JP6996609B2 - Polyimide resin, polyimide varnish and polyimide film - Google Patents

Polyimide resin, polyimide varnish and polyimide film Download PDF

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JP6996609B2
JP6996609B2 JP2020204231A JP2020204231A JP6996609B2 JP 6996609 B2 JP6996609 B2 JP 6996609B2 JP 2020204231 A JP2020204231 A JP 2020204231A JP 2020204231 A JP2020204231 A JP 2020204231A JP 6996609 B2 JP6996609 B2 JP 6996609B2
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洋平 安孫子
紗恵子 佐藤
葵 大東
慎司 関口
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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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 a polyimide resin, a polyimide varnish and a polyimide film.

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、当該プラスチック材料として適するポリイミド樹脂の研究も進められている。そのような用途のポリイミド樹脂には、透明性も求められ、更に、画像表示装置の製造工程の高温プロセスに対応できるように、熱に対する高い寸法安定性（即ち、低い線熱膨張係数）も求められる。 Since the 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, and a polyimide resin suitable as the plastic material is desired. Research is also underway. Transparency is also required for polyimide resins for such applications, and high dimensional stability with respect to heat (that is, a low coefficient of linear thermal expansion) is also required so as to be able to cope with high temperature processes in the manufacturing process of image display devices. Be done.

低い線熱膨張係数を有するポリイミド樹脂としては、例えば、特許文献１には無水ピロメリット酸等の第一のテトラカルボン酸成分と、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物等の第二のテトラカルボン酸成分と、トリジンスルホン骨格ジアミン成分とから合成されるポリイミド樹脂が記載されており、特許文献２にはベンゾオキサゾール基を含むジアミン化合物と芳香族テトラカルボン酸二無水物とから合成されるポリイミド樹脂が記載されている。 As the polyimide resin having a low linear thermal expansion coefficient, for example, Patent Document 1 describes a first tetracarboxylic acid component such as pyromellitic anhydride and 3,3', 4,4'-diphenylsulfone tetracarboxylic acid di. A polyimide resin synthesized from a second tetracarboxylic acid component such as anhydrate and a tridin sulfone skeleton diamine component is described, and Patent Document 2 describes a diamine compound containing a benzoxazole group and an aromatic tetracarboxylic acid dianhydride. Described are polyimide resins synthesized from anhydrides.

また、近年、マイクロエレクトロニクスの分野において、樹脂フィルムが積層された支持体における当該支持体と当該樹脂フィルムを剥離する方法として、レーザーリフトオフ（ＬＬＯ）と呼ばれるレーザー剥離加工が注目を浴びている。したがって、ポリイミドフィルムをレーザー剥離加工に対応可能とするためには、ポリイミドフィルムにはレーザー剥離性も要求される。波長３０８ｎｍのＸｅＣｌエキシマレーザーによる剥離加工に対応可能とするためには、ポリイミドフィルムは波長３０８ｎｍの光を吸収する特性に優れること（即ち、波長３０８ｎｍにおける光線透過率が小さいこと）が求められる。 Further, in recent years, in the field of microelectronics, a laser peeling process called laser lift-off (LLO) has attracted attention as a method for peeling the support and the resin film in a support on which a resin film is laminated. Therefore, in order to make the polyimide film compatible with laser peeling processing, the polyimide film is also required to have laser peeling property. In order to be compatible with the peeling process by the XeCl excimer laser having a wavelength of 308 nm, the polyimide film is required to have excellent characteristics of absorbing light having a wavelength of 308 nm (that is, having a small light transmittance at a wavelength of 308 nm).

特開２０１０－０５３３３６号公報Japanese Unexamined Patent Publication No. 2010-0533336 特開２０１５－０９３９１５号公報Japanese Unexamined Patent Publication No. 2015-039915

一般にポリイミド樹脂は、機械的特性及び耐熱性に優れるものであるが、透明性の向上、更には熱に対する寸法安定性及びレーザー剥離性の向上を目的としてポリイミド樹脂の構造を変更した結果として、それらの特性が損なれる可能性があり、機械的特性、耐熱性、透明性、熱に対する寸法安定性及びレーザー剥離性のバランスが良いポリイミド樹脂の開発は十分ではない。
本発明の課題は、機械的特性、耐熱性及び透明性が良好であって、熱に対する寸法安定性及びレーザー剥離性に優れたポリイミド樹脂を提供することにある。 Generally, polyimide resins are excellent in mechanical properties and heat resistance, but as a result of changing the structure of the polyimide resin for the purpose of improving transparency, dimensional stability against heat, and laser peeling property. There is a possibility that the characteristics of the polyimide resin may be impaired, and the development of a polyimide resin having a good balance between mechanical properties, heat resistance, transparency, dimensional stability against heat and laser peeling property is not sufficient.
An object of the present invention is to provide a polyimide resin having good mechanical properties, heat resistance and transparency, and excellent dimensional stability against heat and laser peeling property.

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］～［７］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と、ジアミンに由来する構成単位Ｂとを含む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）と、下記式（ｂ－２）で表される化合物に由来する構成単位（Ｂ－２）とを含む、ポリイミド樹脂。 That is, the present invention relates to the following [1] to [7].
[1] A polyimide resin containing 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
A structural unit (B-1) in which the structural unit B is derived from a compound represented by the following formula (b-1) and a structural unit (B-2) derived from a compound represented by the following formula (b-2). Polyimide resin, including.

Figure 0006996609000001
Figure 0006996609000001

（式（ａ－２）中、Ｌは単結合又は二価の連結基であり、
式（ｂ－２）中、Ｒはそれぞれ独立して、水素原子、フッ素原子又はメチル基である。） (In formula (a-2), L is a single bond or a divalent linking group.
In formula (b-2), R is independently a hydrogen atom, a fluorine atom or a methyl group. )

［２］構成単位Ａ中における構成単位（Ａ－１）の比率が５０～９５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５～５０モル％である、上記［１］に記載のポリイミド樹脂。
［３］構成単位（Ａ－２）が、下記式（ａ－２－１）で表される化合物に由来する構成単位（Ａ－２－１）、下記式（ａ－２－２）で表される化合物に由来する構成単位（Ａ－２－２）及び下記式（ａ－２－３）で表される化合物に由来する構成単位（Ａ－２－３）からなる群より選ばれる少なくとも一つである、上記［１］又は［２］に記載のポリイミド樹脂。 [2] The ratio of the constituent unit (A-1) in the constituent unit A is 50 to 95 mol%.
The polyimide resin according to the above [1], wherein the ratio of the structural unit (A-2) in the structural unit A is 5 to 50 mol%.
[3] The structural unit (A-2) is a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1), and is represented by the following formula (a-2-2). At least one selected from the group consisting of the structural unit (A-2-2) derived from the compound to be used and the structural unit (A-2-3) derived from the compound represented by the following formula (a-2-3). The polyimide resin according to the above [1] or [2].

Figure 0006996609000002
Figure 0006996609000002

［４］構成単位Ｂ中における構成単位（Ｂ－１）の比率が２０～９０モル％であり、
構成単位Ｂ中における構成単位（Ｂ－２）の比率が１０～８０モル％である、上記［１］～［３］のいずれかにポリイミド樹脂。
［５］Ｒが水素原子を表わす、上記［１］～［４］のいずれかに記載のポリイミド樹脂。
［６］上記［１］～［５］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。
［７］上記［１］～［５］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。 [4] The ratio of the constituent unit (B-1) in the constituent unit B is 20 to 90 mol%.
The polyimide resin according to any one of the above [1] to [3], wherein the ratio of the structural unit (B-2) in the structural unit B is 10 to 80 mol%.
[5] The polyimide resin according to any one of the above [1] to [4], wherein R represents a hydrogen atom.
[6] A polyimide varnish in which the polyimide resin according to any one of [1] to [5] above is dissolved in an organic solvent.
[7] A polyimide film containing the polyimide resin according to any one of the above [1] to [5].

本発明のポリイミド樹脂は、機械的特性、耐熱性及び透明性が良好であって、熱に対する寸法安定性及びレーザー剥離性に優れる。 The polyimide resin of the present invention has good mechanical properties, heat resistance and transparency, and is excellent in dimensional stability against heat and laser peeling property.

［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とジアミンに由来する構成単位Ｂとを含むものであって、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）と下記式（ｂ－２）で表される化合物に由来する構成単位（Ｂ－２）とを含む。 [Polyimide resin]
The polyimide resin of the present invention contains a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, and the structural unit A is represented by the following formula (a-1). A structural unit (A-1) derived from a compound and a structural unit (A-2) derived from a 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 the represented compound and a structural unit (B-2) derived from the compound represented by the following formula (b-2).

Figure 0006996609000003
Figure 0006996609000003

（式（ａ－２）中、Ｌは単結合又は二価の連結基であり、
式（ｂ－２）中、Ｒはそれぞれ独立して、水素原子、フッ素原子又はメチル基である。） (In formula (a-2), L is a single bond or a divalent linking group.
In formula (b-2), R is independently a hydrogen atom, a fluorine atom or a methyl group. )

＜構成単位Ａ＞
構成単位Ａは、テトラカルボン酸二無水物に由来する構成単位であり、式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）及び式（ａ－２）で表される化合物に由来する構成単位（Ａ－２）を含む。構成単位（Ａ－１）によって、耐熱性、透明性及び寸法安定性が向上し、構成単位（Ａ－２）によって、寸法安定性及びレーザー剥離性が向上する。 <Structure unit A>
The structural unit A is a structural unit derived from the tetracarboxylic dianhydride, and is represented by the structural unit (A-1) and the formula (a-2) derived from the compound represented by the formula (a-1). Contains a structural unit (A-2) derived from the compound. The structural unit (A-1) improves heat resistance, transparency and dimensional stability, and the structural unit (A-2) improves dimensional stability and laser peelability.

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。
式（ａ－２）中において、Ｌは単結合又は二価の連結基である。前記二価の連結基は、好ましくは置換又は無置換のアルキレン基であり、より好ましくは－ＣＲ１Ｒ２－（ここで、Ｒ１及びＲ２は、それぞれ独立して、水素原子又は置換若しくは無置換アルキル基であるか、あるいは、Ｒ１及びＲ２は互いに結合して環を形成する。）である。
Ｌは、単結合、下記式（Ｌ－１）で表される基及び下記式（Ｌ－２）で表される基からなる群より選ばれることが好ましい。 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.
In formula (a-2), L is a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group, more preferably -CR 1 R 2- (where R 1 and R 2 are independently hydrogen atoms or substituted or substituted, respectively. It is an unsubstituted alkyl group, or R 1 and R 2 are bonded to each other to form a ring).
L is preferably selected from the group consisting of a single bond, a group represented by the following formula (L-1) and a group represented by the following formula (L-2).

Figure 0006996609000004
Figure 0006996609000004

構成単位（Ａ－２）は、好ましくは下記式（ａ－２－１）で表される化合物に由来する構成単位（Ａ－２－１）、下記式（ａ－２－２）で表される化合物に由来する構成単位（Ａ－２－２）及び下記式（ａ－２－３）で表される化合物に由来する構成単位（Ａ－２－３）からなる群より選ばれる少なくとも一つであり、より好ましくは構成単位（Ａ－２－１）及び構成単位（Ａ－２－２）からなる群より選ばれる少なくとも一つである。 The structural unit (A-2) is preferably a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1), and is represented by the following formula (a-2-2). At least one selected from the group consisting of a structural unit (A-2-2) derived from a compound and a structural unit (A-2-3) derived from a compound represented by the following formula (a-2-3). It is more preferably at least one selected from the group consisting of the constituent unit (A-2-1) and the constituent unit (A-2-2).

Figure 0006996609000005
Figure 0006996609000005

式（ａ－２－１）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－２－１ｓ）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－２－１ａ）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－２－１ｉ）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。 The compound represented by the formula (a-2-1) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof are 3,3 represented by the following formula (a-2-1s). ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride represented by the following formula (a-2-1a) (A-BPDA), 2,2', 3,3'-biphenyltetracarboxylic dianhydride (i-BPDA) represented by the following formula (a-2-1i) can be mentioned.

Figure 0006996609000006
Figure 0006996609000006

式（ａ－２－２）で表される化合物は、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である。
式（ａ－２－３）で表される化合物は、４，４’－(ヘキサフルオロイソプロピリデン)ジフタル酸無水物である。 The compound represented by the formula (a-2-2) is 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride.
The compound represented by the formula (a-2-3) is 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride.

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５０～９５モル％であり、より好ましくは５５～９５モル％であり、更に好ましくは６０～９５モル％であり、特に好ましくは７５～９５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５～５０モル％であり、より好ましくは５～４５モル％であり、更に好ましくは５～４０モル％であり、特に好ましくは５～２５モル％である。
構成単位Ａ中における構成単位（Ａ－１）と構成単位（Ａ－２）の合計の含有比率は、好ましくは５５モル％以上であり、より好ましくは６０モル％以上であり、更に好ましくは６５モル％以上であり、特に好ましくは８０モル％以上である。構成単位（Ａ－１）と構成単位（Ａ－２）の合計の含有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 95 mol%, more preferably 55 to 95 mol%, still more preferably 60 to 95 mol%, and particularly preferably. Is 75-95 mol%.
The ratio of the structural unit (A-2) in the structural unit A is preferably 5 to 50 mol%, more preferably 5 to 45 mol%, still more preferably 5 to 40 mol%, and particularly preferably. Is 5 to 25 mol%.
The total content ratio of the structural unit (A-1) and the structural unit (A-2) in the structural unit A is preferably 55 mol% or more, more preferably 60 mol% or more, still more preferably 65. It is mol% or more, and particularly preferably 80 mol% or more. The upper limit of the total content ratio of the constituent unit (A-1) and the constituent unit (A-2) is not particularly limited, that is, 100 mol%. The constituent unit A may be composed of only the constituent unit (A-1) and the constituent 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。そのような構成単位を形成す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及び１，２，４，５－シクロヘキサ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（即ち、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). The tetracarboxylic acid dianhydride forming such a structural unit is not particularly limited, but is represented by an aromatic tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride (however, represented by the formula (a-2)). Compounds; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and alicyclic tetracarboxylic acid dianhydride such as 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (however) , Excluding compounds represented by the formula (a-1); and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride.
In the present specification, the aromatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing one or more aromatic rings, and the alicyclic tetracarboxylic acid dianhydride has one alicyclic ring. The tetracarboxylic acid dianhydride containing the above and containing no aromatic ring is meant, and the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
The structural unit arbitrarily included in the structural unit A (that is, the structural unit other than the structural units (A-1) and (A-2)) may be one type or two or more types.

＜構成単位Ｂ＞
構成単位Ｂは、ジアミンに由来する構成単位であって、式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）及び式（ｂ－２）で表される化合物に由来する構成単位（Ｂ－２）を含む。構成単位（Ｂ－１）によって、機械的特性及び寸法安定性が向上し、構成単位（Ｂ－２）によって、耐熱性が向上する。 <Structural unit B>
The structural unit B is a structural unit derived from diamine, and is derived from the structural unit (B-1) derived from the compound represented by the formula (b-1) and the compound represented by the formula (b-2). Includes the structural unit (B-2) to be used. The structural unit (B-1) improves mechanical properties and dimensional stability, and the structural unit (B-2) improves heat resistance.

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。
式（ｂ－２）中において、Ｒは、それぞれ独立して、水素原子、フッ素原子、及びメチル基からなる群より選択され、水素原子であることが好ましい。式（ｂ－２）で表される化合物としては、９，９－ビス（４－アミノフェニル）フルオレン、９，９－ビス（３－フルオロ－４－アミノフェニル）フルオレン、及び９，９－ビス（３－メチル－４－アミノフェニル）フルオレン等が挙げられ、９，９－ビス（４－アミノフェニル）フルオレンが好ましい。 The compound represented by the formula (b-1) is 2,2'-bis (trifluoromethyl) benzidine.
In the formula (b-2), R is independently selected from the group consisting of a hydrogen atom, a fluorine atom, and a methyl group, and is preferably a hydrogen atom. The compounds represented by the formula (b-2) include 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-fluoro-4-aminophenyl) fluorene, and 9,9-bis. Examples thereof include (3-methyl-4-aminophenyl) fluorene, and 9,9-bis (4-aminophenyl) fluorene is preferable.

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２０～９０モル％であり、より好ましくは４５～８５モル％であり、更に好ましくは５０～８０モル％である。
構成単位Ｂ中における構成単位（Ｂ－２）の比率は、好ましくは１０～８０モル％であり、より好ましくは１５～５５モル％であり、更に好ましくは２０～５０モル％である。
構成単位Ｂ中における構成単位（Ｂ－１）と構成単位（Ｂ－２）の合計の含有比率は、好ましくは３０モル％以上であるが、より好ましくは６０モル％以上であり、更に好ましくは７０％以上である。構成単位（Ｂ－１）と構成単位（Ｂ－２）の合計の含有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）と構成単位（Ｂ－２）と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 20 to 90 mol%, more preferably 45 to 85 mol%, and further preferably 50 to 80 mol%.
The ratio of the structural unit (B-2) in the structural unit B is preferably 10 to 80 mol%, more preferably 15 to 55 mol%, and further preferably 20 to 50 mol%.
The total content ratio of the structural unit (B-1) and the structural unit (B-2) in the structural unit B is preferably 30 mol% or more, more preferably 60 mol% or more, and further preferably. 70% or more. The upper limit of the total content ratio of the constituent unit (B-1) and the constituent unit (B-2) is not particularly limited, that is, 100 mol%. The constituent unit B may be composed of only the constituent unit (B-1) and the constituent unit (B-2).

構成単位Ｂは構成単位（Ｂ－１）及び（Ｂ－２）以外の構成単位を含んでもよい。そのような構成単位を形成す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、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、ビス（４－アミノフェニル）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、及び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等の芳香族ジアミン（ただし、式（ｂ－１）で表される化合物及び式（ｂ－２）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（即ち、構成単位（Ｂ－１）及び（Ｂ－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 B may include a structural unit other than the structural units (B-1) and (B-2). The diamine forming such a structural unit is not particularly limited, but is limited to 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, and 2,2'-dimethylbiphenyl-4,4'. -Diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, 4,4'-diaminobenz Anilide, 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-aminophenoxy) phenyl] propane, And 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane and other aromatic diamines (provided, compounds represented by the formula (b-1) and represented by the formula (b-2). (Excluding compounds); alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine.
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 does not contain 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 arbitrarily included in the structural unit B (that is, the structural unit other than the structural units (B-1) and (B-2)) 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、機械的特性、耐熱性及び透明性が良好であって、熱に対する寸法安定性及びレーザー剥離性に優れるものであるため、以下のような物性値を有することができる。
本発明のポリイミド樹脂の引張強度は、好ましくは７０ＭＰａ以上であり、より好ましくは８５ＭＰａ以上であり、更に好ましくは９０ＭＰａ以上であり、特に好ましく１０５ＭＰａ以上である。
本発明のポリイミド樹脂の引張弾性率は、好ましくは２．２ＧＰａ以上であり、より好ましくは２．４ＧＰａ以上であり、更に好ましくは２．８ＧＰａ以上であり、特に好ましく３．０ＧＰａ以上である。 Since the polyimide resin of the present invention has good mechanical properties, heat resistance and transparency, and is excellent in dimensional stability against heat and laser peeling property, it can have the following physical property values.
The tensile strength of the polyimide resin of the present invention is preferably 70 MPa or more, more preferably 85 MPa or more, still more preferably 90 MPa or more, and particularly preferably 105 MPa or more.
The tensile elastic modulus of the polyimide resin of the present invention is preferably 2.2 GPa or more, more preferably 2.4 GPa or more, still more preferably 2.8 GPa or more, and particularly preferably 3.0 GPa or more.

本発明のポリイミド樹脂のガラス転移温度（Ｔｇ）は、好ましくは３５０℃以上であり、より好ましくは３８０℃以上であり、更に好ましくは４００℃以上であり、特に好ましく４３０℃以上である。 The glass transition temperature (Tg) of the polyimide resin of the present invention is preferably 350 ° C. or higher, more preferably 380 ° C. or higher, further preferably 400 ° C. or higher, and particularly preferably 430 ° C. or higher.

本発明のポリイミド樹脂は、厚さ１０μｍのポリイミドフィルムとした際に全光線透過率が、好ましくは８５％以上であり、より好ましくは８８％以上であり、更に好ましくは９０％以上であり、特に好ましく９１％以上である。 The polyimide resin of the present invention has a total light transmittance of preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, particularly when it is made into a polyimide film having a thickness of 10 μm. It is preferably 91% or more.

本発明のポリイミド樹脂の線熱膨張係数（ＣＴＥ）は、１００～２００℃のＣＴＥとしては、好ましくは３０ｐｐｍ／℃以下であり、より好ましくは２０ｐｐｍ／℃以下であり、更に好ましくは１５ｐｐｍ／℃以下であり、特に好ましくは１０ｐｐｍ／℃以下であり；１００～３５０℃のＣＴＥとしては、好ましくは３５ｐｐｍ／℃以下であり、より好ましくは３０ｐｐｍ／℃以下であり、更に好ましくは２５ｐｐｍ／℃以下であり、特に好ましくは２０ｐｐｍ／℃以下であり、最も好ましくは１５ｐｐｍ／℃以下である。 The coefficient of linear thermal expansion (CTE) of the polyimide resin of the present invention is preferably 30 ppm / ° C. or lower, more preferably 20 ppm / ° C. or lower, and further preferably 15 ppm / ° C. or lower for a CTE of 100 to 200 ° C. It is particularly preferably 10 ppm / ° C. or lower; the CTE at 100 to 350 ° C. is preferably 35 ppm / ° C. or lower, more preferably 30 ppm / ° C. or lower, and further preferably 25 ppm / ° C. or lower. Particularly preferably, it is 20 ppm / ° C. or less, and most preferably 15 ppm / ° C. or less.

本発明のポリイミド樹脂は、厚さ１０μｍのポリイミドフィルムとした際に波長３０８ｎｍにおける光線透過率が、好ましくは２．５％以下であり、より好ましくは１．５％以下であり、更に好ましくは１．０％以下であり、特に好ましく０．５％以下である。波長３０８ｎｍにおける光線透過率が小さいほど、波長３０８ｎｍのＸｅＣｌエキシマレーザーによるレーザー剥離性に優れる。
なお、本発明における引張弾性率、引張強度、ガラス転移温度（Ｔｇ）、全光線透過率、線熱膨張係数（ＣＴＥ）、波長３０８ｎｍにおける光線透過率は、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 polyimide resin of the present invention has a light transmittance of preferably 2.5% or less, more preferably 1.5% or less, still more preferably 1) at a wavelength of 308 nm when a polyimide film having a thickness of 10 μm is formed. It is 0.0% or less, particularly preferably 0.5% or less. The smaller the light transmittance at a wavelength of 308 nm, the better the laser exfoliation property by the XeCl excimer laser at a wavelength of 308 nm.
The tensile elastic modulus, tensile strength, glass transition temperature (Tg), total light transmittance, linear thermal expansion coefficient (CTE), and light transmittance at a wavelength of 308 nm in the present invention are specifically described in Examples. Can be measured with.

また、本発明の一態様のポリイミド樹脂は、イエローインデックス（ＹＩ）が小さく、即ち、無色透明性に優れる。そのため、厚さ１０μｍのポリイミドフィルムとした際にイエローインデックス（ＹＩ）が、好ましくは３．５以下であり、より好ましくは２．５以下であり、更に好ましくは２．０以下であり、特に好ましくは１．５以下である。
なお、本発明におけるイエローインデックス（ＹＩ）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。 Further, the polyimide resin according to one aspect of the present invention has a small yellow index (YI), that is, is excellent in colorless transparency. Therefore, when a polyimide film having a thickness of 10 μm is prepared, the yellow index (YI) is preferably 3.5 or less, more preferably 2.5 or less, still more preferably 2.0 or less, and particularly preferably. Is 1.5 or less.
The yellow index (YI) 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有するテトラカルボン酸成分と、上述の構成単位（Ｂ－１）を与える化合物及び上述の構成単位（Ｂ－２）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 comprises a tetracarboxylic dian component containing a compound giving the above-mentioned structural unit (A-1) and a compound giving the above-mentioned structural unit (A-2), and the above-mentioned structural unit (B-1). It can be produced by reacting with a diamine component containing a compound giving the above-mentioned structural unit (B-2).

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、同じ構成単位を形成でき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。
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、同じ構成単位を形成でき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。 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 can be formed. The derivative is a tetracarboxylic acid corresponding to the tetracarboxylic acid 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.
Examples of the compound giving the structural unit (A-2) include the 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 can be formed. 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.

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、同じ構成単位を形成でき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。
構成単位（Ｂ－２）を与える化合物としては、式（ｂ－２）で表される化合物が挙げられるが、それに限られず、同じ構成単位を形成でき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－２）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－２）を与える化合物としては、式（ｂ－２）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 the compound represented by the formula (b-1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit can be formed. Examples of the derivative include diisocyanates corresponding to the diamine represented by the formula (b-1). As the compound giving the structural unit (B-1), the compound represented by the formula (b-1) (that is, a diamine) is preferable.
Examples of the compound giving the structural unit (B-2) include the compound represented by the formula (b-2), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit can be formed. Examples of the derivative include diisocyanates corresponding to the diamine represented by the formula (b-2). As the compound giving the structural unit (B-2), the compound represented by the formula (b-2) (that is, a diamine) is preferable.

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５０～９５モル％含み、より好ましくは５５～９５モル％含み、更に好ましくは６０～９５モル％含み、特に好ましくは７５～９５モル％含む。また、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５～５０モル％含み、より好ましくは５～４５モル％含み、更に好ましくは５～４０モル％含み、特に好ましくは５～２５モル％含む。
テトラカルボン酸成分は、構成単位（Ａ－１）を与える化合物と構成単位（Ａ－２）を与える化合物を合計で、好ましくは５５モル％以上含み、より好ましくは６０モル％以上含み、更に好ましくは６５モル％以上含み、特に好ましくは８０モル％以上含む。構成単位（Ａ－１）を与える化合物と構成単位（Ａ－２）を与える化合物の合計の含有比率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 contains, preferably 50 to 95 mol%, more preferably 55 to 95 mol%, still more preferably 60 to 95 mol%, and particularly preferably the compound giving the constituent unit (A-1). Contains 75-95 mol%. Further, the tetracarboxylic acid component preferably contains 5 to 50 mol%, more preferably 5 to 45 mol%, still more preferably 5 to 40 mol%, and particularly contains a compound that gives a constituent unit (A-2). It preferably contains 5 to 25 mol%.
The tetracarboxylic acid component contains, in total, a compound giving the constituent unit (A-1) and a compound giving the constituent unit (A-2) in an amount of preferably 55 mol% or more, more preferably 60 mol% or more, still more preferable. Contains 65 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the total content ratio 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 that gives a constituent unit (A-1) and a compound that gives a constituent 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、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化合物（即ち、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), and the compound includes the above-mentioned aromatic tetracarboxylic acid dianhydride. , Alicyclic tetracarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.).
The compound arbitrarily contained in the tetracarboxylic acid component (that is, a compound other than the compound giving the structural unit (A-1) and the compound giving the structural unit (A-2)) may be one kind or two or more kinds. There may be.

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２０～９０モル％含み、より好ましくは４５～８５モル％含み、更に好ましくは５０～８０モル％含む。また、ジアミン成分は、構成単位（Ｂ－２）を与える化合物を、好ましくは１０～８０モル％含み、より好ましくは１５～５５モル％含み、更に好ましくは２０～５０モル％含む。
ジアミン成分は、構成単位（Ｂ－１）を与える化合物と構成単位（Ｂ－２）を与える化合物を合計で、好ましくは３０モル％以上含み、より好ましくは６０モル％以上含み、更に好ましくは７０モル％以上含む。構成単位（Ｂ－１）を与える化合物と構成単位（Ｂ－２）を与える化合物の合計の含有比率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）を与える化合物と構成単位（Ｂ－２）を与える化合物とのみからなっていてもよい。 The diamine component contains, preferably 20 to 90 mol%, more preferably 45 to 85 mol%, and further preferably 50 to 80 mol% of the compound giving the structural unit (B-1). Further, the diamine component preferably contains 10 to 80 mol%, more preferably 15 to 55 mol%, and further preferably 20 to 50 mol% of the compound giving the constituent unit (B-2).
The diamine component contains, in total, a compound giving a structural unit (B-1) and a compound giving a structural unit (B-2) in an amount of preferably 30 mol% or more, more preferably 60 mol% or more, still more preferably 70. Contains more than mol%. The upper limit of the total content ratio of the compound giving the structural unit (B-1) and the compound giving the structural unit (B-2) is not particularly limited, that is, 100 mol%. The diamine component may consist only of a compound that gives a constituent unit (B-1) and a compound that gives a constituent unit (B-2).

ジアミン成分は構成単位（Ｂ－１）を与える化合物及び構成単位（Ｂ－２）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化合物（即ち、構成単位（Ｂ－１）を与える化合物及び構成単位（Ｂ－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 diamine component may contain a compound that gives a constituent unit (B-1) and a compound other than the compound that gives a constituent unit (B-2), and the compound includes the above-mentioned aromatic diamine, alicyclic diamine, and fat. Examples thereof include group diamines and derivatives thereof (diisocyanate, etc.).
The compound arbitrarily contained in the diamine component (that is, a compound other than the compound giving the structural unit (B-1) and the compound giving the structural unit (B-2)) may be one kind or two or more kinds. May be good.

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 ratio of the amount of the tetracarboxylic acid component to the diamine component charged 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-cyclohexene-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 and the diamine component is not particularly limited, and a known method can be used.
As a specific reaction method, (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged in a reactor, stirred at room temperature to 80 ° C. for 0.5 to 30 hours, and then heated to imidize. Method of carrying out the reaction, (2) The diamine component and the reaction solvent are charged into a reactor and dissolved, then 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 acid 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 for producing the polyimide resin may be any 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-methylcaprolactum, 1,3-dimethylimidazolidinone, tetramethylurea and the like. Amide-based solvent, lactone-based solvent such as γ-butyrolactone and γ-valerolactone, phosphorus-containing amide-based solvent such as hexamethylphosphoric amide and hexamethylphosphintriamide, and sulfur-containing solvent such as dimethylsulfone, dimethylsulfoxide, and sulfolane. Examples thereof include a system solvent, a ketone solvent such as acetone, cyclohexanone and methylcyclohexanone, an amine solvent such as picolin and pyridine, and an ester solvent 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. Further, the above reaction solvent may be used alone or in combination of two or more.

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 by 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 or 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 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 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。
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。 [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.
Since the polyimide resin of the present invention has solvent solubility, it can be a varnish having a high concentration stable at room temperature. The polyimide varnish of the present invention preferably contains 5 to 40% by mass of the polyimide resin of the present invention, and 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.
Further, the polyimide varnish of the present invention has an inorganic filler, an adhesion accelerator, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, an antifoaming agent, and a fluorescence increase as long as the required characteristics 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、耐熱性及び透明性が良好であって、熱に対する寸法安定性及びレーザー剥離性に優れる。
本発明のポリイミドフィルムの作製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フィルム状に塗布又は成形した後、有機溶媒を除去する方法等が挙げられる。 [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 has good mechanical properties, heat resistance and transparency, and is excellent in dimensional stability against heat and laser peeling property.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. For example, a method of removing the organic solvent after applying or molding the polyimide varnish of the present invention in the form of a film can be mentioned.

本発明のポリイミドフィルムは、機械的特性、耐熱性及び透明性が良好であって、熱に対する寸法安定性及びレーザー剥離性に優れるものであるため、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。 Since the polyimide film of the present invention has good mechanical properties, heat resistance and transparency, and is excellent in dimensional stability against heat and laser peeling property, color filters, flexible displays, semiconductor parts, optical members, etc. It is suitably used as a film for various members of the above. 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ポリイミド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 polyimide 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）引張強度、引張弾性率
測定は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」を用いて行った。
（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Ｔｇ以上まで昇温して残留応力を取り除き、その後同条件で５０℃から５００℃までＴＭＡ測定を行い、Ｔｇを求めた。
（５）全光線透過率、イエローインデックス（ＹＩ）
測定はＪＩＳ Ｋ７３６１－１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」を用いて行った。
（６）線熱膨張係数（ＣＴＥ）
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ＴＭＡ測定を行い、１００～２００℃のＣＴＥ及び１００～３５０℃のＣＴＥを求めた。
（７）波長３０８ｎｍにおける光線透過率
株式会社島津製作所製の紫外可視近赤外分光光度計「ＵＶ－３１００ＰＣ」を用いて測定した。 (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 strength and tensile elastic modulus were measured in accordance with JIS K7127 using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd.
(4) Glass transition temperature (Tg)
Using the thermomechanical analyzer "TMA / SS6100" manufactured by Hitachi High-Tech Science Co., Ltd., the temperature is raised to Tg or more in the tension mode under the conditions of sample size 2 mm x 20 mm, load 0.1 N, and heating rate 10 ° C / min. Then, the residual stress was removed, and then TMA measurement was performed from 50 ° C. to 500 ° C. under the same conditions to determine Tg.
(5) Total light transmittance, yellow index (YI)
The measurement was carried out in accordance with JIS K7361-1 using a color / turbidity simultaneous measuring device "COH400" manufactured by Nippon Denshoku Industries Co., Ltd.
(6) Coefficient of linear thermal expansion (CTE)
Using the thermomechanical analyzer "TMA / SS6100" manufactured by Hitachi High-Tech Science Co., Ltd., TMA measurement was performed under the conditions of sample size 2 mm x 20 mm, load 0.1 N, and heating rate 10 ° C / min in tensile mode. A CTE of 100 to 200 ° C. and a CTE of 100 to 350 ° C. were determined.
(7) Light transmittance at a wavelength of 308 nm The measurement was performed using an ultraviolet-visible near-infrared spectrophotometer "UV-3100PC" manufactured by Shimadzu Corporation.

＜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５００ｍＬの５つ口丸底フラスコに、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）１６．０１２ｇ（０．０５０モル）、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）１７．４２３ｇ（０．０５０モル）、γ－ブチロラクトン（三菱化学株式会社製）８７．５７３ｇ、を投入し、系内温度７０℃、窒素雰囲気下、回転数２００ｒｐｍで撹拌して溶液を得た。
この溶液に、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）３４．５９４ｇ（０．０９０モル）、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（ＪＦＥケミカル株式会社製）４．５８４ｇ（０．０１０モル）、及びγ－ブチロラクトン（三菱化学株式会社製）２１．８９３ｇ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）０．５０６ｇ及びトリエチレンジアミン（東京化成工業株式会社製）０．０５６ｇを投入し、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５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）１９３．５２４ｇを添加して、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、固形分濃度２０質量％のポリイミドワニスを得た。続いてガラス板上へ、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１－１に示す。 <Example 1>
2,2'-Bis (trifluoromethyl) in a 500 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. Benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.) 16.012 g (0.050 mol), 9,9-bis (4-aminophenyl) fluorolen (manufactured by Taoka Chemical Industry Co., Ltd.) 17.423 g (0.050 mol), 87.573 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.
In this solution, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (JX Energy Co., Ltd.) ) 34.594 g (0.090 mol), 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.) 4.584 g (0.010 mol), and γ -After adding 21.893 g of butyrolactone (manufactured by Mitsubishi Chemical Corporation) in a batch, 0.506 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) and 0.056 g of triethylenediamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) are added as imidization catalysts. Then, it was heated with a mantle heater, and the temperature inside the reaction system was raised 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 5 hours while adjusting the rotation speed according to the increase in viscosity.
Then, 193.524 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added to cool the temperature inside the reaction system to 120 ° C., and then the mixture was further stirred for about 3 hours to homogenize the polyimide to have a solid content concentration of 20% by mass. I got a varnish. Subsequently, the obtained polyimide varnish was applied onto a glass plate, 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 evaporate the solvent to make the thickness. A 10 μm film was obtained. The results are shown in Table 1-1.

＜実施例２＞
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（ＪＦＥケミカル株式会社製）を同じモル量の３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）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２０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１１μｍのフィルムを得た。結果を表１－１に示す。 <Example 2>
9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.) in the same molar amount of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (s) -A polyimide varnish was produced by the same method as in Example 1 except that it was changed to BPDA) (manufactured by Mitsubishi Chemical Corporation) to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 11 μm. The results are shown in Table 1-1.

＜実施例３＞
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）の量を１６．０１２ｇ（０．０５０モル）から２５．６１９ｇ（０．０８０モル）に変更し、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）の量を１７．４２３ｇ（０．０５０モル）から６．９６９ｇ（０．０２０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２０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１０μｍのフィルムを得た。結果を表１－１に示す。 <Example 3>
The amount of 2,2'-bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.) was changed from 16.012 g (0.050 mol) to 25.619 g (0.080 mol), and 9,9. -Same as Example 1 except that the amount of bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) was changed from 17.423 g (0.050 mol) to 6.969 g (0.020 mol). A polyimide varnish was produced by the above method to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-1.

＜実施例４＞
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（ＪＦＥケミカル株式会社製）を同じモル量の３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）に変更した以外は、実施例３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２０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１０μｍのフィルムを得た。結果を表１－１に示す。 <Example 4>
9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.) in the same molar amount of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (s) -A polyimide varnish was produced by the same method as in Example 3 except that it was changed to BPDA) (manufactured by Mitsubishi Chemical Corporation) to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-1.

＜実施例５＞
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）の量を３４．５９４ｇ（０．０９０モル）から３０．７５０ｇ（０．０８０モル）に変更し、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（ＪＦＥケミカル株式会社製）の量を４．５８４ｇ（０．０１０モル）から９．１６９ｇ（０．０２０モル）に変更した以外は、実施例３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２０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１０μｍのフィルムを得た。結果を表１－１に示す。 <Example 5>
Amount of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.) Was changed from 34.594 g (0.090 mol) to 30.750 g (0.080 mol), and 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.). A polyimide varnish was prepared by the same method as in Example 3 except that the amount of the mixture was changed from 4.584 g (0.010 mol) to 9.169 g (0.020 mol), and the polyimide having a solid content concentration of 20% by mass was prepared. I got a crocodile. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-1.

＜実施例６＞
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（ＪＦＥケミカル株式会社製）を同じモル量の４，４’－(ヘキサフルオロイソプロピリデン)ジフタル酸無水物に変更した以外は、実施例５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２０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１１μｍのフィルムを得た。結果を表１－１に示す。 <Example 6>
Except for changing 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.) to the same molar amount of 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride. Made a polyimide varnish by the same method as in Example 5 to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 11 μm. The results are shown in Table 1-1.

＜実施例７＞
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（ＪＦＥケミカル株式会社製）を同じモル量の３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）に変更した以外は、実施例５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２０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１１μｍのフィルムを得た。結果を表１－１に示す。 <Example 7>
9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.) in the same molar amount of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (s) -A polyimide varnish was produced by the same method as in Example 5 except that it was changed to BPDA) (manufactured by Mitsubishi Chemical Corporation) to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 11 μm. The results are shown in Table 1-1.

＜実施例８＞
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）の量を２５．６１９ｇ（０．０８０モル）から１９．２１４ｇ（０．０６０モル）に変更し、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）の量を６．９６９ｇ（０．０２０モル）から１３．９３８ｇ（０．０４０モル）に変更した以外は、実施例４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２０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１－１に示す。 <Example 8>
The amount of 2,2'-bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.) was changed from 25.619 g (0.080 mol) to 19.214 g (0.060 mol), and 9,9. -Same as Example 4 except that the amount of bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) was changed from 6.969 g (0.020 mol) to 13.938 g (0.040 mol). A polyimide varnish was produced by the above method to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 14 μm. The results are shown in Table 1-1.

＜実施例９＞
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）の量を３４．５９４ｇ（０．０９０モル）から３０．７５０ｇ（０．０８０モル）に変更し、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）の量を２．９４２ｇ（０．０１０モル）を５．８８４ｇ（０．０２０モル）に変更した以外は、実施例８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２０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１０μｍのフィルムを得た。結果を表１－２に示す。 <Example 9>
Amount of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.) Was changed from 34.594 g (0.090 mol) to 30.750 g (0.080 mol), and 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) (Mitsubishi Chemical Co., Ltd.) A polyimide varnish was prepared by the same method as in Example 8 except that the amount of (manufactured by the company) was changed from 2.942 g (0.010 mol) to 5.884 g (0.020 mol), and the solid content concentration was 20 mass. % Polyimide varnish was obtained. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-2.

＜実施例１０＞
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）の量を３０．７５０ｇ（０．０８０モル）から２３．０６３ｇ（０．０６０モル）に変更し、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）の量を５．８８４ｇ（０．０２０モル）から１１．７６８ｇ（０．０４０モル）に変更した以外は、実施例９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２０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１１μｍのフィルムを得た。結果を表１－２に示す。 <Example 10>
Amount of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.) Was changed from 30.750 g (0.080 mol) to 23.063 g (0.060 mol), and 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) (Mitsubishi Chemical Co., Ltd.) A polyimide varnish was prepared by the same method as in Example 9 except that the amount of (manufactured by the company) was changed from 5.884 g (0.020 mol) to 11.768 g (0.040 mol), and the solid content concentration was 20 mass. % Polyimide varnish was obtained. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 11 μm. The results are shown in Table 1-2.

＜実施例１１＞
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）の量を３４．５９４ｇ（０．０９０モル）から１９．２１９ｇ（０．０５０モル）に変更し、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）の量を２．９４２ｇ（０．０１０モル）から１４．７１１ｇ（０．０５０モル）に変更し、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）の量を１６．０１２ｇ（０．０５０モル）から６．４０５ｇ（０．０２０モル）に変更し、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）の量を１７．４２３ｇ（０．０５０モル）から２７．８７６ｇ（０．０８０モル）に変更した以外は、実施例２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２０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１０μｍのフィルムを得た。結果を表１－２に示す。 <Example 11>
Amount of norbornan-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.) Was changed from 34.594 g (0.090 mol) to 19.219 g (0.050 mol), and 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) (Mitsubishi Chemical Co., Ltd.) The amount of (manufactured by the company) was changed from 2.942 g (0.010 mol) to 14.711 g (0.050 mol), and 2,2'-bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.). The amount of 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) was changed from 16.012 g (0.050 mol) to 6.405 g (0.020 mol). A polyimide varnish was prepared by the same method as in Example 2 except that the amount was changed from .423 g (0.050 mol) to 27.876 g (0.080 mol) to obtain a polyimide varnish having a solid content concentration of 20% by mass. .. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-2.

＜実施例１２＞
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）の量を３４．５９４ｇ（０．０９０モル）から２６．９０６ｇ（０．０７０モル）に変更し、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（ＪＦＥケミカル株式会社製）の量を４．５８４ｇ（０．０１０モル）から１３．７５３ｇ（０．０３０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２０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１０μｍのフィルムを得た。結果を表１－２に示す。 <Example 12>
Amount of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.) Was changed from 34.594 g (0.090 mol) to 26.906 g (0.070 mol), and 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.). A polyimide varnish was prepared by the same method as in Example 1 except that the amount of the mixture was changed from 4.584 g (0.010 mol) to 13.753 g (0.030 mol), and the polyimide having a solid content concentration of 20% by mass was prepared. I got a crocodile. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-2.

＜実施例１３＞
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）の量を３４．５９４ｇ（０．０９０モル）から１９．２１９ｇ（０．０５０モル）に変更し、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（ＪＦＥケミカル株式会社製）の量を４．５８４ｇ（０．０１０モル）から２２．９２２ｇ（０．０５０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２０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１０μｍのフィルムを得た。結果を表１－２に示す。 <Example 13>
Amount of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.) Was changed from 34.594 g (0.090 mol) to 19.219 g (0.050 mol), and 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.). A polyimide varnish was prepared by the same method as in Example 1 except that the amount of the mixture was changed from 4.584 g (0.010 mol) to 22.922 g (0.050 mol), and the polyimide having a solid content concentration of 20% by mass was prepared. I got a crocodile. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-2.

＜実施例１４＞
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）の量を３４．５９４ｇ（０．０９０モル）から１９．２１９ｇ（０．０５０モル）に変更し、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）の量を２．９４２ｇ（０．０１０モル）から１４．７１１ｇ（０．０５０モル）に変更した以外は、実施例４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２０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１０μｍのフィルムを得た。結果を表１－２に示す。 <Example 14>
Amount of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (manufactured by JX Energy Co., Ltd.) Was changed from 34.594 g (0.090 mol) to 19.219 g (0.050 mol), and 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) (Mitsubishi Chemical Co., Ltd.) A polyimide varnish was prepared by the same method as in Example 4 except that the amount of (manufactured by the company) was changed from 2.942 g (0.010 mol) to 14.711 g (0.050 mol), and the solid content concentration was 20 mass. % Polyimide varnish was obtained. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-2.

＜実施例１５＞
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）の量を２５．６１９ｇ（０．０８０モル）から１７．６１３ｇ（０．０５５モル）に変更し、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）の量を６．９６９ｇ（０．０２０モル）から１５．６８０ｇ（０．０４５モル）に変更した以外は、実施例３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２０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１０μｍのフィルムを得た。結果を表１－２に示す。 <Example 15>
The amount of 2,2'-bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.) was changed from 25.619 g (0.080 mol) to 17.613 g (0.055 mol), and 9,9. -Same as Example 3 except that the amount of bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) was changed from 6.969 g (0.020 mol) to 15.680 g (0.045 mol). A polyimide varnish was produced by the above method to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1-2.

＜比較例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５００ｍＬの５つ口丸底フラスコに、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）３４．８４５ｇ（０．１００モル）、γ－ブチロラクトン（三菱化学株式会社製）８８．３９５ｇ、を投入し、系内温度７０℃、窒素雰囲気下、回転数２００ｒｐｍで撹拌して溶液を得た。
この溶液に、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）３８．４３８ｇ（０．１００モル）及びγ－ブチロラクトン（三菱化学株式会社製）２２．０９９ｇ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）０．５０６ｇ及びトリエチレンジアミン（東京化成工業株式会社製）０．０５６ｇを投入し、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５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）１９１．８４０ｇを添加して、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、固形分濃度２０質量％のポリイミドワニスを得た。続いてガラス板上へ、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２に示す。 <Comparative Example 1>
9,9-bis (4-aminophenyl) in a 500 mL five-necked round-bottom flask equipped with a stainless half-moon agitator, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. 34.845 g (0.100 mol) of flask (manufactured by Taoka Chemical Industry Co., Ltd.) and 88.395 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and the system temperature was 70 ° C., a nitrogen atmosphere, and the rotation speed was 200 rpm. The solution was obtained by stirring with.
In this solution, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (JX Energy Co., Ltd.) (Manufactured by) 38.438 g (0.100 mol) and γ-butyrolactone (manufactured by Mitsubishi Chemical Industry Co., Ltd.) 22.099 g, and then triethylamine (manufactured by Kanto Chemical Co., Inc.) 0.506 g and triethylenediamine as imidization catalysts. (Manufactured by Tokyo Chemical Industry Co., Ltd.) 0.056 g was added and 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 5 hours while adjusting the rotation speed according to the increase in viscosity.
After that, 191.840 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added to cool the temperature inside the reaction system to 120 ° C., and then the mixture was further stirred for about 3 hours to homogenize the polyimide to have a solid content concentration of 20% by mass. I got a varnish. Subsequently, the obtained polyimide varnish was applied onto a glass plate, 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 evaporate the solvent to make the thickness. A 10 μm film was obtained. The results are shown in Table 2.

＜比較例２＞
９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）の量を３４．８４５ｇ（０．１００モル）から６．９６９ｇ（０．０２０モル）に変更し、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）を２５．６１９ｇ（０．０８０モル）追加した以外は、比較例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２０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１０μｍのフィルムを得た。結果を表２に示す。 <Comparative Example 2>
The amount of 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) was changed from 34.845 g (0.100 mol) to 6.969 g (0.020 mol), and 2,2' -A polyimide varnish was prepared by the same method as in Comparative Example 1 except that 25.619 g (0.080 mol) of bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.) was added, and the solid content concentration was 20. A weight% polyimide varnish was obtained. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 2.

＜比較例３＞
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）の量を２５．６１９ｇ（０．０８０モル）から１６．０１２ｇ（０．０５０モル）に変更し、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）の量を６．９６９ｇ（０．０２０モル）から１７．４２３ｇ（０．０５０モル）に変更した以外は、比較例２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２０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１０μｍのフィルムを得た。結果を表２に示す。 <Comparative Example 3>
The amount of 2,2'-bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.) was changed from 25.619 g (0.080 mol) to 16.012 g (0.050 mol), and 9,9. -Same as Comparative Example 2 except that the amount of bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) was changed from 6.969 g (0.020 mol) to 17.423 g (0.050 mol). A polyimide varnish was produced by the above method to obtain a polyimide varnish having a solid content concentration of 20% by mass. Using the obtained polyimide varnish, a film was produced by the same method as in Example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 2.

＜比較例４＞
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５００ｍＬの５つ口丸底フラスコに、９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）３４．８４５ｇ（０．１００モル）、Ｎ，Ｎ－ジメチルホルムアミド（三菱ガス化学株式会社製）７７．４０４ｇ、を投入し、系内温度５０℃、窒素雰囲気下、回転数２００ｒｐｍで撹拌して溶液を得た。
この溶液に、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）（三菱化学株式会社製）２９．４２０ｇ（０．１００モル）及びＮ，Ｎ－ジメチルホルムアミド（三菱ガス化学株式会社製）１９．３５１ｇを一括で添加した後、約２０分かけて溶解し、回転数を粘度上昇に合わせて調整しつつ、室温で５時間撹拌した。
その後、Ｎ，Ｎ－ジメチルホルムアミド（三菱ガス化学株式会社製）１６６．１９４ｇを添加して、約１時間撹拌して均一化し、固形分濃度２０質量％のポリアミック酸ワニスを得た。続いてガラス板上へ、得られたポリアミック酸ワニスを塗布し、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分加熱することで、ポリアミック酸をイミド化するとともに、ワニス中の溶媒を蒸発させ、厚み８μｍのフィルムを得た。結果を表２に示す。 <Comparative Example 4>
9,9-Bis (4-aminophenyl) in a 500 mL five-necked round-bottom flask equipped with a stainless half-moon agitator, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. 34.845 g (0.100 mol) of flask (manufactured by Taoka Chemical Industry Co., Ltd.) and 77.404 g of N, N-dimethylformamide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were added, and the temperature inside the system was 50 ° C. under a nitrogen atmosphere. , The solution was obtained by stirring at a rotation speed of 200 rpm.
In this solution, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (s-BPDA) (manufactured by Mitsubishi Chemical Corporation) 29.420 g (0.100 mol) and N, N-dimethylformamide (0.100 mol) and N, N-dimethylformamide ( After adding 19.351 g (manufactured by Mitsubishi Gas Chemical Corporation) in a batch, it was dissolved over about 20 minutes, and the mixture was stirred at room temperature for 5 hours while adjusting the number of revolutions according to the increase in viscosity.
Then, 166.194 g of N, N-dimethylformamide (manufactured by Mitsubishi Gas Chemical Company, Inc.) was added, and the mixture was stirred for about 1 hour to homogenize to obtain a polyamic acid varnish having a solid content concentration of 20% by mass. Subsequently, the obtained polyamic acid varnish was applied onto a glass plate, 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 obtain the polyamic acid. Was imidized and the solvent in the varnish was evaporated to obtain a film having a thickness of 8 μm. The results are shown in Table 2.

＜比較例５＞
９，９－ビス（４－アミノフェニル）フルオレン（田岡化学工業株式会社製）を同じモル量の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）に変更した以外は、比較例４と同様の方法によりポリアミック酸ワニスを作製し、固形分濃度２０質量％のポリアミック酸ワニスを得た。得られたポリアミック酸ワニスを用いて、比較例４と同様の方法によりフィルムを作製し、厚み２２μｍのフィルムを得た。結果を表２に示す。 <Comparative Example 5>
Other than changing 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) to 2,2'-bis (trifluoromethyl) benzidine (manufactured by Wakayama Seika Kogyo Co., Ltd.) in the same molar amount. Made a polyamic acid varnish by the same method as in Comparative Example 4 to obtain a polyamic acid varnish having a solid content concentration of 20% by mass. Using the obtained polyamic acid varnish, a film was prepared by the same method as in Comparative Example 4 to obtain a film having a thickness of 22 μm. The results are shown in Table 2.

Figure 0006996609000007
Figure 0006996609000007

Figure 0006996609000008
Figure 0006996609000008

Figure 0006996609000009
Figure 0006996609000009

表１－１、表１－２及び表２中の略号は以下のとおりである。
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（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（式（ａ－２）で表される化合物）
ＢＰＡＦ：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（式（ａ－２）で表される化合物）
６ＦＤＡ：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（式（ａ－２）で表される化合物）
ＴＦＭＢ：２，２’－ビス（トリフルオロメチル）ベンジジン（式（ｂ－１）で表される化合物）
ＢＡＦＬ：９，９－ビス（４－アミノフェニル）フルオレン（式（ｂ－２）で表される化合物） The abbreviations in Table 1-1, Table 1-2 and Table 2 are as follows.
CpODA: Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride (formula (a-1)) Compound represented by)
BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride (compound represented by formula (a-2))
BPAF: 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (compound represented by the formula (a-2))
6FDA: 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride (compound represented by the formula (a-2))
TFMB: 2,2'-bis (trifluoromethyl) benzidine (compound represented by the formula (b-1))
BAFL: 9,9-bis (4-aminophenyl) fluorene (compound represented by the formula (b-2))

表１－１及び表１－２に示すように、実施例１～１５のポリイミドフィルムは、機械的特性、耐熱性及び透明性が良好であって、熱に対する寸法安定性及びレーザー剥離性に優れている。また、実施例１～１０、１２、１３、及び１５のポリイミドフィルムは、ＹＩが小さく、即ち、無色透明性に優れている。
一方、表２に示すように、比較例１のポリイミドフィルムは熱に対する寸法安定性が大きく劣り、比較例２及び３のポリイミドフィルムはレーザー剥離性が大きく劣り、比較例４のポリイミドフィルムは熱に対する寸法安定性が大きく劣るだけでなく、さらに機械的特性も劣り、比較例５のポリイミドフィルムは熱に対する寸法安定性が大きく劣るだけでなく、さらに耐熱性も劣る。 As shown in Table 1-1 and Table 1-2, the polyimide films of Examples 1 to 15 have good mechanical properties, heat resistance and transparency, and are excellent in dimensional stability against heat and laser peeling property. ing. Further, the polyimide films of Examples 1 to 10, 12, 13, and 15 have a small YI, that is, they are excellent in colorless transparency.
On the other hand, as shown in Table 2, the polyimide film of Comparative Example 1 is significantly inferior in dimensional stability to heat, the polyimide films of Comparative Examples 2 and 3 are significantly inferior in laser peelability, and the polyimide film of Comparative Example 4 is significantly inferior to heat. Not only is the dimensional stability significantly inferior, but also the mechanical properties are inferior. The polyimide film of Comparative Example 5 is not only significantly inferior in dimensional stability to heat, but also inferior in heat resistance.

Claims (6)

テトラカルボン酸二無水物に由来する構成単位Ａと、ジアミンに由来する構成単位Ｂとを含む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）と、下記式（ｂ－２）で表される化合物に由来する構成単位（Ｂ－２）とを含み、
構成単位（Ａ－２）が、下記式（ａ－２－１）で表される化合物に由来する構成単位（Ａ－２－１）、下記式（ａ－２－２）で表される化合物に由来する構成単位（Ａ－２－２）及び下記式（ａ－２－３）で表される化合物に由来する構成単位（Ａ－２－３）からなる群より選ばれる少なくとも一つである、ポリイミド樹脂。
Figure 0006996609000010
（式（ａ－２）中、Ｌは単結合又は二価の連結基であり、
式（ｂ－２）中、Ｒはそれぞれ独立して、水素原子、フッ素原子又はメチル基である。）
Figure 0006996609000011
 A polyimide resin containing a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a 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
A structural unit (B-1) in which the structural unit B is derived from a compound represented by the following formula (b-1) and a structural unit (B-2) derived from a compound represented by the following formula (b-2). Including and
The structural unit (A-2) is derived from the compound represented by the following formula (a-2-1), the structural unit (A-2-1), and the compound represented by the following formula (a-2-2). It is at least one selected from the group consisting of the structural unit (A-2-2) derived from and the structural unit (A-2-3) derived from the compound represented by the following formula (a-2-3). , Polyimide resin.
Figure 0006996609000010
(In formula (a-2), L is a single bond or a divalent linking group.
In formula (b-2), R is independently a hydrogen atom, a fluorine atom or a methyl group. )
Figure 0006996609000011
 構成単位Ａ中における構成単位（Ａ－１）の比率が５０～９５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５～５０モル％である、請求項１に記載のポリイミド樹脂。 The ratio of the constituent unit (A-1) in the constituent unit A is 50 to 95 mol%.
The polyimide resin according to claim 1, wherein the ratio of the structural unit (A-2) in the structural unit A is 5 to 50 mol%. 構成単位Ｂ中における構成単位（Ｂ－１）の比率が２０～９０モル％であり、
構成単位Ｂ中における構成単位（Ｂ－２）の比率が１０～８０モル％である、請求項１又は２にポリイミド樹脂。 The ratio of the constituent unit (B-1) in the constituent unit B is 20 to 90 mol%.
The polyimide resin according to claim 1 or 2, wherein the ratio of the structural unit (B-2) in the structural unit B is 10 to 80 mol%. Ｒが水素原子を表わす、請求項１～３のいずれかに記載のポリイミド樹脂。 The polyimide resin according to any one of claims 1 to 3, wherein R represents a hydrogen atom. 請求項１～４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 obtained by dissolving the polyimide resin according to any one of claims 1 to 4 in an organic solvent. 請求項１～４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 4.
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CN111133033A (en) 2020-05-08
JPWO2019065523A1 (en) 2020-04-30

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