JP7073712B2 - Cyclic olefin ring-opening polymer hydrides, medical resin materials, containers, and films - Google Patents
Cyclic olefin ring-opening polymer hydrides, medical resin materials, containers, and films Download PDFInfo
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Description
本発明は、環状オレフィン開環重合体水素化物、並びに、当該環状オレフィン開環重合体水素化物を含んでなる医療用樹脂材料、容器、及びフィルム関するものである。 The present invention relates to a cyclic olefin ring-opening polymer hydride and a medical resin material, a container, and a film containing the cyclic olefin ring-opening polymer hydride.
環状オレフィン開環重合体水素化物は、透明性、耐熱性、低複屈折、成形加工性、及び耐薬品性などに優れているので、各種用途に適用可能な成形材料としてとして注目されている。そこで、近年、環状オレフィン開環重合体水素化物の物性を向上させるべく、種々提案がなされている。 Cyclic olefin ring-opening polymer hydrides are attracting attention as molding materials applicable to various applications because they are excellent in transparency, heat resistance, low birefringence, molding processability, chemical resistance and the like. Therefore, in recent years, various proposals have been made to improve the physical properties of the cyclic olefin ring-opening polymer hydride.
例えば、特許文献１では、ジシクロペンタジエン化合物由来の構造単位（Ａ）、テトラシクロドデセン化合物由来の構造単位（Ｂ）、及びノルボルネン化合物由来の構造単位（Ｃ）を含有する開環重合体の水素添加物が開示されている。特許文献１には、上記開環重合体における、上記構造単位（Ａ）～（Ｃ）の合計量が１００モル％を占め、さらに、構造単位（Ａ）～（Ｃ）のそれぞれの含有比率が所定の関係を満たすことが開示されている。 For example, in Patent Document 1, a ring-opening polymer containing a structural unit (A) derived from a dicyclopentadiene compound, a structural unit (B) derived from a tetracyclododecene compound, and a structural unit (C) derived from a norbornene compound. Hydrogenated substances are disclosed. In Patent Document 1, the total amount of the structural units (A) to (C) in the ring-opening polymer occupies 100 mol%, and the content ratio of each of the structural units (A) to (C) is further described. It is disclosed that a predetermined relationship is satisfied.
また、特許文献２には、テトラシクロドデセン由来の繰り返し単位と、その他のノルボルネン系単量体由来の繰り返し単位とからなり、テトラシクロドデセン由来の繰り返し単位の含有量が、全繰り返し単位に対して５５質量％以上１００質量％未満、その他のノルボルネン系単量体由来の繰り返し単位の含有量が、全繰り返し単位に対して０質量％超４５質量％以下であり、テトラシクロドデセン由来の繰り返し単位のラセモダイアットの割合が、６５％以上であり、かつ、重量平均分子量（Ｍｗ）が１０，０００～４０，０００の環状オレフィン開環重合体水素化物が開示されている。 Further, Patent Document 2 is composed of a repeating unit derived from tetracyclododecene and a repeating unit derived from other norbornene-based monomers, and the content of the repeating unit derived from tetracyclododecene is the total repeating unit. On the other hand, the content of the repeating unit derived from 55% by mass or more and less than 100% by mass and other norbornene-based monomers is more than 0% by mass and 45% by mass or less with respect to all the repeating units, and is derived from tetracyclododecene. A cyclic olefin ring-opening polymer hydride having a repeating unit with a racemodiat ratio of 65% or more and a weight average molecular weight (Mw) of 10,000 to 40,000 is disclosed.
ここで、環状オレフィン開環重合体水素化物には、用途によっては、上記のような各種属性に加えて、湿気を透過し難いこと、即ち、防湿性に優れることや、皮脂等に対する耐性が高いこと、即ち耐脂性に優れることが求められている。しかし、特許文献１～２に記載された環状オレフィン開環重合体水素化物は、防湿性及び耐脂性の点で改善の余地があった。 Here, depending on the application, the cyclic olefin ring-opening polymer hydride has high resistance to moisture, that is, excellent moisture resistance and sebum, in addition to the above-mentioned various attributes. That is, it is required to have excellent oil resistance. However, the cyclic olefin ring-opening polymer hydrides described in Patent Documents 1 and 2 have room for improvement in terms of moisture resistance and oil resistance.
そこで、本発明は、防湿性及び耐脂性に優れる環状オレフィン開環重合体水素化物を提供することを目的とする。
さらに、本発明は、防湿性及び耐脂性に優れる環状オレフィン開環重合体水素化物を含んでなる、医療用樹脂材料、容器、及びフィルムを提供することを目的とする。
Therefore, an object of the present invention is to provide a cyclic olefin ring-opening polymer hydride having excellent moisture resistance and oil resistance.
Furthermore, an object of the present invention is to provide a medical resin material, a container, and a film containing a cyclic olefin ring-opening polymer hydride having excellent moisture resistance and oil resistance.
本発明者は、上記課題を解決することを目的として鋭意検討を行った。そして、本発明者は、環状オレフィン開環重合体水素化物の製造にあたり、テトラシクロドデセン由来の構造単位及びノルボルネン由来の構造単位の占有比率をそれぞれ所定範囲内とするとともに、開環重合体水素化物中に含まれるテトラシクロドデセン由来の構造単位よりなるラセモダイアッドの割合が所定割合以上となるようにすることで、得られる環状オレフィン開環重合体水素化物の防湿性を高めうることを見出し、本発明を完成させた。 The present inventor has made diligent studies for the purpose of solving the above problems. Then, in producing the cyclic olefin ring-opening polymer hydride, the present inventor keeps the occupancy ratios of the structural unit derived from tetracyclododecene and the structural unit derived from norbornene within a predetermined range, and hydrogen of the ring-opening polymer. We have found that the moisture-proof property of the obtained cyclic olefin ring-opening polymer hydride can be enhanced by setting the ratio of racemodiad, which is a structural unit derived from tetracyclododecene, contained in the product to a predetermined ratio or more. The present invention has been completed.
即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の環状オレフィン開環重合体水素化物は、テトラシクロドデセン由来の構造単位（Ａ）、及びノルボルネン由来の構造単位（Ｂ）を含む環状オレフィン開環重合体水素化物であって、前記環状オレフィン開環重合体水素化物に含まれる全繰り返し単位を１００．０質量％として、前記構造単位（Ａ）の含有割合が４７．０質量％以上８８．０質量%以下であり、且つ、前記構造単位（Ｂ）の含有割合が１２．０質量％以上５３．０質量％以下であり、さらに、前記構造単位（Ａ）よりなるラセモダイアッドの割合が６５モル％以上である、ことを特徴とする。このように、テトラシクロドデセン由来の構造単位（Ａ）、及びノルボルネン由来の構造単位（Ｂ）の含有割合が、上記所定範囲内であり、且つ、構造単位（Ａ）よりなるラセモダイアッドの割合が６５モル％以上である環状オレフィン開環重合体水素化物は、防湿性及び耐脂性に優れる。
なお、環状オレフィン開環重合体水素化物に含まれる、「構造単位（Ａ）及び前記構造単位（Ｂ）の含有割合」は、1Ｈ－ＮＭＲ測定により求めることができる。また、「構造単位（Ａ）よりなるラセモダイアッドの割合」は、実施例に従う13Ｃ－ＮＭＲ測定により求めることができる。
That is, the present invention aims to advantageously solve the above problems, and the cyclic olefin ring-opening polymer hydride of the present invention is derived from the structural unit (A) derived from tetracyclododecene and norbornene. The cyclic olefin ring-opening polymer hydride containing the structural unit (B) of the above structural unit (A), wherein the total number of repeating units contained in the cyclic olefin ring-opening polymer hydride is 100.0% by mass. The content ratio is 47.0% by mass or more and 88.0% by mass or less, and the content ratio of the structural unit (B) is 12.0% by mass or more and 53.0% by mass or less, and further, the structural unit. It is characterized in that the ratio of the racemodiad composed of (A) is 65 mol% or more. As described above, the content ratio of the structural unit (A) derived from tetracyclododecene and the structural unit (B) derived from norbornene is within the above-mentioned predetermined range, and the ratio of the racemodiad composed of the structural unit (A) is The cyclic olefin ring-opening polymer hydride having a content of 65 mol% or more is excellent in moisture resistance and fat resistance.
The "content ratio of the structural unit (A) and the structural unit (B)" contained in the cyclic olefin ring-opening polymer hydride can be determined by 1 H-NMR measurement. Further, the "ratio of the racemodiad composed of the structural unit (A)" can be obtained by 13 C-NMR measurement according to the examples.
ここで、本発明の環状オレフィン開環重合体水素化物は、前記構造単位（Ａ）及び前記構造単位（Ｂ）の合計含有割合が１００．０質量％であることが好ましい。構造単位（Ａ）及び構造単位（Ｂ）の合計含有割合が１００．０質量％である環状オレフィン開環重合体水素化物は、一層、防湿性及び耐脂性に優れる。 Here, the cyclic olefin ring-opening polymer hydride of the present invention preferably has a total content ratio of the structural unit (A) and the structural unit (B) of 100.0% by mass. The cyclic olefin ring-opening polymer hydride having a total content of the structural unit (A) and the structural unit (B) of 100.0% by mass is further excellent in moisture resistance and oil resistance.
この発明は、上記課題を有利に解決することを目的とするものであり、本発明の医療用樹脂材料は、上述した何れかの環状オレフィン開環重合体水素化物を含んでなることを特徴とする。上述したような環状オレフィン開環重合体水素化物を含む医療用樹脂材料は、防湿性及び耐脂性に優れる。 The present invention is intended to advantageously solve the above problems, and the medical resin material of the present invention is characterized by containing any of the above-mentioned cyclic olefin ring-opening polymer hydrides. do. The medical resin material containing the cyclic olefin ring-opening polymer hydride as described above is excellent in moisture resistance and oil resistance.
この発明は、上記課題を有利に解決することを目的とするものであり、本発明の容器は、ガラス転移温度が１２０℃以上である上述した医療用樹脂材料を含んでなることを特徴とする。ガラス転移温度が１２０℃以上である本発明の医療用樹脂材料を含んでなる容器は、防湿性、耐脂性、及び耐熱性に優れる。
なお、「ガラス転移温度」は、ＪＩＳ Ｋ ６９１１に従って測定することができる。
An object of the present invention is to advantageously solve the above-mentioned problems, and the container of the present invention is characterized by containing the above-mentioned medical resin material having a glass transition temperature of 120 ° C. or higher. .. The container containing the medical resin material of the present invention having a glass transition temperature of 120 ° C. or higher is excellent in moisture resistance, grease resistance, and heat resistance.
The "glass transition temperature" can be measured according to JIS K 6911.
この発明は、上記課題を有利に解決することを目的とするものであり、本発明のフィルムは、ガラス転移温度が１２０℃以下である上述した医療用樹脂材料を含んでなることを特徴とする。ガラス転移温度が１２０℃以下である本発明の医療用樹脂材料を含んでなるフィルムは、防湿性、耐脂性、及び熱軟化性に優れる。 An object of the present invention is to advantageously solve the above-mentioned problems, and the film of the present invention is characterized by containing the above-mentioned medical resin material having a glass transition temperature of 120 ° C. or lower. .. The film containing the medical resin material of the present invention having a glass transition temperature of 120 ° C. or lower is excellent in moisture resistance, grease resistance, and heat softening property.
本発明によれば、防湿性及び耐脂性に優れる環状オレフィン開環重合体水素化物を提供することができる。
本発明によれば、防湿性及び耐脂性に優れる環状オレフィン開環重合体水素化物を含んでなる、医療用樹脂材料、容器、及びフィルムを提供することができる。
According to the present invention, it is possible to provide a cyclic olefin ring-opening polymer hydride having excellent moisture resistance and oil resistance.
According to the present invention, it is possible to provide a medical resin material, a container, and a film containing a cyclic olefin ring-opening polymer hydride having excellent moisture resistance and oil resistance.
以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
（環状オレフィン開環重合体水素化物）
本発明の環状オレフィン開環重合体水素化物（以下、単に「本発明の開環重合体水素化物」とも称する）は、テトラシクロドデセン由来の構造単位（Ａ）、及びノルボルネン由来の構造単位（Ｂ）を含む環状オレフィン開環重合体水素化物である。そして、本発明の開環重合体水素化物において、構造単位（Ａ）及び構造単位（Ｂ）の含有割合が、それぞれ所定範囲内であるとともに、構造単位（Ａ）よりなるラセモダイアッドの割合が６５モル％以上であることを特徴とする。このように、テトラシクロドデセン由来の構造単位（Ａ）、及びノルボルネン由来の構造単位（Ｂ）の含有割合が、上記所定範囲内であり、且つ、構造単位（Ａ）よりなるラセモダイアッドの割合が６５モル％以上である環状オレフィン開環重合体水素化物は、防湿性及び耐脂性に優れる。
(Cyclic olefin ring-opening polymer hydride)
The cyclic olefin ring-opening polymer hydride of the present invention (hereinafter, also simply referred to as “the ring-opening polymer hydride of the present invention”) is a structural unit (A) derived from tetracyclododecene and a structural unit derived from norbornene (hereinafter, structural unit). It is a cyclic olefin ring-opening polymer hydride containing B). In the ring-opening polymer hydride of the present invention, the content ratios of the structural unit (A) and the structural unit (B) are each within a predetermined range, and the ratio of the racemodiad composed of the structural unit (A) is 65 mol. It is characterized by being% or more. As described above, the content ratio of the structural unit (A) derived from tetracyclododecene and the structural unit (B) derived from norbornene is within the above-mentioned predetermined range, and the ratio of the racemodiad composed of the structural unit (A) is The cyclic olefin ring-opening polymer hydride having a content of 65 mol% or more is excellent in moisture resistance and fat resistance.
＜テトラシクロドデセン由来の構造単位（Ａ）＞
本発明の開環重合体水素化物に含まれるテトラシクロドデセン由来の構造単位（Ａ）は、テトラシクロドデセン（テトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン）を開環重合し、主鎖中の炭素-炭素二重結合を水素化して得られる、下式（Ｉ）にて表されうる構造単位である。
The structural unit (A) derived from tetracyclododecene contained in the ring-opening polymer hydride of the present invention is tetracyclododecene (tetracyclo [6.2.1.1 3,6.0 2,7 ] dodeca-4-ene). Is a structural unit that can be represented by the following formula (I), which is obtained by ring-opening polymerization and hydrogenating a carbon-carbon double bond in the backbone.
＜ノルボルネン由来の構造単位（Ｂ）＞
本発明の開環重合体水素化物に含まれるノルボルネン由来の構造単位（Ｂ）は、ノルボルネン（ビシクロ[2.2.1]ヘプタ-2-エン）を開環重合し、主鎖中の炭素-炭素二重結合を水素化して得られる、下式（ＩＩ）にて表されうる構造単位である。
The structural unit (B) derived from norbornene contained in the ring-opening polymer hydride of the present invention is obtained by ring-opening polymerization of norbornene (bicyclo [2.2.1] hepta-2-ene) and carbon-carbon in the main chain. It is a structural unit that can be represented by the following formula (II), which is obtained by hydrogenating the heavy bond.
＜構造単位（Ａ）及び構造単位（Ｂ）の含有割合＞
上記構造単位（Ａ）の含有割合は、本発明の開環重合体水素化物に含まれる全繰り返し単位を１００．０質量％として、４７．０質量％以上８８．０質量%以下である必要がある。また、上記構造単位（Ｂ）の含有割合は、本発明の開環重合体水素化物に含まれる全繰り返し単位を１００．０質量％として、１２．０質量％以上５３．０質量％以下である必要がある。なお、本発明の開環重合体水素化物は、上記構造単位（Ａ）及び（Ｂ）以外に、例えば、テトラシクロドデセン及びノルボルネンとは異なる、他のノルボルネン骨格を有する単量体由来の構造単位等を含んでいても良い。しかし、防湿性及び耐脂性を一層向上させる観点から、本発明の開環重合体水素化物に含まれる、構造単位（Ａ）の含有割合と、構造単位（Ｂ）の含有割合との合計が、１００．０質量％であること、即ち、本発明の開環重合体水素化物が、構造単位（Ａ）及び構造単位（Ｂ）のみからなることが好ましい。
<Content ratio of structural unit (A) and structural unit (B)>
The content ratio of the structural unit (A) needs to be 47.0% by mass or more and 88.0% by mass or less, assuming that all the repeating units contained in the ring-opening polymer hydride of the present invention are 100.0% by mass. be. The content ratio of the structural unit (B) is 12.0% by mass or more and 53.0% by mass or less, with 100.0% by mass as the total repeating unit contained in the ring-opening polymer hydride of the present invention. There is a need. In addition to the structural units (A) and (B), the ring-opening polymer hydride of the present invention has a structure derived from a monomer having another norbornene skeleton, which is different from, for example, tetracyclododecene and norbornene. It may include a unit or the like. However, from the viewpoint of further improving the moisture resistance and the oil resistance, the total of the content ratio of the structural unit (A) and the content ratio of the structural unit (B) contained in the ring-opening polymer hydride of the present invention is It is preferable that the content is 100.0% by mass, that is, the ring-opening polymer hydride of the present invention comprises only the structural unit (A) and the structural unit (B).
さらに、上記構造単位（Ａ）よりなるラセモダイアッドの割合は、６５モル％以上である必要があり、７５モル％以上であることがより好ましい。なお、「構造単位（Ａ）よりなるラセモダイアッドの割合」は、本発明の開環重合体水素化物に含まれる、構造単位（Ａ）よりなるラセモダイアッド及びメソダイアッドの合計を１００モル％とした場合の、ラセモダイアッドの割合である。ラセモダイアッドの割合が上記下限値以上である開環重合体は防湿性及び耐脂性に優れるとともに、例えば、有機溶媒中にて水素化反応を行うことにより水素化した場合に、有機溶媒に対する溶解性が高いため、水素化率を効率的に高めることができる。なお、ラセモダイアッドの割合は、例えば、開環重合時に用いる開環重合触媒の種類を変更することにより、制御することができる。 Further, the ratio of the racemodiad composed of the structural unit (A) needs to be 65 mol% or more, more preferably 75 mol% or more. The "ratio of racemodiad composed of structural unit (A)" is based on the case where the total of racemodiad and mesodiad composed of structural unit (A) contained in the ring-opening polymer hydride of the present invention is 100 mol%. The percentage of racemodiad. A ring-opening polymer in which the ratio of racemodiad is at least the above lower limit is excellent in moisture resistance and oil resistance, and, for example, when hydrogenated by conducting a hydrogenation reaction in an organic solvent, the solubility in the organic solvent is high. Since it is high, the hydrogenation rate can be efficiently increased. The ratio of racemodiad can be controlled, for example, by changing the type of the ring-opening polymerization catalyst used in the ring-opening polymerization.
＜環状オレフィン開環重合体水素化物の製造方法＞
本発明の開環重合体水素化物の製造方法としては、特に限定されることなく、例えば、有機溶媒中にて、開環重合触媒の存在下に開環重合反応を行って開環重合体を得る開環重合工程と、かかる開環重合工程にて得られた開環重合体を有機溶媒中にて水素化触媒の存在下で水素化する水素化工程とを含む製造方法が挙げられる。より具体的には、本発明の開環重合体水素化物は、国際公開第２０１６／０５２３０２号に開示された製造方法に従って調製することができる。
<Method for Producing Cyclic Olefin Ring-Opening Polymer Hydride>
The method for producing the ring-opening polymer hydride of the present invention is not particularly limited, and for example, a ring-opening polymerization reaction is carried out in the presence of a ring-opening polymerization catalyst in an organic solvent to obtain a ring-opening polymer. Examples thereof include a production method including a ring-opening polymerization step of obtaining the ring-opening polymerization step and a hydrogenation step of hydrogenating the ring-opening polymer obtained in the ring-opening polymerization step in the presence of a hydrogenation catalyst in an organic solvent. More specifically, the ring-opening polymer hydride of the present invention can be prepared according to the production method disclosed in International Publication No. 2016/052302.
例えば、開環重合工程では、開環重合触媒として、タングステン等の周期表第６族遷移金属に対して、配位子として、アルキルイミド又はアリールイミドが結合した構造を有する遷移金属イミド化合物を含む開環重合触媒を用いることができる。かかる開環重合触媒として好適なものとしては、構造単位（Ａ）よりなるラセモダイアッドの割合を効果的に高める観点から、タングステン（フェニルイミド）（テトラクロリド）（テトラヒドロフラン）等が挙げられる。なお、開環重合工程にて用い得る開環重合触媒、有機溶媒及び分子量調整剤等の種類及び配合量、並びに、開環重合時間及び開環重合温度等の諸条件についても、国際公開第２０１６／０５２３０２号の開示内容に従うことができる。 For example, in the ring-opening polymerization step, the ring-opening polymerization catalyst contains a transition metalimide compound having a structure in which an alkylimide or an arylimide is bonded as a ligand to a transition metal of Group 6 of the periodic table such as tungsten. A ring-opening polymerization catalyst can be used. Suitable examples of such a ring-opening polymerization catalyst include tungsten (phenylimide) (tetrachloride) (tetrahydrofuran) and the like from the viewpoint of effectively increasing the proportion of racemodiad composed of the structural unit (A). The types and blending amounts of the ring-opening polymerization catalyst, the organic solvent, the molecular weight modifier, etc. that can be used in the ring-opening polymerization step, and various conditions such as the ring-opening polymerization time and the ring-opening polymerization temperature are also disclosed in International Publication No. 2016. The disclosure content of / 052302 can be followed.
また、例えば、水素化工程では、珪藻土等の吸着性を有する担体に担持されたＮｉ等の金属触媒を用いることができる。水素化工程にて用い得る水素化触媒及び有機溶媒等の種類及び配合量、並びに、水素化反応時間、水素化温度、及び水素化圧力等の諸条件についても、国際公開第２０１６／０５２３０２号の開示内容に従うことができる。 Further, for example, in the hydrogenation step, a metal catalyst such as Ni supported on a carrier having adsorptivity such as diatomaceous earth can be used. Regarding the types and amounts of hydrogenation catalysts and organic solvents that can be used in the hydrogenation step, as well as various conditions such as hydrogenation reaction time, hydrogenation temperature, and hydrogenation pressure, see International Publication No. 2016/052302. You can follow the disclosure.
＜開環重合体水素化物の性状＞
［透湿度］
本発明の開環重合体水素化物は、実施例にて記載した方法にてフィルムを形成した場合に、所定の方法（ＪＩＳ Ｋ ７１２９ Ａ法）により測定した透湿度を、２．００（ｇ／（ｍ2・２４ｈ））／１００μｍ）未満としうることが好ましい。なお、上記のようにして測定することができる透湿度は、開環重合体水素化物の組成に基づいて主として制御することができる。
<Characteristics of ring-opening polymer hydride>
[Humidity permeability]
The ring-opening polymer hydride of the present invention has a moisture permeability of 2.00 (g / g / g / g /) measured by a predetermined method (JIS K 7129 A method) when a film is formed by the method described in Examples. It is preferably less than (m 2.24h )) / 100μm). The moisture permeability that can be measured as described above can be mainly controlled based on the composition of the ring-opening polymer hydride.
［ガラス転移温度］
本発明の開環重合体水素化物のガラス転移温度は、例えば、４０℃以上２００℃以下であり得る。なお、ガラス転移温度は、例えば、開環重合体水素化物を合成する際に用いる単量体組成物の組成を調節すること等に基づいて、制御することができる。
[Glass-transition temperature]
The glass transition temperature of the ring-opening polymer hydride of the present invention can be, for example, 40 ° C. or higher and 200 ° C. or lower. The glass transition temperature can be controlled, for example, by adjusting the composition of the monomer composition used for synthesizing the ring-opening polymer hydride.
［水素化率］
本発明の開環重合体水素化物の水素化率は、９０モル％以上であることが好ましく、９５モル％以上であることがより好ましく、９９モル％以上であることが更に好ましい。水素化率の値が上記下限値以上であれば、開環重合体水素化物の防湿性、透明性及び耐熱性を高めることができる。なお、開環重合体の水素化率は、主鎖中の炭素-炭素二重結合の水素化率である。
[Hydrogenation rate]
The hydrogenation rate of the ring-opening polymer hydride of the present invention is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more. When the value of the hydrogenation rate is at least the above lower limit value, the moisture resistance, transparency and heat resistance of the ring-opening polymer hydride can be enhanced. The hydrogenation rate of the ring-opening polymer is the hydrogenation rate of the carbon-carbon double bond in the backbone.
（医療用樹脂材料）
本発明の医療用樹脂材料は、上述した本発明の開環重合体水素化物を含んでなる。例えば、本発明の医療用樹脂材料は、上述した開環重合体水素化物を含む粉末状又はペレット状の樹脂材料であり得る。本発明の医療用樹脂材料は、本発明の開環重合体水素化物を含むため、防湿性及び耐脂性に優れる。なお、本発明の医療用樹脂材料が「本発明の開環重合体水素化物を含む」とは、医療用樹脂材料の全質量を１００質量％として、５０質量％以上が本発明の開環重合体水素化物よりなることを意味する。そして、医療用樹脂材料は、任意の方法で成形されることにより、例えば、包装パッケージ、ボトル、ボトルキャップ、バイアル、アンプル、プレフィルドシリンジ、輸液用バッグ、密封薬袋、プレス・スルー・パッケージ、点眼薬容器等の液体、粉体、または固体の薬品容器；血液検査用のサンプリング用試験管、採血管、検査セル、検体容器等のサンプル容器；シリンジ、シリンジ用ロッド等の医療用具；メス、鉗子、ガーゼ、コンタクトレンズ等の医療機具等の滅菌容器；ビーカー、シャーレ、フラスコ、試験管、遠心管等の実験・分析器具；医療検査用プラスチックレンズ等の医療用光学部品；医量用輸液チューブ、カテーテル、配管、継ぎ手、バルブ、フィルター等の配管材料；義歯床、義歯、人工心臓、人造歯根、人工骨、人工関節等の人工臓器やその部品；等の物品に加工されうる。本発明の医療用樹脂材料は防湿性が高いため、本発明の医療用樹脂材料を用いて形成された各種物品により外部環境から離隔される内部空間に湿気が侵入することを防ぎ、内部空間内に収容した被収容物等が湿気に起因して変質し、劣化することを抑制することができる。
(Medical resin material)
The medical resin material of the present invention comprises the above-mentioned ring-opening polymer hydride of the present invention. For example, the medical resin material of the present invention may be a powdery or pellet-shaped resin material containing the above-mentioned ring-opening polymer hydride. Since the medical resin material of the present invention contains the ring-opening polymer hydride of the present invention, it is excellent in moisture resistance and oil resistance. In addition, the medical resin material of the present invention "contains the ring-opening polymer hydride of the present invention" means that the total mass of the medical resin material is 100% by mass, and 50% by mass or more is the ring-opening weight of the present invention. It means that it consists of a coalesced hydride. The medical resin material can be molded by any method, for example, packaging package, bottle, bottle cap, vial, ampoule, prefilled syringe, infusion bag, sealed medicine bag, press-through package, eye drops. Liquid, powder, or solid chemical containers such as containers; sample containers such as sampling test tubes for blood tests, blood collection tubes, test cells, sample containers; medical tools such as syringes and rods for syringes; scalpels, forceps, Sterile containers for medical equipment such as gauze and contact lenses; Experimental / analytical instruments such as beakers, chalices, flasks, test tubes, and centrifuge tubes; Medical optical parts such as plastic lenses for medical examinations; Medical infusion tubes, catheters , Piping materials such as pipes, joints, valves, filters; artificial organs such as artificial tooth beds, artificial teeth, artificial hearts, artificial tooth roots, artificial bones, artificial joints, and parts thereof; and the like. Since the medical resin material of the present invention has high moisture resistance, it is possible to prevent moisture from entering the internal space separated from the external environment by various articles formed by using the medical resin material of the present invention, and to prevent moisture from entering the internal space. It is possible to prevent the objects to be contained in the container from deteriorating and deteriorating due to moisture.
本発明の医療用樹脂材料は、特に限定されることなく、任意で、酸化防止剤、紫外線吸収剤、光安定剤、近赤外線吸収剤、可塑剤、及び帯電防止剤等の各種添加剤、並びに、本発明の開環重合体水素化物以外の他の高分子材料等を含みうる。 The medical resin material of the present invention is not particularly limited, and optionally includes various additives such as antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, plasticizers, and antistatic agents, and antistatic agents. , Other polymer materials other than the ring-opening polymer hydride of the present invention may be included.
添加剤としては、例えば、国際公開第２０１６／０５２３０２号に開示されたような既知のもの用いることができる。また、添加剤の含有量は、医療用樹脂材料の用途に応じて適宜設定することができ、例えば、本発明の開環重合体水素化物１００質量部に対して、５質量部以下であり得る。 As the additive, for example, a known additive as disclosed in International Publication No. 2016/052302 can be used. The content of the additive can be appropriately set according to the use of the medical resin material, and may be, for example, 5 parts by mass or less with respect to 100 parts by mass of the ring-opening polymer hydride of the present invention. ..
他の高分子材料としては、例えば、特開２０１０－６９８５号公報に開示されたようなゴム質重合体やその他の熱可塑性樹脂等が挙げられる。これらの高分子材料の含有量は、医療用樹脂材料の用途に応じて適宜設定することができ、例えば、本発明の開環重合体水素化物１００質量部に対して、１００質量部以下であり得る。 Examples of other polymer materials include rubbery polymers and other thermoplastic resins disclosed in Japanese Patent Application Laid-Open No. 2010-6985. The content of these polymer materials can be appropriately set according to the use of the medical resin material, and is, for example, 100 parts by mass or less with respect to 100 parts by mass of the ring-opening polymer hydride of the present invention. obtain.
医療用樹脂材料が添加剤を含有する場合、その製造方法は特に限定されることなく、例えば、上述した＜環状オレフィン開環重合体水素化物の製造方法＞に従って得られた開環重合体水素化物に対して、有機溶媒中において、所望の添加剤を添加してから固形分を分離精製して、乾燥する方法が挙げられる。なお、乾燥を経て得られた固形物は、既知の方法でペレット化することができる。そして、得られたペレットを医療用樹脂材料として、所望形状に成形して上記物品を得ることができる。 When the medical resin material contains an additive, the production method thereof is not particularly limited, and for example, the ring-opening polymer hydride obtained according to the above-mentioned <Method for producing a cyclic olefin ring-opening polymer hydride>. On the other hand, a method of adding a desired additive in an organic solvent, separating and purifying the solid content, and drying the solid content can be mentioned. The solid matter obtained through drying can be pelletized by a known method. Then, the obtained pellet can be used as a medical resin material and molded into a desired shape to obtain the above-mentioned article.
なお、本発明の医療用樹脂材料は、＜開環重合体水素化物の性状＞の項目にて上述した、各種好適性状を満たすことが好ましい。 The medical resin material of the present invention preferably satisfies the various suitability described above in the item <Characteristics of ring-opening polymer hydride>.
（容器）
本発明の容器は、上述した本発明の医療用樹脂材料のうち、ガラス転移温度が１２０℃以上である医療用樹脂材料を含んでなることを特徴とする。従って、本発明の容器は、ガラス転移温度が１２０℃以上と比較的高く、且つ、防湿性及び耐脂性に優れる。このため、本発明の容器は、耐熱性、耐脂性、及び防湿性が必要とされる用途に好適に用いることができる。
(container)
The container of the present invention is characterized by containing the medical resin material having a glass transition temperature of 120 ° C. or higher among the above-mentioned medical resin materials of the present invention. Therefore, the container of the present invention has a relatively high glass transition temperature of 120 ° C. or higher, and is excellent in moisture resistance and oil resistance. Therefore, the container of the present invention can be suitably used for applications that require heat resistance, grease resistance, and moisture resistance.
本発明の容器の製造方法は特に限定されることなく、例えば、本発明の医療用樹脂材料を、容器形状に応じた既知の成形方法により成形することにより製造することができる。例えば、成形方法としては、射出成形法、押出成形法、及びプレス成形法等が挙げられる。成形時の温度条件等は開環重合体水素化物のガラス転移温度等に応じて、適宜設定することができる。
なお、本発明の容器は、（医療用樹脂材料）の項目にて上述した任意成分である各種添加剤及びその他の高分子材料等を上述したような任意の割合で含有していても良い。
The method for producing the container of the present invention is not particularly limited, and for example, the medical resin material of the present invention can be produced by molding by a known molding method according to the shape of the container. For example, examples of the molding method include an injection molding method, an extrusion molding method, a press molding method, and the like. The temperature conditions at the time of molding can be appropriately set according to the glass transition temperature of the ring-opening polymer hydride and the like.
The container of the present invention may contain various additives and other polymer materials, which are the above-mentioned optional components in the item (medical resin material), in any proportion as described above.
（フィルム）
本発明のフィルムは、上述した本発明の医療用樹脂材料のうち、ガラス転移温度が１２０℃以下である医療用樹脂材料を含んでなることを特徴とする。従って、本発明のフィルムは、ガラス転移温度が１２０℃以下であるとともに、防湿性及び耐脂性に優れるため、熱軟化性、防湿性、及び耐脂性が必要とされる用途に好適に用いることができる。
(the film)
The film of the present invention is characterized by containing the medical resin material having a glass transition temperature of 120 ° C. or lower among the above-mentioned medical resin materials of the present invention. Therefore, the film of the present invention has a glass transition temperature of 120 ° C. or lower and is excellent in moisture resistance and oil resistance, so that it can be suitably used for applications requiring heat softening property, moisture resistance and oil resistance. can.
本発明のフィルムの製造方法は特に限定されることなく、例えば、本発明の医療用樹脂材料を、所望のフィルム厚み等に応じた既知の成形方法により成形することにより製造することができる。例えば、成形方法としては、射出成形法、押出成形法、プレス成形法、キャスト成形法、及びインフレーション成形法等が挙げられる。成形時の温度条件等は開環重合体水素化物のガラス転移温度等に応じて、適宜設定することができる。なお、本発明のフィルムの製造にあたり、任意で延伸加工等を施すこともできる。
なお、本発明のフィルムは、（医療用樹脂材料）の項目にて上述した任意成分である各種添加剤及びその他の高分子材料等を上述したような任意の割合で含有していても良い。
The method for producing the film of the present invention is not particularly limited, and for example, the medical resin material of the present invention can be produced by molding by a known molding method according to a desired film thickness or the like. For example, examples of the molding method include an injection molding method, an extrusion molding method, a press molding method, a cast molding method, an inflation molding method, and the like. The temperature conditions at the time of molding can be appropriately set according to the glass transition temperature of the ring-opening polymer hydride and the like. In the production of the film of the present invention, stretching processing or the like can be optionally performed.
The film of the present invention may contain various additives and other polymer materials, which are the above-mentioned optional components in the item (medical resin material), in any proportion as described above.
また、本発明のフィルムの厚みは、特に限定されることなく、例えば、１μｍ以上１０ｍｍ以下であり得る。なお、本発明のフィルムは、厚さ１００μｍとして、実施例にて記載した所定の方法（ＪＩＳ Ｋ ７１２９ Ａ法）により測定した透湿度が、２．００（ｇ／（ｍ2・２４ｈ）／１００μｍ）未満であることが好ましい。 The thickness of the film of the present invention is not particularly limited and may be, for example, 1 μm or more and 10 mm or less. The film of the present invention has a thickness of 100 μm and has a moisture permeability of 2.00 (g / ( m 2.24 h) / 100 μm) measured by a predetermined method (JIS K 7129 A method) described in Examples. ) Is preferable.
以下、本発明について実施例および比較例を挙げて、本発明を具体的に説明するが、本発明はこれらの例に何ら限定されるものではない。なお、以下の説明において、量を表す「部」は、特に断らない限り、質量基準である。また、圧力はゲージ圧力である。さらに、ある組成の単量体組成物を重合して得られた重合体における各単量体由来の構造単位の割合は、1Ｈ－ＮＭＲ測定等により測定することができる重合体の組成と同一である。
各例における測定及び評価は、以下の方法により行った。なお、下記（１）～（５）の項目に関する測定及び評価にあたり、実施例、比較例で得られたペレット（医療用樹脂材料）を用いた。ここで、ペレット（医療用樹脂材料）は、開環重合体水素化物の他に、添加剤としての酸化防止剤を含有しているが、表１に示した結果については、仮に、酸化防止剤を配合しなかった場合についても、略同一となる。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. In the following description, the "part" representing the quantity is based on mass unless otherwise specified. The pressure is a gauge pressure. Further, the ratio of the structural units derived from each monomer in the polymer obtained by polymerizing the monomer composition having a certain composition is the same as the composition of the polymer that can be measured by 1 H-NMR measurement or the like. Is.
The measurement and evaluation in each example were carried out by the following methods. In the measurement and evaluation of the following items (1) to (5), the pellets (medical resin materials) obtained in Examples and Comparative Examples were used. Here, the pellet (medical resin material) contains an antioxidant as an additive in addition to the ring-opening polymer hydride, but the results shown in Table 1 are tentatively an antioxidant. It is almost the same even when is not blended.
（１）ガラス転移温度（Ｔｇ）
実施例、比較例で得られたペレット（医療用樹脂材料）について、示差走査熱量分析計（ナノテクノロジー社製、ＤＳＣ６２２０ＳＩＩ）を用いて、ＪＩＳ Ｋ ６９１１に基づき、昇温速度１０℃／ｍｉｎの条件で、ガラス転移温度を測定した。
(1) Glass transition temperature (Tg)
The pellets (medical resin materials) obtained in Examples and Comparative Examples were subjected to a differential scanning calorimetry (DSC6220SII manufactured by Nanotechnology) under the conditions of a heating rate of 10 ° C./min based on JIS K 6911. Then, the glass transition temperature was measured.
（２）構造単位（Ａ）よりなるラセモダイアッドの割合
実施例、比較例で得られたペレット（医療用樹脂材料）について、テトラシクロドデセン由来の構造単位（Ａ）よりなるラセモダイアッドの割合を測定した。重水素化オルトジクロロベンゼンを溶媒として、２００℃でｉｎｖｅｒｓｅ－ｇａｔｅｄ ｄｅｃｏｕｐｌｉｎｇ法を適用して１３Ｃ－ＮＭＲ測定を行った。構造単位（Ａ）よりなるラセモダイアッドの割合を算出するに当たり、構造単位（Ａ）が連続して結合している部分に対応する１３Ｃ－ＮＭＲ測定値のみを用い、構造単位（Ａ）と構造単位（Ｂ）とが結合している部分に対応する１３Ｃ－ＮＭＲ測定値は用いなかった。そして、構造単位（Ａ）が連続して結合している部分に対応する１３Ｃ－ＮＭＲ測定値に含まれる、構造単位（Ａ）よりなるラセモ・ダイアッド由来の信号の割合を求めた。具体的には、オルトジクロロベンゼン－ｄ４の１２７．５ｐｐｍのピークを基準シフトとして、ラセモダイアッド由来のシグナル（５１．７ｐｐｍ）とメソダイアッド由来のシグナル（５１．６ｐｐｍ）の強度比に基づいて、構造単位（Ａ）よりなるラセモダイアッド及びメソダイアッドの合計を１００モル％とした場合の、ラセモダイアッドの割合（モル％）を求めた。
(2) Percentage of racemodiad consisting of structural unit (A) With respect to the pellets (medical resin materials) obtained in Examples and Comparative Examples, the ratio of racemodiad consisting of structural unit (A) derived from tetracyclododecene was measured. .. 13 C-NMR measurement was carried out by applying the inverted-gated decoupling method at 200 ° C. using deuterated ortho-dichlorobenzene as a solvent. In calculating the ratio of the racemodiad consisting of the structural unit (A), only the 13 C-NMR measurement values corresponding to the portion where the structural unit (A) is continuously bonded are used, and the structural unit (A) and the structural unit are used. The 13 C-NMR measurement value corresponding to the portion bonded to (B) was not used. Then, the ratio of the signal derived from the racemo diad consisting of the structural unit (A) contained in the 13 C-NMR measured value corresponding to the portion where the structural unit (A) is continuously bonded was determined. Specifically, the structural unit is based on the intensity ratio of the signal derived from racemodiad (51.7 ppm) and the signal derived from mesodiad (51.6 ppm) with the peak of 127.5 ppm of orthodichlorobenzene-d 4 as a reference shift. The ratio (mol%) of racemodiad was determined when the total of racemodiad and mesodiad consisting of (A) was 100 mol%.
（３）水素化率
実施例、比較例で得られたペレット（医療用樹脂材料）について、主鎖中の炭素-炭素二重結合の水素化率は、１Ｈ－ＮＭＲスペクトルを測定し算出した。
(3) Hydrogenation rate For the pellets (medical resin materials) obtained in Examples and Comparative Examples, the hydrogenation rate of the carbon-carbon double bond in the main chain was calculated by measuring 1 1 H-NMR spectrum. ..
（４）透湿度（防湿性）
実施例、比較例で得られたペレット（医療用樹脂材料）を、厚さ１００μｍとなるよう押出成形したフィルムを試験片とし、ＪＩＳ ７１２９（Ａ法）に基づいて、温度５０℃、湿度９０％ＲＨの条件下で水蒸気透過度テスター（ＬＹＳＳＹ社製：Ｌ８０－５０００型）を用いて透湿度（ｇ／（ｍ2・２４ｈ）／１００μｍ）測定した。透湿度の値が低ければ、蒸気透過性が低く、且つ防湿性が高いことを意味する。
(4) Moisture permeability (moisture proof)
A film obtained by extruding pellets (medical resin material) obtained in Examples and Comparative Examples to a thickness of 100 μm was used as a test piece, and the temperature was 50 ° C. and the humidity was 90% based on JIS 7129 (Method A). Moisture vapor transmission rate (g / (m 2.24h ) / 100μm) was measured using a water vapor transmission rate tester (manufactured by LYSSY: L80-5000 type) under RH conditions. If the value of moisture permeability is low, it means that the vapor permeability is low and the moisture resistance is high.
（５）疑似皮脂試験（耐脂性）
実施例、比較例で得られたペレット（医療用樹脂材料）を、射出成形機（ファナック社製、ロボショットα－１００Ｂ、型締め力最大１００ｔ）により、樹脂温度３５０℃、金型温度１３５℃、射出圧力１００ＭＰａの条件で、長さ１００ｍｍ×幅１０ｍｍ×厚さ１ｍｍの試験片を１０枚作成した。擬似皮脂（オレイン酸５０％、パルミチン酸イソステアリル４０％、スクアレン１０％）を試薬とし、ＩＳＯ１７８に基づいて、支点間距離３０ｍｍ、クロスヘッドスピード５ｍｍ／ｍｉｎ．の条件で曲げ強度試験を実施した。試験片の外観検査を行い下記基準で判定した。疑似皮脂試験の結果が良好であるものは、耐脂性に優れる。
Ａ：試験片上にクラックの発生が無い。
Ｂ：試験片上に1個のクラックが発生した。
Ｃ：試験片上に２個以上のクラックが発生、もしくは試験片が破断した。
(5) Pseudo sebum test (fat resistance)
The pellets (medical resin materials) obtained in Examples and Comparative Examples were subjected to a resin temperature of 350 ° C. and a mold temperature of 135 ° C. by an injection molding machine (FANUC, Roboshot α-100B, mold clamping force maximum 100t). , Ten test pieces having a length of 100 mm, a width of 10 mm, and a thickness of 1 mm were prepared under the condition of an injection pressure of 100 MPa. Using simulated sebum (50% oleic acid, 40% isostearyl palmitate, 10% squalene) as a reagent, the distance between fulcrums was 30 mm and the crosshead speed was 5 mm / min. The bending strength test was carried out under the conditions of. The appearance of the test piece was inspected and the judgment was made according to the following criteria. Those with good results in the pseudo-sebum test have excellent oil resistance.
A: No cracks are generated on the test piece.
B: One crack was generated on the test piece.
C: Two or more cracks were generated on the test piece, or the test piece was broken.
（６）溶液安定性
実施例、比較例で得られた水素化反応溶液の一部を採取して、開環重合体水素化物を分離した。分離した開環重合体水素化物を２部と、シクロヘキサン８部とをガラス製アンプルに加え、２０％シクロヘキサン溶液を調製した。開環重合体水素化物を完全に溶解させた後、ガラス製アンプルを２５℃の水浴につけ、３日経過後の溶液の性状変化を目視で観察して、以下の基準に従って評価した。
Ａ：固化が生じなかった。
Ｂ：固化が生じた。
(6) Solution stability A part of the hydrogenation reaction solutions obtained in Examples and Comparative Examples was collected, and the ring-opening polymer hydride was separated. Two parts of the separated ring-opening polymer hydride and 8 parts of cyclohexane were added to a glass ampoule to prepare a 20% cyclohexane solution. After the ring-opening polymer hydride was completely dissolved, a glass ampoule was placed in a water bath at 25 ° C., and the change in the properties of the solution after 3 days was visually observed and evaluated according to the following criteria.
A: No solidification occurred.
B: Solidification has occurred.
（実施例１）
＜開環重合工程＞
内部を乾燥し、窒素置換した重合反応器に、テトラシクロドデセン（ＴＣＤ）８５％とノルボルネン（ＮＢ）１５％からなる単量体混合物２．０部（重合に使用するモノマー全量に対して１％）、有機溶媒としての脱水シクロヘキサン７８５部、分子量調節剤としての１－ヘキセン０．５部、有機金属還元剤としてのジエチルアルミニウムエトキシドのｎ－ヘキサン溶液（濃度：１９％）０．９８部、及び開環重合触媒としてのタングステン（フェニルイミド）テトラクロリド・テトラヒドロフランのトルエン溶液（濃度：２．０％）１１．７部を入れ、４５℃で１０分間攪拌した。次いで、全容を５０℃に保持し、攪拌しながら、前記重合反応器中に、前記組成と同じ単量体混合物１９８．０部を１５０分かけて連続的に滴下した。滴下終了後３０分間攪拌を継続した後、イソプロピルアルコール４部を添加して重合反応を停止させた。ガスクロマトグラフィーによって重合反応溶液を測定したしたところ、単量体の重合体への転化率は１００％であった。
(Example 1)
<Ring-opening polymerization process>
2.0 parts of a monomer mixture consisting of 85% tetracyclododecene (TCD) and 15% norbornene (NB) in a polymerization reactor whose inside has been dried and substituted with nitrogen (1 for the total amount of monomers used for polymerization). %), 785 parts of dehydrated cyclohexane as an organic solvent, 0.5 part of 1-hexene as a molecular weight modifier, and 0.98 parts of an n-hexane solution of diethylaluminum ethoxydo as an organic metal reducing agent (concentration: 19%). , And 11.7 parts of a toluene solution (concentration: 2.0%) of tungsten (phenylimide) tetrachloride and tetrahydrofuran as a ring-opening polymerization catalyst were added, and the mixture was stirred at 45 ° C. for 10 minutes. Then, 198.0 parts of the monomer mixture having the same composition as the above composition was continuously added dropwise over 150 minutes into the polymerization reactor while keeping the whole volume at 50 ° C. and stirring. After the stirring was continued for 30 minutes after the completion of the dropping, 4 parts of isopropyl alcohol was added to stop the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion rate of the monomer to the polymer was 100%.
＜水素化工程＞
次いで、得られた重合反応溶液３００部を攪拌器付きオートクレーブに移し、有機溶媒としてのシクロヘキサン３２部、水素化触媒としての珪藻土担持ニッケル触媒（日揮化学社製；「Ｔ８４００ＲＬ」、ニッケル担持率５８％）３．８部を加えた。オートクレーブ内を水素で置換した後、１９０℃、４．５ＭＰａの水素圧力下で６時間反応させた。
水素化反応終了後、珪藻土（「ラヂオライト（登録商標）♯５００」）を濾過床として、加圧濾過器（石川島播磨重工社製；「フンダフィルタ－」）を使用し、圧力０．２５ＭＰａで加圧濾過して、無色透明の水素化反応溶液を得た。得られた水素化反応溶液を溶液安定性の評価に供した。
<Hydrogenation process>
Next, 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, and 32 parts of cyclohexane as an organic solvent and a nickel algae soil-supported nickel catalyst as a hydrogenation catalyst (manufactured by Nikki Kagaku Co., Ltd .; "T8400RL", nickel carrying ratio 58%). ) 3.8 parts were added. After replacing the inside of the autoclave with hydrogen, the reaction was carried out at 190 ° C. under a hydrogen pressure of 4.5 MPa for 6 hours.
After the hydrogenation reaction is completed, a pressure filter (manufactured by Ishikawajima Harima Heavy Industries; "Funda Filter-") is used with diatomaceous soil ("Radiolite (registered trademark) # 500") as a filtration bed at a pressure of 0.25 MPa. Pressure filtration was performed to obtain a colorless and transparent hydrogenation reaction solution. The obtained hydrogenation reaction solution was used for evaluation of solution stability.
＜医療用樹脂材料製造工程＞
この水素化反応溶液に、重合体水素化物１００部当り、酸化防止剤として、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］（チバ・スペシャルティ・ケミカルズ社製、製品名「イルガノックス（登録商標）１０１０」）０．５部を加えた後、フィルター（キュノーフィルター社製；「ゼータプラス（登録商標）３０Ｈ」、孔径０．５～１μｍ）、及び金属ファイバー製フィルター（ニチダイ社製、孔径０．４μｍ）を用いて異物を濾別除去した。
次いで、上記で得られた濾液を、円筒型濃縮乾燥機（日立製作所製）に入れ、温度２９０℃、圧力１ｋＰａ以下の条件で、溶媒であるシクロヘキサン及びその他の揮発成分を除去し、濃縮機に直結したダイから溶融状態でストランド状に押出し、水冷後、ペレタイザー（長田製作所製；「ＯＳＰ－２」）でカッティングしてペレット（医療用樹脂材料）を得た。このペレットを用いて、上記の測定及び評価を行った。結果を表１に示す。
<Medical resin material manufacturing process>
In this hydrogenation reaction solution, per 100 parts of the polymer hydride, as an antioxidant, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty). -After adding 0.5 part of the product name "Irganox (registered trademark) 1010" manufactured by Chemicals, a filter (manufactured by Cuno Filter Co.; "Zetaplus (registered trademark) 30H", pore diameter 0.5 to 1 μm) ) And a metal fiber filter (manufactured by Nichidai Corporation, pore diameter 0.4 μm) were used to remove foreign substances by filtration.
Next, the filtrate obtained above was placed in a cylindrical concentrator / dryer (manufactured by Hitachi, Ltd.), and the solvent cyclohexane and other volatile components were removed under the conditions of a temperature of 290 ° C. and a pressure of 1 kPa or less, and the concentrator was used. It was extruded into a strand shape in a molten state from a directly connected die, cooled with water, and then cut with a pelletizer (manufactured by Nagata Seisakusho; "OSP-2") to obtain pellets (medical resin material). The above measurements and evaluations were performed using these pellets. The results are shown in Table 1.
（実施例２～５、比較例１）
単量体混合物の組成を、得られる重合体水素化物の組成が表１に示す通りになるようにそれぞれ変更した以外は、実施例１と同様にして各種操作、測定、及び評価を行った。結果を表１に示す。なお、比較例１にて得られたペレットは、ガラス転移温度が４３℃であったため、上記条件下（温度５０℃）では透湿度を評価することができなかった。
(Examples 2 to 5, Comparative Example 1)
Various operations, measurements, and evaluations were carried out in the same manner as in Example 1 except that the composition of the monomer mixture was changed so that the composition of the obtained polymer hydride was as shown in Table 1. The results are shown in Table 1. Since the pellet obtained in Comparative Example 1 had a glass transition temperature of 43 ° C., the moisture permeability could not be evaluated under the above conditions (temperature 50 ° C.).
（比較例２）
単量体混合物の組成を、得られる重合体水素化物の組成が表１に示す通りになるように変更した以外は、実施例１と同様にして水素化工程まで実施した。そして、得られた水素化溶液について、上記に従って溶液安定性を評価した結果、３日経過時点で水素化溶液が固化していたため、以降の操作、測定、及び評価を実施しなかった。
(Comparative Example 2)
The hydrogenation step was carried out in the same manner as in Example 1 except that the composition of the monomer mixture was changed so that the composition of the obtained polymer hydride was as shown in Table 1. Then, as a result of evaluating the solution stability of the obtained hydrogenated solution according to the above, since the hydrogenated solution had solidified after 3 days, the subsequent operations, measurements, and evaluations were not performed.
（比較例３）
＜開環重合工程＞
内部を乾燥し、窒素置換した重合反応器に、テトラシクロドデセン（ＴＣＤ）２９％とノルボルネン（ＮＢ）５３％とジシクロペンタジエン（ＤＣＰ）１８％とからなる単量体混合物２．０部（重合に使用するモノマー全量に対して１％）、有機溶媒としての脱水シクロヘキサン７８５部、分子量調節剤としての１－ヘキセン０．８６部、ジイソプロピルエーテル０．４２部、イソブチルアルコール０．１１部、トリイソブチルアルミニウムのｎ－ヘキサン溶液（濃度：１５％）１．８０部、及び六塩化タングステンのシクロヘキサン溶液（濃度：０．６５％）１３．４部を入れ、５５℃で１０分間攪拌した。次いで、全容を５０℃に保持し、攪拌しながら、前記重合反応器中に前記単量体混合物１９８．０部と六塩化タングステン０．６５％シクロヘキサン溶液２０．１部とを各々１５０分かけて連続的に滴下した。滴下終了後３０分間攪拌を継続した後、イソプロピルアルコール０．４部を添加して重合反応を停止させた。単量体の重合体への転化率は１００％であった。
この後、実施例１と同様にして水素化工程～医療用樹脂材料製造工程を実施して、ペレット（医療用樹脂材料）を得た。このペレットを用いて、上記の測定及び評価を行った。結果を表１に示す。
(Comparative Example 3)
<Ring-opening polymerization process>
2.0 parts of a monomer mixture consisting of 29% tetracyclododecene (TCD), 53% norbornene (NB) and 18% dicyclopentadiene (DCP) in a polymerization reactor obtained by drying the inside and substituting with nitrogen (2 parts). 1% of the total amount of monomer used for polymerization), 785 parts of dehydrated cyclohexane as an organic solvent, 0.86 parts of 1-hexene as a molecular weight regulator, 0.42 parts of diisopropyl ether, 0.11 parts of isobutyl alcohol, tri 1.80 parts of an isobutylaluminum n-hexane solution (concentration: 15%) and 13.4 parts of a cyclohexane solution of tungsten hexachloride (concentration: 0.65%) were added, and the mixture was stirred at 55 ° C. for 10 minutes. Then, while maintaining the whole volume at 50 ° C. and stirring, 198.0 parts of the monomer mixture and 20.1 parts of a 0.65% tungsten hexachloride cyclohexane solution were each placed in the polymerization reactor over 150 minutes. Dropped continuously. After the stirring was continued for 30 minutes after the completion of the dropping, 0.4 part of isopropyl alcohol was added to stop the polymerization reaction. The conversion rate of the monomer to the polymer was 100%.
After that, the hydrogenation step to the medical resin material manufacturing step were carried out in the same manner as in Example 1 to obtain pellets (medical resin material). The above measurements and evaluations were performed using these pellets. The results are shown in Table 1.
（比較例４～６）
単量体混合物の組成を、得られる重合体水素化物の組成が表１に示す通りになるようにそれぞれ以外は、比較例３と同様にしてペレット（医療用樹脂材料）を得た。このペレットを用いて、上記の測定及び評価を行った。結果を表１に示す。
(Comparative Examples 4 to 6)
Pellets (medical resin materials) were obtained in the same manner as in Comparative Example 3 except that the composition of the monomer mixture was as shown in Table 1 so that the composition of the obtained polymer hydride was as shown in Table 1. The above measurements and evaluations were performed using these pellets. The results are shown in Table 1.
（比較例７～８）
単量体混合物の組成を、得られる重合体水素化物の組成が表１に示す通りになるようにそれぞれ変更した以外は、実施例１と同様にして水素化工程まで実施した。そして、得られた水素化溶液について、上記に従って溶液安定性を評価した結果、両比較例共に、３日経過時点で水素化溶液が固化していたため、以降の操作、測定、及び評価を実施しなかった。
(Comparative Examples 7 to 8)
The hydrogenation step was carried out in the same manner as in Example 1 except that the composition of the monomer mixture was changed so that the composition of the obtained polymer hydride was as shown in Table 1. Then, as a result of evaluating the solution stability of the obtained hydrogenated solution according to the above, since the hydrogenated solution was solidified after 3 days in both comparative examples, the subsequent operations, measurements, and evaluations were carried out. There wasn't.
表１中
「ＴＣＤ」は、テトラシクロドデセン（テトラシクロ[6.2.1.13,6.02,7]ドデカ-4-エン）を、
「ＮＢ」は、ノルボルネン（ビシクロ[2.2.1]ヘプタ-2-エン）を、
「ＤＣＰＤ」は、ジシクロペンタジエンを、
「ＭＴＦ」は、１，４－メタノ－１，４，４ａ，９ａ－テトラヒドロフルオレンを、それぞれ示す。
"NB" is norbornene (bicyclo [2.2.1] hepta-2-en),
"DCPD" is dicyclopentadiene,
"MTF" indicates 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, respectively.
表１より明らかなように、テトラシクロドデセン由来の構造単位（Ａ）、及びノルボルネン由来の構造単位（Ｂ）を含む開環重合体水素化物であって、構造単位（Ａ）の含有割合が４７．０質量％以上８８．０質量%以下であり、且つ、構造単位（Ｂ）の含有割合が１２．０質量％以上５３．０質量％以下であり、さらに、構造単位（Ａ）よりなるラセモダイアッドの割合が６５モル％以上である、開環重合体水素化物は、透湿度が低く防湿性に優れ、且つ、疑似皮脂試験の結果が良好であり耐脂性に優れる医療用樹脂材料を提供し得たことが分かる。
一方、構造単位（Ａ）及び構造単位（Ｂ）の割合が上記範囲外であるか、或いは、ラセモダイアッドの割合が６５モル％未満である比較例１～８では、防湿性及び耐脂性に優れる医療用樹脂材料を提供できなかったことが分かる。
なお、比較例３～６より明らかなように、本発明の範囲外である種々のガラス転移温度の開環重合体水素化物では、ガラス転移温度が高いと、透湿度の値も大きくなる傾向があることが分かる。一方、実施例１～５から明らかなように、本発明に従う開環重合体水素化物では、ガラス転移温度が高い場合であっても、透湿度の値が一定であったことが分かる。このことから、本発明によれば、防湿性に優れた、所望のガラス転移温度を呈し得る開環重合体水素化物を良好に提供可能であることが分かる。
As is clear from Table 1, it is a ring-opening polymer hydride containing the structural unit (A) derived from tetracyclododecene and the structural unit (B) derived from norbornene, and the content ratio of the structural unit (A) is It is 47.0% by mass or more and 88.0% by mass or less, and the content ratio of the structural unit (B) is 12.0% by mass or more and 53.0% by mass or less, and further comprises the structural unit (A). The ring-opening polymer hydride having a ratio of racemodiad of 65 mol% or more provides a medical resin material having low moisture permeability, excellent moisture resistance, good results of pseudo-skin oil test, and excellent oil resistance. You can see that it was obtained.
On the other hand, in Comparative Examples 1 to 8 in which the ratio of the structural unit (A) and the structural unit (B) is out of the above range or the ratio of the racemodiad is less than 65 mol%, medical treatment having excellent moisture resistance and oil resistance It can be seen that the resin material for use could not be provided.
As is clear from Comparative Examples 3 to 6, in the ring-opening polymer hydride having various glass transition temperatures outside the range of the present invention, the value of moisture permeability tends to increase when the glass transition temperature is high. It turns out that there is. On the other hand, as is clear from Examples 1 to 5, in the ring-opening polymer hydride according to the present invention, it can be seen that the value of moisture permeability was constant even when the glass transition temperature was high. From this, it can be seen that according to the present invention, it is possible to satisfactorily provide a ring-opening polymer hydride having excellent moisture resistance and capable of exhibiting a desired glass transition temperature.
本発明によれば、防湿性及び耐脂性に優れる環状オレフィン開環重合体水素化物を提供することができる。
さらに、本発明によれば、防湿性及び耐脂性に優れる環状オレフィン開環重合体水素化物を含んでなる、医療用樹脂材料、容器、及びフィルムを提供することができる。
According to the present invention, it is possible to provide a cyclic olefin ring-opening polymer hydride having excellent moisture resistance and oil resistance.
Further, according to the present invention, it is possible to provide a medical resin material, a container, and a film containing a cyclic olefin ring-opening polymer hydride having excellent moisture resistance and oil resistance.
Claims (5)
前記環状オレフィン開環重合体水素化物に含まれる全繰り返し単位を１００．０質量％として、前記構造単位（Ａ）の含有割合が４７．０質量％以上８８．０質量%以下であり、且つ、前記構造単位（Ｂ）の含有割合が１２．０質量％以上５３．０質量％以下であり、さらに、
前記構造単位（Ａ）よりなるラセモダイアッドの割合が６５モル％以上であり、
ガラス転移温度が１３４℃以下である、
環状オレフィン開環重合体水素化物。 A cyclic olefin ring-opening polymer hydride containing a structural unit (A) derived from tetracyclododecene and a structural unit (B) derived from norbornene.
The content ratio of the structural unit (A) is 47.0% by mass or more and 88.0% by mass or less, assuming that the total repeating unit contained in the cyclic olefin ring-opening polymer hydride is 100.0% by mass. The content ratio of the structural unit (B) is 12.0% by mass or more and 53.0% by mass or less, and further.
The ratio of the racemodiad composed of the structural unit (A) is 65 mol% or more, and the ratio is 65 mol% or more.
The glass transition temperature is 134 ° C or lower ,
Cyclic olefin ring-opening polymer hydride.
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| JP2007137935A (en) | 2005-11-15 | 2007-06-07 | Nippon Zeon Co Ltd | Hydrogenated tetracyclododecene ring-opened polymer, method for producing the same and optical material |
| US20080033112A1 (en) | 2006-08-04 | 2008-02-07 | Squire Kevin R | Polymer compositions comprising cyclic olefin copolymers and polyolefin modifiers |
| WO2015137434A1 (en) | 2014-03-14 | 2015-09-17 | 日本ゼオン株式会社 | Tetracyclododecene ring-opened polymer hydride and method for producing same |
| WO2016052302A1 (en) | 2014-09-29 | 2016-04-07 | 日本ゼオン株式会社 | Cyclic olefin ring-opened polymer hydride, resin molded article, and optical member |
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| JP2007137935A (en) | 2005-11-15 | 2007-06-07 | Nippon Zeon Co Ltd | Hydrogenated tetracyclododecene ring-opened polymer, method for producing the same and optical material |
| US20080033112A1 (en) | 2006-08-04 | 2008-02-07 | Squire Kevin R | Polymer compositions comprising cyclic olefin copolymers and polyolefin modifiers |
| WO2015137434A1 (en) | 2014-03-14 | 2015-09-17 | 日本ゼオン株式会社 | Tetracyclododecene ring-opened polymer hydride and method for producing same |
| WO2016052302A1 (en) | 2014-09-29 | 2016-04-07 | 日本ゼオン株式会社 | Cyclic olefin ring-opened polymer hydride, resin molded article, and optical member |
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