JP2017197687A - Polymer comprising aromatic ring and quaternary carbon atom-containing alicycle, method for producing polymer, composition, film, base material with film, optical element, image display device, coating material and molding - Google Patents
Polymer comprising aromatic ring and quaternary carbon atom-containing alicycle, method for producing polymer, composition, film, base material with film, optical element, image display device, coating material and molding Download PDFInfo
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Description
本発明は、芳香環及び四級炭素原子含有脂環を含む重合体、重合体の製造方法、組成物、膜、膜付基材、光学素子、画像表示装置、被覆材料及び成形体に関する。 The present invention relates to a polymer containing an aromatic ring and a quaternary carbon atom-containing alicyclic ring, a method for producing the polymer, a composition, a film, a substrate with a film, an optical element, an image display device, a coating material, and a molded article.
主鎖に芳香環を有する芳香族ポリマーは、優れた耐熱性と機械特性を有しており、エンジニアリングプラスチックとして利用されている(例えば、特許文献1、及び特許文献2参照)。なかでも主鎖に芳香環と脂環を有する構造のポリマーは、耐熱性に優れるとともに透明性にも優れることから、光学部品への適用が期待されている(例えば、特許文献3参照)。特に、嵩高く剛直な骨格を分子構造中に有するポリマーは、優れた耐熱性と透明性が期待できる。 An aromatic polymer having an aromatic ring in the main chain has excellent heat resistance and mechanical properties, and is used as an engineering plastic (see, for example, Patent Document 1 and Patent Document 2). Among them, polymers having a structure having an aromatic ring and an alicyclic ring in the main chain are expected to be applied to optical components because they are excellent in heat resistance and transparency (see, for example, Patent Document 3). In particular, a polymer having a bulky and rigid skeleton in the molecular structure can be expected to have excellent heat resistance and transparency.
樹脂材料を光学部品に適用する場合には、金属材料を含む種々の材料と組み合わせて用いる場合が多い。そのため、寸法安定性及び信頼性の観点から、耐熱性及び透明性に優れていることに加えて吸水率が低いことが望ましい。
しかしながら、ポリイミドのような耐熱性の高いポリマーは、一般に極性を有する官能基を多く含み、吸水率が高い傾向にある。
When a resin material is applied to an optical component, it is often used in combination with various materials including a metal material. Therefore, from the viewpoint of dimensional stability and reliability, it is desirable that the water absorption is low in addition to being excellent in heat resistance and transparency.
However, a polymer having high heat resistance such as polyimide generally contains many functional groups having polarity and tends to have a high water absorption rate.
本発明は上記状況に鑑みなされたものであり、優れた耐熱性と透明性を有し、さらに吸水率の低い重合体及びその製造方法、並びに重合体を含む組成物、膜、膜付基材、光学素子、画像表示装置、被覆材料及び成形体を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has a polymer having excellent heat resistance and transparency, a low water absorption rate, a method for producing the same, a composition containing the polymer, a film, and a substrate with a film An object of the present invention is to provide an optical element, an image display device, a coating material, and a molded body.
<1>芳香環と、前記芳香環に結合した四級炭素原子を有する脂環と、を含む重合体。
<2>下記一般式(I)で示される構造単位を含む、<1>に記載の重合体。
<1> A polymer comprising an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring.
<2> The polymer according to <1>, comprising a structural unit represented by the following general formula (I).
〔一般式(I)において、Xは芳香環を含む2価の基を示し、Yは前記芳香環に結合した四級炭素原子を有する脂環を含む2価の基を示す。nは一般式(I)で示される構造単位の数を示す。〕
<3>前記一般式(I)において、Yは下記一般式(IV−1)、下記一般式(IV−2)及び下記一般式(IV−3)からなる群より選択される少なくとも一種で示される基を含む、<2>に記載の重合体。
[In General Formula (I), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring. n represents the number of structural units represented by the general formula (I). ]
<3> In the general formula (I), Y represents at least one selected from the group consisting of the following general formula (IV-1), the following general formula (IV-2), and the following general formula (IV-3). <2> The polymer according to <2>.
<4>前記一般式(I)において、Xが2個以上の芳香環を含む2価の基を含む、<2>又は<3>に記載の重合体。
<5>前記一般式(I)において、Xが、下記一般式(II−1)、下記一般式(II−2)及び下記一般式(II−3)からなる群より選択される少なくとも1種の2価の基を含む、<2>〜<4>のいずれか1項に記載の重合体。
<4> The polymer according to <2> or <3>, wherein, in the general formula (I), X includes a divalent group including two or more aromatic rings.
<5> In the general formula (I), X is at least one selected from the group consisting of the following general formula (II-1), the following general formula (II-2), and the following general formula (II-3). <2>-<4> The polymer of any one of <2> containing the bivalent group of these.
〔一般式(II−1)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕 [In General Formula (II-1), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]
〔一般式(II−2)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示し、Zは酸素原子又は下記一般式(III)で示される2価の基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕 [In General Formula (II-2), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. ]
〔一般式(III)中、R3及びR4はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示す。〕 [In General Formula (III), R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]
〔一般式(II−3)中、R5はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。nはそれぞれ独立に、0〜4の整数を示す。〕
<6>カルボニル基をさらに含む、<1>〜<5>のいずれか1項に記載の重合体。
<7>下記一般式(VI)で示される化合物と、芳香環を含む化合物と、を酸性媒体中で反応させる反応工程を含む、<1>〜<6>のいずれか1項に記載の重合体の製造方法。
[In General Formula (II-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently. ]
<6> The polymer according to any one of <1> to <5>, further including a carbonyl group.
<7> The compound according to any one of <1> to <6>, comprising a reaction step of reacting a compound represented by the following general formula (VI) with a compound containing an aromatic ring in an acidic medium. Manufacturing method of coalescence.
〔一般式(VI)においてYは、前記芳香環を含む化合物の前記芳香環と結合して四級炭素原子となる炭素原子を含む脂環を示す。〕
<8>前記芳香環を含む化合物は、下記一般式(VII−1)、下記一般式(VII−2)及び下記一般式(VII−3)からなる群より選択される少なくとも1種を含む、<7>に記載の重合体の製造方法。
[In General Formula (VI), Y represents an alicyclic ring containing a carbon atom that is bonded to the aromatic ring of the compound containing the aromatic ring to form a quaternary carbon atom. ]
<8> The compound containing an aromatic ring includes at least one selected from the group consisting of the following general formula (VII-1), the following general formula (VII-2), and the following general formula (VII-3). <7> The method for producing a polymer according to item 7.
〔一般式(VII−1)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕 [In General Formula (VII-1), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]
〔一般式(VII−2)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示し、Zは酸素原子又は下記一般式(III)で示される2価の基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕 [In General Formula (VII-2), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. ]
〔一般式(III)中、R3及びR4はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示す。〕 [In General Formula (III), R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]
一般式(VII−3)中、R5はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。nはそれぞれ独立に、0〜4の整数を示す。
<9>前記反応工程は、前記一般式(VI)で示される化合物と酸性媒体との混合物を調製する工程と、前記混合物に前記芳香環を含む化合物を加える工程と、をこの順に有する、<7>又は<8>に記載の重合体の製造方法。
<10><1>〜<6>のいずれか1項に記載の重合体を含む、組成物。
<11><1>〜<6>のいずれか1項に記載の重合体を含む、膜。
<12>基材と、前記基材の表面の少なくとも一部に設けられる<11>に記載の膜と、を有する膜付基材。
<13><11>に記載の膜又は<12>に記載の膜付基材を有する、光学素子。
<4><11>に記載の膜又は<12>に記載の膜付基材を有する、画像表示装置。
<15><1>〜<6>のいずれか1項に記載の重合体を含む、被覆材料。
<16><1>〜<6>のいずれか1項に記載の重合体を含む、成形体。
In General Formula (VII-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently.
<9> The reaction step includes a step of preparing a mixture of the compound represented by the general formula (VI) and an acidic medium, and a step of adding the compound containing the aromatic ring to the mixture in this order. The manufacturing method of the polymer as described in 7> or <8>.
<10> A composition comprising the polymer according to any one of <1> to <6>.
<11> A film comprising the polymer according to any one of <1> to <6>.
<12> A substrate with a film having a substrate and the film according to <11> provided on at least part of the surface of the substrate.
<13> An optical element having the film according to <11> or the substrate with a film according to <12>.
<4> An image display device having the film according to <11> or the film-coated substrate according to <12>.
<15> A coating material comprising the polymer according to any one of <1> to <6>.
<16> A molded article comprising the polymer according to any one of <1> to <6>.
本発明によれば、優れた耐熱性と透明性を有し、さらに吸水率の低い重合体及びその製造方法、並びに重合体を含む組成物、膜、膜付基材、光学素子、画像表示装置、被覆材料及び成形体が提供される。 According to the present invention, a polymer having excellent heat resistance and transparency and a low water absorption rate, a method for producing the same, a composition containing the polymer, a film, a substrate with a film, an optical element, and an image display device A coating material and a molded body are provided.
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素(要素ステップ等も含む)は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。
本明細書において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
本明細書において「〜」を用いて示された数値範囲には、「〜」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において組成物中の各成分の含有率又は含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本明細書において「層」又は「膜」との語には、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本明細書において「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
本明細書において「透明性」とは、可視光の透過性(少なくとも波長400nmの可視光の透過性)が80%以上(膜厚10μm換算)である性質を意味する。
本明細書において「耐熱性」とは、200℃、空気下で10分間加熱しても視認可能な黄変又は変形が生じない性質を意味する。
Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.
In this specification, the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. It is.
In the present specification, the numerical ranges indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present specification, the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total content or content of substances.
In the present specification, the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
In this specification, the term “layer” or “film” refers to a part of the region in addition to the case where the layer or the film is formed when the region where the layer or film exists is observed. It is also included when it is formed only.
In this specification, the term “lamination” indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
In the present specification, the “transparency” means a property that the visible light transmittance (visible light transmittance of at least 400 nm wavelength) is 80% or more (in terms of film thickness of 10 μm).
As used herein, “heat resistance” means a property that does not cause visible yellowing or deformation even when heated at 200 ° C. for 10 minutes in air.
<重合体>
本実施形態の重合体は、芳香環と、前記芳香環に結合した四級炭素原子を有する脂環(以下、四級炭素原子含有脂環とも称する)と、を含む。本発明者らの検討により、本実施形態の重合体は優れた耐熱性と透明性を有し、さらに吸水率が低いことがわかった。その理由は明らかではないが、まず、芳香環と、前記芳香環に結合した脂環を有することで、耐熱性と透明性を有すると考えられる。さらに、四級炭素原子は、わずかながら極性を有するC−H結合をまったく持たないため、水分子との相互作用が弱く、水分子が重合体の分子鎖の集合体又は凝集体の中に浸透しにくい結果、吸水率が低くなると考えられる。
<Polymer>
The polymer of this embodiment includes an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring (hereinafter also referred to as a quaternary carbon atom-containing alicyclic ring). As a result of studies by the present inventors, it has been found that the polymer of the present embodiment has excellent heat resistance and transparency, and has a low water absorption rate. The reason for this is not clear, but first, it is considered to have heat resistance and transparency by having an aromatic ring and an alicyclic ring bonded to the aromatic ring. Furthermore, since the quaternary carbon atom has no C—H bond having a slight polarity, the interaction with the water molecule is weak, and the water molecule penetrates into an aggregate or aggregate of polymer molecular chains. As a result, the water absorption rate is considered to be low.
本実施形態の重合体に含まれる芳香環の構造は、特に制限されない。透明性の観点からは、炭素数が3〜24の芳香環であることが好ましい。このような芳香環としては、ベンゼン環、ナフタレン環、アントラセン環等が挙げられる。これらの中でも、重合の反応性を高める観点からは、ベンゼン環が好ましい。また、芳香環は、置換基を有していてもよい。置換基としては、アルキル基、ハロゲン原子、ヒドロキシ基、エポキシ基、オキセタニル基、アルコキシ基、アシル基等が挙げられる。 The structure of the aromatic ring contained in the polymer of this embodiment is not particularly limited. From the viewpoint of transparency, it is preferably an aromatic ring having 3 to 24 carbon atoms. Examples of such an aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Among these, a benzene ring is preferable from the viewpoint of increasing the polymerization reactivity. Moreover, the aromatic ring may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group, and an acyl group.
本実施形態の重合体に含まれる四級炭素原子含有脂環は、特に制限されない。耐熱性の観点からは、炭素数が5〜30の脂環であることが好ましい。このような脂環としては、キュバン骨格、ノルボルナン骨格、トリシクロ[5.2.1.0]デカン骨格、アダマンタン骨格、ジアダマンタン骨格、ビシクロ[2.2.2]オクタン骨格、デカヒドロナフタレン骨格等が挙げられる。 The quaternary carbon atom-containing alicyclic ring contained in the polymer of this embodiment is not particularly limited. From the viewpoint of heat resistance, an alicyclic ring having 5 to 30 carbon atoms is preferable. Examples of such alicyclic rings include cubane skeleton, norbornane skeleton, tricyclo [5.2.1.0] decane skeleton, adamantane skeleton, diadamantane skeleton, bicyclo [2.2.2] octane skeleton, decahydronaphthalene skeleton, and the like. Is mentioned.
四級炭素原子を有する脂環には、不飽和結合が含まれていてもよい。また、四級炭素原子を有する脂環は、置換基を有していてもよい。置換基としては、アルキル基、ハロゲン原子、ヒドロキシ基、エポキシ基、オキセタニル基、アルコキシ基、アシル基等が挙げられる。 The alicyclic ring having a quaternary carbon atom may contain an unsaturated bond. Moreover, the alicyclic ring having a quaternary carbon atom may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group, and an acyl group.
本実施形態の重合体は、芳香環を含む2価の基と、四級炭素原子含有脂環を含む2価の基と、を含むことが好ましく、芳香環を含む2価の基と、四級炭素原子含有脂環を含む2価の基とが交互に結合した構造を含む(すなわち、下記一般式(I)で示される構造単位を含む)ことがより好ましい。 The polymer of the present embodiment preferably contains a divalent group containing an aromatic ring and a divalent group containing a quaternary carbon atom-containing alicyclic ring. The divalent group containing an aromatic ring, More preferably, it includes a structure in which divalent groups containing a secondary carbon atom-containing alicyclic ring are alternately bonded (that is, includes a structural unit represented by the following general formula (I)).
一般式(I)において、Xは芳香環を含む2価の基を示し、Yは四級炭素原子含有脂環を含む2価の基を示す。一般式(I)において、n個の構造単位中のXは同じでも異なっていてもよく、Yは同じでも異なっていてもよい。nは一般式(I)で示される構造単位の数を示す。nは特に制限されず、3〜1000の整数であってよい。 In the general formula (I), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing a quaternary carbon atom-containing alicyclic ring. In general formula (I), X in n structural units may be the same or different, and Y may be the same or different. n represents the number of structural units represented by the general formula (I). n is not particularly limited, and may be an integer of 3 to 1000.
芳香環を含む2価の基の炭素数は特に制限されず、例えば、6〜50であってよい。重合体の耐熱性の観点からは、芳香環を含む2価の基の少なくとも一部は、芳香環を2個以上含むことが好ましい。芳香環を含む2価の基が芳香環を2個以上含む場合、2個以上の芳香環同士は、単結合で結合されていても、2価の連結基で結合されていてもよい。 The carbon number of the divalent group containing an aromatic ring is not particularly limited, and may be 6 to 50, for example. From the viewpoint of the heat resistance of the polymer, at least a part of the divalent group containing an aromatic ring preferably contains two or more aromatic rings. When the bivalent group containing an aromatic ring contains two or more aromatic rings, the two or more aromatic rings may be bonded with a single bond or may be bonded with a divalent linking group.
2個以上の芳香環同士を結合する2価の連結基としては、酸素原子、硫黄原子、置換基を有していてもよいアルキレン基、置換基を有していてもよいアルケニレン基、置換基を有していてもよいアルキニレン基、イミノ基、カルボニル基等が挙げられる。さらに、上述の連結基から選ばれる任意の連結基同士を2個以上連結した2価の連結基が挙げられる。これらの中でも、2価の連結基としては、酸素原子又は置換基を有していてもよいアルキレン基が好ましい。 Examples of the divalent linking group that connects two or more aromatic rings include an oxygen atom, a sulfur atom, an alkylene group that may have a substituent, an alkenylene group that may have a substituent, and a substituent. An alkynylene group, an imino group, a carbonyl group, and the like, which may have an alkyl group. Furthermore, the bivalent coupling group which connected two or more arbitrary coupling groups chosen from the above-mentioned coupling group is mentioned. Among these, as the divalent linking group, an oxygen atom or an alkylene group which may have a substituent is preferable.
芳香環を含む2価の基として具体的には、下記一般式(II−1)、下記一般式(II−2)及び下記一般式(II−3)からなる群より選択される少なくとも一種で示される基が挙げられる。 Specifically, the divalent group containing an aromatic ring is at least one selected from the group consisting of the following general formula (II-1), the following general formula (II-2) and the following general formula (II-3). And the groups shown.
一般式(II−1)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。mはそれぞれ独立に、0〜3の整数を示す。また、波線部は結合部位を示し、以降も同様である。 In General Formula (II-1), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. Moreover, a wavy line shows a coupling | bond part and it is the same after that.
一般式(II−1)中、反応制御の観点から、R1は置換基を有していてもよい炭素数1〜20の炭化水素基が好ましい。
R1で示される炭化水素基としては、飽和脂肪族炭化水素基、不飽和脂肪族炭化水素基、脂環式炭化水素基、これらの炭化水素基の組み合わせ等が挙げられる。R1で示される炭化水素基が置換基を有する場合の置換基としては、ハロゲン原子、ヒドロキシ基、エポキシ基、オキセタニル基、炭素数1〜5のアルコキシ基、炭素数2〜5のアシル基等が挙げられる。なお、R1で示される炭化水素基が置換基を有する場合、炭化水素基の炭素数には、置換基の炭素数を含めないものとする。以降、同様である。
In general formula (II-1), from the viewpoint of reaction control, R 1 is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
Examples of the hydrocarbon group represented by R 1 include saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and combinations of these hydrocarbon groups. Examples of the substituent when the hydrocarbon group represented by R 1 has a substituent include a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Is mentioned. When the hydrocarbon group represented by R 1 has a substituent, the carbon number of the hydrocarbon group does not include the carbon number of the substituent. The same applies thereafter.
R1で示される飽和脂肪族炭化水素基としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、sec−ブチル基、t−ブチル基、n−ペンチル基、イソペンチル基、sec−ペンチル基、neo−ペンチル基、t−ペンチル基、n−ヘキシル基、n−ヘプチル基、n−オクチル基、n−ノニル基、n−デシル基、n−イコサニル基、n−トリアコンタニル基等が挙げられる。 Examples of the saturated aliphatic hydrocarbon group represented by R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and n-pentyl group. , Isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, n -A triacontanyl group etc. are mentioned.
R1で示される不飽和脂肪族炭化水素基としては、ビニル基、アリル基等のアルケニル基、エチニル基等のアルキニル基などが挙げられる。 Examples of the unsaturated aliphatic hydrocarbon group represented by R 1 include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethynyl groups.
R1で示される脂環式炭化水素基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、アダマンチル基等のシクロアルキル基、シクロヘキセニル基等のシクロアルケニル基などが挙げられる。 Examples of the alicyclic hydrocarbon group represented by R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cycloalkyl group such as a norbornyl group, an adamantyl group, a cyclohexenyl group, and the like. And the like.
反応制御の観点から、R2で示される炭化水素基としては、置換基を有していてもよい炭素数1〜20の炭化水素基が好ましい。R2で示される炭化水素基としては、R1で例示したものと同様のものが挙げられる。また、置換基としては、ハロゲン原子、ヒドロキシ基、エポキシ基、オキセタニル基、炭素数1〜5のアルコキシ基、炭素数2〜5のアシル基等が挙げられる。mは、0〜2の整数であることが好ましい。 From the viewpoint of reaction control, the hydrocarbon group represented by R 2 is preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Examples of the hydrocarbon group represented by R 2 include the same as those exemplified for R 1 . Examples of the substituent include a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. m is preferably an integer of 0 to 2.
一般式(II−2)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示し、Zは酸素原子又は下記一般式(III)で示される2価の基を示す。mはそれぞれ独立に、0〜3の整数を示す。一般式(II−2)中のR1、R2及びmのそれぞれの詳細は、一般式(II−1)中のR1、R2及びmの詳細と同様である。 In general formula (II-2), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. A hydrocarbon group having 1 to 30 carbon atoms which may be present, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. Each of the details of the R 1, R 2 and m in formula (II-2), the same as in the general formula (II-1) of R 1, R 2 and m in detail.
一般式(III)中、R3及びR4はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示す。反応制御の観点から、R3及びR4としては、置換基を有していてもよい炭素数1〜20の炭化水素基が好ましい。R3及びR4で示される炭化水素基としては、一般式(II−1)中のR1で例示したものと同様のものが挙げられる。また置換基としては、ハロゲン原子、ヒドロキシ基、エポキシ基、オキセタニル基、炭素数1〜5のアルコキシ基、炭素数2〜5のアシル基等が挙げられる。 In general formula (III), R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of reaction control, R 3 and R 4 are preferably a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. As the hydrocarbon group represented by R 3 and R 4 , the same groups as those exemplified for R 1 in formula (II-1) can be mentioned. Examples of the substituent include a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
一般式(II−3)中、R5はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。nはそれぞれ独立に、0〜4の整数を示す。 In General Formula (II-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently.
反応制御の観点から、R5としては、炭素数1〜20の炭化水素基が好ましい。R5で示される炭化水素基としては、一般式(II−1)中のR1で例示したものと同様のものが挙げられる。また置換基としては、ハロゲン原子、ヒドロキシ基、エポキシ基、オキセタニル基、炭素数1〜5のアルコキシ基、炭素数2〜5のアシル基等が挙げられる。nは、0〜2の整数であることが好ましい。 From the viewpoint of reaction control, R 5 is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group represented by R 5 include the same groups as those exemplified for R 1 in formula (II-1). Examples of the substituent include a halogen atom, a hydroxy group, an epoxy group, an oxetanyl group, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. n is preferably an integer of 0 to 2.
四級炭素原子含有脂環を含む2価の基としては、上述した四級炭素原子含有脂環を含む2価の基が挙げられる。耐熱性、透明性、低吸水性、及び溶剤への溶解性を並立させる観点からは、四級炭素原子含有脂環を含む2価の基は、下記一般式(IV−1)、下記一般式(IV−2)及び下記一般式(IV−3)からなる群より選択される少なくとも一種で示される基であることが好ましい。 As a bivalent group containing a quaternary carbon atom containing alicyclic ring, the bivalent group containing the quaternary carbon atom containing alicyclic ring mentioned above is mentioned. From the viewpoint of paralleling heat resistance, transparency, low water absorption, and solubility in a solvent, the divalent group containing a quaternary carbon atom-containing alicyclic ring is represented by the following general formula (IV-1) or the following general formula. A group represented by at least one selected from the group consisting of (IV-2) and the following general formula (IV-3) is preferable.
重合体の溶剤に対する溶解性の観点からは、本実施形態の重合体は、カルボニル基を含むことが好ましい。例えば、下記一般式(V)で示される構造単位を含むことが好ましい。 From the viewpoint of the solubility of the polymer in the solvent, the polymer of this embodiment preferably contains a carbonyl group. For example, it is preferable to include a structural unit represented by the following general formula (V).
一般式(V)において、Xは芳香環を含む2価の基を表し、Yはカルボニル基の炭素原子に結合した四級炭素原子を有する脂環を含む2価の基を示す。Xの詳細は、一般式(I)におけるXの詳細と同様である。Yの詳細は、一般式(I)におけるYの詳細(ただし、四級炭素原子は芳香環の代わりにカルボニル基の炭素原子に結合している)と同様である。mは一般式(V)で示される構造単位の数を示す。mの値は特に制限されず、重合体に含まれるカルボニル基の所望の量に応じて選択できる。例えば、一般式(I)で示される構造単位の数であるnとの比(n:m)が100:0〜5:95となる範囲から選択できる。 In the general formula (V), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing an alicyclic ring having a quaternary carbon atom bonded to a carbon atom of a carbonyl group. The details of X are the same as the details of X in general formula (I). The details of Y are the same as the details of Y in formula (I) (wherein the quaternary carbon atom is bonded to the carbon atom of the carbonyl group instead of the aromatic ring). m represents the number of structural units represented by the general formula (V). The value of m is not particularly limited and can be selected according to the desired amount of the carbonyl group contained in the polymer. For example, the ratio (n: m) to n, which is the number of structural units represented by the general formula (I), can be selected from a range of 100: 0 to 5:95.
本実施形態の重合体が一般式(I)で示される構造単位と、一般式(V)で示される構造単位とを含む場合、一般式(I)で示される構造単位と一般式(V)で示される構造単位の配置の状態は特に制限されない。例えば、一般式(I)で示される構造単位と一般式(V)で示される構造単位とが交互に配置されても、ランダムに配置されても、ブロック状に配置されてもよい。 When the polymer of this embodiment includes the structural unit represented by the general formula (I) and the structural unit represented by the general formula (V), the structural unit represented by the general formula (I) and the general formula (V) The arrangement state of the structural unit represented by is not particularly limited. For example, the structural unit represented by the general formula (I) and the structural unit represented by the general formula (V) may be alternately arranged, randomly arranged, or arranged in blocks.
本実施形態の重合体の分子量は特に制限されず、用途等に応じて選択できる。耐熱性の観点からは、本実施形態の重合体の重量平均分子量(Mw)は、10000以上であることが好ましく、20000以上であることがより好ましい。また、数平均分子量(Mn)は1000以上であることが好ましく、2000以上であることがより好ましい。 The molecular weight of the polymer of the present embodiment is not particularly limited, and can be selected according to the use. From the viewpoint of heat resistance, the weight average molecular weight (Mw) of the polymer of the present embodiment is preferably 10,000 or more, and more preferably 20,000 or more. Further, the number average molecular weight (Mn) is preferably 1000 or more, and more preferably 2000 or more.
溶剤に対する溶解性の観点からは、本実施形態の重合体の重量平均分子量(Mw)は、350000以下であることが好ましく、300000以下であることがより好ましい。また、数平均分子量(Mn)は、200000以下であることが好ましく、100000以下であることがより好ましい。 From the viewpoint of solubility in a solvent, the weight average molecular weight (Mw) of the polymer of this embodiment is preferably 350,000 or less, and more preferably 300000 or less. The number average molecular weight (Mn) is preferably 200000 or less, and more preferably 100000 or less.
本実施形態の重合体の分子量(Mw及びMn)は、溶離液としてテトラヒドロフラン(THF)を用いて、GPC法によって測定し、標準ポリスチレン換算にて求められる値である。
・装置名:Ecosec HLC−8320GPC(東ソー株式会社)
・カラム:TSKgel Supermultipore HZ−M(東ソー株式会社)
・検出器:UV検出器、RI検出器併用
・流速:0.4ml/min
The molecular weight (Mw and Mn) of the polymer of the present embodiment is a value determined by standard polystyrene conversion, measured by GPC method using tetrahydrofuran (THF) as an eluent.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
Column: TSKgel Supermultipore HZ-M (Tosoh Corporation)
・ Detector: UV detector and RI detector combined use
・ Flow rate: 0.4ml / min
本実施形態の重合体は、透明性及び耐熱性に優れる。そして、後述する本実施形態の重合体を含む膜その他の実施態様は、吸水率が低く、吸水による寸法変化等の不具合を起こしにくい。そのため、本実施形態の重合体は、高温高湿環境で使用される部材にも好適に利用することができる。 The polymer of this embodiment is excellent in transparency and heat resistance. And the film | membrane and other embodiment containing the polymer of this embodiment mentioned later have a low water absorption, and it is hard to raise | generate malfunctions, such as a dimensional change by water absorption. Therefore, the polymer of this embodiment can be suitably used for members used in a high temperature and high humidity environment.
<重合体の製造方法>
本実施形態の重合体の製造方法は、下記一般式(VI)で示される化合物(以下、ジカルボン酸モノマと称する)と、芳香環を含む化合物(以下、芳香族モノマとも称する)と、を酸性媒体中で反応させる工程(以下、反応工程とも称する)を含む。
<Method for producing polymer>
The method for producing a polymer according to this embodiment comprises a compound represented by the following general formula (VI) (hereinafter referred to as a dicarboxylic acid monomer) and a compound containing an aromatic ring (hereinafter also referred to as an aromatic monomer). A step of reacting in a medium (hereinafter also referred to as a reaction step).
一般式(VI)においてYは、芳香環を含む化合物の芳香環と結合して四級炭素原子となる炭素原子を含む脂環を示す。Yの詳細及び好ましい態様は、上述した実施形態の重合体に含まれる四級炭素原子含有脂環の詳細及び好ましい態様と同様である。 In general formula (VI), Y represents an alicyclic ring containing a carbon atom that is bonded to an aromatic ring of a compound containing an aromatic ring to form a quaternary carbon atom. The details and preferred aspects of Y are the same as the details and preferred aspects of the quaternary carbon atom-containing alicyclic ring contained in the polymer of the embodiment described above.
上記方法によれば、芳香環と、前記芳香環に結合した四級炭素原子を有する脂環と、を含む本実施形態の重合体を効率よく合成することができる。すなわち、一般式(VI)で示されるジカルボン酸モノマは、酸性媒体中でまずアシルカチオンとなる。その後、カルボニル部位が脱離してアルキルカチオンとなる。このように、アルキルカチオンとなった状態で芳香族モノマと縮合反応させることで、芳香環と、前記芳香環に結合した四級炭素原子を有する脂環と、を含む重合体を得ることができる。 According to the said method, the polymer of this embodiment containing an aromatic ring and the alicyclic ring which has the quaternary carbon atom couple | bonded with the said aromatic ring is efficiently compoundable. That is, the dicarboxylic acid monomer represented by the general formula (VI) first becomes an acyl cation in an acidic medium. Thereafter, the carbonyl moiety is eliminated to become an alkyl cation. Thus, a polymer containing an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring can be obtained by a condensation reaction with an aromatic monomer in a state of being an alkyl cation. .
なお、酸性媒体中でジカルボン酸モノマから生じるアシルカチオンがアルキルカチオンとなる前に芳香族モノマと反応させると、カルボニル基が形成される。従って、酸性媒体中でジカルボン酸モノマと芳香族モノマを反応させる条件を制御することで、重合体の構造中に所望の量のカルボニル基を導入することができる。カルボニル基を導入することで、重合体の溶剤に対する溶解性が向上する傾向にある。 When an acyl cation generated from a dicarboxylic acid monomer is reacted with an aromatic monomer before becoming an alkyl cation in an acidic medium, a carbonyl group is formed. Therefore, a desired amount of carbonyl group can be introduced into the structure of the polymer by controlling the conditions for reacting the dicarboxylic acid monomer and the aromatic monomer in an acidic medium. By introducing a carbonyl group, the solubility of the polymer in the solvent tends to be improved.
ジカルボン酸モノマと芳香族モノマを反応させる条件を充分に制御する観点からは、上記反応工程は、ジカルボン酸モノマと酸性媒体との混合物を調製する工程と、前記混合物に芳香族モノマを加える工程と、をこの順に有することが好ましい。 From the viewpoint of sufficiently controlling the conditions for reacting the dicarboxylic acid monomer and the aromatic monomer, the reaction step includes a step of preparing a mixture of the dicarboxylic acid monomer and the acidic medium, and a step of adding the aromatic monomer to the mixture. Are preferably provided in this order.
ジカルボン酸モノマと反応させる芳香族モノマは特に制限されず、重合体の所望の特性等に応じて選択できる。耐熱性の観点からは、芳香環を2つ以上含む芳香族モノマを用いることが好ましい。芳香環を2つ以上含む芳香族モノマとしては、ビフェニル系モノマ、ジフェニルエーテル系モノマ、ビスフェノール系モノマ、フルオレン系モノマ等が挙げられる。 The aromatic monomer to be reacted with the dicarboxylic acid monomer is not particularly limited, and can be selected according to the desired characteristics of the polymer. From the viewpoint of heat resistance, it is preferable to use an aromatic monomer containing two or more aromatic rings. Examples of the aromatic monomer containing two or more aromatic rings include a biphenyl monomer, a diphenyl ether monomer, a bisphenol monomer, a fluorene monomer, and the like.
ある実施態様では、芳香族モノマは、下記一般式(VII−1)、下記一般式(VII−2)及び下記一般式(VII−3)からなる群より選択される少なくとも一種である。 In one embodiment, the aromatic monomer is at least one selected from the group consisting of the following general formula (VII-1), the following general formula (VII-2), and the following general formula (VII-3).
一般式(VII−1)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。mはそれぞれ独立に、0〜3の整数を示す。 In General Formula (VII-1), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3.
一般式(VII−1)中のR1、R2及びmの詳細は、一般式(II−1)中のR1、R2及びmの詳細と同様である。 Details of R 1, R 2 and m in the general formula (VII-1), the same as in the general formula (II-1) of R 1, R 2 and m in detail.
一般式(VII−2)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示し、Zは酸素原子又は下記一般式(III)で示される2価の基を示す。mはそれぞれ独立に、0〜3の整数を示す。 In General Formula (VII-2), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. A hydrocarbon group having 1 to 30 carbon atoms which may be present, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3.
一般式(III)中、R3及びR4はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示す。
In general formula (III), R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
一般式(VII−2)中のR1、R2、Z及びmの詳細、並びに一般式(III)におけるR3及びR4の詳細は、一般式(II−2)中のR1、R2、Z及びm、並びに一般式(III)におけるR3及びR4の詳細と同様である。 Details of R 1 , R 2 , Z and m in the general formula (VII-2) and details of R 3 and R 4 in the general formula (III) are as follows: R 1 , R in the general formula (II-2) 2 , Z and m, and the details of R 3 and R 4 in formula (III) are the same.
一般式(VII−3)中、R5はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。nはそれぞれ独立に、0〜4の整数を示す。 In General Formula (VII-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently.
一般式(VII−3)中のR5及びnの詳細は、一般式(II−3)中のR5及びnの詳細と同様である。 The general formula (VII-3) R 5 and n details in, is the same as the general formula (II-3) R 5 and n in detail.
耐熱性、透明性、低吸水性、及び溶剤への溶解性を並立させる観点からは、一般式(VI)で示されるジカルボン酸モノマは、下記一般式(VIII−1)、下記一般式(VIII−2)及び下記一般式(VIII−3)からなる群より選択される少なくとも1種で示されるジカルボン酸モノマであることが好ましい。 The dicarboxylic acid monomer represented by the general formula (VI) is represented by the following general formula (VIII-1) and the following general formula (VIII) from the viewpoint of making heat resistance, transparency, low water absorption, and solubility in a solvent side by side. -2) and a dicarboxylic acid monomer represented by at least one selected from the group consisting of the following general formula (VIII-3).
上記方法に用いる酸性媒体は、特に制限されない。本明細書において「酸性媒体」とは、酸性物質(ブレンステッド酸又はルイス酸)を含む媒体を意味し、酸性物質は有機酸であっても無機酸であってもよい。酸性媒体は、反応条件下で液状であることが好ましい。例えば、塩化アルミニウムの有機溶媒溶液、トリフルオロアルカンスルホン酸の有機溶媒溶液、ポリリン酸、五酸化二リンと有機スルホン酸の混合物などを用いることができる。反応性と扱いやすさとの観点からは、五酸化二リンと有機スルホン酸の混合物が好ましい。得られる重合体の透明性の観点からは、有機スルホン酸としてメタンスルホン酸を用いることが好ましい。酸性媒体は1種を単独で用いても、2種以上を併用してもよい。 The acidic medium used in the above method is not particularly limited. In this specification, the “acidic medium” means a medium containing an acidic substance (Bronsted acid or Lewis acid), and the acidic substance may be an organic acid or an inorganic acid. The acidic medium is preferably liquid under the reaction conditions. For example, an organic solvent solution of aluminum chloride, an organic solvent solution of trifluoroalkanesulfonic acid, polyphosphoric acid, a mixture of diphosphorus pentoxide and organic sulfonic acid, or the like can be used. From the viewpoint of reactivity and ease of handling, a mixture of diphosphorus pentoxide and an organic sulfonic acid is preferable. From the viewpoint of the transparency of the obtained polymer, it is preferable to use methanesulfonic acid as the organic sulfonic acid. An acidic medium may be used individually by 1 type, or may use 2 or more types together.
酸性媒体として五酸化二リンと有機スルホン酸の混合物を用いる場合、五酸化二リンと有機スルホン酸の混合比は、混合比の制御及び反応性の観点から、質量比(五酸化二リン:有機スルホン酸)が1:5〜1:20であることが好ましく、1:5〜1:10であることがより好ましい。五酸化二リンの比率が大きいほど、ジカルボン酸モノマと芳香族モノマの反応性が向上する傾向にある。 When a mixture of diphosphorus pentoxide and organic sulfonic acid is used as the acidic medium, the mixing ratio of diphosphorus pentoxide and organic sulfonic acid is a mass ratio (diphosphorus pentoxide: organic from the viewpoint of control of the mixing ratio and reactivity. The sulfonic acid) is preferably 1: 5 to 1:20, more preferably 1: 5 to 1:10. As the ratio of diphosphorus pentoxide is larger, the reactivity between the dicarboxylic acid monomer and the aromatic monomer tends to be improved.
ジカルボン酸モノマと酸性媒体との混合物の調製は、撹拌しながら行ってもよい。撹拌の時間は特に制限されず、ジカルボン酸モノマの種類及び量、カルボニル基を導入する場合はその量等に応じて選択できる。例えば、1分〜60分とすることができる。撹拌の方法は特に限定されず、マグネチックスターラ、メカニカルスターラ等を用いる一般的な方法で行うことができる。 The mixture of the dicarboxylic acid monomer and the acidic medium may be prepared with stirring. The stirring time is not particularly limited, and can be selected according to the type and amount of the dicarboxylic acid monomer and the amount when introducing a carbonyl group. For example, it may be 1 minute to 60 minutes. The stirring method is not particularly limited, and the stirring can be performed by a general method using a magnetic stirrer, a mechanical stirrer, or the like.
上記方法で使用する酸性媒体の量は、芳香族モノマとジカルボン酸モノマを溶解しうる量であれば特に制限されず、触媒量から溶媒量までの範囲で用いることができる。反応性と扱いやすさとの観点から、酸性媒体の量は、ジカルボン酸モノマ1質量部に対して5質量部〜100質量部の範囲が好ましい。 The amount of the acidic medium used in the above method is not particularly limited as long as it can dissolve the aromatic monomer and the dicarboxylic acid monomer, and can be used in a range from a catalyst amount to a solvent amount. From the viewpoint of reactivity and ease of handling, the amount of the acidic medium is preferably in the range of 5 to 100 parts by mass with respect to 1 part by mass of the dicarboxylic acid monomer.
芳香族モノマとジカルボン酸モノマとを反応させる際の温度は、反応生成物である重合体の着色と副反応を抑制する観点からは10℃〜100℃であることが好ましく、反応速度を上げて生産性を向上させる観点からは20℃〜100℃であることがより好ましい。 The temperature at the time of reacting the aromatic monomer and the dicarboxylic acid monomer is preferably 10 ° C. to 100 ° C. from the viewpoint of suppressing coloring and side reaction of the polymer as the reaction product, and increases the reaction rate. From the viewpoint of improving productivity, the temperature is more preferably 20 ° C to 100 ° C.
芳香族モノマとジカルボン酸モノマとの縮合反応における反応の雰囲気は、特に制限されず、閉鎖系であっても開放系であってもよい。水分の存在による酸性媒体の反応性の低下を抑制する観点からは、乾燥空気又は窒素、アルゴン等の不活性ガス雰囲気が好ましい。想定外の副反応を防ぐ観点からは、窒素、アルゴン等の不活性ガス雰囲気がより好ましい。 The atmosphere of the reaction in the condensation reaction between the aromatic monomer and the dicarboxylic acid monomer is not particularly limited, and may be a closed system or an open system. From the viewpoint of suppressing the decrease in the reactivity of the acidic medium due to the presence of moisture, an inert gas atmosphere such as dry air or nitrogen or argon is preferable. From the viewpoint of preventing an unexpected side reaction, an inert gas atmosphere such as nitrogen or argon is more preferable.
ジカルボン酸モノマと芳香族モノマとを反応させる際は、ジカルボン酸モノマと芳香族モノマを含む酸性媒体を撹拌することで、反応を促進してもよい。撹拌の方法は特に限定されず、マグネチックスターラ、メカニカルスターラ等を用いる一般的な方法により行うことができる。 When the dicarboxylic acid monomer and the aromatic monomer are reacted, the reaction may be promoted by stirring an acidic medium containing the dicarboxylic acid monomer and the aromatic monomer. The stirring method is not particularly limited, and the stirring can be performed by a general method using a magnetic stirrer, a mechanical stirrer, or the like.
芳香族モノマとジカルボン酸モノマとを反応させる時間は、反応温度、目標とする重合体の分子量、反応に用いるモノマの種類等によって調節できる。分子量が充分に大きい重合体を得る観点からは、反応時間は1時間〜120時間程度であることが好ましく、生産性の観点からは、1時間〜72時間であることがより好ましい。 The time for reacting the aromatic monomer and the dicarboxylic acid monomer can be adjusted by the reaction temperature, the molecular weight of the target polymer, the kind of monomer used for the reaction, and the like. From the viewpoint of obtaining a polymer having a sufficiently high molecular weight, the reaction time is preferably about 1 hour to 120 hours, and more preferably 1 hour to 72 hours from the viewpoint of productivity.
芳香族モノマとジカルボン酸モノマとを反応させる際の圧力は特に限定されず、常圧下、加圧下、又は減圧下のいずれで行ってもよい。コストの観点からは、常圧下で反応を行うことが好ましい。 The pressure when the aromatic monomer and the dicarboxylic acid monomer are reacted is not particularly limited, and the reaction may be performed under normal pressure, increased pressure, or reduced pressure. From the viewpoint of cost, it is preferable to carry out the reaction under normal pressure.
芳香族モノマとジカルボン酸モノマとを反応させた後、重合体を取り出す方法は特に制限されない。例えば、反応液(反応生成物を含む酸性触媒)と、反応生成物である重合体の貧溶媒とを接触させて重合体を析出させ、不純物を貧溶媒層に抽出し、析出した重合体を濾過、デカンテーション、遠心分離等の方法で反応液から分離して取り出すことができる。さらにこの後、分離した重合体を再度重合体の良溶媒に溶解させ、再び重合体の貧溶媒と接触させて重合体を析出させ、不純物を貧溶媒層に抽出し、析出した重合体を濾過、デカンテーション、遠心分離等の方法で液体から分離する工程を繰り返してもよい。 The method for taking out the polymer after reacting the aromatic monomer and the dicarboxylic acid monomer is not particularly limited. For example, a reaction solution (an acidic catalyst containing a reaction product) is contacted with a poor solvent of a polymer that is a reaction product to precipitate a polymer, and impurities are extracted into a poor solvent layer. It can be separated and removed from the reaction solution by methods such as filtration, decantation, and centrifugation. Further, after that, the separated polymer is dissolved again in the good solvent of the polymer, and again brought into contact with the poor solvent of the polymer to precipitate the polymer, the impurities are extracted into the poor solvent layer, and the precipitated polymer is filtered. The step of separating from the liquid by a method such as decantation or centrifugation may be repeated.
<組成物>
本実施形態の重合体の組成物は、本実施形態の重合体を含む。組成物の状態は特に制限されず、組成物の用途等に応じて選択できる。例えば、ワニス、スラリー、混合粉末等が挙げられる。本実施形態の組成物は、本実施形態の重合体に加えてその他の成分を含んでもよい。その他の成分としては、溶媒、添加剤、架橋剤等が挙げられる。
<Composition>
The polymer composition of the present embodiment includes the polymer of the present embodiment. The state of the composition is not particularly limited and can be selected according to the use of the composition. For example, varnish, slurry, mixed powder, etc. are mentioned. The composition of this embodiment may contain other components in addition to the polymer of this embodiment. Examples of other components include a solvent, an additive, and a crosslinking agent.
添加剤としては、接着助剤、界面活性剤、レベリング剤、酸化防止剤、紫外線劣化防止剤等が挙げられる。これらの添加剤は1種を単独で用いても、2種以上を併用してもよい。 Examples of the additive include an adhesion assistant, a surfactant, a leveling agent, an antioxidant, and an ultraviolet deterioration preventing agent. These additives may be used alone or in combination of two or more.
架橋剤としては、多官能エポキシ化合物、多官能アクリル化合物、多官能オキセタン化合物、複数のヒドロキシ基を有する化合物、複数のヒドロキシメチル基を有する化合物、複数のアルコキシメチル基を有する化合物等が挙げられる。これらの架橋剤は1種を単独で用いても、2種以上を併用してもよい。 Examples of the crosslinking agent include polyfunctional epoxy compounds, polyfunctional acrylic compounds, polyfunctional oxetane compounds, compounds having a plurality of hydroxy groups, compounds having a plurality of hydroxymethyl groups, compounds having a plurality of alkoxymethyl groups, and the like. These crosslinking agents may be used alone or in combination of two or more.
溶媒としては、γ−ブチロラクトン、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、酢酸ベンジル、エトキシエチルプロピオネート、3−メチルメトキシプロピオネート、N−メチル−2−ピロリドン、N−シクロヘキシル−2−ピロリドン、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホリルアミド、テトラメチレンスルホン、ジエチルケトン、ジイソブチルケトン、メチルアミルケトン、シクロヘキサノン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、キシレン、メシチレン、エチルベンゼン、プロピルベンゼン、クメン、ジイソプロピルベンゼン、ヘキシルベンゼン、アニソール、ジグライム、ジメチルスルホキシド、クロロホルム、ジクロロメタン、ジクロロエタン、クロロベンゼン等が挙げられる。これらの溶媒は1種を単独で用いても、2種以上を併用してもよい。 Solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-cyclohexyl-2 -Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl Ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, xylene, mesitylene, ethylbenzene, pro Rubenzen, cumene, diisopropylbenzene, hexyl benzene, anisole diglyme, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene and the like. These solvents may be used alone or in combination of two or more.
<膜及び膜付基材>
本実施形態の膜は、本実施形態の重合体を含む。本実施形態の膜は、ポリイミド膜に匹敵する耐熱性を有し、ポリイミド膜よりも吸水率が小さい。従って、本実施形態の膜は、高湿度環境下で使用する場合であっても寸法安定性や信頼性に優れている。
<Membrane and substrate with membrane>
The film of this embodiment includes the polymer of this embodiment. The film of this embodiment has heat resistance comparable to that of a polyimide film, and has a lower water absorption rate than the polyimide film. Therefore, the film of this embodiment is excellent in dimensional stability and reliability even when used in a high humidity environment.
本実施形態の膜の製造方法は、特に限定されない。例えば、溶媒を含む本実施形態の組成物を基材の表面に付与して組成物層を形成し、必要に応じて乾燥して組成物層から溶媒を除去することで、本実施形態の膜を製造することができる。製造した膜は、基材から分離せずに膜付基材として用いても、基材から分離して用いてもよい。
組成物を基材に付与する方法は特に制限されず、浸漬法、スプレー法、スクリーン印刷法、バーコート法、スピンコート法等が挙げられる。組成物層を乾燥する方法は特に制限されず、ホットプレート、オーブン等を用いて加熱する方法、自然乾燥などが挙げられる。
The manufacturing method of the film | membrane of this embodiment is not specifically limited. For example, the film of the present embodiment is formed by applying the composition of the present embodiment containing a solvent to the surface of the substrate to form a composition layer, and drying it as necessary to remove the solvent from the composition layer. Can be manufactured. The produced membrane may be used as a substrate with a film without being separated from the substrate, or may be used after being separated from the substrate.
The method for applying the composition to the substrate is not particularly limited, and examples include dipping, spraying, screen printing, bar coating, and spin coating. The method for drying the composition layer is not particularly limited, and examples thereof include a method of heating using a hot plate and an oven, and natural drying.
必要に応じて、乾燥した本実施形態の重合体の膜を更に熱処理してもよい。熱処理の方法は特に限定されず、箱型乾燥機、熱風式コンベアー型乾燥機、石英チューブ炉、ホットプレート、ラピッドサーマルアニール、縦型拡散炉、赤外線硬化炉、電子線硬化炉、マイクロ波硬化炉等のオーブンを用いて行なうことができる。また、熱処理工程における雰囲気条件としては、大気中又は窒素等の不活性雰囲気中のいずれを選択することもできる。 If necessary, the dried polymer film of this embodiment may be further heat-treated. The heat treatment method is not particularly limited, and is a box dryer, hot air conveyor dryer, quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace. Etc. can be performed using an oven. In addition, as an atmospheric condition in the heat treatment step, any of air or an inert atmosphere such as nitrogen can be selected.
本実施形態の膜付基材は、基材と、前記基材の表面の少なくとも一部に設けられる本実施形態の膜と、を有する。本実施形態の膜付基材は、基材の一方の面に膜を有していても、両面に膜を有していてもよい。また、基材上に形成される膜は、一層でも、二層以上が積層された複数層構造であってもよい。 The base material with a film according to the present embodiment includes the base material and the film according to the present embodiment provided on at least a part of the surface of the base material. The film-coated substrate of the present embodiment may have a film on one surface of the substrate or may have a film on both surfaces. The film formed on the substrate may be a single layer or a multi-layer structure in which two or more layers are laminated.
基材の種類は、特に制限されない。例えば、ガラス基板、半導体基板、金属酸化物絶縁体基板(例えば、酸化チタン基板及び酸化ケイ素基板)、窒化ケイ素基板等の無機基板、トリアセチルセルロース、ポリイミド、ポリカルボナート、アクリル系樹脂、シクロオレフィン樹脂等の樹脂基板などを例示することができる。基材は透明であっても、透明でなくてもよい。基材の形状は特に限定されず、板状、フィルム状等が挙げられる。 The type of substrate is not particularly limited. For example, glass substrate, semiconductor substrate, metal oxide insulator substrate (for example, titanium oxide substrate and silicon oxide substrate), inorganic substrate such as silicon nitride substrate, triacetyl cellulose, polyimide, polycarbonate, acrylic resin, cycloolefin A resin substrate such as a resin can be exemplified. The substrate may be transparent or not transparent. The shape of the substrate is not particularly limited, and examples thereof include a plate shape and a film shape.
<光学素子及び画像表示装置>
本実施形態の光学素子及び画像表示装置は、それぞれ、本実施形態の膜又は膜付基材を有する。
<Optical element and image display device>
The optical element and the image display device of the present embodiment each have the film or the substrate with the film of the present embodiment.
光学素子及び画像表示装置は、例えば、本実施形態の膜が形成された基材の基材側を、粘着剤、接着剤等を介してLCD(液晶ディスプレイ)、ELD(エレクトロルミネッセンスディスプレイ)等に用いられている部材に貼り合せることにより、得ることができる。 The optical element and the image display device, for example, the substrate side of the substrate on which the film according to the present embodiment is formed, to an LCD (liquid crystal display), an ELD (electroluminescence display) or the like via an adhesive, an adhesive, or the like. It can be obtained by bonding to a member that is being used.
本実施形態の光学素子は、偏光板等として、液晶表示装置等の各種画像表示装置に好ましく用いることができる。画像表示装置は、本実施形態の膜を用いる以外は、従来の画像表示装置と同様の構成であってよい。画像表示装置が液晶表示装置である場合は、液晶セル、偏光板等の光学素子、及び必要に応じ照明システム(バックライト等)等の各構成部品を適宜に組み立てて駆動回路を組み込むことなどにより製造できる。液晶セルのタイプは特に制限されず、TN型、STN型、π型等を使用できる。 The optical element of this embodiment can be preferably used for various image display devices such as a liquid crystal display device as a polarizing plate or the like. The image display device may have the same configuration as that of the conventional image display device except that the film of the present embodiment is used. When the image display device is a liquid crystal display device, by appropriately assembling each component such as a liquid crystal cell, an optical element such as a polarizing plate, and an illumination system (backlight, etc.) as necessary, and incorporating a drive circuit, etc. Can be manufactured. The type of the liquid crystal cell is not particularly limited, and a TN type, STN type, π type, or the like can be used.
画像表示装置の用途は、特に制限されない。例えば、デスクトップパソコン、ノートパソコン、コピー機等のOA機器、携帯電話、時計、デジタルカメラ、携帯情報端末(PDA)、携帯ゲーム機等の携帯機器、ビデオカメラ、テレビ、電子レンジ等の家庭用電気機器、バックモニター、カーナビゲーションシステム用モニター、カーオーディオ等の車載用機器、商業店舗用インフォメーション用モニター等の展示機器、監視用モニター等の警備機器、介護用モニター等の介護機器、医療用モニター等の医療機器などが挙げられる。 The use of the image display device is not particularly limited. For example, OA equipment such as desktop personal computers, notebook personal computers, copiers, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, home electric appliances such as video cameras, televisions, microwave ovens, etc. Equipment, back monitor, car navigation system monitor, in-car equipment such as car audio, display equipment such as information monitor for commercial stores, security equipment such as monitoring monitor, care equipment such as care monitor, medical monitor, etc. Medical equipment.
<被覆材料>
本実施形態の被覆材料は、本実施形態の重合体を含む。被覆材料で被覆される対象は特に制限されず、デスクトップパソコン、ノートパソコン、コピー機等のOA機器、携帯電話、デジタルカメラ、携帯情報端末(PDA)、携帯ゲーム機等の携帯機器、ビデオカメラ、テレビ、各種ディスプレイ、窓ガラス、車載ガラス、カメラレンズなどが挙げられる。被覆材料を用いて被覆を形成する方法は特に制限されず、例えば、膜状の被覆材料をラミネート等の方法で被覆対象に接着することで被覆を形成してもよく、液状の被覆材料を被覆対象に塗布してから乾燥させて被覆を形成してもよい。
<Coating material>
The coating material of this embodiment contains the polymer of this embodiment. The object to be coated with the coating material is not particularly limited, and is an OA device such as a desktop personal computer, a notebook personal computer, a copy machine, a mobile phone, a digital camera, a personal digital assistant (PDA), a portable device such as a portable game machine, a video camera, TV, various displays, window glass, in-vehicle glass, camera lens, and the like. The method of forming the coating using the coating material is not particularly limited. For example, the coating may be formed by adhering a film-shaped coating material to the object to be coated by a method such as laminating, or coating a liquid coating material. The coating may be formed by applying to an object and then drying.
<成形体>
本実施形態の成形体は、本実施形態の重合体を含む。成形体の製造方法は特に制限されず、当該技術分野で既知の方法を用いることができる。例えば、押出成形法、射出成形法、カレンダー成形法、ブロー成形法、FRP(Fiber Reinforced Plastic)成形法、積層成形法、注型法、粉末成形法、溶液流延法、真空成形法、圧空成形法、押出複合成形法、延伸成形法、発泡成形法などが挙げられる。
<Molded body>
The molded body of the present embodiment includes the polymer of the present embodiment. The method for producing the molded body is not particularly limited, and a method known in the technical field can be used. For example, extrusion molding method, injection molding method, calender molding method, blow molding method, FRP (Fiber Reinforced Plastic) molding method, laminate molding method, casting method, powder molding method, solution casting method, vacuum molding method, compressed air molding Method, extrusion composite molding method, stretch molding method, foam molding method and the like.
本実施体の成形品は、必要に応じて所望の機能の付与、特性の改善、成形性の向上等のために、種々の添加剤を加えてもよい。添加剤としては、摺動剤(例えばポリテトラフルオロエチレン粒子)、光拡散剤(アクリル架橋粒子、シリコーン架橋粒子、極薄ガラスフレーク、炭酸カルシウム粒子等)、蛍光染料、無機系蛍光体(アルミン酸塩を母結晶とする蛍光体等)、帯電防止剤、結晶核剤、無機及び有機の抗菌剤、光触媒系防汚剤(酸化チタン粒子、酸化亜鉛粒子等)、架橋剤、硬化剤、反応促進剤、赤外線吸収剤(熱線吸収剤)、フォトクロミック剤などが挙げられる。 Various additives may be added to the molded product of the present embodiment as necessary to impart a desired function, improve characteristics, improve moldability, and the like. Additives include sliding agents (eg, polytetrafluoroethylene particles), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (aluminic acid) Phosphors with a salt as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (titanium oxide particles, zinc oxide particles, etc.), crosslinking agents, curing agents, reaction acceleration Agents, infrared absorbers (heat ray absorbers), photochromic agents and the like.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[実施例1]
(芳香環と四級炭素原子含有脂環を含む重合体「AD」の合成)
撹拌機と窒素風船を備えた四つ口フラスコに、1,3−アダマンタンジカルボン酸10mmolと、五酸化二リンとメタンスルホン酸の混合液(質量比1:10)30mlと、を加え、60℃で10分間撹拌した。続いて、フラスコ中に2,2’−ジメトキシビフェニルを10mmol加え、60℃で40時間撹拌した。反応後、反応液をメタノール500ml中に投じ、生成した析出物を濾取した。得られた固体を蒸留水とメタノールとで洗浄した後、乾燥し、ADを得た。ADの分子量を後述する方法で測定したところ、重量平均分子量は52,000であり、数平均分子量は9,100であった。また、ADの熱分解温度を、後述する方法で測定した。結果を表1に示す。
[Example 1]
(Synthesis of polymer "AD" containing aromatic ring and quaternary carbon atom-containing alicyclic ring)
To a four-necked flask equipped with a stirrer and a nitrogen balloon, 10 mmol of 1,3-adamantane dicarboxylic acid and 30 ml of a mixed solution of diphosphorus pentoxide and methanesulfonic acid (mass ratio 1:10) were added, For 10 minutes. Subsequently, 10 mmol of 2,2′-dimethoxybiphenyl was added to the flask and stirred at 60 ° C. for 40 hours. After the reaction, the reaction solution was poured into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain AD. When the molecular weight of AD was measured by the method described later, the weight average molecular weight was 52,000 and the number average molecular weight was 9,100. Further, the thermal decomposition temperature of AD was measured by the method described later. The results are shown in Table 1.
ADが芳香環と、芳香環に結合した四級炭素原子を有する脂環を含んでいることは、炭素−13核磁気共鳴分光法(13C−NMR)により、四級炭素原子が結合した芳香環上の炭素のピークが142ppmに存在することで確認した。詳細は次のとおりである。
・装置名:AVANCE300(Bruker社)
・共鳴周波数:300MHz(プロトン核として)
・溶媒:重クロロホルム
The fact that AD contains an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring indicates that an aromatic quaternary carbon atom bonded by carbon-13 nuclear magnetic resonance spectroscopy ( 13 C-NMR). This was confirmed by the presence of a carbon peak on the ring at 142 ppm. Details are as follows.
・ Device name: AVANCE300 (Bruker)
・ Resonance frequency: 300 MHz (as proton nucleus)
・ Solvent: Deuterated chloroform
(ワニスの調製)
ADをN−メチル−2−ピロリドン(NMP)に濃度が20質量%となるように溶解し、ポリテトラフルオロエチレン製のメンブレンフィルター(孔径:5μm)でろ過して、ADのワニスを得た。
(Preparation of varnish)
AD was dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 20% by mass and filtered through a polytetrafluoroethylene membrane filter (pore size: 5 μm) to obtain an AD varnish.
(透明性の評価)
ADのワニスを、スピンコート法によりガラス基板上に塗布し、120℃のホットプレート上で3分間乾燥し、更に200℃の窒素ガスオーブン中で1時間乾燥して、AD膜付ガラス板を作製した。これを用いて、ADの透明性を後述する方法で評価した。結果を表1に示す。
(Evaluation of transparency)
AD varnish is applied onto a glass substrate by spin coating, dried on a hot plate at 120 ° C for 3 minutes, and further dried in a nitrogen gas oven at 200 ° C for 1 hour to produce a glass plate with an AD film. did. Using this, the transparency of AD was evaluated by the method described later. The results are shown in Table 1.
(吸水率の評価)
ADのワニスを、バーコート法によりポリイミドフィルム上に塗布し、120℃のホットプレート上で3分間乾燥した後、ポリイミドフィルムから重合体ADの膜を剥がし、ADの単独膜を得た。得られた単独膜を、ポリテトラフルオロエチレン製の板上に固定し、200℃の窒素ガスオーブン中で1時間乾燥した。これを用いて、ADの吸水率を後述する方法で測定した。結果を表1に示す。
(Evaluation of water absorption)
An AD varnish was applied onto a polyimide film by a bar coating method and dried on a hot plate at 120 ° C. for 3 minutes, and then the polymer AD film was peeled off from the polyimide film to obtain an AD single film. The obtained single membrane was fixed on a plate made of polytetrafluoroethylene and dried in a nitrogen gas oven at 200 ° C. for 1 hour. Using this, the water absorption of AD was measured by the method described later. The results are shown in Table 1.
[実施例2]
(芳香環と四級炭素原子含有脂環を含む重合体「BO」の合成)
1,3−アダマンタンジカルボン酸の代わりに10mmolの1,4−ビシクロ[2.2.2]オクタンジカルボン酸を用いた以外は実施例1と同様にして、BOを得た。BOの分子量を後述する方法で測定したところ、重量平均分子量は65,000であり、数平均分子量は10,000であった。また、実施例1と同様にしてBOが芳香環と、芳香環に結合した四級炭素原子を有する脂環を含んでいることを確認し、熱分解温度を測定した。結果を表1に示す。
[Example 2]
(Synthesis of polymer "BO" containing aromatic ring and quaternary carbon atom-containing alicyclic ring)
BO was obtained in the same manner as in Example 1 except that 10 mmol of 1,4-bicyclo [2.2.2] octane dicarboxylic acid was used instead of 1,3-adamantane dicarboxylic acid. When the molecular weight of BO was measured by the method described later, the weight average molecular weight was 65,000 and the number average molecular weight was 10,000. Further, in the same manner as in Example 1, it was confirmed that BO contains an aromatic ring and an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring, and the thermal decomposition temperature was measured. The results are shown in Table 1.
BOを用いて実施例1と同様にしてワニスを調製し、BOの透明性の評価と吸水率の評価を行った。結果を表1に示す。 A varnish was prepared in the same manner as in Example 1 using BO, and the transparency of the BO and the water absorption rate were evaluated. The results are shown in Table 1.
[比較例1]
(透明ポリイミド「PI」の前駆体の合成)
撹拌機と窒素風船を備えた四つ口フラスコに、N−メチル−2−ピロリドン49gと、トランス−1,4−シクロヘキサンジアミン30mmolと、を加え、撹拌して溶解した。その後、3,3,4,4−ビフェニルテトラカルボン酸二無水物30mmolを加えた。このとき、白色の固体(酸とアミンの塩)が生成した。引き続き、80℃の湯浴中で10分間撹拌し、生成した塩を完全に溶解させた。その後、室温で70時間撹拌し、PIの前駆体(PI前駆体)の溶液を得た。得られたPI前駆体の分子量を後述する方法で測定したところ、PI前駆体の重量平均分子量は53,000であり、数平均分子量は14,000であった。また、実施例1と同様にして熱分解温度を測定した。結果を表1に示す。
[Comparative Example 1]
(Synthesis of transparent polyimide "PI" precursor)
In a four-necked flask equipped with a stirrer and a nitrogen balloon, 49 g of N-methyl-2-pyrrolidone and 30 mmol of trans-1,4-cyclohexanediamine were added and dissolved by stirring. Thereafter, 30 mmol of 3,3,4,4-biphenyltetracarboxylic dianhydride was added. At this time, a white solid (acid and amine salt) was formed. Subsequently, the mixture was stirred in a hot water bath at 80 ° C. for 10 minutes to completely dissolve the produced salt. Thereafter, the mixture was stirred at room temperature for 70 hours to obtain a PI precursor (PI precursor) solution. When the molecular weight of the obtained PI precursor was measured by the method described later, the weight average molecular weight of the PI precursor was 53,000, and the number average molecular weight was 14,000. Further, the thermal decomposition temperature was measured in the same manner as in Example 1. The results are shown in Table 1.
(ワニスの調製)
PI前駆体をN−メチル−2−ピロリドン(NMP)に濃度が20質量%となるように溶解し、ポリテトラフルオロエチレン製のメンブレンフィルター(孔径:5μm)でろ過して、PI前駆体のワニスを得た。
(Preparation of varnish)
The PI precursor was dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 20% by mass, filtered through a polytetrafluoroethylene membrane filter (pore size: 5 μm), and the PI precursor varnish. Got.
(透明性の評価)
PI前駆体のワニスを、スピンコート法によりガラス基板上に塗布し、120℃のホットプレート上で3分間乾燥し、更に300℃の窒素ガスオーブン中で1時間乾燥してPI前駆体を完全にPIに変化させて、PI膜付ガラス板を作製した。これを用いて、PIの透明性を後述する方法で評価した。結果を表1に示す。
(Evaluation of transparency)
The PI precursor varnish was applied onto a glass substrate by spin coating, dried on a hot plate at 120 ° C. for 3 minutes, and further dried in a nitrogen gas oven at 300 ° C. for 1 hour to completely remove the PI precursor. A glass plate with a PI film was prepared by changing to PI. Using this, the transparency of PI was evaluated by the method described later. The results are shown in Table 1.
(吸水率の評価)
PI前駆体のワニスを、バーコート法によりシリコン基板上に塗布し、120℃のホットプレート上で3分間乾燥した後、シリコン基板からPI前駆体の膜を剥がし、PI前駆体の単独膜を得た。得られた単独膜を、ポリテトラフルオロエチレン製の板上に固定し、300℃の窒素ガスオーブン中で1時間乾燥してPI前駆体を完全PIに変化させた。これを用いて、PIの吸水率を後述する方法で測定した。結果を表1に示す。
(Evaluation of water absorption)
The PI precursor varnish was applied onto a silicon substrate by a bar coating method, dried on a hot plate at 120 ° C. for 3 minutes, and then the PI precursor film was peeled off from the silicon substrate to obtain a single film of the PI precursor. It was. The obtained single membrane was fixed on a plate made of polytetrafluoroethylene and dried in a nitrogen gas oven at 300 ° C. for 1 hour to change the PI precursor into complete PI. Using this, the water absorption of PI was measured by the method described later. The results are shown in Table 1.
[比較例2]
(シクロオレフィンポリマー「COP」の合成)
撹拌機と窒素風船を備えた四つ口フラスコに、脱水したシクロヘキサン500質量部と、1−ヘキセン0.55質量部と、ジイソプロピルエーテル0.30質量部と、トリイソブチルアルミニウム0.20質量部と、イソブチルアルコール0.075質量部と、を加え、撹拌して混合した。その後、55℃に保ちながら、2−ノルボルネン250質量部と、六塩化タングステンの1.0質量%トルエン溶液15質量部と、を2時間かけて連続的に加え、重合反応を生じさせた。得られた反応液を、珪藻土をろ過助剤としてステンレス製金網を備えたろ過器によりろ過し、触媒を除去した。次いで、反応溶液をイソプロピルアルコール3000質量部中に投じ、生成した析出物を濾取した。濾取した固体をアセトンで洗浄した後、乾燥し、COPを得た。得られたCOPの分子量を後述する方法で測定したところ、重量平均分子量は62,000であり、数平均分子量は33,000であった。また、実施例1と同様にして熱分解温度を測定した。結果を表1に示す。
[Comparative Example 2]
(Synthesis of cycloolefin polymer “COP”)
In a four-necked flask equipped with a stirrer and a nitrogen balloon, 500 parts by mass of dehydrated cyclohexane, 0.55 parts by mass of 1-hexene, 0.30 parts by mass of diisopropyl ether, 0.20 parts by mass of triisobutylaluminum, Then, 0.075 parts by mass of isobutyl alcohol was added and mixed by stirring. Thereafter, while maintaining the temperature at 55 ° C., 250 parts by mass of 2-norbornene and 15 parts by mass of a 1.0 mass% toluene solution of tungsten hexachloride were continuously added over 2 hours to cause a polymerization reaction. The resulting reaction solution was filtered through a filter equipped with a stainless steel wire mesh using diatomaceous earth as a filter aid to remove the catalyst. Next, the reaction solution was poured into 3000 parts by mass of isopropyl alcohol, and the produced precipitate was collected by filtration. The solid collected by filtration was washed with acetone and then dried to obtain COP. When the molecular weight of the obtained COP was measured by the method described later, the weight average molecular weight was 62,000 and the number average molecular weight was 33,000. Further, the thermal decomposition temperature was measured in the same manner as in Example 1. The results are shown in Table 1.
(ワニスの調製)
COPをN−メチル−2−ピロリドン(NMP)に濃度が20質量%となるように溶解し、ポリテトラフルオロエチレン製のメンブレンフィルター(孔径:5μm)でろ過して、COPのワニスを得た。
(Preparation of varnish)
COP was dissolved in N-methyl-2-pyrrolidone (NMP) so as to have a concentration of 20% by mass and filtered with a polytetrafluoroethylene membrane filter (pore size: 5 μm) to obtain a COP varnish.
(透明性の評価)
COPのワニスを、スピンコート法によりガラス基板上に塗布し、120℃のホットプレート上で3分間乾燥し、更に200℃の窒素ガスオーブン中で1時間乾燥して、COP膜付ガラス板を作製した。これを用いて、COPの透明性を後述する方法で評価した。結果を表1に示す。
(Evaluation of transparency)
COP varnish is applied on a glass substrate by spin coating, dried on a hot plate at 120 ° C for 3 minutes, and further dried in a nitrogen gas oven at 200 ° C for 1 hour to produce a glass plate with a COP film. did. Using this, the transparency of COP was evaluated by the method described later. The results are shown in Table 1.
(吸水率の評価)
COPのワニスを、バーコート法によりポリイミドフィルム上に塗布し、120℃のホットプレート上で3分間乾燥した後、ポリイミドフィルムからCOPの膜を剥がし、COPの単独膜を得た。得られた単独膜を、ポリテトラフルオロエチレン製の板上に固定し、300℃の窒素ガスオーブン中で1時間乾燥した。これを用いて、COPの吸水率を後述する方法で測定した。結果を表1に示す。
(Evaluation of water absorption)
A COP varnish was applied on a polyimide film by a bar coating method and dried on a hot plate at 120 ° C. for 3 minutes, and then the COP film was peeled off from the polyimide film to obtain a COP single film. The obtained single membrane was fixed on a plate made of polytetrafluoroethylene and dried in a nitrogen gas oven at 300 ° C. for 1 hour. Using this, the water absorption of COP was measured by the method described later. The results are shown in Table 1.
(分子量の測定)
実施例1、実施例2及び比較例2において、分子量は、溶離液としてテトラヒドロフラン(THF)を用いて、GPC法によって測定し、標準ポリスチレン換算にて求めた。詳細は次のとおりである。
・装置名:Ecosec HLC−8320GPC(東ソー株式会社)
・カラム:TSKgel Supermultipore HZ−M(東ソー株式会社)
・検出器:UV検出器、RI検出器併用
・流速:0.4ml/min
(Measurement of molecular weight)
In Example 1, Example 2, and Comparative Example 2, the molecular weight was measured by GPC method using tetrahydrofuran (THF) as an eluent, and determined in terms of standard polystyrene. Details are as follows.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
Column: TSKgel Supermultipore HZ-M (Tosoh Corporation)
・ Detector: UV detector and RI detector combined use
・ Flow rate: 0.4ml / min
比較例1において、分子量は、溶離液としてN−メチル−2−ピロリドン(NMP)を用いて、GPC法によって測定し、標準ポリスチレン換算にて求めた。詳細は次のとおりである。
・装置名:Ecosec HLC−8320GPC(東ソー株式会社)
・カラム:TSKgel Super AW(東ソー株式会社)
・検出器:UV検出器、RI検出器併用
・流速:0.4ml/min
In Comparative Example 1, the molecular weight was measured by the GPC method using N-methyl-2-pyrrolidone (NMP) as an eluent, and determined in terms of standard polystyrene. Details are as follows.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
・ Column: TSKgel Super AW (Tosoh Corporation)
・ Detector: UV detector and RI detector combined use
・ Flow rate: 0.4ml / min
(熱分解温度の測定)
実施例1、実施例2、比較例1及び比較例2で得た重合体の粉末をアルミパンに量り取り、熱重量天秤(「TG−DTA6300」、株式会社日立ハイテクサイエンス)を用いて重量減少を測定した。加熱により重量が大きく減少する曲線の接線の交点を熱分解温度と定義する。
(Measurement of thermal decomposition temperature)
The polymer powders obtained in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were weighed into an aluminum pan and reduced in weight using a thermogravimetric balance (“TG-DTA6300”, Hitachi High-Tech Science Co., Ltd.). Was measured. The intersection of the tangents of the curves where the weight is greatly reduced by heating is defined as the pyrolysis temperature.
(透明性の評価)
実施例1、実施例2、比較例1及び比較例2で作製した重合体の膜付きガラス基板の波長400nmにおける透過率を、紫外可視分光光度計(「U−3310 Spectrophotometer」、日立ハイテク株式会社)を用いた紫外可視吸収スペクトル法によって測定した。膜の付いていないガラス基板をリファレンスとして、膜厚10μmに換算した値を透過率(%)とした。膜厚は、触針式段差計(「Dektak3 ST」、アルバック株式会社(Veeco))を用いて3点測定した値の数平均値とした。
(Evaluation of transparency)
The transmittance of a polymer-coated glass substrate prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Tech, Ltd.). ) And UV-visible absorption spectrum method. Using a glass substrate without a film as a reference, a value converted to a film thickness of 10 μm was defined as transmittance (%). The film thickness was the number average value of the values measured at three points using a stylus profilometer ("Dektak 3 ST", ULVAC, Inc. (Veeco)).
(吸水率の測定)
実施例1、実施例2、比較例1及び比較例2で作製した重合体の単独膜を切断して吸水率測定用の試料を作製した。これを50℃で24時間乾燥したのち、デシケーター中で室温(25℃)まで冷却した。室温に冷却した試料の質量を精密天秤で測定してから、イオン交換水に24時間浸漬した。その後、試料の表面に付着している水分をキムタオルで拭き取り、試料の質量を精密天秤で測定した。イオン交換水に浸漬する前の試料の質量をW1、イオン交換水に浸漬した後の試料の質量をW2とし、以下の式に基づき吸水率を計算した。
(Measurement of water absorption)
Samples for measuring water absorption were prepared by cutting the polymer single membranes prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2. This was dried at 50 ° C. for 24 hours, and then cooled to room temperature (25 ° C.) in a desiccator. The mass of the sample cooled to room temperature was measured with a precision balance and then immersed in ion-exchanged water for 24 hours. Then, the moisture adhering to the surface of the sample was wiped off with a Kim towel, and the mass of the sample was measured with a precision balance. The water absorption was calculated based on the following equation, where W1 was the mass of the sample before being immersed in ion-exchanged water, and W2 was the mass of the sample after being immersed in ion-exchanged water.
表1に示すとおり、本実施形態の重合体は、従来の透明ポリイミドと同等又はそれ以上の透明性及び耐熱性を有し、かつ透明ポリイミドよりも吸水率が低かった。また、本実施形態の重合体の吸水率は、低吸水率の樹脂として知られるシクロオレフィンポリマーと同等であり、かつシクロオレフィンポリマーよりも熱分解温度が高かった。 As shown in Table 1, the polymer of this embodiment had transparency and heat resistance equal to or higher than those of conventional transparent polyimides, and had a lower water absorption than transparent polyimides. Moreover, the water absorption rate of the polymer of this embodiment is equivalent to the cycloolefin polymer known as resin with a low water absorption rate, and its thermal decomposition temperature was higher than that of the cycloolefin polymer.
以上より、本実施形態の重合体は、透明性、耐熱性及び低吸水性に優れていることがわかった。 As mentioned above, it turned out that the polymer of this embodiment is excellent in transparency, heat resistance, and low water absorption.
Claims (16)
〔一般式(I)において、Xは芳香環を含む2価の基を示し、Yは前記芳香環に結合した四級炭素原子を有する脂環を含む2価の基を示す。nは一般式(I)で示される構造単位の数を示す。〕 The polymer of Claim 1 containing the structural unit shown by the following general formula (I).
[In General Formula (I), X represents a divalent group containing an aromatic ring, and Y represents a divalent group containing an alicyclic ring having a quaternary carbon atom bonded to the aromatic ring. n represents the number of structural units represented by the general formula (I). ]
〔一般式(II−1)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕
〔一般式(II−2)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示し、Zは酸素原子又は下記一般式(III)で表わされる2価の基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕
〔一般式(III)中、R3及びR4はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示す。〕
〔一般式(II−3)中、R5はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。nはそれぞれ独立に、0〜4の整数を示す。〕 In the general formula (I), X is at least one divalent selected from the group consisting of the following general formula (II-1), the following general formula (II-2), and the following general formula (II-3). The polymer of any one of Claims 2-4 containing the group of these.
[In General Formula (II-1), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]
[In General Formula (II-2), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. ]
[In General Formula (III), R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]
[In General Formula (II-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently. ]
〔一般式(VI)においてYは、前記芳香環を含む化合物の前記芳香環と結合して四級炭素原子となる炭素原子を含む脂環を示す。〕 The production of the polymer according to any one of claims 1 to 6, comprising a reaction step of reacting a compound represented by the following general formula (VI) with a compound containing an aromatic ring in an acidic medium. Method.
[In General Formula (VI), Y represents an alicyclic ring containing a carbon atom that is bonded to the aromatic ring of the compound containing the aromatic ring to form a quaternary carbon atom. ]
〔一般式(VII−1)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕
〔一般式(VII−2)中、R1はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示し、R2はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示し、Zは酸素原子又は下記一般式(III)で示される2価の基を示す。mはそれぞれ独立に、0〜3の整数を示す。〕
〔一般式(III)中、R3及びR4はそれぞれ独立に、水素原子又は置換基を有していてもよい炭素数1〜30の炭化水素基を示す。〕
〔一般式(VII−3)中、R5はそれぞれ独立に、置換基を有していてもよい炭素数1〜30の炭化水素基を示す。nはそれぞれ独立に、0〜4の整数を示す。〕 The compound containing an aromatic ring contains at least one selected from the group consisting of the following general formula (VII-1), the following general formula (VII-2), and the following general formula (VII-3). A method for producing the polymer described in 1.
[In General Formula (VII-1), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. The C1-C30 hydrocarbon group which may have is shown. Each m independently represents an integer of 0 to 3. ]
[In General Formula (VII-2), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 independently represents a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom, and Z represents an oxygen atom or a divalent group represented by the following general formula (III). Each m independently represents an integer of 0 to 3. ]
[In General Formula (III), R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. ]
[In General Formula (VII-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n shows the integer of 0-4 each independently. ]
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