TWI778125B - Polyimide, polyimide varnish, and polyimide film - Google Patents
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Abstract
Description
本發明關於聚醯亞胺、以及包含該聚醯亞胺之聚醯亞胺清漆及聚醯亞胺薄膜。The present invention relates to polyimide, and polyimide varnishes and polyimide films comprising the polyimide.
聚醯亞胺具有其優良的耐熱性,更在機械特性、耐藥品性、電特性等具有優良的特性,故於成形材料、複合材料、電氣-電子零件、光學材料、顯示器、航太等領域中,以聚醯亞胺作為材料之薄膜受到廣泛地應用。 已有人探討藉由在以液晶顯示器(LCD)為代表之光學設備中使用塑膠薄膜來代替玻璃基板,以求實現輕量化、薄型化、及可撓化,並冀望作為塑膠薄膜所要求特性即相位差小,且相位延遲低。Polyimide has excellent heat resistance, and has excellent mechanical properties, chemical resistance, electrical properties, etc., so it is used in molding materials, composite materials, electrical-electronic parts, optical materials, displays, aerospace and other fields. Among them, films made of polyimide are widely used. It has been discussed to use plastic films instead of glass substrates in optical devices represented by liquid crystal displays (LCDs) in order to achieve light weight, thinning, and flexibility. The difference is small and the phase delay is low.
就能符合如上所述之要求的塑膠薄膜材料而言,例如,專利文獻1揭示使用1,2,4,5-環己烷四羧酸二酐作為四羧酸成分,並使用9,9-雙(3-甲基-4-胺基苯基)茀及4,4’-二胺基二苯醚作為二胺成分來合成的聚醯亞胺等。 [先前技術文獻] [專利文獻]For plastic film materials that can meet the above requirements, for example, Patent Document 1 discloses the use of 1,2,4,5-cyclohexanetetracarboxylic dianhydride as the tetracarboxylic acid component, and the use of 9,9- Polyimide etc. which are synthesized by bis(3-methyl-4-aminophenyl) fluoride and 4,4'-diaminodiphenyl ether as diamine components. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利第6010533號公報[Patent Document 1] Japanese Patent No. 6010533
[發明所欲解決之課題][The problem to be solved by the invention]
但是,專利文獻1所揭示的聚醯亞胺雖然透明性及耐熱性優良且相位差小,惟係強韌性的指標之一的延伸性並未達到令人滿意的水平,為了達成塑膠薄膜之薄型化及可撓化,有必要進一步改良。 亦即,本發明所欲解決的課題係提供一種可形成低相位延遲與延伸性優良的薄膜之聚醯亞胺,以及包含該聚醯亞胺之聚醯亞胺清漆及聚醯亞胺薄膜。 [解決課題之手段]However, although the polyimide disclosed in Patent Document 1 is excellent in transparency and heat resistance and has a small retardation, the elongation, which is one of the indicators of toughness and toughness, has not reached a satisfactory level. In order to achieve a thin plastic film In order to be flexible and flexible, further improvement is necessary. That is, the subject to be solved by the present invention is to provide a polyimide that can form a film having low retardation and excellent stretchability, and a polyimide varnish and a polyimide film containing the polyimide. [Means of Solving Problems]
本發明人等經過深入探討後之結果發現,以特定構成單元構成的聚醯亞胺可形成低相位延遲與延伸性優良的薄膜。根據這些見解乃至完成本發明。亦即本發明關於下述[1]~[3]。 [1]一種聚醯亞胺,具有來自四羧酸或其衍生物之構成單元A及來自二胺之構成單元B, 構成單元A包含來自下式(a-1)表示之化合物之構成單元(A-1), 構成單元B包含來自下式(b-1)表示之化合物之構成單元(B-1)、來自下式(b-2)表示之化合物之構成單元(B-2)、以及選自於來自下式(b-3)表示之化合物之構成單元(B-3)、來自下式(b-4)表示之化合物之構成單元(B-4)、及來自下式(b-5)表示之化合物之構成單元(B-5)中之至少1種構成單元, 構成單元(B-1)相對於構成單元B之比例未達50莫耳%,構成單元(B-2)相對於構成單元B之比例為15莫耳%以上,構成單元(B-1)及構成單元(B-2)之合計在構成單元B中所佔之比例為40莫耳%以上。As a result of intensive research, the present inventors found that a polyimide composed of a specific structural unit can form a thin film with low retardation and excellent stretchability. Based on these findings, the present invention has been completed. That is, the present invention relates to the following [1] to [3]. [1] A polyimide having a structural unit A derived from a tetracarboxylic acid or a derivative thereof and a structural unit B derived from a diamine, The structural unit A includes the structural unit (A-1) derived from the compound represented by the following formula (a-1), The constitutional unit B includes a constitutional unit (B-1) derived from a compound represented by the following formula (b-1), a constitutional unit (B-2) derived from a compound represented by the following formula (b-2), and a constitutional unit (B-2) selected from the following Structural unit (B-3) of compound represented by formula (b-3), constituent unit (B-4) derived from compound represented by following formula (b-4), and compound derived from compound represented by following formula (b-5) at least one of the constituent units (B-5), The ratio of the constituent unit (B-1) to the constituent unit B is less than 50 mol %, the ratio of the constituent unit (B-2) to the constituent unit B is 15 mol % or more, and the constituent unit (B-1) and The ratio of the total of the structural units (B-2) to the structural unit B is 40 mol % or more.
[化1] [化2] 式(b-1)中,R各別獨立地表示氫原子、氟原子或甲基。[hua 1] [hua 2] In formula (b-1), R each independently represents a hydrogen atom, a fluorine atom or a methyl group.
[2]一種聚醯亞胺清漆,係將前述[1]所記載之聚醯亞胺溶解於有機溶劑而成。 [3]一種聚醯亞胺薄膜,含有前述[1]所記載之聚醯亞胺。 [發明之效果][2] A polyimide varnish obtained by dissolving the polyimide according to the above [1] in an organic solvent. [3] A polyimide film comprising the polyimide according to the aforementioned [1]. [Effect of invention]
根據本發明可提供能形成低相位延遲與延伸性優良的薄膜之聚醯亞胺,以及包含該聚醯亞胺之聚醯亞胺清漆及聚醯亞胺薄膜。According to the present invention, a polyimide film capable of forming a film with low retardation and excellent elongation, and a polyimide varnish and a polyimide film comprising the polyimide can be provided.
本發明之聚醯亞胺,具有來自四羧酸或其衍生物之構成單元A及來自二胺之構成單元B, 構成單元A包含來自上述式(a-1)表示之化合物之構成單元(A-1), 構成單元B包含來自上述式(b-1)表示之化合物之構成單元(B-1)、來自上述式(b-2)表示之化合物之構成單元(B-2)、以及選自於來自上述式(b-3)表示之化合物之構成單元(B-3)、來自上述式(b-4)表示之化合物之構成單元(B-4)、及來自上述式(b-5)表示之化合物之構成單元(B-5)中之至少1種構成單元, 構成單元(B-1)相對於構成單元B之比例未達50莫耳%,構成單元(B-2)相對於構成單元B之比例為15莫耳%以上,構成單元(B-1)及構成單元(B-2)之合計在構成單元B中所佔之比例為40莫耳%以上。 以下,針對本發明之聚醯亞胺進行說明。The polyimide of the present invention has a structural unit A derived from tetracarboxylic acid or a derivative thereof and a structural unit B derived from a diamine, The structural unit A includes the structural unit (A-1) derived from the compound represented by the above formula (a-1), The constitutional unit B includes the constitutional unit (B-1) derived from the compound represented by the above formula (b-1), the constitutional unit (B-2) derived from the compound represented by the above formula (b-2), and selected from the above The structural unit (B-3) of the compound represented by the formula (b-3), the structural unit (B-4) derived from the compound represented by the above formula (b-4), and the compound represented by the above formula (b-5) at least one of the constituent units (B-5), The ratio of the constituent unit (B-1) to the constituent unit B is less than 50 mol %, the ratio of the constituent unit (B-2) to the constituent unit B is 15 mol % or more, and the constituent unit (B-1) and The ratio of the total of the structural units (B-2) to the structural unit B is 40 mol % or more. Hereinafter, the polyimide of the present invention will be described.
[構成單元A] 本發明之聚醯亞胺所含的構成單元A係來自四羧酸或其衍生物之構成單元。四羧酸或其衍生物可單獨使用或將2種以上組合使用。 就四羧酸之衍生物而言,可列舉四羧酸的酐或烷基酯。就四羧酸的烷基酯而言,烷基之碳數為1~3較理想,可列舉例如:四羧酸之二甲基酯、二乙基酯、及二丙基酯。就四羧酸或其衍生物而言,為四羧酸二酐較理想。 本發明中的構成單元A包含來自下式(a-1)表示之化合物之構成單元(A-1)。式(a-1)表示之化合物係1,2,4,5-環己烷四羧酸二酐。藉由構成單元A包含構成單元(A-1),聚醯亞胺之透明性及耐熱性會改善。[Constituent Unit A] The structural unit A contained in the polyimide of the present invention is a structural unit derived from a tetracarboxylic acid or a derivative thereof. A tetracarboxylic acid or its derivative(s) can be used individually or in combination of 2 or more types. As the derivatives of tetracarboxylic acids, anhydrides or alkyl esters of tetracarboxylic acids can be mentioned. As for the alkyl ester of a tetracarboxylic acid, it is preferable that the carbon number of an alkyl group is 1-3, For example, the dimethyl ester of a tetracarboxylic acid, a diethyl ester, and a dipropyl ester are mentioned. As a tetracarboxylic acid or its derivative(s), tetracarboxylic dianhydride is preferable. The structural unit A in the present invention includes the structural unit (A-1) derived from the compound represented by the following formula (a-1). The compound represented by formula (a-1) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride. When the structural unit A includes the structural unit (A-1), the transparency and heat resistance of the polyimide are improved.
[化3] [hua 3]
構成單元(A-1)相對於構成單元A之比例宜為70~100莫耳%,為85~100莫耳%更佳,為99~100莫耳%再更佳,為100莫耳%又更佳。The proportion of the constituent unit (A-1) relative to the constituent unit A is preferably 70-100 mol %, more preferably 85-100 mol %, more preferably 99-100 mol %, still more preferably 100 mol % better.
本發明之聚醯亞胺在不損及本發明之效果的範圍內,也可在構成單元A中包含來自式(a-1)表示之化合物以外的四羧酸二酐之構成單元作為前述構成單元(A-1)以外的構成單元,但不含較理想。The polyimide of the present invention may include, as the aforementioned structure, a structural unit derived from a tetracarboxylic dianhydride other than the compound represented by the formula (a-1) in the structural unit A within the range that does not impair the effects of the present invention. Structural units other than the unit (A-1) are preferably not included.
[構成單元B] 本發明之聚醯亞胺所含的構成單元B係來自二胺之構成單元。 前述構成單元B包含來自下式(b-1)表示之化合物之構成單元(B-1)。[Constituent Unit B] The structural unit B contained in the polyimide of the present invention is a structural unit derived from a diamine. The aforementioned structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1).
[化4] [hua 4]
上述式(b-1)中,R各別獨立地選自於由氫原子、氟原子、及甲基構成之群組,宜為氫原子。 就上述式(b-1)表示之化合物而言,可列舉:9,9-雙(4-胺基苯基)茀、9,9-雙(3-氟-4-胺基苯基)茀、及9,9-雙(3-甲基-4-胺基苯基)茀等,宜為選自於由這3種化合物構成之群組中之至少1種,為9,9-雙(4-胺基苯基)茀更佳。 本發明之聚醯亞胺藉由包含前述構成單元(B-1),可減小相位差並展現低相位延遲。 本發明中,構成單元(B-1)相對於構成單元B之比例未達50莫耳%。前述構成單元(B-1)之比例為50莫耳%以上的話,形成延伸性優良的薄膜會變得困難。考慮展現低相位延遲並形成延伸性優良的薄膜之觀點,前述構成單元(B-1)之比例宜為45莫耳%以下,為42莫耳%以下更佳,為40莫耳%以下再更佳,且宜為5莫耳%以上,為10莫耳%以上更佳,為15莫耳%以上再更佳,為20莫耳%以上又更佳。考慮和前述同樣的觀點,前述構成單元(B-1)之比例宜為5~45莫耳%,為10~45莫耳%更佳,為15~45莫耳%再更佳,為20~40莫耳%又更佳。In the above formula (b-1), 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. Examples of the compound represented by the above formula (b-1) include 9,9-bis(4-aminophenyl)fluoride, 9,9-bis(3-fluoro-4-aminophenyl)fluoride , and 9,9-bis(3-methyl-4-aminophenyl) fluoride, etc., preferably at least one selected from the group consisting of these three compounds, which is 9,9-bis( 4-aminophenyl) phenyl) is more preferred. By including the aforementioned structural unit (B-1), the polyimide of the present invention can reduce the phase difference and exhibit low phase retardation. In the present invention, the ratio of the structural unit (B-1) to the structural unit B is less than 50 mol %. When the ratio of the said structural unit (B-1) is 50 mol% or more, it becomes difficult to form a thin film which is excellent in extensibility. From the viewpoint of exhibiting low phase retardation and forming a thin film with excellent stretchability, the ratio of the aforementioned constituent unit (B-1) is preferably 45 mol % or less, more preferably 42 mol % or less, and even more preferably 40 mol % or less. Preferably, it is 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and even more preferably 20 mol% or more. Considering the same viewpoint as above, the ratio of the aforementioned constituent unit (B-1) is preferably 5 to 45 mol %, preferably 10 to 45 mol %, more preferably 15 to 45 mol %, and more preferably 20 to 20 mol %. 40 mol% is even better.
本發明中的構成單元B包含來自下式(b-2)表示之化合物之構成單元(B-2)。The structural unit B in the present invention includes the structural unit (B-2) derived from the compound represented by the following formula (b-2).
[化5] [hua 5]
上述式(b-2)表示之化合物係2,2-雙[4-(4-胺基苯氧基)苯基]丙烷。 本發明之聚醯亞胺藉由包含前述構成單元(B-2),可減小相位差並形成低相位延遲優良且延伸性優良的薄膜。 本發明中,前述構成單元(B-2)相對於構成單元B之比例為15莫耳%以上。前述構成單元(B-2)之比例未達15莫耳%的話,形成低相位延遲與延伸性優良的薄膜會變得困難。考慮形成低相位延遲與延伸性優良的薄膜之觀點,前述構成單元(B-2)之比例宜為20莫耳%以上,為25莫耳%以上更佳,為30莫耳%以上再更佳,為35莫耳%以上又更佳,為40莫耳%以上再更佳,且宜為70莫耳%以下,為60莫耳%以下更佳,為50莫耳%以下再更佳。考慮和前述同樣的觀點,前述構成單元(B-2)之比例宜為15~70莫耳%,為15~60莫耳%更佳,為20~50莫耳%再更佳,為30~50莫耳%又更佳,為35~50莫耳%再更佳,為40~50莫耳%又更佳。The compound represented by the above formula (b-2) is 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Since the polyimide of the present invention contains the aforementioned structural unit (B-2), the retardation can be reduced, and a thin film having excellent low retardation and excellent stretchability can be formed. In this invention, the ratio of the said structural unit (B-2) with respect to the structural unit B is 15 mol% or more. When the ratio of the aforementioned structural unit (B-2) is less than 15 mol %, it becomes difficult to form a thin film with low retardation and excellent stretchability. Considering the viewpoint of forming a film with low retardation and excellent extensibility, the proportion of the aforementioned constituent unit (B-2) is preferably 20 mol % or more, more preferably 25 mol % or more, and even more preferably 30 mol % or more , more preferably 35 mol% or more, more preferably 40 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. Considering the same viewpoint as above, the ratio of the aforementioned constituent unit (B-2) is preferably 15-70 mol %, more preferably 15-60 mol %, more preferably 20-50 mol %, 30-30 mol % 50 mol % is still better, 35-50 mol % is still better, 40-50 mol % is still more preferred.
本發明中,構成單元(B-1)及(B-2)之合計在構成單元B中所佔的比例為40莫耳%以上。前述構成單元(B-1)及(B-2)之合計所佔的比例未達40莫耳%的話,形成低相位延遲與延伸性優良的薄膜會變得困難。前述構成單元(B-1)及(B-2)之合計所佔的比例宜為50莫耳%以上,為55莫耳%以上更佳,為60莫耳%以上再更佳,且宜為95莫耳%以下,為90莫耳%以下更佳。考慮和前述同樣的觀點,前述構成單元(B-1)及(B-2)之合計所佔的比例宜為40~95莫耳%,為50~95莫耳%更佳,為55~95莫耳%再更佳,為60~90莫耳%又更佳。In the present invention, the ratio of the total of the structural units (B-1) and (B-2) to the structural unit B is 40 mol % or more. If the ratio of the total of the aforementioned constituent units (B-1) and (B-2) is less than 40 mol %, it will be difficult to form a thin film with low retardation and excellent stretchability. The proportion of the total of the aforementioned constituent units (B-1) and (B-2) is preferably 50 mol % or more, more preferably 55 mol % or more, more preferably 60 mol % or more, and preferably 95 mol % or less, more preferably 90 mol % or less. Considering the same viewpoint as above, the proportion of the total of the aforementioned constituent units (B-1) and (B-2) is preferably 40 to 95 mol %, more preferably 50 to 95 mol %, and 55 to 95 mol %. The molar % is even better, and it is 60 to 90 molar %.
本發明中的構成單元B包含選自於由來自下式(b-3)表示之化合物之構成單元(B-3)、來自下式(b-4)之構成單元(B-4)、及來自下式(b-5)表示之化合物之構成單元(B-5)構成之群組中之至少1種構成單元(以下有時會將該構成單元稱為「構成單元B’」)。藉由前述構成單元B包含前述構成單元B’,可獲得低相位延遲與延伸性間的平衡優良的薄膜。The constitutional unit B in the present invention includes a constitutional unit (B-3) selected from a compound derived from the following formula (b-3), a constitutional unit (B-4) derived from the following formula (b-4), and At least one kind of structural unit (hereinafter, this structural unit may be referred to as "constitutive unit B'") from the group consisting of the structural unit (B-5) of the compound represented by the following formula (b-5). When the structural unit B includes the structural unit B', a thin film having an excellent balance between low retardation and stretchability can be obtained.
[化6] [hua 6]
上述式(b-3)表示之化合物係2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷。上述式(b-4)表示之化合物係5-胺基-1,3,3-三甲基-1-(4-胺基苯基)二氫茚。上述式(b-5)表示之化合物係4,4’-二胺基-2,2’-雙(三氟甲基)聯苯(別名:2,2’-雙(三氟甲基)聯苯胺)。 前述構成單元B’可包含前述構成單元(B-3)~(B-5)全部,但包含選自於由前述構成單元(B-3)、前述構成單元(B-4)、及前述構成單元(B-5)構成之群組中之1種或2種構成單元較理想,包含1種構成單元更佳。The compound represented by the above formula (b-3) is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. The compound represented by the above formula (b-4) is 5-amino-1,3,3-trimethyl-1-(4-aminophenyl)indene. The compound represented by the above formula (b-5) is 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (alias: 2,2'-bis(trifluoromethyl)biphenyl) aniline). The above-mentioned structural unit B' may include all of the above-mentioned structural units (B-3) to (B-5), but includes a structure selected from the above-mentioned structural unit (B-3), the above-mentioned structural unit (B-4), and the above-mentioned structure. One or two kinds of constituent units in the group constituted by the unit (B-5) are preferable, and it is more preferable to include one kind of constituent units.
前述構成單元(B-3)、前述構成單元(B-4)及前述構成單元(B-5)之合計在構成單元B中所佔的比例宜為5~60莫耳%,為10~50莫耳%更佳,為10~45莫耳%再更佳,為10~40莫耳%又更佳。 包含前述構成單元(B-3)作為構成單元B’時,前述構成單元(B-3)相對於構成單元B之比例宜為10~60莫耳%,為25~55莫耳%更佳,為35~50莫耳%再更佳,為40~50莫耳%又更佳。 包含前述構成單元(B-4)作為構成單元B’時,前述構成單元(B-4)相對於構成單元B之比例宜為10~60莫耳%,為20~55莫耳%更佳,為30~50莫耳%再更佳,為35~50莫耳%又更佳。 包含前述構成單元(B-5)作為構成單元B’時,前述構成單元(B-5)相對於構成單元B之比例宜為5~40莫耳%,為5~30莫耳%更佳,為5~20莫耳%再更佳,為5~15莫耳%又更佳。The proportion of the total of the aforementioned constituent unit (B-3), the aforementioned constituent unit (B-4) and the aforementioned constituent unit (B-5) in the constituent unit B is preferably 5 to 60 mol %, and 10 to 50 mol %. The molar % is more preferably, 10-45 mol %, still more preferably, 10-40 mol %. When the aforementioned constituent unit (B-3) is included as the constituent unit B', the ratio of the aforementioned constituent unit (B-3) relative to the constituent unit B is preferably 10 to 60 mol %, more preferably 25 to 55 mol %, 35-50 mol % is still more preferable, and 40-50 mol % is still more preferable. When including the aforementioned constituent unit (B-4) as the constituent unit B', the ratio of the aforementioned constituent unit (B-4) to the constituent unit B is preferably 10-60 mol %, more preferably 20-55 mol %, 30-50 mol % is still more preferable, and 35-50 mol % is still more preferable. When the aforementioned constituent unit (B-5) is included as the constituent unit B', the ratio of the aforementioned constituent unit (B-5) relative to the constituent unit B is preferably 5 to 40 mol %, more preferably 5 to 30 mol %, 5-20 mol % is still better, and 5-15 mol % is still better.
本發明之聚醯亞胺在不損及本發明之效果的範圍內,也可在構成單元B中包含來自式(b-1)~(b-5)表示之化合物以外之二胺之構成單元,但不含較理想。 來自上述式(b-1)~(b-5)表示之化合物以外之二胺之構成單元相對於構成單元B之比例宜為10莫耳%以下,為5莫耳%以下更佳,為1莫耳%以下再更佳,為0莫耳%又更佳。The polyimide of the present invention may include, in the structural unit B, structural units derived from diamines other than the compounds represented by the formulae (b-1) to (b-5) within the range that does not impair the effects of the present invention. , but not ideal. The ratio of constituent units derived from diamines other than the compounds represented by the above formulae (b-1) to (b-5) relative to constituent unit B is preferably 10 mol % or less, more preferably 5 mol % or less, and 1 Molar % or less is still better, and 0 molar % is still better.
[聚醯亞胺之製造方法] 本發明之聚醯亞胺係藉由使二胺成分與四羧酸成分反應而獲得。[Production method of polyimide] The polyimide of the present invention is obtained by reacting a diamine component and a tetracarboxylic acid component.
就四羧酸成分而言,可列舉四羧酸或其衍生物。四羧酸成分可單獨使用或將2種以上組合使用。 就四羧酸之衍生物而言,可列舉該四羧酸的酐或烷基酯。 就四羧酸之烷基酯而言,烷基之碳數為1~3較理想,可列舉例如:四羧酸的二甲基酯、二乙基酯、及二丙基酯。 本發明所使用的四羧酸成分中,1,2,4,5-環己烷四羧酸或其衍生物為必要,其中,宜包含1,2,4,5-環己烷四羧酸二酐[上述式(a-1)]。As a tetracarboxylic acid component, a tetracarboxylic acid or its derivative(s) can be mentioned. A tetracarboxylic-acid component can be used individually or in combination of 2 or more types. As a derivative of a tetracarboxylic acid, the anhydride or alkyl ester of the said tetracarboxylic acid is mentioned. As for the alkyl ester of a tetracarboxylic acid, it is preferable that the carbon number of an alkyl group is 1-3, For example, the dimethyl ester of a tetracarboxylic acid, a diethyl ester, and a dipropyl ester are mentioned. Among the tetracarboxylic acid components used in the present invention, 1,2,4,5-cyclohexanetetracarboxylic acid or a derivative thereof is essential, and among them, 1,2,4,5-cyclohexanetetracarboxylic acid is preferably contained Dianhydride [above formula (a-1)].
相對於全部四羧酸成分,1,2,4,5-環己烷四羧酸或其衍生物的使用量宜為70~100莫耳%,為85~100莫耳%更佳,為99~100莫耳%再更佳,為100莫耳%又更佳。Relative to all the tetracarboxylic acid components, the usage amount of 1,2,4,5-cyclohexanetetracarboxylic acid or its derivatives is preferably 70~100 mol%, more preferably 85~100 mol%, 99% ~100 mol% is still better, and 100 mol% is even better.
此外,也可包含1,2,4,5-環己烷四羧酸或其衍生物以外的四羧酸成分。就該四羧酸成分而言,可列舉選自於由含有芳香環之四羧酸或其衍生物、及含有脂環族烴結構之四羧酸或其衍生物構成之群組中之至少1種。該四羧酸成分可單獨使用或將2種以上組合使用。 就含有芳香環之四羧酸而言,可列舉:均苯四甲酸、3,3’,4,4’-二苯碸四羧酸、3,3’,4,4’-二苯甲酮四羧酸、4,4’-氧二鄰苯二甲酸、4,4’-(六氟異亞丙基)二鄰苯二甲酸、2,2’,3,3’-二苯甲酮四羧酸、3,3’,4,4’-聯苯四羧酸、2,3,3’,4’-聯苯四羧酸、2,2’,3,3’-聯苯四羧酸、2,2-雙(3,4-二羧基苯基)丙烷、2,2-雙(2,3-二羧基苯基)丙烷、2,2-雙(3,4-二羧基苯氧基苯基)丙烷、1,1-雙(2,3-二羧基苯基)乙烷、1,2-雙(2,3-二羧基苯基)乙烷、1,1-雙(3,4-二羧基苯基)乙烷、1,2-雙(3,4-二羧基苯基)乙烷、雙(2,3-二羧基苯基)甲烷、雙(3,4-二羧基苯基)甲烷、4,4’-(對伸苯基二氧基)二鄰苯二甲酸、4,4’-(間伸苯基二氧基)二鄰苯二甲酸、2,3,6,7-萘四羧酸、1,4,5,8-萘四羧酸及它們的衍生物。In addition, tetracarboxylic acid components other than 1,2,4,5-cyclohexanetetracarboxylic acid or a derivative thereof may be contained. The tetracarboxylic acid component includes at least one selected from the group consisting of an aromatic ring-containing tetracarboxylic acid or a derivative thereof, and an alicyclic hydrocarbon structure-containing tetracarboxylic acid or a derivative thereof. kind. The tetracarboxylic acid component may be used alone or in combination of two or more. Examples of aromatic ring-containing tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-diphenyltetracarboxylic acid, and 3,3',4,4'-benzophenone Tetracarboxylic acid, 4,4'-oxydiphthalic acid, 4,4'-(hexafluoroisopropylidene)diphthalic acid, 2,2',3,3'-benzophenone tetra Carboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid , 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenoxy) Phenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 1,2-bis(2,3-dicarboxyphenyl)ethane, 1,1-bis(3,4 -Dicarboxyphenyl)ethane, 1,2-bis(3,4-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl) ) methane, 4,4'-(p-phenylenedioxy)diphthalic acid, 4,4'-(m-phenylenedioxy)diphthalic acid, 2,3,6,7 - Naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and their derivatives.
就含有脂環族烴結構之四羧酸而言,可列舉:1,2,3,4-環丁烷四羧酸、1,2,4,5-環戊烷四羧酸、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸、二環己基四羧酸、環戊酮雙螺降莰烷四羧酸或它們的位置異構物、及它們的衍生物。 就不含脂環族烴結構且不含芳香環之四羧酸成分而言,可列舉:1,2,3,4-丁烷四羧酸、1,2,3,4-戊烷四羧酸等或它們的衍生物。As the tetracarboxylic acid containing an alicyclic hydrocarbon structure, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, bicyclo[2.2 .2] Oct-7-ene-2,3,5,6-tetracarboxylic acid, dicyclohexyltetracarboxylic acid, cyclopentanone bisspironorbornane tetracarboxylic acid or their positional isomers, and their derivative. As a tetracarboxylic acid component which does not contain an alicyclic hydrocarbon structure and does not contain an aromatic ring, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid can be mentioned. acid, etc. or their derivatives.
相對於全部四羧酸成分,1,2,4,5-環己烷四羧酸或其衍生物以外的四羧酸成分之使用量宜為30莫耳%以下,為15莫耳%以下更佳,為1莫耳%以下再更佳,為0莫耳%又更佳。The amount of tetracarboxylic acid components other than 1,2,4,5-cyclohexanetetracarboxylic acid or its derivatives is preferably 30 mol % or less, more preferably 15 mol % or less, relative to all tetracarboxylic acid components. Preferably, it is 1 mol % or less, even more preferably, it is 0 mol %.
就本發明所使用的二胺成分而言,不限於提供構成單元B之二胺,也可為對應於該二胺之二異氰酸酯,但二胺較理想。 本發明所使用的二胺成分包含上述式(b-1)表示之化合物、及上述式(b-2)表示之化合物,更包含選自於上述式(b-3)表示之化合物、上述式(b-4)表示之化合物、及上述式(b-5)表示之化合物中之至少1種化合物較理想。 另外,上述式(b-4)表示之5-胺基-1,3,3-三甲基-1-(4-胺基苯基)二氫茚(以下有時稱為「5-胺基異構物」)有時會混有係異構物之6-胺基-1,3,3-三甲基-1-(4-胺基苯基)二氫茚(以下有時稱為「6-胺基異構物」)的情況。亦即,使用上述式(b-4)表示之化合物作為二胺成分時,有時會有5-胺基異構物及6-胺基異構物混在一起的情況。The diamine component used in the present invention is not limited to the diamine that provides the structural unit B, and may be a diisocyanate corresponding to the diamine, but a diamine is preferable. The diamine component used in the present invention includes the compound represented by the above formula (b-1) and the compound represented by the above formula (b-2), and further includes a compound selected from the group consisting of the compound represented by the above formula (b-3), the above formula At least one of the compound represented by (b-4) and the compound represented by the above formula (b-5) is preferable. In addition, 5-amino-1,3,3-trimethyl-1-(4-aminophenyl)indene (hereinafter sometimes referred to as "5-aminophenyl") represented by the above formula (b-4) Isomer") is sometimes mixed with 6-amino-1,3,3-trimethyl-1-(4-aminophenyl)indene (hereinafter sometimes referred to as " 6-amino isomer"). That is, when the compound represented by the said formula (b-4) is used as a diamine component, a 5-amino isomer and a 6-amino isomer may be mixed.
相對於全部二胺成分,上述式(b-1)表示之化合物的使用量未達50莫耳%,宜為5~45莫耳%,為10~45莫耳%更佳,為15~45莫耳%再更佳,為20~40莫耳%又更佳。 相對於全部二胺成分,上述式(b-2)表示之化合物的使用量為15莫耳%以上,宜為15~70莫耳%,為15~60莫耳%更佳,為20~50莫耳%再更佳,為30~50莫耳%又更佳,為35~50莫耳%再更佳,為40~50莫耳%又更佳。 相對於全部二胺成分,上述式(b-1)表示之化合物及上述式(b-2)表示之化合物的合計使用量為40莫耳%以上,宜為40~95莫耳%,為50~95莫耳%更佳,為55~95莫耳%再更佳,為60~90莫耳%又更佳。 相對於全部二胺成分,上述式(b-3)表示之化合物、上述式(b-4)表示之化合物、及上述式(b-5)表示之化合物的合計使用量宜為5~60莫耳%,為10~55莫耳%更佳,為10~50莫耳%再更佳,為10~45莫耳%又更佳,為10~40莫耳%再更佳。 相對於全部二胺成分,上述式(b-3)表示之化合物的使用量宜為10~60莫耳%,為25~55莫耳%更佳,為35~50莫耳%再更佳,為40~50莫耳%又更佳。 相對於全部二胺成分,上述式(b-4)表示之化合物的使用量宜為10~60莫耳%,為20~55莫耳%更佳,為30~50莫耳%再更佳,為35~50莫耳%又更佳。 相對於全部二胺成分,上述式(b-5)表示之化合物的使用量宜為5~40莫耳%,為5~30莫耳%更佳,為5~20莫耳%再更佳,為5~15莫耳%又更佳。Relative to all the diamine components, the usage amount of the compound represented by the above formula (b-1) is less than 50 mol %, preferably 5-45 mol %, more preferably 10-45 mol %, 15-45 mol %. The molar % is even better, and it is even more preferably 20-40 molar %. Relative to all the diamine components, the usage amount of the compound represented by the above formula (b-2) is 15 mol % or more, preferably 15-70 mol %, more preferably 15-60 mol %, 20-50 mol %. The molar % is still better, 30-50 mol % is still better, 35-50 mol % is still better, 40-50 mol % is still better. The total usage amount of the compound represented by the above formula (b-1) and the compound represented by the above formula (b-2) is 40 mol % or more, preferably 40 to 95 mol %, and 50 mol % relative to all the diamine components. It is more preferably ~95 mol%, still more preferably 55~95 mol%, still more preferably 60~90 mol%. The total amount of the compound represented by the above formula (b-3), the compound represented by the above formula (b-4), and the compound represented by the above formula (b-5) is preferably 5 to 60 mol with respect to all the diamine components. %, preferably 10-55 mol%, still more preferably 10-50 mol%, still more preferably 10-45 mol%, still more preferably 10-40 mol%. Relative to all the diamine components, the usage amount of the compound represented by the above formula (b-3) is preferably 10-60 mol %, preferably 25-55 mol %, more preferably 35-50 mol %, 40~50 mol% is better. Relative to all diamine components, the usage amount of the compound represented by the above formula (b-4) is preferably 10-60 mol %, preferably 20-55 mol %, more preferably 30-50 mol %, 35~50 mol% is better. With respect to all the diamine components, the usage amount of the compound represented by the above formula (b-5) is preferably 5-40 mol %, preferably 5-30 mol %, more preferably 5-20 mol %, 5~15 mol% is better.
二胺成分也可包含上述式(b-1)~(b-5)表示之化合物以外的二胺成分。就該二胺成分而言,可列舉選自於由芳香族二胺、及脂肪族二胺構成之群組中之至少1種。該二胺成分可單獨使用或將2種以上組合使用。另外,“芳香族二胺”係表示胺基直接鍵結於芳香族環之二胺,且其結構的一部分也可包含脂肪族烴基、脂環族烴基、其他取代基(例如:鹵素原子、磺醯基、羰基、氧原子等)。“脂肪族二胺”係表示胺基直接鍵結於脂肪族烴基或脂環族烴基之二胺,且其結構的一部分也可包含芳香族烴基、其他取代基(例如:鹵素原子、磺醯基、羰基、氧原子等)。The diamine component may contain diamine components other than the compounds represented by the above formulae (b-1) to (b-5). As this diamine component, at least 1 sort(s) chosen from the group which consists of an aromatic diamine and an aliphatic diamine can be mentioned. This diamine component can be used individually or in combination of 2 or more types. In addition, "aromatic diamine" refers to a diamine in which an amine group is directly bonded to an aromatic ring, and a part of its structure may contain an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, other substituents (for example, a halogen atom, a sulfonic acid group) acyl group, carbonyl group, oxygen atom, etc.). "Aliphatic diamine" refers to a diamine in which the amine group is directly bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and a part of its structure may also contain an aromatic hydrocarbon group, other substituents (for example: halogen atom, sulfonyl group) , carbonyl group, oxygen atom, etc.).
就芳香族二胺而言,可列舉例如:對苯二胺、間苯二胺、2,4-二胺基甲苯、2,6-二胺基甲苯、聯苯胺、鄰聯甲苯胺、間聯甲苯胺、八氟聯苯胺、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、3,3’-二氟-4,4’-二胺基聯苯、2,6-二胺基萘、1,5-二胺基萘、4,4’-二胺基二苯醚、3,4’-二胺基二苯醚、4,4’-二胺基二苯甲烷、4,4’-二胺基二苯碸、3,4’-二胺基二苯碸、4,4’-二胺基二苯甲酮、2,2-雙[4-(2-甲基-4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(2,6-二甲基-4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(2-甲基-4-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(2,6-二甲基-4-胺基苯氧基)苯基]六氟丙烷、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-雙(2-甲基-4-胺基苯氧基)聯苯、4,4’-雙(2,6-二甲基-4-胺基苯氧基)聯苯、4,4’-雙(3-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(2-甲基-4-胺基苯氧基)苯基]碸、雙[4-(2,6-二甲基-4-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(2-甲基-4-胺基苯氧基)苯基]醚、雙[4-(2,6-二甲基-4-胺基苯氧基)苯基]醚、1,4-雙(4-胺基苯氧基)苯、1,4-雙(2-甲基-4-胺基苯氧基)苯、1,4-雙(2,6-二甲基-4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(2-甲基-4-胺基苯氧基)苯、1,3-雙(2,6-二甲基-4-胺基苯氧基)苯、1,4-雙(4-胺基-α,α-二甲基苄基)苯、2,2-雙(4-胺基苯基)丙烷、2,2-雙(2-甲基-4-胺基苯基)丙烷、2,2-雙(3-甲基-4-胺基苯基)丙烷、2,2-雙(3-乙基-4-胺基苯基)丙烷、2,2-雙(3,5-二甲基-4-胺基苯基)丙烷、2,2-雙(2,6-二甲基-4-胺基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙(2-甲基-4-胺基苯基)六氟丙烷、2,2-雙(2,6-二甲基-4-胺基苯基)六氟丙烷、α,α’-雙(4-胺基苯基)-1,4-二異丙基苯、α,α’-雙(2-甲基-4-胺基苯基)-1,4-二異丙基苯、α,α’-雙(2,6-二甲基-4-胺基苯基)-1,4-二異丙基苯、α,α’-雙(3-胺基苯基)-1,4-二異丙基苯、α,α’-雙(4-胺基苯基)-1,3-二異丙基苯、α,α’-雙(2-甲基-4-胺基苯基)-1,3-二異丙基苯、α,α’-雙(2,6-二甲基-4-胺基苯基)-1,3-二異丙基苯、α,α’-雙(3-胺基苯基)-1,3-二異丙基苯、9,9-雙(2-甲基-4-胺基苯基)茀、9,9-雙(2,6-二甲基-4-胺基苯基)茀、1,1-雙(4-胺基苯基)環戊烷、1,1-雙(2-甲基-4-胺基苯基)環戊烷、1,1-雙(2,6-二甲基-4-胺基苯基)環戊烷、1,1-雙(4-胺基苯基)環己烷、1,1-雙(2-甲基-4-胺基苯基)環己烷、1,1-雙(2,6-二甲基-4-胺基苯基)環己烷、1,1-雙(4-胺基苯基)-4-甲基-環己烷、1,1-雙(4-胺基苯基)降莰烷、1,1-雙(2-甲基-4-胺基苯基)降莰烷、1,1-雙(2,6-二甲基-4-胺基苯基)降莰烷、1,1-雙(4-胺基苯基)金剛烷、1,1-雙(2-甲基-4-胺基苯基)金剛烷、1,1-雙(2,6-二甲基-4-胺基苯基)金剛烷等。Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, benzidine, o-tolidine, m-phenylenediamine Toluidine, Octafluorobenzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3, 3'-Dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,5-diaminobiphenyl Aminonaphthalene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl bismuth, 3,4'-diaminodiphenylene, 4,4'-diaminobenzophenone, 2,2-bis[4-(2-methyl-4-aminophenoxy)benzene yl]propane, 2,2-bis[4-(2,6-dimethyl-4-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-methyl-4- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2,6-dimethyl-4-aminophenoxy)phenyl]hexafluoropropane, 4,4'- Bis(4-aminophenoxy)biphenyl, 4,4'-bis(2-methyl-4-aminophenoxy)biphenyl, 4,4'-bis(2,6-dimethyl -4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]diphenyl, bis[ 4-(2-Methyl-4-aminophenoxy)phenyl]sine, bis[4-(2,6-dimethyl-4-aminophenoxy)phenyl]sine, bis[4 -(4-Aminophenoxy)phenyl]ether, bis[4-(2-methyl-4-aminophenoxy)phenyl]ether, bis[4-(2,6-dimethyl -4-Aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(2-methyl-4-aminophenoxy)benzene , 1,4-bis(2,6-dimethyl-4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(2-methyl) Alkyl-4-aminophenoxy)benzene, 1,3-bis(2,6-dimethyl-4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene -Dimethylbenzyl)benzene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(2-methyl-4-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane 3-Methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl-4-aminophenyl)propane, 2,2-bis(3,5-dimethyl-4- Aminophenyl)propane, 2,2-bis(2,6-dimethyl-4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2 -Bis(2-methyl-4-aminophenyl)hexafluoropropane, 2,2-bis(2,6-dimethyl-4-aminophenyl)hexafluoropropane, α,α'-bis (4-Aminophenyl)-1,4-diisopropylbenzene, α,α'-bis(2-methyl-4-aminophenyl)-1,4-diisopropylbenzene, α ,α'-bis(2,6-dimethyl-4-aminophenyl)-1,4- Diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,4-diisopropylbenzene, α,α'-bis(4-aminophenyl)-1,3- Diisopropylbenzene, α,α'-bis(2-methyl-4-aminophenyl)-1,3-diisopropylbenzene, α,α'-bis(2,6-dimethylbenzene) -4-Aminophenyl)-1,3-diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,3-diisopropylbenzene, 9,9-bis( 2-Methyl-4-aminophenyl) fluoride, 9,9-bis(2,6-dimethyl-4-aminophenyl) fluoride, 1,1-bis(4-aminophenyl) Cyclopentane, 1,1-bis(2-methyl-4-aminophenyl)cyclopentane, 1,1-bis(2,6-dimethyl-4-aminophenyl)cyclopentane , 1,1-bis(4-aminophenyl)cyclohexane, 1,1-bis(2-methyl-4-aminophenyl)cyclohexane, 1,1-bis(2,6- Dimethyl-4-aminophenyl)cyclohexane, 1,1-bis(4-aminophenyl)-4-methyl-cyclohexane, 1,1-bis(4-aminophenyl) ) norbornane, 1,1-bis(2-methyl-4-aminophenyl)norbornane, 1,1-bis(2,6-dimethyl-4-aminophenyl)norbornane Alkane, 1,1-bis(4-aminophenyl)adamantane, 1,1-bis(2-methyl-4-aminophenyl)adamantane, 1,1-bis(2,6-bis Methyl-4-aminophenyl)adamantane, etc.
它們可單獨使用或將2種以上組合使用。These can be used individually or in combination of 2 or more types.
就脂肪族二胺而言,可列舉例如:乙二胺、六亞甲基二胺、聚乙二醇雙(3-胺基丙基)醚、聚丙二醇雙(3-胺基丙基)醚、1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、間苯二甲胺、對苯二甲胺、1,4-雙(2-胺基-異丙基)苯、1,3-雙(2-胺基-異丙基)苯、異佛爾酮二胺、降莰烷二胺、矽氧烷二胺、4,4’-二胺基二環己基甲烷、3,3’-二甲基-4,4’-二胺基二環己基甲烷、3,3’-二乙基-4,4’-二胺基二環己基甲烷、3,3’,5,5’-四甲基-4,4’-二胺基二環己基甲烷、2,3-雙(胺基甲基)-雙環[2.2.1]庚烷、2,5-雙(胺基甲基)-雙環[2.2.1]庚烷、2,6-雙(胺基甲基)-雙環[2.2.1]庚烷、2,2-雙(4,4’-二胺基環己基)丙烷、2,2-雙(4,4’-二胺基甲基環己基)丙烷等。Aliphatic diamines include, for example, ethylenediamine, hexamethylenediamine, polyethylene glycol bis(3-aminopropyl) ether, and polypropylene glycol bis(3-aminopropyl) ether , 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, m-xylylenediamine, p-xylylenediamine, 1,4-bis(2 -Amino-isopropyl)benzene, 1,3-bis(2-amino-isopropyl)benzene, isophoronediamine, norbornanediamine, siloxanediamine, 4,4' -Diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminobicyclo Hexylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 2,3-bis(aminomethyl)-bicyclo[2.2.1]heptane , 2,5-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,2-bis(4 , 4'-diaminocyclohexyl) propane, 2,2-bis(4,4'-diaminomethylcyclohexyl) propane, etc.
相對於全部二胺成分,上述式(b-1)~(b-5)表示之化合物以外的二胺成分的使用量宜為10莫耳%以下,為5莫耳%以下更佳,為1莫耳%以下再更佳,為0莫耳%又更佳。The use amount of diamine components other than the compounds represented by the above formulas (b-1) to (b-5) is preferably 10 mol % or less, more preferably 5 mol % or less, 1 Molar % or less is still better, and 0 molar % is still better.
製造本發明之聚醯亞胺時,就四羧酸成分與二胺成分之進料量比而言,相對於四羧酸成分1莫耳,二胺成分宜為0.9~1.1莫耳。When producing the polyimide of the present invention, in terms of the feed ratio of the tetracarboxylic acid component and the diamine component, the diamine component is preferably 0.9 to 1.1 mol relative to 1 mol of the tetracarboxylic acid component.
製造本發明之聚醯亞胺時,會使用前述四羧酸成分、前述二胺成分,除此之外也可使用封端劑。就封端劑而言,宜為單胺類或二羧酸類。相對於四羧酸成分1莫耳,加入的封端劑之進料量宜為0.0001~0.1莫耳,為0.001~0.06莫耳更佳。就單胺類封端劑而言,建議為例如:甲胺、乙胺、丙胺、丁胺、苄胺、4-甲基苄胺、4-乙基苄胺、4-十二烷基苄胺、3-甲基苄胺、3-乙基苄胺、苯胺、3-甲基苯胺、4-甲基苯胺等。它們之中,可使用苄胺、苯胺較理想。就二羧酸類封端劑而言,宜為二羧酸類,且其一部分也可閉環。建議為例如:鄰苯二甲酸、鄰苯二甲酸酐、4-氯鄰苯二甲酸、四氟鄰苯二甲酸、2,3-二苯甲酮二羧酸、3,4-二苯甲酮二羧酸、環己烷-1,2-二羧酸、環戊烷-1,2-二羧酸、4-環己烯-1,2-二羧酸等。它們之中,可使用鄰苯二甲酸、鄰苯二甲酸酐較理想。When producing the polyimide of the present invention, the above-mentioned tetracarboxylic acid component and the above-mentioned diamine component are used, and a blocking agent may be used in addition to these. As the end-capping agent, monoamines or dicarboxylic acids are suitable. With respect to 1 mol of the tetracarboxylic acid component, the feed amount of the added end-capping agent is preferably 0.0001-0.1 mol, more preferably 0.001-0.06 mol. For monoamine end-capping agents, for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine are suggested. , 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. Among them, benzylamine and aniline can be preferably used. The dicarboxylic acid-based end-capping agent is preferably a dicarboxylic acid, and a part thereof may be ring-closed. Suggested for example: phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenone Dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, and the like. Among them, phthalic acid and phthalic anhydride can be preferably used.
使前述四羧酸成分與二胺成分反應之方法並無特別限制,可使用公知的方法。 就具體的反應方法而言,可列舉:(1)將四羧酸成分、二胺成分、及反應溶劑進料於反應器中,於室溫~80℃攪拌0.5~30小時,然後昇溫來實施醯亞胺化反應之方法;(2)將二胺成分及反應溶劑進料於反應器中並使其溶解後,再進料四羧酸成分,因應需要於室溫~80℃攪拌0.5~30小時,然後昇溫來實施醯亞胺化反應之方法;(3)將四羧酸成分、二胺成分、及反應溶劑進料於反應器中,並立即昇溫來實施醯亞胺化反應之方法等。The method of making the said tetracarboxylic-acid component and a diamine component react is not specifically limited, A well-known method can be used. In terms of a specific reaction method, (1) the tetracarboxylic acid component, the diamine component, and the reaction solvent are fed into the reactor, stirred at room temperature to 80° C. for 0.5 to 30 hours, and then heated to implement The method of imidization reaction; (2) after feeding the diamine component and the reaction solvent into the reactor and making it dissolved, then feeding the tetracarboxylic acid component, and stirring at room temperature to 80 ° C for 0.5 to 30 minutes as required. (3) the tetracarboxylic acid component, the diamine component, and the reaction solvent are fed into the reactor, and the temperature is raised immediately to implement the method of the imidization reaction, etc. .
製造聚醯亞胺所使用的反應溶劑若為不妨礙醯亞胺化反應且可溶解所生成的聚醯亞胺者即可。可列舉例如:非質子性溶劑、酚系溶劑、醚系溶劑、碳酸酯系溶劑等。The reaction solvent used for the production of polyimide may be one that can dissolve the produced polyimide without inhibiting the imidization reaction. For example, an aprotic solvent, a phenol type solvent, an ether type solvent, a carbonate type solvent, etc. are mentioned.
就非質子性溶劑之具體例而言,可列舉:N,N-二甲基異丁醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、1,3-二甲基咪唑啶酮、四甲基脲等醯胺系溶劑;γ-丁內酯、γ-戊內酯等內酯系溶劑;六甲基磷醯胺、六甲基膦三醯胺等含磷系醯胺系溶劑;二甲基碸、二甲基亞碸、環丁碸等含硫系溶劑;丙酮、環己酮、甲基環己酮等酮系溶劑;甲吡啶、吡啶等胺系溶劑;乙酸-2-甲氧基-1-甲基乙酯等酯系溶劑等。Specific examples of the aprotic solvent include N,N-dimethylisobutylamide, N,N-dimethylformamide, N,N-dimethylacetamide, N- Amide-based solvents such as methyl-2-pyrrolidone, N-methylcaprolactone, 1,3-dimethylimidazolidinone, tetramethylurea; γ-butyrolactone, γ-valerolactone Isolactone-based solvents; phosphorus-containing amide-based solvents such as hexamethylphosphine, hexamethylphosphine triamide, etc.; sulfur-containing solvents such as dimethyl sulfoxide, dimethyl sulfoxide, and cyclobutane; , ketone-based solvents such as cyclohexanone and methylcyclohexanone; amine-based solvents such as picoline and pyridine; ester-based solvents such as acetic acid-2-methoxy-1-methylethyl ester, etc.
就酚系溶劑之具體例而言,可列舉:酚、鄰甲酚、間甲酚、對甲酚、2,3-二甲基酚、2,4-二甲基酚、2,5-二甲基酚、2,6-二甲基酚、3,4-二甲基酚、3,5-二甲基酚等。 就醚系溶劑之具體例而言,可列舉:1,2-二甲氧基乙烷、雙(2-甲氧基乙基)醚、1,2-雙(2-甲氧基乙氧基)乙烷、雙[2-(2-甲氧基乙氧基)乙基]醚、四氫呋喃、1,4-二㗁烷等。 又,就碳酸酯系溶劑之具體例而言,可列舉:碳酸二乙酯、碳酸甲基乙酯、碳酸乙烯酯、碳酸丙烯酯等。 上述反應溶劑之中,宜為非質子性溶劑,為醯胺系溶劑或內酯系溶劑更佳,為γ-丁內酯再更佳。又,上述反應溶劑可單獨使用或將2種以上混合使用。Specific examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol Methylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, etc. Specific examples of the ether-based solvent include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, and 1,2-bis(2-methoxyethoxy) ) ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, etc. Moreover, as a specific example of a carbonate type solvent, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, etc. are mentioned. Among the above-mentioned reaction solvents, an aprotic solvent is preferable, an amide-based solvent or a lactone-based solvent is more preferable, and γ-butyrolactone is even more preferable. Moreover, the said reaction solvent can be used individually or in mixture of 2 or more types.
在醯亞胺化反應中宜使用迪安-斯塔克(Dean-Stark)裝置等,邊將製造時所生成的水去除邊實施反應。藉由實施如此的操作,可使聚合度及醯亞胺化率更進一步上昇。In the imidization reaction, a Dean-Stark apparatus or the like is preferably used, and the reaction is carried out while removing water generated during production. By carrying out such an operation, the degree of polymerization and the imidization rate can be further increased.
上述醯亞胺化反應中可使用公知的醯亞胺化觸媒。就醯亞胺化觸媒而言,可列舉鹼觸媒或酸觸媒。 就鹼觸媒而言,可列舉:吡啶、喹啉、異喹啉、α-甲基吡啶、β-甲基吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶、三甲胺、三乙胺、三丙胺、三丁胺、咪唑、N,N-二甲基苯胺、N,N-二乙基苯胺等有機鹼觸媒;氫氧化鉀、氫氧化鈉、碳酸鉀、碳酸鈉、碳酸氫鉀、碳酸氫鈉等無機鹼觸媒。 又,就酸觸媒而言,可列舉:巴豆酸、丙烯酸、反式-3-己烯酸、桂皮酸、苯甲酸、甲基苯甲酸、羥基苯甲酸、對苯二甲酸、苯磺酸、對甲苯磺酸、萘磺酸等。上述醯亞胺化觸媒可單獨使用或將2種以上組合使用。 上述之中,考慮操作性的觀點,宜為鹼觸媒,為有機鹼觸媒更佳,為三乙胺再更佳。A known imidization catalyst can be used for the above imidization reaction. As the imidization catalyst, an alkali catalyst or an acid catalyst can be mentioned. Examples of the base catalyst include pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, and trimetidine Amine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline and other organic base catalysts; potassium hydroxide, sodium hydroxide, potassium carbonate, carbonic acid Inorganic alkali catalysts such as sodium, potassium bicarbonate and sodium bicarbonate. Moreover, as acid catalysts, crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, toluic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. The above-mentioned imidization catalysts may be used alone or in combination of two or more. Among the above, from the viewpoint of operability, an alkali catalyst is preferable, an organic alkali catalyst is more preferable, and triethylamine is even more preferable.
使用上述觸媒時,考慮反應率及抑制凝膠化等的觀點,醯亞胺化反應的溫度宜為120~250℃,為160~190℃更佳,為180~190℃再更佳。又,反應時間在生成水餾出開始後,宜為0.5~10小時。 另外,不使用觸媒時的醯亞胺化反應的溫度宜為200~350℃。When using the above-mentioned catalyst, the temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 190°C, and even more preferably 180 to 190°C in consideration of the reaction rate and the inhibition of gelation. In addition, the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water. In addition, the temperature of the imidization reaction when a catalyst is not used is preferably 200 to 350°C.
[聚醯亞胺] 考慮獲得的聚醯亞胺薄膜之機械性強度之觀點,本發明之聚醯亞胺的重量平均分子量宜為500~1,000,000。另外,聚醯亞胺的重量平均分子量可利用凝膠過濾層析等進行測定。 就重量平均分子量之測定例而言,可列舉使用N,N-二甲基甲醯胺作為展開溶劑並利用光散射檢測器來測定絕對分子量之方法。[Polyimide] From the viewpoint of the mechanical strength of the obtained polyimide film, the weight average molecular weight of the polyimide of the present invention is preferably 500 to 1,000,000. In addition, the weight average molecular weight of polyimide can be measured by gel filtration chromatography or the like. As a measurement example of a weight average molecular weight, the method of using N,N- dimethylformamide as a developing solvent and measuring the absolute molecular weight with a light scattering detector is mentioned.
本發明之聚醯亞胺在不損及本發明之效果的範圍內,也可再混合各種添加劑。就添加劑而言,可列舉例如:抗氧化劑、光安定劑、界面活性劑、阻燃劑、塑化劑、無機填料、前述聚醯亞胺以外的高分子化合物等。 就高分子化合物而言,可列舉本發明之聚醯亞胺以外的聚醯亞胺、聚碳酸酯、聚苯乙烯、聚醯胺、聚醯胺醯亞胺、聚對苯二甲酸乙二酯等聚酯、聚醚碸、聚羧酸、聚縮醛、聚苯醚、聚碸、聚丁烯、聚丙烯、聚丙烯醯胺、聚氯乙烯等。The polyimide of the present invention may be further mixed with various additives within a range that does not impair the effects of the present invention. Examples of additives include antioxidants, photostabilizers, surfactants, flame retardants, plasticizers, inorganic fillers, and polymer compounds other than the aforementioned polyimide. The polymer compound includes polyimide other than the polyimide of the present invention, polycarbonate, polystyrene, polyimide, polyimide, and polyethylene terephthalate. Such as polyester, polyether dust, polycarboxylic acid, polyacetal, polyphenylene ether, poly dust, polybutene, polypropylene, polypropylene amide, polyvinyl chloride, etc.
[聚醯亞胺清漆] 本發明之聚醯亞胺清漆係將本發明之聚醯亞胺溶解於有機溶劑而成。亦即,本發明之聚醯亞胺清漆係含有本發明之聚醯亞胺的溶液,其包含本發明之聚醯亞胺及有機溶劑,且該聚醯亞胺溶解於該有機溶劑中。 有機溶劑若為會溶解聚醯亞胺者即可,並無特別限制,宜單獨或混合2種以上之例示作為製造聚醯亞胺所使用的反應溶劑之上述化合物來使用。 本發明之聚醯亞胺具有溶劑溶解性,故可在室溫製成安定的高濃度之清漆。[Polyimide Varnish] The polyimide varnish of the present invention is obtained by dissolving the polyimide of the present invention in an organic solvent. That is, the polyimide varnish of the present invention is a solution containing the polyimide of the present invention, which contains the polyimide of the present invention and an organic solvent, and the polyimide is dissolved in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyimide, and it is preferable to use singly or in combination of two or more of the above-mentioned compounds exemplified as the reaction solvent used for the production of the polyimide. The polyimide of the present invention has solvent solubility, so it can be made into a stable high-concentration varnish at room temperature.
前述聚醯亞胺清漆也可為利用聚合法獲得的聚醯亞胺溶解於反應溶劑而成的含有聚醯亞胺之溶液本身。又,也可為在前述含有聚醯亞胺之溶液中混合選自於作為溶解聚醯亞胺之溶劑而於前述例示之溶劑中之至少1種而成者。The above-mentioned polyimide varnish may be a polyimide-containing solution itself obtained by dissolving a polyimide obtained by a polymerization method in a reaction solvent. Moreover, at least 1 sort(s) chosen from the solvent exemplified above as a solvent for dissolving polyimide may be mixed with the said polyimide containing solution.
含有本發明之聚醯亞胺之溶液(本發明之聚醯亞胺清漆)的固體成分濃度可因應後述形成聚醯亞胺薄膜時的作業性等而適當地選擇,可使製造本發明之聚醯亞胺時所使用的反應溶劑揮發而濃縮、或藉由添加有機溶劑來調整該固體成分濃度、黏度。該有機溶劑若為可使本發明之聚醯亞胺溶解者則無特別限制。 含有本發明之聚醯亞胺之溶液(本發明之聚醯亞胺清漆)的固體成分濃度宜為5~60質量%,為10~45質量%更佳。本發明之聚醯亞胺的溶液黏度宜為1~200Pa・s,為5~150Pa・s更佳。 聚醯亞胺的溶液黏度係使用E型黏度計於23℃測得的值。The solid content concentration of the solution containing the polyimide of the present invention (the polyimide varnish of the present invention) can be appropriately selected according to the workability and the like when forming a polyimide film, which will be described later, and the polyimide of the present invention can be produced. The reaction solvent used for imide is evaporated and concentrated, or the solid content concentration and viscosity are adjusted by adding an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyimide of the present invention. The solid content concentration of the solution containing the polyimide of the present invention (polyimide varnish of the present invention) is preferably 5 to 60 mass %, more preferably 10 to 45 mass %. The solution viscosity of the polyimide of the present invention is preferably 1~200Pa・s, more preferably 5~150Pa・s. The solution viscosity of polyimide is a value measured at 23°C using an E-type viscometer.
[聚醯亞胺薄膜] 本發明之聚醯亞胺薄膜的特徵為含有本發明之聚醯亞胺,且低相位延遲與延伸性優良。本發明之聚醯亞胺薄膜宜由本發明之聚醯亞胺構成。 本發明之聚醯亞胺薄膜的製作方法並無特別限制,可使用公知的方法。可列舉例如:將含有本發明之聚醯亞胺之溶液(本發明之聚醯亞胺清漆)、或含有含本發明之聚醯亞胺之溶液與上述各種添加劑之溶液塗佈於玻璃板、金屬板、塑膠等平滑的支持體上、或成形成薄膜狀後,再將該溶液中所含的有機溶劑等溶劑成分去除之方法等。[Polyimide film] The polyimide film of the present invention is characterized in that it contains the polyimide of the present invention, and has low phase retardation and excellent stretchability. The polyimide film of the present invention is preferably composed of the polyimide of the present invention. The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. For example, the solution containing the polyimide of the present invention (polyimide varnish of the present invention), or the solution containing the polyimide of the present invention and the above-mentioned various additives are coated on a glass plate, A method of removing solvent components such as organic solvents contained in the solution on a smooth support such as a metal plate or plastic, or after forming it into a thin film.
前述含有聚醯亞胺之溶液也可為利用聚合法獲得的聚醯亞胺溶解於反應溶劑而成的聚醯亞胺溶液本身。又,也可為在前述聚醯亞胺溶液中混合選自於作為溶解聚醯亞胺之溶劑而於前述例示之溶劑中之至少1種而成者。藉由如上述般地調整含有聚醯亞胺之溶液的固體成分濃度、黏度,可輕易控制本發明之聚醯亞胺薄膜的厚度。The solution containing the above-mentioned polyimide may be a polyimide solution itself obtained by dissolving the polyimide obtained by the polymerization method in the reaction solvent. Moreover, at least 1 sort(s) chosen from the solvent exemplified above as a solvent for dissolving polyimide may be mixed in the said polyimide solution. The thickness of the polyimide film of the present invention can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide-containing solution as described above.
在前述支持體的表面也可因應需要塗佈脫模劑。就在前述支持體塗佈含有前述聚醯亞胺之溶液後進行加熱使溶劑成分蒸發的方法而言,宜為以下方法。亦即,宜在120℃以下之溫度使溶劑蒸發而製成自支承性薄膜後,將該自支承性薄膜從支持體剝離,再將該自支承性薄膜之端部固定,並於所使用的溶劑成分之沸點以上350℃以下之溫度進行乾燥來製造聚醯亞胺薄膜。又,宜在氮氣環境下進行乾燥。乾燥環境氣體的壓力為減壓、常壓、加壓任一均可。A mold release agent may also be coated on the surface of the aforementioned support as required. The following method is suitable for the method of heating and evaporating a solvent component after coating the said support body with the solution containing the said polyimide. That is, after evaporating the solvent at a temperature of 120°C or less to form a self-supporting film, peel the self-supporting film from the support, fix the end of the self-supporting film, and place it on the used film. A polyimide film is produced by drying at a temperature higher than or equal to the boiling point of the solvent component and not higher than 350°C. In addition, drying is preferably performed in a nitrogen atmosphere. The pressure of the drying atmosphere gas may be any of reduced pressure, normal pressure, and increased pressure.
本發明之聚醯亞胺薄膜的厚度可因應用途等而適當選擇,但宜為1~250μm,為5~100μm更佳,為10~90μm之範圍再更佳。厚度為1~250μm的話,能有製成自支撐膜之實用性上的應用。The thickness of the polyimide film of the present invention can be appropriately selected according to the application, etc., but is preferably 1-250 μm, more preferably 5-100 μm, and even more preferably 10-90 μm. If the thickness is 1 to 250 μm, the practical application of making a self-supporting film is possible.
在本發明中,可製成厚度80μm時的全光線透射率宜為85%以上,更佳為88%以上,再更佳為89%以上之聚醯亞胺薄膜。 在本發明中,可製成黃色指數(YI值)宜為2.7以下,更佳為2.5以下,再更佳為2.2以下之聚醯亞胺薄膜。 在本發明中,可製成玻璃轉移溫度宜為220℃以上,更佳為250℃以上,再更佳為280℃以上之聚醯亞胺薄膜。 具體而言,聚醯亞胺薄膜之全光線透射率、YI值、及玻璃轉移溫度可利用實施例所記載之方法進行測定。In the present invention, a polyimide film with a total light transmittance of preferably 85% or more, more preferably 88% or more, and even more preferably 89% or more at a thickness of 80 μm can be prepared. In the present invention, a polyimide film having a yellowness index (YI value) of preferably 2.7 or less, more preferably 2.5 or less, and even more preferably 2.2 or less can be prepared. In the present invention, a polyimide film having a glass transition temperature of preferably 220°C or higher, more preferably 250°C or higher, and still more preferably 280°C or higher can be prepared. Specifically, the total light transmittance, YI value, and glass transition temperature of the polyimide film can be measured by the methods described in the examples.
在本發明中,可製成厚度方向之相位延遲值(Rth)宜為200nm以下,更佳為150nm以下,再更佳為120nm以下,又更佳為90nm以下之聚醯亞胺薄膜。另外,本說明書中,「低相位延遲」係指厚度方向之相位延遲值(Rth)低,且厚度方向之相位延遲值(Rth)宜落在前述範圍內之意。 在本發明中,可製成雙折射率宜為0.003以下,更佳為0.0025以下,再更佳為0.002以下,又更佳為0.0012以下之聚醯亞胺薄膜。 在本發明中,可製成拉伸斷裂延伸率(測定溫度23℃、濕度50%RH)宜為8%以上,更佳為8.2%以上,再更佳為8.5%以上,又更佳為9%以上之聚醯亞胺薄膜。 具體而言,聚醯亞胺薄膜在厚度方向之相位延遲值(Rth)、雙折射率、及拉伸斷裂延伸率可利用實施例所記載之方法進行測定。In the present invention, the retardation value (Rth) in the thickness direction is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 120 nm or less, and still more preferably 90 nm or less. In addition, in this specification, "low retardation" means that the retardation value (Rth) in the thickness direction is low, and the retardation value (Rth) in the thickness direction preferably falls within the aforementioned range. In the present invention, a polyimide film having a birefringence of preferably 0.003 or less, more preferably 0.0025 or less, still more preferably 0.002 or less, and still more preferably 0.0012 or less can be prepared. In the present invention, the tensile elongation at break (measurement temperature of 23° C., humidity of 50% RH) is preferably 8% or more, more preferably 8.2% or more, still more preferably 8.5% or more, and still more preferably 9%. % or more of polyimide film. Specifically, the retardation value (Rth), birefringence, and tensile elongation at break of the polyimide film in the thickness direction can be measured by the methods described in Examples.
含有本發明之聚醯亞胺的聚醯亞胺薄膜可適當地使用作為彩色濾光片、可撓性顯示器、半導體零件、光學構件等各種構件用之薄膜。 [實施例]The polyimide film containing the polyimide of the present invention can be suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members. [Example]
以下依據實施例具體地說明本發明。但本發明不受這些實施例任何限制。 下述實施例及比較例所獲得的聚醯亞胺溶液及聚醯亞胺薄膜之物性係利用如下所示之方法進行測定。 (1)固體成分濃度: 聚醯亞胺溶液(聚醯亞胺清漆)之固體成分濃度的測定係將樣本於AS ONE股份有限公司製之小型電氣爐MMF-1中,以300℃×30min進行加熱,並由加熱前後之樣本重量差計算而得。 (2)薄膜厚度: 薄膜厚度之測定係利用Mitutoyo股份有限公司製之測微計進行測定。The present invention will be specifically described below based on examples. However, the present invention is not limited by these examples. The physical properties of the polyimide solutions and polyimide films obtained in the following Examples and Comparative Examples were measured by the methods shown below. (1) Solid content concentration: The determination of the solid content concentration of the polyimide solution (polyimide varnish) is performed by heating the sample in a small electric furnace MMF-1 manufactured by AS ONE Co., Ltd. at 300°C × 30min. The sample weight difference is calculated. (2) Film thickness: The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
(3)全光線透射率、YI值 測定係依據JIS K7361-1:1997,使用日本電色工業股份有限公司製之色彩-濁度同時測定器「COH400」實施。 (4)玻璃轉移溫度 測定係使用SII NanoTechnology股份有限公司製之差示掃描熱量計裝置(DSC6200),以昇溫速度10℃/min之條件實施DSC測定,並求得玻璃轉移溫度。(3) Total light transmittance, YI value The measurement was carried out in accordance with JIS K7361-1:1997, using a color-turbidity simultaneous measuring device "COH400" manufactured by Nippon Denshoku Kogyo Co., Ltd. (4) Glass transition temperature The measurement was performed using a differential scanning calorimeter device (DSC6200) manufactured by SII NanoTechnology Co., Ltd., and the glass transition temperature was obtained by performing DSC measurement on the condition of a temperature increase rate of 10° C./min.
(5)雙折射率、Rth 使用日本分光股份有限公司製橢圓偏光計「M-220」,測得在測定波長590nm的nx、ny及nz之值。使用該值求得以下式定義之厚度方向之相位延遲值(Rth),再除以薄膜之厚度求得雙折射率(Δn)。 Rth=[(nx+ny)/2-nz]×d Δn=(nx+ny)/2-nz [式中,nx表示聚醯亞胺薄膜之面內的折射率之中最大的折射率;ny表示最小的折射率;nz表示厚度方向之折射率;d表示薄膜的厚度(nm)。](5) Birefringence, Rth The values of nx, ny, and nz at a measurement wavelength of 590 nm were measured using an ellipsometer "M-220" manufactured by JASCO Corporation. This value was used to obtain the retardation value (Rth) in the thickness direction defined by the following formula, and then divided by the thickness of the film to obtain the birefringence (Δn). Rth=[(nx+ny)/2-nz]×d Δn=(nx+ny)/2-nz [In the formula, nx represents the largest refractive index among the in-plane refractive indices of the polyimide film; ny represents the smallest refractive index; nz represents the refractive index in the thickness direction; d represents the thickness (nm) of the film. ]
(6)延伸性 測定係依據ASTM-882-88,使用東洋精機股份有限公司製之拉伸試驗機「STROGRAPH VC-1」,以測定溫度23℃、濕度50%RH、夾具間距離50mm、拉伸速度50mm/分鐘之條件實施拉伸試驗,求得拉伸斷裂延伸率。拉伸斷裂延伸率愈高則表示薄膜的延伸性愈良好。(6) Extensibility The measurement is based on ASTM-882-88, using a tensile testing machine "STROGRAPH VC-1" manufactured by Toyo Seiki Co., Ltd. to measure a temperature of 23°C, a humidity of 50% RH, a distance between jigs of 50mm, and a tensile speed of 50mm/min. The tensile test was carried out under the same conditions, and the tensile elongation at break was obtained. The higher the tensile elongation at break, the better the stretchability of the film.
<實施例1> 將作為二胺成分之9,9-雙(4-胺基苯基)茀(田岡化學工業股份有限公司製)9.76g(0.028莫耳)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(和歌山精化工業股份有限公司製)8.62g(0.021莫耳)、及4,4’-二胺基-2,2’-雙(三氟甲基)聯苯(和歌山精化工業股份有限公司製)6.72g(0.021莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)46.86g投入於具備不銹鋼製半月形攪拌葉片、氮氣導入管、安裝有冷卻管之迪安-斯塔克裝置、溫度計、玻璃製端蓋之300mL的5口圓底燒瓶中,並以系內溫度70℃、氮氣環境下、轉速200rpm之條件攪拌獲得溶液。 將作為四羧酸成分之1,2,4,5-環己烷四羧酸二酐(三菱瓦斯化學股份有限公司製)16.47g(0.07莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)11.72g一次性地添加於該溶液後,投入作為醯亞胺化觸媒之三乙胺(關東化學股份有限公司製)3.54g,並以加熱包(mantle heater)進行加熱,歷時約20分鐘將反應系內溫度提昇至190℃。收集餾出之成分,配合黏度上昇調整轉速,同時保持反應系內溫度於190℃並回流5小時。 其後,添加γ-丁內酯(三菱化學股份有限公司製)97.62g,將反應系內溫度冷卻至120℃後,再攪拌約3小時使其均勻化,獲得固體成分濃度20質量%之聚醯亞胺溶液。然後將得到的聚醯亞胺溶液塗佈到玻璃板上,並以加熱板於100℃保持60分鐘使溶劑揮發,藉此獲得具有自支承性之無色透明的一次乾燥薄膜。將該薄膜固定於不銹鋼框架,並於熱風乾燥機中在250℃加熱2小時使溶劑蒸發,獲得厚度56μm之薄膜。結果如表1所示。<Example 1> As a diamine component, 9,9-bis(4-aminophenyl) fluoride (manufactured by Taoka Chemical Industry Co., Ltd.) 9.76 g (0.028 mol), 2,2-bis[4-(4-aminophenyl) Phenoxy)phenyl]propane (manufactured by Wakayama Seika Industry Co., Ltd.) 8.62 g (0.021 mol), and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (manufactured by Wakayama Seika Industry Co., Ltd.) 6.72 g (0.021 mol), and 46.86 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were put into a stainless steel half-moon-shaped stirring blade, a nitrogen gas introduction pipe, and a The Dean-Stark apparatus of the cooling tube, the thermometer, and the 300 mL 5-neck round-bottomed flask with the glass end cap were stirred to obtain a solution at a temperature of 70° C. in the system, under a nitrogen atmosphere, and a rotation speed of 200 rpm. 16.47 g (0.07 moles) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as tetracarboxylic acid components Co., Ltd.) 11.72 g was added to the solution at one time, then 3.54 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst, and heated with a mantle heater for a period of time. The temperature in the reaction system was raised to 190°C in about 20 minutes. Collect the distillate components, adjust the rotation speed according to the viscosity increase, and keep the temperature in the reaction system at 190°C and reflux for 5 hours. After that, 97.62 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and the temperature in the reaction system was cooled to 120° C., followed by stirring for about 3 hours to homogenize, to obtain a polymer with a solid content concentration of 20% by mass. Imide solution. Then, the obtained polyimide solution was coated on a glass plate, and the solvent was volatilized by maintaining the heating plate at 100° C. for 60 minutes, thereby obtaining a colorless and transparent primary drying film with self-supporting properties. The film was fixed on a stainless steel frame, and heated in a hot air dryer at 250° C. for 2 hours to evaporate the solvent to obtain a film with a thickness of 56 μm. The results are shown in Table 1.
<實施例2> 將作為二胺成分之9,9-雙(4-胺基苯基)茀(田岡化學工業股份有限公司製)9.76g(0.028莫耳)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(和歌山精化工業股份有限公司製)14.37g(0.035莫耳)、及4,4’-二胺基-2,2’-雙(三氟甲基)聯苯(和歌山精化工業股份有限公司製)2.24g(0.007莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)48.38g投入於具備不銹鋼製半月形攪拌葉片、氮氣導入管、安裝有冷卻管之迪安-斯塔克裝置、溫度計、玻璃製端蓋之300mL的5口圓底燒瓶中,並以系內溫度70℃、氮氣環境下、轉速200rpm之條件攪拌獲得溶液。 將作為四羧酸成分之1,2,4,5-環己烷四羧酸二酐(三菱瓦斯化學股份有限公司製)16.47g(0.07莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)12.09g一次性地添加於該溶液後,投入作為醯亞胺化觸媒之三乙胺(關東化學股份有限公司製)3.54g,並以加熱包進行加熱,歷時約20分鐘將反應系內溫度提昇至190℃。收集餾出的成分,配合黏度上昇調整轉速,同時保持反應系內溫度於190℃並回流5小時。 其後,添加γ-丁內酯(三菱化學股份有限公司製)100.8g,將反應系內溫度冷卻至120℃後,再攪拌約3小時使其均勻化,獲得固體成分濃度20質量%之聚醯亞胺溶液。然後將得到的聚醯亞胺溶液塗佈到玻璃板上,並以加熱板於100℃保持60分鐘使溶劑揮發,藉此獲得具有自支承性之無色透明的一次乾燥薄膜。將該薄膜固定於不銹鋼框架,並於熱風乾燥機中在250℃加熱2小時使溶劑蒸發,獲得厚度89μm之薄膜。結果如表1所示。<Example 2> As a diamine component, 9,9-bis(4-aminophenyl) fluoride (manufactured by Taoka Chemical Industry Co., Ltd.) 9.76 g (0.028 mol), 2,2-bis[4-(4-aminophenyl) Phenoxy)phenyl]propane (manufactured by Wakayama Seika Industry Co., Ltd.) 14.37 g (0.035 mol), and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (manufactured by Wakayama Seika Industry Co., Ltd.) 2.24 g (0.007 mol), and 48.38 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were put into a stainless steel half-moon-shaped stirring blade, a nitrogen gas introduction pipe, and a The Dean-Stark apparatus of the cooling tube, the thermometer, and the 300 mL 5-neck round-bottomed flask with the glass end cap were stirred to obtain a solution at a temperature of 70° C. in the system, under a nitrogen atmosphere, and a rotation speed of 200 rpm. 16.47 g (0.07 moles) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as tetracarboxylic acid components Co., Ltd.) 12.09 g was added to the solution at one time, then 3.54 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst, and heated with a heating pack for about 20 minutes. The temperature in the reaction system was raised to 190°C. The distilled components were collected, and the rotational speed was adjusted in accordance with the increase in viscosity, while maintaining the temperature in the reaction system at 190° C. and refluxing for 5 hours. Then, 100.8 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and the temperature in the reaction system was cooled to 120° C., followed by stirring for about 3 hours to homogenize, to obtain a polymer with a solid content concentration of 20% by mass. Imide solution. Then, the obtained polyimide solution was coated on a glass plate, and the solvent was volatilized by maintaining the heating plate at 100° C. for 60 minutes, thereby obtaining a colorless and transparent primary drying film with self-supporting properties. The film was fixed on a stainless steel frame and heated in a hot air dryer at 250° C. for 2 hours to evaporate the solvent to obtain a film with a thickness of 89 μm. The results are shown in Table 1.
<實施例3> 將作為二胺成分之9,9-雙(4-胺基苯基)茀(田岡化學工業股份有限公司製)7.32g(0.021莫耳)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(和歌山精化工業股份有限公司製)5.75g(0.014莫耳)、及2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(和歌山精化工業股份有限公司製)18.15g(0.035莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)54.20g投入於具備不銹鋼製半月形攪拌葉片、氮氣導入管、安裝有冷卻管之迪安-斯塔克裝置、溫度計、玻璃製端蓋之300mL的5口圓底燒瓶中,並以系內溫度70℃、氮氣環境下、轉速200rpm之條件攪拌獲得溶液。 將作為四羧酸成分之1,2,4,5-環己烷四羧酸二酐(三菱瓦斯化學股份有限公司製)16.47g(0.07莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)13.55g一次性地添加於該溶液後,投入作為醯亞胺化觸媒之三乙胺(關東化學股份有限公司製)3.54g,並以加熱包進行加熱,歷時約20分鐘將反應系內溫度提昇至190℃。收集餾出之成分,配合黏度上昇調整轉速,同時保持反應系內溫度於190℃並回流5小時。 其後,添加γ-丁內酯(三菱化學股份有限公司製)112.9g,將反應系內溫度冷卻至120℃後,再攪拌約3小時使其均勻化,獲得固體成分濃度20質量%之聚醯亞胺溶液。然後將得到的聚醯亞胺溶液塗佈到玻璃板上,並以加熱板於100℃保持60分鐘使溶劑揮發,藉此獲得具有自支承性之無色透明的一次乾燥薄膜。將該薄膜固定於不銹鋼框架,並於熱風乾燥機中在250℃加熱2小時使溶劑蒸發,獲得厚度62μm之薄膜。結果如表1所示。<Example 3> 7.32 g (0.021 moles) of 9,9-bis(4-aminophenyl) fluoride (manufactured by Taoka Chemical Industry Co., Ltd.) as a diamine component, 2,2-bis[4-(4-aminophenyl) Phenoxy)phenyl]propane (manufactured by Wakayama Seika Industry Co., Ltd.) 5.75 g (0.014 moles), and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (manufactured by Wakayama Seika Industry Co., Ltd.) 18.15 g (0.035 mol), and 54.20 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) The Dean-Stark apparatus of the cooling tube, the thermometer, and the 300 mL 5-neck round-bottomed flask with the glass end cap were stirred to obtain a solution at a temperature of 70° C. in the system, under a nitrogen atmosphere, and a rotation speed of 200 rpm. 16.47 g (0.07 moles) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as tetracarboxylic acid components Co., Ltd.) 13.55g was added to the solution at one time, then 3.54g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst, and heated with a heating pack, and the solution was heated for about 20 minutes. The temperature in the reaction system was raised to 190°C. Collect the distillate components, adjust the rotation speed according to the viscosity increase, and keep the temperature in the reaction system at 190°C and reflux for 5 hours. Then, 112.9 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and the temperature in the reaction system was cooled to 120° C., followed by stirring for about 3 hours to homogenize, to obtain a polymer with a solid content concentration of 20% by mass. Imide solution. Then, the obtained polyimide solution was coated on a glass plate, and the solvent was volatilized by maintaining the heating plate at 100° C. for 60 minutes, thereby obtaining a colorless and transparent primary drying film with self-supporting properties. The film was fixed on a stainless steel frame and heated in a hot air dryer at 250° C. for 2 hours to evaporate the solvent to obtain a film with a thickness of 62 μm. The results are shown in Table 1.
<實施例4> 將作為二胺成分之9,9-雙(4-胺基苯基)茀(田岡化學工業股份有限公司製)4.88g(0.014莫耳)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(和歌山精化工業股份有限公司製)11.49g(0.028莫耳)、及2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(和歌山精化工業股份有限公司製)14.52g(0.028莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)53.81g投入於具備不銹鋼製半月形攪拌葉片、氮氣導入管、安裝有冷卻管之迪安-斯塔克裝置、溫度計、玻璃製端蓋之300mL的5口圓底燒瓶中,並以系內溫度70℃、氮氣環境下、轉速200rpm之條件攪拌獲得溶液。 將作為四羧酸成分之1,2,4,5-環己烷四羧酸二酐(三菱瓦斯化學股份有限公司製)16.47g(0.07莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)13.45g一次性地添加於該溶液後,投入作為醯亞胺化觸媒之三乙胺(關東化學股份有限公司製)3.54g,並以加熱包進行加熱,歷時約20分鐘將反應系內溫度提昇至190℃。收集餾出之成分,配合黏度上昇調整轉速,同時保持反應系內溫度於190℃並回流5小時。 其後,添加γ-丁內酯(三菱化學股份有限公司製)112.1g,將反應系內溫度冷卻至120℃後,再攪拌約3小時使其均勻化,獲得固體成分濃度20質量%之聚醯亞胺溶液。然後將得到的聚醯亞胺溶液塗佈到玻璃板上,並以加熱板於100℃保持60分鐘使溶劑揮發,藉此獲得具有自支承性之無色透明的一次乾燥薄膜。將該薄膜固定於不銹鋼框架,並於熱風乾燥機中在250℃加熱2小時使溶劑蒸發,獲得厚度74μm之薄膜。結果如表1所示。<Example 4> 4.88 g (0.014 moles) of 9,9-bis(4-aminophenyl) fluoride (manufactured by Taoka Chemical Industry Co., Ltd.) as a diamine component, 2,2-bis[4-(4-amino) Phenoxy)phenyl]propane (manufactured by Wakayama Seika Industry Co., Ltd.) 11.49 g (0.028 mol), and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (manufactured by Wakayama Seika Industry Co., Ltd.) 14.52 g (0.028 mol), and 53.81 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) The Dean-Stark apparatus of the cooling tube, the thermometer, and the 300 mL 5-neck round-bottomed flask with the glass end cap were stirred to obtain a solution at a temperature of 70° C. in the system, under a nitrogen atmosphere, and a rotation speed of 200 rpm. 16.47 g (0.07 moles) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as tetracarboxylic acid components Co., Ltd.) 13.45g was added to the solution at one time, and then 3.54g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst, and heated with a heating pack for about 20 minutes. The temperature in the reaction system was raised to 190°C. Collect the distillate components, adjust the rotation speed according to the viscosity increase, and keep the temperature in the reaction system at 190°C and reflux for 5 hours. After that, 112.1 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and the temperature in the reaction system was cooled to 120° C., followed by stirring for about 3 hours to homogenize, and a polymer having a solid content concentration of 20% by mass was obtained. Imide solution. Then, the obtained polyimide solution was coated on a glass plate, and the solvent was volatilized by maintaining the heating plate at 100° C. for 60 minutes, thereby obtaining a colorless and transparent primary drying film with self-supporting properties. The film was fixed on a stainless steel frame and heated in a hot air dryer at 250° C. for 2 hours to evaporate the solvent to obtain a film with a thickness of 74 μm. The results are shown in Table 1.
<實施例5> 將作為二胺成分之9,9-雙(4-胺基苯基)茀(田岡化學工業股份有限公司製)4.88g(0.014莫耳)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(和歌山精化工業股份有限公司製)11.49g(0.028莫耳)、及5(6)-胺基-1,3,3-三甲基-1-(4-胺基苯基)二氫茚(日本純良藥品股份有限公司製)7.46g(0.028莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)45.34g投入於具備不銹鋼製半月形攪拌葉片、氮氣導入管、安裝有冷卻管之迪安-斯塔克裝置、溫度計、玻璃製端蓋之300mL的5口圓底燒瓶中,並以系內溫度70℃、氮氣環境下、轉速200rpm之條件攪拌獲得溶液。 將作為四羧酸成分之1,2,4,5-環己烷四羧酸二酐(三菱瓦斯化學股份有限公司製)16.47g(0.07莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)11.33g一次性地添加於該溶液後,投入作為醯亞胺化觸媒之三乙胺(關東化學股份有限公司製)3.54g,並以加熱包進行加熱,歷時約20分鐘將反應系內溫度提昇至190℃。收集餾出之成分,配合黏度上昇調整轉速,同時保持反應系內溫度於190℃並回流5小時。 其後,添加γ-丁內酯(三菱化學股份有限公司製)94.45g,將反應系內溫度冷卻至120℃後,再攪拌約3小時使其均勻化,獲得固體成分濃度20質量%之聚醯亞胺溶液。然後將得到的聚醯亞胺溶液塗佈到玻璃板上,並以加熱板於100℃保持60分鐘使溶劑揮發,藉此獲得具有自支承性之無色透明的一次乾燥薄膜。將該薄膜固定於不銹鋼框架,並於熱風乾燥機中在250℃加熱2小時使溶劑蒸發,獲得厚度85μm之薄膜。結果如表1所示。<Example 5> 4.88 g (0.014 moles) of 9,9-bis(4-aminophenyl) fluoride (manufactured by Taoka Chemical Industry Co., Ltd.) as a diamine component, 2,2-bis[4-(4-amino) Phenoxy)phenyl]propane (manufactured by Wakayama Seika Industry Co., Ltd.) 11.49 g (0.028 mol), and 5(6)-amino-1,3,3-trimethyl-1-(4- Aminophenyl)dihydroindene (manufactured by Junyo Pharmaceutical Co., Ltd.) 7.46 g (0.028 mol) and γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) 45.34 g were put into a half-moon-shaped stirring blade made of stainless steel. , nitrogen introduction tube, Dean-Stark device equipped with cooling tube, thermometer, 300mL 5-neck round-bottom flask with glass end cap, and the temperature inside the system is 70°C, under nitrogen atmosphere, and the speed of rotation is 200rpm. Stir to obtain a solution. 16.47 g (0.07 moles) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as tetracarboxylic acid components Co., Ltd.) 11.33 g was added to the solution at one time, then 3.54 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst, and heated with a heating pack for about 20 minutes. The temperature in the reaction system was raised to 190°C. Collect the distillate components, adjust the rotation speed according to the viscosity increase, and keep the temperature in the reaction system at 190°C and reflux for 5 hours. After that, 94.45 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and the temperature in the reaction system was cooled to 120° C., followed by stirring for about 3 hours to homogenize, to obtain a polymer with a solid content concentration of 20% by mass. Imide solution. Then, the obtained polyimide solution was coated on a glass plate and kept at 100° C. for 60 minutes on a hot plate to volatilize the solvent, thereby obtaining a colorless and transparent primary drying film with self-supporting properties. The film was fixed on a stainless steel frame and heated in a hot air dryer at 250° C. for 2 hours to evaporate the solvent to obtain a film with a thickness of 85 μm. The results are shown in Table 1.
<比較例1> 將作為二胺成分之9,9-雙(4-胺基苯基)茀(田岡化學工業股份有限公司製)9.76g(0.028莫耳)、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(和歌山精化工業股份有限公司製)2.87g(0.007莫耳)、及4,4’-二胺基-2,2’-雙(三氟甲基)聯苯(和歌山精化工業股份有限公司製)11.21g(0.035莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)45.35g投入於具備不銹鋼製半月形攪拌葉片、氮氣導入管、安裝有冷卻管之迪安-斯塔克裝置、溫度計、玻璃製端蓋之300mL的5口圓底燒瓶中,並以系內溫度70℃、氮氣環境下、轉速200rpm之條件攪拌獲得溶液。 將作為四羧酸成分之1,2,4,5-環己烷四羧酸二酐(三菱瓦斯化學股份有限公司製)16.47g(0.07莫耳)、以及γ-丁內酯(三菱化學股份有限公司製)11.34g一次性地添加於該溶液後,投入作為醯亞胺化觸媒之三乙胺(關東化學股份有限公司製)3.54g,並以加熱包進行加熱,歷時約20分鐘將反應系內溫度提昇至190℃。收集餾出之成分,配合黏度上昇調整轉速,同時保持反應系內溫度於190℃並回流5小時。 其後,添加γ-丁內酯(三菱化學股份有限公司製)94.47g,將反應系內溫度冷卻至120℃後,再攪拌約3小時使其均勻化,獲得固體成分濃度20質量%之聚醯亞胺溶液。然後將得到的聚醯亞胺溶液塗佈到玻璃板上,並以加熱板於100℃保持60分鐘使溶劑揮發,藉此獲得具有自支承性之無色透明的一次乾燥薄膜。將該薄膜固定於不銹鋼框架,並於熱風乾燥機中在250℃加熱2小時使溶劑蒸發,獲得厚度69μm之薄膜。結果如表1所示。<Comparative Example 1> As a diamine component, 9,9-bis(4-aminophenyl) fluoride (manufactured by Taoka Chemical Industry Co., Ltd.) 9.76 g (0.028 mol), 2,2-bis[4-(4-aminophenyl) Phenoxy)phenyl]propane (manufactured by Wakayama Seika Co., Ltd.) 2.87 g (0.007 moles), and 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (manufactured by Wakayama Seika Industry Co., Ltd.) 11.21 g (0.035 mol) and 45.35 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were put into a stainless steel half-moon-shaped stirring blade, a nitrogen gas introduction pipe, and a The Dean-Stark apparatus of the cooling tube, the thermometer, and the 300 mL 5-neck round-bottomed flask with the glass end cap were stirred to obtain a solution at a temperature of 70° C. in the system, under a nitrogen atmosphere, and a rotation speed of 200 rpm. 16.47 g (0.07 moles) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as tetracarboxylic acid components Co., Ltd.) 11.34 g was added to the solution at one time, then 3.54 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst, and heated with a heating pack, and the solution was heated for about 20 minutes. The temperature in the reaction system was raised to 190°C. Collect the distillate components, adjust the rotation speed according to the viscosity increase, and keep the temperature in the reaction system at 190°C and reflux for 5 hours. After that, 94.47 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and the temperature in the reaction system was cooled to 120° C., followed by stirring for further about 3 hours to homogenize to obtain a polymer with a solid content concentration of 20% by mass. Imide solution. Then, the obtained polyimide solution was coated on a glass plate, and the solvent was volatilized by maintaining the heating plate at 100° C. for 60 minutes, thereby obtaining a colorless and transparent primary drying film with self-supporting properties. The film was fixed on a stainless steel frame and heated in a hot air dryer at 250° C. for 2 hours to evaporate the solvent to obtain a film with a thickness of 69 μm. The results are shown in Table 1.
[表1]
表中的縮寫詳如下述。 HPMDA:1,2,4,5-環己烷四羧酸二酐[式(a-1)表示之化合物] BAFL:9,9-雙(4-胺基苯基)茀[式(b-1)表示之化合物(R:氫原子)] BAPP:2,2-雙[4-(4-胺基苯氧基)苯基]丙烷[式(b-2)表示之化合物] HFBAPP:2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷[式(b-3)表示之化合物] TMDA:5(6)-胺基-1,3,3-三甲基-1-(4-胺基苯基)二氫茚[式(b-4)表示之化合物] TFMB:4,4’-二胺基-2,2’-雙(三氟甲基)聯苯[式(b-5)表示之化合物]Abbreviations in the table are detailed below. HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride [compound represented by formula (a-1)] BAFL: 9,9-bis(4-aminophenyl)pyrene [compound represented by formula (b-1) (R: hydrogen atom)] BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane [compound represented by formula (b-2)] HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane [compound represented by formula (b-3)] TMDA: 5(6)-amino-1,3,3-trimethyl-1-(4-aminophenyl)indene [compound represented by formula (b-4)] TFMB: 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl [compound represented by formula (b-5)]
由表1可知實施例1~5之聚醯亞胺薄膜,無色透明性及耐熱性優良且低相位延遲與延伸性亦優良,故上述所有特性皆取得良好的平衡。相對於此,比較例1之聚醯亞胺薄膜在厚度方向之相位延遲值(Rth)高且延伸性不佳,無法獲得低相位延遲與延伸性優良的薄膜。It can be seen from Table 1 that the polyimide films of Examples 1 to 5 are excellent in colorless transparency and heat resistance, as well as low phase retardation and elongation, so all the above-mentioned properties are well balanced. On the other hand, the polyimide film of Comparative Example 1 had a high retardation value (Rth) in the thickness direction and poor extensibility, so that a film with low retardation and excellent extensibility could not be obtained.
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