JPWO2013133226A1 - Polymer composition containing alicyclic structure - Google Patents
Polymer composition containing alicyclic structure Download PDFInfo
- Publication number
- JPWO2013133226A1 JPWO2013133226A1 JP2014503841A JP2014503841A JPWO2013133226A1 JP WO2013133226 A1 JPWO2013133226 A1 JP WO2013133226A1 JP 2014503841 A JP2014503841 A JP 2014503841A JP 2014503841 A JP2014503841 A JP 2014503841A JP WO2013133226 A1 JPWO2013133226 A1 JP WO2013133226A1
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- norbornene
- alicyclic structure
- ring
- carbon nanotube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
Abstract
本発明に係るノルボルネン系開環重合体組成物は、ノルボルネン系開環重合体（Ａ）と、カーボンナノチューブ（Ｂ）と、高分子顔料分散剤（Ｃ）を含有し、カーボンナノチューブ（Ｂ）が０．０１〜１０重量％である。The norbornene-based ring-opening polymer composition according to the present invention contains a norbornene-based ring-opening polymer (A), a carbon nanotube (B), and a polymer pigment dispersant (C). 0.01 to 10% by weight.
Description
本発明は、導電性に優れた成形体を与えることのできる、カーボンナノチューブを配合した重合体組成物に関する。
に関する。The present invention relates to a polymer composition blended with carbon nanotubes, which can give a molded article having excellent conductivity.
About.
特許文献１では、ノルボルネン系開環重合体などの脂環式構造含有重合体に、カーボンナノチューブを配合し、導電性と低アウトガス性に優れた樹脂組成物が提案されている。ここでは、重合体１００重量部に対して、カーボンナノチューブ１重量部を配合した樹脂組成物からなる成形体で、１０６オーダー（Ω／□）の表面抵抗値を得ている。Patent Document 1 proposes a resin composition excellent in conductivity and low outgassing properties by blending carbon nanotubes with an alicyclic structure-containing polymer such as a norbornene-based ring-opening polymer. Here, a surface resistance value of the order of 10 6 (Ω / □) is obtained with a molded body made of a resin composition in which 1 part by weight of carbon nanotubes is blended with 100 parts by weight of polymer.
また、特許文献２では、カーボンナノチューブ存在下、スチレン系単量体を乳化剤水溶液中で懸濁重合することで得られるスチレン系樹脂組成物が、カーボンナノチューブ含量２％の樹脂組成物からなる成形体で、１０４オーダー（Ω・ｃｍ）の体積抵抗値を得ている。Further, in Patent Document 2, a styrene resin composition obtained by suspension polymerization of a styrene monomer in an emulsifier aqueous solution in the presence of carbon nanotubes is a molded article comprising a resin composition having a carbon nanotube content of 2%. Thus, a volume resistance value of 10 4 order (Ω · cm) is obtained.
上述した文献の組成物には、高価なカーボンナノチューブを大量に配合されている。しかも、得られる成形体の導電性は、必ずしも高いものではない。 A large amount of expensive carbon nanotubes are blended in the composition of the literature described above. And the electroconductivity of the molded object obtained is not necessarily high.
本発明者らは、上記課題に鑑み鋭意検討を行い、脂環構造含有重合体とカーボンナノチューブとが、ある種の分散剤存在下で混合された重合体組成物は、少量のカーボンナノチューブ量であっても、高い導電性を得ることを見いだし、本発明を完成させるに至った。 The present inventors have conducted intensive studies in view of the above problems, and a polymer composition in which an alicyclic structure-containing polymer and carbon nanotubes are mixed in the presence of a certain type of dispersant has a small amount of carbon nanotubes. Even so, it has been found that high conductivity is obtained, and the present invention has been completed.
本発明によれば、少量のカーボンナノチューブ量であっても、高い導電性を有する脂環構造含有重合体組成物を得ることができるという効果を奏する。 According to the present invention, there is an effect that an alicyclic structure-containing polymer composition having high conductivity can be obtained even with a small amount of carbon nanotubes.
以下、本発明を実施形態に基づいて具体的に説明する。本発明の脂環構造含有重合体組成物は、高分子顔料分散剤存在下、カーボンナノチューブと単量体とを溶媒中で分散させ、当該単量体を重合し、必要に応じて水素添加する方法（以下、Ａ法）の他、高分子顔料分散剤存在下、カーボンナノチューブと脂環構造含有重合体やその水素添加物とを混合する方法（以下、Ｂ法）によっても製造することができる。 Hereinafter, the present invention will be specifically described based on embodiments. The alicyclic structure-containing polymer composition of the present invention is obtained by dispersing carbon nanotubes and a monomer in a solvent in the presence of a polymer pigment dispersant, polymerizing the monomer, and hydrogenating as necessary. In addition to the method (hereinafter referred to as method A), it can also be produced by a method of mixing carbon nanotubes with an alicyclic structure-containing polymer or a hydrogenated product thereof in the presence of a polymer pigment dispersant (hereinafter referred to as method B). .
この脂環構造含有重合体の具体例としては、（１）ノルボルネン系重合体、（２）単環の環状オレフィン系重合体、（３）環状共役ジエン系重合体、（４）ビニル脂環式炭化水素系重合体、及び（１）〜（４）の水素化物などが挙げられる。これらの中でも、耐熱性、機械的強度等の観点から、ノルボルネン系重合体及びその水素化物が好ましい。 Specific examples of the alicyclic structure-containing polymer include (1) norbornene-based polymer, (2) monocyclic olefin-based polymer, (3) cyclic conjugated diene-based polymer, and (4) vinyl alicyclic. Examples thereof include hydrocarbon polymers and hydrides (1) to (4). Among these, norbornene-based polymers and hydrides thereof are preferable from the viewpoints of heat resistance, mechanical strength, and the like.
（１）ノルボルネン系重合体
ノルボルネン系重合体は、ノルボルネン骨格を有する単量体であるノルボルネン系単量体を重合してなるものであり、開環重合によって得られるものと、付加重合によって得られるものに大別される。(1) Norbornene-based polymer The norbornene-based polymer is obtained by polymerizing a norbornene-based monomer that is a monomer having a norbornene skeleton, and is obtained by ring-opening polymerization or by addition polymerization. Broadly divided into things.
ノルボルネン系単量体としては、ビシクロ［２．２．１］ヘプト−２−エン（慣用名：ノルボルネン）及びその誘導体（環に置換基を有するもの）、トリシクロ［４．３．０１，６．１２，５］デカ−３，７−ジエン（慣用名：ジシクロペンタジエン）及びその誘導体、７，８−ベンゾトリシクロ［４．３．０．１２，５］デカ−３−エン（１，４−メタノ−１，４，４ａ，９ａ−テトラヒドロフルオレンとも言う）及びその誘導体、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ−３−エン（慣用名：テトラシクロドデセン）及びその誘導体、などが挙げられる。Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof (having a substituent in the ring), tricyclo [4.3.0 1,6 . 1 2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (1 , 4-methano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene (common name: tetracyclododecene) and its derivatives.
これらのノルボルネン系単量体は、それぞれ単独であるいは２種以上を組み合わせて用いられる。 These norbornene monomers are used alone or in combination of two or more.
これらの中でも特に、７，８−ベンゾトリシクロ［４．３．０．１２，５］デカ−３−エンをノルボルネン系単量体として用いたノルボルネン系単量体の開環重合体及びその水素化物が耐熱性に関して著効を示すので好ましい。７，８−ベンゾトリシクロ［４．３．０．１２，５］デカ−３−エンをノルボルネン系単量体として用いたノルボルネン系単量体の開環重合体及びその水素化物は、ノルボルネン系単量体中、７，８−ベンゾトリシクロ［４．３．０．１２，５］デカ−３−エンの割合が好ましくは５０重量％以上、より好ましくは７０重量％以上、とりわけ好ましくは８５重量％以上のものである。Among these, a ring-opening polymer of a norbornene monomer using 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene as a norbornene monomer and its Hydride is preferable because it exhibits a remarkable effect on heat resistance. A ring-opening polymer of a norbornene monomer using 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene as a norbornene monomer and a hydride thereof are norbornene. The proportion of 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene in the monomer is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably Is 85% by weight or more.
開環重合によって得られるものとして、ノルボルネン系単量体の開環重合体及びノルボルネン系単量体とこれと開環共重合可能なその他の単量体との開環重合体、ならびにこれらの水素化物などが挙げられる。付加重合によって得られるものとしてノルボルネン系単量体の付加重合体及びノルボルネン系単量体とこれと共重合可能なその他の単量体との付加重合体などが挙げられる。これらの中でも、ノルボルネン系単量体の開環重合体水素化物が、耐熱性、機械的強度等の観点から好ましい。 As ring-opening polymerization, ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization, and hydrogens thereof. And the like. Examples of the polymers obtained by addition polymerization include addition polymers of norbornene monomers and addition polymers of norbornene monomers and other monomers copolymerizable therewith. Among these, a ring-opening polymer hydride of a norbornene-based monomer is preferable from the viewpoint of heat resistance, mechanical strength, and the like.
ノルボルネン系単量体の開環重合体、又はノルボルネン系単量体とこれと開環共重合可能なその他の単量体との開環重合体は、単量体成分を、例えば以下のような公知の開環重合触媒の存在下で重合して得ることができる。 A ring-opening polymer of a norbornene-based monomer or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the monomer component includes, for example, the following components: It can be obtained by polymerization in the presence of a known ring-opening polymerization catalyst.
ノルボルネン系単量体の開環重合は、メタセシス重合触媒を用い、公知の方法に従って行うことができる。メタセシス重合触媒としては、特に限定はなく公知のものが用いられる。具体的には、例えば、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム及び白金などから選ばれる金属のハロゲン化物、硝酸塩又はアセチルアセトン化合物と、還元剤とからなる触媒系；チタン、バナジウム、ジルコニウム、タングステン及びモリブデンから選ばれる金属のハロゲン化物又はアセチルアセトン化合物と、助触媒の有機アルミニウム化合物とからなる触媒系；あるいは、日本国公開特許公報「特開平７−１７９５７５号」、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９８６年，１０８，ｐ．７３３、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９９３年，１１５，ｐ．９８５８、及びＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９９６年，１１８，ｐ．１００などに開示されている公知のシュロック型やグラブス型のリビング開環メタセシス触媒などを用いることができる。 The ring-opening polymerization of the norbornene-based monomer can be performed according to a known method using a metathesis polymerization catalyst. The metathesis polymerization catalyst is not particularly limited and known ones are used. Specifically, for example, a catalyst system comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent; titanium, vanadium, zirconium, tungsten and molybdenum A catalyst system comprising a metal halide selected from the group consisting of a metal halide or an acetylacetone compound and a co-catalyst organoaluminum compound; or JP-A-7-179575, J. Pat. Am. Chem. Soc. 1986, 108, p. 733, J. et al. Am. Chem. Soc. 1993, 115, p. 9858, and J.H. Am. Chem. Soc. 1996, 118, p. A known Schrock-type or Grubbs-type living ring-opening metathesis catalyst disclosed in No. 100 can be used.
特に、以下の一般式で記載されるグラブス型のリビング開環メタセシス触媒が好ましい。 In particular, a Grubbs-type living ring-opening metathesis catalyst described by the following general formula is preferable.
一般式（６）において、Ｒ１、Ｒ２は、それぞれ独立して水素原子、ハロゲン原子、又は酸素原子、窒素原子、イオウ原子、リン原子もしくはケイ素原子を含んでもよい炭素数１〜２０の炭化水素基を表す。Ｙ１及びＹ２は、それぞれ独立して任意のアニオン性配位子を示す。Ｌ１、Ｌ２は任意の中性の電子供与性化合物を表す。また、Ｒ１、Ｒ２、Ｙ１、Ｙ２、Ｌ１及びＬ２の２個、３個、４個、５個又は６個は、互いに結合して多座キレート化配位子を形成してもよい。In General Formula (6), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. Y 1 and Y 2 each independently represent an arbitrary anionic ligand. L 1 and L 2 represent any neutral electron-donating compound. In addition, 2, 3, 4, 5 or 6 of R 1 , R 2 , Y 1 , Y 2 , L 1 and L 2 are bonded to each other to form a multidentate chelating ligand. May be.
前記一般式において、アニオン性配位子Ｙ１、Ｙ２は、中心金属から引き離されたときに負の電荷を持つ配位子であり、例えば、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、ジケトネート基、置換シクロペンタジエニル基、アルコキシ基、アリールオキシ基、カルボキシル基などを挙げることができる。これらの中でもハロゲン原子が好ましく、塩素原子がより好ましい。In the general formula, the anionic ligands Y 1 and Y 2 are ligands having a negative charge when separated from the central metal, and examples thereof include halogen atoms such as F, Cl, Br, and I, Examples thereof include a diketonate group, a substituted cyclopentadienyl group, an alkoxy group, an aryloxy group, and a carboxyl group. Among these, a halogen atom is preferable and a chlorine atom is more preferable.
また、中性の電子供与性化合物Ｌ１、Ｌ２は、中心金属から引き離されたときに中性の電荷を持つ配位子であればいかなるものでもよい。その具体例としては、カルボニル、アミン類、ピリジン類、エーテル類、ニトリル類、エステル類、ホスフィン類、チオエーテル類、芳香族化合物、オレフィン類、イソシアニド類、チオシアネート類、ヘテロ原子含有カルベン化合物等が挙げられる。これらの中でも、ホスフィン類、ピリジン類、ヘテロ原子含有カルベン化合物が好ましく、トリアルキルホスフィンやＮ原子含有カルベン化合物がより好ましい。The neutral electron-donating compounds L 1 and L 2 may be any ligand as long as it has a neutral charge when pulled away from the central metal. Specific examples thereof include carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, heteroatom-containing carbene compounds, and the like. It is done. Among these, phosphines, pyridines, and hetero atom-containing carbene compounds are preferable, and trialkylphosphine and N atom-containing carbene compounds are more preferable.
これらの触媒は、それぞれ単独で、あるいは２種以上を組み合わせて用いられる。触媒の使用量は、重合条件等により適宜選択されればよいが、全単量体量に対するモル比で、例えば、１／１，０００，０００〜１／１０、好ましくは、１／１００，０００〜１／１００である。 These catalysts are used alone or in combination of two or more. The amount of the catalyst used may be appropriately selected depending on the polymerization conditions and the like, but is, for example, 1 / 1,000,000 to 1/10, preferably 1 / 100,000 in terms of molar ratio to the total monomer amount. ~ 1/100.
ノルボルネン系単量体の開環重合には、分子量調節剤として、直鎖α−オレフィンを用いることができる。直鎖α−オレフィンとしては、１−ブテン、１−ヘキセン、１−デセンなど炭素数４〜４０の物が挙げられる。 In the ring-opening polymerization of the norbornene-based monomer, a linear α-olefin can be used as a molecular weight regulator. Examples of the linear α-olefin include those having 4 to 40 carbon atoms such as 1-butene, 1-hexene and 1-decene.
直鎖α−オレフィンの添加量は、全単量体１００モルに対して、例えば、０．１〜３モル、好ましくは０．３〜２モル、より好ましくは０．５〜１．５モルである。 The addition amount of the linear α-olefin is, for example, 0.1 to 3 mol, preferably 0.3 to 2 mol, more preferably 0.5 to 1.5 mol, with respect to 100 mol of all monomers. is there.
更に、極性化合物を加えて、重合活性や開環重合の選択性を高めることができる。極性化合物としては、例えば、分子状酸素、アルコール、エーテル、過酸化物、カルボン酸、酸無水物、酸クロリド、エステル、ケトン、含窒素化合物、含硫黄化合物、含ハロゲン化合物、分子状ヨウ素、その他のルイス酸などが挙げられる。 Furthermore, polar compounds can be added to increase polymerization activity and ring-opening polymerization selectivity. Examples of polar compounds include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, and others And Lewis acid.
含窒素化合物としては、脂肪族又は芳香族第三級アミンが好ましく、具体例としては、トリエチルアミン、ジメチルアニリン、トリ−ｎ−ブチルアミン、ピリジン、α−ピコリンなどが挙げられる。これらの極性化合物は、それぞれ単独で、あるいは２種以上を組み合わせて用いられる。その用量は、適宜選択されるが、上記触媒中の金属との比、すなわち、極性化合物／金属の比（モル比）で、例えば、１〜１００，０００、好ましくは５〜１０，０００の範囲である。 As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferable, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like. These polar compounds are used alone or in combination of two or more. The dose is appropriately selected, but the ratio to the metal in the catalyst, that is, the polar compound / metal ratio (molar ratio), for example, in the range of 1 to 100,000, preferably 5 to 10,000. It is.
重合反応は、高い導電率を得るために、極性基を有する有機溶媒中で行うのが好ましい。具体的には、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミドなどのアミド系溶媒；メチルイソブチルケトン、メチルエチルケトンなどのケトン系溶媒、テトラヒドロフランのエーテル類などが挙げられる。カーボンナノチューブ（Ｂ）の分散安定性が優れている点、ノルボルネン系開環重合体（Ａ）と高分子顔料分散剤（Ｃ）とが溶解しやすい点などから、アミド系溶媒は特に好ましい。 The polymerization reaction is preferably performed in an organic solvent having a polar group in order to obtain high conductivity. Specific examples include amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone; and ethers of tetrahydrofuran. An amide solvent is particularly preferable from the viewpoints of excellent dispersion stability of the carbon nanotube (B) and easy dissolution of the norbornene ring-opening polymer (A) and the polymer pigment dispersant (C).
本発明で用いるノルボルネン系開環重合体を重合する形態は、格別制限はないが、一括重合法（バッチ法）、モノマー連続添加法（モノマーを連続添加して重合を進る方法）等が挙げられ、特にモノマー連続添加法を用いるとよりランダムな連鎖構造を有し好ましい。 The form of polymerizing the norbornene-based ring-opening polymer used in the present invention is not particularly limited, but examples include a batch polymerization method (batch method), a continuous monomer addition method (a method in which polymerization is continued by continuously adding monomers), and the like. In particular, the continuous monomer addition method is preferred because it has a more random chain structure.
本発明のノルボルネン系開環重合体組成物を、ノルボルネン系開環重合体とカーボンナノチューブとを、高分子顔料分散剤存在下で混合する上記Ｂ法によって得る場合は、常法に従ってノルボルネン系開環重合体を得れば良いが、カーボンナノチューブ存在下でノルボルネン系単量体を重合する上記Ａ法によって得る場合、重合溶媒にカーボンナノチューブと高分子顔料分散剤とノルボルネン系単量体とを加え（添加順序は問わない）、超音波ホモジナイザーなどの分散器を用いて分散処理した後、開環重合触媒と必要に応じて分子量調整剤等とを加え、開環重合反応を行うことになる。 When the norbornene-based ring-opening polymer composition of the present invention is obtained by the above-mentioned method B in which a norbornene-based ring-opening polymer and a carbon nanotube are mixed in the presence of a polymer pigment dispersant, the norbornene-based ring-opening polymer composition is obtained according to a conventional method. A polymer may be obtained, but when obtained by the above method A in which a norbornene monomer is polymerized in the presence of carbon nanotubes, a carbon nanotube, a polymer pigment dispersant, and a norbornene monomer are added to a polymerization solvent ( The order of addition does not matter), and after a dispersion treatment using a disperser such as an ultrasonic homogenizer, a ring-opening polymerization catalyst and, if necessary, a molecular weight adjusting agent or the like are added to perform a ring-opening polymerization reaction.
重合温度は、例えば、−５０℃〜２５０℃、好ましくは−３０℃〜２００℃、より好ましくは−２０℃〜１５０℃の範囲である。重合圧力は、例えば、０〜５０ｋｇ／ｃｍ２、好ましくは０〜２０ｋｇ／ｃｍ２の範囲である。重合時間は、重合条件により適宜選択されるが、例えば、３０分〜２０時間、好ましくは１〜１０時間の範囲である。The polymerization temperature is, for example, in the range of −50 ° C. to 250 ° C., preferably −30 ° C. to 200 ° C., more preferably −20 ° C. to 150 ° C. The polymerization pressure is, for example, in the range of 0 to 50 kg / cm 2 , preferably 0 to 20 kg / cm 2 . Although superposition | polymerization time is suitably selected according to superposition | polymerization conditions, For example, it is 30 minutes-20 hours, Preferably it is the range of 1 to 10 hours.
本発明において、ノルボルネン系開環重合体は、水素化されたものであってもよい。このようなノルボルネン系開環重合体水素化物は、前記のノルボルネン系開環重合体中の炭素−炭素の二重結合を水素化することによって得られる。 In the present invention, the norbornene-based ring-opening polymer may be hydrogenated. Such a hydride of norbornene-based ring-opening polymer can be obtained by hydrogenating a carbon-carbon double bond in the norbornene-based ring-opening polymer.
・水素化触媒及び水素化方法
水素化は、常法に従って、水素化触媒の存在下にノルボルネン系開環重合体を水素と接触させて行うことができる。水素化触媒としては、日本国公開特許公報「特開昭５８−４３４１２号公報」、日本国公開特許公報「特開昭６０−２６０２４号公報」、日本国公開特許公報「特開昭６４−２４８２６号公報」、日本国公開特許公報「特開平１−１３８２５７号公報」、日本国公開特許公報「特開平７−４１５５０号公報」などに記載されているものを使用することができる。-Hydrogenation catalyst and hydrogenation method Hydrogenation can be carried out by bringing a norbornene-based ring-opening polymer into contact with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. Examples of the hydrogenation catalyst include Japanese Patent Publication “JP-A-58-43412”, Japanese Patent Publication “JP-A-60-26024”, Japanese Patent Publication “JP-A 64-24826”. No. ", Japanese published patent publication" Japanese Unexamined Patent Publication No. 1-138257 ", Japanese published patent publication" Japanese Unexamined Patent Publication No. 7-41550 ", and the like can be used.
触媒は均一系でも不均一系でもよい。均一系触媒は、水素化反応液中で分散しやすいので添加量が少なくてよく、また、高温高圧にしなくとも活性を有するので重合体の分解やゲル化が起こらず、低コスト性及び品質安定性などに優る。不均一系触媒は、高温高圧下に高活性となり、短時間で水素化でき、更に除去が容易であるなど、生産効率の面で優る。 The catalyst may be homogeneous or heterogeneous. Homogeneous catalyst is easy to disperse in the hydrogenation reaction solution, so it can be added in a small amount, and since it is active without high temperature and high pressure, the polymer does not decompose or gel, resulting in low cost and stable quality. It is superior to sex. Heterogeneous catalysts are highly active at high temperatures and pressures, can be hydrogenated in a short time, and are easy to remove.
均一系触媒としては、例えば、ウィルキンソン錯体、すなわち、クロロトリス（トリフェニルホスフィン）ロジウム（Ｉ）；遷移金属化合物とアルキル金属化合物の組み合わせからなる触媒、具体的には、酢酸コバルト／トリエチルアルミニウム、ニッケルアセチルアセトナート／トリイソブチルアルミニウム、チタノセンジクロリド／ｎ−ブチルリチウム、ジルコノセンジクロリド／ｓｅｃ−ブチルリチウム、テトラブトキシチタネート／ジメチルマグネシウム等の組み合わせが挙げられる。 Examples of the homogeneous catalyst include, for example, a Wilkinson complex, that is, a catalyst comprising a combination of chlorotris (triphenylphosphine) rhodium (I); a transition metal compound and an alkyl metal compound, specifically, cobalt acetate / triethylaluminum, nickel acetyl Examples include combinations of acetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, and the like.
不均一系触媒としては、例えば、Ｎｉ、Ｐｄ、Ｐｔ、Ｒｕ、Ｒｈ等の水素化触媒金属を担体に担持させたものが挙げられる。特に、不純物等の混入が少ないほど好ましい場合は、担体として、アルミナや珪藻土等の吸着剤を用いることが好ましい。 Examples of the heterogeneous catalyst include a catalyst in which a hydrogenation catalyst metal such as Ni, Pd, Pt, Ru, and Rh is supported on a carrier. In particular, in the case where it is preferable that the amount of impurities or the like is less, it is preferable to use an adsorbent such as alumina or diatomaceous earth as a carrier.
水素化反応は、例えば、有機溶媒中で実施する。有機溶媒としては、触媒に不活性なものであれば格別な限定はないが、生成する水素化物の溶解性に優れていることから、例えば、炭化水素系溶媒が用いられる。炭化水素系溶媒としては、例えば、ベンゼン、トルエン等の芳香族炭化水素類；ｎ−ペンタン、ヘキサン等の脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン、デカリン、ビシクロノナン等の脂環族炭化水素類；などを挙げることができ、これらの中でも、シクロヘキサノンなどの低沸点の脂環族炭化水素類が好ましい。 The hydrogenation reaction is performed, for example, in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the catalyst. However, for example, a hydrocarbon solvent is used because it is excellent in solubility of the hydride to be generated. Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin, and bicyclononane; Among these, low boiling point alicyclic hydrocarbons such as cyclohexanone are preferable.
これらの有機溶媒は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。これらの有機溶媒は、例えば、重合反応溶媒と同じでよく、重合反応液にそのまま水素化触媒を添加して反応させればよい。 These organic solvents can be used alone or in combination of two or more. These organic solvents may be the same as the polymerization reaction solvent, for example, and may be reacted by adding the hydrogenation catalyst to the polymerization reaction solution as it is.
本発明に係る脂環構造含有重合体組成物に含まれるノルボルネン系開環重合体水素化物が、芳香族環を有する繰り返し単位を有する場合には、主鎖構造中の炭素−炭素二重結合の水素化反応において、側鎖の芳香環族構造を残存させることもできるが、完全に水素化しても構わない。尚、１Ｈ−ＮＭＲによる分析により、主鎖構造中の炭素−炭素二重結合は、芳香族環構造中の不飽和結合と区別して認識することができる。When the born ring-opening polymer hydride contained in the alicyclic structure-containing polymer composition according to the present invention has a repeating unit having an aromatic ring, the carbon-carbon double bond in the main chain structure In the hydrogenation reaction, the side-chain aromatic ring structure can be left, but it may be completely hydrogenated. In addition, by the analysis by 1 H-NMR, the carbon-carbon double bond in the main chain structure can be distinguished from the unsaturated bond in the aromatic ring structure.
水素化反応は、常法に従って行えばよい。水素化触媒の種類や反応温度によって水素化率は変わり、ノルボルネン系単量体が芳香族環を有する場合、芳香族環の残存率も変化させることがでる。上記の水素化触媒を用いた場合、芳香族環の不飽和結合をある程度以上残存させるためには、反応温度を低くしたり、水素圧力を下げたり、反応時間を短くする等の制御を行えばよい。 The hydrogenation reaction may be performed according to a conventional method. The hydrogenation rate varies depending on the type of hydrogenation catalyst and the reaction temperature, and when the norbornene monomer has an aromatic ring, the residual rate of the aromatic ring can also be changed. When the above hydrogenation catalyst is used, in order to leave the unsaturated bonds of the aromatic ring to a certain extent or more, control such as lowering the reaction temperature, lowering the hydrogen pressure, or shortening the reaction time can be performed. Good.
水素化反応終了後、触媒は、遠心、ろ過等の常法に従って除去することができる。必要に応じて、水やアルコール等の触媒不活性化剤を利用したり、活性白土やアルミナ等の吸着剤を添加したりしてもよい。医療用器材等、残留した遷移金属が溶出するのが好ましくない用途では、実質的に遷移金属が残留しないようにする。そのようなノルボルネン系開環重合体水素化物を得るためには、特開平５−３１７４１１号公報などで開示されているような、特定の細孔容積と比表面積を持ったアルミナ類等の吸着剤を用いたり、ノルボルネン系開環重合体水素化物溶液を酸性水と純水で洗浄したりすることが好ましい。 After completion of the hydrogenation reaction, the catalyst can be removed according to a conventional method such as centrifugation or filtration. If necessary, a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added. In applications where it is not preferable that the transition metal remains, such as medical equipment, the transition metal is substantially prevented from remaining. In order to obtain such a norbornene-based ring-opening polymer hydride, an adsorbent such as alumina having a specific pore volume and specific surface area as disclosed in JP-A-5-317411 Or a norbornene-based ring-opening polymer hydride solution is preferably washed with acidic water and pure water.
遠心方法やろ過方法は、用いた触媒が除去できる条件であれば、特に限定されない。ろ過による除去は、簡便かつ効率的であるので好ましい。ろ過する場合、加圧ろ過しても、吸引ろ過してもよく、また、効率の点から、珪藻土、パーライト等のろ過助剤を用いることが好ましい。 The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by filtration is preferred because it is simple and efficient. In the case of filtration, pressure filtration or suction filtration may be used, and it is preferable to use a filter aid such as diatomaceous earth or pearlite from the viewpoint of efficiency.
ノルボルネン系重合体の内、付加重合によって得られるものは、上述したノルボルネン系単量体と、これと付加共重合可能な単量体とを、公知の付加重合触媒、例えば、チタン、ジルコニウム又はバナジウム化合物と有機アルミニウム化合物とからなる触媒を用いて重合することにより得られる。 Among the norbornene-based polymers, those obtained by addition polymerization are obtained by combining the above-described norbornene-based monomer and a monomer capable of addition copolymerization with a known addition polymerization catalyst such as titanium, zirconium or vanadium. It can be obtained by polymerization using a catalyst comprising a compound and an organoaluminum compound.
ノルボルネン系単量体と付加共重合可能なその他の単量体としては、例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセンなどの炭素数２〜２０のα−オレフィン、及びこれらの誘導体；シクロブテン、シクロペンテン、シクロヘキセン、シクロオクテン、３ａ，５，６，７ａ−テトラヒドロ−４，７−メタノ−１Ｈ−インデンなどのシクロオレフィン、及びこれらの誘導体；１，４−ヘキサジエン、４−メチル−１，４−ヘキサジエン、５−メチル−１，４−ヘキサジエン、１，７−オクタジエンなどの非共役ジエン；などが挙げられる。これらの中でも、α−オレフィンが好ましく、エチレンが特に好ましい。 Examples of other monomers that can be addition copolymerized with norbornene-based monomers include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and the like. A cycloolefin such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, and derivatives thereof; 1,4-hexadiene, 4-methyl -1,4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene; and the like. Among these, α-olefins are preferable and ethylene is particularly preferable.
これらの、ノルボルネン系単量体と付加共重合可能なその他の単量体は、それぞれ単独で、あるいは２種以上を組み合わせて使用することができる。ノルボルネン系単量体とこれと付加共重合可能なその他の単量体とを付加共重合する場合は、付加重合体中のノルボルネン系単量体由来の構造単位と付加共重合可能なその他の単量体由来の構造単位との割合が、重量比で例えば３０：７０〜９９：１、好ましくは５０：５０〜９７：３、より好ましくは７０：３０〜９５：５の範囲となるように適宜選択される。 These other monomers capable of addition copolymerization with norbornene monomers can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer capable of addition copolymerization, other units capable of addition copolymerization with the structural unit derived from the norbornene monomer in the addition polymer. Appropriately, the ratio with the structural unit derived from the monomer is, for example, in the range of 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5 by weight. Selected.
（２）単環の環状オレフィン系重合体
単環の環状オレフィン系重合体としては、例えば、シクロヘキセン、シクロヘプテン、シクロオクテンなどの、単環の環状オレフィン系単量体の付加重合体を用いることができる。(2) Monocyclic cyclic olefin polymer As the monocyclic olefin polymer, for example, an addition polymer of a monocyclic olefin monomer such as cyclohexene, cycloheptene, or cyclooctene can be used. it can.
（３）環状共役ジエン系重合体
環状共役ジエン系重合体としては、例えば、シクロペンタジエン、シクロヘキサジエンなどの環状共役ジエン系単量体を１，２−又は１，４−付加重合した重合体及びその水素化物などを用いることができる。(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization, and The hydride can be used.
（４）ビニル脂環式炭化水素重合体
ビニル脂環式炭化水素重合体としては、例えば、ビニルシクロヘキセン、ビニルシクロヘキサンなどのビニル脂環式炭化水素系単量体の重合体及びその水素化物；スチレン、α−メチルスチレンなどのビニル芳香族系単量体の重合体の芳香環部分の水素化物；などが挙げられ、ビニル脂環式炭化水素重合体やビニル芳香族系単量体と、これらの単量体と共重合可能な他の単量体とのランダム共重合体、ブロック共重合体などの共重合体及びその水素化物など、いずれでもよい。ブロック共重合体としては、ジブロック、トリブロック、又はそれ以上のマルチブロックや傾斜ブロック共重合体などが挙げられ、特に制限はない。(4) Vinyl alicyclic hydrocarbon polymer Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinyl cyclohexene and vinyl cyclohexane and their hydrides; , Hydrides of aromatic ring moieties of polymers of vinyl aromatic monomers such as α-methylstyrene; and the like, and vinyl alicyclic hydrocarbon polymers and vinyl aromatic monomers, and these Any of random copolymers with other monomers copolymerizable with monomers, copolymers such as block copolymers, and hydrides thereof may be used. Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, and are not particularly limited.
本発明に係る脂環構造含有重合体組成物に含まれる脂環構造含有重合体の分子量は、使用目的に応じて適宜選択されるが、シクロヘキサン溶液（重合体樹脂が溶解しない場合はトルエン溶液）のゲル・パーミエーション・クロマトグラフで測定したポリスチレン換算の重量平均分子量で、例えば５，０００以上であり、好ましくは５，０００〜５００，０００、より好ましくは８，０００〜２００，０００、特に好ましくは１０，０００〜１００，０００の範囲であるときに、機械的強度と成形加工性とが高度にバランスし、好適である。 The molecular weight of the alicyclic structure-containing polymer contained in the alicyclic structure-containing polymer composition according to the present invention is appropriately selected according to the purpose of use, but a cyclohexane solution (a toluene solution when the polymer resin does not dissolve). The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of, for example, 5,000 or more, preferably 5,000 to 500,000, more preferably 8,000 to 200,000, particularly preferably Is preferably in the range of 10,000 to 100,000, since mechanical strength and moldability are highly balanced.
本発明に用いる脂環構造含有重合体のガラス転移温度（Ｔｇ）は、例えば５０〜２５０℃、好ましくは７０〜２２０℃である。Ｔｇが５０℃以上であれば十分な耐熱性を有するため様々な環境で使用でき、Ｔｇが２５０℃以下であれば、十分な流動性を有するため成形性が向上する。脂環構造含有重合体のガラス転移温度は、示差走査熱量分析計を用いてＪＩＳ Ｋ ７１２１に基づいて測定することができる。 The glass transition temperature (Tg) of the alicyclic structure-containing polymer used in the present invention is, for example, 50 to 250 ° C, preferably 70 to 220 ° C. If Tg is 50 ° C. or higher, it has sufficient heat resistance and can be used in various environments, and if Tg is 250 ° C. or lower, it has sufficient fluidity to improve moldability. The glass transition temperature of the alicyclic structure-containing polymer can be measured based on JIS K 7121 using a differential scanning calorimeter.
（カーボンナノチューブ）
本発明に係るカーボンナノチューブは、平均直径（Ａｖ）と直径分布（３σ）とが０．６０＞３σ／Ａｖ＞０．２０を満たす。ここでいう平均直径（Ａｖ）、直径分布（３σ）は、それぞれ透過型電子顕微鏡でカーボンナノチューブ１００本の直径を測定した際の平均値、並びに標準偏差（σ）に３を乗じたものである。なお、本明細書における標準偏差は、標本標準偏差である。(carbon nanotube)
In the carbon nanotube according to the present invention, the average diameter (Av) and the diameter distribution (3σ) satisfy 0.60> 3σ / Av> 0.20. Here, the average diameter (Av) and the diameter distribution (3σ) are obtained by multiplying the average value when the diameter of 100 carbon nanotubes is measured with a transmission electron microscope and the standard deviation (σ) by 3. . In addition, the standard deviation in this specification is a sample standard deviation.
平均直径（Ａｖ）と直径分布（３σ）とが０．６０＞３σ／Ａｖ＞０．２０を満たすカーボンナノチューブを用いることにより、カーボンナノチューブが少量であっても、優れた導電性を示す組成物を得ることができる。得られる組成物の特性の観点から、０．６０＞３σ／Ａｖ＞０．２５がより好ましく、０．６０＞３σ／Ａｖ＞０．５０がさらに好ましい。 A composition exhibiting excellent conductivity even when the amount of carbon nanotubes is small by using carbon nanotubes having an average diameter (Av) and a diameter distribution (3σ) satisfying 0.60> 3σ / Av> 0.20. Can be obtained. From the viewpoint of the characteristics of the obtained composition, 0.60> 3σ / Av> 0.25 is more preferable, and 0.60> 3σ / Av> 0.50 is more preferable.
３σ／Ａｖは、カーボンナノチューブの直径分布を表し、この値が大きいほど直径分布が広いことを意味する。本発明において直径分布は正規分布を取るものが好ましい。ここで言う直径分布は、透過型電子顕微鏡を用いて観察できる、無作為に選択された１００本のカーボンナノチューブの直径を測定し、その結果を用いて、横軸に直径、縦軸に頻度を取り、得られたデータをプロットし、ガウシアンで近似することで得られるものとする。異なる製法で得られたカーボンナノチューブなどを複数種類組み合わせることでも３σ／Ａｖの値を大きくすることはできるが、その場合正規分布の直径分布を得ることは難しい。即ち、本発明においては、単独のカーボンナノチューブ又は単独のカーボンナノチューブに、その直径分布に影響しない量の他のカーボンナノチューブを配合したものを用いるのが好ましい。 3σ / Av represents the diameter distribution of the carbon nanotube, and the larger the value, the wider the diameter distribution. In the present invention, the diameter distribution is preferably a normal distribution. The diameter distribution here refers to the diameter of 100 randomly selected carbon nanotubes that can be observed using a transmission electron microscope, and the results are used to calculate the diameter on the horizontal axis and the frequency on the vertical axis. And plotting the obtained data and approximating with Gaussian. The value of 3σ / Av can also be increased by combining a plurality of types of carbon nanotubes obtained by different production methods, but in this case, it is difficult to obtain a normal distribution of diameters. That is, in the present invention, it is preferable to use a single carbon nanotube or a single carbon nanotube mixed with another carbon nanotube in an amount that does not affect the diameter distribution.
カーボンナノチューブの平均直径は、高い導電性を付与するといった観点から、０．５ｎｍ以上、１５ｎｍ以下であることが好ましく、１ｎｍ以上、１０ｎｍ以下であることが、より好ましい。 The average diameter of the carbon nanotubes is preferably 0.5 nm or more and 15 nm or less, and more preferably 1 nm or more and 10 nm or less from the viewpoint of imparting high conductivity.
本発明に係るカーボンナノチューブは、０．６０＞３σ／Ａｖ＞０．２０を満たすカーボンナノチューブであれば特に制限なく使用することができるが、日本国特許第４，６２１，８９６号公報（欧州公開特許第１７８７９５５号）、及び日本国特許第４，８１１，７１２号公報（米国公開特許第２００９−２９７８４６号）に記載されているスーパーグロース法により得られるカーボンナノチューブ（以下、「ＳＧＣＮＴ」ということがある）が好ましく、さらにスーパーグロース法により得られるカーボンナノチューブの中でもＢＥＴ比表面積が６００ｍ２／ｇ以上のカーボンナノチューブが、組成物への改質効果が高いためさらに好ましい。The carbon nanotube according to the present invention can be used without particular limitation as long as it is a carbon nanotube satisfying 0.60> 3σ / Av> 0.20. Japanese Patent No. 4,621,896 (published in Europe) Patent No. 1787955), and Japanese Patent No. 4,811,712 (US Published Patent No. 2009-297847), carbon nanotubes obtained by the super-growth method (hereinafter referred to as “SGCNT”) Among them, carbon nanotubes having a BET specific surface area of 600 m 2 / g or more are more preferable because they have a high modifying effect on the composition.
本発明に係るカーボンナノチューブは、ラマン分光法においてＲａｄｉａｌ Ｂｒｅａｔｈｉｎｇ Ｍｏｄｅ（ＲＢＭ）のピークを有するカーボンナノチューブであるのが好ましい。なお、三層以上の多層のカーボンナノチューブのラマンスペクトルには、ＲＢＭが存在しない。 The carbon nanotube according to the present invention is preferably a carbon nanotube having a peak of Radial Breathing Mode (RBM) in Raman spectroscopy. Note that there is no RBM in the Raman spectrum of multi-walled carbon nanotubes of three or more layers.
また、本発明に係る脂環構造含有重合体組成物に含まれるカーボンナノチューブはＧ／Ｄ比が１以上、２０以下、カーボンナノチューブ合成時における構造体の長さが１００μｍ以上、５０００μｍ以下のカーボンナノチューブであることがより好ましい。これは例えば上述のスーパーグロース法により得ることができる。 The carbon nanotubes contained in the alicyclic structure-containing polymer composition according to the present invention have a G / D ratio of 1 or more and 20 or less, and the length of the structure at the time of carbon nanotube synthesis is 100 μm or more and 5000 μm or less. It is more preferable that This can be obtained, for example, by the super growth method described above.
スーパーグロース法によって製造されるカーボンナノチューブのＧ／Ｄ比の範囲については、１以上、２０以下の範囲になる。これは、実際に製造したもののＧ／Ｄ比を測定結果から得られたばらつきの範囲に基づく。 The range of the G / D ratio of the carbon nanotubes produced by the super growth method is in the range of 1 or more and 20 or less. This is based on the range of variation obtained from the measurement result of the G / D ratio of the actually manufactured product.
また、カーボンナノチューブ合成時における構造体の長さが１００μｍ以上、５０００μｍ以下のカーボンナノチューブを用いることで、得られるエラストマー組成物はより優れた導電性を発揮する。 Moreover, the elastomer composition obtained exhibits more excellent electroconductivity by using the carbon nanotube whose length of the structure at the time of carbon nanotube synthesis | combination is 100 micrometers or more and 5000 micrometers or less.
このように、Ｇ／Ｄ比が１以上、２０以下、カーボンナノチューブ合成時における構造体の長さが１００μｍ以上、５０００μｍ以下のカーボンナノチューブを用いることにより、少量でも優れた導電性を得ることができる。 Thus, by using carbon nanotubes having a G / D ratio of 1 or more and 20 or less and the length of the structure during the synthesis of carbon nanotubes of 100 μm or more and 5000 μm or less, excellent conductivity can be obtained even in a small amount. .
また、カーボンナノチューブの比表面積は、６００ｍ２／ｇ以上であることが好ましく、カーボンナノチューブが主として未開口のものにあっては、６００ｍ２／ｇ以上であり、カーボンナノチューブが主として開口したものにあっては、１３００ｍ２／ｇ以上であることが改質効果に優れるため好ましい。The specific surface area of the carbon nanotube is preferably 600 m 2 / g or more. If the carbon nanotube is mainly unopened, the specific surface area is 600 m 2 / g or more, and the carbon nanotube is mainly open. Is preferably 1300 m 2 / g or more because of excellent reforming effect.
また、カーボンナノチューブの重量密度は、０．００２ｇ／ｃｍ３〜０．２ｇ／ｃｍ３であることがより好ましい。重量密度が０．２ｇ／ｃｍ３以下であれば、カーボンナノチューブを構成するカーボンナノチューブ同士の結びつきが弱くなるので、カーボンナノチューブを溶媒などに攪拌した際に、均質に分散させることが容易になる。つまり、重量密度が０．２ｇ／ｃｍ３以下とすることで、均質な分散液を得ることが容易となる。また重量密度が０．００２ｇ／ｃｍ３以上であれば、カーボンナノチューブの一体性を向上させ、バラけることを抑制できるため取り扱いが容易になる。The weight density of the carbon nanotubes is more preferably 0.002g / cm 3 ~0.2g / cm 3 . If the weight density is 0.2 g / cm 3 or less, since the carbon nanotubes constituting the carbon nanotubes are weakly bonded, it becomes easy to uniformly disperse the carbon nanotubes when they are stirred in a solvent or the like. That is, when the weight density is 0.2 g / cm 3 or less, it is easy to obtain a homogeneous dispersion. Further, when the weight density is 0.002 g / cm 3 or more, the integrity of the carbon nanotubes can be improved and the looseness can be suppressed, so that handling becomes easy.
また、脂環構造含有重合体（Ａ）の量に対するカーボンナノチューブ（Ｂ）の量が０．０１〜１０重量％であり、０．０１〜８重量％であることがより好ましい。 Further, the amount of the carbon nanotube (B) relative to the amount of the alicyclic structure-containing polymer (A) is 0.01 to 10% by weight, and more preferably 0.01 to 8% by weight.
（高分子顔料分散剤）
本発明に用いられる高分子顔料分散剤は、顔料を分散させる機能を有する高分子材料（アクリル系共重合体、ポリウレタン、ポリエステルやこれらの変性体など）であり、好ましくは極性官能基である酸価及びアミン価の少なくともいずれかが５ｍｇＫＯＨ／ｇ以上である分散剤である。本発明において、分散剤は、単独で又は２種以上を混合して使用することができる。(Polymer pigment dispersant)
The polymer pigment dispersant used in the present invention is a polymer material (acrylic copolymer, polyurethane, polyester, modified products thereof, etc.) having a function of dispersing a pigment, preferably an acid having a polar functional group. And / or an amine value is 5 mgKOH / g or more. In this invention, a dispersing agent can be used individually or in mixture of 2 or more types.
分散剤の酸価（ｍｇＫＯＨ／ｇ）は、好ましくは５〜１００、更に好ましくは１０〜５０、特に好ましくは２０〜５０であり、アミン価（ｍｇＫＯＨ／ｇ）は、好ましくは１〜１００、更に好ましくは１０〜７０、特に好ましくは２０〜７０である。ここでアミン価とは、分散剤固形分１ｇを中和するのに必要なＨＣｌ量に対して当量となるＫＯＨのｍｇ数を表す。また酸価とは、分散剤固形分１ｇを中和するのに必要なＫＯＨのｍｇ数を表す。酸価又はアミン価がこの範囲であれば、一度分散したカーボンナノチューブの再凝集が発生しないという利点がある。 The acid value (mgKOH / g) of the dispersant is preferably 5 to 100, more preferably 10 to 50, particularly preferably 20 to 50, and the amine value (mgKOH / g) is preferably 1 to 100, more preferably Preferably it is 10-70, Most preferably, it is 20-70. Here, the amine value represents the number of mg of KOH equivalent to the amount of HCl required to neutralize 1 g of the solid content of the dispersant. Moreover, an acid value represents the mg number of KOH required in order to neutralize 1 g of solid content of a dispersing agent. If the acid value or the amine value is within this range, there is an advantage that re-aggregation of the carbon nanotubes once dispersed does not occur.
顔料分散剤の極性官能基量は、電位差滴定、指示薬滴定により測定することができ、酸価はＪＩＳ Ｋ ００７０、アミン価はＪＩＳ Ｋ ７２３７記載の方法により測定することができる。 The amount of the polar functional group of the pigment dispersant can be measured by potentiometric titration or indicator titration, and the acid value can be measured by the method described in JIS K 0070 and the amine value can be measured by the method described in JIS K 7237.
このような分散剤は市販されているものであり、例えば、ビックケミー社製「Ｄｉｓｐｅｒｂｙｋ（登録商標）」シリーズの、１４２番（アミン価＝４３、酸価＝４６）、１６１番（アミン価＝１１）、１７０番（酸価＝１１）、１８２番（アミン価＝１３）、２０００番（アミン価＝４）、２００１番（アミン価＝２９、酸価＝１９）、２０２０番（アミン価＝３８、酸価＝３５）、９０７６（アミン価＝４４、酸価＝３８）；味の素ファインテクノ社製「アジスパー（登録商標）」シリーズの、ＰＢ−７１１番（アミン価＝４５）、ＰＢ−８２１番（アミン価＝１０、酸価＝１７）、ＰＢ−８２２番（アミン価＝１７、酸価＝１４）、ＰＢ−８８０番（アミン価＝１７、酸価＝１４）、ＰＢ−８８１番（アミン価＝１７、酸価＝１４）；リューブリゾル社製「ソルスパース（登録商標）」シリーズの、２４０００番（アミン価＝４２、酸価＝２５）、３２０００番（アミン価＝３１、酸価＝１５）、３２５００番（アミン価＝１２、酸価＝７）、３２５５０番（アミン価＝１５、酸価＝７）、３２６００番（アミン価＝１２、酸価＝６）、３５１００番（アミン価＝１４、酸価＝６）、３５２００番（アミン価＝１４、酸価＝６）３７５００番（アミン価＝１１、酸価＝５）などが挙げられる。 Such dispersants are commercially available. For example, No. 142 (amine number = 43, acid number = 46), 161 (amine number = 11) of “Disperbyk (registered trademark)” series manufactured by BYK Chemie. ), 170 (acid number = 11), 182 (amine number = 13), 2000 (amine number = 4), 2001 (amine number = 29, acid number = 19), 2020 (amine number = 38) , Acid value = 35), 9076 (amine value = 44, acid value = 38); Ajinomoto Fine Techno Co., Ltd. “Ajisper®” series, PB-711 (amine value = 45), PB-821 (Amine number = 10, Acid number = 17), PB-822 (Amine number = 17, Acid number = 14), PB-880 (Amine number = 17, Acid number = 14), PB-881 (Amine Value = 17, acid value = 14); No. 24000 (amine number = 42, acid number = 25), number 32000 (amine number = 31, acid number = 15), number 32500 (amine number = 12, acid) of “Solsperse (registered trademark)” series manufactured by UB No. = 7), No. 32550 (Amine number = 15, Acid number = 7), No. 32600 (Amine number = 12, Acid number = 6), No. 35100 (Amine number = 14, Acid number = 6), No. 35200 Amine number = 14, acid value = 6) No. 37500 (amine value = 11, acid value = 5) and the like.
高分子顔料分散剤の含有量（固形分換算）は、カーボンナノチューブの量に対して、例えば、０．１〜１０００倍、好ましくは１〜１００倍である。好ましい濃度範囲であれば、粘度が増大せず、かつ、ＣＮＴ自身の凝集が少ないＣＮＴ分散液を得ることができる。 The content (in terms of solid content) of the polymer pigment dispersant is, for example, 0.1 to 1000 times, preferably 1 to 100 times the amount of carbon nanotubes. If it is a preferable density | concentration range, a viscosity will not increase and the CNT dispersion liquid with few aggregation of CNT itself can be obtained.
本発明においては、上述した高分子顔料分散剤の他に、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリエチレングリコールジ脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸変性ポリエステル等の他の分散剤を、本発明の効果を損なわない範囲で併用することもできる。他の分散剤の割合は、高分子顔料分散剤の通常５０重量％以下、好ましくは２０重量％以下である。 In the present invention, in addition to the above-described polymer pigment dispersant, other dispersants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol difatty acid ester, sorbitan fatty acid ester, fatty acid-modified polyester, It can also be used in combination as long as the effects of the present invention are not impaired. The ratio of the other dispersant is usually 50% by weight or less, preferably 20% by weight or less of the polymer pigment dispersant.
脂環構造含有重合体（Ａ）とカーボンナノチューブ（Ｂ）とを混合し、脂環構造含有重合体組成物を調製する方法に格別な制限はない。分散方法としては例えば、例えば、（ｉ）脂環構造含有重合体（Ａ）、カーボンナノチューブ（Ｂ）および高分子顔料分散剤（Ｃ）を、一軸押出機、二軸押出機、ロール、バンバリーミキサ、ニーダ、ブラベンダ等の混合機を用いて溶融混合する方法；（ｉｉ）脂環構造含有重合体（Ａ）、カーボンナノチューブ（Ｂ）および高分子顔料分散剤（Ｃ）を有機溶剤と混合して分散液とし、該分散液中の溶剤を除去、或いは脂環構造含有重合体が溶解しない貧溶媒に前記分散液を滴下し組成物を得る方法などを挙げることができる。これらの中でも、各成分の均一分散が図られる点で前記（ｉｉ）の方法が好ましい。 There is no particular limitation on the method for preparing the alicyclic structure-containing polymer composition by mixing the alicyclic structure-containing polymer (A) and the carbon nanotube (B). Examples of the dispersion method include (i) alicyclic structure-containing polymer (A), carbon nanotube (B), and polymer pigment dispersant (C), a single screw extruder, a twin screw extruder, a roll, a Banbury mixer. A melt mixing method using a mixer such as kneader, brabender, etc .; (ii) an alicyclic structure-containing polymer (A), a carbon nanotube (B) and a polymer pigment dispersant (C) are mixed with an organic solvent. Examples thereof include a method of obtaining a composition by preparing a dispersion, removing the solvent in the dispersion, or dropping the dispersion into a poor solvent in which the alicyclic structure-containing polymer is not dissolved. Among these, the method (ii) is preferable in that uniform dispersion of each component is achieved.
（導電性成形部材）
導電性成形部材の形状は、シート状（フィルム状）であっても、板状であっても、その他いかなる形状であってもよい。また、成形部材の成型方法も、成形部材の形状に応じた手段を採用すれば良く、例えば射出成形、押出成形、プレス成形、ブロー成形、カレンダー成形などの溶融成形法が好適である。また、成形体を得るにあたっては、必要に応じて、各種の添加剤を重合体に配合してもよい。添加剤の具体例としては、酸化防止剤、核剤、充填剤、難燃剤、難燃助剤、顔料、着色剤、帯電防止剤、可塑剤、紫外線吸収剤、光安定剤、近赤外線吸収剤、滑剤を挙げることができる。(Conductive molding member)
The shape of the conductive molded member may be a sheet shape (film shape), a plate shape, or any other shape. Also, as a molding method of the molded member, means corresponding to the shape of the molded member may be adopted, and for example, melt molding methods such as injection molding, extrusion molding, press molding, blow molding, and calendar molding are suitable. Moreover, when obtaining a molded object, you may mix | blend various additives with a polymer as needed. Specific examples of additives include antioxidants, nucleating agents, fillers, flame retardants, flame retardant aids, pigments, colorants, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, and near infrared absorbers. And a lubricant.
＜製造例１＞（カーボンナノチューブの合成）
特許４６２１８９６号公報に記載のスーパーグロース法で得たカーボンナノチューブ（以下、「ＳＧＣＮＴ」と略記）を用いた。<Production Example 1> (Synthesis of carbon nanotube)
Carbon nanotubes (hereinafter abbreviated as “SGCNT”) obtained by the super-growth method described in Japanese Patent No. 4621896 were used.
具体的には次の条件において、ＳＧＣＮＴ−１を成長させた。 Specifically, SGCNT-1 was grown under the following conditions.
炭素化合物：エチレン；供給速度５０ｓｃｃｍ
雰囲気（ガス）（Ｐａ）：ヘリウム、水素混合ガス；供給速度１０００ｓｃｃｍ
圧力１大気圧
水蒸気添加量（ｐｐｍ）：３００ｐｐｍ
反応温度（℃）：７５０℃
反応時間（分）：１０分
金属触媒（存在量）：鉄薄膜；厚さ１ｎｍ
基板：シリコンウェハー
得られたＳＧＣＮＴ−１は、ＢＥＴ比表面積１，０５０ｍ２／ｇ、ラマン分光光度計での測定において、単層ＣＮＴに特長的な１００〜３００ｃｍ−１の低波数領域にラジアルブリージングモード（ＲＢＭ）のスペクトルが観察された。また、透過型電子顕微鏡を用い、無作為に１００本のＳＧＣＮＴ−１の直径を測定した結果、平均直径（Ａｖ）が３．３ｎｍ、直径分布（３σ）が１．９ｎｍ、（３σ／Ａｖ）が０．５８であった。Carbon compound: ethylene; supply rate 50 sccm
Atmosphere (gas) (Pa): Helium, hydrogen mixed gas; supply rate 1000 sccm
Pressure 1 atmospheric pressure Water vapor addition amount (ppm): 300 ppm
Reaction temperature (° C): 750 ° C
Reaction time (min): 10 minutes Metal catalyst (abundance): Iron thin film; thickness 1 nm
Substrate: silicon wafer The obtained SGCNT-1 has a BET specific surface area of 1,050 m 2 / g, and is subjected to radial breathing in a low wavenumber region of 100 to 300 cm −1 , which is characteristic of a single-walled CNT in measurement with a Raman spectrophotometer. A mode (RBM) spectrum was observed. Moreover, as a result of measuring the diameter of 100 SGCNT-1 at random using a transmission electron microscope, average diameter (Av) is 3.3 nm, diameter distribution (3σ) is 1.9 nm, (3σ / Av) Was 0.58.
＜製造例２＞（カーボンナノチューブの合成）
製造例１の金属触媒の鉄薄膜層の厚みを、５ｎｍにした以外は同様の手法により、ＳＧＣＮＴ−２を得た。得られたＳＧＣＮＴ−２は、ＢＥＴ比表面積６２０ｍ２／ｇ、ラマン分光光度計での測定において、単層ＣＮＴに特長的な１００〜３００ｃｍ−１の低波数領域にラジアルブリージングモード（ＲＢＭ）のスペクトルが観察された。また、透過型電子顕微鏡を用い、無作為に１００本のＳＧＣＮＴ−２の直径を測定した結果、平均直径（Ａｖ）が５．９ｎｍ、直径分布（３σ）が３．３ｎｍ、（３σ／Ａｖ）が０．５６であった。<Production Example 2> (Synthesis of carbon nanotube)
SGCNT-2 was obtained by the same method except that the thickness of the iron thin film layer of the metal catalyst of Production Example 1 was changed to 5 nm. The obtained SGCNT-2 has a BET specific surface area of 620 m 2 / g and a spectrum of a radial breathing mode (RBM) in a low wavenumber region of 100 to 300 cm −1 characteristic of a single-walled CNT when measured with a Raman spectrophotometer. Was observed. Moreover, as a result of measuring the diameter of 100 SGCNT-2 at random using a transmission electron microscope, an average diameter (Av) was 5.9 nm, a diameter distribution (3σ) was 3.3 nm, and (3σ / Av) Was 0.56.
＜実施例１＞
窒素雰囲気下で１００ｃｃのフラスコの中にカーボンナノチューブ（ＣＮＴ）として製造例１で作製したＳＧＣＮＴ−１を５ｍｇ、高分子顔料分散剤としてＰＢ−８２１（製品名「アジスパー（登録商標）ＰＢ−８２１」、味の素ファインテクノ社製；アミン価１０ｍｇＫＯＨ／ｇ、酸価１７ｍｇＫＯＨ／ｇ）１００ｍｇ、環状オレフィンモノマーとして７，８−ベンゾトリシクロ［４．３．０．１２，５］デカ−３−エン（ＭＴＦ）２ｇ、及び、重合溶媒としてＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）が重合液の総重量を２０ｇになるように導入し、超音波洗浄機を用いて１時間分散処理を行った。得られたＣＮＴ含有ＭＴＦ重合液に、次の化学式で表されるグラブス触媒のトルエン溶液２ｍｇ（触媒量＝２．３６×１０−３ｍｍｏｌ）を添加し、６０℃、２時間でＭＴＦの開環重合を行った。重合を停止するためにエチルビニルエーテル０．１ｍｌを添加した。得られたＣＮＴ分散ＭＴＦ重合体溶液をメタノール中に滴下することで、ＣＮＴ含有ＭＴＦ樹脂複合体を析出させ、ろ過後、減圧乾燥器でＣＮＴ含有ＭＴＦ樹脂複合体を乾燥した。<Example 1>
5 mg of SGCNT-1 produced in Production Example 1 as a carbon nanotube (CNT) in a 100 cc flask under a nitrogen atmosphere and PB-821 as a polymer pigment dispersant (product name “Azisper (registered trademark) PB-821”) Manufactured by Ajinomoto Fine Techno Co .; amine value 10 mgKOH / g, acid value 17 mgKOH / g) 100 mg, and cyclic olefin monomer 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene ( 2 g of MTF) and N, N-dimethylacetamide (DMAc) as a polymerization solvent were introduced so that the total weight of the polymerization solution became 20 g, and dispersion treatment was performed for 1 hour using an ultrasonic cleaner. To the obtained CNT-containing MTF polymerization solution, 2 mg of a toluene solution of a Grubbs catalyst represented by the following chemical formula (catalyst amount = 2.36 × 10 −3 mmol) was added, and the MTF was opened at 60 ° C. for 2 hours. Polymerization was performed. To stop the polymerization, 0.1 ml of ethyl vinyl ether was added. The obtained CNT-dispersed MTF polymer solution was dropped into methanol to precipitate a CNT-containing MTF resin composite. After filtration, the CNT-containing MTF resin composite was dried with a vacuum dryer.
（式中のＣｙは、シクロヘキシル環である。）
得られたＣＮＴ含有ＭＴＦ樹脂複合体は真空ホットプレス成形機を用いて厚さ１ｍｍ、横２０ｍｍ、縦１０ｍｍの成形体フィルムを作製した。フィルム状のＣＮＴ含有ＭＴＦ樹脂複合体サンプルを、抵抗計（製品名「ロレスタ（登録商標）ＧＰ ＭＣＰ−Ｔ６１０」、三菱化学社製）を用いて、導電率（体積抵抗率の逆数）を測定したところ、４．５８×１０−３Ｓ／ｃｍであった。一方、ＣＮＴを含有しない、ＭＴＦ樹脂の電気導電率は約１．０×１０−１６Ｓ／ｃｍであった。(Cy in the formula is a cyclohexyl ring.)
The obtained CNT-containing MTF resin composite was formed into a molded film having a thickness of 1 mm, a width of 20 mm, and a length of 10 mm using a vacuum hot press molding machine. The electrical conductivity (reciprocal of volume resistivity) of the film-like CNT-containing MTF resin composite sample was measured using a resistance meter (product name “Loresta (registered trademark) GP MCP-T610”, manufactured by Mitsubishi Chemical Corporation). However, it was 4.58 × 10 −3 S / cm. On the other hand, the electrical conductivity of the MTF resin not containing CNTs was about 1.0 × 10 −16 S / cm.
開環重合体の収率は重合後回収したポリマー重量とモノマーの仕込み量から計算し、またＣＮＴの割合は用いたＣＮＴ重量と回収したポリマー重量に対して計算した。 The yield of the ring-opening polymer was calculated from the polymer weight recovered after polymerization and the charged amount of monomer, and the CNT ratio was calculated based on the CNT weight used and the recovered polymer weight.
＜実施例２＞
ＣＮＴ量を１０ｍｇに変えたこと以外は実施例１と同様にして、ＣＮＴ含有ＭＴＦ樹脂複合体フィルムを作製した。実施例１と同様に電気導電率を測定したところ、１．３９×１０−２Ｓ／ｃｍであった。<Example 2>
A CNT-containing MTF resin composite film was produced in the same manner as in Example 1 except that the amount of CNT was changed to 10 mg. The electrical conductivity was measured in the same manner as in Example 1. As a result, it was 1.39 × 10 −2 S / cm.
＜実施例３＞
ＣＮＴ量を２０ｍｇ、高分子顔料分散剤量を２００ｍｇに変えたこと以外は実施例１と同様にして、ＣＮＴ含有ＭＴＦ樹脂複合体フィルムを作製した。実施例１と同様に電気導電率を測定したところ、９．２９×１０−１Ｓ／ｃｍであった。<Example 3>
A CNT-containing MTF resin composite film was produced in the same manner as in Example 1 except that the amount of CNT was changed to 20 mg and the amount of the polymer pigment dispersant was changed to 200 mg. The electric conductivity was measured in the same manner as in Example 1. As a result, it was 9.29 × 10 −1 S / cm.
＜実施例４＞
製造例２で作製したＳＧＣＮＴ−２の量を４０ｍｇ、高分子顔料分散剤量を４０００ｍｇに変えたこと以外は実施例１と同様にして、ＣＮＴ含有ＭＴＦ樹脂複合体フィルムを作製した。実施例１と同様に電気導電率を測定したところ、１．０２Ｓ／ｃｍであった。<Example 4>
A CNT-containing MTF resin composite film was produced in the same manner as in Example 1 except that the amount of SGCNT-2 produced in Production Example 2 was changed to 40 mg and the amount of the polymer pigment dispersant was changed to 4000 mg. The electrical conductivity was measured in the same manner as in Example 1. As a result, it was 1.02 S / cm.
＜実施例５＞
多層カーボンナノチューブ（ＭＷＣＮＴ；Ｎａｎｏｃｙｌ社製、製品名「ＮＣ７０００」、ＢＥＴ比表面積２９０ｍ２／ｇ）に変えた以外は実施例１と同様にして、ＣＮＴ含有ＭＴＦ樹脂複合体フィルムを作製した。なお、透過型電子顕微鏡を用い、無作為に１００本のＮＣ７０００の直径を測定した結果、平均直径（Ａｖ）が９．３ｎｍ、直径分布（３σ）が２．６ｎｍ、（３σ／Ａｖ）が０．２であった。実施例１と同様に電気導電率を測定したところ、１．０１×１０−３Ｓ／ｃｍであった。<Example 5>
A CNT-containing MTF resin composite film was produced in the same manner as in Example 1 except that the carbon nanotubes were changed to multi-walled carbon nanotubes (MWCNT; manufactured by Nanocyl, product name “NC7000”, BET specific surface area 290 m 2 / g). In addition, as a result of measuring the diameter of 100 NC7000s at random using a transmission electron microscope, the average diameter (Av) was 9.3 nm, the diameter distribution (3σ) was 2.6 nm, and (3σ / Av) was 0. .2. The electrical conductivity was measured in the same manner as in Example 1. As a result, it was 1.01 × 10 −3 S / cm.
＜実施例６＞
窒素雰囲気下で１００ｃｃのフラスコの中に環状オレフィンモノマー（ＭＴＦ）２ｇ、重合溶媒としてトルエン２０ｇを導入した後、グラブス触媒のトルエン溶液２ｍｇ（触媒量＝２．３６×１０−３ｍｍｏｌ）を添加し、６０℃、２時間でＭＴＦの開環重合を行いＭＴＦ／トルエン重合体溶液を得た。別途、ＣＮＴと高分子顔料分散剤とのＤＭＡｃ分散液を作るために、別の１００ｃｃのフラスコ中に、製造例１で作製したＣＮＴ１０ｍｇ、高分子顔料分散剤（製品名「アジスパー（登録商標）ＰＢ−８２１」、味の素ファインテクノ社製）１００ｍｇとＤＭＡｃ２０ｇを導入し、超音波洗浄機を用いて１時間分散処理し、ＣＮＴ分散液を調整した。得られたＭＴＦポリマー重合液をマグネチックスターラーで撹拌しながら、別途調整したＣＮＴ分散液を滴下混合して、ＣＮＴ分散ＭＴＦ重合体溶液を得た。以降は実施例１と同様方法でフィルム状のＣＮＴ含有ＭＴＦ樹脂複合体を作製した後、電気導電率を測定したところ、２．３６×１０−３Ｓ／ｃｍであった。<Example 6>
After introducing 2 g of cyclic olefin monomer (MTF) and 20 g of toluene as a polymerization solvent into a 100 cc flask under a nitrogen atmosphere, 2 mg of toluene solution of Grubbs catalyst (catalyst amount = 2.36 × 10 −3 mmol) was added. The ring-opening polymerization of MTF was performed at 60 ° C. for 2 hours to obtain an MTF / toluene polymer solution. Separately, in order to make a DMAc dispersion of CNT and polymer pigment dispersant, 10 mg of the CNT prepared in Production Example 1 and the polymer pigment dispersant (product name “Azisper (registered trademark) PB”) were placed in another 100 cc flask. -821 "(manufactured by Ajinomoto Fine Techno Co., Ltd.) 100 mg and DMAc 20 g were introduced, and dispersion treatment was performed for 1 hour using an ultrasonic cleaner to prepare a CNT dispersion. While stirring the obtained MTF polymer polymerization solution with a magnetic stirrer, a separately prepared CNT dispersion was dropped and mixed to obtain a CNT-dispersed MTF polymer solution. Thereafter, a film-like CNT-containing MTF resin composite was prepared in the same manner as in Example 1, and the electrical conductivity was measured to be 2.36 × 10 −3 S / cm.
＜実施例７＞
脱水したシクロヘキサン５００ｇ、１−ヘキセン（分子量調節剤）０．８２ｇ、ジブチルエーテル（開環重合触媒系成分）０．１５ｇおよびトリイソブチルアルミニウム（開環重合触媒系成分）０．３ｇを窒素雰囲気下に反応器に入れ、室温で混合した後、４５℃に保持しながら、８−メチル−テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ−３−エン（以下、「ＭＴＣＤ」と略記する。）１００ｇおよび六塩化タングステン（０．７質量％トルエン溶液：開環重合触媒系成分）４０ｇを、２時間に亘り連続的に添加して重合した。得られた重合溶液にブチルグリシジルエーテル１．０６ｇおよびイソプロピルアルコール０．５２ｇを加えて重合触媒を不活性化して重合反応を停止させ、ＭＴＣＤ開環重合体を含む重合反応溶液を得た。<Example 7>
500 g of dehydrated cyclohexane, 0.82 g of 1-hexene (molecular weight regulator), 0.15 g of dibutyl ether (ring-opening polymerization catalyst system component) and 0.3 g of triisobutylaluminum (ring-opening polymerization catalyst system component) under a nitrogen atmosphere It was put into a reactor, mixed at room temperature, and then kept at 45 ° C. while maintaining 8-methyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene (hereinafter abbreviated as “MTCD”) 100 g and tungsten hexachloride (0.7 mass% toluene solution: ring-opening polymerization catalyst system component) 40 g were continuously added over 2 hours. Added and polymerized. To the resulting polymerization solution, 1.06 g of butyl glycidyl ether and 0.52 g of isopropyl alcohol were added to inactivate the polymerization catalyst to stop the polymerization reaction, thereby obtaining a polymerization reaction solution containing an MTCD ring-opening polymer.
次いで、得られた重合反応溶液１００ｇにシクロヘキサン２７０ｇを加え、さらにニッケル−アルミナ触媒（日揮化学社製：水素化触媒）５ｇを加え、水素で５ＭＰａに加圧し、撹拌しながら２００℃まで加温して４時間反応させて、ＭＴＣＤ開環重合体水素化物を２０％含有する反応溶液を得た。得られた反応溶液をろ過して水素化触媒を除去した後、ろ液に、重合体１００ｇに対して０．１ｇの割合で酸化防止剤（イルガノックス（登録商標）１０１０、ＢＡＳＦジャパン社製）を添加して溶解させた。続いて、円筒型濃縮乾燥機（日立製作所社製）を用い、２７０℃、１ｋＰａ以下で、シクロヘキサンおよびその他の揮発成分を除去し、次いで、押出機により直径３ｍｍのストランド状に押出し、冷却後、長さ３ｍｍで切断して、ＭＴＣＤ開環重合体水素化物ペレットを作製した。 Next, 270 g of cyclohexane was added to 100 g of the resulting polymerization reaction solution, and 5 g of nickel-alumina catalyst (manufactured by JGC Chemicals Co., Ltd .: hydrogenation catalyst) was added. The pressure was increased to 5 MPa with hydrogen, and the mixture was heated to 200 ° C. with stirring. For 4 hours to obtain a reaction solution containing 20% MTCD ring-opening polymer hydride. The resulting reaction solution was filtered to remove the hydrogenation catalyst, and then the antioxidant was added to the filtrate at a ratio of 0.1 g with respect to 100 g of the polymer (Irganox (registered trademark) 1010, manufactured by BASF Japan). Was added and dissolved. Subsequently, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), cyclohexane and other volatile components were removed at 270 ° C. and 1 kPa or less, then extruded into a strand having a diameter of 3 mm by an extruder, and after cooling, MTCD ring-opening polymer hydride pellets were cut by cutting at a length of 3 mm.
熱可塑性樹脂ａ（ＭＴＣＤ開環重合体水素化物）のＭｗは４０，０００、水素化率は９９．９％、Ｔｇは１４８℃であった。 The Mw of the thermoplastic resin a (MTCD ring-opening polymer hydride) was 40,000, the hydrogenation rate was 99.9%, and the Tg was 148 ° C.
製造例１で作製したＳＧＣＮＴ−１を５ｇ、高分子顔料分散剤（製品名「Ｄｉｓｐｅｒｂｙｋ（登録商標）」シリーズの１４２番、ビックケミー社製；アミン価４３ｍｇＫＯＨ／ｇ、酸価４６ｍｇＫＯＨ／ｇ、固形分濃度６０％）８．３ｇとメトキシプロピルアセテート１５０ｇとを混合した後、高速旋回分散機（フィルミックス（登録商標）ＦＭ８０−５０型、プライミクス社製）で、その高速旋回分散機における撹拌部の先端速度が２０ｍ／ｓｅｃとなるようにして分散処理を実施した。この分散処理液に、作製したＭＴＣＤ開環重合体水素化物ペレット１００ｇをトルエン３００ｇに溶解させた溶液を加え、さらに高速旋回分散機で、その高速旋回分散機における撹拌部の先端速度が２０ｍ／ｓｅｃとなるようにして追加で分散処理した後、円筒型濃縮乾燥機（日立製作所社製）で、２７０℃、１ｋＰａ以下にて溶媒を除去した。次いで、円筒型濃縮乾燥機から吐出された溶融物を二軸混練押出機（東芝機械社製）の混練ゾーンにステンレス製配管を経由して供給して混練し、直径３ｍｍのストランド状に押出し、冷却後約３ｍｍ長に切断して熱可塑性樹脂組成物ペレットを得た。 5 g of SGCNT-1 produced in Production Example 1, polymer pigment dispersant (product name “Disperbyk (registered trademark)” series No. 142, manufactured by Big Chemie; amine value 43 mgKOH / g, acid value 46 mgKOH / g, solid content After mixing 8.3 g (concentration 60%) and 150 g of methoxypropyl acetate, with a high-speed swirling disperser (Filmix (registered trademark) FM80-50, manufactured by Primix), the tip of the stirring unit in the high-speed swirling disperser The dispersion process was performed so that the speed was 20 m / sec. A solution obtained by dissolving 100 g of the prepared MTCD ring-opening polymer hydride pellets in 300 g of toluene was added to this dispersion treatment liquid, and the tip speed of the stirring unit in the high-speed swirling disperser was 20 m / sec. Then, the dispersion treatment was additionally performed, and then the solvent was removed at 270 ° C. and 1 kPa or less with a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.). Next, the melt discharged from the cylindrical concentration dryer is supplied to the kneading zone of the biaxial kneading extruder (manufactured by Toshiba Machine Co.) via a stainless steel pipe and kneaded, and extruded into a strand shape having a diameter of 3 mm. After cooling, it was cut into a length of about 3 mm to obtain a thermoplastic resin composition pellet.
得られた熱可塑性樹脂組成物ペレットを射出成形機（IＳ４５０、東芝機械社製）で、金型温度１１０℃、シリンダー温度２９０℃、ノズル温度２６０℃、射出圧１００ＭＰａ、保圧８０ＭＰａ、型締め圧１２０ＭＰａ、射出速度４０ｍｌ／ｓｅｃ、スクリュー背圧０．７ＭＰａ、スクリュー回転数３０ｒｐｍの条件で成形して、厚さ１ｍｍの成形体フィルムを作製した。実施例１と同様に電気導電率を測定したところ、５．４２×１０−１Ｓ／ｃｍであった。The resulting thermoplastic resin composition pellets were molded with an injection molding machine (IS450, manufactured by Toshiba Machine Co., Ltd.) at a mold temperature of 110 ° C., a cylinder temperature of 290 ° C., a nozzle temperature of 260 ° C., an injection pressure of 100 MPa, a holding pressure of 80 MPa, and a mold clamping pressure. Molding was performed under the conditions of 120 MPa, injection speed of 40 ml / sec, screw back pressure of 0.7 MPa, screw rotation speed of 30 rpm, and a molded body film having a thickness of 1 mm was produced. The electrical conductivity was measured in the same manner as in Example 1. As a result, it was 5.42 × 10 −1 S / cm.
＜比較例１＞
高分子顔料分散剤を用いないこと以外は実施例１と同様にして、ＣＮＴ含有ＭＴＦ樹脂複合体のフィルムを作製した。実施例１と同様に電気導電率を測定したところ、２．１９×１０−４Ｓ／ｃｍであった。実施例１で得られたＣＮＴ含有ＭＴＦ樹脂複合体の導電率と比べて、１０倍以上電気伝導率が低下した。<Comparative Example 1>
A CNT-containing MTF resin composite film was produced in the same manner as in Example 1 except that the polymer pigment dispersant was not used. The electric conductivity was measured in the same manner as in Example 1. As a result, it was 2.19 × 10 −4 S / cm. Compared with the conductivity of the CNT-containing MTF resin composite obtained in Example 1, the electrical conductivity decreased by 10 times or more.
＜比較例２＞
ＣＮＴ量を１０ｍｇに変えたこと以外は比較例１と同様にＣＮＴ含有ＭＴＦ樹脂複合体フィルムを作製した。電気導電率を測定したところ、７．５７×１０−４Ｓ／ｃｍであった。<Comparative Example 2>
A CNT-containing MTF resin composite film was produced in the same manner as in Comparative Example 1 except that the amount of CNT was changed to 10 mg. When the electric conductivity was measured, it was 7.57 × 10 −4 S / cm.
＜比較例３＞
実施例１で使用したＣＮＴを、ＳＧＣＮＴ−１からＨｉＰＣＯ（ＮａｎｏＩｎｔｅｇｒｉｓ Ｉｎｃ．社製、ＢＥＴ比表面積７００ｍ２／ｇ）に変えた以外は同様にＣＮＴ含有ＭＴＦ樹脂複合体フィルムを作製した。なお、用いたＨｉＰＣＯを、透過型電子顕微鏡を用い、無作為に１００本のＨｉＰＣＯの直径を測定した結果、平均直径（Ａｖ）が１．１ｎｍ、直径分布（３σ）が０．２ｎｍ、（３σ／Ａｖ）が０．１８であった。電気導電率を測定したところ、２．１０×１０−４Ｓ／ｃｍであった。<Comparative Example 3>
A CNT-containing MTF resin composite film was produced in the same manner except that the CNT used in Example 1 was changed from SGCNT-1 to HiPCO (manufactured by NanoIntegrity Inc., BET specific surface area 700 m 2 / g). As a result of measuring the diameter of 100 HiPCOs randomly using a transmission electron microscope, the average diameter (Av) was 1.1 nm, the diameter distribution (3σ) was 0.2 nm, (3σ / Av) was 0.18. The electric conductivity was measured and found to be 2.10 × 10 −4 S / cm.
実施例、及び、比較例の結果を、表１にまとめて記載した。 The results of Examples and Comparative Examples are summarized in Table 1.
本発明で得られるＣＮＴ／高分子顔料分散剤／脂環式構造含有重合体からなる組成物は、ＣＮＴの含有量が１％未満でも、高い導電率が得られることがわかる（実施例１及び２）。これに対して、同量のＣＮＴを含有していても、高分子顔料分散剤を用いない場合（比較例１及び２）や本願発明で規定する３σ／Ａｖを外れたＣＮＴを用いた場合（比較例３）、導電率は十分には高まらないことがわかる。 It can be seen that the composition comprising the CNT / polymer pigment dispersant / alicyclic structure-containing polymer obtained in the present invention can provide high conductivity even when the CNT content is less than 1% (Example 1 and 2). On the other hand, even when the same amount of CNT is contained, when the polymer pigment dispersant is not used (Comparative Examples 1 and 2), or when CNT deviating from 3σ / Av defined in the present invention is used ( Comparative Example 3), it can be seen that the conductivity is not sufficiently increased.
また、ノルボルネン系開環重合体をカーボンナノチューブ存在下で重合して得られるノルボルネン系開環重合体組成物と同様に、ノルボルネン系開環重合体溶液とカーボンナノチューブ分散液をそれぞれ別途調整後、混合して得られたノルボルネン系開環重合体組成物であっても、高分子顔料分散剤を介すことで、高い導電率の得られることがわかる（実施例５）。 In addition, the norbornene-based ring-opening polymer composition obtained by polymerizing the norbornene-based ring-opening polymer in the presence of carbon nanotubes is separately prepared after mixing the norbornene-based ring-opening polymer solution and the carbon nanotube dispersion liquid separately. It can be seen that even the norbornene-based ring-opening polymer composition obtained in this way has high electrical conductivity obtained through the polymer pigment dispersant (Example 5).
一方、ＣＮＴの含有量が０．３７から５．４１％までに増大すると、対応するＣＮＴ樹脂複合体の電気導電率は１．０１×１０−３Ｓ／ｃｍから１．０２Ｓ／ｃｍまで著しく増大した。On the other hand, when the CNT content increases from 0.37 to 5.41%, the electrical conductivity of the corresponding CNT resin composite increases significantly from 1.01 × 10 −3 S / cm to 1.02 S / cm. did.
本発明に係る脂環構造含有重合体組成物は、電子デバイス材料、光学素子材料、導電性材料などの分野に好適に利用できる。 The alicyclic structure-containing polymer composition according to the present invention can be suitably used in fields such as electronic device materials, optical element materials, and conductive materials.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014503841A JPWO2013133226A1 (en) | 2012-03-05 | 2013-03-04 | Polymer composition containing alicyclic structure |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012047545 | 2012-03-05 | ||
| JP2012047545 | 2012-03-05 | ||
| JP2014503841A JPWO2013133226A1 (en) | 2012-03-05 | 2013-03-04 | Polymer composition containing alicyclic structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPWO2013133226A1 true JPWO2013133226A1 (en) | 2015-07-30 |
Family
ID=49116701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014503841A Pending JPWO2013133226A1 (en) | 2012-03-05 | 2013-03-04 | Polymer composition containing alicyclic structure |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPWO2013133226A1 (en) |
| WO (1) | WO2013133226A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6155615B2 (en) * | 2012-12-13 | 2017-07-05 | 日本ゼオン株式会社 | Counter electrode for dye-sensitized solar cell, dye-sensitized solar cell, and solar cell module |
| JP6326834B2 (en) * | 2014-01-31 | 2018-05-23 | 日本ゼオン株式会社 | Carbon nanotube dispersion and conductive film |
| JP6281391B2 (en) * | 2014-04-11 | 2018-02-21 | セイコーエプソン株式会社 | Ultraviolet curable inkjet composition and container |
| JP6660556B2 (en) * | 2016-01-15 | 2020-03-11 | 株式会社リコー | Active energy ray-curable composition, active energy ray-curable ink, three-dimensional modeling material, active energy ray-curable composition containing container, two-dimensional or three-dimensional image forming method, two-dimensional or three-dimensional image forming apparatus, And cured products |
| JP7291351B2 (en) * | 2020-05-28 | 2023-06-15 | 国立大学法人 奈良先端科学技術大学院大学 | CARBON NANOTUBE DISPERSION AND METHOD FOR MANUFACTURING SAME |
| CN112812487A (en) * | 2021-02-10 | 2021-05-18 | 浙江沪通模具有限公司 | Carbon nano tube modified polytriacyclopentadiene PTCPD composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004075706A (en) * | 2002-08-09 | 2004-03-11 | Sekisui Chem Co Ltd | Resin sheet |
| WO2004029152A1 (en) * | 2002-09-26 | 2004-04-08 | Zeon Corporation | Alicyclic structure containing polymer resin composition and formed article |
| WO2006011655A1 (en) * | 2004-07-27 | 2006-02-02 | National Institute Of Advanced Industrial Scienceand Technology | Single-layer carbon nanotube and alinged single-layer carbon nanotube bulk structure, and their production process, production apparatus and use |
| JP2008308583A (en) * | 2007-06-14 | 2008-12-25 | Mitsubishi Rayon Co Ltd | Structure containing carbon nanotube, method for observation of the same and composite material |
-
2013
- 2013-03-04 WO PCT/JP2013/055881 patent/WO2013133226A1/en active Application Filing
- 2013-03-04 JP JP2014503841A patent/JPWO2013133226A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004075706A (en) * | 2002-08-09 | 2004-03-11 | Sekisui Chem Co Ltd | Resin sheet |
| WO2004029152A1 (en) * | 2002-09-26 | 2004-04-08 | Zeon Corporation | Alicyclic structure containing polymer resin composition and formed article |
| WO2006011655A1 (en) * | 2004-07-27 | 2006-02-02 | National Institute Of Advanced Industrial Scienceand Technology | Single-layer carbon nanotube and alinged single-layer carbon nanotube bulk structure, and their production process, production apparatus and use |
| JP2008308583A (en) * | 2007-06-14 | 2008-12-25 | Mitsubishi Rayon Co Ltd | Structure containing carbon nanotube, method for observation of the same and composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013133226A1 (en) | 2013-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPWO2013133226A1 (en) | Polymer composition containing alicyclic structure | |
| Mülhaupt | Catalytic polymerization and post polymerization catalysis fifty years after the discovery of Ziegler's catalysts | |
| EP2248839B1 (en) | Crystalline norbornene ring-opening polymer hydride and molded article of same | |
| WO2001014446A1 (en) | Norbornene open-ring polymers, products of hydrogenation thereof and processes for the production of both | |
| WO2018173838A1 (en) | Method for producing molding material | |
| US11322269B2 (en) | Electrically conductive film | |
| JP2014524487A (en) | Cyclic olefin polymer compound and method for producing the same | |
| JP2016155327A (en) | Production method of container made of resin, and container made of resin | |
| WO2005019277A1 (en) | Process for producing cycloolefin addition polymer | |
| WO2016017528A1 (en) | Resin molded article | |
| JP2002249645A (en) | Polymer composition | |
| Ban et al. | Synthesis of cyclo‐olefin copolymer latexes and their carbon nanotube composite nanoparticles | |
| JP2010006985A (en) | Molding material for packaging member | |
| JP5942539B2 (en) | Optical resin composition | |
| JP2012031305A (en) | Method of manufacturing cyclic olefin addition polymer of high gas permeability | |
| JP6557108B2 (en) | Transparent conductive film and touch panel | |
| JP5682321B2 (en) | Norbornene-based ring-opening copolymer hydride and use thereof | |
| JP5381939B2 (en) | Film made of hydride of norbornene-based ring-opening copolymer | |
| JP2013227396A (en) | Reactive composition and reaction injection molding body | |
| JP7255180B2 (en) | Polymer production method | |
| JP2012066518A (en) | Method of joining microchip substrate | |
| JP2009079088A (en) | Hydrogenation product of ring opening block copolymer of norbornene compound, its manufacturing process, and molded product | |
| WO2019188720A1 (en) | Norbornene ring-opening polymer hydride and method for producing same | |
| JP2020050745A (en) | Film and method for producing the same | |
| JP6331560B2 (en) | Ring-opening polymer hydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150925 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160412 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20160610 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160812 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160927 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20161125 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20170321 |