TW202222913A - Polyimide resin, polyimide varnish, and polyimide film - Google Patents
Polyimide resin, polyimide varnish, and polyimide film Download PDFInfo
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Abstract
Description
本發明關於聚醯亞胺樹脂、聚醯亞胺清漆及聚醯亞胺薄膜。The present invention relates to polyimide resins, polyimide varnishes and polyimide films.
聚醯亞胺樹脂已有人探討其在電氣及電子零件等領域中各種的利用。例如期望將液晶顯示器、OLED顯示器等圖像顯示裝置所使用的玻璃基板,以器件之輕量化、撓性化為目的,而替換成塑膠基板,適合作為該塑膠基板之聚醯亞胺薄膜的研究已在進行。 圖像顯示裝置用途所使用的薄膜要求各種光學特性。例如在從顯示元件發出的光會透過塑膠基板而射出之類的情況,則塑膠基板要求透明性。 Polyimide resins have been studied for various applications in the fields of electrical and electronic parts. For example, it is expected to replace the glass substrate used in image display devices such as liquid crystal displays and OLED displays with plastic substrates for the purpose of reducing the weight and flexibility of the devices, which is suitable for the research on polyimide films of the plastic substrates. is already in progress. Various optical properties are required for thin films used in image display device applications. For example, when light emitted from a display element is emitted through a plastic substrate, the plastic substrate requires transparency.
為了滿足如上述之性能,已進行各種組成之聚醯亞胺樹脂的開發。例如專利文獻1揭示為了獲得透明性及高耐熱性優良的聚醯亞胺薄膜而含有由具有降莰烷骨架之酸二酐與作為二胺成分之2,2’-雙(三氟甲基)聯苯胺的組合構成的結構之聚醯亞胺薄膜。 [先前技術文獻] [專利文獻] In order to satisfy the above-mentioned properties, the development of polyimide resins of various compositions has been carried out. For example, Patent Document 1 discloses that in order to obtain a polyimide film excellent in transparency and high heat resistance, it contains an acid dianhydride having a norbornane skeleton and 2,2'-bis(trifluoromethyl) as a diamine component. A polyimide film composed of a combination of benzidines. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利第6431369號[Patent Document 1] Japanese Patent No. 6431369
[發明所欲解決之課題][The problem to be solved by the invention]
就聚醯亞胺薄膜而言,要求替代玻璃基板,並要求透明性。 在此,於製造圖像顯示裝置時,例如會以將無機膜疊層於聚醯亞胺薄膜的狀態實施加熱處理,故產生自聚醯亞胺薄膜之散逸氣體會累積在聚醯亞胺薄膜和無機膜之層間,因此有時會有在聚醯亞胺薄膜發生黃變等著色的情況。據此,就聚醯亞胺薄膜而言,要求在以疊層有無機膜之狀態暴露於高溫時,使著色受到抑制之耐熱性。 又,在製造圖像顯示裝置時,有可能成為例如超過400℃之製程溫度,故就成為基板之聚醯亞胺薄膜而言,要求耐受400℃以上之高溫的耐熱性。玻璃轉移溫度(Tg)高且耐熱性優良的聚醯亞胺薄膜,在以疊層有無機膜之狀態暴露於高溫時,會存有無機膜發生裂紋等瑕疵之顧慮。據此,就聚醯亞胺薄膜而言,要求在以疊層有無機膜之狀態暴露於高溫時,使無機膜不發生裂紋等瑕疵之耐熱性。 本發明係鑑於如此的狀況而成,本發明之課題係提供可獲得透明性及疊層無機膜時之耐熱性優良的聚醯亞胺薄膜之聚醯亞胺樹脂及聚醯亞胺清漆、以及提供透明性及疊層無機膜時之耐熱性優良的聚醯亞胺薄膜。 [解決課題之手段] In the case of the polyimide film, it is required to replace the glass substrate, and transparency is required. Here, when an image display device is manufactured, for example, a heat treatment is performed in a state where an inorganic film is laminated on a polyimide film, so the escape gas generated from the polyimide film accumulates in the polyimide film and the inorganic film, so the polyimide film may be colored such as yellowing in some cases. Accordingly, the polyimide thin film is required to have heat resistance which suppresses coloration when exposed to high temperature in the state where the inorganic film is laminated. In addition, when manufacturing an image display device, for example, the process temperature may exceed 400°C. Therefore, the polyimide film used as a substrate is required to be heat resistant to a high temperature of 400°C or higher. A polyimide film with a high glass transition temperature (Tg) and excellent heat resistance may cause defects such as cracks in the inorganic film when exposed to high temperature in a state where the inorganic film is laminated. Accordingly, when the polyimide thin film is exposed to high temperature in a state where the inorganic film is laminated, heat resistance such that defects such as cracks are not generated in the inorganic film is required. The present invention is made in view of such a situation, and an object of the present invention is to provide a polyimide resin and a polyimide varnish which can obtain a polyimide film excellent in transparency and heat resistance when an inorganic film is laminated, and Provides a polyimide film excellent in transparency and heat resistance when an inorganic film is laminated. [Means of Solving Problems]
本發明人們發現含有來自分子內具有2個降莰烷骨架之四羧酸二酐之構成單元及來自特定之二胺之構成單元的聚醯亞胺樹脂可解決上述課題,乃至完成發明。The present inventors have found that a polyimide resin containing a structural unit derived from a tetracarboxylic dianhydride having two norbornane skeletons in the molecule and a structural unit derived from a specific diamine can solve the above-mentioned problems, and the invention has been completed.
亦即,本發明關於下述<1>~<11>。 <1>一種聚醯亞胺樹脂,含有來自四羧酸二酐之構成單元A、及來自二胺之構成單元B; 構成單元A包含來自分子內具有2個降莰烷骨架之四羧酸二酐之構成單元(A1), 構成單元B包含來自下式(b1)表示之化合物之構成單元(B1)。 [化1] <2>如<1>所記載之聚醯亞胺樹脂,其中,構成單元(A1)包含選自由來自下式(a11)表示之化合物之構成單元(A11)、來自下式(a12)表示之化合物之構成單元(A12)、來自下式(a13)表示之化合物之構成單元(A13)、及來自下式(a14)表示之化合物之構成單元(A14)構成之群組中之至少1種。 [化2] <3>如<1>或<2>所記載之聚醯亞胺樹脂,其中,構成單元A更包含構成單元(A2),且構成單元(A2)包含選自由來自下式(a21)表示之化合物之構成單元(A21)、及來自下式(a22)表示之化合物之構成單元(A22)構成之群組中之至少1種。 [化3] <4>如<1>~<3>中任一項所記載之聚醯亞胺樹脂,其中,構成單元B更包含構成單元(B2),且構成單元(B2)包含選自由來自下式(b21)表示之化合物之構成單元(B21)、來自下式(b22)表示之化合物之構成單元(B22)、及來自下式(b23)表示之化合物之構成單元(B23)構成之群組中之至少1種。 [化4] [化5] [化6] <5>如<4>所記載之聚醯亞胺樹脂,其中,構成單元(B2)包含來自下式(b21)表示之化合物之構成單元(B21)。 [化7] <6>一種聚醯亞胺清漆,係將如<1>~<5>中任一項所記載之聚醯亞胺樹脂溶解於有機溶劑而成。 <7>一種聚醯亞胺薄膜,含有如<1>~<5>中任一項所記載之聚醯亞胺樹脂。 <8>如<7>所記載之聚醯亞胺薄膜,其中,依據JIS K7136:2000測定之全光線透射率為80%以上。 <9>如<7>或<8>所記載之聚醯亞胺薄膜,其係作為構成顯示裝置之透明性基板使用。 <10>一種聚醯亞胺薄膜之製造方法,包含下列步驟: 將<6>所記載之聚醯亞胺清漆塗佈成或成形成薄膜狀後,將有機溶劑去除。 <11>一種圖像顯示裝置,具備<7>~<9>中任一項所記載之聚醯亞胺薄膜作為透明性基板。 [發明之效果] That is, the present invention relates to the following <1> to <11>. <1> A polyimide resin comprising a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from a diamine; the structural unit A includes a tetracarboxylic acid dibasic derived from two norbornane skeletons in the molecule The structural unit (A1) of the anhydride, and the structural unit B include the structural unit (B1) derived from the compound represented by the following formula (b1). [hua 1] <2> The polyimide resin according to <1>, wherein the structural unit (A1) includes a structural unit (A11) selected from the group consisting of a compound represented by the following formula (a11), a At least one of the group consisting of the structural unit (A12) of the compound, the structural unit (A13) derived from the compound represented by the following formula (a13), and the structural unit (A14) derived from the compound represented by the following formula (a14). [hua 2] <3> The polyimide resin according to <1> or <2>, wherein the structural unit A further comprises a structural unit (A2), and the structural unit (A2) contains a compound selected from the group consisting of the following formula (a21) At least one of the group consisting of the structural unit (A21) of the compound and the structural unit (A22) of the compound represented by the following formula (a22). [hua 3] <4> The polyimide resin according to any one of <1> to <3>, wherein the structural unit B further comprises a structural unit (B2), and the structural unit (B2) contains a structure selected from the group consisting of the following formula ( Among the group consisting of the constitutional unit (B21) of the compound represented by b21), the constitutional unit (B22) derived from the compound represented by the following formula (b22), and the constitutional unit (B23) derived from the compound represented by the following formula (b23) At least 1 species. [hua 4] [hua 5] [hua 6] <5> The polyimide resin according to <4>, wherein the structural unit (B2) includes the structural unit (B21) derived from the compound represented by the following formula (b21). [hua 7] <6> A polyimide varnish obtained by dissolving the polyimide resin according to any one of <1> to <5> in an organic solvent. <7> A polyimide film comprising the polyimide resin according to any one of <1> to <5>. <8> The polyimide film according to <7>, wherein the total light transmittance measured in accordance with JIS K7136:2000 is 80% or more. <9> The polyimide film according to <7> or <8>, which is used as a transparent substrate constituting a display device. <10> A method for producing a polyimide film, comprising the following steps: After coating or forming the polyimide varnish described in <6> into a film, the organic solvent is removed. <11> An image display device including the polyimide film according to any one of <7> to <9> as a transparent substrate. [Effect of invention]
根據本發明,能提供可獲得透明性及疊層無機膜時之耐熱性優良的聚醯亞胺薄膜之聚醯亞胺樹脂及聚醯亞胺清漆,以及能提供透明性及疊層無機膜時之耐熱性優良的聚醯亞胺薄膜。According to the present invention, a polyimide resin and a polyimide varnish that can obtain a polyimide film excellent in transparency and heat resistance when an inorganic film is laminated can be provided, and a polyimide resin and a polyimide varnish that can provide transparency and when an inorganic film is laminated can be provided Polyimide film with excellent heat resistance.
針對用以實施本發明之形態(以下簡稱為「本實施形態」)進行詳細地說明。下列本實施形態係用以說明本發明之例示,並非限定本發明之內容。本發明在其要旨之範圍內可適當地變化並實施。本實施形態中,定義為理想之界定可任意地採用,藉由組合理想的內容彼此,可謂其為更佳。本實施形態中,「XX~YY」之記載意指「XX以上且YY以下」。A mode for implementing the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and does not limit the content of the present invention. The present invention can be appropriately changed and implemented within the scope of its gist. In this embodiment, the definition defined as ideal can be arbitrarily adopted, and it can be said that it is better by combining the contents of ideal. In this embodiment, the description of "XX~YY" means "XX or more and YY or less".
[聚醯亞胺樹脂] 本發明之聚醯亞胺樹脂係含有來自四羧酸二酐之構成單元A、及來自二胺之構成單元B之聚醯亞胺樹脂;構成單元A包含來自分子內具有2個降莰烷骨架之四羧酸二酐之構成單元(A1),構成單元B包含來自下式(b1)表示之化合物之構成單元(B1)。 [Polyimide resin] The polyimide resin of the present invention is a polyimide resin containing a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from a diamine; the structural unit A contains two norbornane skeletons derived from the molecule In the structural unit (A1) of the tetracarboxylic dianhydride, the structural unit B includes the structural unit (B1) derived from the compound represented by the following formula (b1).
[化8] [hua 8]
使用本發明之聚醯亞胺樹脂的話,可獲得透明性及疊層無機膜時之耐熱性優良的聚醯亞胺薄膜之理由尚未闡明,但據認為由於具有降莰烷骨架、及具有彎曲結構但因立體障礙大的三氟甲基而可期待分子運動受抑制之構成單元(B1),故可將透明性保持為良好,同時可改善耐熱性,因此透明性及疊層無機膜時之耐熱性(著色的抑制、無機膜之裂紋的抑制)優良。The reason why a polyimide film excellent in transparency and heat resistance when an inorganic film is laminated by using the polyimide resin of the present invention has not been elucidated, but it is considered that it has a norbornane skeleton and a curved structure. However, due to the trifluoromethyl group having a large steric hindrance, the structural unit (B1) in which molecular motion is inhibited can be expected, so that the transparency can be kept good and the heat resistance can be improved, so the transparency and the heat resistance when the inorganic film is laminated Excellent properties (suppression of coloration, suppression of cracks in inorganic films).
<構成單元A> 構成單元A係聚醯亞胺樹脂中所佔之來自四羧酸二酐之構成單元。 構成單元A包含來自分子內具有2個降莰烷骨架之四羧酸二酐之構成單元(A1)。 構成單元(A1)考慮耐熱性、透明性及光學各向同性之觀點,宜包含選自由來自下式(a11)表示之化合物之構成單元(A11)、來自下式(a12)表示之化合物之構成單元(A12)、來自下式(a13)表示之化合物之構成單元(A13)、及來自下式(a14)表示之化合物之構成單元(A14)構成之群組中之至少1種,考慮使分子骨架更為剛直且更改善耐熱性之觀點,包含選自由來自下式(a11)表示之化合物之構成單元(A11)、來自下式(a12)表示之化合物之構成單元(A12)、及來自下式(a14)表示之化合物之構成單元(A14)構成之群組中之至少1種更佳,包含選自由來自下式(a11)表示之化合物之構成單元(A11)、及來自下式(a14)表示之化合物之構成單元(A14)構成之群組中之至少1種再更佳,包含來自下式(a11)表示之化合物之構成單元(A11)又更佳。 <Construction Unit A> The structural unit A is a structural unit derived from tetracarboxylic dianhydride in the polyimide resin. The structural unit A contains the structural unit (A1) derived from the tetracarboxylic dianhydride which has two norbornane skeletons in a molecule|numerator. From the viewpoint of heat resistance, transparency, and optical isotropy, the structural unit (A1) preferably includes a structural unit (A11) derived from a compound represented by the following formula (a11) and a structure derived from a compound represented by the following formula (a12) At least one of the group consisting of the unit (A12), the structural unit (A13) derived from the compound represented by the following formula (a13), and the structural unit (A14) derived from the compound represented by the following formula (a14), it is considered that the molecular The viewpoint that the skeleton is more rigid and the heat resistance is further improved includes a constituent unit (A11) derived from a compound represented by the following formula (a11), a constituent unit (A12) derived from a compound represented by the following formula (a12), and More preferably, at least one of the group consisting of the structural unit (A14) of the compound represented by the formula (a14) includes a structural unit (A11) derived from the compound represented by the following formula (a11), and a structural unit (A11) derived from the following formula (a14) At least one of the group consisting of the structural unit (A14) of the compound represented by ) is even more preferable, and it is even more preferable to include the structural unit (A11) derived from the compound represented by the following formula (a11).
[化9] [Chemical 9]
構成單元A藉由包含來自分子內具有2個降莰烷骨架之四羧酸二酐之構成單元(A1),可使得到的聚醯亞胺薄膜之耐熱性、透明性及光學各向同性改善。Structural unit A includes structural unit (A1) derived from tetracarboxylic dianhydride having two norbornane skeletons in the molecule, so that the heat resistance, transparency and optical isotropy of the obtained polyimide film can be improved .
構成單元A除了包含構成單元(A1),也可更包含構成單元(A2)。構成單元(A2)例如可列舉選自由來自下式(a21)表示之化合物之構成單元(A21)、及來自下式(a22)表示之化合物之構成單元(A22)構成之群組中之至少1種。The structural unit A may further include the structural unit (A2) in addition to the structural unit (A1). The structural unit (A2) includes, for example, at least 1 selected from the group consisting of the structural unit (A21) derived from the compound represented by the following formula (a21) and the structural unit (A22) derived from the compound represented by the following formula (a22). kind.
[化10] [Chemical 10]
式(a21)表示之化合物為聯苯四甲酸二酐(BPDA),其具體例可列舉下式(a211s)表示之3,3’,4,4’-聯苯四甲酸二酐(s-BPDA)、下式(a211a)表示之2,3,3’,4’-聯苯四甲酸二酐(a-BPDA)、下式(a211i)表示之2,2’,3,3’-聯苯四甲酸二酐(i-BPDA)。其中,宜為下式(a211s)表示之3,3’,4,4’-聯苯四甲酸二酐(s-BPDA)。The compound represented by the formula (a21) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a211s) ), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a211a), 2,2',3,3'-biphenyl represented by the following formula (a211i) Tetracarboxylic dianhydride (i-BPDA). Among them, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a211s) is preferable.
[化11] [Chemical 11]
構成單元A中的構成單元(A1)的比率考慮耐熱性、透明性及光學各向同性之觀點,宜為40莫耳%以上,為50莫耳%以上更佳,為60莫耳%以上再更佳,為80莫耳%以上又更佳,為85莫耳%以上再更佳,為90莫耳%以上又更佳,為95莫耳%以上再更佳,為99莫耳%以上又更佳。該比率之上限值並無特別限制,但為100莫耳%以下。 又,構成單元A更包含構成單元(A2)時,構成單元A中之構成單元(A2)的比率考慮耐熱性、透明性及光學各向同性之觀點,宜為60莫耳%以下,為50莫耳%以下更佳,為40莫耳%以下再更佳,為20莫耳%以下又更佳,為15莫耳%以下再更佳,為10莫耳%以下又更佳,為5莫耳%以下再更佳,為1莫耳%以下又更佳。該比率之下限值並無特別限制,但為0.01莫耳%以上。 The ratio of the structural unit (A1) in the structural unit A is preferably 40 mol % or more, more preferably 50 mol % or more, and 60 mol % or more, considering heat resistance, transparency, and optical isotropy. More preferably, it is 80 mol% or more, still more preferably, it is 85 mol% or more, still better, it is 90 mol% or more, and it is more preferably 95 mol% or more, and it is 99 mol% or more. better. The upper limit of the ratio is not particularly limited, but is 100 mol % or less. In addition, when the structural unit A further includes the structural unit (A2), the ratio of the structural unit (A2) in the structural unit A is preferably 60 mol % or less, and 50 mol % or less, considering heat resistance, transparency, and optical isotropy. More preferably below 40 mol%, still more preferably below 20 mol%, still more preferably below 15 mol%, still more preferably below 10 mol%, still more preferably 5 mol% or less Less than 1 mol % is more preferable, and less than 1 mol % is more preferable. The lower limit value of the ratio is not particularly limited, but is 0.01 mol % or more.
構成單元A也可包含構成單元(A1)及構成單元(A2)以外之構成單元。提供如此的構成單元之四羧酸二酐並無特別限制,可列舉:4,4’-氧二鄰苯二甲酸酐、均苯四甲酸二酐、及4,4’-(六氟亞異丙基)二苯二甲酸酐等芳香族四羧酸二酐(惟,排除式(a21)或(a22)表示之化合物);1,2,4,5-環己烷四甲酸二酐、1,2,3,4-環丁烷四甲酸二酐等脂環族四羧酸二酐(惟,排除式(a11)~(a14)中任一者表示之化合物);以及1,2,3,4-丁烷四甲酸二酐等脂肪族四羧酸二酐。 另外,本說明書中,芳香族四羧酸二酐意指含有1個以上之芳香環之四羧酸二酐,脂環族四羧酸二酐意指含有1個以上之脂環且不含芳香環之四羧酸二酐,脂肪族四羧酸二酐意指不含芳香環也不含脂環之四羧酸二酐。 任意地包含於構成單元A中之構成單元可為1種,也可為2種以上。 The structural unit A may include structural units other than the structural unit (A1) and the structural unit (A2). The tetracarboxylic dianhydride that provides such a structural unit is not particularly limited, and examples thereof include 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride, and 4,4'-(hexafluoroiso Aromatic tetracarboxylic dianhydride such as propyl) diphthalic anhydride (only, excluding compounds represented by formula (a21) or (a22)); 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1 , Alicyclic tetracarboxylic dianhydrides such as 2,3,4-cyclobutanetetracarboxylic dianhydride (only, excluding compounds represented by any one of formulae (a11) to (a14)); and 1,2,3 , 4-butane tetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydrides. In addition, in this specification, aromatic tetracarboxylic dianhydride means tetracarboxylic dianhydride containing one or more aromatic rings, and alicyclic tetracarboxylic dianhydride means containing one or more alicyclic rings and does not contain aromatic Cyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride mean tetracarboxylic dianhydride containing neither aromatic ring nor alicyclic ring. The structural unit arbitrarily included in the structural unit A may be one type or two or more types.
<構成單元B> 構成單元B係聚醯亞胺樹脂中所佔之來自二胺之構成單元。 構成單元B包含來自下式(b1)表示之化合物之構成單元(B1)。 <Construction unit B> The structural unit B is a structural unit derived from a diamine that occupies in the polyimide resin. The structural unit B includes the structural unit (B1) derived from the compound represented by the following formula (b1).
[化12] [Chemical 12]
式(b1)表示之化合物為2,2-雙(4-胺基苯基)六氟丙烷。構成單元B藉由包含構成單元(B1),可在維持耐熱性的狀態下使韌性改善。The compound represented by formula (b1) is 2,2-bis(4-aminophenyl)hexafluoropropane. By including the structural unit (B1), the structural unit B can improve the toughness while maintaining the heat resistance.
構成單元B中的構成單元(B1)的比率考慮使疊層無機膜時之耐熱性改善之觀點,宜為20莫耳%以上,為40莫耳%以上更佳,為50莫耳%以上再更佳,為55莫耳%以上又更佳,為60莫耳%以上再更佳,為80莫耳%以上又更佳,為99莫耳%以上再更佳。該比率之上限值並無特別限制,但為100莫耳%以下。The ratio of the structural unit (B1) in the structural unit B is preferably 20 mol % or more, more preferably 40 mol % or more, and 50 mol % or more, from the viewpoint of improving the heat resistance when the inorganic film is laminated. More preferably, it is 55 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more, and still more preferably 99 mol% or more. The upper limit of the ratio is not particularly limited, but is 100 mol % or less.
構成單元B也可包含構成單元(B1)以外之構成單元。 構成單元B除了包含構成單元(B1)之外,宜更包含構成單元(B2)。構成單元(B2)宜包含例如選自由來自下式(b21)表示之化合物之構成單元(B21)、來自下式(b22)表示之化合物之構成單元(B22)、及來自下式(b23)表示之化合物之構成單元(B23)構成之群組中之至少1種,考慮使分子骨架更為剛直且更改善耐熱性之觀點,宜包含來自下式(b21)表示之化合物之構成單元(B21)。構成單元B藉由包含構成單元(B2),尤其會改善耐熱性,也會進一步改善光學各向同性。 The structural unit B may include structural units other than the structural unit (B1). The structural unit B preferably includes the structural unit (B2) in addition to the structural unit (B1). The constitutional unit (B2) preferably contains, for example, a constitutional unit (B21) selected from a compound represented by the following formula (b21), a constitutional unit (B22) derived from a compound represented by the following formula (b22), and a constitutional unit (B22) represented by the following formula (b23) At least one of the group consisting of the structural unit (B23) of the compound preferably includes the structural unit (B21) derived from the compound represented by the following formula (b21) from the viewpoint of making the molecular skeleton more rigid and improving heat resistance. . When the structural unit B includes the structural unit (B2), especially the heat resistance is improved, and the optical isotropy is further improved.
[化13] [Chemical 13]
[化14] [Chemical 14]
[化15] [Chemical 15]
構成單元B更包含構成單元(B2)時,構成單元B中之構成單元(B2)的比率宜為10莫耳%以上,為20莫耳%以上更佳,為30莫耳%以上再更佳,而且宜為70莫耳%以下,為60莫耳%以下更佳,為50莫耳%以下再更佳。 構成單元B更包含構成單元(B2)時,構成單元B中之構成單元(B1)及構成單元(B2)的合計之比率宜為50莫耳%以上,為70莫耳%以上更佳,為90莫耳%以上再更佳,為95莫耳%以上又更佳,為99莫耳%以上再更佳。構成單元B中之構成單元(B1)及構成單元(B2)的合計之比率的上限值並無特別限制,例如為100莫耳%以下。構成單元B也可僅由構成單元(B1)及構成單元(B2)構成。 構成單元B更包含構成單元(B2)時,構成單元B中之構成單元(B1)與構成單元(B2)的莫耳比[(B1)/(B2)]考慮使透明性、光學各向同性、韌性及耐熱性改善之觀點,宜為30/70~90/10,為40/60~80/20更佳,為50/50~70/30再更佳。 When the structural unit B further comprises the structural unit (B2), the ratio of the structural unit (B2) in the structural unit B is preferably 10 mol % or more, more preferably 20 mol % or more, more preferably 30 mol % or more , and is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. When the structural unit B further includes the structural unit (B2), the ratio of the total of the structural unit (B1) and the structural unit (B2) in the structural unit B is preferably 50 mol % or more, more preferably 70 mol % or more, and is More preferably 90 mol % or more, more preferably 95 mol % or more, still more preferably 99 mol % or more. The upper limit of the ratio of the total of the structural unit (B1) and the structural unit (B2) in the structural unit B is not particularly limited, but is, for example, 100 mol % or less. The structural unit B may be composed of only the structural unit (B1) and the structural unit (B2). When the structural unit B further includes the structural unit (B2), the molar ratio [(B1)/(B2)] of the structural unit (B1) in the structural unit B and the structural unit (B2) in the structural unit B considers transparency and optical isotropy. From the viewpoint of improving toughness and heat resistance, it should be 30/70~90/10, 40/60~80/20 is better, and 50/50~70/30 is even better.
構成單元B也可包含構成單元(B1)及構成單元(B2)以外之構成單元。提供如此的構成單元之二胺並無特別限制,可列舉:1,4-苯二胺、對苯二甲胺、1,5-二胺基萘、2,2’-二甲基聯苯-4,4’-二胺、4,4’-二胺基二苯基醚、4,4’-二胺基-2,2’-雙三氟甲基二苯基醚、4,4’-二胺基二苯基甲烷、4,4’-二胺基苯甲醯苯胺、1-(4-胺基苯基)-2,3-二氫-1,3,3-三甲基-1H-茚-5-胺、α,α’-雙(4-胺基苯基)-1,4-二異丙苯、N,N’-雙(4-胺基苯基)對苯二甲醯胺、4,4’-雙(4-胺基苯氧基)聯苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、及2,2-雙(4-(4-胺基苯氧基)苯基)六氟丙烷等芳香族二胺(惟,排除式(b1)、(b21)~(b23)中任一者表示之化合物);1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷等脂環族二胺;以及乙二胺及六亞甲基二胺等脂肪族二胺。 另外,本說明書中,芳香族二胺意指含有1個以上之芳香環之二胺,脂環族二胺意指含有1個以上之脂環且不含芳香環之二胺,脂肪族二胺意指不含芳香環也不含脂環之二胺。 任意地包含於構成單元B中之構成單元可為1種,也可為2種以上。 The structural unit B may include structural units other than the structural unit (B1) and the structural unit (B2). The diamine that provides such a structural unit is not particularly limited, and examples thereof include 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl- 4,4'-diamine, 4,4'-diaminodiphenyl ether, 4,4'-diamino-2,2'-bistrifluoromethyl diphenyl ether, 4,4'- Diaminodiphenylmethane, 4,4'-diaminobenzylaniline, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H -Indene-5-amine, α,α'-bis(4-aminophenyl)-1,4-dicumene, N,N'-bis(4-aminophenyl)terephthalic acid Amine, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2,2-bis(4 Aromatic diamines such as -(4-aminophenoxy)phenyl)hexafluoropropane (only, excluding compounds represented by any one of formulae (b1), (b21) to (b23)); 1,3- Alicyclic diamines such as bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine. In addition, in this specification, an aromatic diamine means a diamine containing one or more aromatic rings, an alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring, and an aliphatic diamine It means a diamine containing neither aromatic ring nor alicyclic ring. The structural unit arbitrarily included in the structural unit B may be one type or two or more types.
<聚醯亞胺樹脂之特性> 聚醯亞胺樹脂的重量平均分子量考慮得到的聚醯亞胺薄膜之機械性強度的觀點,宜為5,000~300,000。另外,聚醯亞胺樹脂的重量平均分子量例如可利用凝膠過濾層析測定所為之標準聚甲基丙烯酸甲酯(PMMA)換算值來求得。 <Characteristics of polyimide resin> The weight average molecular weight of the polyimide resin is preferably 5,000 to 300,000 from the viewpoint of the mechanical strength of the obtained polyimide film. In addition, the weight average molecular weight of a polyimide resin can be calculated|required by the standard polymethyl methacrylate (PMMA) conversion value measured by gel filtration chromatography, for example.
聚醯亞胺樹脂也可含有聚醯亞胺鏈(構成單元A及構成單元B經醯亞胺鍵結而成的結構)以外之結構。聚醯亞胺樹脂中所能含有之聚醯亞胺鏈以外之結構可列舉例如含有醯胺鍵結之結構等。 聚醯亞胺樹脂宜含有聚醯亞胺鏈(構成單元A及構成單元B經醯亞胺鍵結而成的結構)作為主要結構。因此,聚醯亞胺樹脂中聚醯亞胺鏈所佔的比率宜為50質量%以上,為70質量%以上更佳,為90質量%以上再更佳,為99質量%以上特佳,又,為100質量%以下。聚醯亞胺樹脂也可僅由聚醯亞胺鏈構成。 The polyimide resin may contain a structure other than the polyimide chain (the structure in which the structural unit A and the structural unit B are bonded by an imide). As a structure other than a polyimide chain which can be contained in a polyimide resin, the structure etc. which contain an amide bond are mentioned, for example. The polyimide resin preferably contains a polyimide chain (a structure in which the constituent unit A and the constituent unit B are bonded by imide) as the main structure. Therefore, the ratio of the polyimide chain in the polyimide resin is preferably 50 mass % or more, more preferably 70 mass % or more, still more preferably 90 mass % or more, particularly preferably 99 mass % or more, and , is 100 mass % or less. The polyimide resin may also consist only of polyimide chains.
含有上述聚醯亞胺樹脂之聚醯亞胺樹脂組成物可形成維持透明性及光學各向同性,同時耐熱性優良的聚醯亞胺薄膜,該聚醯亞胺薄膜具有的理想物性值如下所述。The polyimide resin composition containing the above-mentioned polyimide resin can form a polyimide film having excellent heat resistance while maintaining transparency and optical isotropy. The ideal physical properties of the polyimide film are as follows: described.
全光線透射率在將聚醯亞胺樹脂製成厚度10μm之薄膜時,宜為80%以上,為85%以上更佳,為88%以上再更佳,為88.5%以上又更佳,為89%以上再更佳。 黃色指數(YI)在將聚醯亞胺樹脂製成厚度10μm之薄膜時,宜為5.0以下,為3.0以下更佳,為2.5以下再更佳,為2.0以下又更佳。 厚度相位差(Rth)的絕對值在將聚醯亞胺樹脂製成厚度10μm之薄膜時,宜為200nm以下,為180nm以下更佳,為160nm以下再更佳。 When the polyimide resin is made into a film with a thickness of 10 μm, the total light transmittance should be more than 80%, more preferably more than 85%, more preferably more than 88%, more preferably more than 88.5%, and 89% % or more is better. When the polyimide resin is made into a film with a thickness of 10 μm, the yellowness index (YI) is preferably 5.0 or less, more preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. The absolute value of the thickness retardation (Rth) is preferably 200 nm or less, more preferably 180 nm or less, and even more preferably 160 nm or less, when the polyimide resin is made into a thin film with a thickness of 10 μm.
又,使用上述聚醯亞胺樹脂可形成的薄膜之耐熱性亦良好,且具有如下之理想物性值。 玻璃轉移溫度(Tg)宜為380℃以上,為390℃以上更佳,為400℃以上再更佳。 5%重量減少溫度(Td5%)宜為480℃以上,為490℃以上更佳,為495℃以上再更佳。 疊層無機膜時之耐熱性,在於聚醯亞胺薄膜上利用濺鍍形成厚度300nm之SiO 2膜,再於其上形成厚度1230nm之ITO(氧化銦錫)膜並製成疊層膜時,宜為以「400℃、1小時之退火處理」而不會在疊層膜發生裂紋、黃變等瑕疵,為以「420℃、1小時之退火處理」而不會在疊層膜發生裂紋、黃變等瑕疵更佳。 另外,本發明中的上述物性值具體可利用實施例所記載之方法進行測定。 Moreover, the heat resistance of the film which can be formed using the said polyimide resin is also favorable, and has the following desirable physical property values. The glass transition temperature (Tg) is preferably 380°C or higher, more preferably 390°C or higher, and even more preferably 400°C or higher. The 5% weight reduction temperature (Td5%) is preferably 480°C or higher, more preferably 490°C or higher, and even more preferably 495°C or higher. The heat resistance when laminating an inorganic film is to form a SiO 2 film with a thickness of 300 nm on the polyimide film by sputtering, and then form an ITO (indium tin oxide) film with a thickness of 1230 nm on it to make a laminated film. In order to prevent cracks, yellowing and other defects in the laminated film by "annealing treatment at 400°C for 1 hour", and in order to prevent cracks and yellowing in the laminated film by "annealing treatment at 420°C for 1 hour" Change and other defects are better. In addition, the said physical-property value in this invention can be measured by the method described in an Example specifically.
<聚醯亞胺樹脂之製造方法> 本發明之聚醯亞胺樹脂可藉由使包含提供上述構成單元(A1)之化合物之四羧酸成分與包含提供上述構成單元(B1)之化合物之二胺成分進行反應來製造。 <Method for producing polyimide resin> The polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component containing a compound providing the above-mentioned structural unit (A1) with a diamine component containing a compound providing the above-mentioned structural unit (B1).
提供構成單元(A1)之化合物可列舉式(a11)~式(a14)中任一者表示之化合物,但不限於此,在提供相同構成單元之範圍內,也可為其衍生物。該衍生物可列舉對應於式(a11)~式(a14)中任一者表示之四羧酸二酐之四羧酸及該四羧酸之烷基酯。其中,宜為式(a11)表示之四羧酸二酐。The compound that provides the structural unit (A1) can be a compound represented by any one of the formulae (a11) to (a14), but it is not limited thereto, and a derivative thereof may be also provided within the scope of providing the same structural unit. Examples of the derivatives include tetracarboxylic acids corresponding to tetracarboxylic dianhydrides represented by any one of formula (a11) to formula (a14), and alkyl esters of the tetracarboxylic acids. Among them, tetracarboxylic dianhydride represented by formula (a11) is suitable.
四羧酸成分除了包含提供構成單元(A1)之化合物之外,也可更包含提供構成單元(A2)之化合物。 提供構成單元(A2)之化合物可列舉式(a21)表示之化合物、式(a22)表示之化合物等,但不限於此,在提供相同構成單元之範圍內,也可為其衍生物。 A tetracarboxylic-acid component may contain the compound which provides a structural unit (A2) in addition to the compound which provides a structural unit (A1). The compound that provides the structural unit (A2) includes the compound represented by the formula (a21), the compound represented by the formula (a22), and the like, but is not limited thereto, and a derivative thereof may be used within the scope of providing the same structural unit.
四羧酸成分宜包含40莫耳%以上之提供構成單元(A1)之化合物,包含50莫耳%以上更佳,包含60莫耳%以上再更佳,包含80莫耳%以上又更佳,包含85莫耳%以上再更佳,包含90莫耳%以上又更佳,包含95莫耳%以上再更佳,包含99莫耳%以上又更佳。該比率之上限值並無特別限制,但為100莫耳%以下。The tetracarboxylic acid component preferably contains more than 40 mol % of the compound providing the constituent unit (A1), more preferably more than 50 mol %, more preferably more than 60 mol %, more preferably more than 80 mol %, More preferably, it contains 85 mol% or more, more preferably contains 90 mol% or more, more preferably contains 95 mol% or more, and more preferably contains 99 mol% or more. The upper limit of the ratio is not particularly limited, but is 100 mol % or less.
四羧酸成分也可包含提供構成單元(A1)之化合物及提供構成單元(A2)之化合物以外之任意的化合物。 如此之任意的化合物可列舉:上述芳香族四羧酸二酐、脂環族四羧酸二酐、及脂肪族四羧酸二酐、以及它們的衍生物(四羧酸、四羧酸之烷基酯等)。 任意地包含於四羧酸成分中之化合物可為1種,也可為2種以上。 A tetracarboxylic-acid component may contain arbitrary compounds other than the compound which provides a structural unit (A1) and the compound which provides a structural unit (A2). Such arbitrary compounds include the above-mentioned aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and derivatives thereof (tetracarboxylic acids, alkanes of tetracarboxylic acids) base ester, etc.). The compound arbitrarily contained in a tetracarboxylic-acid component may be 1 type, and may be 2 or more types.
提供構成單元(B1)之化合物可列舉式(b1)表示之化合物,但不限於此,在提供相同構成單元之範圍內,也可為其衍生物。該衍生物可列舉對應於式(b1)表示之化合物之二異氰酸酯。提供構成單元(B1)之化合物宜為式(b1)表示之化合物(亦即二胺)。 二胺成分除了包含提供構成單元(B1)之化合物之外,也可包含提供構成單元(B2)之化合物。提供構成單元(B2)之化合物可列舉式(b21)表示之化合物、式(b22)表示之化合物、式(b23)表示之化合物等,但不限於此,在提供相同構成單元之範圍內,也可為其衍生物。該衍生物可列舉對應於式(b21)表示之化合物、式(b22)表示之化合物及式(b23)表示之化合物之二異氰酸酯。提供構成單元(B2)之化合物宜為式(b21)表示之化合物、式(b22)表示之化合物、式(b23)表示之化合物(亦即二胺)。 The compound that provides the structural unit (B1) includes the compound represented by the formula (b1), but it is not limited thereto, and a derivative thereof may be also provided within the scope of providing the same structural unit. Examples of the derivatives include diisocyanates corresponding to the compounds represented by the formula (b1). The compound providing the structural unit (B1) is preferably a compound represented by the formula (b1) (ie, a diamine). A diamine component may contain the compound which provides a structural unit (B2) in addition to the compound which provides a structural unit (B1). The compound that provides the structural unit (B2) includes the compound represented by the formula (b21), the compound represented by the formula (b22), the compound represented by the formula (b23), etc., but is not limited thereto, and within the scope of providing the same structural unit, it is also possible to can be its derivatives. Examples of the derivatives include diisocyanates corresponding to the compound represented by the formula (b21), the compound represented by the formula (b22), and the compound represented by the formula (b23). The compound providing the structural unit (B2) is preferably a compound represented by the formula (b21), a compound represented by the formula (b22), or a compound represented by the formula (b23) (ie, a diamine).
二胺成分宜包含20莫耳%以上之提供構成單元(B1)之化合物,包含40莫耳%以上更佳,包含50莫耳%以上再更佳,包含60莫耳%以上又更佳,包含80莫耳%以上再更佳,包含99莫耳%以上特佳。該比率之上限值並無特別限制,但為100莫耳%以下。 二胺成分包含提供構成單元(B2)之化合物時,宜包含10莫耳%以上之提供構成單元(B2)之化合物,包含20莫耳%以上更佳,包含30莫耳%以上再更佳,而且宜包含70莫耳%以下,包含60莫耳%以下更佳,包含50莫耳%以下再更佳。 二胺成分包含提供構成單元(B2)之化合物時,提供構成單元(B1)之化合物及提供構成單元(B2)之化合物合計宜包含50莫耳%以上,包含70莫耳%以上更佳,包含90莫耳%以上再更佳,包含95莫耳%以上又更佳,包含99莫耳%以上再更佳。上限值並無特別限制,二胺成分中,提供構成單元(B1)之化合物及提供構成單元(B2)之化合物合計例如包含100莫耳%以下。二胺成分也可僅由提供構成單元(B1)之化合物及提供構成單元(B2)之化合物構成。 二胺成分包含提供構成單元(B2)之化合物時,二胺成分中之提供構成單元(B1)之化合物與提供構成單元(B2)之化合物的莫耳比[(B1)/(B2)]考慮使透明性、光學各向同性、韌性及耐熱性改善之觀點,宜為30/70~90/10,為40/60~80/20更佳,為50/50~70/30再更佳。 The diamine component preferably contains more than 20 mol % of the compound providing the constituent unit (B1), more preferably more than 40 mol %, more preferably more than 50 mol %, more preferably more than 60 mol %, including More than 80 mol% is even better, including more than 99 mol%. The upper limit of the ratio is not particularly limited, but is 100 mol % or less. When the diamine component contains the compound providing the structural unit (B2), it is preferable to contain the compound providing the structural unit (B2) in 10 mol % or more, more preferably 20 mol % or more, more preferably 30 mol % or more, Moreover, it is preferable to contain 70 mol % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less. When the diamine component contains the compound providing the structural unit (B2), the compound providing the structural unit (B1) and the compound providing the structural unit (B2) are preferably contained in a total of 50 mol% or more, more preferably 70 mol% or more, including More preferably 90 mol % or more, more preferably 95 mol % or more, more preferably 99 mol % or more. The upper limit is not particularly limited, but the total of the compound providing the structural unit (B1) and the compound providing the structural unit (B2) in the diamine component is, for example, 100 mol % or less. The diamine component may be composed of only the compound providing the structural unit (B1) and the compound providing the structural unit (B2). When the diamine component contains the compound providing the structural unit (B2), the molar ratio [(B1)/(B2)] of the compound providing the structural unit (B1) and the compound providing the structural unit (B2) in the diamine component is considered From the viewpoint of improving transparency, optical isotropy, toughness and heat resistance, it is preferably 30/70~90/10, more preferably 40/60~80/20, and even more preferably 50/50~70/30.
二胺成分也可更包含提供構成單元(B1)之化合物及提供構成單元(B2)之化合物以外之任意的化合物。 如此之任意的化合物可列舉:上述芳香族二胺、脂環族二胺、及脂肪族二胺、以及它們的衍生物(二異氰酸酯等)。 任意地包含於二胺成分中之化合物可為1種,也可為2種以上。 The diamine component may further contain arbitrary compounds other than the compound providing the structural unit (B1) and the compound providing the structural unit (B2). As such an arbitrary compound, the said aromatic diamine, alicyclic diamine, and aliphatic diamine, and these derivatives (diisocyanate etc.) are mentioned. The compound arbitrarily contained in the diamine component may be one type or two or more types.
本發明之聚醯亞胺樹脂之製造中,聚醯亞胺樹脂之製造所使用的四羧酸成分與二胺成分之進料量比,相對於四羧酸成分1莫耳,二胺成分宜為0.9~1.1莫耳。In the production of the polyimide resin of the present invention, the feeding amount ratio of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin is preferably 1 mole of the diamine component relative to 1 mole of the tetracarboxylic acid component. It is 0.9~1.1 moles.
又,本發明之聚醯亞胺樹脂之製造中,就聚醯亞胺樹脂之製造而言,除了使用前述四羧酸成分及二胺成分之外,也可使用末端封端劑。末端封端劑宜為單胺類或二羧酸類。導入的末端封端劑之進料量相對於四羧酸成分1莫耳,宜為0.0001~0.1莫耳,為0.001~0.06莫耳更佳。單胺類末端封端劑可列舉例如: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,宜為苄胺、苯胺。二羧酸類末端封端劑宜為二羧酸類,且也可將其一部分予以閉環。可列舉例如:苯二甲酸、苯二甲酸酐、4-氯苯二甲酸、四氟苯二甲酸、2,3-二苯甲酮二甲酸、3,4-二苯甲酮二甲酸、環己烷-1,2-二甲酸、環戊烷-1,2-二甲酸、4-環己烯-1,2-二甲酸等,宜為苯二甲酸、苯二甲酸酐。Moreover, in the manufacture of the polyimide resin of the present invention, in addition to the aforementioned tetracarboxylic acid component and diamine component, a terminal blocking agent may be used for the manufacture of the polyimide resin. The terminal blocking agent is preferably a monoamine or a dicarboxylic acid. The feed amount of the introduced end capping agent is preferably 0.0001-0.1 mol, more preferably 0.001-0.06 mol, relative to 1 mol of the tetracarboxylic acid component. Examples of monoamine-based terminal blocking agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3- Methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc., preferably benzylamine, aniline. The dicarboxylic acid-based terminal blocking agent is preferably a dicarboxylic acid, and a part thereof may be ring-closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclohexane Alkane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc., preferably phthalic acid and phthalic anhydride.
使前述四羧酸成分與二胺成分進行反應之方法並無特別限制,可使用公知的方法。 具體的反應方法可列舉:(1)將四羧酸成分、二胺成分、及反應溶劑進料於反應器,於0~10℃攪拌0.5~30小時,其後昇溫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並使其溶解後,進料四羧酸成分,因應需要於0~10℃攪拌0.5~30小時,其後昇溫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,立刻昇溫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. Specific reaction methods include: (1) The tetracarboxylic acid component, the diamine component, and the reaction solvent are fed into the reactor, stirred at 0 to 10° C. for 0.5 to 30 hours, and then heated to carry out the imidization reaction. Method, (2) After the diamine component and the reaction solvent are fed into the reactor and dissolved, the tetracarboxylic acid component is fed, and stirred at 0 to 10° C. for 0.5 to 30 hours as required, and then the temperature is raised to implement imide (3) The tetracarboxylic acid component, the diamine component, and the reaction solvent are fed into the reactor, and the temperature is immediately raised to carry out the imidization reaction.
聚醯亞胺樹脂之製造所使用的反應溶劑,若為不妨礙醯亞胺化反應而可溶解生成的聚醯亞胺者即可。例如可列舉: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 the polyimide resin may be one that can dissolve the produced polyimide without interfering with the imidization reaction. For example, an aprotic solvent, a phenol type solvent, an ether type solvent, a carbonate type solvent, etc. are mentioned.
非質子性溶劑之具體例可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮(NMP)、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(GBL)、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-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), N-methylcaprolactone amide-based solvents such as amide, 1,3-dimethylimidazolidinone, and tetramethylurea; lactone-based solvents such as γ-butyrolactone (GBL) and γ-valerolactone; hexamethylphosphamide , hexamethylphosphine triamide and other phosphorus-containing amide solvents; dimethyl sulfite, dimethyl sulfoxide, cyclobutane and other sulfur-containing solvents; acetone, cyclohexanone, methyl cyclohexanone and other ketones solvents; amine-based solvents such as picoline and pyridine; ester-based solvents such as acetic acid (2-methoxy-1-methylethyl ester), and the like.
酚系溶劑之具體例可列舉:苯酚、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。 醚系溶劑之具體例可列舉: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,碳酸酯系溶劑之具體例可列舉:碳酸二乙酯、碳酸甲乙酯、碳酸伸乙酯、碳酸伸丙酯等。 上述反應溶劑之中,宜為非質子系溶劑,為醯胺系溶劑及內酯系溶劑更佳,為內酯系溶劑再更佳。又,上述反應溶劑可單獨使用或也可混合使用2種以上。 Specific examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 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, 1,2-bis(2-methoxyethoxy)ethane, Bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, etc. In addition, specific examples of the carbonate-based solvent include diethyl carbonate, ethyl methyl carbonate, ethylidene carbonate, propylene carbonate, and the like. Among the above reaction solvents, an aprotic solvent is preferred, an amide-based solvent and a lactone-based solvent are more preferred, and a lactone-based solvent is even more preferred. Moreover, the said reaction solvent may be used individually or in mixture of 2 or more types.
醯亞胺化反應宜使用迪安-斯塔克(Dean-Stark)裝置等,邊將製造時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為上昇。For 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。醯亞胺化觸媒可列舉鹼觸媒或酸觸媒。 鹼觸媒可列舉:吡啶、喹啉、異喹啉、α-甲吡啶、β-甲吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶、三甲胺、三乙胺(TEA)、三丙胺、三丁胺、三伸乙二胺、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、或氫氧化鈉、碳酸鉀、碳酸鈉、碳酸氫鉀、碳酸氫鈉等無機鹼觸媒。 又,酸觸媒可列舉: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也可組合使用2種以上。 上述之中,考慮操作性之觀點,宜使用鹼觸媒,使用有機鹼觸媒更佳,使用三乙胺、三伸乙二胺再更佳。 A known imidization catalyst can be used for the above imidization reaction. The imidization catalyst includes an alkali catalyst or an acid catalyst. Examples of the base catalyst include: pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine ( TEA), tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline and other organic base catalysts; potassium hydroxide, or sodium hydroxide, Inorganic base catalysts such as potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate. Moreover, as an acid catalyst, crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, toluic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid can be mentioned. , naphthalene sulfonic 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 workability, it is preferable to use an alkali catalyst, more preferably an organic alkali catalyst, and even more preferably triethylamine and triethylenediamine.
醯亞胺化反應的溫度,考慮反應率及抑制凝膠化等之觀點,宜為120~250℃,為160~200℃更佳。又,反應時間自生成水餾出開始後,宜為0.5~10小時。The temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°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.
[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樹脂溶解於有機溶劑而成者。亦即,本發明之聚醯亞胺清漆含有本發明之聚醯亞胺樹脂及有機溶劑,且該聚醯亞胺樹脂溶解於該有機溶劑中。 有機溶劑若為會溶解聚醯亞胺樹脂者即可,並無特別限制,宜將上述作為聚醯亞胺樹脂之製造所使用的反應溶劑之化合物予以單獨使用或混合使用2種以上。 本發明之聚醯亞胺清漆可為係利用聚合法而得的聚醯亞胺樹脂溶解於反應溶劑而成的聚醯亞胺溶液本身、或也可為對該聚醯亞胺溶液進一步追加溶劑並進行稀釋而成者。 [Polyimide Varnish] The polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyimide resin, and the above-mentioned compounds as the reaction solvent used in the production of the polyimide resin are preferably used alone or in combination of two or more. The polyimide varnish of the present invention may be a polyimide solution itself obtained by dissolving a polyimide resin obtained by a polymerization method in a reaction solvent, or a further solvent may be added to the polyimide solution and diluted.
本發明之聚醯亞胺樹脂具有溶劑溶解性,故可製成在室溫安定的高濃度之清漆。本發明之聚醯亞胺清漆宜含有本發明之聚醯亞胺樹脂5~40質量%,含有5~20質量%更佳。聚醯亞胺清漆的黏度宜為1~200Pa・s,為1~100Pa・s更佳。聚醯亞胺清漆的黏度係使用E型黏度計於25℃測定而得的值。 又,本發明之聚醯亞胺清漆在不損及聚醯亞胺薄膜的要求特性之範圍內,也可含有無機填料、黏接促進劑、剝離劑、阻燃劑、紫外線安定劑、界面活性劑、整平劑、消泡劑、螢光增白劑、交聯劑、聚合起始劑、感光劑等各種添加劑。 本發明之聚醯亞胺清漆之製造方法並無特別限制,可使用公知的方法。 The polyimide resin of the present invention has solvent solubility, so it can be made into a high-concentration varnish that is stable at room temperature. The polyimide varnish of the present invention preferably contains the polyimide resin of the present invention in an amount of 5 to 40% by mass, more preferably 5 to 20% by mass. The viscosity of the polyimide varnish is preferably 1~200Pa・s, more preferably 1~100Pa・s. The viscosity of the polyimide varnish is a value measured at 25°C using an E-type viscometer. In addition, the polyimide varnish of the present invention may also contain inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, interfacial active agents within the range that does not impair the required properties of the polyimide film. agents, leveling agents, defoaming agents, optical brighteners, cross-linking agents, polymerization initiators, sensitizers and other additives. The manufacturing method in particular of the polyimide varnish of this invention is not restrict|limited, A well-known method can be used.
[聚醯亞胺薄膜] 本發明之聚醯亞胺薄膜含有本發明之聚醯亞胺樹脂。因此,本發明之聚醯亞胺薄膜之耐熱性、透明性、韌性、光學各向同性、剝離性及耐藥品性優良。本發明之聚醯亞胺薄膜具有的理想物性值如上述<聚醯亞胺樹脂之特性>所述。 本發明之聚醯亞胺薄膜之製造方法並無特別限制,可使用公知的方法。可列舉例如將本發明之聚醯亞胺清漆成薄膜狀地塗佈於玻璃板、金屬板、塑膠等平滑的支持體上、或成形成薄膜狀後,將該清漆中所含的反應溶劑、稀釋溶劑等有機溶劑利用加熱去除之方法等。本發明之聚醯亞胺薄膜之製造方法宜為包含將聚醯亞胺清漆塗佈成或成形成薄膜狀後,將有機溶劑去除之步驟的方法。 [Polyimide film] The polyimide film of the present invention contains the polyimide resin of the present invention. Therefore, the polyimide film of the present invention is excellent in heat resistance, transparency, toughness, optical isotropy, peelability and chemical resistance. The desirable physical properties of the polyimide film of the present invention are as described in the above-mentioned <Characteristics of Polyimide Resin>. The manufacturing method of the polyimide film of this invention is not specifically limited, A well-known method can be used. For example, the polyimide varnish of the present invention is applied to a smooth support such as a glass plate, metal plate, plastic, etc. in the form of a thin film, or after the polyimide varnish is formed into a thin film, the reaction solvent contained in the varnish, A method of removing organic solvents such as dilution solvents by heating, etc. The manufacturing method of the polyimide film of the present invention is preferably a method including the step of removing the organic solvent after coating or forming the polyimide varnish into a film.
塗佈方法可列舉:旋塗、縫塗、刀塗等公知的塗佈方法,宜為旋塗、縫塗。其中,縫塗考慮控制分子間配向並改善耐藥品性、作業性之觀點較為理想。 將清漆中所含的有機溶劑利用加熱去除之方法宜為於150℃以下之溫度使有機溶劑蒸發成為無黏性後,以使用的有機溶劑之沸點以上的溫度(宜為200~500℃,但並非特別限制)進行乾燥。又,宜在空氣環境下或氮氣環境下進行乾燥。乾燥環境之壓力為減壓、常壓、加壓中任一者皆可。 將已製膜於支持體上之聚醯亞胺薄膜從支持體剝離之方法並無特別限制,可使用機械剝離法、雷射剝離(lift-off)法等。 Examples of the coating method include known coating methods such as spin coating, slit coating, and knife coating, and spin coating and slit coating are preferred. Among them, slit coating is preferable from the viewpoint of controlling intermolecular alignment and improving chemical resistance and workability. The method of removing the organic solvent contained in the varnish by heating is preferably at a temperature below 150°C to evaporate the organic solvent to become non-viscous, and then at a temperature above the boiling point of the organic solvent used (preferably 200~500°C, but not particularly limited) to be dried. In addition, drying is preferably carried out in an air atmosphere or a nitrogen atmosphere. The pressure of the dry environment may be any of reduced pressure, normal pressure, and increased pressure. The method of peeling the polyimide film formed on the support from the support is not particularly limited, and a mechanical peeling method, a laser lift-off method, or the like can be used.
又,本發明之聚醯亞胺薄膜也可使用將聚醯胺酸溶解於有機溶劑而成聚醯胺酸清漆來製造。 前述聚醯胺酸清漆所含的聚醯胺酸為本發明之聚醯亞胺樹脂的前驅體,係包含上述提供構成單元(A1)之化合物之四羧酸成分及包含上述提供構成單元(B1)之化合物之二胺成分的加成聚合反應之產物。藉由將該聚醯胺酸予以醯亞胺化(脫水閉環),可獲得最終產物即本發明之聚醯亞胺樹脂。 前述聚醯胺酸清漆所含的有機溶劑可使用本發明之聚醯亞胺清漆所含的有機溶劑。 本發明之聚醯亞胺薄膜之製造中,聚醯胺酸清漆可為使四羧酸成分與二胺成分於反應溶劑中進行加成聚合反應而得的聚醯胺酸溶液本身、或也可為對該聚醯胺酸溶液進一步追加溶劑並進行稀釋而成者。 In addition, the polyimide film of the present invention can also be produced using a polyamic acid varnish obtained by dissolving polyamic acid in an organic solvent. The polyamic acid contained in the above-mentioned polyamic acid varnish is a precursor of the polyimide resin of the present invention, and comprises the above-mentioned tetracarboxylic acid component of the compound providing the structural unit (A1) and the above-mentioned providing structural unit (B1). ) is the product of the addition polymerization reaction of the diamine component of the compound. The polyimide resin of the present invention can be obtained as the final product by imidizing the polyimide (dehydration ring closure). As the organic solvent contained in the aforementioned polyimide varnish, the organic solvent contained in the polyimide varnish of the present invention can be used. In the production of the polyimide film of the present invention, the polyimide varnish may be a polyimide solution itself obtained by addition-polymerizing a tetracarboxylic acid component and a diamine component in a reaction solvent, or it may be It was obtained by further adding a solvent to the polyamic acid solution and diluting it.
使用聚醯胺酸清漆來製造聚醯亞胺薄膜之方法並無特別限制,可使用公知的方法。例如可將聚醯胺酸清漆薄膜狀地塗佈於玻璃板、金屬板、塑膠等平滑的支持體上、或成形成薄膜狀,將該清漆中所含的反應溶劑、稀釋溶劑等有機溶劑利用加熱去除來獲得聚醯胺酸薄膜,再將該聚醯胺酸薄膜中之聚醯胺酸利用加熱予以醯亞胺化,藉此可製造聚醯亞胺薄膜。 使聚醯胺酸清漆乾燥來獲得聚醯胺酸薄膜時之加熱溫度宜為50~120℃。將聚醯胺酸利用加熱予以醯亞胺化時之加熱溫度宜為200~450℃。 另外,醯亞胺化之方法不限於熱醯亞胺化,也可使用化學醯亞胺化。 There is no restriction|limiting in particular in the method of manufacturing a polyimide film using a polyimide varnish, and a well-known method can be used. For example, a polyamide varnish can be applied to a smooth support such as a glass plate, metal plate, plastic, etc. in a thin film, or formed into a thin film, and the organic solvent such as a reaction solvent and a dilution solvent contained in the varnish can be used. The polyamic acid film is obtained by removing by heating, and then the polyamic acid in the polyamic acid film is imidized by heating, whereby a polyimide film can be produced. The heating temperature for drying the polyamide varnish to obtain the polyamide film is preferably 50 to 120°C. The heating temperature when the polyamic acid is imidized by heating is preferably 200 to 450°C. In addition, the method of imidization is not limited to thermal imidization, and chemical imidization can also be used.
本發明之聚醯亞胺薄膜的厚度可因應用途等而適當地選擇,宜為1~250μm,為5~100μm更佳,為8~80μm再更佳,為10~80μm之範圍又更佳。厚度藉由為1~250μm,實用上可作為自支撐膜使用。 聚醯亞胺薄膜的厚度可藉由調整聚醯亞胺清漆之固體成分濃度、黏度而輕易地控制。 The thickness of the polyimide film of the present invention can be appropriately selected according to the application, etc., and is preferably 1 to 250 μm, more preferably 5 to 100 μm, more preferably 8 to 80 μm, and even more preferably in the range of 10 to 80 μm. Since the thickness is 1 to 250 μm, it can be practically used as a self-supporting film. The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide varnish.
本發明之聚醯亞胺薄膜中,依據JIS K7136:2000進行測定之全光線透射率,考慮使透明性更為改善之觀點,宜為80%以上,為85%以上更佳,為88%以上再更佳,為88.5%以上又更佳,為89%以上再更佳。In the polyimide film of the present invention, the total light transmittance measured in accordance with JIS K7136:2000 is preferably 80% or more, more preferably 88% or more, from the viewpoint of improving transparency. Even better, 88.5% or more is still better, and 89% or more is still better.
本發明之聚醯亞胺薄膜可作為彩色濾光片、撓性顯示器、半導體零件、光學構件、太陽能電池、圖像顯示裝置等各種構件用之薄膜理想地使用,尤其可作為構成這些裝置的透明性基板理想地使用。本發明之聚醯亞胺薄膜特別可作為構成液晶顯示器、或OLED顯示器、觸控面板等圖像顯示裝置的透明性基板理想地使用。The polyimide film of the present invention can be ideally used as a film for various components such as color filters, flexible displays, semiconductor components, optical components, solar cells, and image display devices, and is particularly useful as a transparent film constituting these devices. Sexual substrates are ideally used. In particular, the polyimide film of the present invention can be preferably used as a transparent substrate constituting image display devices such as liquid crystal displays, OLED displays, and touch panels.
[圖像顯示裝置] 本發明之圖像顯示裝置具備本發明之聚醯亞胺薄膜作為透明性基板。 本發明之圖像顯示裝置例如具備由本發明之聚醯亞胺薄膜構成的透明性基板、及設置於上述透明性基板上之顯示部。 顯示部並無特別限制,可列舉例如:使用了TFT元件、有機EL元件、彩色濾光片、LED、電晶體、電子釋放元件、電子印墨、電氣泳動元件、GLV(光柵光閥,grating light valve)、MEMS(微機電系統,micro electro mechanical system)之顯示元件;使用了DMD(數位微鏡器件,digital micromirror device)、DMS(數位微鏡快門,digital micro shutter)、IMOD(干涉調變器,interferometric modulator)元件、電潤濕(electrowetting)元件、壓電陶瓷顯示器、奈米碳管之顯示元件等。 本發明之圖像顯示裝置可列舉例如:液晶顯示器、OLED顯示器、觸控面板等。 本發明之圖像顯示裝置除了使用本發明之聚醯亞胺薄膜作為透明性基板之外,還可根據公知的資訊來製造。 本發明之圖像顯示裝置由於使用疊層無機膜時之耐熱性優良的本發明之聚醯亞胺薄膜作為透明性基板,故不易發生無機膜之裂紋、透明性基板之著色等,可靠性優良。 [實施例] [image display device] The image display device of the present invention includes the polyimide film of the present invention as a transparent substrate. The image display device of the present invention includes, for example, a transparent substrate made of the polyimide film of the present invention, and a display portion provided on the transparent substrate. The display portion is not particularly limited, and examples include those using TFT elements, organic EL elements, color filters, LEDs, transistors, electron emission elements, electronic inks, electrophoretic elements, and GLV (grating light valves). valve), MEMS (micro electro mechanical system, micro electro mechanical system) display components; using DMD (digital micro mirror device, digital micromirror device), DMS (digital micro mirror shutter, digital micro shutter), IMOD (interference modulator) , Interferometric modulator) components, electrowetting (electrowetting) components, piezoelectric ceramic displays, carbon nanotube display components, etc. The image display device of the present invention includes, for example, a liquid crystal display, an OLED display, a touch panel, and the like. In addition to using the polyimide film of the present invention as a transparent substrate, the image display device of the present invention can be manufactured according to known information. In the image display device of the present invention, since the polyimide film of the present invention, which is excellent in heat resistance when an inorganic film is laminated, is used as a transparent substrate, cracks in the inorganic film and coloring of the transparent substrate are unlikely to occur, and the reliability is excellent. . [Example]
以下利用實施例具體地說明本發明。惟,本發明不受這些實施例任何限制。Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited in any way by these examples.
<薄膜物性及評價> 實施例及比較例得到的薄膜之各種物性係利用如下所示之方法進行測定。 <Film properties and evaluation> Various physical properties of the thin films obtained in Examples and Comparative Examples were measured by the methods shown below.
(1)薄膜厚度 薄膜厚度使用Mitutoyo Corporation股份有限公司製之測微計進行測定。 (1) Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
(2)玻璃轉移溫度(Tg) 使用Hitachi High-Tech Science股份有限公司製之熱機械分析裝置「TMA/SS6100」,於拉伸模式以樣本尺寸3mm×20mm、荷重0.1N、昇溫速度10℃/min之條件,昇溫至足以去除殘留應力的溫度將殘留應力去除,之後冷卻至室溫。其後,以和前述用以去除殘留應力之處理相同之條件實施試驗片延伸度之測定,將延伸度之反曲點外插求出玻璃轉移溫度。 (2) Glass transition temperature (Tg) Using the thermomechanical analyzer "TMA/SS6100" manufactured by Hitachi High-Tech Science Co., Ltd., in the tensile mode, the sample size is 3mm×20mm, the load is 0.1N, and the heating rate is 10℃/min, and the temperature is high enough to remove the residue. The temperature of the stress removes the residual stress and then cools to room temperature. Then, the measurement of the degree of elongation of the test piece was performed under the same conditions as the above-mentioned treatment for removing residual stress, and the glass transition temperature was obtained by extrapolating the inflection point of the degree of elongation.
(3)全光線透射率、及黃色指數(YI) 全光線透射率係依據JIS K7136:2000,YI係依據ASTM E313-05(D光源,65°),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「COH7700」分別進行測定。 (3) Total light transmittance and yellow index (YI) The total light transmittance was measured according to JIS K7136:2000, and the YI was measured according to ASTM E313-05 (D light source, 65°).
(4)5%重量減少溫度(Td5%) 使用Hitachi High-Tech Science股份有限公司製之差示熱熱重量同時測定裝置「NEXTA STA200RV」。將樣本以昇溫速度10℃/min從40昇溫至150℃,於150℃保持30分鐘將水分去除後,昇溫至510℃。和在150℃保持30分鐘後的重量進行比較,將重量減少5%時的溫度定義為5%重量減少溫度。重量減少溫度之數值愈大則耐熱性愈優良。 (4) 5% weight reduction temperature (Td5%) A differential thermogravimetric simultaneous measuring apparatus "NEXTA STA200RV" manufactured by Hitachi High-Tech Science Co., Ltd. was used. The sample was heated from 40 to 150°C at a heating rate of 10°C/min, held at 150°C for 30 minutes to remove moisture, and then heated to 510°C. The temperature at which the weight was reduced by 5% was defined as the 5% weight reduction temperature in comparison with the weight after holding at 150°C for 30 minutes. The larger the value of the weight reduction temperature, the better the heat resistance.
(5)厚度相位差(Rth)(光學各向同性之評價) 厚度相位差(Rth)係使用日本分光股份有限公司製之橢圓偏光計「M-220」進行測定。測量測定波長590nm時的厚度相位差之值。另外,Rth係令聚醯亞胺薄膜之面內的折射率之中最大者為nx、最小者為ny、厚度方向之折射率為nz、薄膜之厚度為d時,利用下式所表示者。 Rth={[(nx+ny)/2]-nz}×d (5) Thickness retardation (Rth) (evaluation of optical isotropy) The thickness retardation (Rth) was measured using an ellipsometer "M-220" manufactured by JASCO Corporation. The value of the thickness retardation at the measurement wavelength of 590 nm was measured. In addition, Rth is represented by the following formula when the largest in-plane refractive index of the polyimide film is nx, the smallest is ny, the refractive index in the thickness direction is nz, and the thickness of the film is d. Rth={[(nx+ny)/2]-nz}×d
(6)疊層膜之耐熱性評價 模擬圖像顯示裝置之製造步驟,製造疊層膜,並評價該疊層膜之耐熱性。疊層膜係如下般製得。 不將實施例及比較例得到的聚醯亞胺薄膜從玻璃板剝離,而在聚醯亞胺薄膜上利用濺鍍形成厚度300nm之SiO 2膜,在於其上形成厚度1230nm之ITO(氧化銦錫)膜,獲得疊層膜。 然後,對得到的疊層膜實施360℃、1小時之退火(加熱),或400℃、1小時之退火(加熱)。 以目視觀察退火前後之疊層膜是否有瑕疵(裂紋、黃變等),並利用下述基準評價疊層有無機膜之聚醯亞胺薄膜(疊層膜)的耐熱性。 〇:退火前後於疊層膜未發生裂紋、黃變等瑕疵 ×(裂紋或黃變):退火前後於疊層膜發生裂紋、黃變等瑕疵 無瑕疵則聚醯亞胺薄膜之疊層無機膜時之耐熱性優良。 (6) Evaluation of Heat Resistance of Laminated Film The production steps of an image display device were simulated, a laminated film was produced, and the heat resistance of the laminated film was evaluated. The laminated film was prepared as follows. The polyimide films obtained in the examples and comparative examples were not peeled off from the glass plate, but a SiO 2 film with a thickness of 300 nm was formed on the polyimide film by sputtering, and ITO (indium tin oxide) with a thickness of 1230 nm was formed thereon. ) film to obtain a laminated film. Then, annealing (heating) at 360° C. for 1 hour or annealing (heating) at 400° C. for 1 hour was performed on the obtained laminated film. The presence or absence of flaws (cracks, yellowing, etc.) in the laminated film before and after annealing was visually observed, and the heat resistance of the polyimide film (laminated film) laminated with the inorganic film was evaluated by the following criteria. 〇: There are no defects such as cracks and yellowing in the laminated film before and after annealing × (cracks or yellowing): There are defects such as cracks and yellowing in the laminated film before and after annealing. When the heat resistance is excellent.
<成分等之縮寫> 實施例及比較例所使用的四羧酸成分及二胺成分、以及其縮寫如下所述。 <Abbreviation of ingredients, etc.> The tetracarboxylic acid component, the diamine component, and the abbreviations thereof used in Examples and Comparative Examples are as follows.
(四羧酸成分) CpODA:降莰烷-2-螺-α-環戊酮-α’-螺-2’’-降莰烷-5,5’’,6,6’’-四甲酸二酐(ENEOS股份有限公司製;式(a11)表示之化合物) BNBDA:5,5’-雙-2-降莰烯-5,5’,6,6’-四甲酸-5,5’,6,6’-二酐(ENEOS股份有限公司製;式(a12)表示之化合物) BPDA:3,3’,4,4’-聯苯四甲酸二酐(三菱化學股份有限公司製,式(a211s)表示之化合物(s-BPDA)) BPAF:9,9-雙(3,4-二羧基苯基)茀二酸酐(JFE化學股份有限公司製;式(a22)表示之化合物) (tetracarboxylic acid component) CpODA: norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (ENEOS Co., Ltd. system; compound represented by formula (a11)) BNBDA: 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic acid-5,5',6,6'-dianhydride (manufactured by ENEOS Co., Ltd.; formula (a12 ) represents the compound) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, compound represented by formula (a211s) (s-BPDA)) BPAF: 9,9-bis(3,4-dicarboxyphenyl)perylene anhydride (manufactured by JFE Chemical Co., Ltd.; compound represented by formula (a22))
(二胺成分) HFDA:2,2-雙(4-胺基苯基)六氟丙烷(東京化成工業股份有限公司製;式(b1)表示之化合物) BAFL:9,9-雙(4-胺基苯基)茀(JFE化學股份有限公司製;式(b21)表示之化合物) TFMB:2,2’-雙(三氟甲基)聯苯胺(SEIKA股份有限公司製;式(b22)表示之化合物) 6FODA:2,2’-雙(三氟甲基)-4,4’-二胺基二苯基醚(ChinaTech (Tianjin) Chemical Co., Ltd.製) (diamine component) HFDA: 2,2-bis(4-aminophenyl)hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.; compound represented by formula (b1)) BAFL: 9,9-bis(4-aminophenyl) fluoride (manufactured by JFE Chemical Co., Ltd.; compound represented by formula (b21)) TFMB: 2,2'-bis(trifluoromethyl)benzidine (manufactured by SEIKA Co., Ltd.; compound represented by formula (b22)) 6FODA: 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (manufactured by ChinaTech (Tianjin) Chemical Co., Ltd.)
<聚醯亞胺樹脂、清漆及聚醯亞胺薄膜之製造> 實施例1 於具備不鏽鋼製半月型攪拌葉片、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500mL之5口圓底燒瓶中投入33.427g(0.100莫耳)之HFDA、及86.238g之γ-丁內酯(三菱化學股份有限公司製),並於系內溫度70℃、氮氣環境下,以轉速200rpm進行攪拌,獲得溶液。 於該溶液中一次性地添加38.438g(0.100莫耳)之CpODA、及21.560g之γ-丁內酯(三菱化學股份有限公司製)後,投入作為醯亞胺化觸媒之0.506g之三乙胺(關東化學股份有限公司製)、0.056g之三伸乙二胺(東京化成工業股份有限公司製),以加熱包(mantle heater)進行加熱,歷時約20分鐘將反應系內溫度上昇至190℃。收集餾出的成分,配合黏度上昇調整轉速同時將反應系內溫度保持在190℃回流5小時。 其後,以成為固體成分濃度15質量%的方式添加γ-丁內酯(三菱化學股份有限公司製),將反應系內溫度冷卻至100℃後,再攪拌約1小時使其均勻化,獲得聚醯亞胺清漆。 然後將得到的聚醯亞胺清漆利用旋塗塗佈於玻璃板上,以加熱板於80℃保持20分鐘,其後,於氮氣環境下,在熱風乾燥機中以400℃加熱30分鐘(昇溫速度5℃/分鐘),使溶劑蒸發,獲得薄膜。 <Manufacture of polyimide resins, varnishes and polyimide films> Example 1 Put 33.427 g (0.100 mol) in a 500 mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a Dean-Stark apparatus equipped with a cooling tube, a thermometer, and a glass end cap. HFDA and 86.238 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were stirred at 200 rpm at a temperature of 70° C. in the system under a nitrogen atmosphere to obtain a solution. To this solution, 38.438 g (0.100 mol) of CpODA and 21.560 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at one time, and then 0.506 g of the third imidization catalyst was added. Ethylamine (manufactured by Kanto Chemical Co., Ltd.) and 0.056 g of triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were heated with a mantle heater, and the temperature in the reaction system was raised to 190°C. The distilled components were collected, and the rotation speed was adjusted in accordance with the increase in viscosity while maintaining the temperature in the reaction system at 190° C. for 5 hours under reflux. Then, γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so as to have a solid content concentration of 15% by mass, and the temperature in the reaction system was cooled to 100° C., followed by stirring for further about 1 hour to homogenize, to obtain Polyimide varnish. Then, the obtained polyimide varnish was coated on a glass plate by spin coating, kept at 80° C. for 20 minutes with a hot plate, and then heated in a hot air dryer at 400° C. for 30 minutes under a nitrogen atmosphere (heating up speed 5°C/min), the solvent was evaporated, and a thin film was obtained.
實施例2 將HFDA的量從33.427g(0.100莫耳)變更為20.056g(0.060莫耳),並使用13.938g(0.040莫耳)之BAFL,除此之外,利用和實施例1同樣的方法,獲得固體成分濃度15質量%之聚醯亞胺清漆。 使用得到的聚醯亞胺清漆,利用和實施例1同樣的方法獲得薄膜。 Example 2 A solid was obtained in the same manner as in Example 1, except that the amount of HFDA was changed from 33.427 g (0.100 mol) to 20.056 g (0.060 mol) and 13.938 g (0.040 mol) of BAFL was used. Polyimide varnish with a component concentration of 15% by mass. Using the obtained polyimide varnish, a film was obtained in the same manner as in Example 1.
實施例3 將CpODA的量從38.438g(0.100莫耳)變更為23.063g(0.060莫耳),使用11.769g(0.040莫耳)之BPDA,將HFDA的量從33.427g(0.100莫耳)變更為20.056g(0.060莫耳),並使用13.938g(0.040莫耳)之BAFL,除此之外,利用和實施例1同樣的方法,獲得固體成分濃度15質量%之聚醯亞胺清漆。 使用得到的聚醯亞胺清漆,利用和實施例1同樣的方法獲得薄膜。 Example 3 The amount of CpODA was changed from 38.438g (0.100mol) to 23.063g (0.060mol), 11.769g (0.040mol) of BPDA was used, and the amount of HFDA was changed from 33.427g (0.100mol) to 20.056g ( 0.060 mol), except that 13.938 g (0.040 mol) of BAFL was used, a polyimide varnish having a solid content concentration of 15 mass % was obtained in the same manner as in Example 1. Using the obtained polyimide varnish, a film was obtained in the same manner as in Example 1.
實施例4 將38.438g(0.100莫耳)之CpODA變更為33.034g(0.100莫耳)之BNBDA,將反應及稀釋所使用的溶劑從GBL變更為NMP,除此之外,利用和實施例2同樣的方法,獲得固體成分濃度15質量%之聚醯亞胺清漆。 使用得到的聚醯亞胺清漆,利用和實施例1同樣的方法獲得薄膜。 Example 4 Except that the CpODA of 38.438g (0.100 mol) was changed to the BNBDA of 33.034g (0.100 mol), and the solvent used for the reaction and dilution was changed from GBL to NMP, the same method as in Example 2 was used, A polyimide varnish having a solid content concentration of 15% by mass was obtained. Using the obtained polyimide varnish, a film was obtained in the same manner as in Example 1.
比較例1 將33.427g(0.100莫耳)之HFDA變更為32.024g(0.100莫耳)之TFMB,將反應及稀釋所使用的溶劑從GBL變更為NMP,除此之外,利用和實施例1同樣的方法,獲得固體成分濃度15質量%之聚醯亞胺清漆。 使用得到的聚醯亞胺清漆,利用和實施例1同樣的方法獲得薄膜。 Comparative Example 1 Except that 33.427 g (0.100 mol) of HFDA was changed to 32.024 g (0.100 mol) of TFMB, and the solvent used for the reaction and dilution was changed from GBL to NMP, the same method as in Example 1 was used, A polyimide varnish having a solid content concentration of 15% by mass was obtained. Using the obtained polyimide varnish, a film was obtained in the same manner as in Example 1.
比較例2 將33.427g(0.100莫耳)之HFDA變更為33.624g(0.100莫耳)之6FODA,除此之外,利用和實施例1同樣的方法,獲得固體成分濃度15質量%之聚醯亞胺清漆。 使用得到的聚醯亞胺清漆,利用和實施例1同樣的方法獲得薄膜。 Comparative Example 2 A polyimide varnish having a solid content concentration of 15 mass % was obtained by the same method as in Example 1, except that 33.427 g (0.100 mol) of HFDA was changed to 33.624 g (0.100 mol) of 6FODA. Using the obtained polyimide varnish, a film was obtained in the same manner as in Example 1.
比較例3 將CpODA的量從38.438g(0.100莫耳)變更為23.063g(0.060莫耳),使用11.769g(0.040莫耳)之BPDA,並將20.056g(0.060莫耳)之HFDA變更為19.214g(0.060莫耳)之TFMB,除此之外,利用和實施例2同樣的方法,獲得固體成分濃度15質量%之聚醯亞胺清漆。 使用得到的聚醯亞胺清漆,利用和實施例1同樣的方法獲得薄膜。 Comparative Example 3 Change the amount of CpODA from 38.438g (0.100 mol) to 23.063g (0.060 mol), use 11.769g (0.040 mol) of BPDA, and change 20.056g (0.060 mol) of HFDA to 19.214g (0.060 A polyimide varnish having a solid content concentration of 15% by mass was obtained by the same method as in Example 2, except that it was TFMB of mol). Using the obtained polyimide varnish, a film was obtained in the same manner as in Example 1.
比較例4 將CpODA的量從38.438g(0.100莫耳)變更為34.594g(0.090莫耳),使用4.584g(0.010莫耳)之BPAF,不使用HFDA,將BAFL的量從13.938g(0.040莫耳)變更為15.680g(0.045莫耳),並使用17.613g(0.055莫耳)之TFMB,除此之外,利用和實施例2同樣的方法,獲得固體成分濃度15質量%之聚醯亞胺清漆。 使用得到的聚醯亞胺清漆,利用和實施例1同樣的方法獲得薄膜。 Comparative Example 4 Change the amount of CpODA from 38.438g (0.100mol) to 34.594g (0.090mol), use 4.584g (0.010mol) of BPAF without using HFDA, and change the amount of BAFL from 13.938g (0.040mol) A polyimide varnish having a solid content concentration of 15 mass % was obtained by the same method as in Example 2, except that 15.680 g (0.045 mol) and 17.613 g (0.055 mol) of TFMB were used. Using the obtained polyimide varnish, a film was obtained in the same manner as in Example 1.
比較例5 於具備不鏽鋼製半月型攪拌葉片、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之5口圓底燒瓶中投入33.427g(0.100莫耳)之HFDA、及201.117g之NMP,並於系內溫度25℃、氮氣環境下,以轉速200rpm攪拌,獲得溶液。 於該溶液中一次性地投入29.422g(0.100莫耳)之BPDA、及50.279g之NMP,攪拌3小時,獲得固體成分濃度20.0質量%之聚醯胺酸清漆。 然後將得到的聚醯胺酸清漆利用旋塗塗佈於玻璃板上,以加熱板於80℃保持20分鐘,其後,於氮氣環境下,在熱風乾燥機中以400℃加熱60分鐘(昇溫速度5℃/分鐘),使溶劑蒸發,獲得薄膜。 Comparative Example 5 Put 33.427 g (0.100 mol) in a 300 mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a Dean-Stark apparatus equipped with a cooling tube, a thermometer, and a glass end cap. HFDA and 201.117 g of NMP were stirred at a rotational speed of 200 rpm at a temperature of 25° C. in the system and a nitrogen atmosphere to obtain a solution. In this solution, 29.422 g (0.100 mol) of BPDA and 50.279 g of NMP were put into the solution at once, and the mixture was stirred for 3 hours to obtain a polyamide varnish having a solid content concentration of 20.0 mass %. Then, the obtained polyamic acid varnish was coated on a glass plate by spin coating, kept at 80° C. for 20 minutes with a hot plate, and then heated in a hot air dryer at 400° C. for 60 minutes under a nitrogen atmosphere (heating up speed 5°C/min), the solvent was evaporated, and a thin film was obtained.
針對實施例及比較例得到的聚醯亞胺薄膜實施前述物性測定及評價。得到的結果如表1所示。The aforementioned physical property measurements and evaluations were performed on the polyimide films obtained in the Examples and Comparative Examples. The obtained results are shown in Table 1.
[表1]
由表1所示可知實施例之聚醯亞胺薄膜,其透明性及疊層無機膜時之耐熱性優良。此外可知實施例之聚醯亞胺薄膜,其光學各向同性良好。比較例1及比較例2,其光學各向同性、疊層膜之耐熱性差。比較例3及比較例4,其Tg良好,但光學各向同性、疊層膜之耐熱性差。比較例5,其光學各向同性良好,但Tg、無色透明性、疊層膜之耐熱性差。 因此,四羧酸成分使用分子內具有2個降莰烷骨架之酸二酐,且二胺成分使用HFDA來製造的聚醯亞胺薄膜,可製成透明性、光學各向同性、及疊層膜之耐熱性優良的薄膜,並可作為構成液晶顯示器、OLED顯示器、觸控面板等顯示裝置之透明性之基板理想地使用。 As shown in Table 1, it can be seen that the polyimide films of Examples are excellent in transparency and heat resistance when an inorganic film is laminated. In addition, it can be seen that the polyimide films of the examples have good optical isotropy. In Comparative Example 1 and Comparative Example 2, the optical isotropy and the heat resistance of the laminated film were poor. In Comparative Example 3 and Comparative Example 4, the Tg was good, but the optical isotropy and the heat resistance of the laminated film were poor. Comparative Example 5 had good optical isotropy, but was inferior in Tg, colorless transparency, and heat resistance of the laminated film. Therefore, a polyimide film produced by using an acid dianhydride having two norbornane skeletons in the molecule as the tetracarboxylic acid component and using HFDA as the diamine component can be used for transparency, optical isotropy, and lamination. The film is excellent in heat resistance, and can be ideally used as a substrate constituting the transparency of display devices such as liquid crystal displays, OLED displays, and touch panels.
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