TW201105737A - Polyester composition for forming thermoset film - Google Patents
Polyester composition for forming thermoset film Download PDFInfo
- Publication number
- TW201105737A TW201105737A TW99109907A TW99109907A TW201105737A TW 201105737 A TW201105737 A TW 201105737A TW 99109907 A TW99109907 A TW 99109907A TW 99109907 A TW99109907 A TW 99109907A TW 201105737 A TW201105737 A TW 201105737A
- Authority
- TW
- Taiwan
- Prior art keywords
- component
- group
- forming
- polyester
- film
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/54—Amino amides>
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Nonlinear Science (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
201105737 六、發明說明: 【發明所屬之技術領域】 本發明係有關熱硬化膜形成用聚酯組成物及從其所得 到之硬化膜。更詳而言之’係有關一種具有高的透明性、 平坦化性’且具有液晶配向能、高的耐溶劑性及耐熱性之 熱硬化膜形成用聚酯組成物及其硬化膜、以及該硬化膜之 適用。此熱硬化膜形成用聚酯組成物係特別適宜於兼備液 晶顯甲器中之液晶配向功能的彩色濾光片被覆劑。 【先前技術】 一般’在液晶顯不兀件、有機EL(electroluminescent) 兀件 '固體攝影兀件等之光裝置中,係設有用以防止元件 表面在製造步驟中曝露於溶劑或熱之保護膜。此保護膜係 與保護之基板的密著性高,不僅耐溶劑性高,亦要求透明 性、耐熱性等之性能。 如此之保護膜係當使用來作爲彩色液晶顯示裝置或固 體攝影元件所使用的彩色濾光片之保護膜時,一般要求具 有使其基底基板之彩色濾光片或黑色矩陣樹脂平坦化的性 能,亦即作爲平坦化膜之性能。尤其,製造STN方式或 T F T方式之彩色液晶顯示元件時,必須非常嚴密地進行彩 色濾光片基板與對向基板之張貼精度,使基板間之胞間隙 均一化爲不可或缺。尙且,爲維持透過彩色濾光片之光的 透過率’於其保護膜之此等平坦化膜必須爲高的透明性。 另外,近年於液晶顯示器之胞內導入相位差材,硏究 -5- 201105737 低成本化、輕量化,於如此之相位差材一般係使用塗佈液 晶單體,並配向後,使之光硬化之材料。爲使此相位差材 配向,必須下層膜擦摩處理後,具有配向性之材料。因此 ,於彩色濾光片之被覆層上形成液晶配向層後,可形成相 位差材(參照圖2(a))。若可形成兼具此液晶配向層與 彩色濾光片之被覆層的膜(參照圖2 ( b )),從可得到低 成本化、製程數之減少等大的優點,強烈希望如此之材料 e 一般此彩色濾光片的被覆層係可使用透明性高的丙烯 酸樹脂。於此等之丙烯酸樹脂係從安全性、操作性之觀點 ,可廣泛使用丙二醇單甲基醚或丙二醇單甲基醚乙酸酯之 甘醇系之溶劑或乳酸乙酯、乳酸丁酯之酯系溶劑。如此之 丙烯酸樹脂係以熱硬化或光硬化賦予耐熱性或耐溶劑性( 專利文獻1、2 )。但,在習知之熱硬化性或光硬化性之丙 烯酸樹脂雖顯示適當的透明性或平坦化性,但即使擦摩處 理如此之平坦化膜,亦無法顯示充分的配向性。 另外,於液晶配向層一般可使用溶劑可溶性聚醯亞胺 或聚醯胺酸所構成之材料。此等之材料係後烘烤時完全醯 亞胺化以賦予耐溶劑性,藉擦摩處理顯示充分的配向性已 被報告(專利文獻3 )。但,就彩色濾光片之平坦化膜來 看時,有平坦化性與透明性降低很多等之問題。又,聚醯 亞胺或聚醯胺酸係可溶於N-甲基-2-吡咯烷酮或r-丁內酯 之溶劑,但對於甘醇系之溶劑或酯系之溶劑的溶解性低, 很難適用於平坦化膜製作生產線。 -6- 201105737 【發明內容】 [發明之槪要] [發明欲解決之課題] 本發明係依據上述之事情而成者,其欲解決之課題係 提供一種材料,其係硬化膜形成後,顯示高的耐溶解性、 液晶配向性、耐熱性、高透明性及高平坦化性,而且在硬 化膜形成時,係可溶解於在彩色濾光片之平坦化膜的製作 生產線上適用的甘醇系溶劑或乳酸酯系溶劑之材料。 [用以解決課題之手段] 本發明人係爲解決上述之課題,進行專心硏究之結果 ,終發現本發明。 亦即,第1觀點,係有關一種熱硬化膜形成用聚酯組 成物,其係含有(A)成分、(B)成分及(C)成分; (A )成分:使四羧酸二酐與二醇化合物反應所得到 之聚酯、 (B)成分:具有2個以上環氧基之環氧化合物、 (C )成分:使二胺化合物與二羧酸酐反應所得到之 含胺基之羧酸化合物。 第2觀點,係有關第i觀點記載之熱硬化膜形成用聚 酯組成物,其中前述(A )成分係含有以下述式(1 )所示 的構造單元之聚酯; 201105737 【化1】[Technical Field] The present invention relates to a polyester composition for forming a thermosetting film and a cured film obtained therefrom. More specifically, the present invention relates to a polyester composition for forming a thermosetting film having a high transparency and flatness, and having liquid crystal alignment energy, high solvent resistance and heat resistance, and a cured film thereof, and The application of the cured film. The polyester composition for forming a thermosetting film is particularly suitable for a color filter coating agent having a liquid crystal alignment function in a liquid crystal display. [Prior Art] Generally, in an optical device such as a liquid crystal display element or an organic EL (electroluminescent) element, a protective film for preventing exposure of a component surface to a solvent or heat in a manufacturing step is provided. . This protective film has high adhesion to the substrate to be protected, and has high solvent resistance and performance such as transparency and heat resistance. When such a protective film is used as a protective film for a color filter used for a color liquid crystal display device or a solid-state imaging device, it is generally required to have a performance of flattening a color filter or a black matrix resin of the base substrate. That is, the performance as a planarizing film. In particular, when manufacturing a color liquid crystal display device of the STN method or the T F T method, it is necessary to perform the adhesion precision of the color filter substrate and the counter substrate very closely, and it is indispensable to uniformize the inter-substrate gap. Further, in order to maintain the transmittance of light transmitted through the color filter, the planarizing film of the protective film must have high transparency. In addition, in recent years, phase difference materials have been introduced into the cells of liquid crystal displays, and the cost is reduced to 0.5-201105737. In such a phase difference, a liquid crystal monomer is generally used, and after being aligned, the light is hardened. Material. In order to align this phase difference material, it is necessary to have an alignment material after the underlying film rubbing treatment. Therefore, after the liquid crystal alignment layer is formed on the coating layer of the color filter, a phase difference material can be formed (see Fig. 2(a)). When a film having a coating layer of the liquid crystal alignment layer and the color filter can be formed (see FIG. 2( b )), it is possible to obtain a material having a large cost and a large number of processes, and the like. Generally, an acrylic resin having high transparency can be used as the coating layer of the color filter. The acrylic resin of the above-mentioned type can be widely used as a glycol solvent of propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate or an ester of ethyl lactate or butyl lactate from the viewpoints of safety and workability. Solvent. Such an acrylic resin imparts heat resistance or solvent resistance by thermosetting or photocuring (Patent Documents 1 and 2). However, the conventional thermosetting or photocurable acrylic resin exhibits appropriate transparency or flattening property, but even if such a flattening film is rubbed, sufficient alignment property cannot be exhibited. Further, as the liquid crystal alignment layer, a material composed of a solvent-soluble polyimine or polylysine can be generally used. These materials are completely imidized at the time of post-baking to impart solvent resistance, and sufficient alignment property has been reported by rubbing treatment (Patent Document 3). However, when the flattening film of the color filter is viewed, there are problems such as flatness and transparency being lowered. Further, polyimine or polylysine is a solvent which is soluble in N-methyl-2-pyrrolidone or r-butyrolactone, but has low solubility in a glycol-based solvent or an ester-based solvent. Difficult to apply to the flat film production line. -6- 201105737 [Summary of the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems, and the object to be solved is to provide a material which is formed after the formation of a cured film. High solubility, liquid crystal alignment, heat resistance, high transparency, and high flatness, and when the cured film is formed, it is soluble in the glycol produced on the production line of the flattening film of the color filter. It is a material of a solvent or a lactic acid ester solvent. [Means for Solving the Problem] The present inventors have found out the present invention by focusing on the above-mentioned problems and focusing on the results. In other words, the first aspect relates to a polyester composition for forming a thermosetting film comprising (A) component, (B) component, and (C) component; (A) component: tetracarboxylic dianhydride and Polyester obtained by the reaction of a diol compound, component (B): an epoxy compound having two or more epoxy groups, and (C) component: an amine group-containing carboxylic acid obtained by reacting a diamine compound with a dicarboxylic anhydride Compound. The second aspect of the invention relates to a polyester composition for forming a thermosetting film according to the first aspect, wherein the component (A) contains a polyester having a structural unit represented by the following formula (1); 201105737 [Chemical Formula 1]
(式中,A表示於脂環式基或脂肪族基上4個鍵結鍵已鍵 結之4價的有機基’ B表示於脂環式基或脂肪族基上2個 鍵結鍵已鍵結之2價的有機基)。 第3觀點’係有關弟1或第2觀點g己載之熱硬化膜形 成用聚酯組成物,其中前述(A)成分係使以下述式(i) 所示之四羧酸二酐與以式(i i )所示之二醇化合物反應所 得之聚酯; 【化2】 Ο Ο〇«〇 (i) HO-B-OH (ii) (式中,A表示於脂環式基或脂肪族基上4個鍵結鍵已鍵 結之4價的有機基,B表示於脂環式基或脂肪族基上2個 鍵結鍵已鍵結之2價的有機基)。 第4觀點,係有關第2或3觀點記載之熱硬化膜形成 用聚酯組成物’其中前述式(1)中,A表示由下述式( A-1)〜式(A-8)所示之基選出的至少一種之基,B表示 由下述式(B-1) ~式(B-5)所示之基選出的至少一種之 基。 -8- 201105737 【化3】 » W V® (Α·1) (Α-2) (Α-3) (Α-4) (Α-5) (Α-6)(wherein, A represents a tetravalent organic group to which four bonding bonds have been bonded on an alicyclic group or an aliphatic group, and B represents two bonding bonds on an alicyclic group or an aliphatic group. A 2 valent organic group). The third aspect is a polyester composition for forming a thermosetting film which is contained in the first aspect or the second aspect, wherein the component (A) is a tetracarboxylic dianhydride represented by the following formula (i). a polyester obtained by reacting a diol compound represented by the formula (ii); [Chemical 2] Ο Ο〇 «〇 (i) HO-B-OH (ii) (wherein, A is represented by an alicyclic group or an aliphatic group A 4-valent organic group to which four bonding bonds have been bonded, and B represents a divalent organic group to which two bonding bonds have been bonded to an alicyclic group or an aliphatic group. The fourth aspect is the polyester composition for forming a thermosetting film according to the second or third aspect, wherein in the above formula (1), A is represented by the following formula (A-1) to formula (A-8). At least one selected from the group shown, and B represents at least one selected from the group represented by the following formula (B-1) to formula (B-5). -8- 201105737 【化3】 » W V® (Α·1) (Α-2) (Α-3) (Α-4) (Α-5) (Α-6)
(Α-7) (Α-8) 【化4】(Α-7) (Α-8) 【化4】
(Β-4) (Β*5) χ>ΕΡ ^ (Β_1 ) ( Β·2 > (Β-3) 第5觀點,係有關第1〜4觀點中任一項之熱硬化膜形 成用聚酯組成物,其中(Α)成分之聚酯的重量平均分子 量係以聚苯乙烯換算爲1 000-30000。 第6觀點,係有關第1〜5觀點中任一項之熱硬化膜形 成用聚酯組成物,其中(C)成分爲使二胺化合物1莫耳 與二羧酸酐1.7〜2莫耳反應所得之含胺基之羧酸化合物。 第7觀點,係有關第1〜6觀點中任一項之熱硬化膜形 成用聚酯組成物,其中基於(Α)成分之100質量份,含 有3〜5 0質量份之(Β)成分、3〜50質量份之(C)成分。 第8觀點,係有關第丨〜7觀點中任—項之熱硬化膜形 成用聚酯組成物’其係進一步含有雙馬來醯亞胺化合物作 爲(D)成分。 第9觀點,係有關第8觀點之熱硬化膜形成用聚酯組 成物,其中基於(A)成分之1〇〇質量份,含有〇 5〜5〇質 量份之(D )成分。 -9- 201105737 第10觀點,係有關一種硬化膜,其係使用第1〜9觀 點中任一項之熱硬化膜形成用聚酯組成物所得到。 第11觀點,係有關一種液晶配向層,其係使用第1〜9 觀點中任一項之熱硬化膜形成用聚酯組成物所得。 [發明之效果] 本發明之熱硬化膜形成用聚酯組成物係除了高的平坦 化性、高的透明性、高的耐溶劑性、高的耐熱性外,尙且 可形成具有液晶配向能之硬化膜,故可使用來作爲液晶配 向膜或平坦化膜之形成材料。尤其,可使以往獨立所形成 之液晶配向膜與彩色濾光片之被覆層,一次形成作爲兼備 兩者特性之「液晶配向層」,可實現製造步驟的簡略化及 製程數降低所產生的低成本化等。 進一步’本發明之熱硬化膜形成用聚酯組成物係可溶 於甘醇系溶劑及乳酸酯系溶劑,故可適宜使用於使用此等 溶劑爲主之平坦化膜的製作生產線。 [用以實施發明之形態] 如前述般’在以往所提出之丙烯酸樹脂系及聚醯亞胺 系之硬化膜中,無法充分滿足於液晶配向膜或平坦化膜所 求取之平坦化性、透明性、配向性等全部的性能。 又’至今亦已提出使用聚酯作爲液晶顯示元件之配向 材料(參照特開平5-158055號公報、特開2002-229039號 公報)’但此等係任一者均不具有熱硬化性,所形成之膜 -10- 201105737 的耐溶劑性差者。 本發明係於使用熱硬化性之聚酯而謀求前述 之點上有特徵,亦即,含有(A)成分之聚酯、( 之具有2個以上環氧基之環氧化合物、(C)成 具胺基的羧酸化合物之熱硬化膜形成用聚酯組成: 步係除了(A)成分、(B)成分及(C)成分之: 含有雙馬來醯亞胺化合物作爲(D)成分之熱硬/ 用聚酯組成物。 以下,說明各成分之內容。 [(A )成分] (A)成分之聚酯較佳係含有以下述式(1) 造單元之聚酯’更較佳係以式(1)所示的構造 成之聚醋。 【化5】 能提昇 )成分 之含有 。進一 ,亦可 膜形成 示的構 元所構(Β-4) (Β*5) χ>ΕΡ ^ (Β_1) ( Β·2 > (Β-3) The fifth aspect relates to the formation of a thermosetting film for use in any one of the first to fourth aspects In the ester composition, the weight average molecular weight of the polyester of the (Α) component is from 1 000 to 30,000 in terms of polystyrene. The sixth aspect of the invention relates to the thermosetting film forming composition according to any one of the first to fifth aspects The ester composition, wherein the component (C) is an amine group-containing carboxylic acid compound obtained by reacting a diamine compound 1 molar with a dicarboxylic anhydride of 1.7 to 2 mol. The seventh aspect is related to the first to sixth aspects. A polyester composition for forming a thermosetting film, which contains 3 to 50 parts by mass of the (Β) component and 3 to 50 parts by mass of the component (C) based on 100 parts by mass of the (Α) component. In view of the above, the polyester composition for forming a thermosetting film of the above-mentioned item No. 7 to the above-mentioned item further contains a bismaleimide compound as the component (D). The ninth point is about the eighth aspect. The polyester composition for forming a thermosetting film, which contains (5) parts by mass of the component (D) based on 1 part by mass of the component (A). -9- 20110573 The tenth aspect relates to a cured film obtained by using the polyester composition for forming a thermosetting film according to any one of the first to ninth aspects. The eleventh aspect relates to a liquid crystal alignment layer which is used. The polyester composition for forming a thermosetting film according to any one of the first to ninth aspects of the present invention. [Effect of the Invention] The polyester composition for forming a thermosetting film of the present invention has high flatness and high transparency. In addition to high solvent resistance and high heat resistance, it can form a cured film having liquid crystal alignment energy, so it can be used as a material for forming a liquid crystal alignment film or a planarization film. In the coating layer of the liquid crystal alignment film and the color filter, the "liquid crystal alignment layer" having both characteristics can be formed at one time, and the manufacturing process can be simplified and the number of processes can be reduced, etc. Further, the present invention The polyester composition for forming a thermosetting film is soluble in a glycol solvent and a lactic acid ester solvent, and therefore can be suitably used in a production line for using a flattening film mainly composed of such a solvent. In the cured film of the acrylic resin and the polyimine which have been proposed in the past, the flatness, transparency, alignment, etc. which are obtained by the liquid crystal alignment film or the planarizing film cannot be sufficiently satisfied. In addition, it has been proposed that polyester is used as an alignment material for a liquid crystal display element (see Japanese Patent Laid-Open No. Hei 5-158055, No. 2002-229039), but none of them has any heat. The curable property, the formed film -10- 201105737 is inferior in solvent resistance. The present invention is characterized in that it is characterized by using a thermosetting polyester, that is, a polyester containing (A) component, The epoxy resin compound having two or more epoxy groups and (C) the carboxylic acid compound having an amine group is composed of a polyester for forming a thermosetting film: Step (A) component, (B) component, and (C) Ingredients: A thermosetting/polyester composition containing a bismaleimide compound as the component (D). Hereinafter, the contents of each component will be described. [(A) component] The polyester of the component (A) preferably contains a polyester having a unit of the following formula (1), and more preferably a polyester having a structure represented by the formula (1). [Chem. 5] can improve the content of the ingredients. Further, it can also be constructed by the structure of the film formation.
HOOCwC〇OH 0—C-A—C-O-B II Ο 〇HOOCwC〇OH 0—C-A—C-O-B II Ο 〇
(1) 上述式中’ Α表示於脂環式基或脂肪族基上4 鍵已鍵結之4價的有機基’ B表示於脂環式基或龍 上2個鍵結鍵已鍵結之2價的有機基。 上述A係宜以下述式(1A1)、式(1A2)或〕 )所示之基。 個鍵結 肪族基 i ( 1A3 -11- 201105737 【化6】 X X >1-< (1A1) (1A2) (1A3) 式中之A1表示環狀飽和烴基,較佳係表示碳原子數 4〜8的環狀飽和烴基,更宜表示碳原子數4〜6之環狀飽和 烴基。此處,A1基中所含有之任意的氫原子亦可分別獨立 以脂肪族基取代,又,其等之中亦可2個之取代基互相結 合而形成4~6員環。 此處,該取代基之脂肪族基係宜爲碳原子數1〜5的脂 肪族基,更宜爲碳原子數1〜3的脂肪族基。此等取代基結 合而形成環時,例如降冰片烯基或金剛烷基等的架橋環式 烴基、一部或全部被氫化之縮合多環式烴基。 上述式中,R1表示單鍵、羰基、醚基、磺醯基、碳原 子數1〜8的飽和烴基或被氟原子取代之碳原子數1〜8的飽 和烴基。較佳係單鍵、羰基、醚基、磺醯基、碳原子數 1~5的飽和烴基或被氟原子取代之碳原子數1〜5的飽和烴 基。 R2表示碳原子數1~8的飽和烴基,較佳係碳原子數 1~5的飽和烴基,更較佳係碳原子數1〜3的飽和烴基。 將式(1)中之4價的有機基的A較佳的具體例表示 於下述之式(A-1)〜式(A-8)中。於以下述(A-1)〜式 (A-8)所示之基中,A尤宜爲由式(A-1)或(A-2)選 出之基。 -12- 201105737 【化7】 XX w (Α·1 ) (Α-2) (Α-3) (A·4) (A-5) (Α-β) 上述式(1)中’ B表示於脂環式基或脂肪族基上2 個鍵結鍵已鍵結之2價的有機基’宜爲以下述式(1B1) 或式(1B2)所示之基。 【化8】 一R4_B1+R3_B1 荃 R5— —R6-B2-R7- (1B1) (1B2) 式中之B1表示環狀飽和烴基,較佳係表示碳原子數 4〜8的環狀飽和烴基,更宜表示碳原子數4~6之環狀飽和 烴基。此處,B1基中所含有之任意的氫原子亦可分別獨立 以脂肪族基取代。 此處,該取代基之脂肪族基係宜爲碳原子數1〜5的脂 肪族基,更宜爲碳原子數1〜3的脂肪族基。此等取代基結 合而形成環時,例如降冰片烯基或金剛烷基等的架橋環式 烴基、一部或全部被氫化之縮合多環式烴基。 B 2表示苯伸基。 式中,R3表示單鍵、羰基 '醚基、磺醯基 '碳原子數 1~8的飽和烴基或被氟原子取代之碳原子數1〜8的飽和烴 -13- 201105737 基,較佳係單鍵、羰基、醚基、磺醯基、碳原子數1〜5的 飽和烴基或被氟原子取代之碳原子數1〜5的飽和烴基。 R4、R5分別獨立表示單鍵或碳原子數1〜5之伸烷基, 宜表示單鍵、碳原子數1〜3之伸烷基。 R6、R7分別獨立表示碳原子數1~5之伸烷基,宜表示 碳原子數1~3之伸烷基。 又k表示〇或1。 將式(1)中之2價的有機基的B較佳的具體例表示 於下述之式(B-1)〜式(B-5)中。於以下述(B-1) ~式 (B-5)所示之基中,B尤宜爲由式(B-1)或(B-4)選 出之基。 【化9】(1) In the above formula, 'Α denotes a 4-valent organic group to which a 4-bond has been bonded to an alicyclic group or an aliphatic group. 'B indicates that two bonding bonds are bonded to an alicyclic group or a dragon. A divalent organic group. The above A is preferably a group represented by the following formula (1A1), formula (1A2) or 〕). Bonded aliphatic group i (1A3 -11- 201105737 [Chem. 6] XX >1-< (1A1) (1A2) (1A3) wherein A1 represents a cyclic saturated hydrocarbon group, preferably a carbon atom The cyclic saturated hydrocarbon group of 4 to 8 is more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, any hydrogen atom contained in the A1 group may be independently substituted with an aliphatic group, and In addition, two substituents may be bonded to each other to form a 4 to 6 membered ring. Here, the aliphatic group of the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably a carbon number. An aliphatic group of 1 to 3, wherein when these substituents are combined to form a ring, for example, a bridged cyclic hydrocarbon group such as a norbornene group or an adamantyl group, or a partially or wholly hydrogenated condensed polycyclic hydrocarbon group. R1 represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms substituted by a fluorine atom. It is preferably a single bond, a carbonyl group or an ether group. a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted by a fluorine atom. R2 represents a carbon number of 1 to 8 The saturated hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. A preferred specific example of A of the tetravalent organic group in the formula (1) In the following formula (A-1) to formula (A-8), in the group represented by the following (A-1) to (A-8), A is particularly preferably of the formula (A-). 1) or (A-2) selected base. -12- 201105737 【化7】 XX w (Α·1 ) (Α-2) (Α-3) (A·4) (A-5) (Α- β) In the above formula (1), 'B' represents a divalent organic group to which two bonding bonds are bonded to an alicyclic group or an aliphatic group, and is preferably a formula (1B1) or a formula (1B2) A group of R4_B1+R3_B1 荃R5-R6-B2-R7- (1B1) (1B2) wherein B1 represents a cyclic saturated hydrocarbon group, preferably a ring having 4 to 8 carbon atoms. The saturated hydrocarbon group preferably represents a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, any hydrogen atom contained in the B1 group may be independently substituted with an aliphatic group. Here, the fat of the substituent The family group is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. In the ring, a bridged cyclic hydrocarbon group such as a norbornene group or an adamantyl group, or a hydrogenated condensed polycyclic hydrocarbon group. B 2 represents a benzene group. In the formula, R 3 represents a single bond, a carbonyl 'ether. a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon having 1 to 8 carbon atoms substituted by a fluorine atom, preferably a single bond, a carbonyl group, an ether group or a sulfonyl group. A saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted by a fluorine atom. R4 and R5 each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and preferably represent a single bond or an alkylene group having 1 to 3 carbon atoms. R6 and R7 each independently represent an alkylene group having 1 to 5 carbon atoms, and preferably represent an alkylene group having 1 to 3 carbon atoms. Again k means 〇 or 1. A preferred specific example of B of the divalent organic group in the formula (1) is shown in the following formula (B-1) to formula (B-5). In the group represented by the following formula (B-1) to (B-5), B is particularly preferably a group selected from the formula (B-1) or (B-4). 【化9】
(B-3)(B-3)
(B-5) (B-4) (A)成分之聚酯係宜爲以式(1)所示之構造單元中 ,A宜爲含有至少一種選自由式(1A1) ~式(1A3)所示 之基所構成的群中之構造,但亦可含有以式(1A1) ~式( 1A3)所示之基以外之構造。其時,只要爲形成聚酯之構 造,其構造無特別限定,但宜爲至少一種選自由以下述式 (1A4)〜式(1A5)所示之基所構成的群中之構造。(B-5) (B-4) The polyester of the component (A) is preferably a structural unit represented by the formula (1), and A preferably contains at least one selected from the group consisting of the formula (1A1) to the formula (1A3). The structure in the group formed by the base of the formula may have a structure other than the group represented by the formula (1A1) to the formula (1A3). In the meantime, the structure of the polyester is not particularly limited, and it is preferably at least one selected from the group consisting of the groups represented by the following formulas (1A4) to (1A5).
201105737 上述式中,R8、R9、R1Q分別獨立表示單鍵、羰基、 醚基、磺醯基、碳原子數1〜8的飽和烴基或被氟原子取代 之碳原子數1~8的飽和烴基,較佳係單鍵、羰基、醚基、 磺醯基、碳原子數1~5的飽和烴基或被氟原子取代之碳原 子數1~5的飽和烴基。 尤其宜R8表示單鍵、羰基、醚基、磺醯基、碳原子 數1〜5的飽和烴基或被氟原子取代之碳原子數1~5的飽和 烴基,宜R9表示醚基、碳原子數1〜5的飽和烴基或被氟 原子取代之碳原子數1〜5的飽和烴基,宜R1()表示羰基、 醚基、磺醯基、碳原子數1~5的飽和烴基或被氟原子取代 之碳原子數1~5的飽和烴基。 又h表示0或1。 將前述式(1 A4 )〜式(1 A5 )之較佳具體例表示於下 述之式(al)〜式(a7)。 【化1 1】201105737 In the above formula, R8, R9 and R1Q each independently represent a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms substituted by a fluorine atom. It is preferably a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms which is substituted by a fluorine atom. In particular, R8 represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted by a fluorine atom, and R9 represents an ether group and a carbon number. a saturated hydrocarbon group of 1 to 5 or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted by a fluorine atom, preferably R1() represents a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a fluorine atom; A saturated hydrocarbon group having 1 to 5 carbon atoms. Also h represents 0 or 1. Preferred specific examples of the above formula (1 A4 ) to formula (1 A5 ) are shown in the following formulas (al) to (a7). [1 1]
^CC (a1 > (a2) (a3) (a4) (a6) (a5) (a7) 在本發明所使用之(A)成分的聚酯中,在以上述式 (1)所示之構造單元中,A宜含有由式(1A1)〜式(1A3 )所示之基所構成的群中選出之至少一種的構造單元至少 -15- 201105737 6〇莫耳%以上。 (A)成分之聚酯的重量平均分子量宜爲1 000〜3 0000 ’更宜爲1,500~10,0〇〇。(A)成分之聚酯的重量平均分 子量小於前述範圍時,配向性及耐溶劑性有降低之傾向’ 若超過前述範圍,有時平坦化性會降低。 <(A)成分之製造方法> 在本發明中,(A )成分之聚酯係例如可使四羧酸二 酐與二醇化合物聚合而得到。更詳而言之,使含有以下述 式(i)所示之四羧酸二酐的四羧酸二酐(以下,亦稱爲 酸成分)、與以下述式(ii )所示之二醇化合物的二醇化 合物(以下’亦稱爲二醇成分)反應而得到。 【化1 2】^CC (a1 > (a2) (a3) (a4) (a6) (a5) (a7) In the polyester of the component (A) used in the present invention, the structure represented by the above formula (1) In the unit, A preferably contains at least -15-201105737 6 〇 mol% or more of at least one selected from the group consisting of the groups represented by the formulas (1A1) to (1A3). The weight average molecular weight of the ester is preferably from 1 000 to 3 0000 ', more preferably from 1,500 to 10,0 Å. When the weight average molecular weight of the polyester of the component (A) is less than the above range, the alignment property and the solvent resistance are lowered. When the content exceeds the above range, the planarization property may be lowered. <Production Method of Component (A)> In the present invention, the polyester of the component (A) may be, for example, tetracarboxylic dianhydride and More specifically, a tetracarboxylic dianhydride (hereinafter, also referred to as an acid component) containing a tetracarboxylic dianhydride represented by the following formula (i), and a formula (ii) The diol compound (hereinafter referred to as a diol component) of the diol compound shown is obtained by reacting. [Chemical 1 2]
⑴ HO-B-OH (ii) 上述式中’ A及B係與上述之式(1)中的定義相同 ,較佳之形態亦與上述者相同。 在本發明中,以式(i)所示之四羧酸二酐、以式(ii )所示之二醇化合物係可分別獨立地1種單獨使用,亦或 使用2種以上。 上述(A)成分之聚酯係就酸成分而言,不僅以上述 式(i)所示之四羧酸二酐’可倂用其以外之四羧酸二酐 (以下’亦稱爲其他之酸二酐)。其時,其他之酸二酐係 -16- 201105737 只要在無損本發明之效果下,並無特別限定。較佳係以下 述式(i2)所示之四羧酸二酐。 【化1 3】 Ο 〇(1) HO-B-OH (ii) The 'A and B systems in the above formula are the same as defined in the above formula (1), and the preferred embodiment is also the same as the above. In the present invention, the tetracarboxylic dianhydride represented by the formula (i) and the diol compound represented by the formula (ii) may be used singly or in combination of two or more kinds. In the polyester component of the above (A) component, not only the tetracarboxylic dianhydride represented by the above formula (i) but also a tetracarboxylic dianhydride other than the above-mentioned formula (i) can be used (hereinafter also referred to as other Acid dianhydride). In the meantime, the other acid dianhydride-16-201105737 is not particularly limited as long as the effects of the present invention are not impaired. The tetracarboxylic dianhydride represented by the following formula (i2) is preferred. [化1 3] Ο 〇
此處’上述式(i2)之W係在上述之式(1)中所定 義的式(1A4)及式(1A5)所示之基所構成的群中選出 之至少一種的構造,R8、R9、R1G、h亦如上述定義》 尙且,式(1A4 )及式(1A5 )之較佳的具體例亦以 上述之式(al) ~式(a7)所示。 在本發明中’宜以式(i)所示之四羧酸二酐含有酸 成分中至少60莫耳%以上。 在前述(A)成分之聚酯中,四羧酸二酐之合計量( 酸成分之合計量)與二醇化合物之合計量(二醇化合物之 合計量)的調配比,亦即,(二醇化合物之合計莫耳數) /(四羧酸二酐化合物之合計莫耳數)宜爲0·5〜1.5。一般 之聚縮合反應同樣,此莫耳比愈接近1,生成之聚酯的聚 合度愈大,分子量愈增加》 (A)成分之聚酯係爲避免保存安定性之降低,宜使 其末端爲酸酐末端。 上述聚酯之末端係依存於酸成分與二醇成分之調配比 而變化。例如,使酸成分過剩地反應時,末端易成爲酸酐 -17- 201105737 又,過剩地使用二醇成分而聚合時係末端易成 。此時,使該末端羥基與羧酸酐反應,可以酸酐封 羥基。如此之羧酸酐的例可舉例如酞酸酐、偏苯三 、馬來酸酐、萘酸酐、氫化酞酸酐、衣康酸酐 '四 酐' I,2-環己烷二羧酸酐、4-甲基- I,2-環己烷二羧 4-苯基-1,2-環己烷二羧酸酐、甲基-5-降冰片烯基 羧酸酐、四氫酞酸酐、甲基四氫酞酸酐、雙環[2 烯-2,3-二羧酸酐等。 在上述(A)成分之聚酯製造中,酸成分與二 之反應溫度係可選擇50~20(TC、宜 80~170°C之任 度。例如,反應溫度可以100~140°C、反應時間2 時得到聚酯。 又,以酸酐保護末端羥基時之反應溫度係選擇 °C,宜80〜l7〇°C之任意的溫度。 上述酸成分與二醇成分之反應係一般在溶劑中 其時可使用之溶劑只要不含有羥基或胺基等、與酸 之官能基者即可,並無特別限定。可舉例如N,N-二 醯胺、N,N-二甲基乙醯胺、N -甲基-2-吡咯烷酮、 基吡咯烷酮、N_甲基己內醯胺、二甲基亞楓、四甲 、二甲基碾、六甲基亞碾、間甲酚、丁內酯、 、環戊酮、甲乙酮、甲基異丁基酮、2-庚嗣 '丙二 基醚乙酸酯、丙二醇丙基醚乙酸酯、3-甲氧基丙酸 2-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、2-甲氧基 爲羥基 閉末端 甲酸酐 氫酞酸 酸酐、 -2,3-二 •2.2]辛 醇成分 意的溫 ~ 4 8 /J\ 50〜200 進行。 酐反應 甲基甲 N-乙烯 基尿素 環己酮 醇單甲 甲醋、 丙酸乙 •18· 201105737 酯、3-乙氧基丙酸乙酯、2-乙氧基丙酸乙酯等。 此等之溶劑係可單獨,亦可混合而使用,但,從安全 性、彩色濾光片之被覆劑的生產線之適用性而言,更宜爲 丙二醇單甲基醚乙酸酯。 進一步,可爲不溶劑聚酯之溶劑,在依聚合反應所生 成之聚酯不析出的範圍,亦可混合於上述溶劑而使用。 又’上述酸成分(式(i)及式(i2))與二醇成分( 式(ii))之反應時亦可使用觸媒。 使用於聚酯聚合時之觸媒的具體例可舉例如氯化苯甲 基三甲基銨、溴化苯甲基三甲基銨、氯化苯甲基三乙基銨 、溴化苯甲基三乙基銨、氯化苯甲基三丙基銨、溴化苯甲 基三丙基銨、氯化四甲基銨、溴化四乙基銨、氯化四丙基 銨、溴化四丙基銨等之四級銨鹽、氯化四苯基磷鑰、溴化 四苯基磷鏺、氯化苯甲基三苯基磷鑰、溴化苯甲基三苯基 磷鑰、氯化乙基三苯基磷鑰、溴化乙基三苯基磷鎗等之4 級磷鎗鹽。 含有如此做法所得到之(A )成分的聚酯之溶液,係 可直接使用於熱硬化膜形成用聚酯組成物之調製。又,使 所得到之聚酯於水、甲醇、乙醇、二乙基醚、己烷等之弱 溶劑沉澱單離而回收後,亦可使用。 < (B )成分> I S1 具有本發明之(B)成分的環氧基2個以上之環氧化 合物,可舉例如三(2,3_環氧基丙基)三聚異氰酸酯、 -19- 201105737 1,4-丁二醇二縮水甘油基醚、1,2-環氧基-4-(環氧基乙基 )環己烷、甘醇三縮水甘油基醚、二乙二醇二縮水甘油基 醚、2,6-二縮水甘油基苯基縮水甘油基醚、1,1,3-三[對-( 2,3-環氧基丙氧基)苯基]丙烷、1,2-環己烷二羧酸二縮水 甘油基酯、4,4’-亞甲基雙(N,N-二縮水甘油基苯胺)、 3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、三羥甲 基乙烷三縮水甘油基醚及雙酚-A-二縮水甘油基醚及季戊 四醇聚縮水甘油基醚等。 又,從容易取得而言,亦可使用市售品之化合物。以 下舉出其具體例(商品名),但不限定於此等:YH-434、 YH434L (東都化成(股)製)等之具有胺基的環氧樹脂; Epolead GT-401、Epolead GT-403、Ερο 1 ead GT-301、 Epolead GT-3 02、Celoxide 202 1、Celoxide 3000 ( Daicel 化學工業(股)製)等之具有環己烯氧化物構造之環氧樹脂 ;Epikote 1001、Epikote 1 002、Epikote 1 0 0 3、Epikote 1004 、 Epikote 1007 、 Epikote 1009 、 Epikote 1010 、 Epikote 828 (以上,油化 Shell Epoxy(股)(現 Japan Epoxy Resin(股)製))等之雙酚 A型環氧樹脂;Epikote 807 (油化 Shell Epoxy(股)(現 Japan Epoxy Resin(股)製 ))等之雙酚F型環氧樹脂;Epikote 152、Epikotel54( 以上,油化 Shell Epoxy(股)(現 Japan Epoxy Resin(股)製 ))、EPPN 20 1、EPPN 202 (以上,日本化藥(股)製)等 之酚酚醛清漆型環氧樹脂:EOCN-102、EOCN-103S、 EOCN-104S ' EOCN- 1 020、EOCN-1 025、EOCN-1027 (以 -20- 201105737 上,日本化藥(股)製)、Epikotel80S75 (油化 Shell Epoxy(股)(現Japan Epoxy Resin(股)製))等之間甲酹 酹醒清漆型環氧樹脂;Denacol EX-252 (Nagase Chemtex( 股)製)、CY 1 75 ' CY 1 77、CY 1 79、Araldite CY-1 82、 Araldite CY-192、Araldite CY-184 (以上,CIBA-GEIGY A.G 製)、Epiclon 200、Epiclon 400 (以上,大日本油墨 化學工業(股)(現 DIC(股))製)、Epikote871、 Epikote872 (以上,油化 Shell Epoxy(股)(現 Japan Epoxy Resin(股)製))、ED-566 1、ED-5662 (以上, Celanese Coating(股)製)等之脂環式環氧樹脂;Denacol EX-611 ' Denacol EX-612 ' Denacol EX-614 ' Denacol EX-622 ' Denacol EX-411、Denacol EX-512、Denacol EX-522 、Denacol EX- 421、Denacol EX-313、Denacol EX-314、 Denacol EX-32 1 ( Nagase Chemtex(股)製)等之脂肪族聚 縮水甘油基醚等。 又,至少具有2個環氧基之化合物係可使用具有環氧 基之聚合物。如此之聚合物只要爲具有環氧基者即可使用 ,無特別限制。 上述具有環氧基之聚合物例如可藉由使用具有環氧基 之加成聚合性單體之加成聚合來製造。就一例而言,可舉 例如聚縮水甘油基丙烯酸酯、縮水甘油基甲基丙烯酸酯與 乙基甲基丙烯酸酯之共聚物、縮水甘油基甲基丙烯酸酯與 苯乙烯與2-羥基乙基甲基丙烯酸酯之共聚物等的加成聚合 聚合物、或環氧基酚醛清漆等之縮聚合聚合物。 -21- 201105737 亦或,上述具有環氧基之聚合物係亦可藉由具有羥基 之高分子化合物與表氯醇、縮水甘油基對甲苯磺酸酯等之 具有環氧基的化合物之反應來製造。 如此之聚合物的重量平均分子量例如300〜200,000。 至少具有2個環氧基之環氧化合物係可單獨或2種以 上之組合而使用。 具有本發明之熱硬化膜形成用聚酯組成物中的(B) 成分之環氧基2個以上的環氧基化合物含量,依據(a) 成分之聚酯1〇〇質量份宜爲3〜50質量份,更宜爲5~40質 量份,尤宜爲1 〇〜3 0質量份。此比率太小時,從熱硬化膜 形成用聚酯組成物所得到之硬化膜的耐溶劑性或耐熱性會 降低,另外,太大時係有時耐溶劑性降低,或保存安定性 降低》 < (C)成分> (C )成分係使二胺化合物與二羧酸二酐反應所得到 之含有胺基的羧酸化合物。詳細內容係使以下述式(iii) 所示之二胺化合物1莫耳與以式(iv)所示之二竣酸二酐 1.7〜2莫耳,較佳係1.8~2莫耳反應所得到之含有胺基的 羧酸化合物。Here, the structure of the above formula (i2) is at least one selected from the group consisting of the formulas represented by the formula (1A4) and the formula (1A5) defined in the above formula (1), R8 and R9. Further, R1G and h are also as defined above, and preferred specific examples of the formula (1A4) and the formula (1A5) are also represented by the above formula (al) to (a7). In the present invention, the tetracarboxylic dianhydride represented by the formula (i) preferably contains at least 60 mol% or more of the acid component. In the polyester of the above component (A), the ratio of the total amount of the tetracarboxylic dianhydride (the total amount of the acid components) to the total amount of the diol compound (the total amount of the diol compound), that is, The total number of moles of the alcohol compound) / (the total number of moles of the tetracarboxylic dianhydride compound) is preferably from 0.5 to 1.5. In general, the polycondensation reaction is similar. The closer the molar ratio is to 1, the greater the degree of polymerization of the resulting polyester, and the higher the molecular weight. The polyester of the component (A) is preferably such that the stability of the preservation stability is lowered. Anhydride end. The end of the polyester varies depending on the blending ratio of the acid component to the diol component. For example, when the acid component is excessively reacted, the terminal tends to be an acid anhydride. -17-201105737 Further, when the diol component is excessively used, the terminal is easily formed. At this time, the terminal hydroxyl group is reacted with a carboxylic acid anhydride to form a hydroxyl group by an acid anhydride. Examples of such a carboxylic acid anhydride include phthalic anhydride, trimellitic acid, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, itaconic anhydride 'tetrahydride' I, 2-cyclohexanedicarboxylic anhydride, 4-methyl- I,2-cyclohexanedicarboxy-4-phenyl-1,2-cyclohexanedicarboxylic anhydride, methyl-5-norbornene-based carboxylic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, double ring [2ene-2,3-dicarboxylic anhydride and the like. In the production of the polyester of the above component (A), the reaction temperature of the acid component and the second component may be 50 to 20 (TC, preferably 80 to 170 ° C. For example, the reaction temperature may be 100 to 140 ° C, the reaction The polyester is obtained at time 2. Further, the reaction temperature at the time of protecting the terminal hydroxyl group with an acid anhydride is selected to be any temperature of ° C, preferably 80 to 17 ° C. The reaction between the above acid component and the diol component is generally in a solvent. The solvent which can be used is not particularly limited as long as it does not contain a functional group such as a hydroxyl group or an amine group and an acid, and examples thereof include N,N-diamine and N,N-dimethylacetamide. N-methyl-2-pyrrolidone, pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl, dimethyl milling, hexamethyl argon, m-cresol, butyrolactone, Cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2-glyoxime propylene glycol acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 2-methoxy group is a hydroxyl-terminated terminal anhydride anhydride hydroquinic acid anhydride, -2,3-di-2.2] octanol component temperature ~ 4 8 /J\ 50~ 200. Reaction methyl N-vinyl urea cyclohexanol monomethyl ketone, propionic acid B · 18 · 201105737 ester, 3-ethoxy propionate ethyl ester, 2-ethoxy propionate ethyl ester, etc. The solvent may be used singly or in combination, but it is more preferably propylene glycol monomethyl ether acetate from the viewpoint of safety and the production line of the color filter coating agent. Further, it may be The solvent of the solvent polyester may be used in combination with the solvent in the range in which the polyester formed by the polymerization reaction does not precipitate. Further, the above-mentioned acid components (formula (i) and formula (i2)) and the diol component ( A catalyst may be used in the reaction of the formula (ii)). Specific examples of the catalyst used in the polymerization of the polyester include, for example, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and chlorine. Benzyltriethylammonium, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetrabromide bromide a quaternary ammonium salt such as ammonium amide, tetrapropylammonium chloride or tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyl chloride 4-phosphorus salt, such as a phosphonium phosphate, a benzyltriphenylphosphonium bromide, an ethyltriphenylphosphoric acid chloride, or an ethyltriphenylphosphonium bromide gun. The polyester solution of the component can be directly used in the preparation of the polyester composition for forming a thermosetting film. Further, the obtained polyester is weak in water, methanol, ethanol, diethyl ether, hexane, or the like. After the solvent is precipitated and recovered, it may be used. <(B) Component> I S1 The epoxy compound having two or more epoxy groups of the component (B) of the present invention, for example, three (2, 3) _Epoxypropyl)trimeric isocyanate, -19- 201105737 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, Gan Alcohol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxy) Propyl)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate An acid ester, a trimethylolethane triglycidyl ether, a bisphenol-A-diglycidyl ether, and a pentaerythritol polyglycidyl ether. Further, a compound of a commercially available product can also be used from the viewpoint of easy availability. Specific examples (trade names) are listed below, but are not limited thereto: epoxy groups having an amine group such as YH-434 and YH434L (manufactured by Tosho Kasei Co., Ltd.); Epolead GT-401, Epolead GT-403 Ερο 1 ead GT-301, Epolead GT-3 02, Celoxide 202 1, Celoxide 3000 (made by Daicel Chemical Industry Co., Ltd.), epoxy resin having a cyclohexene oxide structure; Epikote 1001, Epikote 1 002, Epikote 1 0 0 3, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above, oiled Shell Epoxy (now Japan Epoxy Resin)), etc. ; Epikote 807 (oiled Shell Epoxy (now Japan Epoxy Resin)) and other bisphenol F-type epoxy resin; Epikote 152, Epikotel54 (above, oiled Shell Epoxy (share) (now Japan Epoxy Resin () system)), EPPN 20 1, EPPN 202 (above, Nippon Chemical Co., Ltd.), etc. Phenolic novolac type epoxy resin: EOCN-102, EOCN-103S, EOCN-104S 'EOCN- 1 020, EOCN-1 025, EOCN-1027 (on -20-201105737, Japanese chemical medicine ( )), Epikotel 80S75 (oiled Shell Epoxy (now Japan Epoxy Resin)), etc. between the enamel-type epoxy resin; Denacol EX-252 (Nagase Chemtex) CY 1 75 ' CY 1 77, CY 1 79, Araldite CY-1 82, Araldite CY-192, Araldite CY-184 (above, manufactured by CIBA-GEIGY AG), Epiclon 200, Epiclon 400 (above, Dainippon Ink Chemical Industry) (shares) (current DIC (share)) system, Epikote871, Epikote872 (above, oiled Shell Epoxy (shares) (now Japan Epoxy Resin (share))), ED-566 1, ED-5662 (above, Celanese Epoxy epoxy resin such as Coating Co., Ltd.; Denacol EX-611 ' Denacol EX-612 ' Denacol EX-614 ' Denacol EX-622 ' Denacol EX-411, Denacol EX-512, Denacol EX-522, An aliphatic polyglycidyl ether such as Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-32 1 (manufactured by Nagase Chemtex Co., Ltd.). Further, as the compound having at least two epoxy groups, a polymer having an epoxy group can be used. Such a polymer can be used as long as it has an epoxy group, and is not particularly limited. The above epoxy group-containing polymer can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. As an example, for example, polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate, and styrene and 2-hydroxyethyl group can be mentioned. An addition polymerizable polymer such as a acrylate copolymer or a polycondensation polymer such as an epoxy novolac. -21-201105737 Alternatively, the above epoxy group-containing polymer may be reacted with a compound having a hydroxyl group and a compound having an epoxy group such as epichlorohydrin or glycidyl p-toluenesulfonate. Manufacturing. The weight average molecular weight of such a polymer is, for example, 300 to 200,000. The epoxy compound having at least two epoxy groups may be used singly or in combination of two or more kinds. The content of the epoxy group having two or more epoxy groups of the component (B) in the polyester composition for forming a thermosetting film of the present invention is preferably 3 parts by mass based on the mass of the polyester of the component (a). 50 parts by mass, more preferably 5 to 40 parts by mass, particularly preferably 1 to 30 parts by mass. When the ratio is too small, the solvent resistance and heat resistance of the cured film obtained from the polyester composition for thermosetting film formation are lowered, and when it is too large, the solvent resistance may be lowered or the storage stability may be lowered. (C) Component> The component (C) is an amine group-containing carboxylic acid compound obtained by reacting a diamine compound with a dicarboxylic acid dianhydride. The details are obtained by reacting the diamine compound 1 mol represented by the following formula (iii) with the diacetyl dianhydride represented by the formula (iv) by 1.7 to 2 mol, preferably 1.8 to 2 mol. An amine group-containing carboxylic acid compound.
【化1 4】 H2N—P—NH2 (iii) -22- 201105737 在式(iii )及式(iv) 有機基。 中’ P及Q分別獨立爲2價之 二胺化合物與以式( 下述式(2 )所示之 因此’使以上述式(iii)所示之 i v )所示之二羧酸反應,俾可得到以 化合物。 【化1 5】 Ο Ο HOOC、[Chem. 1 4] H2N-P-NH2 (iii) -22- 201105737 The organic group in formula (iii) and formula (iv). In the case where the 'P and Q are each independently a divalent diamine compound and reacted with a dicarboxylic acid represented by the formula (2) and thus represented by the above formula (iii), 俾Compounds are available. 【化1 5】 Ο Ο HOOC,
Q NH P、Q NH P,
NHNH
Q /C〇〇h (2) 在式(2)中’ P及Q係與前述式(iH)及式(i〇 中之定義同義。 在本發明中’二胺化合物與二羧酸酐係可分別只使用 一種類,亦可使用複數種。因此,本發明之(C)成分的 含有胺基之羧酸化合物係不僅可只使用一種以式(2)所 示的化合物,亦可使用複數種。 前述P及Q係,其中宜爲分別獨立具有環構造之2價 的有機基。此處,環構造可舉例如苯環、脂環、縮合多環 式烴。 式(iii)中,P具有之環構造宜爲苯環、碳原子數 4〜8之脂環、碳原子數7〜16之縮合多環式烴。 因此,具有如此之環構造的二胺化合物之具體例可舉 例如以下者:對苯二胺、間苯二胺、2,4-二胺基甲苯、 2,5-二胺基甲苯、2,6-二胺基甲苯、2,4-二甲基-1,3-二胺基 -23- 201105737 苯、2,5-二甲基-1,4-二胺基苯、2,3,5,6-四甲基-1,4-二胺 基苯、2,4-二胺基酚、2,5-二胺基酚、4,6-二胺基間二甲酚 、2,5-二胺基安息香酸、3,5-二胺基安息香酸、N,N-二烯 丙基-2,4-二胺基苯胺、N,N-二烯丙基-2,5-二胺基苯胺、4-胺基苯甲基胺、3_胺基苯甲基胺、2- ( 4-胺基苯基)乙基 胺、2- ( 3-胺基苯基)乙基胺、1,5-萘二胺、2,7-萘二胺、 4,4’-二胺基聯苯基、3,4’-二胺基聯苯基、3,3’-二胺基聯 苯基、2,2’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲氧基-4,4’-二胺基聯苯基、3,3’-二羥基-4,4’-二胺基聯苯基、3,3’-二羧基-4,4’-二胺基聯苯 基、3,3’-二氟-4,4’-二胺基聯苯基、2,2’-三氟甲基-4,4’-二 胺基聯苯基、3,3’-三氟甲基-4,4’-二胺基聯苯基、4,4’-二 胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二 苯基甲烷' 4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、 3,4’-二胺基二苯基醚、4,4’-二胺基二苯基颯、3,3’-二胺 基二苯基颯、4,4’-二胺基二苯基胺、3,3’-二胺基二苯基胺 、3,4’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺 、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基 二苯基)胺、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮 、3,4’-二胺基二苯甲酮、4,4’-二胺基苯甲醯苯胺、1,2-雙 (4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、4,4’-二胺基二苯乙炔(diaminotolane) 、1,3-雙(4-胺基苯基 )丙烷、I,3·雙(3-胺基苯基)丙烷、2,2-雙(4-胺基苯基 )丙烷、2,2-雙(3-胺基苯基)丙烷、2,2-雙(3-胺基-4- -24- 201105737 甲基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙(3-胺基苯基)六氟丙烷、2,2-雙(3-胺基-4-甲基苯基 )六氟丙烷、1,3-雙(4-胺基苯氧基)丙烷、1,4-雙(4-胺 基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,6-雙 (4-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、 1,8-雙(4-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬 烷、1,10-雙(4-胺基苯氧基)癸烷、1,11-雙(4-胺基苯氧 基)十一碳烷、1,12-雙(4-胺基苯氧基)十二碳烷、雙( 4-胺基苯基)丙烷二酸酯、雙(4-胺基苯基)丁烷二酸酯 、雙(4-胺基苯基)戊烷二酸酯、雙(4-胺基苯基)己烷 二酸酯、雙(4-胺基苯基)庚烷二酸酯、雙(4-胺基苯基 )辛烷二酸酯、雙(4-胺基苯基)壬烷二酸酯、雙(4-胺 基苯基)癸烷二酸酯、1,4-雙(4-胺基苯基)苯、1,3-雙 (4-胺基苯基)苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙( 4_胺基苯氧基)苯、1,4_雙(4_胺基苯甲基)苯、1,3-雙( 4-胺基苯甲基)苯、雙(4-胺基苯基)對酞酸酯、雙(3-胺基苯基)對酞酸酯、雙(4-胺基苯基)異酞酸酯、雙( 3-胺基苯基)異酞酸酯、I,4·苯伸基雙[(4-胺基苯基)甲 酮]、1,4-苯伸基雙[(3-胺基苯基)甲酮]、1,3-苯伸基雙[ (4-胺基苯基)甲酮]、1,3-苯伸基雙[(3-胺基苯基)甲酮 ]、1,4-苯伸基雙(4-胺基苯甲酸酯)、1,4-苯伸基雙(3-胺基苯甲酸酯)、1,3-苯伸基雙(4-胺基苯甲酸酯)、 1,3-苯伸基雙(3-胺基苯甲酸酯)、N,N’- ( 1,4-苯伸基) 雙(4-胺基苯並醯胺)、Ν,Ν’-(1,3-苯伸基)雙(4-胺基 -25- 201105737 苯並醯胺)、N,N’-(1,4·苯伸基)雙(3-胺基苯並 、1^少’-(1,3-苯伸基)雙(3-胺基苯並醯胺)、雙 基苯基)對酞醯胺、雙(3-胺基苯基)對酞醯胺、 胺基苯基)異酞醯胺、雙(3-胺基苯基)異酞醯辟 雙[4- ( 4-胺基苯氧基)苯基]丙烷、2,2-雙[4- ( 4-氧基)苯基]六氟丙烷、4,4’-雙(4_胺基苯氧基) 颯、2,6-二胺吡啶、2,4-二胺吡啶、2,4-二胺基-1,3 、2,6-二胺基二苯並呋喃、2,7-二胺基二苯並呋喃、 胺基二苯並呋喃、2,6-二胺基味唑、2,7-二胺基咔吗 二胺基咔唑、2,4-二胺基-6-異丙基-1,3,5-三嗪、2 4_胺基苯基)-1,3,4-噁二唑、1,4-二胺基環己烷、1 基環己烷、雙(4-胺基環己基)甲烷、雙(4-胺基. 環己基)甲院等。 又,前述式(iv)中,Q具有之環構造宜爲苯 原子數4〜8的脂環、碳原子數7〜16之縮合多環式 佳之Q爲苯環、碳原子數4~8的脂環、碳原子數: 縮合多環式烴。 具有如此之環構造的二羧酸酐之具體例,可舉 酸酐、偏苯三甲酸酐、馬來酸酐、萘酸酐、氫化酞 甲基-5-降冰片烯基_2,3 -二殘酸酐、衣康酸酐、四 酐等。 在上述(C)成分之化合物的製造中,二胺化 二殘酸酐之反應溫度係可選擇5~8(rc、宜1〇〜5〇t 的溫度。 醯胺) (4-胺 雙(4-c ' 2,2-胺基苯 二苯基 ,5 -三嗪 3,6-二 卜 3,6-,5-雙( ,3-二胺 -3-甲基 環、碳 烴。更 7〜16之 例如酞 酸酐、 氫酞酸 合物與 之任意 -26- 201105737 上述反應一般係在溶劑中進行。其時可使用= 要不含有羥基或胺基等、與酸酐反應之官能基者I 無特別限定。可舉例如Ν,Ν-二甲基甲醯胺、N,N-二 醯胺、N-甲基-2-吡咯烷酮、N-乙烯基吡咯烷酮、 己內醯胺、二甲基咪唑、二甲基亞颯、四甲基尿素 基楓、六甲基亞颯、間甲酚、r-丁內酯、環己酮 酮、甲乙酮、甲基異丁基酮、2-庚酮、丙二醇單甲 酸酯、丙二醇丙基醚乙酸酯、3-甲氧基丙酸甲酯、 基丙酸甲酯、3-甲氧基丙酸乙酯、2-甲氧基丙酸乙 乙氧基丙酸乙酯、2-乙氧基丙酸乙酯、甲基溶纖劑 、乙基溶纖劑乙酸酯、甲基溶纖劑、乙基溶纖劑、 纖劑、丙二醇單甲基醚、丙二醇丙基醚、乳酸乙醋 丁酯、環己醇、醋酸乙酯、醋酸丁酯 '乳酸乙酯、 酯等。 此等之溶劑可單獨,亦可混合而使用,但從溶 言,宜爲丙二醇單甲基醚、丙二醇單甲基醚乙酸醋 二甲基乙醯胺、N-甲基-2-吡咯烷酮、二甲基咪唑。 進一步,即使爲不溶解含有胺基之羧酸化合物 ,在藉聚合反應所生成之該化合物不析出的範圍, 合於上述溶劑而使用。 在本發明之熱硬化膜形成用聚酯組成物中的 分之含量係依據(A)成分之聚酯100質量份宜爲 量份,更宜爲5〜40質量份。此比率太小時,由_ 形成用聚酯組成物所得到之硬化膜的配向性會降佔 .溶劑只 I可,並 甲基乙 N-甲基 、二甲 、環戊 基醚乙 2-甲氧 丨酯、3-乙酸酯 丁基溶 、乳酸 乳酸丁 解性而 、N,N- 之溶劑 亦可混 (C )成 3~50 質 I硬化膜 ,,另外 ί. S 1 -27- 201105737 ,太大時係有時透過率降低’或平坦性降低° < (D )成分> 在本發明中(D)成分亦可含有以下述之式(3)所示 的雙馬來醯亞胺化合物。 在(D)成分的雙馬來醯亞胺化合物進一步在提昇平 坦化性中很有效。 【化1 6】Q /C〇〇h (2) In the formula (2), the 'P and Q systems are synonymous with the above formula (iH) and the formula (i〇). In the present invention, the 'diamine compound and the dicarboxylic anhydride system may be Only one type may be used, and a plurality of types may be used. Therefore, the amine group-containing carboxylic acid compound of the component (C) of the present invention may be used alone or in combination with a compound of the formula (2). The P and Q systems are preferably a divalent organic group each having a ring structure independently. Here, the ring structure may, for example, be a benzene ring, an alicyclic ring or a condensed polycyclic hydrocarbon. In the formula (iii), P has The ring structure is preferably a benzene ring, an alicyclic ring having 4 to 8 carbon atoms, or a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms. Therefore, specific examples of the diamine compound having such a ring structure include the following : p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-dimethyl-1,3- Diamino-23- 201105737 Benzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3,5,6-tetramethyl-1,4-diaminobenzene, 2,4 -diaminophenol, 2,5-diaminophenol, 4,6-diaminoxyxylenol, 2,5-Diaminobenzoic acid, 3,5-diaminobenzoic acid, N,N-diallyl-2,4-diaminoaniline, N,N-diallyl-2,5 -diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 2-(3-aminophenyl)ethyl Amine, 1,5-naphthalenediamine, 2,7-naphthalenediamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3' -dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4' -diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3, 4'-Diaminodiphenylmethane '4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, N-methyl (4,4'-di Aminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, 4,4' -diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzimidamide, 1, 2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 4,4'-diaminotolane (diaminotolane), 1,3-double (4-Aminophenyl)propane, I,3·bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-amino group Phenyl)propane, 2,2-bis(3-amino-4--24-201105737 methylphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2- Bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 1,3-bis(4-aminophenoxy)propane , 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexyl Alkane, 1,7-double (4 -aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis ( 4-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, double (4-Aminophenyl)propane diester, bis(4-aminophenyl)butane dicarboxylate, bis(4-aminophenyl)pentane dicarboxylate, bis(4-aminobenzene) Hexanedicarboxylate, bis(4-aminophenyl)heptanedioate, bis(4-aminophenyl)octanedioate, bis(4-aminophenyl)decane Acid ester, bis(4-aminophenyl)decane diester, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1, 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3- Bis(4-aminobenzyl)benzene, bis(4-aminophenyl)p-phthalate, bis(3-aminophenyl)p-phthalate, bis(4-aminophenyl) Phthalate, bis(3-aminophenyl)isodecanoate, I,4·phenylexyl bis[(4-aminophenyl)methanone], 1 4-phenylexyl bis[(3-aminophenyl)methanone], 1,3-phenylexyl bis[(4-aminophenyl)methanone], 1,3-benzeneexyl bis[( 3-aminophenyl)methanone], 1,4-phenylexyl bis(4-aminobenzoate), 1,4-phenylexyl bis(3-aminobenzoate), 1 , 3-phenylexyl bis(4-aminobenzoate), 1,3-phenylexyl bis(3-aminobenzoate), N,N'- (1,4-phenylene) Bis(4-aminobenzophthalamide), hydrazine, Ν'-(1,3-phenylexyl) bis(4-amino-25-201105737 benzoguanamine), N,N'-(1 , 4·Benzene) bis(3-aminobenzo, 1^ less '-(1,3-phenylexyl) bis(3-aminobenzophthalamide), bisphenyl) Amine, bis(3-aminophenyl)-p-amine, aminophenyl)isodecylamine, bis(3-aminophenyl)isoindole [4-(4-aminophenoxy) Phenyl]propane, 2,2-bis[4-(4-oxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)anthracene, 2,6-di Aminopyridine, 2,4-diamine pyridine, 2,4-diamino-1,3,2,6-diaminodibenzofuran, 2,7-diaminodibenzofuran, amine II Benzofuran, 2,6-diamine taste Azole, 2,7-diaminopurine oxime carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2 4-aminophenyl)-1 , 3,4-oxadiazole, 1,4-diaminocyclohexane, 1-cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino.cyclohexyl), etc. . Further, in the above formula (iv), the ring structure of Q is preferably an alicyclic ring having a benzene atom number of 4 to 8, and a condensed polycyclic ring having 7 to 16 carbon atoms. Preferably, Q is a benzene ring and a carbon number is 4-8. Alicyclic ring, number of carbon atoms: Condensed polycyclic hydrocarbon. Specific examples of the dicarboxylic acid anhydride having such a ring structure include an acid anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrazine methyl-5-norbornyl-2,3-diresin anhydride, and clothes. Kang anhydride, tetraanhydride, and the like. In the production of the compound of the above (C) component, the reaction temperature of the diamined di-residual acid anhydride may be selected from 5 to 8 (rc, preferably 1 Torr to 5 Torr). The amine amine (4-amine double (4) -c ' 2,2-aminophenyldiphenyl, 5-triazine 3,6-dibu 3,6-,5-bis(,3-diamine-3-methylcyclo, hydrocarbon). For example, phthalic anhydride, hydroquinone hydride, and any of them -26-201105737 The above reaction is generally carried out in a solvent, and it is possible to use a functional group which does not contain a hydroxyl group or an amine group and reacts with an acid anhydride. There is no particular limitation, and examples thereof include hydrazine, hydrazine-dimethylformamide, N,N-diamine, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, caprolactam, dimethylimidazole. , dimethyl hydrazine, tetramethyl urethanyl maple, hexamethyl hydrazine, m-cresol, r-butyrolactone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, propylene glycol Monoformate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, methyl propyl propionate, ethyl 3-methoxypropionate, ethyl ethoxylate 2-methoxypropionate Ethyl propionate, ethyl 2-ethoxypropionate, methyl cellosolve, ethyl Fibril acetate, methyl cellosolve, ethyl cellosolve, fiber, propylene glycol monomethyl ether, propylene glycol propyl ether, butyl acetate, cyclohexanol, ethyl acetate, butyl acetate Ethyl lactate, ester, etc. These solvents may be used singly or in combination, but from the perspective of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate dimethyl acetamide, N-A Further, even if the carboxylic acid compound containing an amine group is not dissolved, the compound formed by the polymerization reaction does not precipitate, and is used in combination with the above solvent. The content of the polyester composition for forming a thermosetting film is preferably 100 parts by mass or more based on 100 parts by mass of the polyester of the component (A), and is preferably from 5 to 40 parts by mass. The alignment of the cured film obtained by the ester composition will be reduced. The solvent is only I, and methyl ethyl N-methyl, dimethyl, cyclopentyl ether ethyl 2-methoxy decyl ester, 3-acetate butyl solution The solvent of lactic acid lactic acid and N, N- may be mixed (C) into a 3~50 type I hardened film. Further, S 1 -27-201105737, when the ratio is too large, the transmittance is lowered or the flatness is lowered. <(D) component> In the present invention, the component (D) may also contain the following formula (3). The bismaleimide compound shown in the formula. The bismaleimide compound of the component (D) is further effective in improving the planarization property.
式中,Y係選自由脂肪族基、含有環式構造之脂肪族 基及芳香族基所構成之群的有機基或選自其等之群的複數 之有機基的組合所構成之有機基。而且,於Y亦可含有酯 鍵、醚鍵、醯胺鍵、胺基甲酸酯等之結合。 如此之雙馬來醯亞胺化合物,可舉例如N,N’-3,3-二 苯基甲烷雙馬來醯亞胺、N,N’- ( 3,3 -二乙基- 5,5 -二甲基 )-4,4 -二苯基-甲烷雙馬來醯亞胺、n,N’-4,4 -二苯基甲烷 雙馬來醯亞胺、3,3-二苯基碾雙馬來醯亞胺、4,4-二苯基 颯雙馬來醯亞胺、N,N,-對-二苯甲酮雙馬來醯亞胺、n,N,- 二苯乙烷雙馬來醯亞胺、N,N,-二苯基醚雙馬來醯亞胺、 N,N’-(亞甲基二-雙四氫苯基)雙馬來醯亞胺、n,N,-(3- 乙基)-4,4-二苯基甲烷雙馬來醯亞胺、n,N,-( 3,3-二甲基 )-4,4-二苯基甲烷雙馬來醯亞胺、:^1^’-(3,3-二乙基)- -28- 201105737 4.4- 二苯基甲烷雙馬來醯亞胺、N,N’-( 3,3-二氯)-4,4-二 苯基甲烷雙馬來醯亞胺、N,N’-異佛爾酮雙馬來醯亞胺、 N,N,-二甲基對二胺基苯雙馬來醯亞胺、N,N’-二苯基丙烷 雙馬來醯亞胺、N,N’-萘雙馬來醯亞胺、N,N’-間苯伸基雙 馬來醯亞胺、N,N,-5-甲氧基-1,3-苯伸基雙馬來醯亞胺' 2,2-雙(4-(4-馬來醯亞胺苯氧基)苯基)丙烷、2,2_雙( 3- 氯-4- (4-馬來醯亞胺苯氧基)苯基)丙烷、2,2-雙(3-溴-4- (4-馬來醯亞胺苯氧基)苯基)丙烷、2,2-雙(3-乙 基-4- (4-馬來醯亞胺苯氧基)苯基)丙烷、2,2-雙(3-丙 基-4-( 4-馬來醯亞胺苯氧基)苯基)丙烷、2,2-雙(3-異 丙基-4- (4-馬來醯亞胺苯氧基)苯基)丙烷、2,2-雙(3-丁基_4- ( 4_馬來醯亞胺苯氧基)苯基)丙烷、2,2-雙(3-甲氧基-4-(4-馬來醯亞胺苯氧基)苯基)丙烷、丨,1·雙( 4·(4-馬來醯亞胺苯氧基)苯基)乙烷、1,1-雙(3-甲基- 4- (4-馬來醯亞胺苯氧基)苯基)乙院、1,1-雙(3-氯·4-(4-馬來醯亞胺苯氧基)苯基)乙烷、1,1-雙(3-溴-4-( 馬來醯亞胺苯氧基)苯基)乙烷、3,3-雙(4-(4-馬來 醯亞胺苯氧基)戊烷、1,1,1,3,3,3-六氟-2,2-雙(4- ( 4-馬 來醯亞胺苯氧基)苯基)丙烷、1,1,1,3,3,3 -六氟-2,2_雙( 3.5- 二甲基-4- ( 4-馬來醯亞胺苯氧基)苯基)丙烷、 1,1,1,3,3,3 -六氟- 2,2-雙(3,5-二溴-4- ( 4-馬來醯亞胺苯氧 基)苯基)丙烷、N,M,-亞乙基二馬來醯亞胺、Ν,Ν’-六亞 甲基雙馬來醯亞胺、Ν,Ν’-十二亞甲基雙馬來醯亞胺、 Ν,Ν’-間二甲苯伸基雙馬來醯亞胺、ν,Ν,-對二甲苯伸基雙 -29- 201105737 馬來醯亞胺、N,N’-1,3 -雙亞甲基環己烷雙馬來醯亞胺、 比:^_2,4-甲苯伸基雙馬來醯亞胺、:^,:1^-2,6-甲苯伸基雙馬 來醯亞胺。此等之雙馬來醯亞胺化合物並無特別限定於上 述者。此等係可單獨或倂用2種以上之成分。 此等之雙馬來醯亞胺中,宜爲2,2-雙(4- (4·馬來醯 亞胺苯氧基)苯基)丙烷、N,N’-4,4-二苯基甲烷雙馬來酿 亞胺、N,N’-( 3,3·二乙基-5,5-二甲基)-4,4-二苯基-甲院 雙馬來醯亞胺等之芳香族雙馬來醯亞胺。 又,此等之芳香族雙馬來醯亞胺中,爲得到更高的平 坦化性,宜爲分子量1 000以下者。 在本發明中(D)成分之雙馬來醯亞胺化合物的使用 比率宜相對於(A)成分之聚酯1〇〇質量份爲〇.5〜5 0質量 份,更宜爲1〜30質量份,尤宜爲2~2 0質量份。此比率太 小時,由熱硬化膜形成用聚酯組成物所得到之硬化膜的平 坦化性會降低,太大時係有時硬化膜之透過率會降低,或 塗膜粗糙。 <溶劑> 本發明之熱硬化膜形成用聚酯組成物係常在溶解於溶 劑之溶液狀態使用。其時所使用之溶劑係溶解(A )成分〜 (C)成分、依需要之(D)成分、及/或後述之其他添加 劑,若爲具有如此之溶解能之溶劑,其種類及構造等並特 別限定。 如此之溶劑可舉例如使用於(A)成分之聚合的溶劑 •30- 201105737 或下述之溶劑。可舉例如甲基溶纖劑乙酸酯、乙基溶纖劑 乙酸酯、甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、丙二醇 單甲基醚、丙二醇丙基醚、乳酸乙酯、乳酸丁酯、環己醇 、醋酸乙酯、醋酸丁酯等。 此等之溶劑係可一種單獨,或二種以上之組合而使用 <其他之添加劑> 進一步,本發明之熱硬化膜形成用聚酯組成物係只要 無損本發明之效果,可依需要而含有界面活性劑、流變調 整劑、矽烷偶合劑等之接著補助劑、顏料、染料、保存安 定劑、消泡劑、多價酚或多價羧酸等之溶解促進劑、抗氧 化劑等。 抗氧化劑尤宜爲酚類,其具體例可舉例如2,6-二-第 三丁基-4-甲酚、2,6-二-第三丁基-酚、2,4,6-三(3’,5’_ 二 第三丁基-4’-羥基苯甲基)三甲基苯、季戊四醇四[3-( 3’,5’-二第三丁基-4’-羥基苯基)丙酸酯]、丙酮雙(3,5-二 第三丁基-4’-羥基苯基)硫醇、4,4’-亞甲基雙(2,6-二第 三丁基酚)、3-(3,5-二第三丁基-4-羥基苯基)丙酸甲酯 、4,4’-硫二(2,6-二第三丁基酚)、三(3,5-二第三丁基-4-羥基苯甲基)三聚異氰酸 '雙(3,5-二第三丁基_4-羥基 苯甲基)硫醚等。 <熱硬化膜形成用聚酯組成物> -31- 201105737 本發明之熱硬化膜形成用聚酯組成物係含有(A)成 分之聚酯、(B)成分之具有2個以上環氧基之環氧化合 物、(C)成分之含有胺基的羧酸化合物,依希望可含有 (D)成分之雙馬來醯亞胺化合物、進一步含有其他添加 劑之中一種以上的組成物。繼而,常使用來作爲其等溶解 於溶劑之溶液。 其中,本發明之熱硬化膜形成用聚酯組成物的較佳例 ,如以下般。 [1] :依據(A)成分100質量份,含有3〜5 0質量份 之(B )成分、3〜50質量份之(C)成分的熱硬化膜形成 用聚酯組成物。 [2] :依據(A)成分100質量份,含有3~50質量份 之(B )成分、3~5〇質量份之(C)成分、溶劑的熱硬化 膜形成用聚酯組成物。 [3] :依據(A)成分100質量份,含有3〜50質量份 之(B)成分、3 ~5 0質量份之(C)成分、0.5-50質量份 之(D)成分的熱硬化膜形成用聚酯組成物。 [4] :依據(A)成分100質量份,含有3〜50質量份 之(B)成分、3〜5 0質量份之(C)成分、〇_5〜50質量份 之(D)成分、溶劑的熱硬化膜形成用聚酯組成物。 本發明之熱硬化膜形成用聚酯組成物爲溶液形態時之 調配比率、調製方法等詳述於以下。 本發明之熱硬化膜形成用聚酯組成物中的固形分之比 率,只要各成分均一地溶解於溶劑中即可’無特別限定’ -32- 201105737 但爲1〜80質量%,宜爲5~60質量%,更宜爲10 。此處,固形分謂從熱硬化膜形成用聚酯組成衫 除去溶劑者。 本發明之熱硬化膜形成用聚酯組成物的調製 特別限定,但其調製法可舉例如使(A)成分溶 ,於此溶液中以特定的比率混合(B)成分、(( 進而(D)成分,形成均一之溶液的方法,或在 之適當的階段中,依需要而進一步添加其他添加 之方法。 當本發明之熱硬化膜形成用聚酯組成物的調 可直接使用依溶劑中之聚合反應所得到的聚酯溶 ,於此(A)成分之溶液中與前述同樣地置入(Ϊ (C)成分、(D)成分等而形成均一的溶液時, 整作爲目的而進一步追加投入溶劑。此時,於聚 過程所使用的溶劑、與熱硬化膜形成用聚酯組成 時濃度調整所使用之溶劑係可爲相同,亦可爲相 繼而,所調製之熱硬化膜形成用聚酯組成物 宜使用孔徑爲〇.2μιη左右的過濾器等而進行過濾 使用。 <塗膜、硬化膜及液晶配向層> 使本發明之熱硬化膜形成用聚酯組成物於基 矽/二氧化矽被覆基板、氮化矽基板、金屬、例 、鉻等被覆之基板、玻璃基板 '石英基板、IT Ο 〜5 0質量% I之全成分 方法,無 解於溶劑 〕)成分、 此調製法 劑而混合 製時,係 液。此時 Ο成分、 以濃度調 酯之生成 物之調製 異。 的溶液係 後,進行 板(例如 如錕 '鉬 基板等) -33- 201105737 或薄膜(例如三乙醯基纖維素薄膜、聚酯薄膜、丙烯酸薄 膜等之樹脂薄膜)等上,藉由旋轉塗佈、垂流塗佈、輕塗 佈、模縫塗佈、繼模縫之旋轉塗佈、噴墨塗佈、印刷等而 進行塗佈,其後,以加熱板或烘箱等進行預備乾燥(預烘 烤),俾可形成塗膜。其後,藉由加熱處理此塗膜,俾可 形成被膜。 此加熱處理之條件係可採用例如從溫度70°C〜16(TC、 時間0.3〜60分鐘之範圍中適當選擇的加熱溫度及加熱時 間。加熱溫度及加熱時間宜爲80°C〜140°C,0.5〜10分鐘 〇 又,由熱硬化膜形成用聚酯組成物所形成之被膜的膜 厚例如0.1〜3 Ομιη,可考慮所使用之基板的段差或光學性 、電氣性質,適當選擇。 後烘烤一般係可採用由以溫度1 40 °C ~2 5 〇 °C之範圍中 所選擇之加熱溫度,於加熱板上時爲5〜3 0分鐘,烘箱中 時係進行處理30〜90分鐘之方法。 依如上述之條件,藉由使本發明之熱硬化膜形成用聚 酯組成物硬化,俾可使基板之段差充分地平坦化,可形成 具有高透明性之硬化膜。 如此做法所形成之硬.化膜係進行擦磨處理,可發揮作 爲液晶材配向層,亦即使具有液晶性之化合物配向的層功 能。 擦磨處理之條件一般可使用旋轉速度300~1000rpm, 輸送速度3~200mm/秒,押入量之條件。 -34- 201105737 其後,使用純水等而藉超音波洗淨,可除去擦磨所產 生之殘渣。 於如此做法所形成之液晶配向層上,塗佈相位差材料 後,使相位差材料形成液晶狀態而光硬化,可形成具有光 學異方性之層。 相位差材料係可使用例如具有聚合性基之液晶單體或 含有其之組成物等。 繼而,形成液晶配向層之基材爲薄膜時,可用來作爲 光學異方性薄膜。 又,具有如此做法所形成之液晶配向層的2片基板, 介由間隔物而以液晶配向層相向之方式貼合後,於其等之 基板間,注入液晶,而可形成液晶配向之液晶顯示元件。 因此,本發明之熱硬化膜形成用聚酯組成物係可適宜 使用各種光學異方性薄膜、液晶顯示元件。 又,本發明之熱硬化膜形成用聚酯組成物係因具有至 少必需水準之平坦化性,故亦可用來作爲形成薄膜電晶體 (TFT )型液晶顯示元件、有機EL元件等之各種顯示器 中的保護膜、平坦化膜、絕緣膜等之硬化膜的材料,尤其 ,亦適宜作爲形成彩色濾光片之被覆層材、TFT型液晶元 件之層間絕緣膜、有機EL元件的絕緣膜等之材料》 【實施方式】 [實施例] 以下’舉出實施例而更詳細說明本發明,但本發明不 -35- 201105737 限定於此等實施例。 [於實施例所使用之簡稱] 於以下之實施例所使用之簡稱的意義如以下般。 <聚酯原料> HBPDA: 3,3,-4,4’-雙環己基四羧酸二酐 BPDA :聯苯基四羧酸二酐 BPADA: 4,4’-(4,4’-異亞丙基二苯氧基)雙酞酸酐In the formula, Y is an organic group selected from the group consisting of an aliphatic group, an organic group containing a group of an aliphatic group and an aromatic group having a cyclic structure, or a combination of a plurality of organic groups selected from the group. Further, Y may also contain a combination of an ester bond, an ether bond, a guanamine bond, a urethane or the like. Such a bismaleimide compound may, for example, be N,N'-3,3-diphenylmethane bismaleimide, N,N'-(3,3-diethyl-5,5 -Dimethyl)-4,4-diphenyl-methane bismaleimide, n,N'-4,4-diphenylmethane bismaleimide, 3,3-diphenyl mill Bismaleimide, 4,4-diphenylfluorene, bismaleimide, N,N,-p-benzophenone, bismaleimide, n,N,-diphenylethane Maleic imine, N,N,-diphenyl ether bismaleimide, N,N'-(methylenebis-bistetrahydrophenyl) bismaleimide, n,N, -(3-ethyl)-4,4-diphenylmethane bismaleimide, n,N,-(3,3-dimethyl)-4,4-diphenylmethane bismale Imine, :^1^'-(3,3-diethyl)- -28- 201105737 4.4- Diphenylmethane bismaleimide, N,N'-(3,3-dichloro)- 4,4-diphenylmethane bismaleimide, N,N'-isophorone bismaleimide, N,N,-dimethyl-p-diaminobenzoicinide , N,N'-diphenylpropane, bismaleimide, N,N'-naphthalene, bismaleimide, N,N'-m-phenylexene, Bismale Amine, N,N,-5-methoxy-1,3-benzene-extended bismaleimide '2,2-bis(4-(4-maleimidophenoxy)phenyl) Propane, 2,2-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-bromo-4-(4-mala) Amine phenoxy)phenyl)propane, 2,2-bis(3-ethyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-propyl -4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-isopropyl-4-(4-maleimidophenoxy)phenyl)propane , 2,2-bis(3-butyl_4-(4_maleimide phenoxy)phenyl)propane, 2,2-bis(3-methoxy-4-(4-male)醯iminophenoxy)phenyl)propane, anthracene, 1·bis(4·(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-methyl- 4 - (4-maleimide phenoxy)phenyl) phenyl, 1,1-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)ethane, 1 , 1-bis(3-bromo-4-(maleimidophenoxy)phenyl)ethane, 3,3-bis(4-(4-maleimidophenoxy)pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-(4-maleimide) Oxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3.5-dimethyl-4-(4-maleimidophenoxy)benzene Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dibromo-4-(4-maleimidophenoxy)phenyl)propane , N,M,-Ethylene dimaleimide, anthracene, Ν'-hexamethylene bismaleimide, anthracene, Ν'-docamethylene bis-maleimide, hydrazine ,Ν'-m-xylene-extension, bismaleimide, ν, Ν,-p-xylene, bis--29-201105737, maleimine, N, N'-1,3-bismethylene Cyclohexane Bismaleimide, ratio: ^ 2,4-toluene extended bismaleimide, :^,:1^-2,6-toluene extended bismaleimide. These bismaleimide compounds are not particularly limited to those described above. These may be used alone or in combination of two or more components. Among these bismaleimides, 2,2-bis(4-(4·maleimidephenoxy)phenyl)propane, N,N'-4,4-diphenyl is preferred. Aroma of methane bismaleimide, N,N'-(3,3·diethyl-5,5-dimethyl)-4,4-diphenyl-methyl sulphate The family is a double horse. Further, in such aromatic bismaleimine, in order to obtain higher flatness, it is preferably one having a molecular weight of 1,000 or less. In the present invention, the use ratio of the bismaleimide compound of the component (D) is preferably from 0.5 to 50 parts by mass, more preferably from 1 to 30, per part by mass of the polyester of the component (A). The mass part is particularly preferably 2 to 20 parts by mass. When the ratio is too small, the flatness of the cured film obtained from the polyester composition for forming a thermosetting film is lowered, and when it is too large, the transmittance of the cured film may be lowered or the coating film may be rough. <Solvent> The polyester composition for forming a thermosetting film of the present invention is usually used in the form of a solution dissolved in a solvent. The solvent used at this time dissolves the components (A) to (C), the component (D), and/or other additives described later, and is a solvent having such a solubility, and the type and structure thereof. Specially limited. Such a solvent may, for example, be a solvent used for the polymerization of the component (A), 30-201105737 or a solvent described below. For example, methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, lactate B Ester, butyl lactate, cyclohexanol, ethyl acetate, butyl acetate, and the like. These solvents may be used alone or in combination of two or more. <Other additives> Further, the polyester composition for forming a thermosetting film of the present invention may be used as needed as long as the effects of the present invention are not impaired. A solution accelerator, a pigment, a dye, a storage stabilizer, an antifoaming agent, a dissolution promoter such as a polyvalent phenol or a polyvalent carboxylic acid, an antioxidant, and the like are contained in a surfactant, a rheology modifier, a decane coupling agent, or the like. The antioxidant is particularly preferably a phenol, and specific examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-phenol, and 2,4,6-three. (3',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene, pentaerythritol tetra[3-(3',5'-di-t-butyl-4'-hydroxyphenyl) Propionate], acetone bis(3,5-di-t-butyl-4'-hydroxyphenyl)thiol, 4,4'-methylenebis(2,6-di-t-butylphenol) , methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, 4,4'-thiobis(2,6-di-t-butylphenol), three (3,5) -Di-tert-butyl-4-hydroxybenzyl)trimeric isocyanate bis(3,5-di-t-butyl-4-cyclobenzyl) sulfide. <Polyester composition for forming a thermosetting film> -31-201105737 The polyester composition for forming a thermosetting film of the present invention contains the polyester of the component (A) and the component (B) having two or more epoxy resins. The epoxy group-containing compound and the amine group-containing carboxylic acid compound of the component (C) may contain one or more of the other compounds, and may further contain the bismaleimide compound of the component (D). Then, it is often used as a solution in which it is dissolved in a solvent. Among them, preferred examples of the polyester composition for forming a thermosetting film of the present invention are as follows. [1] A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 3 to 50 parts by mass of the component (C), based on 100 parts by mass of the component (A). [2] A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B), 3 to 5 parts by mass of the component (C), and a solvent, based on 100 parts by mass of the component (A). [3]: According to 100 parts by mass of the component (A), it contains 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), and 0.5 to 50 parts by mass of the component (D). A polyester composition for film formation. [4]: According to 100 parts by mass of the component (A), it contains 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), and 〇5 to 50 parts by mass of the component (D). A polyester composition for forming a thermosetting film of a solvent. The blending ratio, the preparation method, and the like in the case where the polyester composition for forming a thermosetting film of the present invention is in the form of a solution are described in detail below. The ratio of the solid content in the polyester composition for forming a thermosetting film of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent - 32-201105737 but 1 to 80% by mass, preferably 5 ~60% by mass, more preferably 10%. Here, the solid form is a person who removes a solvent from a polyester formed of a thermosetting film. The preparation of the polyester composition for forming a thermosetting film of the present invention is particularly limited. However, the preparation method may be, for example, dissolving the component (A), and mixing the component (B) at a specific ratio in the solution, ((further (D) a component, a method of forming a uniform solution, or a further addition method as needed in an appropriate stage. When the polyester composition for forming a thermosetting film of the present invention is adjusted, it can be directly used in a solvent. When the polyester obtained by the polymerization reaction is dissolved in the solution of the component (A) in the same manner as described above, the Ϊ (C) component, the component (D), and the like are formed to form a uniform solution, and further added for the purpose. In this case, the solvent used in the polymerization process and the solvent used for the concentration adjustment of the polyester for forming a thermosetting film may be the same, or may be a polyester for forming a thermosetting film which is prepared in succession. The composition is preferably filtered using a filter having a pore diameter of about 2 μm or the like. <Coating film, cured film, and liquid crystal alignment layer> The polyester composition for forming a thermosetting film of the present invention is based on a base/two oxygen矽 coated substrate, tantalum nitride substrate, metal, example, coated substrate such as chrome, glass substrate 'quartz substrate, total composition of IT 〜 ~50% by mass I, no solvent solution), this preparation agent In the case of mixing, the liquid is liquid. At this time, the composition of the bismuth component and the product of the concentration-adjusting ester are different, and then the plate is used (for example, a 锟' molybdenum substrate, etc.) -33-201105737 or a film (for example, three-ethyl A spin coating, a vertical coating, a light coating, a die coating, a spin coating of a die slit, an inkjet, etc., a resin film such as a mercapto cellulose film, a polyester film, or an acrylic film) Coating is carried out by coating, printing, etc., and then pre-drying (prebaking) is performed by a hot plate or an oven, etc., and a coating film can be formed by 俾. Then, this coating film is heat-processed, and a film can be formed by 俾. The heat treatment conditions may be, for example, a heating temperature and a heating time appropriately selected from a temperature of 70 ° C to 16 (TC, time 0.3 to 60 minutes. The heating temperature and heating time are preferably 80 ° C to 140 ° C. , 0.5~10 minutes 〇 again, by hot hard The film thickness of the film formed of the polyester composition for film formation is, for example, 0.1 to 3 μm, which can be appropriately selected in consideration of the step difference, optical properties, and electrical properties of the substrate to be used. Post-baking is generally performed by a temperature of 40 The heating temperature selected in the range of °C ~ 2 5 〇 °C is 5 to 30 minutes on the hot plate, and the method is carried out in the oven for 30 to 90 minutes. When the polyester composition for forming a thermosetting film of the present invention is cured, the step of the substrate can be sufficiently flattened to form a cured film having high transparency. The hardened film formed by the method is subjected to rubbing treatment. It can exhibit a layer function as a liquid crystal material alignment layer and even a liquid crystal compound. The conditions of the rubbing treatment can generally be as follows: a rotation speed of 300 to 1000 rpm, a conveying speed of 3 to 200 mm/sec, and a pushing amount. -34- 201105737 Thereafter, it is washed with ultrasonic waves using pure water or the like to remove the residue generated by the rubbing. After coating the phase difference material on the liquid crystal alignment layer formed in this manner, the phase difference material is formed into a liquid crystal state and photohardened, whereby a layer having optical anisotropy can be formed. As the phase difference material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the same can be used. Then, when the substrate on which the liquid crystal alignment layer is formed is a film, it can be used as an optical anisotropic film. Further, the two substrates having the liquid crystal alignment layer formed in this manner are bonded to each other via a spacer and the liquid crystal alignment layer is opposed to each other, and then liquid crystal is injected between the substrates to form a liquid crystal alignment liquid crystal display. element. Therefore, various polyester anisotropic films and liquid crystal display elements can be suitably used as the polyester composition for forming a thermosetting film of the present invention. Further, since the polyester composition for forming a thermosetting film of the present invention has at least an indispensable level of flatness, it can be used as various types of displays for forming a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and the like. The material of the cured film such as a protective film, a flattening film, or an insulating film is particularly suitable as a material for forming a coating layer of a color filter, an interlayer insulating film of a TFT-type liquid crystal element, or an insulating film of an organic EL element. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. [Abbreviation used in the examples] The meanings of the abbreviations used in the following examples are as follows. <Polyester raw material> HBPDA: 3,3,-4,4'-dicyclohexyltetracarboxylic dianhydride BPDA: biphenyltetracarboxylic dianhydride BPADA: 4,4'-(4,4'-iso Propylenediphenoxy)bisphthalic anhydride
HBPA :氫化雙酚A THPA : 1,2,5,6-四氫酞酸酐 <聚酯聚合觸媒> BTEAC :氯化苯甲基三乙銨 <含有胺基之羧酸化合物原料> DA-4P : 1,3-雙(4-胺基苯基)苯 DA-1M : 4,4’-雙(4-胺基苯氧基)二苯基颯 TA :偏苯三甲酸酐 DDM: 4,4’-二胺基二苯基甲烷 <聚醯亞胺前驅體原料> CBDA :環己烷四羧酸二酐 PDA :對苯二胺 -36- 201105737 <丙烯酸共聚合物原料> MAA :甲基丙烯酸 MMA :甲基丙烯酸甲酯 HEMA: 2-羥基乙基甲基丙烯酸酯 CHMI : N-環己基馬來醯亞胺 AIBN :偶氮雙異丁腈 <環氧化合物> CEL: Dai cel 化學工業(股(製 Celoxide P-2021 ( 製品名)(化合物名:3,4-環氧基環己烯基甲基-3,,4’-環 氧基環己烯羧酸酯) <雙馬來醯亞胺化合物〉 BM11: N,N’-(3,3-二乙基- 5,5-二甲基)-4,4-二苯基-甲烷雙馬來醯亞胺 <溶劑> PGMEA:丙二醇單甲基醚乙酸酯 PGME :丙二醇單甲基醚 DMAc: Ν,Ν -二甲基乙醯胺 ΝΜΡ: Ν -甲基-2-吡咯烷酮 依以下之合成例’所得到之聚酯、聚醯亞胺前驅體及 丙烯酸共聚物之數目平均分子量及重量平均分子量係使用 L S } -37- 201105737 日本分光(股)製GPC裝置(Shodex (註冊商標)管柱 KF803 L及KF804L),以使溶出溶劑四氫呋喃流量lml/分 於管柱中(管柱溫度4〇°C )流動而溶離之條件進行測定。 又’下述之數目平均分子量(以下稱爲Μη)及重量平均 分子量(以下,稱爲Mw)以聚苯乙烯換算値表示。 <合成例1 > 藉由使 HBPDA 18.Og' BP DA 4.54g' ΗΒΡΑ 15.9g' THPA 2.01g、BTEAC 0.19g 在 PGMEA 95.1g 中以 120 °C 反 應19小時,俾可得到聚酯溶液(固形分濃度:30.0質量 % ) (P1)。所得到之聚酯的Μη爲1510,Mw爲3570。 <合成例2 > 藉由使 HBPDA 12.0g、HBPA 10.2g、THPA 0.95g、 BTEAC 0.22g 在 PGMEA 54.8g 中以 120°C 反應 19 小時, 俾可得到聚酯溶液(固形分濃度:30.0質量%) ( P2)。 所得到之聚酯的Μη爲2820,Mw爲4200。 <合成例3 > 藉由使 HBPDA 18.0g、BPADA 7.37g、HBPA 17.0g、 THPA 2.15g、BTEAC 0.10g 在 PGMEA l〇4.2g 中以 120°C 反應1 9小時,俾可得到聚酯溶液(固形分濃度:3 0.0質 量% ) ( P3 )。所得到之聚酯的Μη爲1640,Mw爲3480 -38- 201105737 <合成例4 > 藉由使 DA-4P 10.23g(〇.〇35mol)、THPA 10.64g( 0.070mol)在PGME 48.71g中以23°C反應24小時’俾可 得到含有胺基的羧酸化合物溶液(固形分濃度:3 〇 · 〇質量 % ) ( A 1 )。 <合成例5 > 藉由使 DA-1M 15.14g ( 0.03 5mol) 、THPA l〇-64g ( 0.070mol)在PGME 60.15g中以23°C反應24小時’俾可 得到含有胺基的羧酸化合物溶液(固形分濃度:3〇.0質® % ) ( A 2 )。 <合成例6 > 藉由使 DA-4P 10.23g ( 0.03 5mol ) 、ΤΑ 13.45g ( 0.070mol)在PGME 55.25g中以23°C反應24小時,俾可 得到含有胺基的羧酸化合物溶液(固形分濃度:3 Ο · 0質量 % ) (A3)。 <合成例7 > 藉由使 DDM 6.94g ( 0.035mol ) 、ΤΑ 13.45g ( 0.070mol)在PGME 40.78g中以23°C反應24小時,俾可 得到含有胺基的羧酸化合物溶液(固形分濃度:30.0質量 % ) ( A4 )。 -39- 201105737 <合成例8 > 藉由使 CBDA l7.7g、pDA 10.2g 在 NMP 66.4g 中以 2 3 °C反應24小時,俾可得到聚醯亞胺前驅體溶液(固形 分濃度:30.0質量。/。)( P4)。所得到之聚醯亞胺前驅體 的 Μη 爲 5800,Mw 爲 1 2 5 00。 <合成例9 > 使用 MAA 1 〇.9g、CHMI 3 5.3g、HEMA 25.5g、MMA 28.3g作爲單體成分,使用AIBN 5g作爲自由基聚合起始 劑,使此等在溶劑PGMEA 150g中以溫度 60°C〜100°C聚 合反應,俾可得到丙烯酸共聚物溶液(固形分濃度:40.0 質量%) ( P5 )。所得到之丙烯酸共聚物溶液的Μη爲 3 800,Mw 爲 6700。 <實施例1〜實施例9及比較例1〜比較例3 > 以表1所示之組成調製實施例1 ~實施例9及比較例 1 ~比較例3之各組成物,對於各別進行平坦化性、耐溶劑 性、透過率及配向性之評估。 -40- 201105737HBPA: hydrogenated bisphenol A THPA : 1,2,5,6-tetrahydrophthalic anhydride <polyester polymerization catalyst> BTEAC : benzyltriethylammonium chloride <amino acid-containing carboxylic acid compound raw material > DA-4P : 1,3-bis(4-aminophenyl)benzene DA-1M : 4,4'-bis(4-aminophenoxy)diphenylphosphonium TA: trimellitic anhydride DDM: 4,4'-Diaminodiphenylmethane<Polyimide precursor raw material> CBDA: Cyclohexanetetracarboxylic dianhydride PDA: p-phenylenediamine-36- 201105737 <Acrylic copolymer raw material > MAA: Methacrylic acid MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide AIBN: azobisisobutyronitrile <epoxy compound> CEL: Dai cel Chemical Industry (Celoxide P-2021 (product name) (Compound name: 3,4-epoxycyclohexenylmethyl-3,, 4'-epoxycyclohexene carboxylate Acid ester) <Bismaleimide compound> BM11: N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismale醯imine <solvent> PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether DMAc: Ν, Ν - II The number average molecular weight and weight average molecular weight of the polyester, the polyimide precursor and the acrylic copolymer obtained by the following synthesis example ' Ν 甲基 -methyl-2-pyrrolidone are LS } -37 - 201105737 GSP unit (Shodex (registered trademark) column KF803 L and KF804L) manufactured by Japan Separation Co., Ltd., so that the elution solvent tetrahydrofuran flow rate lml/min flows in the column (column temperature 4〇 °C) and dissolves Further, the following numerical average molecular weight (hereinafter referred to as Μη) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene 値. <Synthesis Example 1 > By making HBPDA 18. Og' BP DA 4.54g' ΗΒΡΑ 15.9g' THPA 2.01g, BTEAC 0.19g In PGMEA 95.1g, the reaction was carried out at 120 °C for 19 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P1). The obtained polyester had a Μη of 1510 and a Mw of 3570. <Synthesis Example 2 > By reacting HBPDA 12.0 g, HBPA 10.2 g, THPA 0.95 g, BTEAC 0.22 g in PGMEA 54.8 g at 120 ° C 19 Hours, 俾 can get polyester solution (solid content concentration: 30.0 Quality %) ( P2). The obtained polyester had a Tn of 2820 and a Mw of 4,200. <Synthesis Example 3 > Polyester was obtained by reacting HBPDA 18.0 g, BPADA 7.37 g, HBPA 17.0 g, THPA 2.15 g, and BTEAC 0.10 g in PGMEA 104 g at 120 ° C for 19 hours. Solution (solid content concentration: 3 0.0% by mass) (P3). The obtained polyester had a Tn of 1640 and Mw of 3480 - 38 to 201105737 < Synthesis Example 4 > By making DA-4P 10.23 g (〇.〇35 mol), THPA 10.64 g (0.070 mol) in PGME 48.71 g The reaction was carried out at 23 ° C for 24 hours to obtain a solution of a carboxylic acid compound containing an amine group (solid content concentration: 3 〇·〇% by mass) (A 1 ). <Synthesis Example 5 > An amine group-containing carboxy group was obtained by reacting DA-1M 15.14 g (0.03 5 mol) and THPA l〇-64 g (0.070 mol) in PGME 60.15 g at 23 ° C for 24 hours. Acid compound solution (solids concentration: 3〇.0 mass%) (A 2 ). <Synthesis Example 6 > By reacting DA-4P 10.23 g (0.03 5 mol ) and iridium 13.45 g (0.070 mol) in PGME 55.25 g at 23 ° C for 24 hours, an amide group-containing carboxylic acid compound was obtained. Solution (solid content concentration: 3 Ο · 0 mass%) (A3). <Synthesis Example 7 > By reacting DDM 6.94 g (0.035 mol) and cesium 13.45 g (0.070 mol) in PGME 40.78 g at 23 ° C for 24 hours, a carboxylic acid compound solution containing an amine group was obtained. Solid content concentration: 30.0% by mass) (A4). -39-201105737 <Synthesis Example 8 > By reacting CBDA 17.7 g and pDA 10.2 g in NMP 66.4 g at 23 ° C for 24 hours, a polyimine precursor solution (solid concentration) was obtained. : 30.0 mass. /.) (P4). The obtained polybendimimine precursor had a Μη of 5,800 and a Mw of 1 2 5 00. <Synthesis Example 9 > MAA 1 〇.9 g, CHMI 3 5.3 g, HEMA 25.5 g, MMA 28.3 g were used as a monomer component, and AIBN 5 g was used as a radical polymerization initiator, and these were used in a solvent PGMEA 150 g. The polymerization was carried out at a temperature of from 60 ° C to 100 ° C to obtain an acrylic copolymer solution (solid content concentration: 40.0% by mass) (P5). The obtained acrylic copolymer solution had a Tn of 3 800 and a Mw of 6,700. <Example 1 to Example 9 and Comparative Example 1 to Comparative Example 3 > The compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 1, for each Evaluation of planarization, solvent resistance, transmittance, and alignment. -40- 201105737
(Α)成分* 之溶液(g) (B)成分 (g) (C)成分 (g) (D)成分 (g) 溶劑 (g) 實施例1 P1 20 CEL 1. 2 A1 2. 0 - PGME 8* 0 實施例2 P1 20 CEL 1. 2 A1 4. 0 — PGME 8. 4 實施例3 P1 20 CEL 1· 2 A1 8. 0 一 PGME 9. 2 實施例4 P1 20 CEL 1. 2 A2 3. 0 BMI1 0. 6 PGME 10. 0 實施例5 P1 20 CEL 1. 2 A2 3. 0 — PGME 8. 2 實施例6 P1 20 CEL 1. 2 A3 3. 0 — PGME 8. 2 實施例7 P1 20 CEL 1. 2 A4 3. 0 BMI1 0. 6 PGME 10. 0 實施例8 P2 20 CEL 1. 2 A2 3. 0 BMT1 0. 6 PGME 10. 0 實施例9 比較例1 P3 20 P1 20 CEL 1. 2 A2 3. 0 BMI1 0. 6 PGME 10. 0 — - PGMEA 2. 22 比較例2 P4 20 CEL 1. 2 - NMP 2. 97 比較例3 P5 20 CEL 1. 2 一 PGMEA 2. 80 ※P1〜P 3:聚酯溶液、P4:聚醯亞胺前驅體溶液、P5:丙 烯酸共聚合物溶液 [平坦化性之評估] 使實施例1 ~實施例9及比較例1〜比較例3之各組成 物於高〇 · 5 μ m、線寬10 μ m、線間距5 0 μ m之段差基板(玻 璃製)上使用旋塗器而塗佈後,以溫度100 °C在加熱板上 進行預烘烤1 2 0秒鐘,形成膜厚2.8 μπι之塗膜。膜厚係使 用 FILMETRICS公司製F20而測定。藉由此塗膜以溫度 23 0 °C加熱30分鐘俾進行後烘烤,形成膜厚2.5 μπι之硬化 -41- 201105737 膜》 測定段差基板生產線上之塗膜與間隙上之塗膜的膜厚 差(參照圖1)、平坦化率(DOP) =100x[l-{塗膜之膜厚 差(μιη) /段差基板之高度(0·5μιη) }]的式而求出平坦化 率〇 [耐溶劑性之評估] 使實施例1〜實施例9及比較例1〜比較例3之各組成 物於矽晶圓上使用旋塗器而塗佈後,以溫度1 00 °C在加熱 板上進行預烘烤120秒鐘,形成膜厚2.8μηι之塗膜。膜厚 係使用FILMETRICS公司製F20而測定。藉由此塗膜以溫 度23 0°C於加熱板上進行後烘烤30分鐘,形成膜厚2.5μπι 之硬化膜。 將此硬化膜浸漬於PGMEA或ΝΜΡ中60秒後,分別 以溫度l〇〇°C乾燥60秒鐘,測定膜厚。以PGMEA或ΝΜΡ 浸漬後無膜厚變化者作爲〇,於浸漬後可看到膜厚的減少 者作爲X。 [光透過率(透明性)之評估] 使實施例1~實施例9及比較例卜比較例3之各組成 物於石英基板上使用旋塗器而塗佈後,以溫度1〇〇 °C在加 熱板上進行預烘烤12〇秒鐘,形成膜厚2.8 μιη之塗膜。膜 厚係使用FILMETRICS公司製F20而測定。藉由此塗膜以 溫度23〇t於加熱板上進行後烘烤30分鐘,形成硬化膜。 •42- 201105737 此硬化膜使用紫外線可見光分光光度計( 作製SHIMADSU UV-2550型號)而測定波長 透過率。 [配向性之評估] 使實施例1〜實施例9及比較例1〜比較例 物於ITO基板上使用旋塗器而塗佈後,以溫度 熱板上進行預烘烤120秒鐘,形成膜厚2.8μιη 厚係使用FILMETRICS公司製F20而測定。藉 度23 0°C於加熱板上進行後烘烤30分鐘,形成 使此硬化膜以旋轉速度300rpm、輸送速度 押入量0.45mm進行擦磨處理。使所擦磨處理 水超音波洗淨5分鐘。於此基板上使由液晶單 相位差材料使用旋塗器而塗佈後,以1 〇〇 °C 40 秒鐘在加熱板上進行預烘烤,形成膜厚1 . 1 μιη 此基板以氮環境下以20〇〇mJ曝光。將所製作 於偏向板,以目視確認配向性。若使基板傾斜 不傾斜時,光之透過性明顯變化者作爲〇,不 [耐熱性之評估](Α) Component* Solution (g) (B) Component (g) (C) Component (g) (D) Component (g) Solvent (g) Example 1 P1 20 CEL 1. 2 A1 2. 0 - PGME 8* 0 Example 2 P1 20 CEL 1. 2 A1 4. 0 — PGME 8. 4 Example 3 P1 20 CEL 1· 2 A1 8. 0 One PGME 9. 2 Example 4 P1 20 CEL 1. 2 A2 3 0 BMI1 0. 6 PGME 10. 0 Example 5 P1 20 CEL 1. 2 A2 3. 0 — PGME 8. 2 Example 6 P1 20 CEL 1. 2 A3 3. 0 — PGME 8. 2 Example 7 P1 20 CEL 1. 2 A4 3. 0 BMI1 0. 6 PGME 10. 0 Example 8 P2 20 CEL 1. 2 A2 3. 0 BMT1 0. 6 PGME 10. 0 Example 9 Comparative Example 1 P3 20 P1 20 CEL 1 2 A2 3. 0 BMI1 0. 6 PGME 10. 0 — - PGMEA 2. 22 Comparative Example 2 P4 20 CEL 1. 2 - NMP 2. 97 Comparative Example 3 P5 20 CEL 1. 2 A PGMEA 2. 80 ※P1 ~P 3 : Polyester solution, P4: Polyimine precursor solution, P5: Acrylic copolymer solution [Evaluation of planarization property] Each of Examples 1 to 9 and Comparative Examples 1 to 3 was subjected to The composition was coated on a stepped substrate (glass made of sorghum 5 μm, line width 10 μm, line pitch 50 μm) using a spin coater, and then heated at a temperature of 100 ° C on a hot plate. Prebaking was performed for 120 seconds to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The film is heated at a temperature of 23 ° C for 30 minutes, and then post-baked to form a film thickness of 2.5 μm. -41-201105737 Membrane. The film thickness of the coating film on the step substrate production line and the gap is measured. The flatness (〇1), the flattening ratio (DOP) =100x [l-{film thickness difference (μιη) / the height of the step substrate (0·5μιη) }], and the flattening rate 〇[ Evaluation of Solvent Resistance] Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was coated on a tantalum wafer using a spin coater, and then placed on a hot plate at a temperature of 100 ° C. Prebaking was carried out for 120 seconds to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked on a hot plate at a temperature of 23 ° C for 30 minutes by this coating film to form a cured film having a film thickness of 2.5 μm. The cured film was immersed in PGMEA or mash for 60 seconds, and then dried at a temperature of 10 ° C for 60 seconds, and the film thickness was measured. When PGMEA or yttrium was used, the film thickness was not changed, and the film thickness was reduced as X. [Evaluation of Light Transmittance (Transparency)] The respective compositions of Examples 1 to 9 and Comparative Example 3 were coated on a quartz substrate using a spin coater at a temperature of 1 ° C. Prebaking was performed on a hot plate for 12 sec to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The resulting film was post-baked on a hot plate at a temperature of 23 Torr for 30 minutes to form a cured film. • 42- 201105737 This cured film was measured for wavelength transmittance using an ultraviolet-visible spectrophotometer (manufactured by SHIMADSU UV-2550). [Evaluation of Orientation] The coatings of Examples 1 to 9 and Comparative Examples 1 to 1 were applied onto an ITO substrate using a spin coater, and then prebaked on a hot plate for 120 seconds to form a film. The thickness of 2.8 μm was measured using F20 manufactured by FILMETRICS. The post-baking was carried out on a hot plate at 23 ° C for 30 minutes to form a rubbing treatment at a rotational speed of 300 rpm and a transport speed of 0.45 mm. Wash the scrubbed water for 5 minutes. On the substrate, the liquid crystal single phase difference material is coated with a spin coater, and then prebaked on a hot plate at 1 〇〇 ° C for 40 seconds to form a film thickness of 1.1 μm. Exposure at 20 〇〇 mJ in the environment. The alignment plate was prepared to visually confirm the alignment. If the substrate is tilted without tilting, the light transmittance is significantly changed as a defect, and [heat resistance evaluation]
使實施例1~實施例9及比較例1〜比較例 物於石英基板上使用旋塗器而塗佈後,以溫度 熱板上進行預烘烤12〇秒鐘後,以溫度230°C (股)島津製 400nm時之 3之各組成 1 〇 0 °C在加 之塗膜。膜 由此膜以溫 硬化膜。 1 0 m m / 秒, 之基板以純 體所構成之 秒、55 °C 3 0 之塗膜。使 之基板挾住 45度時, 變化者作爲 3之各組成 l〇〇°C在加 在加熱板上 -43- 201105737 進行後烘烤 30分鐘,形成硬化膜,膜厚係使用 FILMETRICS公司製F20而測定。其後進一步使硬化膜於 溫度230°C在加熱板上燒成60分鐘,再度測定膜厚,算出 從後烘烤之膜厚的變化率。又,可看出具有耐熱性之硬化 膜,期望至少具有膜厚變化率±5 %以下之性能者。 [評估之結果] 將以上評估的結果,表示於如下之表2中。 [表2] 平坦化率 耐溶劑性 配向性 耐熱性 透過率 (%) PGMEA NMP (%) (%) 實施例1 82 〇 〇 〇 一 2 93 實施例2 80 〇 〇 〇 -2 91 實施例3 76 〇 〇 〇 -3 90 實施例4 85 〇 〇 〇 -2 1 96 實施例5 83 〇 〇 〇 -1 96 實施例6 80 〇 〇 〇 一 2 90 實施例7 81 〇 〇 〇 -2 92 實施例8 80 〇 〇 〇 -1 98 實施例9 88 〇 〇 〇 -1 94 比較例1 一 X X - — — 比較例2 25 〇 〇 〇 一 3 85 比較例3 88 〇 〇 X -0· 5 96 實施例1〜實施例9係平坦化率、耐熱性高’對於 PGMEA ' NMP之任一者均可看到耐性。又,任—者均顯 示良好的配向性,高溫燒成後亦達成高的透過率(透明性 -44- 201105737 另外,比較例1未形成硬化膜。 又,比較例2係耐溶劑性、耐熱性及配向性良好,但 成爲平坦化率非常低之結果。 繼而比較例3係平坦化率、耐熱性、耐溶劑性及透過 率係可得到良好之結果,但成爲配向性差之結果。 如以上般,本發明之熱硬化膜形成用聚酯組成物係硬 化膜形成時可使用丙二醇單基醚乙酸酯等之甘醇系溶劑, 而且所得到之硬化膜係優異之光透過性、耐溶劑性、耐熱 性、平坦化性及配向性之任一者的性能亦可得到良好的結 果。 [產業上之利用可能性] 本發明之熱硬化膜形成用聚酯組成物係非常可用來爲 光學異方性薄膜或液晶顯示元件之液晶配向層,進一步, 亦適宜作爲形成薄膜電晶體(TFT )型液晶顯示元件、有 機EL元件等之各種顯示器中的保護膜、平坦化膜、絕緣 膜等之硬化膜的材料、尤其,TFT型液晶元件之層間絕緣 膜、彩色濾光片之保護膜、有機EL元件之絕緣膜等的材 料。 [先前技術文獻] [專利文獻] [專利文獻1]特開2000-103937號公報 [專利文獻2]特開2000-119472號公報 L S1 -45- 201105737 [專利文獻3]特開2005 -03 7920號公報 【圖式簡單說明】 圖1係表示於段差基板塗佈本發明之熱硬化膜形成用 聚酯組成物時所形成的硬化膜之模式圖。 圖2係使藉習知技術形成液晶配向膜之液晶胞(a ) 與使用本發明之熱硬化膜形成用聚酯組成物而形成平坦化 膜之液晶胞(b )對比而顯示之模式圖。 -46-The coatings of Examples 1 to 9 and Comparative Examples 1 to 1 were applied onto a quartz substrate by a spin coater, and then prebaked on a hot plate for 12 seconds, at a temperature of 230 ° C ( Share) Shimadzu's composition of 3 at 400 nm is 1 〇 0 °C in addition to the coating film. Film This film is a hard cured film. 10 m m / s, the substrate is composed of pure body seconds, 55 ° C 3 0 coating film. When the substrate is held at 45 degrees, the changer is subjected to post-baking for 30 minutes on a hot plate at -43 to 201105737 to form a cured film. The film thickness is F20 manufactured by FILMETRICS. And measured. Thereafter, the cured film was further fired on a hot plate at a temperature of 230 ° C for 60 minutes, and the film thickness was measured again to calculate the rate of change in film thickness from post-baking. Further, it can be seen that the cured film having heat resistance is desired to have at least a film thickness change rate of ± 5% or less. [Results of Evaluation] The results of the above evaluations are shown in Table 2 below. [Table 2] Flattening Rate Solvent Resistance Alignment Heat Resistance Transmittance (%) PGMEA NMP (%) (%) Example 1 82 〇〇〇1 2 93 Example 2 80 〇〇〇-2 91 Example 3 76 〇〇〇-3 90 Example 4 85 〇〇〇-2 1 96 Example 5 83 〇〇〇-1 96 Example 6 80 〇〇〇1 2 90 Example 7 81 〇〇〇-2 92 Example 8 80 〇〇〇-1 98 Example 9 88 〇〇〇-1 94 Comparative Example 1 XX - - Comparative Example 2 25 〇〇〇 1 3 85 Comparative Example 3 88 〇〇X -0· 5 96 Example 1 to 9 are flattening ratio and high heat resistance. For any of PGMEA 'NMP, resistance can be seen. In addition, all of them showed good alignment, and high transmittance was achieved even after high-temperature firing (transparency - 44 - 201105737. Further, Comparative Example 1 did not form a cured film. Further, Comparative Example 2 was solvent resistant and heat resistant. Although the properties and the alignment were good, the flattening rate was extremely low. Then, in Comparative Example 3, the flatness, heat resistance, solvent resistance, and transmittance were excellent, but the results were poor in the alignment. In the case of forming a cured film of a polyester composition for forming a thermosetting film of the present invention, a glycol solvent such as propylene glycol monoether ether acetate can be used, and the obtained cured film is excellent in light transmittance and solvent resistance. Good results can be obtained by the performance of any of properties, heat resistance, flatness, and alignment. [Industrial Applicability] The polyester composition for forming a thermosetting film of the present invention is very useful for optical use. The liquid crystal alignment layer of the anisotropic film or the liquid crystal display element is further suitable as a protective film in various displays for forming a thin film transistor (TFT) type liquid crystal display element, an organic EL element, or the like. A material of a cured film such as a flattening film or an insulating film, in particular, an interlayer insulating film of a TFT-type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, etc. [Prior Art] [Patent Literature] [Patent Document 1] JP-A-2000-119472 (Patent Document 3) JP-A-2005-79077 Fig. 1 is a schematic view showing a cured film formed when a polyester composition for forming a thermosetting film of the present invention is applied to a step substrate. Fig. 2 is a liquid crystal cell (a) in which a liquid crystal alignment film is formed by a conventional technique. A pattern diagram in which a liquid crystal cell (b) which forms a planarizing film is formed by using a thermosetting film of the present invention to form a flattening film. -46-
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009087370 | 2009-03-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201105737A true TW201105737A (en) | 2011-02-16 |
TWI523911B TWI523911B (en) | 2016-03-01 |
Family
ID=42828233
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW099109907A TWI523911B (en) | 2009-03-31 | 2010-03-31 | Polyester composition for forming thermoset film |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5641250B2 (en) |
KR (1) | KR101736885B1 (en) |
CN (1) | CN102369230B (en) |
TW (1) | TWI523911B (en) |
WO (1) | WO2010113944A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101660827B1 (en) * | 2009-04-14 | 2016-09-28 | 닛산 가가쿠 고교 가부시키 가이샤 | Photosensitive polyester composition for use in forming thermally cured film |
CN113308091B (en) * | 2020-02-26 | 2023-04-07 | 广东生益科技股份有限公司 | Liquid crystal polyester resin composition and application thereof |
JPWO2022270209A1 (en) * | 2021-06-23 | 2022-12-29 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5146559B2 (en) * | 1973-08-20 | 1976-12-09 | ||
JPS5388097A (en) * | 1977-03-04 | 1978-08-03 | Nitto Electric Ind Co Ltd | Epoxy resin composition |
JPH02178370A (en) * | 1988-12-29 | 1990-07-11 | Toyo Ink Mfg Co Ltd | Thermosetting paint |
EP0410514A1 (en) * | 1989-07-28 | 1991-01-30 | Dsm N.V. | Polyetherimide-polyamide blend |
GB9304940D0 (en) * | 1993-03-11 | 1993-04-28 | Ucb Sa | Thermosetting powder compositions based on polyesters and acrylic copolymers |
JP2001043732A (en) * | 1999-07-29 | 2001-02-16 | Hitachi Chem Co Ltd | Polymeric solid electrolyte, manufacture thereof, and electrochemical device |
JP2002317022A (en) * | 2001-04-20 | 2002-10-31 | Nippon Kayaku Co Ltd | Resin composition, solder resist resin composition, and cured products of compositions |
CN1272361C (en) * | 2002-02-26 | 2006-08-30 | 日本化药株式会社 | Photosensitive resins, resin compositions and products of curing thereof |
JP4569233B2 (en) * | 2003-09-09 | 2010-10-27 | チッソ株式会社 | Thermosetting resin composition and cured film |
JP4779670B2 (en) * | 2005-03-08 | 2011-09-28 | Jnc株式会社 | Thermosetting polymer composition |
KR100782437B1 (en) * | 2005-12-30 | 2007-12-05 | 제일모직주식회사 | Alignment Agent of Liquid Crystal |
JP5061709B2 (en) * | 2006-06-29 | 2012-10-31 | Jnc株式会社 | Composition for liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
JP5018197B2 (en) * | 2007-04-09 | 2012-09-05 | Jnc株式会社 | Thermosetting resin composition and cured film |
CN101679633B (en) * | 2007-06-15 | 2012-09-19 | 日产化学工业株式会社 | Resin composition for forming heat-cured film |
-
2010
- 2010-03-30 JP JP2011507212A patent/JP5641250B2/en active Active
- 2010-03-30 WO PCT/JP2010/055699 patent/WO2010113944A1/en active Application Filing
- 2010-03-30 CN CN201080014439.XA patent/CN102369230B/en active Active
- 2010-03-30 KR KR1020117025356A patent/KR101736885B1/en active IP Right Grant
- 2010-03-31 TW TW099109907A patent/TWI523911B/en active
Also Published As
Publication number | Publication date |
---|---|
JPWO2010113944A1 (en) | 2012-10-11 |
KR20120000104A (en) | 2012-01-03 |
JP5641250B2 (en) | 2014-12-17 |
KR101736885B1 (en) | 2017-05-17 |
WO2010113944A1 (en) | 2010-10-07 |
TWI523911B (en) | 2016-03-01 |
CN102369230B (en) | 2013-07-10 |
CN102369230A (en) | 2012-03-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5382346B2 (en) | Thermosetting film forming resin composition | |
JP5477607B2 (en) | Polyester composition for thermosetting film formation | |
TWI568796B (en) | A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device | |
TW201224043A (en) | Resin composition, liquid crystal alignment material and retardation material | |
TW201323521A (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element | |
TW201211108A (en) | Liquid crystal aligning agent, liquid crystal alignment film produced using same, and liquid crystal display element | |
TW201313780A (en) | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element | |
TWI513715B (en) | Resin composition, liquid crystal alignment material and retardation material | |
KR20160076142A (en) | Composition for liquid crystal alignment layer and liquid crystal alignment layer | |
TWI523911B (en) | Polyester composition for forming thermoset film | |
JP5626536B2 (en) | Photosensitive polyester composition for thermosetting film formation | |
TWI488914B (en) | Polyester composition for forming thermoset film | |
KR101736902B1 (en) | Polyester composite for forming thermoset films | |
JPWO2009051187A1 (en) | Polyester resin solution for thermosetting film formation |