JP7010757B2 - Molding materials and moldings containing cyclic olefin copolymers - Google Patents

Description

The present invention relates to a molding material and a molded product containing a cyclic olefin copolymer.

Cyclic olefin resins are excellent in transparency and chemical resistance. Therefore, for example, it is being studied to be used as a material for forming a molded product such as a medical container.

As the prior art regarding the cyclic olefin resin, for example, Patent Document 1 can be mentioned. Patent Document 1 describes a cyclic olefin resin composition containing specific cyclic olefin resins (A1) and (B1).

On the other hand, Patent Document 2 describes a ternary copolymer obtained by polymerizing ethylene, norbornene and cyclooctene. However, Patent Document 2 describes that this ternary copolymer is particularly preferable as a film-forming material, and there is no specific description regarding a medical container.

Japanese Unexamined Patent Publication No. 2001-26693 International Publication No. 2013/153901

Medical containers such as syringes and chemical storage containers are required to have heat resistance to withstand sterilization and impact resistance to withstand external impact.
Further, according to the study by the present inventors, it was found that there is room for improvement in the conventional medical container in terms of improving the scratch resistance during transportation of the container and in the sterility line.

The present invention has been made in view of such circumstances. That is, to provide a molding material containing a cyclic olefin resin (copolymer), which can obtain a molded product having excellent scratch resistance while maintaining the heat resistance and impact resistance required for medical containers and the like. With the goal.

As a result of diligent studies, the present inventors have newly invented a molding material containing a cyclic olefin-based copolymer containing three specific structural units, and solved the above-mentioned problems.

The present invention is as follows.

1. 1.
A molding material containing a cyclic olefin-based copolymer, which is a molding material.
The cyclic olefin resin has a structural unit (A) derived from at least one olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms, and a tetracyclo [4.4.0. 1 ^{2, 5 3} . 1 ⁷ , 10] A cyclic olefin having a structural unit (B) derived from -3-dodecene and a structural unit (C) derived from at least one cyclic olefin selected from the group consisting of cyclooctene and cyclohexene. Molding material containing a system copolymer.
2. 2.
1. 1. The molding material described in 1.
A molding material in which the content of the structural unit (A) in the total structural units of the cyclic olefin-based copolymer is 10 to 80 mol%.
3. 3.
1. 1. Or 2. The molding material described in 1.
A molding material in which the content of the structural unit (C) in the total structural units of the cyclic olefin-based copolymer is 0.1 to 50 mol%.
4.
1. 1. ~ 3. The molding material according to any one of the above.
A molding material in which the content of the structural unit (C) in the total structural units of the cyclic olefin-based copolymer is 0.1 to 30 mol%.
5.
1. 1. ~ 4. The molding material according to any one of the above.
A molding material in which the content of the structural unit (C) in the total structural units of the cyclic olefin-based copolymer is 0.1 to 10 mol%.
6.
1. 1. ~ 5. A molded product containing the cyclic olefin-based copolymer according to any one of the above.
7.
6. It is a molded product described in
A molded product that is a medical container.
8.
6. Or 7. It is a molded product described in
A molded product that is a syringe or a chemical storage container.

According to the present invention, a molding material containing a cyclic olefin resin (copolymer) capable of obtaining a molded product having excellent scratch resistance while maintaining the heat resistance and impact resistance required for medical containers and the like. Can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, the notation "a to b" in the description of the numerical range means a or more and b or less unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".
In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The notation "(meth) acrylic" herein represents a concept that includes both acrylic and methacrylic. The same applies to similar notations such as "(meth) acrylate".

<Molding material>
The molding material of this embodiment contains a cyclic olefin-based copolymer.
This cyclic olefin-based copolymer is
-Structural unit (A) derived from at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms (hereinafter, also simply referred to as "structural unit (A)"). ,
-Tetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] -3-Dodecene-derived structural unit (B) (hereinafter, also simply referred to as "structural unit (B)") and
A structural unit (C) derived from at least one cyclic olefin selected from the group consisting of cyclooctene and cyclohexene (hereinafter, also simply referred to as “structural unit (C)”) and
including.
In the following, the above cyclic olefin-based copolymer is also simply referred to as "copolymer" or the like.

The reason why a molded product having excellent heat resistance, impact resistance and scratch resistance can be obtained by a molding material containing a copolymer containing such three types of structural units is as follows, although speculation is included. Can be explained to.

Since the above copolymer contains the tetracyclo structure of the structural unit (B), the main chain becomes very rigid. As a result, the glass transition temperature of the resin can be increased, which is considered to lead to high heat resistance.
Further, if the main chain of the copolymer is made rigid, it is conceivable that the molded body becomes too hard and rather brittle (that is, the impact resistance is lowered) when the resin is used as the molded body as the drawback. .. However, in the present embodiment, since the copolymer contains the structural unit (A) and the structural unit (C), the copolymer becomes moderately flexible and has sufficient impact resistance (property of appropriately absorbing impact). ) Is considered to be obtained. In particular, in the present embodiment, the copolymer contains the structural unit (C) (main chain monocyclic structure), which is more flexible than the structural unit (B) but is somewhat rigid, so that the hardness of the copolymer is high.・ It is presumed that the softness is adjusted appropriately.
Further, the structural unit (B) has a higher density than the structural unit derived from norbornene due to the large molecular weight of the structural unit itself. Similarly, the structural unit (C) has a higher density than the structural unit derived from an olefin having a cyclic structure such as cyclopentene and having 3 to 5 carbon atoms. That is, the above-mentioned copolymer tends to have a higher density than the conventional copolymer. It is speculated that this high density contributes to good scratch resistance.

The evaluation method of heat resistance, impact resistance and scratch resistance is not particularly limited, but for example, heat resistance is quantified by glass transition temperature measurement, impact resistance is measured by high-speed surface impact energy measurement, and scratch resistance is quantified by pencil hardness measurement. Can be evaluated.

The structural units of the copolymer contained in the molding material of the present embodiment, the properties of the copolymer, the physical properties, and the like will be described.

・ Structural unit (A)
As described above, the structural unit (A) is a structural unit derived from at least one olefin selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms.
The α-olefin having 3 to 20 carbon atoms may be linear or branched.
The linear ones include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Can be mentioned.
The branched ones are 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4. -Dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc., which are branched α-olefins having 4 to 20 carbon atoms. Can be mentioned.
As the structural unit (A), a structural unit derived from ethylene or propylene is particularly preferable.

The content of the structural unit (A) in the copolymer is preferably 10 to 80 mol%, more preferably 30 to 75 mol%, based on all the structural units contained in the copolymer (100 mol%). More preferably, it is 40 to 70 mol%. By adjusting to this range, it is considered that heat resistance, impact resistance and scratch resistance can be further improved.
The copolymer may contain only one type of structural unit corresponding to the structural unit (A), or may contain two or more types. For example, the copolymer may contain both a structural unit derived from ethylene and a structural unit derived from propylene.

・ Structural unit (B)
As described above, the structural unit (B) is tetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] -3-Dodecene is a structural unit derived from dodecene.
Tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] -3-Dodecene's structural formula is as follows. In the following, the numbers 1 to 12 indicate the carbon position numbers.

In the polymer, the structure (monomer) usually has a C = C double bond portion as a single bond due to coordination polymerization or the like, and becomes the main chain of the copolymer.

The content of the structural unit (B) in the copolymer is preferably 15 to 50 mol%, more preferably 20 to 45 mol%, based on the total structural unit contained in the copolymer (100 mol%). More preferably, it is 25 to 40 mol%.

・ Structural unit (C)
As described above, the structural unit (C) is a structural unit derived from at least one cyclic olefin selected from the group consisting of cyclooctene and cyclohexene.
Cyclooctene is known to be of cis type and trans type, both of which can be used as a monomer, or a mixture thereof may be used as a monomer, but the cis type is used in terms of reactivity and cost. It is preferable to use one.

The content of the structural unit (C) in the copolymer is preferably 0.1 to 50 mol%, more preferably 0.1 to 0.1, based on the total structural units contained in the copolymer (100 mol%). It is 30 mol%, more preferably 0.1 to 10 mol%.
The copolymer may contain only one type of structural unit corresponding to the structural unit (C), or may contain two or more types.

-Other structural units The copolymer may or may not contain structural units (described as structural units (D)) other than the above structural units (A) to (C).
Examples of the structural unit (D) include a structural unit derived from a conjugated diene, a structural unit derived from a (meth) acrylic monomer, a structural unit derived from norbornene, and the like.
When the copolymer contains the structural unit (D), its content in the copolymer is, for example, about 0.1 to 10 mol% based on all the structural units contained in the copolymer (100 mol%). Is.

-Regarding the arrangement of structural units In the copolymer, the arrangement of each structural unit is not particularly limited. That is, the copolymer may be a random copolymer, a block copolymer, or a copolymer other than these.
The copolymer is preferably a random copolymer from the viewpoint of ease of molding and homogeneity (related to impact resistance and the like) when formed into a molded product.

-Molecular weight, physical properties, etc. of the copolymer The weight average molecular weight of the copolymer is not particularly limited, but is, for example, 500,000 to 500,000, preferably 20,000 to 300,000. Within this range, it is possible to obtain effects such as heat resistance, impact resistance, and scratch resistance while obtaining appropriate moldability.
The dispersity (weight average molecular weight / number average molecular weight) of the copolymer is, for example, 1.0 to 5.0, preferably 1.0 to 3.0.
The weight average molecular weight and the number average molecular weight can be measured using gel permeation chromatography (GPC). For details of the measurement method, refer to the examples described later.

As already mentioned, the molding material containing the above-mentioned copolymer may have good heat resistance. Expressing this in terms of the glass transition temperature (Tg), the Tg of the copolymer (copolymer alone) is preferably 80 ° C. or higher, more preferably 90 to 180 ° C., still more preferably 100 to 150 ° C. be.
The glass transition temperature can be determined by measurement with a differential scanning calorimeter (DSC). For details of the measurement method, refer to the examples described later.

The copolymer is preferably amorphous or low crystallinity. Specifically, the crystallinity measured by the X-ray diffraction method is, for example, 20% or less, preferably 10% or less, and more preferably 2% or less.

The ultimate viscosity [η] of the copolymer (copolymer alone) measured in decalin at 135 ° C. is, for example, 0.01 to 20 dl / g, preferably 0.03 to 10 dl / g. More preferably, it is 0.05 to 5 dl / g.
As for the physical properties of the copolymer (copolymer alone), the melt flow index (MFR) measured at 260 ° C. and a load of 2.16 kg according to ASTM D1238 is, for example, 0.2 to 200 g / 10 minutes, which is preferable. Is 1 to 100 g / 10 minutes, more preferably 5 to 50 g / 10 minutes.

Further, the softening point of the copolymer is a softening point (TMA) measured by a thermal mechanical analyzer, for example, 30 ° C. or higher, preferably 70 ° C. or higher, and more preferably 80 to 260 ° C.

-Copolymer production method (polymerization method)
Examples of the copolymer include JP-A-60-168708, JP-A-61-12816, JP-A-61-115912, JP-A-61-115916, and JP-A-61-271308. According to the methods described in JP-A, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A-2010-241932, etc. , Can be manufactured by appropriately selecting the conditions.
More specifically, the copolymer can be polymerized by using a catalyst formed of a vanadium compound and an organic aluminum compound soluble in an organic solvent such as a hydrocarbon solvent as a catalyst. Specifically, for synthesis using such a catalyst, for example, Polymerization Examples 1 to 7 of International Publication No. 2008/068897 can be referred to (in this document, VO (OC ₂ H ₅ ) as a vanadium compound can be referred to. ) Cl ₂ is used, and ethyl aluminum sesquichloride ((C ₂ H ₅ ) _1.5 AlCl _1.5 ) is used as the organoaluminum compound).

As one aspect, the molding material of the present embodiment contains only the above-mentioned copolymer and may not contain other components. On the other hand, as another aspect, the molding material of the present embodiment may contain other optional components (known additives and the like) for various purposes in addition to the above-mentioned copolymer. For example, even if it contains a hydrophilic agent, an antioxidant, a secondary antioxidant, a lubricant, a mold release agent, an anti-fog agent, a weather-resistant stabilizer, a light-resistant stabilizer, an ultraviolet absorber, an antistatic agent, a metal inactivating agent, and the like. good.

The molding material of the present embodiment is, for example, a method of melting and kneading the above-mentioned copolymer and other components added as necessary using a known kneading device such as an extruder and a Banbury mixer; A method of dissolving the polymer and other components added as needed in a common solvent and then evaporating the solvent; a solution of the above-mentioned copolymer and other components added as needed in a poor solvent. Can be obtained by a method such as a method of adding and precipitating;

The properties of the molding material of this embodiment are not particularly limited. For example, it may be in the form of pellets, powder, granules, or the like. As a method for processing the molding material into these properties (granulation method), a known method can be appropriately applied.

<Molded body and its manufacturing method>
The molded body of this embodiment will be described.
The molded product of this embodiment contains the above-mentioned copolymer. In other words, it is obtained by using the above-mentioned copolymer as a raw material.
The molded product of the present embodiment has good heat resistance, impact resistance, and scratch resistance. Such properties are suitable, for example, as a medical container that requires various durability.

The medical container is, for example, filled with a syringe, a drug solution or a drug used in an outer cylinder of a syringe (hereinafter, a syringe) and an injection tube filled with a drug solution or a drug (hereinafter, also referred to as a prefilled syringe). Examples thereof include a storage container (hereinafter, also referred to as a chemical solution storage container) used for the storage container.

Here, the prefilled syringe is a syringe-shaped preparation that is pre-filled with a drug solution or a drug, and is a single-chamber type that is filled with one type of liquid and a double-chamber type that is filled with two types of drugs. There is. Most prefilled syringes are single-chamber type, but for double-chamber type, there are liquid / powder type preparations consisting of powder and its solution and liquid / liquid type preparations consisting of two types of liquid. An example of a single chamber type internal solution is a heparin solution or the like.

Examples of the drug solution / drug storage container include wide-mouthed bottles, narrow-mouthed bottles, drug bottles, vial bottles, infusion bottles, bulk containers, petri dishes, test tubes, analysis cells and the like. More specifically, liquid, powder or solid drug containers such as ampoules, press-through packages, infusion bags, drip containers, eye drops containers; sampling test tubes for blood tests, blood collection tubes, specimens. Sample containers such as containers; Analytical containers such as UV test cells; Sterilization containers for medical equipment such as scalpels, forceps, gauze, contact lenses; Medical equipment such as disposable syringes and prefilled syringes; Beakers, vials, ampoules, test tube flasks, etc. Experimental equipment; housing of artificial organs and the like.

The molded body may be subjected to known sterilization treatments such as autoclave sterilization, radiation sterilization, electron beam sterilization, γ-ray sterilization, EOG sterilization, ultraviolet sterilization, microwave, boiling water, and steam.
As described above, the molded product of the present embodiment has good heat resistance. Therefore, it is particularly effective for autoclave sterilization.

As the molding method, a known molding method can be appropriately applied. For example, known molding methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, and foam molding can be applied.

As the raw material of the molded product, only the above-mentioned copolymer may be used, or the above-mentioned copolymer and the additive component may be used in combination as long as the object of the present invention is not impaired. Examples of the additive component include any resin, dye, pigment, stabilizer, plasticizer, antistatic agent, ultraviolet absorber, antioxidant, lubricant, filler and the like different from the above-mentioned copolymer.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like to the extent that the object of the present invention can be achieved are included in the present invention.

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. The present invention is not limited to the examples.
In addition, hereinafter, tetracyclo [4.4.0.1 ^2,5 . ^17.10 ] -3-Dodecene is also abbreviated as "TD", bicyclo [2.2.1] hept-2-ene is abbreviated as "NB", and cyclooctene is also abbreviated as "COE". The COE is a cis type unless otherwise specified.

[Synthesis Example 1] Polymerization of Ethylene-TD-COE Copolymer A glass reactor with an internal volume of 1000 ml was prepared with sufficient nitrogen substitution.
This reactor is charged with 540 ml of cyclohexane and 60 ml of normal hexane, further inserted with 15.54 g of TD and 1.80 g of COE, and in a liquid phase with 25 liters / hr of ethylene, 25 liters / hr of nitrogen and 1 liter / hr of hydrogen. And the gas phase was saturated.
Then, 0.90 mmol of ethyl aluminum sesquichloride was added in terms of aluminum atom, and 0.180 mmol of VO (OEt) Cl ₂ was added as a vanadium catalyst to initiate polymerization. Subsequently, polymerization was carried out at 10 ° C. and normal pressure for 5 minutes. Then, the polymerization was stopped by adding a small amount of isobutyl alcohol.
After completion of the polymerization, the reaction product was put into a 1.5 L acetone / methanol (3/1 volume ratio) mixed solvent to which 2 ml of concentrated hydrochloric acid was added to precipitate the entire amount of the polymer, and the mixture was stirred and filtered through a filter paper.
The precipitated polymer was washed with acetone / methanol (3/1 volume ratio) and then dried under reduced pressure at 130 ° C. for 10 hours.
The obtained ethylene / TD / COE copolymer was 4.61 g, and the polymerization activity per 1 mmol of vanadium was 0.369 kg / hr.

¹³ The ethylene content in the polymer determined by C-NMR was 66.1 mol%, the TD content was 33.6 mol%, and the COE content was 0.3 mol%. The ultimate viscosity [η] is 0.48 dl / g, the weight average molecular weight (Mw) is 98600, and the number average molecular weight (Mn) is 40200 (both in terms of polystyrene). Therefore, the dispersity (Mw / Mn) is 2. It was 45.

[Synthesis Example 2] Polymerization of Ethylene-TD-COE Copolymer A glass reactor having an internal volume of 2000 ml was prepared with sufficient nitrogen substitution.
This reactor is charged with 680 ml of cyclohexane and 70 ml of normal hexane, further charged with 13.34 g of TD and 13.58 g of COE, and the liquid phase and vapor phase with 100 liters / hr of ethylene and 1.5 liters / hr of hydrogen. Was saturated. Then, 2.00 mmol of triisobutylaluminum in terms of aluminum atom, 0.010 mmol of the titanium compound represented by the following structural formula, and Ti of a toluene solution (4 mmol / L) of triphenylcarbenium tetrakis (pentafluorophenyl) borate. 2.0 equivalents were added to the above to start polymerization. Subsequently, polymerization was carried out at 50 ° C. and normal pressure for 10 minutes. Then, the polymerization was stopped by adding a small amount of isobutyl alcohol.
After completion of the polymerization, the reaction product was put into a 1.5 L acetone / methanol (3/1 volume ratio) mixed solvent to which 2 ml of concentrated hydrochloric acid was added to precipitate the entire amount of the polymer, and the mixture was stirred and filtered through a filter paper.
The precipitated polymer was washed with acetone / methanol (3/1 volume ratio) and then dried under reduced pressure at 130 ° C. for 10 hours.
The obtained ethylene / TD / COE copolymer was 3.79 g, and the polymerization activity per 1 mmol of titanium was 2.27 kg / hr.

¹³ The ethylene content in the polymer determined by C-NMR was 66.9 mol%, the TD content was 32.4 mol%, and the COE content was 0.7 mol%. The ultimate viscosity [η] is 0.47 dl / g, the weight average molecular weight (Mw) is 101000, and the number average molecular weight (Mn) is 48500 (both in polystyrene conversion). Therefore, the dispersity (Mw / Mn) is 2. It was 09.

[Synthesis Example 3] Polymerization of Ethylene-TD-COE Copolymer A glass reactor with an internal volume of 1000 ml was prepared with sufficient nitrogen substitution.
This reactor is charged with 490 ml of cyclohexane and 50 ml of normal hexane, further charged with 4.96 g of TD and 26.03 g of COE, and 50 liters / hr of ethylene, 50 liters / hr of nitrogen, 0.5 liters / hr of hydrogen. The liquid phase and the gas phase were saturated with.
Then, the amount of triisobutylaluminum in terms of aluminum atom is 6.00 mmol, the amount of the titanium compound of Example 2 is 0.030 mmol, and the amount of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (4 mmol / L) is 2 with respect to Ti. 9.0 equivalents were added and polymerization was started. Subsequently, polymerization was carried out at 50 ° C. and normal pressure for 20 minutes. Then, the polymerization was stopped by adding a small amount of isobutyl alcohol.
After completion of the polymerization, the reaction product was put into a 1.5 L acetone / methanol (3/1 volume ratio) mixed solvent to which 2 ml of concentrated hydrochloric acid was added to precipitate the entire amount of the polymer, and the mixture was stirred and filtered through a filter paper.
The precipitated polymer was washed with acetone / methanol (3/1 volume ratio) and then dried under reduced pressure at 130 ° C. for 10 hours.
The obtained ethylene / TD / COE copolymer was 1.91 g, and the polymerization activity per 1 mmol of titanium was 0.191 kg / hr.

¹³ The ethylene content in the polymer determined by C-NMR was 64.6 mol%, the TD content was 32.1 mol%, and the COE content was 3.3 mol%. The ultimate viscosity [η] is 0.40 dl / g, the weight average molecular weight (Mw) is 90600, and the number average molecular weight (Mn) is 44500 (both in terms of polystyrene). Therefore, the dispersity (Mw / Mn) is 2. It was 03.

[Comparative Synthesis Example 1] Polymerization of Ethylene-NB-COE Copolymer A glass reactor having an internal volume of 2000 ml was prepared with sufficient nitrogen substitution.
This reactor is charged with 680 ml of cyclohexane and 70 ml of normal hexane, and further charged with 13.40 g of NB and 19.02 g of COE, and the liquid phase and vapor phase are charged with 100 liters / hr of ethylene and 2.0 liters / hr of hydrogen. Was saturated.
Then, 2.00 mmol of triisobutylaluminum in terms of aluminum atom, 0.010 mmol of the titanium compound of Example 2, and 2 toluene solutions (4 mmol / L) of triphenylcarbenium tetrakis (pentafluorophenyl) borate with respect to Ti. 9.0 equivalents were added and polymerization was started. Subsequently, polymerization was carried out at 50 ° C. and normal pressure for 10 minutes. Then, the polymerization was stopped by adding a small amount of isobutyl alcohol.
After completion of the polymerization, the reaction product was put into a 1.5 L acetone / methanol (3/1 volume ratio) mixed solvent to which 2 ml of concentrated hydrochloric acid was added to precipitate the entire amount of the polymer, and the mixture was stirred and filtered through a filter paper.
The precipitated polymer was washed with acetone / methanol (3/1 volume ratio) and then dried under reduced pressure at 130 ° C. for 10 hours.
The obtained ethylene / NB / COE copolymer was 4.68 g, and the polymerization activity per 1 mmol of titanium was 2.81 kg / hr.

¹³ The ethylene content in the polymer determined by C-NMR was 52.6 mol%, the NB content was 46.6 mol%, and the COE content was 0.8 mol%. The ultimate viscosity [η] is 0.59 dl / g, the weight average molecular weight (Mw) is 123000, and the number average molecular weight (Mn) is 52800 (both in terms of polystyrene). Therefore, the dispersity (Mw / Mn) is 2. It was 34.

Various physical properties, performance evaluations, etc. of each of the above copolymers are as described below.

[Measurement of the content of each structural unit in the copolymer]
The measurement was performed under the following conditions using an AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by Bruker Biospin.
-Solvent: orthodichlorobenzene / benzene-d6 (4/1 v / v)
-Sample concentration: 100 g / l-solvent
・ Pulse repetition time: 5.5 seconds ・ Number of integrations: 128 times ・ Measurement temperature: 120 ° C
The content of each monomer component was quantified based on the peak area of the ¹³ C-NMR spectrum measured under the above conditions. Regarding how to read the peak indicating the structural unit derived from TD and the peak indicating the structural unit derived from NB in the ¹³ C-NMR spectrum, Japanese Patent Application Laid-Open No. 2011-122146 was referred to. For how to read the peak indicating the structural unit derived from COE, see Angew. Chem. Int. Ed, Vol. 50, pp. I referred to 3566-3571,2011.

[Measurement of number average molecular weight (Mn), weight average molecular weight (Mw) and dispersity (Mw / Mn)]
The number average molecular weight Mn, the weight average molecular weight Mw, and the dispersity Mw / Mn were determined by GPC measurement.
Specifically, two TSKgel GMH _{6-HT manufactured by Tosoh Corporation and two TSKgel GMH 6 -} HTLs (column size is 7.5 mm in inner diameter and 300 mm in length) are connected in series as columns. The measurement was performed using a gel permeation chromatograph (HLC-8321 GPC / HT type manufactured by Tosoh Corporation). The mobile phase medium uses o-dichlorobenzene and 0.025% by mass of BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant, the sample concentration is 0.15% (W / V), the flow rate is 1.0 ml / min, 140. Measured at ° C. As the standard polystyrene, Tosoh Corporation was used for the molecular weights of 590 to 20,600,000. The obtained chromatogram was analyzed using Waters data processing software Emper3 by a known method using a calibration curve using a standard polystyrene sample. As a result, the number average molecular weight Mn, the weight average molecular weight Mw and the degree of dispersion Mw were analyzed. / Mn was calculated.

[Ultimate viscosity]
The ultimate viscosity ([η]) was measured in decalin at 135 ° C.
Specifically, a resin (about 20 mg) was dissolved in a decalin solvent (15 mL), and the specific viscosity η _sp was measured in an oil bath at 135 ° C. A decalin solvent (5 mL) was added to this decalin solution to dilute it, and then the specific viscosity η _sp was measured in the same manner as described above. This dilution operation was repeated twice more, and the value of η _sp / C when the sample concentration (C) was extrapolated to 0 was defined as the ultimate viscosity [η].
Extreme viscosity [η] = lim (η _sp / C) (C → 0)

[Heat resistance: glass transition temperature Tg (° C)]
For each of the above copolymers, DSC measurement was performed under the following conditions.
・ Equipment: DSC6220 manufactured by SI Nanotechnology Co., Ltd.
-Measurement conditions: A sample held at 250 ° C. for 5 minutes under a nitrogen atmosphere was rapidly cooled to -20 ° C., and then the temperature rise rate was 10 ° C./min. The DSC curve in the process of raising the temperature to 250 ° C. was obtained.

In the obtained DSC curve, the temperature at the point where the straight line equidistant from the extended straight line of each baseline and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.

[Impact resistance: High-speed surface impact test (high rate test)]
The impact resistance of each of the above copolymers was evaluated as follows.
The copolymer was sandwiched between a film of Upirex (trade name, manufactured by Ube Industries, Ltd.) and vacuum press-molded at 240 ° C., 5 MPa, and 3 minutes using a 2.0 mm spacer. As a result, a press sheet having a thickness of 2 mm was obtained.
A striker with a load cell having a diameter of 1/2 inch was collided with this press sheet under the condition of 23 ° C. at a test speed of 5 m / s. On the back surface of the press sheet, a base with a support base diameter of 1 inch was used. The energy value from the obtained displacement and test force displacement curve to the maximum point of the test force was calculated as the maximum impact point energy. The larger this value is, the higher the impact resistance is.
The impact resistance of the polymers of the other examples and comparative examples was evaluated in the same manner.

[Scratch resistance: Pencil hardness measurement]
The pencil hardness of each of the above copolymers was evaluated as follows.
The copolymer was sandwiched between a film of Upirex (trade name, manufactured by Ube Industries, Ltd.) and vacuum press-molded at 240 ° C., 5 MPa, and 3 minutes using a 0.3 mm spacer. As a result, a press sheet having a thickness of 0.3 mm was obtained.
Using this press sheet, the pencil hardness at the time when the press sheet was scratched was evaluated according to JIS K 5600-5-6.
The evaluation was made on a 17-point scale of 6B to B, HB, F, and H to 9H. The closer the evaluation is to 6B, the weaker the scratch resistance, and the closer the evaluation is to 9H, the stronger the scratch resistance.

As shown in Table 1, the molding material containing the copolymer having all of the structural units (A), (B) and (C) showed good results in heat resistance, impact resistance and scratch resistance. (Examples 1 to 3). On the other hand, the molding material containing the copolymer of Comparative Synthesis Example 1, in which the structure corresponding to the structural unit (B) is derived from NB instead of TD, has heat resistance and impact resistance as compared with Examples 1 to 3. The results were inferior in all of the properties and scratch resistance (Comparative Example 1).
It is shown that the molding material of the present embodiment can be preferably used as a molding material for a container (medical container, etc.) in that the "three performances" of heat resistance, impact resistance and scratch resistance can be improved at the same time. Was done.

Claims (8)

A molding material containing a cyclic olefin-based copolymer, which is a molding material.
The cyclic olefin resin has a structural unit (A) derived from at least one olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms, and a tetracyclo [4.4.0. 1 ^{2, 5 3} . 1 ⁷ , 10] A cyclic olefin having a structural unit (B) derived from -3-dodecene and a structural unit (C) derived from at least one cyclic olefin selected from the group consisting of cyclooctene and cyclohexene. Molding material containing a system copolymer. The molding material according to claim 1.
A molding material in which the content of the structural unit (A) in the total structural units of the cyclic olefin-based copolymer is 10 to 80 mol%. The molding material according to claim 1 or 2.
A molding material in which the content of the structural unit (C) in the total structural units of the cyclic olefin-based copolymer is 0.1 to 50 mol%. The molding material according to any one of claims 1 to 3.
A molding material in which the content of the structural unit (C) in the total structural units of the cyclic olefin-based copolymer is 0.1 to 30 mol%. The molding material according to any one of claims 1 to 4.
A molding material in which the content of the structural unit (C) in the total structural units of the cyclic olefin-based copolymer is 0.1 to 10 mol%. A molded product containing the cyclic olefin-based copolymer according to any one of claims 1 to 5. The molded product according to claim 6.
A molded product that is a medical container. The molded product according to claim 6 or 7.
A molded product that is a syringe or a chemical storage container.