JPWO2019198709A1 - Polyimide resin, polyimide varnish and polyimide film - Google Patents

Polyimide resin, polyimide varnish and polyimide film Download PDF

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JPWO2019198709A1
JPWO2019198709A1 JP2020513407A JP2020513407A JPWO2019198709A1 JP WO2019198709 A1 JPWO2019198709 A1 JP WO2019198709A1 JP 2020513407 A JP2020513407 A JP 2020513407A JP 2020513407 A JP2020513407 A JP 2020513407A JP WO2019198709 A1 JPWO2019198709 A1 JP WO2019198709A1
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洋平 安孫子
洋平 安孫子
慎司 関口
慎司 関口
末永 修也
修也 末永
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Abstract

テトラカルボン酸二無水物に由来する構成単位A及びジアミンに由来する構成単位Bを有するポリイミド樹脂であって、構成単位Aが下記式(a−1)で表される化合物に由来する構成単位(A−1)と、下記式(a−2)で表される化合物に由来する構成単位(A−2)とを含み、構成単位Bが下記式(b−1)で表される化合物に由来する構成単位(B−1)を含み、構成単位Aが下記式(a−x)で表される化合物に由来する構成単位(A−X)を含まない、ポリイミド樹脂、並びに該ポリイミド樹脂を含むポリイミドワニス及びポリイミドフィルム。A polyimide resin having a structural unit A derived from tetracarboxylic acid dianhydride and a structural unit B derived from diamine, wherein the structural unit A is a structural unit derived from a compound represented by the following formula (a-1). A-1) and a structural unit (A-2) derived from the compound represented by the following formula (a-2) are included, and the structural unit B is derived from the compound represented by the following formula (b-1). Containing a polyimide resin and the polyimide resin, wherein the structural unit A does not contain a structural unit (AX) derived from a compound represented by the following formula (ax). Polyimide varnish and polyimide film.

Description

本発明はポリイミド樹脂、ポリイミドワニス及びポリイミドフィルムに関する。 The present invention relates to polyimide resins, polyimide varnishes and polyimide films.

一般に、ポリイミド樹脂は優れた機械的特性及び耐熱性を有することから、電気・電子部品等の分野において様々な利用が検討されている。例えば、液晶ディスプレイやOLEDディスプレイ等の画像表示装置に用いられるガラス基板を、デバイスの軽量化やフレキシブル化を目的として、プラスチック基板へ代替することが望まれており、当該プラスチック基板として適するポリイミドフィルムの研究が進められている。このような用途のポリイミドフィルムには無色透明性が求められる。 In general, since a polyimide resin has excellent mechanical properties and heat resistance, various uses are being studied in the fields of electrical and electronic parts and the like. For example, it is desired to replace a glass substrate used in an image display device such as a liquid crystal display or an OLED display with a plastic substrate for the purpose of reducing the weight and flexibility of the device. Research is underway. Colorless transparency is required for polyimide films for such applications.

ガラス支持体やシリコンウェハ上に塗布したワニスを加熱硬化してポリイミドフィルムを形成すると、ポリイミドフィルムに残留応力が生じる。ポリイミドフィルムの残留応力が大きいと、ガラス支持体やシリコンウェハが反ってしまうという問題が生じるため、ポリイミドフィルムには残留応力の低減も求められる。
特許文献1には、低残留応力のフィルムを与えるポリイミド樹脂として、テトラカルボン酸成分として4,4’−オキシジフタル酸二無水物を用い、ジアミン成分として数平均分子量1000のα、ω−アミノプロピルポリジメチルシロキサン及び4,4’−ジアミノジフェニルエーテルを用いて合成されたポリイミド樹脂が開示されている。
When a varnish applied on a glass support or a silicon wafer is heat-cured to form a polyimide film, residual stress is generated in the polyimide film. If the residual stress of the polyimide film is large, there is a problem that the glass support and the silicon wafer are warped. Therefore, the polyimide film is also required to reduce the residual stress.
In Patent Document 1, 4,4'-oxydiphthalic dianhydride is used as a tetracarboxylic dian component as a polyimide resin that gives a film having a low residual stress, and α, ω-aminopropyl poly having a number average molecular weight of 1000 is used as a diamine component. A polyimide resin synthesized using dimethylsiloxane and 4,4'-diaminodiphenyl ether is disclosed.

特開2005−232383号公報Japanese Unexamined Patent Publication No. 2005-223383

上述のように、ポリイミドフィルムには無色透明性や低残留応力が要求されるが、優れた機械的特性及び耐熱性を維持しながら、それら特性を向上させることは容易ではない。
本発明はこのような状況に鑑みてなされたものであり、本発明の課題は、機械的特性、耐熱性、及び無色透明性に優れ、更に残留応力が低いフィルムの形成が可能なポリイミド樹脂、並びに該ポリイミド樹脂を含むポリイミドワニス及びポリイミドフィルムを提供することにある。
As described above, the polyimide film is required to have colorless transparency and low residual stress, but it is not easy to improve these properties while maintaining excellent mechanical properties and heat resistance.
The present invention has been made in view of such a situation, and the subject of the present invention is a polyimide resin capable of forming a film having excellent mechanical properties, heat resistance, colorless transparency, and low residual stress. Another object of the present invention is to provide a polyimide varnish and a polyimide film containing the polyimide resin.

本発明者らは、特定の構成単位の組み合わせを含むポリイミド樹脂が上記課題を解決できることを見出し、発明を完成させるに至った。 The present inventors have found that a polyimide resin containing a combination of specific structural units can solve the above-mentioned problems, and have completed the invention.

即ち、本発明は、下記の[1]〜[5]に関する。
[1]
テトラカルボン酸二無水物に由来する構成単位A及びジアミンに由来する構成単位Bを有するポリイミド樹脂であって、
構成単位Aが下記式(a−1)で表される化合物に由来する構成単位(A−1)と、下記式(a−2)で表される化合物に由来する構成単位(A−2)とを含み、
構成単位Bが下記式(b−1)で表される化合物に由来する構成単位(B−1)を含み、
構成単位Aが下記式(a−x)で表される化合物に由来する構成単位(A−X)を含まない、ポリイミド樹脂。

Figure 2019198709
That is, the present invention relates to the following [1] to [5].
[1]
A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine.
A structural unit (A-1) in which the structural unit A is derived from a compound represented by the following formula (a-1) and a structural unit (A-2) derived from a compound represented by the following formula (a-2). Including and
The structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1).
A polyimide resin in which the structural unit A does not contain a structural unit (AX) derived from a compound represented by the following formula (ax).
Figure 2019198709

[2]
構成単位A中における構成単位(A−1)の比率が50〜90モル%であり、
構成単位A中における構成単位(A−2)の比率が10〜50モル%である、上記[1]に記載のポリイミド樹脂。
[3]
構成単位B中における構成単位(B−1)の比率が50モル%以上である、上記[1]又は[2]に記載のポリイミド樹脂。
[4]
上記[1]〜[3]のいずれかに記載のポリイミド樹脂が有機溶媒に溶解してなるポリイミドワニス。
[5]
上記[1]〜[3]のいずれかに記載のポリイミド樹脂を含む、ポリイミドフィルム。
[2]
The ratio of the structural unit (A-1) in the structural unit A is 50 to 90 mol%, and the ratio is 50 to 90 mol%.
The polyimide resin according to the above [1], wherein the ratio of the structural unit (A-2) in the structural unit A is 10 to 50 mol%.
[3]
The polyimide resin according to the above [1] or [2], wherein the ratio of the structural unit (B-1) in the structural unit B is 50 mol% or more.
[4]
A polyimide varnish in which the polyimide resin according to any one of [1] to [3] above is dissolved in an organic solvent.
[5]
A polyimide film containing the polyimide resin according to any one of the above [1] to [3].

本発明によれば、機械的特性、耐熱性、及び無色透明性に優れ、更に残留応力が低いフィルムを形成することができる。 According to the present invention, it is possible to form a film having excellent mechanical properties, heat resistance, colorless transparency, and low residual stress.

[ポリイミド樹脂]
本発明のポリイミド樹脂は、テトラカルボン酸二無水物に由来する構成単位A及びジアミンに由来する構成単位Bを有し、構成単位Aが下記式(a−1)で表される化合物に由来する構成単位(A−1)と、下記式(a−2)で表される化合物に由来する構成単位(A−2)とを含み、構成単位Bが下記式(b−1)で表される化合物に由来する構成単位(B−1)を含み、構成単位Aが下記式(a−x)で表される化合物に由来する構成単位(A−X)を含まない。

Figure 2019198709
[Polyimide resin]
The polyimide resin of the present invention has a structural unit A derived from tetracarboxylic acid dianhydride and a structural unit B derived from diamine, and the structural unit A is derived from a compound represented by the following formula (a-1). The structural unit (A-1) and the structural unit (A-2) derived from the compound represented by the following formula (a-2) are included, and the structural unit B is represented by the following formula (b-1). It contains a structural unit (B-1) derived from a compound, and the structural unit A does not include a structural unit (AX) derived from a compound represented by the following formula (ax).
Figure 2019198709

<構成単位A>
構成単位Aは、ポリイミド樹脂に占めるテトラカルボン酸二無水物に由来する構成単位であって、下記式(a−1)で表される化合物に由来する構成単位(A−1)と、下記式(a−2)で表される化合物に由来する構成単位(A−2)とを含み、下記式(a−x)で表される化合物に由来する構成単位(A−X)を含まない。

Figure 2019198709
<Structural unit A>
The structural unit A is a structural unit derived from the tetracarboxylic dianhydride occupying the polyimide resin, and is a structural unit (A-1) derived from the compound represented by the following formula (a-1) and the following formula. It contains the structural unit (A-2) derived from the compound represented by (a-2), and does not include the structural unit (AX) derived from the compound represented by the following formula (ax).
Figure 2019198709

式(a−1)で表される化合物は、ノルボルナン−2−スピロ−α−シクロペンタノン−α’−スピロ−2’’−ノルボルナン−5,5’’,6,6’’−テトラカルボン酸二無水物である。 The compound represented by the formula (a-1) is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic. It is an acid dianhydride.

式(a−2)で表される化合物は、ビフェニルテトラカルボン酸二無水物(BPDA)であり、その具体例としては、下記式(a−2s)で表される3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(s−BPDA)、下記式(a−2a)で表される2,3,3’,4’−ビフェニルテトラカルボン酸二無水物(a−BPDA)、下記式(a−2i)で表される2,2’,3,3’−ビフェニルテトラカルボン酸二無水物(i−BPDA)が挙げられる。

Figure 2019198709
The compound represented by the formula (a-2) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof are 3,3', 4, represented by the following formula (a-2s). 4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a-2a), Examples thereof include 2,2', 3,3'-biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a-2i).
Figure 2019198709

構成単位Aが構成単位(A−1)と構成単位(A−2)の両方を含むことによって、フィルムの機械的特性、耐熱性及び無色透明性が向上し、残留応力が低下する。 When the structural unit A includes both the structural unit (A-1) and the structural unit (A-2), the mechanical properties, heat resistance and colorless transparency of the film are improved, and the residual stress is reduced.

式(a−x)で表される化合物は、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物である。
本発明においては、構成単位Aは式(a−x)で表される化合物に由来する構成単位(A−X)を含まない。即ち、本発明のポリイミド樹脂は構成単位(A−X)を含まない。
The compound represented by the formula (ax) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
In the present invention, the structural unit A does not include the structural unit (AX) derived from the compound represented by the formula (ax). That is, the polyimide resin of the present invention does not contain a structural unit (AX).

構成単位A中における構成単位(A−1)の比率は、好ましくは50〜90モル%であり、より好ましくは55〜85モル%であり、更に好ましくは60〜80モル%である。
構成単位A中における構成単位(A−2)の比率は、好ましくは10〜50モル%であり、より好ましくは15〜45モル%であり、更に好ましくは20〜40モル%である。
構成単位A中における構成単位(A−1)及び(A−2)の合計の比率は、好ましくは50モル%以上であり、より好ましくは70モル%以上であり、更に好ましくは90モル%以上であり、特に好ましくは99モル%以上である。構成単位(A−1)及び(A−2)の合計の比率の上限値は特に限定されず、即ち、100モル%である。構成単位Aは構成単位(A−1)と構成単位(A−2)とのみからなっていてもよい。
The ratio of the structural unit (A-1) in the structural unit A is preferably 50 to 90 mol%, more preferably 55 to 85 mol%, and further preferably 60 to 80 mol%.
The ratio of the structural unit (A-2) in the structural unit A is preferably 10 to 50 mol%, more preferably 15 to 45 mol%, still more preferably 20 to 40 mol%.
The total ratio of the structural units (A-1) and (A-2) in the structural unit A is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more. It is particularly preferably 99 mol% or more. The upper limit of the total ratio of the structural units (A-1) and (A-2) is not particularly limited, that is, 100 mol%. The structural unit A may consist only of the structural unit (A-1) and the structural unit (A-2).

構成単位Aは、構成単位(A−1)及び(A−2)以外の構成単位を含んでもよい(ただし、構成単位(A−X)を除く)。そのような構成単位を与えるテトラカルボン酸二無水物としては、特に限定されないが、ピロメリット酸二無水物、9,9’−ビス(3,4−ジカルボキシフェニル)フルオレン二無水物、及び4,4’−(ヘキサフルオロイソプロピリデン)ジフタル酸無水物等の芳香族テトラカルボン酸二無水物(ただし、式(a−2)で表される化合物を除く);1,2,3,4−シクロブタンテトラカルボン酸二無水物等の脂環式テトラカルボン酸二無水物(ただし、式(a−1)で表される化合物及び式(a−x)で表される化合物を除く);並びに1,2,3,4−ブタンテトラカルボン酸二無水物等の脂肪族テトラカルボン酸二無水物が挙げられる。
なお、本明細書において、芳香族テトラカルボン酸二無水物とは芳香環を1つ以上含むテトラカルボン酸二無水物を意味し、脂環式テトラカルボン酸二無水物とは脂環を1つ以上含み、かつ芳香環を含まないテトラカルボン酸二無水物を意味し、脂肪族テトラカルボン酸二無水物とは芳香環も脂環も含まないテトラカルボン酸二無水物を意味する。
構成単位Aに任意に含まれる構成単位(A−1)及び(A−2)以外の構成単位は、1種でもよいし、2種以上であってもよい。
The structural unit A may include a structural unit other than the structural units (A-1) and (A-2) (however, the structural unit (AX) is excluded). The tetracarboxylic dianhydride giving such a constituent unit is not particularly limited, but is pyromellitic dianhydride, 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride, and 4 , 4'-(Hexafluoroisopropyridene) Aromatic tetracarboxylic dianhydride such as diphthalic dianhydride (excluding the compound represented by the formula (a-2)); 1,2,3,4- An alicyclic tetracarboxylic dianhydride such as cyclobutanetetracarboxylic dianhydride (excluding compounds represented by the formula (a-1) and compounds represented by the formula (ax)); and 1 , 2,3,4-Butanetetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydrides can be mentioned.
In the present specification, the aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings, and the alicyclic tetracarboxylic dianhydride has one alicyclic ring. It means a tetracarboxylic acid dianhydride containing the above and does not contain an aromatic ring, and the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
The structural units other than the structural units (A-1) and (A-2) arbitrarily included in the structural unit A may be one type or two or more types.

<構成単位B>
構成単位Bは、ポリイミド樹脂に占めるジアミンに由来する構成単位であって、下記式(b−1)で表される化合物に由来する構成単位(B−1)を含む。

Figure 2019198709
<Structural unit B>
The structural unit B is a structural unit derived from a diamine in the polyimide resin, and includes a structural unit (B-1) derived from a compound represented by the following formula (b-1).
Figure 2019198709

式(b−1)で表される化合物は、2,2’−ビス(トリフルオロメチル)ベンジジンである。
構成単位Bが構成単位(B−1)を含むことによって、フィルムの無色透明性及び耐熱性が向上し、残留応力が低下する。
The compound represented by the formula (b-1) is 2,2'-bis (trifluoromethyl) benzidine.
When the structural unit B includes the structural unit (B-1), the colorless transparency and heat resistance of the film are improved, and the residual stress is reduced.

構成単位B中における構成単位(B−1)の比率は、好ましくは50モル%以上であり、より好ましくは70モル%以上であり、更に好ましくは90モル%以上であり、特に好ましくは99モル%以上である。構成単位(B−1)の比率の上限値は特に限定されず、即ち、100モル%である。構成単位Bは構成単位(B−1)のみからなっていてもよい。 The ratio of the structural unit (B-1) in the structural unit B is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol. % Or more. The upper limit of the ratio of the structural unit (B-1) is not particularly limited, that is, 100 mol%. The structural unit B may consist of only the structural unit (B-1).

構成単位Bは構成単位(B−1)以外の構成単位を含んでもよい。そのような構成単位を与えるジアミンとしては、特に限定されないが、1,4−フェニレンジアミン、p−キシリレンジアミン、3,5−ジアミノ安息香酸、1,5−ジアミノナフタレン、2,2’−ジメチルビフェニル−4,4’−ジアミン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルメタン、2,2−ビス(4−アミノフェニル)ヘキサフルオロプロパン、4,4’−ジアミノジフェニルスルホン、4,4’−ジアミノベンズアニリド、1−(4−アミノフェニル)−2,3−ジヒドロ−1,3,3−トリメチル−1H−インデン−5−アミン、α,α’−ビス(4−アミノフェニル)−1,4−ジイソプロピルベンゼン、N,N’−ビス(4−アミノフェニル)テレフタルアミド、4,4’−ビス(4−アミノフェノキシ)ビフェニル、2,2−ビス〔4−(4−アミノフェノキシ)フェニル〕プロパン、2,2−ビス(4−(4−アミノフェノキシ)フェニル)ヘキサフルオロプロパン、及び9,9−ビス(4−アミノフェニル)フルオレン等の芳香族ジアミン(ただし、式(b−1)で表される化合物を除く);1,3−ビス(アミノメチル)シクロヘキサン及び1,4−ビス(アミノメチル)シクロヘキサン等の脂環式ジアミン;並びにエチレンジアミン及びヘキサメチレンジアミン等の脂肪族ジアミンが挙げられる。
なお、本明細書において、芳香族ジアミンとは芳香環を1つ以上含むジアミンを意味し、脂環式ジアミンとは脂環を1つ以上含み、かつ芳香環を含まないジアミンを意味し、脂肪族ジアミンとは芳香環も脂環も含まないジアミンを意味する。
構成単位Bに任意に含まれる構成単位(B−1)以外の構成単位は、1種でもよいし、2種以上であってもよい。
The structural unit B may include a structural unit other than the structural unit (B-1). The diamine that provides such a constituent unit is not particularly limited, but is limited to 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, and 2,2'-dimethyl. Biphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diaminodiphenylsulfone, 4 , 4'-diaminobenzanilide, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, α, α'-bis (4-aminophenyl) ) -1,4-Diisopropylbenzene, N, N'-bis (4-aminophenyl) terephthalamide, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-amino) Aromatic diamines such as phenoxy) phenyl] propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, and 9,9-bis (4-aminophenyl) fluorene (where the formula (b) -1)); alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine. Diamine can be mentioned.
In the present specification, the aromatic diamine means a diamine containing one or more aromatic rings, and the alicyclic diamine means a diamine containing one or more alicyclic rings and not containing an aromatic ring, and is a fat. The group diamine means a diamine that does not contain an aromatic ring or an alicyclic ring.
The structural unit other than the structural unit (B-1) arbitrarily included in the structural unit B may be one type or two or more types.

本発明のポリイミド樹脂の数平均分子量は、得られるポリイミドフィルムの機械的強度の観点から、好ましくは5,000〜100,000である。なお、ポリイミド樹脂の数平均分子量は、例えば、ゲルろ過クロマトグラフィー測定による標準ポリメチルメタクリレート(PMMA)換算値より求めることができる。 The number average molecular weight of the polyimide resin of the present invention is preferably 5,000 to 100,000 from the viewpoint of the mechanical strength of the obtained polyimide film. The number average molecular weight of the polyimide resin can be obtained from, for example, a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography.

本発明のポリイミド樹脂は、ポリイミド鎖(構成単位Aと構成単位Bとがイミド結合してなる構造)以外の構造を含んでもよい。ポリイミド樹脂中に含まれうるポリイミド鎖以外の構造としては、例えばアミド結合を含む構造等が挙げられる。
本発明のポリイミド樹脂は、ポリイミド鎖(構成単位Aと構成単位Bとがイミド結合してなる構造)を主たる構造として含むことが好ましい。したがって、本発明のポリイミド樹脂中に占めるポリイミド鎖の比率は、好ましくは50質量%以上であり、より好ましくは70質量%以上であり、更に好ましくは90質量%以上であり、特に好ましくは99質量%以上である。
The polyimide resin of the present invention may contain a structure other than the polyimide chain (a structure in which the structural unit A and the structural unit B are imide-bonded). Examples of the structure other than the polyimide chain that can be contained in the polyimide resin include a structure containing an amide bond.
The polyimide resin of the present invention preferably contains a polyimide chain (a structure in which a structural unit A and a structural unit B are imide-bonded) as a main structure. Therefore, the ratio of the polyimide chain to the polyimide resin of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 99% by mass. % Or more.

本発明のポリイミド樹脂を用いることで、機械的特性、耐熱性、及び無色透明性に優れ、更に残留応力が低いフィルムを形成することができ、当該フィルムの有する好適な物性値は以下の通りである。 By using the polyimide resin of the present invention, it is possible to form a film having excellent mechanical properties, heat resistance, colorless transparency, and low residual stress, and suitable physical property values of the film are as follows. is there.

引張弾性率は、好ましくは2.5GPa以上であり、より好ましくは3.0GPa以上であり、更に好ましくは3.5GPa以上である。
引張強度は、好ましくは100MPa以上であり、より好ましくは120MPa以上であり、更に好ましくは150MPa以上である。
ガラス転移温度(Tg)は、好ましくは320℃以上であり、より好ましくは350℃以上であり、更に好ましくは365℃以上である。
全光線透過率は、厚さ10μmのフィルムとした際に、好ましくは88%以上であり、より好ましくは89%以上であり、更に好ましくは90%以上である。
イエローインデックス(YI)は、厚さ10μmのフィルムとした際に、好ましくは3.5以下であり、より好ましくは3.0以下であり、更に好ましくは2.8以下である。
残留応力は、好ましくは18.0MPa以下であり、より好ましくは17.0MPa以下であり、更に好ましくは15.0MPa以下である。
なお、本発明における上述の物性値は、具体的には実施例に記載の方法で測定することができる。
The tensile elastic modulus is preferably 2.5 GPa or more, more preferably 3.0 GPa or more, and further preferably 3.5 GPa or more.
The tensile strength is preferably 100 MPa or more, more preferably 120 MPa or more, and further preferably 150 MPa or more.
The glass transition temperature (Tg) is preferably 320 ° C. or higher, more preferably 350 ° C. or higher, and even more preferably 365 ° C. or higher.
The total light transmittance is preferably 88% or more, more preferably 89% or more, and further preferably 90% or more when the film has a thickness of 10 μm.
The yellow index (YI) is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.8 or less when the film has a thickness of 10 μm.
The residual stress is preferably 18.0 MPa or less, more preferably 17.0 MPa or less, and further preferably 15.0 MPa or less.
The above-mentioned physical property values in the present invention can be specifically measured by the method described in Examples.

[ポリイミド樹脂の製造方法]
本発明のポリイミド樹脂は、上述の構成単位(A−1)を与える化合物及び上述の構成単位(A−2)を与える化合物を含み、上述の構成単位(A−X)を与える化合物を含まないテトラカルボン酸成分と、上述の構成単位(B−1)を与える化合物を含むジアミン成分とを反応させることにより製造することができる。
[Manufacturing method of polyimide resin]
The polyimide resin of the present invention contains a compound giving the above-mentioned structural unit (A-1) and a compound giving the above-mentioned structural unit (A-2), and does not contain a compound giving the above-mentioned structural unit (AX). It can be produced by reacting a tetracarboxylic acid component with a diamine component containing the compound giving the above-mentioned structural unit (B-1).

構成単位(A−1)を与える化合物としては、式(a−1)で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式(a−1)で表されるテトラカルボン酸二無水物に対応するテトラカルボン酸(即ち、ノルボルナン−2−スピロ−α−シクロペンタノン−α’−スピロ−2’’−ノルボルナン−5,5’’,6,6’’−テトラカルボン酸)、及び当該テトラカルボン酸のアルキルエステルが挙げられる。構成単位(A−1)を与える化合物としては、式(a−1)で表される化合物(即ち、二無水物)が好ましい。
同様に、構成単位(A−2)を与える化合物としては、式(a−2)で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式(a−2)で表されるテトラカルボン酸二無水物に対応するテトラカルボン酸及び当該テトラカルボン酸のアルキルエステルが挙げられる。構成単位(A−2)を与える化合物としては、式(a−2)で表される化合物(即ち、二無水物)が好ましい。
本発明において、テトラカルボン酸成分は構成単位(A−X)を与える化合物を含まない。したがって、テトラカルボン酸成分は式(a−x)で表される化合物を含まず、同じ構成単位を与える範囲でその誘導体も含まない。当該誘導体としては、式(a−x)で表されるテトラカルボン酸二無水物に対応するテトラカルボン酸及び当該テトラカルボン酸のアルキルエステルが挙げられる。
Examples of the compound giving the structural unit (A-1) include the compound represented by the formula (a-1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given. The derivative is a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1) (that is, norbornan-2-spiro-α-cyclopentanone-α'-spiro-2''. -Norbornane-5,5 ", 6,6"-tetracarboxylic acid), and alkyl esters of the tetracarboxylic acid. As the compound giving the structural unit (A-1), the compound represented by the formula (a-1) (that is, dianhydride) is preferable.
Similarly, the compound giving the structural unit (A-2) includes a compound represented by the formula (a-2), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given. .. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-2) and an alkyl ester of the tetracarboxylic acid. As the compound giving the structural unit (A-2), the compound represented by the formula (a-2) (that is, dianhydride) is preferable.
In the present invention, the tetracarboxylic acid component does not contain a compound that gives a structural unit (AX). Therefore, the tetracarboxylic acid component does not contain the compound represented by the formula (ax), and does not contain its derivative as long as it gives the same structural unit. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (ax) and an alkyl ester of the tetracarboxylic acid.

テトラカルボン酸成分は、構成単位(A−1)を与える化合物を、好ましくは50〜90モル%含み、より好ましくは55〜85モル%含み、更に好ましくは60〜80モル%含む。
テトラカルボン酸成分は、構成単位(A−2)を与える化合物を、好ましくは10〜50モル%含み、より好ましくは15〜45モル%含み、更に好ましくは20〜40モル%含む。
テトラカルボン酸成分は、構成単位(A−1)を与える化合物及び構成単位(A−2)を与える化合物を合計で、好ましくは50モル%以上含み、より好ましくは70モル%以上含み、更に好ましくは90モル%以上含み、特に好ましくは99モル%以上含む。構成単位(A−1)を与える化合物及び構成単位(A−2)を与える化合物の合計の含有量の上限値は特に限定されず、即ち、100モル%である。テトラカルボン酸成分は構成単位(A−1)を与える化合物と構成単位(A−2)を与える化合物とのみからなっていてもよい。
The tetracarboxylic acid component preferably contains 50 to 90 mol%, more preferably 55 to 85 mol%, and further preferably 60 to 80 mol% of the compound giving the structural unit (A-1).
The tetracarboxylic acid component preferably contains the compound giving the structural unit (A-2) in an amount of 10 to 50 mol%, more preferably 15 to 45 mol%, still more preferably 20 to 40 mol%.
The tetracarboxylic acid component contains, in total, a compound giving the structural unit (A-1) and a compound giving the structural unit (A-2) in an amount of preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably. Contains 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the total content of the compound giving the structural unit (A-1) and the compound giving the structural unit (A-2) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may consist only of a compound giving a structural unit (A-1) and a compound giving a structural unit (A-2).

テトラカルボン酸成分は、構成単位(A−1)を与える化合物及び構成単位(A−2)を与える化合物以外の化合物を含んでもよく(ただし、構成単位(A−X)を与える化合物を除く)、当該化合物としては、上述の芳香族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物、及び脂肪族テトラカルボン酸二無水物、並びにそれらの誘導体(テトラカルボン酸、テトラカルボン酸のアルキルエステル等)が挙げられる。
テトラカルボン酸成分に任意に含まれる構成単位(A−1)を与える化合物及び構成単位(A−2)を与える化合物以外の化合物は、1種でもよいし、2種以上であってもよい。
The tetracarboxylic acid component may contain a compound other than the compound giving the structural unit (A-1) and the compound giving the structural unit (A-2) (however, excluding the compound giving the structural unit (AX)). Examples of the compound include the above-mentioned aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride, and derivatives thereof (tetracarboxylic dian, tetracarboxylic dianoxide). (Alkyl ester, etc.) can be mentioned.
The compound other than the compound giving the constituent unit (A-1) arbitrarily contained in the tetracarboxylic acid component and the compound giving the constituent unit (A-2) may be one kind or two or more kinds.

構成単位(B−1)を与える化合物としては、式(b−1)で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式(b−1)で表されるジアミンに対応するジイソシアネートが挙げられる。構成単位(B−1)を与える化合物としては、式(b−1)で表される化合物(即ち、ジアミン)が好ましい。 Examples of the compound giving the structural unit (B-1) include, but are not limited to, the compound represented by the formula (b-1), and may be a derivative thereof as long as the same structural unit is given. Examples of the derivative include diisocyanates corresponding to the diamine represented by the formula (b-1). As the compound that gives the structural unit (B-1), the compound represented by the formula (b-1) (that is, a diamine) is preferable.

ジアミン成分は、構成単位(B−1)を与える化合物を、好ましくは50モル%以上含み、より好ましくは70モル%以上含み、更に好ましくは90モル%以上含み、特に好ましくは99モル%以上含む。構成単位(B−1)を与える化合物の含有量の上限値は特に限定されず、即ち、100モル%である。ジアミン成分は構成単位(B−1)を与える化合物のみからなっていてもよい。 The diamine component contains the compound giving the structural unit (B-1) in an amount of preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably 99 mol% or more. .. The upper limit of the content of the compound giving the structural unit (B-1) is not particularly limited, that is, 100 mol%. The diamine component may consist only of the compound giving the structural unit (B-1).

ジアミン成分は構成単位(B−1)を与える化合物以外の化合物を含んでもよく、当該化合物としては、上述の芳香族ジアミン、脂環式ジアミン、及び脂肪族ジアミン、並びにそれらの誘導体(ジイソシアネート等)が挙げられる。
ジアミン成分に任意に含まれる構成単位(B−1)を与える化合物以外の化合物は、1種でもよいし、2種以上であってもよい。
The diamine component may contain a compound other than the compound giving the structural unit (B-1), and the compound includes the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and derivatives thereof (diisocyanate, etc.). Can be mentioned.
The compound other than the compound that gives the structural unit (B-1) arbitrarily contained in the diamine component may be one kind or two or more kinds.

本発明において、ポリイミド樹脂の製造に用いるテトラカルボン酸成分とジアミン成分の仕込み量比は、テトラカルボン酸成分1モルに対してジアミン成分が0.9〜1.1モルであることが好ましい。 In the present invention, the charging amount ratio of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component.

また、本発明において、ポリイミド樹脂の製造には、前述のテトラカルボン酸成分及びジアミン成分の他に、末端封止剤を用いてもよい。末端封止剤としてはモノアミン類あるいはジカルボン酸類が好ましい。導入される末端封止剤の仕込み量としては、テトラカルボン酸成分1モルに対して0.0001〜0.1モルが好ましく、特に0.001〜0.06モルが好ましい。モノアミン類末端封止剤としては、例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ベンジルアミン、4−メチルベンジルアミン、4−エチルベンジルアミン、4−ドデシルベンジルアミン、3−メチルベンジルアミン、3−エチルベンジルアミン、アニリン、3−メチルアニリン、4−メチルアニリン等が推奨される。これらのうち、ベンジルアミン、アニリンが好適に使用できる。ジカルボン酸類末端封止剤としては、ジカルボン酸類が好ましく、その一部を閉環していてもよい。例えば、フタル酸、無水フタル酸、4−クロロフタル酸、テトラフルオロフタル酸、2,3−ベンゾフェノンジカルボン酸、3,4−ベンゾフェノンジカルボン酸、シクロヘキサン−1,2−ジカルボン酸、シクロペンタン−1,2−ジカルボン酸、4−シクロヘキセン−1,2−ジカルボン酸等が推奨される。これらのうち、フタル酸、無水フタル酸が好適に使用できる。 Further, in the present invention, in addition to the above-mentioned tetracarboxylic acid component and diamine component, an end-capping agent may be used for producing the polyimide resin. As the terminal encapsulant, monoamines or dicarboxylic acids are preferable. The amount of the terminal encapsulant to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. Examples of the monoamine terminal encapsulant include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-. Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Of these, benzylamine and aniline can be preferably used. As the dicarboxylic acid terminal encapsulant, dicarboxylic acids are preferable, and a part thereof may be ring-closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2 -Dicarboxylic acid, 4-cyclohexane-1,2-dicarboxylic acid and the like are recommended. Of these, phthalic acid and phthalic anhydride can be preferably used.

前述のテトラカルボン酸成分とジアミン成分とを反応させる方法には特に制限はなく、公知の方法を用いることができる。
具体的な反応方法としては、(1)テトラカルボン酸成分、ジアミン成分、及び反応溶剤を反応器に仕込み、室温〜80℃で0.5〜30時間撹拌し、その後に昇温してイミド化反応を行う方法、(2)ジアミン成分及び反応溶剤を反応器に仕込んで溶解させた後、テトラカルボン酸成分を仕込み、必要に応じて室温〜80℃で0.5〜30時間撹拌し、その後に昇温してイミド化反応を行う方法、(3)テトラカルボン酸成分、ジアミン成分、及び反応溶剤を反応器に仕込み、直ちに昇温してイミド化反応を行う方法等が挙げられる。
The method for reacting the above-mentioned tetracarboxylic acid component with the diamine component is not particularly limited, and a known method can be used.
Specific reaction methods include (1) charging a tetracarboxylic dian component, a diamine component, and a reaction solvent into a reactor, stirring at room temperature to 80 ° C. for 0.5 to 30 hours, and then raising the temperature to imidize. Method of carrying out the reaction, (2) After charging the diamine component and the reaction solvent into the reactor and dissolving them, the tetracarboxylic acid component is charged, and if necessary, the mixture is stirred at room temperature to 80 ° C. for 0.5 to 30 hours, and then. Examples thereof include a method of carrying out an imidization reaction by raising the temperature to (3) a method of charging a tetracarboxylic dian component, a diamine component and a reaction solvent into a reactor and immediately raising the temperature to carry out the imidization reaction.

ポリイミド樹脂の製造に用いられる反応溶剤は、イミド化反応を阻害せず、生成するポリイミドを溶解できるものであればよい。例えば、非プロトン性溶剤、フェノール系溶剤、エーテル系溶剤、カーボネート系溶剤等が挙げられる。 The reaction solvent used in the production of the polyimide resin may be one that does not inhibit the imidization reaction and can dissolve the produced polyimide. For example, an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent and the like can be mentioned.

非プロトン性溶剤の具体例としては、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン、N−メチルカプロラクタム、1,3−ジメチルイミダゾリジノン、テトラメチル尿素等のアミド系溶剤、γ−ブチロラクトン、γ−バレロラクトン等のラクトン系溶剤、ヘキサメチルホスホリックアミド、ヘキサメチルホスフィントリアミド等の含リン系アミド系溶剤、ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶剤、アセトン、シクロヘキサノン、メチルシクロヘキサノン等のケトン系溶剤、ピコリン、ピリジン等のアミン系溶剤、酢酸(2−メトキシ−1−メチルエチル)等のエステル系溶剤等が挙げられる。 Specific examples of the aprotonic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea and the like. Amide solvents, lactone solvents such as γ-butyrolactone and γ-valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphintriamide, and sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane. Examples thereof include based solvents, ketone solvents such as acetone, cyclohexanone and methylcyclohexanone, amine solvents such as picolin and pyridine, and ester solvents such as acetic acid (2-methoxy-1-methylethyl).

フェノール系溶剤の具体例としては、フェノール、o−クレゾール、m−クレゾール、p−クレゾール、2,3−キシレノール、2,4−キシレノール、2,5−キシレノール、2,6−キシレノール、3,4−キシレノール、3,5−キシレノール等が挙げられる。
エーテル系溶剤の具体例としては、1,2−ジメトキシエタン、ビス(2−メトキシエチル)エーテル、1,2−ビス(2−メトキシエトキシ)エタン、ビス〔2−(2−メトキシエトキシ)エチル〕エーテル、テトラヒドロフラン、1,4−ジオキサン等が挙げられる。
また、カーボネート系溶剤の具体的な例としては、ジエチルカーボネート、メチルエチルカーボネート、エチレンカーボネート、プロピレンカーボネート等が挙げられる。
上記反応溶剤の中でも、アミド系溶剤又はラクトン系溶剤が好ましい。また、上記の反応溶剤は単独で又は2種以上混合して用いてもよい。
Specific examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. -Xylenol, 3,5-xylenol and the like can be mentioned.
Specific examples of the ether solvent include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
Specific examples of the carbonate solvent include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
Among the above reaction solvents, an amide solvent or a lactone solvent is preferable. Moreover, the above-mentioned reaction solvent may be used alone or in mixture of 2 or more types.

イミド化反応では、ディーンスターク装置などを用いて、製造時に生成する水を除去しながら反応を行うことが好ましい。このような操作を行うことで、重合度及びイミド化率をより上昇させることができる。 In the imidization reaction, it is preferable to carry out the reaction while removing water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.

上記のイミド化反応においては、公知のイミド化触媒を用いることができる。イミド化触媒としては、塩基触媒又は酸触媒が挙げられる。
塩基触媒としては、ピリジン、キノリン、イソキノリン、α−ピコリン、β−ピコリン、2,4−ルチジン、2,6−ルチジン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリエチレンジアミン、イミダゾール、N,N−ジメチルアニリン、N,N−ジエチルアニリン等の有機塩基触媒、水酸化カリウムや水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウム等の無機塩基触媒が挙げられる。
また、酸触媒としては、クロトン酸、アクリル酸、トランス−3−ヘキセノイック酸、桂皮酸、安息香酸、メチル安息香酸、オキシ安息香酸、テレフタル酸、ベンゼンスルホン酸、パラトルエンスルホン酸、ナフタレンスルホン酸等が挙げられる。上記のイミド化触媒は単独で又は2種以上を組み合わせて用いてもよい。
上記のうち、取り扱い性の観点から、塩基触媒を用いることが好ましく、有機塩基触媒を用いることがより好ましく、トリエチルアミンを用いることが更に好ましく、トリエチルアミンとトリエチレンジアミンを組み合わせて用いること特に好ましい。
In the above imidization reaction, a known imidization catalyst can be used. Examples of the imidization catalyst include a base catalyst and an acid catalyst.
Base catalysts include pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N, N. Examples thereof include organic base catalysts such as -dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid and the like. Can be mentioned. The above-mentioned imidization catalyst may be used alone or in combination of two or more.
Of the above, from the viewpoint of handleability, it is preferable to use a base catalyst, more preferably an organic base catalyst, further preferably triethylamine, and particularly preferably a combination of triethylamine and triethylenediamine.

イミド化反応の温度は、反応率及びゲル化等の抑制の観点から、好ましくは120〜250℃、より好ましくは160〜200℃である。また、反応時間は、生成水の留出開始後、好ましくは0.5〜10時間である。 The temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 200 ° C. from the viewpoint of suppressing the reaction rate and gelation. The reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.

[ポリイミドワニス]
本発明のポリイミドワニスは、本発明のポリイミド樹脂が有機溶媒に溶解してなるものである。即ち、本発明のポリイミドワニスは、本発明のポリイミド樹脂及び有機溶媒を含み、当該ポリイミド樹脂は当該有機溶媒に溶解している。
有機溶媒はポリイミド樹脂が溶解するものであればよく、特に限定されないが、ポリイミド樹脂の製造に用いられる反応溶剤として上述した化合物を、単独又は2種以上を混合して用いることが好ましい。
本発明のポリイミドワニスは、重合法により得られるポリイミド樹脂が反応溶剤に溶解したポリイミド溶液そのものであってもよいし、又は当該ポリイミド溶液に対して更に希釈溶剤を追加したものであってもよい。
[Polyimide varnish]
The polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
The organic solvent may be any one that dissolves the polyimide resin, and is not particularly limited, but it is preferable to use the above-mentioned compounds alone or in combination of two or more as the reaction solvent used for producing the polyimide resin.
The polyimide varnish of the present invention may be a polyimide solution itself in which a polyimide resin obtained by a polymerization method is dissolved in a reaction solvent, or a diluting solvent may be further added to the polyimide solution.

本発明のポリイミド樹脂は溶媒溶解性を有しているため、室温で安定な高濃度のワニスとすることができる。本発明のポリイミドワニスは、本発明のポリイミド樹脂を5〜40質量%含むことが好ましく、10〜30質量%含むことがより好ましい。ポリイミドワニスの粘度は1〜200Pa・sが好ましく、5〜150Pa・sがより好ましい。ポリイミドワニスの粘度は、E型粘度計を用いて25℃で測定された値である。
また、本発明のポリイミドワニスは、ポリイミドフィルムの要求特性を損なわない範囲で、無機フィラー、接着促進剤、剥離剤、難燃剤、紫外線安定剤、界面活性剤、レベリング剤、消泡剤、蛍光増白剤、架橋剤、重合開始剤、感光剤等各種添加剤を含んでもよい。
本発明のポリイミドワニスの製造方法は特に限定されず、公知の方法を適用することができる。
Since the polyimide resin of the present invention has solvent solubility, it is possible to obtain a high-concentration varnish that is stable at room temperature. The polyimide varnish of the present invention preferably contains the polyimide resin of the present invention in an amount of 5 to 40% by mass, more preferably 10 to 30% by mass. The viscosity of the polyimide varnish is preferably 1 to 200 Pa · s, more preferably 5 to 150 Pa · s. The viscosity of the polyimide varnish is a value measured at 25 ° C. using an E-type viscometer.
In addition, the polyimide varnish of the present invention contains an inorganic filler, an adhesion accelerator, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, a defoaming agent, and an optical brightener as long as the required properties of the polyimide film are not impaired. Various additives such as a whitening agent, a cross-linking agent, a polymerization initiator, and a photosensitizer may be contained.
The method for producing the polyimide varnish of the present invention is not particularly limited, and a known method can be applied.

[ポリイミドフィルム]
本発明のポリイミドフィルムは、本発明のポリイミド樹脂を含む。したがって、本発明のポリイミドフィルムは、機械的特性、耐熱性、及び無色透明性に優れ、更に残留応力が低い。本発明のポリイミドフィルムが有する好適な物性値は上述の通りである。
本発明のポリイミドフィルムの製造方法には特に制限はなく、公知の方法を用いることができる。例えば、本発明のポリイミドワニスを、ガラス板、金属板、プラスチックなどの平滑な支持体上に塗布、又はフィルム状に成形した後、該ワニス中に含まれる反応溶剤や希釈溶剤等の有機溶媒を加熱により除去する方法等が挙げられる。前記支持体の表面には、必要に応じて、予め離形剤を塗布しておいてもよい。
ワニス中に含まれる有機溶媒を加熱により除去する方法としては、以下の方法が好ましい。即ち、120℃以下の温度で有機溶媒を蒸発させて自己支持性フィルムとした後、該自己支持性フィルムを支持体より剥離し、該自己支持性フィルムの端部を固定し、用いた有機溶媒の沸点以上の温度で乾燥してポリイミドフィルムを製造することが好ましい。また、窒素雰囲気下で乾燥することが好ましい。乾燥雰囲気の圧力は、減圧、常圧、加圧のいずれでもよい。自己支持性フィルムを乾燥してポリイミドフィルムを製造する際の加熱温度は、特に限定されないが、200〜400℃が好ましい。
[Polyimide film]
The polyimide film of the present invention contains the polyimide resin of the present invention. Therefore, the polyimide film of the present invention is excellent in mechanical properties, heat resistance, colorless transparency, and has low residual stress. Suitable physical property values of the polyimide film of the present invention are as described above.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. For example, the polyimide varnish of the present invention is applied onto a smooth support such as a glass plate, a metal plate, or plastic, or formed into a film, and then an organic solvent such as a reaction solvent or a dilution solvent contained in the varnish is applied. Examples thereof include a method of removing by heating. If necessary, a release agent may be applied to the surface of the support in advance.
The following method is preferable as a method for removing the organic solvent contained in the varnish by heating. That is, after evaporating the organic solvent at a temperature of 120 ° C. or lower to form a self-supporting film, the self-supporting film is peeled off from the support, the end portion of the self-supporting film is fixed, and the organic solvent used. It is preferable to produce a polyimide film by drying at a temperature equal to or higher than the boiling point of. Moreover, it is preferable to dry in a nitrogen atmosphere. The pressure in the dry atmosphere may be reduced pressure, normal pressure, or pressurized. The heating temperature when the self-supporting film is dried to produce the polyimide film is not particularly limited, but is preferably 200 to 400 ° C.

また、本発明のポリイミドフィルムは、ポリアミド酸が有機溶媒に溶解してなるポリアミド酸ワニスを用いて製造することもできる。
前記ポリアミド酸ワニスに含まれるポリアミド酸は、本発明のポリイミド樹脂の前駆体であって、上述の構成単位(A−1)を与える化合物及び上述の構成単位(A−2)を与える化合物を含み、上述の構成単位(A−X)を与える化合物を含まないテトラカルボン酸成分と、上述の構成単位(B−1)を与える化合物を含むジアミン成分との重付加反応の生成物である。このポリアミド酸をイミド化(脱水閉環)することで、最終生成物である本発明のポリイミド樹脂が得られる。
前記ポリアミド酸ワニスに含まれる有機溶媒としては、本発明のポリイミドワニスに含まれる有機溶媒を用いることができる。
本発明において、ポリアミド酸ワニスは、上述の構成単位(A−1)を与える化合物及び上述の構成単位(A−2)を与える化合物を含み、上述の構成単位(A−X)を与える化合物を含まないテトラカルボン酸成分と上述の構成単位(B−1)を与える化合物を含むジアミン成分とを反応溶剤中で重付加反応させて得られるポリアミド酸溶液そのものであってもよいし、又は当該ポリアミド酸溶液に対して更に希釈溶剤を追加したものであってもよい。
Further, the polyimide film of the present invention can also be produced by using a polyamic acid varnish in which polyamic acid is dissolved in an organic solvent.
The polyamic acid contained in the polyamic acid varnish is a precursor of the polyimide resin of the present invention and includes a compound giving the above-mentioned structural unit (A-1) and a compound giving the above-mentioned structural unit (A-2). , A product of a polyaddition reaction between a tetracarboxylic acid component that does not contain a compound that gives the above-mentioned structural unit (AX) and a diamine component that contains a compound that gives the above-mentioned structural unit (B-1). By imidizing (dehydrating and ring-closing) this polyamic acid, the polyimide resin of the present invention, which is the final product, can be obtained.
As the organic solvent contained in the polyamic acid varnish, the organic solvent contained in the polyimide varnish of the present invention can be used.
In the present invention, the polyamic acid varnish includes a compound giving the above-mentioned structural unit (A-1) and a compound giving the above-mentioned structural unit (A-2), and a compound giving the above-mentioned structural unit (AX). It may be a polyamic acid solution itself obtained by subjecting a tetracarboxylic acid component that does not contain the tetracarboxylic acid component and a diamine component containing the compound that gives the above-mentioned structural unit (B-1) to a heavy addition reaction in a reaction solvent, or the polyamide. A diluting solvent may be further added to the acid solution.

ポリアミド酸ワニスを用いてポリイミドフィルムを製造する方法には特に制限はなく、公知の方法を用いることができる。例えば、ポリアミド酸ワニスを、ガラス板、金属板、プラスチックなどの平滑な支持体上に塗布、又はフィルム状に成形し、該ワニス中に含まれる反応溶剤や希釈溶剤等の有機溶媒を加熱により除去してポリアミド酸フィルムを得て、該ポリアミド酸フィルム中のポリアミド酸を加熱によりイミド化することで、ポリイミドフィルムを製造することができる。
ポリアミド酸ワニスを乾燥させてポリアミド酸フィルムを得る際の加熱温度としては、好ましくは50〜120℃である。ポリアミド酸を加熱によりイミド化する際の加熱温度としては好ましくは200〜400℃である。
なお、イミド化の方法は熱イミド化に限定されず、化学イミド化を適用することもできる。
The method for producing the polyimide film using the polyamic acid varnish is not particularly limited, and a known method can be used. For example, a polyamic acid varnish is applied onto a smooth support such as a glass plate, a metal plate, or plastic, or formed into a film, and organic solvents such as a reaction solvent and a diluting solvent contained in the varnish are removed by heating. A polyimide film can be produced by obtaining a polyamic acid film and imidizing the polyamic acid in the polyamic acid film by heating.
The heating temperature for drying the polyamic acid varnish to obtain a polyamic acid film is preferably 50 to 120 ° C. The heating temperature for imidizing the polyamic acid by heating is preferably 200 to 400 ° C.
The imidization method is not limited to thermal imidization, and chemical imidization can also be applied.

本発明のポリイミドフィルムの厚みは用途等に応じて適宜選択することができるが、好ましくは1〜250μm、より好ましくは5〜100μm、更に好ましくは10〜80μmの範囲である。厚みが1〜250μmであることで、自立膜としての実用的な使用が可能となる。
ポリイミドフィルムの厚みは、ポリイミドワニスの固形分濃度や粘度を調整することにより、容易に制御することができる。
The thickness of the polyimide film of the present invention can be appropriately selected depending on the intended use and the like, but is preferably in the range of 1 to 250 μm, more preferably 5 to 100 μm, and further preferably 10 to 80 μm. When the thickness is 1 to 250 μm, it can be practically used as a self-supporting film.
The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide varnish.

本発明のポリイミドフィルムは、カラーフィルター、フレキシブルディスプレイ、半導体部品、光学部材等の各種部材用のフィルムとして好適に用いられる。本発明のポリイミドフィルムは、液晶ディスプレイやOLEDディスプレイ等の画像表示装置の基板として、特に好適に用いられる。 The polyimide film of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members. The polyimide film of the present invention is particularly preferably used as a substrate for an image display device such as a liquid crystal display or an OLED display.

以下に、実施例により本発明を具体的に説明する。但し、本発明はこれらの実施例により何ら制限されるものではない。
実施例及び比較例で得たワニスの固形分濃度及びフィルムの各物性は以下に示す方法によって測定した。
Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to these examples.
The solid content concentration of the varnish obtained in Examples and Comparative Examples and the physical characteristics of the film were measured by the methods shown below.

(1)固形分濃度
ワニスの固形分濃度の測定は、アズワン株式会社製の小型電気炉「MMF−1」で試料を320℃×120minで加熱し、加熱前後の試料の質量差から算出した。
(2)フィルム厚さ
フィルム厚さは、株式会社ミツトヨ製のマイクロメーターを用いて測定した。
(3)引張弾性率、引張強度
引張弾性率及び引張強度は、JIS K7127に準拠し、東洋精機株式会社製の引張試験機「ストログラフVG−1E」を用いて測定した。チャック間距離は、10mm×50mm、試験速度は20mm/minとした。引張弾性率及び引張強度は、いずれも数値が大きいほど優れる。
(4)ガラス転移温度(Tg)
株式会社日立ハイテクサイエンス製の熱機械的分析装置「TMA/SS6100」を用いて、引張モードで試料サイズ2mm×20mm、荷重0.1N、昇温速度10℃/minの条件で、残留応力を取り除くのに十分な温度まで昇温して残留応力を取り除き、その後室温まで冷却した。その後、前記残留応力を取り除くための処理と同じ条件で試験片伸びの測定の測定を行い、伸びの変曲点が見られたところをガラス転移温度として求めた。Tgは数値が大きいほど優れる。
(5)全光線透過率、イエローインデックス(YI)
全光線透過率及びYIは、JIS K7361−1:1997に準拠し、日本電色工業株式会社製の色彩・濁度同時測定器「COH400」を用いて測定した。全光線透過率は100%に近いほど、YIは数値が小さいほど優れる。
(6)残留応力
ケーエルエー・テンコール社製の残留応力測定装置「FLX−2320」を用いて、予め「反り量」を測定しておいた、厚み525μm±25μmの4インチシリコンウェハ上に、ポリイミドワニスあるいはポリアミド酸ワニスを、スピンコーターを用いて塗布し、プリベークした。その後、熱風乾燥器を用いて、窒素雰囲気下、400℃1時間の加熱硬化処理を施し、硬化後膜厚8〜20μmのポリイミドフィルムのついたシリコンウェハを作製した。このウェハの反り量を前述の残留応力測定装置を用いて測定し、シリコンウェハとポリイミドフィルムの間に生じた残留応力を評価した。残留応力は数値が小さいほど優れる。
(1) Solid content concentration The solid content concentration of the varnish was measured by heating the sample at 320 ° C. × 120 min in a small electric furnace “MMF-1” manufactured by AS ONE Corporation and calculating from the mass difference of the sample before and after heating.
(2) Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
(3) Tensile elastic modulus and tensile strength The tensile elastic modulus and tensile strength were measured using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7127. The distance between the chucks was 10 mm × 50 mm, and the test speed was 20 mm / min. The larger the numerical value, the better the tensile elastic modulus and the tensile strength.
(4) Glass transition temperature (Tg)
Using the thermomechanical analyzer "TMA / SS6100" manufactured by Hitachi High-Tech Science Co., Ltd., residual stress is removed under the conditions of sample size 2 mm x 20 mm, load 0.1 N, and heating rate 10 ° C / min in tensile mode. The temperature was raised to a sufficient temperature to remove residual stress, and then cooled to room temperature. Then, the measurement of the elongation of the test piece was carried out under the same conditions as the treatment for removing the residual stress, and the place where the inflection point of the elongation was observed was determined as the glass transition temperature. The larger the value of Tg, the better.
(5) Total light transmittance, yellow index (YI)
The total light transmittance and YI were measured in accordance with JIS K7361-1: 1997 using a color / turbidity simultaneous measuring device "COH400" manufactured by Nippon Denshoku Industries Co., Ltd. The closer the total light transmittance is to 100%, and the smaller the value of YI, the better.
(6) Residual stress Polyamide varnish on a 4-inch silicon wafer with a thickness of 525 μm ± 25 μm for which the “warp amount” has been measured in advance using the residual stress measuring device “FLX-2320” manufactured by KLA Tencor. Alternatively, a polyamic acid varnish was applied using a spin coater and prebaked. Then, using a hot air dryer, it was heat-cured at 400 ° C. for 1 hour in a nitrogen atmosphere to prepare a silicon wafer with a polyimide film having a film thickness of 8 to 20 μm after curing. The amount of warpage of this wafer was measured using the above-mentioned residual stress measuring device, and the residual stress generated between the silicon wafer and the polyimide film was evaluated. The smaller the value, the better the residual stress.

実施例及び比較例にて使用したテトラカルボン酸成分及びジアミン成分、並びにその略号は以下の通りである。
<テトラカルボン酸成分>
CpODA:ノルボルナン−2−スピロ−α−シクロペンタノン−α’−スピロ−2’’−ノルボルナン−5,5’’,6,6’’−テトラカルボン酸二無水物(JXエネルギー株式会社製;式(a−1)で表される化合物)
BPDA:3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(三菱化学株式会社製;式(a−2)で表される化合物)
<ジアミン>
TFMB:2,2’−ビス(トリフルオロメチル)ベンジジン(和歌山精化工業株式会社製;式(b−1)で表される化合物)
The tetracarboxylic acid component and diamine component used in Examples and Comparative Examples, and their abbreviations are as follows.
<Tetracarboxylic acid component>
CpODA: Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride (manufactured by JX Energy Co., Ltd .; Compound represented by formula (a-1))
BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation; compound represented by formula (a-2))
<Diamine>
TFMB: 2,2'-bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd .; compound represented by formula (b-1))

<実施例1>
ステンレス製半月型撹拌翼、窒素導入管、冷却管を取り付けたディーンスターク、温度計、ガラス製エンドキャップを備えた1Lの5つ口丸底フラスコに、TFMBを32.024g(0.100モル)とN−メチルピロリドン(三菱化学株式会社製)を82.391g投入し、系内温度70℃、窒素雰囲気下、回転数150rpmで撹拌して溶液を得た。
この溶液に、CpODAを30.750g(0.080モル)、BPDAを5.884g(0.020モル)と、N−メチルピロリドン(三菱化学株式会社製)を20.598gとを一括で添加した後、イミド化触媒としてトリエチルアミン(関東化学株式会社製)を0.506g投入し、マントルヒーターで加熱し、約20分かけて反応系内温度を190℃まで上げた。留去される成分を捕集し、回転数を粘度上昇に合わせて調整しつつ、反応系内温度を190℃に保持して3時間還流した。
その後、γ−ブチロラクトン(三菱化学株式会社製)を482.505g添加して、反応系内温度を120℃まで冷却した後、更に約3時間撹拌して均一化して、固形分濃度10.0質量%のポリイミドワニスを得た。
続いてガラス板上、シリコンウェハへ、得られたポリイミドワニスを塗布し、ホットプレートで80℃、20分間保持し、その後、窒素雰囲気下、熱風乾燥機中400℃で30分加熱し溶媒を蒸発させ、厚み10μmのフィルムを得た。結果を表1に示す。
<Example 1>
32.024g (0.100mol) of TFMB in a 1L 5-necked round-bottom flask equipped with a stainless steel crescent-shaped stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And 82.391 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Corporation) were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
To this solution, 30.750 g (0.080 mol) of CpODA, 5.884 g (0.020 mol) of BPDA, and 20.598 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Co., Inc.) were added in a batch. After that, 0.506 g of triethylamine (manufactured by Kanto Chemical Co., Inc.) was added as an imidization catalyst, and the mixture was heated with a mantle heater to raise the temperature inside the reaction system to 190 ° C. over about 20 minutes. The components to be distilled off were collected, and the temperature inside the reaction system was maintained at 190 ° C. and refluxed for 3 hours while adjusting the rotation speed according to the increase in viscosity.
Then, 482.505 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, the temperature inside the reaction system was cooled to 120 ° C., and the mixture was further stirred for about 3 hours to homogenize, and the solid content concentration was 10.0 mass. % Polyimide varnish was obtained.
Subsequently, the obtained polyimide varnish was applied onto a glass plate and a silicon wafer, held on a hot plate at 80 ° C. for 20 minutes, and then heated in a hot air dryer at 400 ° C. for 30 minutes in a nitrogen atmosphere to evaporate the solvent. A film having a thickness of 10 μm was obtained. The results are shown in Table 1.

<実施例2>
CpODAの量を30.750g(0.080モル)から23.063g(0.060モル)、BPDAの量を5.884g(0.020モル)から11.769g(0.040モル)に変更した以外は、実施例1と同様の方法によりポリイミドワニスを作製し、固形分濃度10.0質量%のポリイミドワニスを得た。
得られたポリイミドワニスを用いて、実施例1と同様の方法によりフィルムを作製し、厚み7μmのフィルムを得た。結果を表1に示す。
<Example 2>
The amount of CpODA was changed from 30.750 g (0.080 mol) to 23.063 g (0.060 mol), and the amount of BPDA was changed from 5.884 g (0.020 mol) to 11.769 g (0.040 mol). A polyimide varnish was prepared in the same manner as in Example 1 except for the above, and a polyimide varnish having a solid content concentration of 10.0% by mass was obtained.
Using the obtained polyimide varnish, a film was prepared in the same manner as in Example 1 to obtain a film having a thickness of 7 μm. The results are shown in Table 1.

<比較例1>
CpODAの量を30.750g(0.080モル)から38.438g(0.100モル)に変更し、BPDAを添加しなかった以外は、実施例1と同様の方法によりポリイミドワニスを作製し、固形分濃度10.0質量%のポリイミドワニスを得た。
得られたポリイミドワニスを用いて、実施例1と同様の方法によりフィルムを作製し、厚み14μmのフィルムを得た。結果を表1に示す。
<Comparative example 1>
A polyimide varnish was prepared by the same method as in Example 1 except that the amount of CpODA was changed from 30.750 g (0.080 mol) to 38.438 g (0.100 mol) and BPDA was not added. A polyimide varnish having a solid content concentration of 10.0% by mass was obtained.
Using the obtained polyimide varnish, a film was prepared in the same manner as in Example 1 to obtain a film having a thickness of 14 μm. The results are shown in Table 1.

<比較例2>
ステンレス製半月型撹拌翼、窒素導入管、冷却管を取り付けたディーンスターク、温度計、ガラス製エンドキャップを備えた1Lの5つ口丸底フラスコに、TFMBを32.024g(0.100モル)とN−メチルピロリドン(三菱化学株式会社製)を196.627g投入し、系内温度50℃、窒素雰囲気下、回転数150rpmで撹拌して溶液を得た。
この溶液に、BPDAを294.22g(0.100モル)と、N−メチルピロリドン(三菱化学株式会社製)を49.157gとを一括で投入し、マントルヒーターで50℃に保持したまま7時間撹拌した。
その後、N−メチルピロリドン(三菱化学株式会社製)を307.230g添加して、更に約3時間撹拌して均一化して、固形分濃度10.0質量%のポリアミド酸ワニスを得た。
続いてガラス板上、シリコンウェハへ、得られたポリアミド酸ワニスを塗布し、ホットプレートで80℃、20分間保持し、その後、窒素雰囲気下、熱風乾燥機中400℃で30分加熱し溶媒を蒸発、さらに熱イミド化させ、厚み12μmのフィルムを得た。結果を表1に示す。
<Comparative example 2>
32.024g (0.100mol) of TFMB in a 1L 5-necked round-bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And N-methylpyrrolidone (manufactured by Mitsubishi Chemical Corporation) were added in an amount of 196.627 g, and the mixture was stirred at a system temperature of 50 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
To this solution, 294.22 g (0.100 mol) of BPDA and 49.157 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Corporation) were added in a batch and kept at 50 ° C. for 7 hours with a mantle heater. Stirred.
Then, 307.230 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was further stirred for about 3 hours to homogenize to obtain a polyamic acid varnish having a solid content concentration of 10.0% by mass.
Subsequently, the obtained polyamic acid varnish was applied onto a glass plate and a silicon wafer, held on a hot plate at 80 ° C. for 20 minutes, and then heated in a hot air dryer at 400 ° C. for 30 minutes under a nitrogen atmosphere to remove the solvent. The film was evaporated and further thermally imidized to obtain a film having a thickness of 12 μm. The results are shown in Table 1.

Figure 2019198709
Figure 2019198709

表1に示すように、実施例1及び2のポリイミドフィルムは、機械的特性、耐熱性、及び無色透明性に優れ、更に残留応力が低かった。
一方、テトラカルボン酸成分としてCpODAのみを使用して製造した比較例1のポリイミドフィルムは、実施例1及び2のポリイミドフィルムと対比して、引張弾性率及び耐熱性に劣り、残留応力が高かった。また、テトラカルボン酸成分としてBPDAのみを使用して製造した比較例2のポリイミドフィルムは、実施例1及び2のポリイミドフィルムと対比して、耐熱性及び無色透明性に劣り、残留応力が高かった。
As shown in Table 1, the polyimide films of Examples 1 and 2 were excellent in mechanical properties, heat resistance, and colorless transparency, and had low residual stress.
On the other hand, the polyimide film of Comparative Example 1 produced using only CpODA as the tetracarboxylic acid component was inferior in tensile elastic modulus and heat resistance and had a high residual stress as compared with the polyimide films of Examples 1 and 2. .. Further, the polyimide film of Comparative Example 2 produced using only BPDA as the tetracarboxylic acid component was inferior in heat resistance and colorless transparency and had a high residual stress as compared with the polyimide films of Examples 1 and 2. ..

Claims (5)

テトラカルボン酸二無水物に由来する構成単位A及びジアミンに由来する構成単位Bを有するポリイミド樹脂であって、
構成単位Aが下記式(a−1)で表される化合物に由来する構成単位(A−1)と、下記式(a−2)で表される化合物に由来する構成単位(A−2)とを含み、
構成単位Bが下記式(b−1)で表される化合物に由来する構成単位(B−1)を含み、
構成単位Aが下記式(a−x)で表される化合物に由来する構成単位(A−X)を含まない、ポリイミド樹脂。
Figure 2019198709
A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine.
A structural unit (A-1) in which the structural unit A is derived from a compound represented by the following formula (a-1) and a structural unit (A-2) derived from a compound represented by the following formula (a-2). Including and
The structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1).
A polyimide resin in which the structural unit A does not contain a structural unit (AX) derived from a compound represented by the following formula (ax).
Figure 2019198709
構成単位A中における構成単位(A−1)の比率が50〜90モル%であり、
構成単位A中における構成単位(A−2)の比率が10〜50モル%である、請求項1に記載のポリイミド樹脂。
The ratio of the structural unit (A-1) in the structural unit A is 50 to 90 mol%, and the ratio is 50 to 90 mol%.
The polyimide resin according to claim 1, wherein the ratio of the structural unit (A-2) in the structural unit A is 10 to 50 mol%.
構成単位B中における構成単位(B−1)の比率が50モル%以上である、請求項1又は2に記載のポリイミド樹脂。 The polyimide resin according to claim 1 or 2, wherein the ratio of the structural unit (B-1) in the structural unit B is 50 mol% or more. 請求項1〜3のいずれかに記載のポリイミド樹脂が有機溶媒に溶解してなるポリイミドワニス。 A polyimide varnish in which the polyimide resin according to any one of claims 1 to 3 is dissolved in an organic solvent. 請求項1〜3のいずれかに記載のポリイミド樹脂を含む、ポリイミドフィルム。 A polyimide film containing the polyimide resin according to any one of claims 1 to 3.
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