 0.005-1: 50 by molar ratio, Preferably it is the range of 1: 1-1: 10.

  The use ratio of the polymerization catalyst with respect to the norbornene monomer is usually a molar ratio of (transition metal in the polymerization catalyst) :( norbornene monomer), usually 1: 100 to 1: 2,000,000, preferably The ratio is 1: 1,000 to 1: 20,000, more preferably 1: 5,000 to 1: 8,000. If the amount of the catalyst is too large, it is difficult to remove the catalyst after the polymerization reaction, and the molecular weight distribution may be widened. If the amount is too small, sufficient polymerization activity cannot be obtained.

  The ring-opening polymerization can be carried out without a solvent, but is preferably carried out in a suitable solvent. The organic solvent is not particularly limited as long as it dissolves or disperses the polymer and the polymer hydride under predetermined conditions and does not affect the polymerization and hydrogenation reaction, and an industrially widely used solvent is preferable. .

  Examples of such organic solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Cycloaliphatic hydrocarbons such as cyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene, Halogen-based aromatic hydrocarbons such as dichlorobenzene; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; Ethers such as diethyl ether and tetrahydrofuran The solvent etc. can be used. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers that are widely used industrially are preferable.

  When the polymerization is performed in an organic solvent, the concentration of the monomer in the solution is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. If the monomer concentration is less than 1% by weight, the productivity may be low. If it is greater than 50% by weight, the solution viscosity after polymerization may be too high, and the subsequent hydrogenation reaction may be difficult. is there.

  In the ring-opening polymerization, it is preferable to add a molecular weight modifier to the reaction system. The molecular weight of the resulting ring-opening polymer can be adjusted by adding a molecular weight regulator.

It does not specifically limit as a molecular weight regulator to be used, A conventionally well-known thing can be used.
For example, α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; allyl chloride and the like A halogen-containing vinyl compound such as glycidyl methacrylate; a nitrogen-containing vinyl compound such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl- Non-conjugated dienes such as 1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3- Conjugates such as butadiene, 1,3-pentadiene, 1,3-hexadiene Mention may be made of the ene or the like. Among these, α-olefins are preferable because of easy molecular weight adjustment.

  The addition amount of the molecular weight regulator may be an amount sufficient to obtain a polymer having a desired molecular weight, and is usually 1:50 to 1: 1 in a molar ratio of (molecular weight regulator) :( monomer). 1,000,000, preferably 1: 100 to 1: 5,000, more preferably 1: 300 to 1: 3,000.

The polymerization reaction is initiated by mixing the monomer and the polymerization catalyst. Although superposition | polymerization temperature is not specifically limited, Usually, -20- + 100 degreeC, Preferably, it is 10-80 degreeC, More preferably, it is 30-60 degreeC. If the polymerization temperature is too low, the reaction rate decreases, and if the polymerization temperature is too high, the molecular weight distribution may be widened due to side reactions.
The polymerization time is not particularly limited, but is usually 1 minute to 100 hours. Although the pressure conditions are not particularly limited, the polymerization is usually performed under a pressure of 0 to 1 MPa.

  After completion of the reaction, the desired norbornene-based ring-opening polymer can be isolated by ordinary post-treatment operation.

  The obtained norbornene-based ring-opening polymer is subjected to the next hydrogenation reaction step. As will be described later, the hydrogenation catalyst may be added to the reaction solution subjected to the ring-opening polymerization to continuously perform the hydrogenation reaction without isolating the norbornene-based ring-opening polymer.

  The hydrogenation reaction of the norbornene ring-opening polymer is a reaction in which hydrogen is added to a carbon-carbon double bond existing in the main chain of the norbornene ring-opening polymer. This hydrogenation reaction is performed by adding a hydrogenation catalyst to an inert solvent solution of a norbornene-based ring-opening polymer and supplying hydrogen into the reaction system.

  As the hydrogenation catalyst to be used, either a homogeneous catalyst or a heterogeneous catalyst can be used as long as it is generally used for hydrogenation of olefin compounds. Considering the removal of residual metals in the resulting polymer, a heterogeneous catalyst is preferable.

  Examples of homogeneous catalysts include combinations of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst systems comprising combinations of transition metal compounds and alkali metal compounds; noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, etc. .

  Examples of heterogeneous catalysts include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, nickel, palladium, platinum, rhodium, ruthenium, Alternatively, a solid catalyst system in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, or titanium oxide can be used.

  The amount of catalyst used is usually 0.05 to 10 parts by weight with respect to 100 parts by weight of the norbornene-based ring-opening polymer.

  As the inert organic solvent used in the hydrogenation reaction, the same aliphatic hydrocarbons, alicyclic hydrocarbons, aromatics as those exemplified as the organic solvent that can be used in the ring-opening polymerization of the norbornene-based monomer described above. Aromatic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing hydrocarbons, ethers and the like.

  The temperature of the hydrogenation reaction varies depending on the hydrogenation catalyst system used, but the hydrogenation temperature is usually -20 ° C to + 300 ° C, preferably 0 ° C to + 250 ° C, more preferably 100 ° C to 220 ° C. ° C. If the hydrogenation temperature is too low, the reaction rate may be slow, and if it is too high, side reactions may occur.

The hydrogenation rate of the main chain double bond of the polymer (α) is usually 80% or more, preferably 90% or more, more preferably 95% or more, still more preferably 99% or more, particularly preferably 99.9% or more. It is. When the hydrogenation rate is high, the heat resistance and moisture resistance are excellent, and resin burning hardly occurs during molding.
The hydrogenation rate of the polymer (α) can be determined by measuring ¹ H-NMR using deuterated chloroform as a solvent.

  After completion of the hydrogenation reaction, the polymer (α) can be obtained by filtering off the hydrogenation catalyst and the like from the reaction solution and removing volatile components such as a solvent from the filtrate.

  As a method for removing volatile components such as a solvent, a known method such as a coagulation method or a direct drying method can be employed.

  The coagulation method is a method for precipitating the polymer (α) by mixing the filtrate with a poor solvent for the polymer (α). Examples of the poor solvent to be used include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate;

  The polymer (α) obtained by solidification may be dried by heating in vacuum, nitrogen or air, and formed into particles, or, if necessary, pelletized using a melt extruder or the like. Can do.

  The direct drying method is a method in which the filtrate is heated under reduced pressure to remove the solvent. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, a high viscosity reactor device or the like. The degree of vacuum and temperature are appropriately selected depending on the apparatus and are not particularly limited.

  The isomerization rate of the obtained polymer (α) is usually 0 to 20%, preferably 0 to 15%, more preferably 1 to 10%. When the isomerization rate is high, heat resistance and moisture resistance may be lowered.

The isomerization rate of the polymer (α) is calculated from 33.0 ppm peak integrated value / (31.8 ppm peak integrated value + 33.0 ppm peak integrated value) × 100 measured by ¹³ C-NMR using deuterated chloroform as a solvent. can do. The 31.8 ppm peak is derived from the cis isomer of the repeating unit of 2-norbornene in the polymer, and the 33.0 ppm peak is derived from the trans isomer of the repeating unit of 2-norbornene in the polymer. is there.

  In order to make the isomerization ratio within the above range, it is preferable to make the reaction conditions for the hydrogenation reaction of the norbornene-based ring-opening polymer appropriate. For example, the reaction temperature is preferably 100 to 240 ° C., more preferably 150 to 230 ° C., particularly preferably 170 to 220 ° C., and the amount of hydrogenation catalyst used is 100 parts by weight of the norbornene-based ring-opening polymer. Preferably it is 0.1-3 weight part, More preferably, it is 0.1-1 weight part.

The total amount of 2-norbornene-derived repeating units and substituent-containing norbornene-based repeating units in the polymer (α) is preferably from 90 to 100 mol%, based on the total repeating unit amount, from 95 to 100 mol% is more preferable and 100% is more preferable.
Ratio of repeating unit derived from 2-norbornene and repeating unit derived from substituent-containing norbornene monomer in the hydride of norbornene-based ring-opening polymer (repeating unit derived from 2-norbornene: repeating unit-containing norbornene-based monomer) The molar ratio of the repeating unit derived from the body is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.
Resin molding that is excellent in water vapor barrier properties and impact resistance and is difficult to adsorb proteins because the amount of the repeating unit derived from 2-norbornene and the repeating unit derived from the substituent-containing norbornene monomer is within the above range. A body is easily obtained.

  The weight average molecular weight (Mw) of the polymer (α) is preferably 20,000 to 150,000, more preferably 40,000 to 100,000. When the weight average molecular weight (Mw) of a polymer ((alpha)) is too small, there exists a possibility that the intensity | strength of a resin molding may fall. On the other hand, if the weight average molecular weight (Mw) of the polymer (α) is too large, the moldability of the resin composition may be reduced.

Although the molecular weight distribution (Mw / Mn) of a polymer ((alpha)) is not specifically limited, Preferably it is 1-5, More preferably, it is 1-4.
When the molecular weight distribution of the polymer (α) is within the above range, a resin molded product having sufficient mechanical strength can be obtained.
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer (α) are standard polystyrene equivalent values by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. .

The polymer (α) is an amorphous polymer. When the polymer (α) is an amorphous polymer, it becomes easy to obtain a resin molded article having excellent impact resistance.
An amorphous polymer refers to a polymer whose melting point is not observed. The amorphous polymer (α) can be efficiently produced by increasing the randomness of the copolymer or conducting a polymerization reaction using a large number of monomers that easily form an amorphous polymer. be able to.

  When the molding material used in the present invention is a resin composition containing a polymer (α), as components other than the polymer (α), an antioxidant, an ultraviolet absorber, a light stabilizer, a near infrared absorber, Additives such as plasticizers, antistatic agents, acid supplements and the like can be mentioned.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.

  Examples of phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2′-methylenebis (6-t-butyl-4-methylphenol), 4,4 ′. -Butylidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), α-tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, [pentaerythritol tetrakis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate]] and the like.

  Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tetrakis (2 , 4-ditertiary butylphenyl) 4,4′-biphenyl diphosphite, trinonylphenyl phosphite and the like.

  Examples of sulfur-based antioxidants include distearyl thiodipropionate and dilauryl thiodipropionate.

Examples of the UV absorber include benzotriazole UV absorbers, bezoate UV absorbers, benzophenone UV absorbers, acrylate UV absorbers, and metal complex UV absorbers.
Examples of the light stabilizer include hindered amine light stabilizers.

As near infrared absorbers, cyanine-based near infrared absorbers; pyrylium-based infrared absorbers; squarylium-based near infrared absorbers; croconium-based infrared absorbers; azulenium-based near infrared absorbers; phthalocyanine-based near infrared absorbers; System near infrared absorbers; naphthoquinone near infrared absorbers; anthraquinone near infrared absorbers; indophenol near infrared absorbers;
Examples of the plasticizer include a phosphoric acid triester plasticizer, a fatty acid monobasic acid ester plasticizer, a dihydric alcohol ester plasticizer, and an oxyacid ester plasticizer.
Examples of the antistatic agent include fatty acid esters of polyhydric alcohols.
Examples of the acid supplement include magnesium oxide and zinc stearate.

  The content of these components can be appropriately determined according to the purpose. Content is 0.001-5 weight part normally with respect to 100 weight part of polymers ((alpha)), Preferably it is the range of 0.01-1 weight part.

  The resin composition containing the polymer (α) can be obtained by mixing each component according to a conventional method. Examples of the mixing method include a method of mixing each component in an appropriate solvent and a method of kneading in a molten state.

Kneading can be performed using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder. The kneading temperature is preferably 200 to 400 ° C, more preferably 240 to 350 ° C. In kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.
After kneading, it can be pelletized by extruding into a rod shape and cutting into an appropriate length with a strand cutter according to a conventional method.

The molding material used in the present invention is formed into a sheet shape, and when a tensile test is performed based on ISO 527 for a B-shaped test piece produced by cutting out the obtained resin sheet, the tensile elongation is 100 to 200%, Preferably it is 150 to 200%.
In this tensile test, when a molding material having a tensile elongation of less than 100% is used, the resulting resin molded product is inferior in impact resistance.
Tensile elongation is a physical property related to the type and proportion of the monomer used and the molecular weight of the polymer. Usually, a polymer containing many repeating units derived from a substituent-containing norbornene-based monomer and having a relatively small molecular weight tends to increase tensile elongation.

[Resin molding]
The resin molded body of the present invention is obtained by molding the molding material.
The shaping | molding method used when manufacturing the resin molding of this invention is not specifically limited. Examples thereof include an injection molding method, a press molding method, an extrusion molding method, and a blow molding method. Among these, when the resin molding is a pharmaceutical container or a medical instrument, an injection molding method or a blow molding method is preferable.

Although the melting temperature at the time of molding varies depending on the molding material to be used, it is usually 150 to 350 ° C, preferably 150 to 300 ° C. The mold temperature in the case of using a mold is usually 10 to 80 ° C, preferably 30 to 50 ° C.
Moreover, when manufacturing a resin molding by a blow molding method, blow mold temperature is 80-200 degreeC normally, Preferably it is 100-180 degreeC.
When the blow mold temperature is within the above range, a resin molded body having a retardation value within the range described later can be easily obtained.

The retardation value of the resin molded body of the present invention is 10 to 100 nm, preferably 10 to 50 nm, when the retardation is measured using at least a part thereof as a test piece.
When the retardation value exceeds 100 nm, the strength of the molded product is lowered. Moreover, it is difficult to obtain a resin molded product having a retardation value of less than 10 nm.
The retardation value is a physical property controlled by molding conditions. In a molding method using a mold, the retardation value tends to increase when the mold temperature is low.

The resin molded body of the present invention is excellent in impact resistance but excellent in water vapor barrier properties and difficult to adsorb proteins.
Since the resin molded body of the present invention has the above characteristics, it is preferably used in the medical field and the like.
Examples of the resin molded body of the present invention include containers such as pharmaceutical containers, cosmetic containers, and food containers; disposable syringes, prefilled syringes, vials, eye drop containers, medical test cells, infusion bags, scalpels, forceps, and liquid feeding tubes. Medical instruments such as petri dish, laboratory instruments such as petri dishes, culture vessels, disposable pipettes, etc.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples. In the following, “parts” and “%” are based on weight unless otherwise specified.

In Examples and Comparative Examples, various physical properties are measured as follows.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer before the hydrogenation reaction were measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using toluene as an eluent.
As a measuring device, GPC-8020 series (DP8020, SD8022, AS8020, CO8020, RI8020) manufactured by Tosoh Corporation was used. As standard polystyrene, Tosoh standard polystyrene, Mw of 500, 2630, 10200, 37900, 96400, 427000, 900000, and 5480000 were used in total.
The sample was prepared by dissolving the measurement sample in toluene so that the sample concentration would be 1 mg / ml, and then filtering through a cartridge filter (porous polytetrafluoroethylene filter having a pore diameter of 0.5 μm).
The measurement was carried out under the conditions of using two TSKgel GMHHR · Hs manufactured by Tosoh Corporation connected in series, a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer after the hydrogenation reaction are measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. did.
As a measuring device, HLC8121GPC / HT manufactured by Tosoh Corporation was used, and measurement was performed at a column temperature of 140 ° C.

(2) Retardation The blow molded body (resin container) having the shape shown in FIG. 1 (a) obtained in the example or the comparative example is subjected to cutting as shown by the dotted line in FIG. 1 (b). Retardation was measured using one of them as a test piece.
As a measuring device, WPA-100 (manufactured by Photonic Lattice) was used. The measurement was performed by shining light in the direction represented by the arrow in FIG.

(3) Tensile test A B-shaped test piece prepared by cutting out the resin sheet obtained in the example or the comparative example was subjected to a tensile test under a condition of a tensile speed of 50 mm / min based on ISO 527, and the tensile elongation was measured. . The measurement was performed using an autograph (product name “AGS-5kNH”, manufactured by Shimadzu Corporation).

(4) Water vapor permeability The water vapor barrier property evaluation test was performed based on JIS K 7129 (Method A) using the resin sheet obtained in the example or the comparative example as a test piece.
The test was performed using a water vapor permeability tester (product name “L80-5000 type”, manufactured by LYSSY) under conditions of a temperature of 40 ° C. and a relative humidity of 90%. It shows that water vapor | steam barrier property is so favorable that water vapor permeability [g / (m < ² > 24h)] is small.

(5) Protein adsorptivity The pellets obtained in Examples or Comparative Examples were dissolved in cyclohexane to obtain a solution having a concentration of 3.0% by weight.
Next, this solution was applied onto a silicon nitride substrate using a spin coater (film formation conditions: rotation speed: 3000 rpm, rotation time: 60 seconds), and the obtained coating film was dried at 80 ° C. for 1 hour. A measurement sample (test sensor chip) formed above was obtained.
The test sensor chip was set in a molecular interaction measuring device (manufactured by Konica Minolta), covered with a dedicated flow cell, and a flow path was produced on the test sensor chip. An aqueous solution of BSA (Bovin Serum Albumin) (concentration: 1000 μg / mL) was allowed to flow through this channel at a rate of 20 μL / min. After drying, the thickness of the thin film was measured, and the amount of protein adsorbed was calculated from the increased amount.
In the calculation of the protein adsorption amount, it was assumed that the molecular weight of BSA was 66 kDa and the particle diameter was 3 × 10 ⁻⁶ mm.

(6) Drop impact test The blow molded product obtained in the example or the comparative example was filled with pure water, sealed with a cap, and allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 1 hour. Thereafter, the bottom surface of the blow-molded product was faced down and repeatedly dropped 10 times in a vertical direction from a height of 1.8 m, and then the presence or absence of deformation and water leakage was confirmed and evaluated according to the following criteria.
○: Neither deformation nor water leakage is observed.
Δ: There is no water leakage, but it is deformed.
X: Water leaks.

[Example 1]
(Synthesis of norbornene-based ring-opening polymer hydride)
7 parts of norbornene monomer mixture shown in Table 1 (1% with respect to the total amount of norbornene monomer used for polymerization) and 1,600 parts of dehydrated cyclohexane in a polymerization reactor which was dried and nitrogen-substituted inside Then, 4.71 parts of 1-hexene, 1.3 parts of diisopropyl ether, 0.33 parts of isobutyl alcohol, 0.84 part of triisobutylaluminum and 30 parts of a 0.66% tungsten hexachloride solution in cyclohexane are added at 55 ° C. Stir for 10 minutes.
Next, while maintaining the reaction system at 55 ° C. and stirring, 693 parts of the monomer mixture and 72 parts of a tungsten hexachloride 0.77% cyclohexane solution are continuously added dropwise to the polymerization reactor over 150 minutes. Further, after stirring for 30 minutes after completion of dropping, 1.0 part of isopropyl alcohol was added to stop the polymerization reaction.
When the polymerization reaction solution was analyzed by gas chromatography, the conversion ratio of the monomer to the polymer was 100%.

Next, 300 parts of the polymerization reaction solution containing the above polymer was transferred to an autoclave equipped with a stirrer, and 100 parts of cyclohexane and a diatomaceous earth-supported nickel catalyst (product name “T8400RL”, nickel support rate 58%) manufactured by JGC Chemical Co., Ltd.) 2.0 Part was added. After replacing the inside of the autoclave with hydrogen, the reaction was carried out for 6 hours at 180 ° C. under a hydrogen pressure of 4.5 MPa.
After completion of the hydrogenation reaction, a pressure filter (made by Ishikawajima-Harima Heavy Industries Co., Ltd., product name “Fundafilter”) with diatomaceous earth (made by Showa Chemical Industry, product name “Radiolite (registered trademark) # 500”) as a filter bed is used. ) And pressure filtered at a pressure of 0.25 MPa to obtain a colorless and transparent solution.
Subsequently, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty) as an antioxidant per 100 parts of the hydride was added to the resulting solution. -0.5 part of Chemicals, product name "Irganox (registered trademark) 1010") was added and dissolved.
This solution was filtered through a filter (Cuneau Filter, product name “Zeta Plus (registered trademark) 30H”, pore size 0.5 to 1 μm), and then the filtrate was a metal fiber filter (Nichidai, pore size 0.4 μm). ) To remove foreign matters.
Next, the obtained filtrate is concentrated at a temperature of 260 ° C. and a pressure of 1 kPa or less by removing a cyclohexane and other volatile components as a solvent from the solution using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.). Extruded into a strand in a molten state from a die directly connected to the machine, cooled with water, and then cut with a pelletizer (product name “OSP-2”, manufactured by Nagata Seisakusho) to obtain a pellet of a born-hydrogenated norbornene-based polymer. The hydrogenation rate of the obtained norbornene-based ring-opening polymer hydride was 99% or more. The molecular weight (Mw) of the norbornene-based ring-opening polymer hydride is shown in Table 1. In addition, when differential scanning calorimetry was performed, the melting point of the norbornene-based ring-opening polymer hydride was not observed.
As described above, a protein adsorption test was performed using the pellet, and the pellet was used as a molding material for a resin molded body as follows.

(Manufacture of resin sheets)
The obtained pellets were subjected to T using a hanger manifold type T-die type film melt extrusion machine having a resin melt kneader equipped with a screw having a screw diameter of 50 mmφ, a compression ratio of 2.5, and L / D = 30. Die molding was performed to obtain a single layer film (resin sheet) having a thickness of 100 μm. Using the obtained resin sheet, a tensile test was performed to measure water vapor permeability. The results are shown in Table 1.

(Manufacture of containers)
The obtained pellets were injection molded at a resin temperature of 220 ° C. and a mold temperature of 30 ° C. to prepare a preform having a total length of 145.4 mm, a maximum outer diameter of 29.7 mm, and a wall thickness of 4.7 mm. This preform was stretched 1.55 times in length and 2.00 times in width on a blow molding machine under conditions of a preform heating temperature of 150 ° C., a blow time of 2.10 seconds, and a mold temperature of 121 ° C. A molded body was produced. Using the obtained blow molded article, the retardation was measured and a drop impact test was performed. The results are shown in Table 1.

[Examples 2 to 5, Comparative Examples 1 to 3]
A resin sheet and a molded body were produced in the same manner as in Example 1 except that the norbornene-based ring-opening polymer hydride described in Table 1 was used and the Puro molding was performed under the conditions described in Table 1. Each test was conducted. The results are shown in Table 1.
In addition, about the norbornene-type ring-opening polymer hydride obtained in Examples 2-5, when the differential scanning calorimetry was conducted, melting | fusing point was not observed.

The following can be seen from Table 1.
The resin moldings obtained in Examples 1 to 5 have low water vapor permeability and are difficult to adsorb proteins. Moreover, the blow molded article is excellent in impact resistance.
On the other hand, the resin molded body obtained in Comparative Example 1 uses a molding material having inferior tensile elongation. The impact resistance of the resin molding obtained in Comparative Example 1 is not high.
Moreover, the resin molding obtained by the comparative example 2 contains the norbornene-type ring-opening polymer hydride which does not have a repeating unit derived from 5-ethylidene norbornene. The resin molded body obtained in Comparative Example 2 is not high in impact resistance. Moreover, protein was easy to adsorb | suck.
The resin molded body obtained in Comparative Example 3 has a large retardation value. The resin molded body obtained in Comparative Example 3 is greatly inferior in impact resistance.

Claims (3)

A resin molded body using a hydride of norbornene-based ring-opening polymer or a resin composition containing a hydride of norbornene-based ring-opening polymer as a molding material,
The hydride of the norbornene-based ring-opening polymer is an amorphous polymer having a repeating unit derived from 2-norbornene and a repeating unit derived from a substituent-containing norbornene-based monomer,
For the B-shaped test piece formed by molding the molding material into a sheet and cutting out the obtained resin sheet, the tensile elongation was 100 to 200% when a tensile test was performed based on ISO 527,
When the retardation is measured using at least a part of the resin molded body as a test piece, the resin molded body has a retardation value of 10 to 100 nm.   The total amount of the repeating unit derived from 2-norbornene and the repeating unit derived from the substituent-containing norbornene monomer in the hydride of the norbornene-based ring-opening polymer is 90 to 100 mol% based on the total repeating unit amount. The resin molded product according to claim 1, wherein   Ratio of repeating unit derived from 2-norbornene and repeating unit derived from substituent-containing norbornene monomer in the hydride of norbornene-based ring-opening polymer (repeating unit derived from 2-norbornene: repeating unit-containing norbornene-based monomer) The resin molding of Claim 1 or 2 whose molar ratio of the repeating unit derived from a body is 20: 80-80: 20.

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