JP6253172B2 - Polyimide film - Google Patents
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- JP6253172B2 JP6253172B2 JP2017507037A JP2017507037A JP6253172B2 JP 6253172 B2 JP6253172 B2 JP 6253172B2 JP 2017507037 A JP2017507037 A JP 2017507037A JP 2017507037 A JP2017507037 A JP 2017507037A JP 6253172 B2 JP6253172 B2 JP 6253172B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Description
本発明は、本質的に無色透明なポリイミド膜、特に、光ファイバー、液晶表示面の基板、エレクトロルミネッセンスの基板、保護シートなどに有用な本質的に無色透明なポリイミド膜に関する。 The present invention relates to an essentially colorless and transparent polyimide film, and more particularly to an essentially colorless and transparent polyimide film useful for optical fibers, liquid crystal display surface substrates, electroluminescent substrates, protective sheets and the like.
ポリイミド膜は、一般的に優れた熱安定性、電気的特定および機械的特性を有しており、比較的厳しい環境下で使用される様々な製品に適用されている。ところで、ポリイミド膜は、膜形成に至るまでの過酷な熱履歴のために白濁化したり、黄色または褐色に着色したりしているものが多い。このように白濁化したポリイミド膜や、着色したポリイミド膜は、液晶ディスプレイ装置のフィルム基板として適用された場合、その視野を暗くするだけでなく、液晶ディスプレイ装置本来の機能を損ねてしまう。そこで、そのような問題を解決するために無色透明のポリイミド膜が開発されてきた。そして、今や、無色透明のポリイミド膜は、液晶ディスプレイ装置、光ファイバーケーブル被膜、導波管および太陽電池用保護被膜などにフィルムとして広範囲に用いられている（例えば、特開昭６２−７７３３号公報、特開２０００−３１３８０４号公報、特開２０１２−０４０８３６号公報等参照）。 Polyimide films generally have excellent thermal stability, electrical characteristics and mechanical properties, and are applied to various products used in relatively harsh environments. By the way, many polyimide films are clouded or colored yellow or brown due to severe heat history until film formation. When such a turbid polyimide film or a colored polyimide film is applied as a film substrate of a liquid crystal display device, it not only darkens the field of view but also impairs the original function of the liquid crystal display device. Therefore, a colorless and transparent polyimide film has been developed to solve such a problem. Now, colorless and transparent polyimide films are widely used as films for liquid crystal display devices, optical fiber cable coatings, waveguides, protective coatings for solar cells, etc. (for example, JP-A-62-27333, JP 2000-313804 A, JP 2012-040836 A, etc.).
しかし、過去に提案された無色透明のポリイミド膜は、高原料コストのために高価格にならざるを得なく、なかなか市場に受け入れられないという問題があった。また、従前の無色透明のポリイミド膜は、フレキシブルプリント回路基板等の作製時に使用されるメチルエチルケトンに対する耐性が低く、張力がかかった場合に破断してしまうという不具合があった。 However, the colorless and transparent polyimide films proposed in the past have had a problem that they have to be expensive due to high raw material costs and are not easily accepted by the market. Further, the conventional colorless and transparent polyimide film has a low resistance to methyl ethyl ketone used in the production of a flexible printed circuit board or the like, and has a problem that it breaks when tension is applied.
本発明の課題は、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前よりも低コストで生産することが可能であり、また、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高い無色透明のポリイミド膜を提供することにある。 The problem of the present invention is that it can be produced at a lower cost than the conventional while exhibiting excellent heat resistance, transparency and strength equivalent to those of the prior art, and methyl ethyl ketone than the conventional colorless and transparent polyimide film. It is an object to provide a colorless and transparent polyimide film having high resistance to water.
本発明の一局面に係るポリイミド膜は、特定のポリイミド樹脂から成る。なお、ここで、ポリイミド膜には、フィルムや、シート、管状体が含まれる。特定のポリイミド樹脂は、ビフェニルテトラカルボン酸系化合物（ＢＰＤＡ）由来部位と、２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物（ＢＰＡＤＡ）由来部位、および、４，４’−オキシジフタル酸系化合物（ＯＤＰＡ）由来部位より成る群から選択される少なくとも１つの部位と、２，２’−ビス（トリフルオロメチル）ベンジジン（ＴＦＭＢ）由来部位と、３，３’−ジアミノジフェニルスルホン（３，３’−ＤＤＳ）由来部位、および、４，４’−ジアミノジフェニルスルホン（４，４’−ＤＤＳ）由来部位より成る群から選択される少なくとも１つの部位とから成る。なお、ここで、テトラカルボン酸系化合物由来部位は、「テトラカルボン酸」または「テトラカルボン酸二無水物や、テトラカルボン酸ジエステル等のテトラカルボン酸誘導体」に由来する部位を意味し、ジアミン由来部位は「ジアミン」に由来する部位を意味する。また、本発明に係るポリイミド膜の膜厚は、５μｍ以上５０μｍ以下の範囲内であるが、７．５μｍ以上４０μｍ以下の範囲内であることが好ましく、１０μｍ以上３０μｍ以下の範囲内であることがより好ましい。そして、このポリイミド膜のヘイズ値は、ポリイミド膜の膜厚が２５μｍであるとき、０．１以上２．０以下の範囲内である。ヘイズ値が２．０以下である無色透明のポリイミド膜は、液晶ディスプレイなどの用途に適用された場合、安定して光を透過させることができる。 Polyimide film of one aspect of the present invention, Ru consists specific polyimide resin. Here, the polyimide film includes a film, a sheet, and a tubular body. Certain polyimide resin, biphenyl tetracarboxylic acid compound (BPDA) and site-derived, 2,2-bis [3,4- (di-carboxy) phenyl] propane compound (BPADA) derived sites, and, 4, At least one site selected from the group consisting of 4′-oxydiphthalic acid compound (ODPA) -derived sites, 2,2′-bis (trifluoromethyl) benzidine (TFMB) -derived sites, and 3,3′-diamino It consists of at least one site selected from the group consisting of a site derived from diphenylsulfone (3,3′-DDS) and a site derived from 4,4′-diaminodiphenylsulfone (4,4′-DDS) . Here, tetracarboxylic acid compound derived portion position means a site derived from "tetracarboxylic acid" or "tetracarboxylic dianhydride or tetracarboxylic acid derivatives such as tetracarboxylic acid diesters" diamine derived from the part position means a site derived from "diamine". It addition, the thickness of the polyimide film according to the present invention are in the range of 5μm or 50μm or less, it is within the scope of the following 40μm or 7.5μm is preferably in the range of 10μm or 30μm or less Is more preferable. And the haze value of this polyimide film exists in the range of 0.1 or more and 2.0 or less, when the film thickness of a polyimide film is 25 micrometers. A colorless and transparent polyimide film having a haze value of 2.0 or less can stably transmit light when applied to uses such as a liquid crystal display.
なお、本発明に係る無色透明のポリイミド膜は、ビフェニルテトラカルボン酸系化合物と、２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物、および、４，４’−オキシジフタル酸系化合物より成る群から選択される少なくとも１つと、２，２’−ビス（トリフルオロメチル）ベンジジンと、３，３’−ジアミノジフェニルスルホン、および、４，４’−ジアミノジフェニルスルホンより成る群から選択される少なくとも１つとを用いて調製されたポリイミド前駆体溶液から形成される。そのポリイミド前駆体溶液は、上述のテトラカルボン酸系化合物と上述のジアミンとが極性有機溶媒中で反応させられることによって得られる。なお、ポリイミド前駆体溶液を調製する際、本発明の本質を損なわない範囲で、既知の全ての芳香族テトラカルボン酸系化合物または芳香族ジアミンを添加することができる。また、無色透明のポリイミド膜の目的や用途に応じて、複数種類のテトラカルボン酸系化合物中の各テトラカルボン酸系化合物のモル比を適宜調整することができる。 The colorless and transparent polyimide film according to the present invention includes a biphenyltetracarboxylic acid compound, a 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane compound, and 4,4′-oxydiphthalate. A group consisting of at least one selected from the group consisting of acid compounds, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-diaminodiphenylsulfone, and 4,4'-diaminodiphenylsulfone Formed from a polyimide precursor solution prepared using at least one selected from: The polyimide precursor solution is obtained by reacting the above-described tetracarboxylic acid compound and the above-described diamine in a polar organic solvent. In preparing the polyimide precursor solution, all known aromatic tetracarboxylic acid compounds or aromatic diamines can be added as long as the essence of the present invention is not impaired. Moreover, according to the objective and use of a colorless and transparent polyimide film, the molar ratio of each tetracarboxylic acid compound in a plurality of types of tetracarboxylic acid compounds can be appropriately adjusted.
上述のポリイミド前駆体溶液の調製のために使用される有機溶媒としては、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、フェノ−ル、クレゾ−ル、キシレノ−ル、レゾルシン、３−クロロフェノ−ル、４−クロロフェノ−ル、３−ブロモフェノ−ル、４−ブロモフェノ−ル、２−クロロ−５−ヒドロキシトルエン、ジグライム、トリグライム、スルホラン、γ−ブチロラクトン、テトラヒドロフランおよびジオキソラン等が挙げられる。これらの中でもＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）は好適に用いられる。また、これらの溶媒は２種以上併用されてもよい。 Examples of the organic solvent used for the preparation of the polyimide precursor solution include N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N, N-diethylacetamide, N, N- Diethylformamide, N-methyl-2-pyrrolidone (NMP), phenol, cresol, xylenol, resorcin, 3-chlorophenol, 4-chlorophenol, 3-bromophenol, 4-bromophenol And 2-chloro-5-hydroxytoluene, diglyme, triglyme, sulfolane, γ-butyrolactone, tetrahydrofuran and dioxolane. Among these, N, N-dimethylacetamide (DMAc) is preferably used. Two or more of these solvents may be used in combination.
また、上述のポリイミド前駆体溶液には、本発明の本質を損なわない範囲内で、分散剤、固体潤滑剤、沈降防止剤、レベリング剤、表面調節剤、水分吸収剤、ゲル化防止剤、酸化防止剤、紫外線吸収剤、光安定剤、可塑剤、皮張り防止剤、界面活性剤、帯電防止剤、消泡剤、抗菌剤、防カビ剤、防腐剤、増粘剤などの公知の添加剤が添加されてもよい。 In addition, the polyimide precursor solution described above includes a dispersant, a solid lubricant, an anti-settling agent, a leveling agent, a surface conditioner, a moisture absorbent, an anti-gelling agent, an oxidation, within a range that does not impair the essence of the present invention. Known additives such as inhibitors, ultraviolet absorbers, light stabilizers, plasticizers, anti-skinning agents, surfactants, antistatic agents, antifoaming agents, antibacterial agents, fungicides, antiseptics, thickeners, etc. May be added.
そして、本発明に係る無色透明のポリイミド膜は、上述のポリイミド前駆体溶液から塗膜を形成し、その塗膜をイミド転化させることによって得られる。 And the colorless and transparent polyimide film which concerns on this invention is obtained by forming a coating film from the above-mentioned polyimide precursor solution, and carrying out the imide conversion of the coating film.
なお、上述のポリイミド膜の特定のポリイミド樹脂において、全てのテトラカルボン酸系化合物由来部位に対するビフェニルテトラカルボン酸系化合物（ＢＰＤＡ）由来部位のモル分率が７０ｍｏｌ％以上９９ｍｏｌ％以下の範囲内であることが好ましく、８０ｍｏｌ％以上９７．５ｍｏｌ％以下の範囲内であることがより好ましく、９０ｍｏｌ％以上９５ｍｏｌ％以下の範囲内であることがより好ましい。テトラカルボン酸系化合物由来部位に対するビフェニルテトラカルボン酸系化合物（ＢＰＤＡ）のモル比が５０ｍｏｌ％以上であるポリイミド膜は、高いガラス転移温度を有し、液晶ディスプレイやフレキシブルプリント基板などの製造時において半田付けなどを行う際に、十分な耐熱性を保持できるためである。 In the specific polyimide resin of the polyimide film described above, the molar fraction of the biphenyltetracarboxylic acid compound (BPDA) -derived portion relative to all the tetracarboxylic acid-based compound-derived portions is in the range of 70 mol% or more and 99 mol% or less. It is more preferable that it is in the range of 80 mol% or more and 97.5 mol% or less, and it is more preferable that it is in the range of 90 mol% or more and 95 mol% or less. A polyimide film in which the molar ratio of biphenyltetracarboxylic acid compound (BPDA) to the tetracarboxylic acid compound-derived moiety is 50 mol% or more has a high glass transition temperature, and is used in the manufacture of liquid crystal displays and flexible printed boards. This is because sufficient heat resistance can be maintained when attaching.
ビフェニルテトラカルボン酸系化合物（ＢＰＤＡ）由来部位はビフェニルテトラカルボン酸系化合物（ＢＰＤＡ）から形成されるが、ビフェニルテトラカルボン酸系化合物（ＢＰＤＡ）としては、「ビフェニルテトラカルボン酸」または「ビフェニルテトラカルボン酸二無水物や、ビフェニルテトラカルボン酸ジエステル等のビフェニルテトラカルボン酸誘導体」が挙げられる。なお、ビフェニルテトラカルボン酸はビフェニルテトラカルボン酸二無水物を公知の方法によって加水分解することによって得ることができ、ビフェニルテトラカルボン酸ジエステルはビフェニルテトラカルボン酸二無水物を公知の方法によってジエステル化することによって得ることができる。 The site derived from the biphenyltetracarboxylic acid compound (BPDA) is formed from the biphenyltetracarboxylic acid compound (BPDA). As the biphenyltetracarboxylic acid compound (BPDA), "biphenyltetracarboxylic acid" or "biphenyltetracarboxylic And acid dianhydrides and biphenyltetracarboxylic acid derivatives such as biphenyltetracarboxylic acid diesters ”. Biphenyltetracarboxylic acid can be obtained by hydrolyzing biphenyltetracarboxylic dianhydride by a known method, and biphenyltetracarboxylic acid diester diesterifies biphenyltetracarboxylic dianhydride by a known method. Can be obtained.
また、上述のポリイミド膜を形成する特定のポリイミド樹脂において、全てのテトラカルボン酸系化合物由来部位に対する２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物（ＢＰＡＤＡ）由来部位、および、４，４’−オキシジフタル酸系化合物（ＯＤＰＡ）由来部位より成る群から選択される少なくとも１つの部位のモル分率が１ｍｏｌ％以上３０ｍｏｌ％以下の範囲内であることが好ましく、２．５ｍｏｌ％以上２０ｍｏｌ％以下の範囲内であることがより好ましく、５ｍｏｌ％以上１０ｍｏｌ％以下の範囲内であることがさらに好ましい。このような特定のポリイミド樹脂から成るポリイミド膜は、白濁化の度合いが極めて低く、高い透明性を維持することができるためである。 Moreover, in the specific polyimide resin which forms the above-mentioned polyimide film, 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane-based compound (BPADA) -derived site relative to all tetracarboxylic acid-based compound- derived sites Preferably, the molar fraction of at least one site selected from the group consisting of sites derived from 4,4′-oxydiphthalic acid compounds (ODPA) is in the range of 1 mol% to 30 mol%. It is more preferably in the range of 5 mol% or more and 20 mol% or less, and further preferably in the range of 5 mol% or more and 10 mol% or less. This is because a polyimide film made of such a specific polyimide resin has a very low degree of white turbidity and can maintain high transparency.
２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物（ＢＰＡＤＡ）由来部位は２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物から形成され、４，４’−オキシジフタル酸系化合物（ＯＤＰＡ）由来部位は４，４’−オキシジフタル酸系化合物から形成されるが、２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物としては、「２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン」または「２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン二無水物や、２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパンジエステル等の２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン誘導体」が挙げられ、４，４’−オキシジフタル酸系化合物としては、「４，４’−オキシジフタル酸」または「４，４’−オキシジフタル酸二無水物や、４，４’−オキシジフタル酸ジエステル等の４，４’−オキシジフタル酸誘導体」が挙げられる。なお、上記芳香族テトラカルボン酸二無水物を公知の方法によって加水分解することによって芳香族テトラカルボン酸を得ることができ、上記芳香族テトラカルボン酸二無水物を公知の方法によってジエステル化することによって芳香族テトラカルボン酸ジエステルを得ることができる。 A site derived from 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane-based compound (BPADA) is formed from 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane-based compound ; 4,4'-oxydiphthalic acid compounds (ODPA) derived sites Ru is formed from 4,4'-oxydiphthalic acid compounds, but 2,2-bis [3,4- (di-carboxy) phenyl] propane compound As " 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane " or " 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane dianhydride , 2-bis [3,4- (di-carboxy) phenyl] propane and the like diester of 2,2-bis [3,4- (dicarboxyphenoxy) Fe Le] propane derivative ", and examples of the 4,4'-oxydiphthalic acid compounds,"4,4'-oxydiphthalic acid "or"4,4'-oxydiphthalic dianhydride and 4,4'-oxydiphthalic 4,4'-oxydiphthalic acid derivatives such as acid diester "is Ru mentioned. Note that known on KiKaoru the aromatic tetracarboxylic acid dianhydride by the hydrolysis by known methods can be obtained Fang aromatic tetracarboxylic acids, upper KiKaoru aromatic tetracarboxylic acid dianhydride it can be by to diester by way obtaining Fang aromatic tetracarboxylic acid diester.
また、上述のポリイミド膜の特定のポリイミド樹脂において、全てのジアミン由来部位に対する２，２’−ビス（トリフルオロメチル）ベンジジン（ＴＦＭＢ）由来部位のモル分率が４０ｍｏｌ％以上９８ｍｏｌ％以下の範囲内であることが好ましく、５０ｍｏｌ％以上９５ｍｏｌ％以下の範囲内であることがより好ましく、６０ｍｏｌ％以上９０ｍｏｌ％以下の範囲内であることがさらに好ましい。このような特定のポリイミド樹脂から成るポリイミド膜は、優れた透明性を示すことができるからである。 Moreover, in the specific polyimide resin of the above-mentioned polyimide film, the molar fraction of the 2,2′-bis (trifluoromethyl) benzidine (TFMB) -derived portion relative to all the diamine-derived portions is in the range of 40 mol% or more and 98 mol% or less. Preferably, it is in the range of 50 mol% or more and 95 mol% or less, and more preferably in the range of 60 mol% or more and 90 mol% or less. This is because a polyimide film made of such a specific polyimide resin can exhibit excellent transparency.
また、上述のポリイミド膜を形成する特定のポリイミド樹脂において、全てのジアミン由来部位に対する３，３’−ジアミノジフェニルスルホン（３，３’−ＤＤＳ）由来部位、および、４，４’−ジアミノジフェニルスルホン（４，４’−ＤＤＳ）由来部位より成る群から選択される少なくとも１つの部位のモル分率が２ｍｏｌ％以上６０ｍｏｌ％以下の範囲内であることが好ましく、５ｍｏｌ％以上５０ｍｏｌ％以下の範囲内であることがより好ましく、１０ｍｏｌ％以上４０ｍｏｌ％以下の範囲内であることがさらに好ましい。このような特定のポリイミド樹脂から成るポリイミド膜は、原料コストが低くなるからである。 Further, in the specific polyimide resin forming the above-described polyimide film, 3,3′-diaminodiphenylsulfone (3,3′-DDS) -derived sites with respect to all diamine-derived sites and 4,4′-diaminodiphenylsulfone The molar fraction of at least one site selected from the group consisting of (4,4′-DDS) -derived sites is preferably in the range of 2 mol% to 60 mol%, preferably in the range of 5 mol% to 50 mol%. It is more preferable that it is in the range of 10 mol% or more and 40 mol% or less. This is because such a polyimide film made of a specific polyimide resin has a low raw material cost.
また、上述のポリイミド膜は、その引張強度が１００ＭＰａ以上５００ＭＰａ以下の範囲内であることが好ましい。 Moreover, it is preferable that the above-mentioned polyimide film has the tensile strength within the range of 100 MPa or more and 500 MPa or less.
また、上述のポリイミド膜の特定のポリイミド樹脂は、そのガラス転移温度が２６０℃以上３５０℃以下の範囲内であることが好ましい。このポリイミド膜のガラス転移温度が２６０℃以上であれば、このポリイミド膜がフレキシブルプリント回路基板等に組み込まれている場合においてそのフレキシブルプリント回路基板等に実装部品が半田付けされる際に、ポリイミド膜が十分な耐熱性を有するため、フレキシブルプリント回路基板等の物性低下などを防ぐことができるからである。 Moreover, it is preferable that the specific polyimide resin of the above-mentioned polyimide film has the glass transition temperature within the range of 260 degreeC or more and 350 degrees C or less. If the glass transition temperature of the polyimide film is 260 ° C. or higher, when the polyimide film is incorporated in a flexible printed circuit board or the like, the polyimide film is used when a mounting component is soldered to the flexible printed circuit board or the like. This is because it has sufficient heat resistance and can prevent deterioration of physical properties of a flexible printed circuit board or the like.
また、上述のポリイミド膜は、片面をメチルエチルケトン（ＭＥＫ）で濡らしたときの引張伸びが３．５％以上３５％以下の範囲内であることが好ましく、５．０％以上２５％以下の範囲内であることがより好ましい。ポリイミド膜がこのような物性を有することにより、フレキシブルプリント回路基板等の作製時においてこのポリイミド膜に銅箔を張り付ける際にポリイミド膜が破断することがないからである。 In addition, the polyimide film described above preferably has a tensile elongation of 3.5% or more and 35% or less when wetted on one side with methyl ethyl ketone (MEK), and is within a range of 5.0% or more and 25% or less. It is more preferable that This is because when the polyimide film has such physical properties, the polyimide film is not broken when a copper foil is attached to the polyimide film during the production of a flexible printed circuit board or the like.
また、上述のポリイミド膜の全光線透過率は、ポリイミド膜の膜厚が２５μｍであるとき、８０％以上であることが好ましく、８５％以上であることがより好ましく、９０％以上であることがさらに好ましい。 The total light transmittance of the polyimide film is preferably 80% or more, more preferably 85% or more, and 90% or more when the film thickness of the polyimide film is 25 μm. Further preferred.
また、上述のポリイミド膜の黄色度は、ポリイミド膜の膜厚が２５μｍであるとき、８．０以下であることが好ましく、６．０以下であることがより好ましく、４．０以下であることがさらに好ましい。 The yellowness of the polyimide film is preferably 8.0 or less, more preferably 6.0 or less, and 4.0 or less when the thickness of the polyimide film is 25 μm. Is more preferable.
以下、実施例を用いて本発明に係るポリイミド膜について詳述する。 Hereinafter, the polyimide film according to the present invention will be described in detail using examples.
１．ポリイミド前駆体溶液の調製
１８．８６ｇのビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）と、０．３４ｇの２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン二無水物（ＢＰＡＤＡ）と、２０．３２ｇの２，２’−ビス（トリフルオロメチル）ベンジジン（ＴＦＭＢ）と、０．３２ｇの４，４’−ジアミノジフェニルスルホン（４，４’−ＤＤＳ）とを、１１０．１７ｇのＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）中で反応させ、固形分２０ｗｔ％のポリイミド前駆体溶液を調製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９９ｍｏｌ％および１ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび４，４’−ＤＤＳのそれぞれのモル分率は９８ｍｏｌ％および２ｍｏｌ％であった。
1. Preparation of polyimide precursor solution 18.86 g of biphenyltetracarboxylic dianhydride (BPDA) and 0.34 g of 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane dianhydride (BPADA) 110.17 g of 2,2′-bis (trifluoromethyl) benzidine (TFMB) and 0.32 g of 4,4′-diaminodiphenyl sulfone (4,4′-DDS). Reaction was carried out in N, N-dimethylacetamide (DMAc) to prepare a polyimide precursor solution having a solid content of 20 wt%. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides were 99 mol% and 1 mol%, respectively, and the molar fractions of TFMB and 4,4′-DDS with respect to all diamines. Were 98 mol% and 2 mol%.
２．ポリイミド膜の作製
上述のポリイミド前駆体溶液をガラス基板上に塗布して塗膜を形成した後、その塗膜を７０℃のオーブンに入れ、２０分経過後にそのオーブンを１２０℃まで昇温させた。なお、このとき、オーブンの温度が７０℃から１２０℃に達するのに２０分の時間を要した。オーブンの温度が１２０℃に達してからその温度を２０分間維持し、その後、オーブンを３００℃まで昇温させた。なお、このとき、オーブンの温度が１２０℃から３００℃に達するのに３９分の時間を要した。オーブンの温度が３００℃に達してからその温度を５分間維持した。その結果、ガラス基板上に膜厚２５μｍのポリイミド膜が形成された。そして、ガラス基板上のポリイミド膜をガラス基板から剥離して目的のポリイミド膜を得た。
2. Preparation of polyimide film After applying the above polyimide precursor solution on a glass substrate to form a coating film, the coating film was placed in an oven at 70 ° C., and the oven was heated to 120 ° C. after 20 minutes. . At this time, it took 20 minutes for the oven temperature to reach 70 ° C. to 120 ° C. After the oven temperature reached 120 ° C, the temperature was maintained for 20 minutes, and then the oven was heated to 300 ° C. At this time, it took 39 minutes for the oven temperature to reach 120 ° C. to 300 ° C. The temperature was maintained for 5 minutes after the oven temperature reached 300 ° C. As a result, a polyimide film having a film thickness of 25 μm was formed on the glass substrate. And the polyimide film on a glass substrate was peeled from the glass substrate, and the target polyimide film was obtained.
３．ポリイミド膜の物性測定
以下の通り、得られたポリイミド膜のヘイズ値、全光線透過率、引張強度（乾燥時）、メチルエチルケトンで濡れた状態の引張伸びおよびガラス転移温度を求めた。
3. Measurement of physical properties of polyimide film The haze value, total light transmittance, tensile strength (at the time of drying), tensile elongation in a state wetted with methyl ethyl ketone, and glass transition temperature were determined as follows.
（１）ポリイミド膜のヘイズ値及び全光線透過率
スガ試験機製ヘイズメータ（ＨＧＭ−２ＤＰ）を用いて、旧ＪＩＳＫ７１０５に基づいて、ポリイミド膜のヘイズ値及び全光線透過率を測定したところ、そのヘイズ値は０．４％、全光線透過率は９０．５％であった。なお、このとき、ｂ＊値や黄色度（Ｙｅｌｌｏｗｎｅｓｓ ｉｎｄｅｘ）も同時に測定された。そのｂ＊値は２．４であり、黄色度は４．０であった。
(1) Haze value and total light transmittance of polyimide film Using haze meter (HGM-2DP) manufactured by Suga Test Instruments Co., Ltd., the haze value and total light transmittance of the polyimide film were measured based on the old JISK7105. Was 0.4%, and the total light transmittance was 90.5%. At this time, b * value and yellowness index were also measured. Its b * value was 2.4, and the yellowness was 4.0.
（２）ポリイミド膜の引張強度
島津製作所製オートグラフＡＧＳ−１０ｋＮＧを用いて、引張速度５０ｍｍ／分でポリイミド膜の引張強度を測定した測定したところ、その引張強度は２００ＭＰａであった。なお、このとき、引張弾性率や引張伸びも同時に測定された。その引張弾性率は４．４ＧＰａであり、引張伸びは２１．３％であった。
(2) Tensile strength of polyimide film Using an autograph AGS-10kNG manufactured by Shimadzu Corporation, the tensile strength of the polyimide film was measured at a tensile speed of 50 mm / min, and the tensile strength was 200 MPa. At this time, the tensile modulus and tensile elongation were also measured. The tensile elastic modulus was 4.4 GPa and the tensile elongation was 21.3%.
（３）メチルエチルケトンで濡れた状態のポリイミド膜の引張伸び
島津製作所製オートグラフＡＧＳ−１０ｋＮＧのチャックにポリイミド膜をセットした後に、そのポリイミド膜の片面全面をメチルエチルケトンで濡らしてから引張速度５０ｍｍ／分でそのポリイミド膜を引っ張り、そのときの引張伸び（破断伸び）を測定したところ、その引張伸びは１７．８％であった。
(3) Tensile elongation of polyimide film wetted with methyl ethyl ketone After setting the polyimide film on a Shimadzu autograph AGS-10kNG chuck, the entire surface of the polyimide film was wetted with methyl ethyl ketone and then pulled at 50 mm / min. When the polyimide film was pulled and the tensile elongation (breaking elongation) at that time was measured, the tensile elongation was 17.8%.
（４）ポリイミド膜のガラス転移温度
セイコーインスツルメント社製動的粘弾性装置（ＤＭ６１００）を用いて、以下に示す条件でポリイミド膜のガラス転移温度を測定したところ、そのガラス転移温度は３４７℃であった。
−測定条件−
測定環境：大気雰囲気下
フィルムサイズ：縦３０ｍｍ×横８ｍｍ
正弦荷重：振幅９８ｍＮ，周波数１．０Ｈｚ
昇温速度：２℃／ｍｉｎ
(4) Glass transition temperature of polyimide film Using a dynamic viscoelastic device (DM6100) manufactured by Seiko Instruments Inc., the glass transition temperature of the polyimide film was measured under the following conditions. The glass transition temperature was 347 ° C. Met.
-Measurement conditions-
Measurement environment: under atmospheric atmosphere Film size: 30mm length x 8mm width
Sine load: amplitude 98mN, frequency 1.0Hz
Temperature increase rate: 2 ° C / min
以上の結果から、本実施例で得られたポリイミド膜は、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is superior in heat resistance, transparency, and strength as before, but has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１８．５３ｇに代え、ＢＰＡＤＡの添加量を０．８４ｇに代え、ＴＦＭＢの添加量を１９．６５ｇに代え、４，４’−ＤＤＳの添加量を０．８０ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９７．５ｍｏｌ％および２．５ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび４，４’−ＤＤＳのそれぞれのモル分率は９５ｍｏｌ％および５ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA was changed to 18.53 g, the addition amount of BPADA was changed to 0.84 g, the addition amount of TFMB was changed to 19.65 g, and the addition amount of 4,4′-DDS was changed to 0.80 g. Prepared a polyimide precursor solution (solid content: 20 wt%) in the same manner as in Example 1, and produced a polyimide film in the same manner as in Example 1. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides were 97.5 mol% and 2.5 mol%, respectively, and TFMB and 4,4′-DDS with respect to all diamines, respectively. The mole fraction of was 95 mol% and 5 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．５％であり、全光線透過率は９０．５％であり、引張強度は１７５ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは１５．２％であり、ガラス転移温度は３４２℃であった。また、引張強度と同時に測定された引張弾性率は４．１ＧＰａであり、引張伸びは２０．０％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は２．４であり、黄色度は３．９であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.5% and the total light transmittance was 90.5. %, Tensile strength was 175 MPa, tensile elongation wet with methyl ethyl ketone was 15.2%, and glass transition temperature was 342 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.1 GPa, and the tensile elongation was 20.0%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 2.4, and the yellowness was 3.9.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１４．３９ｇに代え、ＢＰＡＤＡの添加量を１．３４ｇに代え、ＴＦＭＢの添加量を１４．８４ｇに代え、４，４’−ＤＤＳの添加量を１．２８ｇに代え、ＤＭＡｃの添加量を１１８．１５ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９５ｍｏｌ％および５ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび４，４’−ＤＤＳのそれぞれのモル分率は９０ｍｏｌ％および１０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA was changed to 14.39 g, the addition amount of BPADA was changed to 1.34 g, the addition amount of TFMB was changed to 14.84 g, the addition amount of 4,4′-DDS was changed to 1.28 g, and DMAc A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount added was 118.15 g, and a polyimide film was produced in the same manner as in Example 1. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides are 95 mol% and 5 mol%, respectively, and the molar fractions of TFMB and 4,4′-DDS with respect to all diamines. Were 90 mol% and 10 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．６％であり、全光線透過率は９０．４％であり、引張強度は１５６ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは８．９％であり、ガラス転移温度は３３５℃であった。また、引張強度と同時に測定された引張弾性率は４．３ＧＰａであり、引張伸びは１４．１％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は２．３であり、黄色度は３．９であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.6% and the total light transmittance was 90.4. %, Tensile strength was 156 MPa, tensile elongation when wetted with methyl ethyl ketone was 8.9%, and glass transition temperature was 335 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.3 GPa, and the tensile elongation was 14.1%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 2.3, and the yellowness was 3.9.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１３．５４ｇに代え、ＢＰＡＤＡの添加量を２．６６ｇに代え、ＴＦＭＢの添加量を１３．１０ｇに代え、４，４’−ＤＤＳの添加量を２．５４ｇに代え、ＤＭＡｃの添加量を１１８．１６ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９０ｍｏｌ％および１０ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび４，４’−ＤＤＳのそれぞれのモル分率は８０ｍｏｌ％および２０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA was changed to 13.54 g, the addition amount of BPADA was changed to 2.66 g, the addition amount of TFMB was changed to 13.10 g, the addition amount of 4,4′-DDS was changed to 2.54 g, and DMAc A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount added was 118.16 g, and a polyimide film was prepared in the same manner as in Example 1. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides are 90 mol% and 10 mol%, respectively, and the molar fractions of TFMB and 4,4′-DDS with respect to all diamines. Was 80 mol% and 20 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．５％であり、全光線透過率は９０．３％であり、引張強度は１４３ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは５．１％であり、ガラス転移温度は３２８℃であった。また、引張強度と同時に測定された引張弾性率は４．０ＧＰａであり、引張伸びは９．２％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は２．４であり、黄色度は４．０であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.5% and the total light transmittance was 90.3. %, Tensile strength was 143 MPa, tensile elongation wet with methyl ethyl ketone was 5.1%, and glass transition temperature was 328 ° C. Moreover, the tensile elasticity modulus measured simultaneously with the tensile strength was 4.0 GPa, and the tensile elongation was 9.2%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 2.4, and the yellowness was 4.0.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
４，４’−ＤＤＳを３，３’−ＤＤＳに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９９ｍｏｌ％および１ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は９８ｍｏｌ％および２ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that 4,4′-DDS was replaced with 3,3′-DDS, and a polyimide film was prepared in the same manner as in Example 1. Was made. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides were 99 mol% and 1 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 98 mol% and 2 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．７％であり、全光線透過率は９０．５％であり、引張強度は２０７ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは２０．７％であり、ガラス転移温度は３３９℃であった。また、引張強度と同時に測定された引張弾性率は４．４ＧＰａであり、引張伸びは２２．０％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は１．９であり、黄色度は３．６であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.7% and the total light transmittance was 90.5. %, Tensile strength was 207 MPa, tensile elongation in a state wetted with methyl ethyl ketone was 20.7%, and glass transition temperature was 339 ° C. Moreover, the tensile elasticity modulus measured simultaneously with the tensile strength was 4.4 GPa, and the tensile elongation was 22.0%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 1.9, and the yellowness was 3.6.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１８．５３ｇに代え、ＢＰＡＤＡの添加量を０．８４ｇに代え、ＴＦＭＢの添加量を１９．６５ｇに代え、０．３２ｇの４，４’−ＤＤＳを０．８０ｇの３，３’−ＤＤＳに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９７．５ｍｏｌ％および２．５ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は９５ｍｏｌ％および５ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA is changed to 18.53 g, the addition amount of BPADA is changed to 0.84 g, the addition amount of TFMB is changed to 19.65 g, 0.32 g of 4,4′-DDS is changed to 0.80 g of 3, A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that 3′-DDS was used, and a polyimide film was prepared in the same manner as in Example 1. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides were 97.5 mol% and 2.5 mol%, respectively, and TFMB and 3,3′-DDS with respect to all diamines, respectively. The mole fraction of was 95 mol% and 5 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．６％であり、全光線透過率は９０．４％であり、引張強度は１７６ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは１７．９％であり、ガラス転移温度は３２３℃であった。また、引張強度と同時に測定された引張弾性率は４．２ＧＰａであり、引張伸びは２０．０％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は２．０であり、黄色度は３．７であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.6% and the total light transmittance was 90.4. %, Tensile strength was 176 MPa, tensile elongation wet with methyl ethyl ketone was 17.9%, and glass transition temperature was 323 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.2 GPa and the tensile elongation was 20.0%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 2.0, and the yellowness was 3.7.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１４．３９ｇに代え、ＢＰＡＤＡの添加量を１．３４ｇに代え、ＴＦＭＢの添加量を１４．８４ｇに代え、０．３２ｇの４，４’−ＤＤＳを１．２８ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．１５ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９５ｍｏｌ％および５ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は９０ｍｏｌ％および１０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA is changed to 14.39 g, the addition amount of BPADA is changed to 1.34 g, the addition amount of TFMB is changed to 14.84 g, 0.32 g of 4,4′-DDS is changed to 1.28 g of 3, A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.15 g instead of 3′-DDS. A polyimide film was prepared. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides are 95 mol% and 5 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 90 mol% and 10 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．６％であり、全光線透過率は９０．４％であり、引張強度は１８０ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは１２．５％であり、ガラス転移温度は３１２℃であった。また、引張強度と同時に測定された引張弾性率は４．４ＧＰａであり、引張伸びは１６．６％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は１．９であり、黄色度は３．６であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.6% and the total light transmittance was 90.4. %, Tensile strength was 180 MPa, tensile elongation in a state wetted with methyl ethyl ketone was 12.5%, and glass transition temperature was 312 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.4 GPa, and the tensile elongation was 16.6%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 1.9, and the yellowness was 3.6.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１３．５４ｇに代え、ＢＰＡＤＡの添加量を２．６６ｇに代え、ＴＦＭＢの添加量を１３．１０ｇに代え、０．３２ｇの４，４’−ＤＤＳを２．５４ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．１６ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は９０ｍｏｌ％および１０ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は８０ｍｏｌ％および２０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA is changed to 13.54 g, the addition amount of BPADA is changed to 2.66 g, the addition amount of TFMB is changed to 13.10 g, 0.32 g of 4,4′-DDS is changed to 2.54 g of 3,4 A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc added was changed to 118.16 g instead of 3′-DDS. A polyimide film was prepared. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides are 90 mol% and 10 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Was 80 mol% and 20 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．５％であり、全光線透過率は９０．６％であり、引張強度は１８４ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは８．２％であり、ガラス転移温度は２９７℃であった。また、引張強度と同時に測定された引張弾性率は４．３ＧＰａであり、引張伸びは２７．４％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は２．２であり、黄色度は３．８であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.5% and the total light transmittance was 90.6. %, Tensile strength was 184 MPa, tensile elongation wetted with methyl ethyl ketone was 8.2%, and glass transition temperature was 297 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.3 GPa, and the tensile elongation was 27.4%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 2.2, and the yellowness was 3.8.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１２．７０ｇに代え、ＢＰＡＤＡの添加量を３．９７ｇに代え、ＴＦＭＢの添加量を１１．３８ｇに代え、０．３２ｇの４，４’−ＤＤＳを３．７８ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．１７ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は８５ｍｏｌ％および１５ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は７０ｍｏｌ％および３０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２４μｍであった。 The addition amount of BPDA was changed to 12.70 g, the addition amount of BPADA was changed to 3.97 g, the addition amount of TFMB was changed to 11.38 g, and 0.32 g of 4,4′-DDS was changed to 3.78 g of 3,78 g. A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.17 g instead of 3′-DDS. A polyimide film was prepared. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides are 85 mol% and 15 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 70 mol% and 30 mol%. Moreover, the film thickness of the obtained polyimide film was 24 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．６％であり、全光線透過率は９０．５％であり、引張強度は１６４ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは７．９％であり、ガラス転移温度は２９０℃であった。また、引張強度と同時に測定された引張弾性率は４．１ＧＰａであり、引張伸びは２５．８％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は２．２であり、黄色度は４．０であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.6% and the total light transmittance was 90.5. %, Tensile strength was 164 MPa, tensile elongation wetted with methyl ethyl ketone was 7.9%, and glass transition temperature was 290 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.1 GPa, and the tensile elongation was 25.8%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 2.2, and the yellowness was 4.0.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１３．４２ｇに代え、０．３４ｇのＢＰＡＤＡを２．５０ｇの５，５’−オキシビス（イソベンゾフラン−１，３−ジオン）（ＯＤＰＡ）に代え、ＴＦＭＢの添加量を１２．０３ｇに代え、０．３２ｇの４，４’−ＤＤＳを４．００ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．０７ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＯＤＰＡのそれぞれのモル分率は８５ｍｏｌ％および１５ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は７０ｍｏｌ％および３０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２４μｍであった。 The amount of BPDA added was changed to 13.42 g, 0.34 g of BPADA was changed to 2.50 g of 5,5′-oxybis (isobenzofuran-1,3-dione) (ODPA), and the amount of TFMB added was changed to 12. The polyimide precursor was changed in the same manner as in Example 1 except that 0.32 g of 4,4′-DDS was replaced with 4.00 g of 3,3′-DDS and the amount of DMAc added was changed to 118.07 g. A body solution (solid content: 20 wt%) was prepared, and a polyimide film was produced in the same manner as in Example 1. In this case, the molar fractions of BPDA and ODPA with respect to all tetracarboxylic dianhydrides were 85 mol% and 15 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 70 mol% and 30 mol%. Moreover, the film thickness of the obtained polyimide film was 24 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．８％であり、全光線透過率は９０．３％であり、引張強度は２０９ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは１４．８％であり、ガラス転移温度は２９７℃であった。また、引張強度と同時に測定された引張弾性率は４．２ＧＰａであり、引張伸びは２７．０％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は４．０であり、黄色度は７．４であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.8% and the total light transmittance was 90.3. %, Tensile strength was 209 MPa, tensile elongation when wetted with methyl ethyl ketone was 14.8%, and glass transition temperature was 297 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.2 GPa, and the tensile elongation was 27.0%. Furthermore, the b * value measured simultaneously with the haze value and the total light transmittance was 4.0, and the yellowness was 7.4.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１１．８７ｇに代え、ＢＰＡＤＡの添加量を５．２５ｇに代え、ＴＦＭＢの添加量を９．６９ｇに代え、０．３２ｇの４，４’−ＤＤＳを５．０１ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．１８ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は８０ｍｏｌ％および２０ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は６０ｍｏｌ％および４０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA was changed to 11.87 g, the addition amount of BPADA was changed to 5.25 g, the addition amount of TFMB was changed to 9.69 g, 0.32 g of 4,4′-DDS was changed to 5.01 g of 3, A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc added was changed to 118.18 g instead of 3′-DDS. A polyimide film was prepared. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides are 80 mol% and 20 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 60 mol% and 40 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．５％であり、全光線透過率は９０．５％であり、引張強度は１５５ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは６．２％であり、ガラス転移温度は２８１℃であった。また、引張強度と同時に測定された引張弾性率は４．０ＧＰａであり、引張伸びは２５．２％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は２．３であり、黄色度は４．１であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.5% and the total light transmittance was 90.5. %, Tensile strength was 155 MPa, tensile elongation wetted with methyl ethyl ketone was 6.2%, and glass transition temperature was 281 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.0 GPa and the tensile elongation was 25.2%. Furthermore, the b * value measured simultaneously with the haze value and the total light transmittance was 2.3, and the yellowness was 4.1.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１２．７７ｇに代え、０．３４ｇのＢＰＡＤＡを３．３７ｇのＯＤＰＡに代え、ＴＦＭＢの添加量を１０．４３ｇに代え、０．３２ｇの４，４’−ＤＤＳを５．３９ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．０５ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＯＤＰＡのそれぞれのモル分率は８０ｍｏｌ％および２０ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は６０ｍｏｌ％および４０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２４μｍであった。 The addition amount of BPDA is changed to 12.77 g, 0.34 g of BPADA is changed to 3.37 g of ODPA, the addition amount of TFMB is changed to 10.43 g, and 0.32 g of 4,4′-DDS is changed to 5.39 g. A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc added was changed to 118.05 g instead of 3,3′-DDS in Example 1. A polyimide film was prepared by the method described above. In this case, the molar fractions of BPDA and ODPA with respect to all tetracarboxylic dianhydrides are 80 mol% and 20 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 60 mol% and 40 mol%. Moreover, the film thickness of the obtained polyimide film was 24 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．７％であり、全光線透過率は９０．４％であり、引張強度は１７７ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは１２．１％であり、ガラス転移温度は２９３℃であった。また、引張強度と同時に測定された引張弾性率は４．１ＧＰａであり、引張伸びは２４．３％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は４．２であり、黄色度は７．６であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.7% and the total light transmittance was 90.4. %, Tensile strength was 177 MPa, tensile elongation wet with methyl ethyl ketone was 12.1%, and glass transition temperature was 293 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.1 GPa, and the tensile elongation was 24.3%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 4.2, and the yellowness was 7.6.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１１．０５ｇに代え、ＢＰＡＤＡの添加量を６．５２ｇに代え、ＴＦＭＢの添加量を８．０２ｇに代え、０．３２ｇの４，４’−ＤＤＳを６．２２ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．２０ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は７５ｍｏｌ％および２５ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は５０ｍｏｌ％および５０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２４μｍであった。 The addition amount of BPDA was changed to 11.05 g, the addition amount of BPADA was changed to 6.52 g, the addition amount of TFMB was changed to 8.02 g, and 0.32 g of 4,4′-DDS was changed to 6.22 g of 3,3. A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc added was changed to 118.20 g instead of 3′-DDS. A polyimide film was prepared. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides were 75 mol% and 25 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 50 mol% and 50 mol%. Moreover, the film thickness of the obtained polyimide film was 24 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．５％であり、全光線透過率は９０．４％であり、引張強度は１４０ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは４．１％であり、ガラス転移温度は２７５℃であった。また、引張強度と同時に測定された引張弾性率は３．６ＧＰａであり、引張伸びは１０．２％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は１．７であり、黄色度は２．８であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.5% and the total light transmittance was 90.4. %, The tensile strength was 140 MPa, the tensile elongation when wetted with methyl ethyl ketone was 4.1%, and the glass transition temperature was 275 ° C. The tensile modulus measured simultaneously with the tensile strength was 3.6 GPa, and the tensile elongation was 10.2%. Furthermore, the b * value measured simultaneously with the haze value and the total light transmittance was 1.7, and the yellowness was 2.8.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１０．０１ｇに代え、ＢＰＡＤＡの添加量を７．５９ｇに代え、ＴＦＭＢの添加量を９．３３ｇに代え、０．３２ｇの４，４’−ＤＤＳを４．８３ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．２５ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は７０ｍｏｌ％および３０ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は６０ｍｏｌ％および４０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA was changed to 10.01 g, the addition amount of BPADA was changed to 7.59 g, the addition amount of TFMB was changed to 9.33 g, 0.32 g of 4,4′-DDS was changed to 4.83 g of 3, A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.25 g instead of 3′-DDS. A polyimide film was prepared. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides were 70 mol% and 30 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 60 mol% and 40 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．４％であり、全光線透過率は９０．４％であり、引張強度は１３７ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは３．８％であり、ガラス転移温度は２６９℃であった。また、引張強度と同時に測定された引張弾性率は３．３ＧＰａであり、引張伸びは９．０％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は１．６であり、黄色度は２．６であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.4% and the total light transmittance was 90.4. %, Tensile strength was 137 MPa, tensile elongation in a state wetted with methyl ethyl ketone was 3.8%, and glass transition temperature was 269 ° C. The tensile modulus measured simultaneously with the tensile strength was 3.3 GPa, and the tensile elongation was 9.0%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 1.6, and the yellowness was 2.6.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
ＢＰＤＡの添加量を１０．２４ｇに代え、ＢＰＡＤＡの添加量を７．７７ｇに代え、ＴＦＭＢの添加量を６．３７ｇに代え、０．３２ｇの４，４’−ＤＤＳを７．４１ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．２１ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。なお、この際の全てのテトラカルボン酸二無水物に対するＢＰＤＡおよびＢＰＡＤＡのそれぞれのモル分率は７０ｍｏｌ％および３０ｍｏｌ％であり、全てのジアミンに対するＴＦＭＢおよび３，３’−ＤＤＳのそれぞれのモル分率は４０ｍｏｌ％および６０ｍｏｌ％であった。また、得られたポリイミド膜の膜厚は２５μｍであった。 The addition amount of BPDA is changed to 10.24 g, the addition amount of BPADA is changed to 7.77 g, the addition amount of TFMB is changed to 6.37 g, and 0.32 g of 4,4′-DDS is changed to 7.41 g of 3,4. A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc added was changed to 118.21 g instead of 3′-DDS. A polyimide film was prepared. In this case, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides were 70 mol% and 30 mol%, respectively, and the molar fractions of TFMB and 3,3′-DDS with respect to all diamines. Were 40 mol% and 60 mol%. Moreover, the film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．６％であり、全光線透過率は９０．３％であり、引張強度は１２９ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは３．５％であり、ガラス転移温度は２７２℃であった。また、引張強度と同時に測定された引張弾性率は３．３ＧＰａであり、引張伸びは８．４％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は１．７であり、黄色度は２．７であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.6% and the total light transmittance was 90.3. %, Tensile strength was 129 MPa, tensile elongation when wetted with methyl ethyl ketone was 3.5%, and glass transition temperature was 272 ° C. The tensile modulus measured simultaneously with the tensile strength was 3.3 GPa and the tensile elongation was 8.4%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 1.7, and the yellowness was 2.7.
以上の結果から、本実施例で得られたポリイミド膜も、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いことが確認された。 From the above results, the polyimide film obtained in this example is also excellent in heat resistance, transparency, and strength equivalent to the conventional one, and has higher resistance to methyl ethyl ketone than the conventional colorless transparent polyimide film. confirmed.
（比較例１）
ＢＰＡＤＡおよび４，４’−ＤＤＳを添加せず、ＢＰＤＡの添加量を１５．２６ｇに代え、ＴＦＭＢの添加量を１６．６１ｇに代え、ＤＭＡｃの添加量を１１８．１３ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。得られたポリイミド膜の膜厚は２５μｍであった。
(Comparative Example 1)
Implementation was performed except that BPADA and 4,4′-DDS were not added, the addition amount of BPDA was changed to 15.26 g, the addition amount of TFMB was changed to 16.61 g, and the addition amount of DMAc was changed to 118.13 g. A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1, and a polyimide film was produced in the same manner as in Example 1. The film thickness of the obtained polyimide film was 25 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は７．０％であり、全光線透過率は８７．２％であり、引張強度は２０３ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは２０．４％であり、ガラス転移温度は３３５℃であった。また、引張強度と同時に測定された引張弾性率は４．３ＧＰａであり、引張伸びは２０．２％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は３．０であり、黄色度は５．２であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 7.0% and the total light transmittance was 87.2. %, Tensile strength was 203 MPa, tensile elongation when wetted with methyl ethyl ketone was 20.4%, and glass transition temperature was 335 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.3 GPa, and the tensile elongation was 20.2%. Further, the b * value measured at the same time as the haze value and the total light transmittance was 3.0, and the yellowness was 5.2.
以上の結果から、本比較例で得られたポリイミド膜は、従前と同等の優れた耐熱性および強度を示すと共に、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いが、透明性に著しく乏しいことが明らかとなった。 From the above results, the polyimide film obtained in this comparative example shows the same excellent heat resistance and strength as the previous one, and has a higher resistance to methyl ethyl ketone than the previous colorless and transparent polyimide film, but the transparency is remarkably high. It became clear that it was scarce.
（比較例２）
ＢＰＤＡおよび４，４’−ＤＤＳを添加せず、ＢＰＡＤＡの添加量を１９．４１ｇに代え、ＴＦＭＢの添加量を１１．９４ｇに代え、ＤＭＡｃの添加量を１１８．６６ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。得られたポリイミド膜の膜厚は２４μｍであった。
(Comparative Example 2)
Implementation was carried out except that BPDA and 4,4′-DDS were not added, the addition amount of BPADA was changed to 19.41 g, the addition amount of TFMB was changed to 11.94 g, and the addition amount of DMAc was changed to 118.66 g. A polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1, and a polyimide film was produced in the same manner as in Example 1. The film thickness of the obtained polyimide film was 24 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は０．９％であり、全光線透過率は９０．４％であり、引張強度は１５８ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは２．６％であり、ガラス転移温度は２４２℃であった。また、引張強度と同時に測定された引張弾性率は３．８ＧＰａであり、引張伸びは３４．１％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は１．８であり、黄色度は３．５であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 0.9% and the total light transmittance was 90.4. %, Tensile strength was 158 MPa, tensile elongation wetted with methyl ethyl ketone was 2.6%, and glass transition temperature was 242 ° C. Further, the tensile modulus measured simultaneously with the tensile strength was 3.8 GPa, and the tensile elongation was 34.1%. Furthermore, the b * value measured simultaneously with the haze value and the total light transmittance was 1.8, and the yellowness was 3.5.
以上の結果から、本比較例で得られたポリイミド膜は、従前と同等の優れた透明性および強度を示すが、耐熱性に劣るだけでなく、従前の無色透明のポリイミド膜と同等のメチルエチルケトン耐性しか示さないことが明らかとなった。 From the above results, the polyimide film obtained in this comparative example shows excellent transparency and strength equivalent to the conventional one, but not only has poor heat resistance, but also has the same methyl ethyl ketone resistance as the conventional colorless transparent polyimide film. It became clear that it showed only.
（比較例３）
ＢＰＡＤＡを添加せず、ＢＰＤＡの添加量を１５．８５ｇに代え、ＴＦＭＢの添加量を１２．０８ｇに代え、０．３２ｇの４，４’−ＤＤＳを４．０１ｇの３，３’−ＤＤＳに代え、ＤＭＡｃの添加量を１１８．０６ｇに代えた以外は、実施例１と同様にポリイミド前駆体溶液（固形分：２０ｗｔ％）を調製し、実施例１と同様の方法でポリイミド膜を作製した。得られたポリイミド膜の膜厚は２４μｍであった。
(Comparative Example 3)
BPADA was not added, the amount of BPDA was changed to 15.85 g, the amount of TFMB was changed to 12.08 g, and 0.32 g of 4,4′-DDS was changed to 4.01 g of 3,3′-DDS. Instead, except that the amount of DMAc added was changed to 118.06 g, a polyimide precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1, and a polyimide film was produced in the same manner as in Example 1. . The film thickness of the obtained polyimide film was 24 μm.
得られたポリイミド膜のヘイズ値、全光線透過率、引張強度、ガラス転移温度を実施例１と同様にして測定したところ、ヘイズ値は７．５％であり、全光線透過率は８５．８％であり、引張強度は１６２ＭＰａであり、メチルエチルケトンで濡れた状態の引張伸びは８．１％であり、ガラス転移温度は３００℃であった。また、引張強度と同時に測定された引張弾性率は４．３ＧＰａであり、引張伸びは２１．２％であった。さらに、ヘイズ値及び全光線透過率と同時に測定されたｂ＊値は３．１であり、黄色度は５．６であった。 When the haze value, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze value was 7.5% and the total light transmittance was 85.8. %, Tensile strength was 162 MPa, tensile elongation in a state wetted with methyl ethyl ketone was 8.1%, and glass transition temperature was 300 ° C. The tensile modulus measured simultaneously with the tensile strength was 4.3 GPa, and the tensile elongation was 21.2%. Further, the b * value measured simultaneously with the haze value and the total light transmittance was 3.1, and the yellowness was 5.6.
以上の結果から、本比較例で得られたポリイミド膜は、従前と同等の優れた耐熱性および強度を示すと共に、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いが、透明性に著しく乏しいことが明らかとなった。なお、参考のため、上記実施例および比較例における「ポリイミド前駆体溶液の合成条件およびそのポリイミド前駆体溶液から得られたポリイミド膜の膜厚」および「そのポリイミド膜の諸物性」を以下の表１および表２にそれぞれまとめた。 From the above results, the polyimide film obtained in this comparative example shows the same excellent heat resistance and strength as the previous one, and has a higher resistance to methyl ethyl ketone than the previous colorless and transparent polyimide film, but the transparency is remarkably high. It became clear that it was scarce. For reference, the “synthetic conditions of the polyimide precursor solution and the film thickness of the polyimide film obtained from the polyimide precursor solution” and “the physical properties of the polyimide film” in the above examples and comparative examples are shown in the following table. The results are summarized in Table 1 and Table 2, respectively.
本発明に係るポリイミド膜は、従前と同等の優れた耐熱性、透明性、強度を示しつつも、従前よりも低コストで生産することが可能であり、また、従前の無色透明のポリイミド膜よりもメチルエチルケトンに対する耐性が高いという特徴を有し、例えば、発光素子実装用の回路基板や、カバーレイ、バーコード印刷用基板に好適に用いることができる。 The polyimide film according to the present invention can be produced at a lower cost than before while exhibiting excellent heat resistance, transparency, and strength equivalent to those of the past, and moreover than conventional colorless transparent polyimide films. Has a feature of high resistance to methyl ethyl ketone, and can be suitably used for, for example, a circuit board for mounting a light emitting element, a coverlay, and a barcode printing board.
Claims (9)
２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物（ＢＰＡＤＡ）由来部位、および、４，４’−オキシジフタル酸系化合物（ＯＤＰＡ）由来部位より成る群から選択される少なくとも１つの部位と、
２，２’−ビス（トリフルオロメチル）ベンジジン（ＴＦＭＢ）由来部位と、
３，３’−ジアミノジフェニルスルホン（３，３’−ＤＤＳ）由来部位、および、４，４’−ジアミノジフェニルスルホン（４，４’−ＤＤＳ）由来部位より成る群から選択される少なくとも１つの部位とから成るポリイミド樹脂から成り、
ヘイズ値が０．１以上２．０以下の範囲内である
ポリイミド膜。 Biphenyl tetracarboxylic acid compound (BPDA) and site-derived,
At least selected from the group consisting of a portion derived from 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane-based compound (BPADA) and a portion derived from 4,4′-oxydiphthalic acid-based compound (ODPA) One part ,
A site derived from 2,2′-bis (trifluoromethyl) benzidine (TFMB) ;
At least one site selected from the group consisting of a site derived from 3,3′-diaminodiphenylsulfone (3,3′-DDS) and a site derived from 4,4′-diaminodiphenylsulfone (4,4′-DDS) Made of polyimide resin consisting of
A polyimide film having a haze value in the range of 0.1 to 2.0.
請求項１に記載のポリイミド膜。 All Te tetracarboxylic acid compound from the biphenyltetracarboxylic acid compound for site (BPDA) mole fraction from site is within the range of 70 mol% or more 99 mol% polyimide film of claim 1.
請求項１または２に記載のポリイミド膜。 Wherein for all te tetracarboxylic acid compound derived portion of 2,2-bis [3,4- (di-carboxy) phenyl] propane compound (BPADA) derived site, and the 4,4'-oxydiphthalic acid compounds The polyimide film according to claim 1 or 2, wherein the molar fraction of at least one site selected from the group consisting of (ODPA) -derived sites is in the range of 1 mol% to 30 mol%.
請求項１から３のいずれか１項に記載のポリイミド膜。 All di amine from the relative site 2,2'-bis (trifluoromethyl) benzidine (TFMB) mole fraction from site to any one of claims 1 within the following 40 mol% or more 98 mol% 3 1 The polyimide film as described in the item.
請求項１から４のいずれか１項に記載のポリイミド膜。 Wherein for all di amine from part 3,3'-diaminodiphenyl sulfone (3,3'-DDS) from the site, and, 4,4'-diaminodiphenylsulfone (4,4'-DDS) group consisting of from site 5. The polyimide film according to claim 1, wherein the molar fraction of at least one portion selected from is within a range of 2 mol% to 60 mol%.
請求項１から５のいずれか１項に記載のポリイミド膜。 The polyimide film according to any one of claims 1 to 5 , wherein the tensile strength is in a range of 100 MPa to 500 MPa.
請求項１から６のいずれか１項に記載のポリイミド膜。 Polyimide film according to any one of the claims 1 to 6 glass transition temperature of the polyimide resin is in the range of 260 ° C. or higher 350 ° C. or less.
請求項１から７のいずれか１項に記載のポリイミド膜。 The polyimide film according to any one of claims 1 to 7 , wherein the tensile elongation when one surface is wetted with methyl ethyl ketone (MEK) is in the range of 3.5% to 35%.
２，２−ビス［３，４−（ジカルボキシフェノキシ）フェニル］プロパン系化合物（ＢＰＡＤＡ）由来部位、および、４，４’−オキシジフタル酸系化合物（ＯＤＰＡ）由来部位より成る群から選択される少なくとも１つの部位と、At least selected from the group consisting of a portion derived from 2,2-bis [3,4- (dicarboxyphenoxy) phenyl] propane-based compound (BPADA) and a portion derived from 4,4′-oxydiphthalic acid-based compound (ODPA) One part,
２，２’−ビス（トリフルオロメチル）ベンジジン（ＴＦＭＢ）由来部位と、A site derived from 2,2'-bis (trifluoromethyl) benzidine (TFMB);
３，３’−ジアミノジフェニルスルホン（３，３’−ＤＤＳ）由来部位、および、４，４’−ジアミノジフェニルスルホン（４，４’−ＤＤＳ）由来部位より成る群から選択される少なくとも１つの部位とから成るポリイミド樹脂から成り、At least one site selected from the group consisting of a site derived from 3,3′-diaminodiphenylsulfone (3,3′-DDS) and a site derived from 4,4′-diaminodiphenylsulfone (4,4′-DDS) Made of polyimide resin consisting of
ヘイズ値が０．１以上２．０以下の範囲内であると共に、片面をメチルエチルケトン（ＭＥＫ）で濡らしたときの引張伸びが３．５％以上３５％以下の範囲内であるThe haze value is in the range of 0.1 to 2.0, and the tensile elongation when one surface is wetted with methyl ethyl ketone (MEK) is in the range of 3.5% to 35%.
発光素子実装用の回路基板、カバーレイ、または、バーコード印刷用基板。Circuit board, coverlay, or barcode printing board for mounting light-emitting elements.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| PCT/JP2016/082271 WO2017073782A1 (en) | 2015-10-30 | 2016-10-31 | Polyimide film |
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| JP6253172B2 true JP6253172B2 (en) | 2017-12-27 |
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| KR20190132356A (en) * | 2017-04-07 | 2019-11-27 | 가부시키가이샤 아이.에스.티 | Polyimide film |
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| JP6956524B2 (en) * | 2017-06-06 | 2021-11-02 | 旭化成株式会社 | Polyimide film, products using polyimide film, and laminates |
| KR20210096064A (en) * | 2018-11-28 | 2021-08-04 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyimide resins, polyimide varnishes and polyimide films |
| JP7384170B2 (en) * | 2018-11-28 | 2023-11-21 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish and polyimide film |
| WO2022124195A1 (en) * | 2020-12-08 | 2022-06-16 | 株式会社カネカ | Polyimide resin, polyimide film and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001064388A (en) * | 1999-08-30 | 2001-03-13 | Nissan Chem Ind Ltd | Polyimide, polyimide solution and method for forming polyimide film |
| JP2002148457A (en) * | 2000-11-13 | 2002-05-22 | Mitsui Chemicals Inc | Polymer light guide |
| KR100589067B1 (en) * | 2001-10-30 | 2006-06-14 | 가부시키가이샤 가네카 | Photosensitive resin composition and photosensitive films and laminates made by using the same |
| JP2012041473A (en) * | 2010-08-20 | 2012-03-01 | Kaneka Corp | Polyimide film and method of manufacturing the film |
| JP5667392B2 (en) * | 2010-08-23 | 2015-02-12 | 株式会社カネカ | Laminated body and use thereof |
| KR101808396B1 (en) * | 2013-04-03 | 2017-12-12 | 미쓰이 가가쿠 가부시키가이샤 | Polyamic acid, varnish comprising same and polyimide film |
| KR102119426B1 (en) * | 2013-06-26 | 2020-06-08 | 도레이 카부시키가이샤 | Polyimide precursor, polyimide, flexible substrate prepared therewith, color filter and production method thereof, and flexible display device |
| KR101602686B1 (en) * | 2013-10-22 | 2016-03-11 | 코오롱인더스트리 주식회사 | Polyamic Acid, Polyimide and Display Device |
| WO2016158825A1 (en) * | 2015-03-31 | 2016-10-06 | 旭化成株式会社 | Polyimide film, polyimide varnish, product using polyimide film, and laminate |
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| KR20190132356A (en) * | 2017-04-07 | 2019-11-27 | 가부시키가이샤 아이.에스.티 | Polyimide film |
| JPWO2018186215A1 (en) * | 2017-04-07 | 2020-03-05 | 株式会社アイ．エス．テイ | Polyimide film |
| JP7189619B2 (en) | 2017-04-07 | 2022-12-14 | 株式会社アイ．エス．テイ | Polyimide membrane |
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| JPWO2017073782A1 (en) | 2017-10-26 |
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