TWI500657B

TWI500657B - Photosensitive polyester composition for forming thermoset film

Info

Publication number: TWI500657B
Application number: TW099111627A
Authority: TW
Inventors: Tadashi Hatanaka; Isao Adachi
Original assignee: Nissan Chemical Ind Ltd
Priority date: 2009-04-14
Filing date: 2010-04-14
Publication date: 2015-09-21
Also published as: CN102395614B; CN102395614A; JPWO2010119868A1; JP5626536B2; KR101660827B1; TW201107367A; KR20120013941A; WO2010119868A1

Description

熱硬化膜形成用感光性聚酯組成物Photosensitive polyester composition for forming a thermosetting film

本發明係有關熱硬化膜形成用感光性聚酯組成物及自該組成物形成之硬化膜。更詳細為，有關可形成具有較高透明性、平坦化性、液晶配向能及較高溶劑耐性之硬化膜的熱硬化膜形成用感光性聚酯組成物及其硬化膜，以及該硬化膜之適用法。該熱硬化膜形成用感光性聚酯組成物特別適用為，液晶顯示器中兼具液晶配向機能之彩色濾光片保護劑。The present invention relates to a photosensitive polyester composition for forming a thermosetting film and a cured film formed from the composition. More specifically, the photosensitive polyester composition for forming a thermosetting film having a high transparency, flatness, liquid crystal alignment energy, and high solvent resistance, and a cured film thereof, and a cured film thereof Applicable law. The photosensitive polyester composition for forming a thermosetting film is particularly suitable as a color filter protecting agent having a liquid crystal alignment function in a liquid crystal display.

一般液晶顯示元件、有機EL(Electro Luminescent)元件、固體攝影元件等光裝置中，為了防止元件表面於製造過程中暴露於溶劑或熱而沒有保護膜。又要求該保護膜不僅可提高相對於被保護基板之密合性以提升溶劑耐性，另具有透明性、耐熱性等性能。In general, in an optical device such as a liquid crystal display element, an organic EL (Electro Luminescent) element, or a solid-state imaging element, there is no protective film in order to prevent the surface of the element from being exposed to a solvent or heat during the manufacturing process. Further, the protective film is required to not only improve the adhesion to the substrate to be protected, but also improve the solvent resistance, and further has properties such as transparency and heat resistance.

該類保護膜作為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用時，一般要求具有使基底層基板之彩色濾光片或黑底樹脂平坦化的性能，即平坦化膜用之性能。特別是製造STN方式或TFT方式之彩色液晶顯示元件時，彩色濾光片基板與對向基板需備有非常嚴密的貼合精確度，以使基板間之單元間隔均勻化係不可欠缺之必要性。另外為了維持透過彩色濾光片之光透過率，該保護膜之此等平坦化膜需備有較高透明性。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 flattening effect of flattening a color filter or a black matrix resin of a base layer substrate, that is, planarization. The performance of the film. In particular, when manufacturing a color liquid crystal display device of the STN method or the TFT method, it is necessary to have a very close bonding precision between the color filter substrate and the opposite substrate, so that the uniformity of the cell spacing between the substrates is indispensable. . In addition, in order to maintain the light transmittance through the color filter, the planarizing film of the protective film needs to have high transparency.

又，近年來嘗試檢討將相位差材料導入液晶顯示器之單元內以低成本化、輕量化，又該類相位差材料一般係使用塗布液晶單體且配向後，可光硬化之材料。為了使該相位差材料配向，底層膜需為摩擦處理後具有配向性之材料。如此於彩色濾光片之保護膜上使液晶配向層成膜後，可形成相位差材料(參考圖2(a))。形成兼具該液晶配向層及彩色濾光片之保護膜的膜(參考圖2(b))，可得低成本化、削減步驟數等優點，因此強烈寄望於該類材料。Further, in recent years, attempts have been made to reduce the cost and weight of a phase difference material introduced into a liquid crystal display unit. In general, such a phase difference material is a material which can be photohardened by coating a liquid crystal monomer and after alignment. In order to align the phase difference material, the underlying film needs to be an anisotropic material after rubbing treatment. After the liquid crystal alignment layer is formed on the protective film of the color filter, a phase difference material can be formed (refer to FIG. 2(a)). Forming a film having the protective film of the liquid crystal alignment layer and the color filter (refer to FIG. 2(b)), the advantages of cost reduction, number of steps, and the like can be obtained, and therefore, such materials are strongly expected.

一般該彩色濾光片之保護膜係使用透明性較高之丙烯酸樹脂。相對於丙二醇單甲基醚、丙二醇單甲基醚乙酸酯之二元醇系溶劑及乳酸乙酯、乳酸丁酯之酯系溶劑，就安全性、處理、防止由彩色濾光片溶出顏料成份之觀點係廣泛使用該類丙烯酸樹脂。將該類丙烯酸樹脂熱硬化或光硬化，可賦予耐熱性及耐溶劑性(專利文獻1、2)。先前之熱硬化性或光硬化性丙烯酸樹脂雖具有適當的透明性及平坦化性，但既使對該類平坦化膜進行摩擦處理也無法賦予充分的配向性。Generally, the protective film of the color filter is made of an acrylic resin having high transparency. Relative to propylene glycol monomethyl ether, diol glycol monomethyl ether acetate glycol solvent and ethyl lactate, butyl lactate ester solvent, safety, treatment, prevention of pigmentation by color filter The viewpoint is that such an acrylic resin is widely used. This type of acrylic resin is thermally cured or photocured to impart heat resistance and solvent resistance (Patent Documents 1 and 2). Although the conventional thermosetting or photocurable acrylic resin has appropriate transparency and flatness, it does not provide sufficient alignment properties even if the planarizing film is subjected to rubbing treatment.

又，液晶配向層一般係使用，自溶劑可溶性之聚醯亞胺或聚醯胺酸形成的材料。曾報告此等材料於後烤時可完成醯亞化而賦予耐溶劑性，藉由摩擦處理可賦予充分的配向性(專利文獻3)。但將此等材料視為彩色濾光片之平坦化膜時，會有大幅降低平坦化性及透明性等之問題。Further, the liquid crystal alignment layer is generally a material formed from a solvent-soluble polyimine or polylysine. It has been reported that these materials can be subjected to hydrazine hydride at the time of post-baking to impart solvent resistance, and sufficient alignability can be imparted by rubbing treatment (Patent Document 3). However, when these materials are regarded as flattening films of color filters, problems such as flatness and transparency are greatly reduced.

又，為了提升平坦化性曾報告聚酯－聚醯胺酸及聚酯－聚醯亞胺共聚物(專利文獻4)。但此等聚酯－聚醯胺酸及聚酯－聚醯亞胺共聚物同聚醯亞胺及聚醯胺酸可溶於N－甲基吡咯烷酮及γ-丁內酯之溶劑，而對二元醇系溶劑及酯系溶劑之溶解性較低，因此製作聚醯亞胺膜時會由彩色濾光片溶出顏料成份及液晶污染成份，而難適用於製作平坦化膜步驟中。Moreover, polyester-polyaminic acid and polyester-polyimine copolymer have been reported in order to improve flatness (Patent Document 4). However, these polyester-polyaminic acid and polyester-polyimine copolymers are soluble in the solvent of N-methylpyrrolidone and γ-butyrolactone, and the second is the solvent of poly-imine and poly-proline. Since the solubility of the solvent and the ester solvent is low, the pigment component and the liquid crystal contamination component are eluted from the color filter when the polyimide film is produced, which is difficult to apply to the process of producing the planarization film.

又，為了提升相對於貼合TFT數組側之基板時所使用的密封材料之密合強度，希望能以像片微影法去除接合部分之膜。Moreover, in order to improve the adhesion strength of the sealing material used when bonding the substrate on the TFT array side, it is desirable to remove the film of the joint portion by photolithography.

另外目前為止尚無有關具有感光性之具有配向性的平坦化膜之報告。In addition, there has been no report on a photosensitive planarizing film.

先前技術文獻Prior technical literature

專利文獻Patent literature

專利文獻1：特開2000-103937號公報Patent Document 1: JP-A-2000-103937

專利文獻2：特開2000-119472號公報Patent Document 2: JP-A-2000-119472

專利文獻3：特開2005-037920號公報Patent Document 3: JP-A-2005-037920

專利文獻4：特開2008-033244號公報Patent Document 4: JP-A-2008-033244

有鑑於上述事情，本發明所欲解決之課題為，提供可以鹼顯像液形成圖型，形成硬化膜後具有較高之溶劑耐性、液晶配向性、高透明性及高平坦化性，且硬化膜形成時可溶解於適用於製作彩色濾光片之平坦化膜步驟的二元醇系溶劑及乳酸酯系溶劑之材料。In view of the above, the object of the present invention is to provide a pattern which can be formed by an alkali developing solution, which has high solvent resistance, liquid crystal alignment, high transparency and high flatness, and is hardened after forming a cured film. When the film is formed, it can be dissolved in a material of a glycol solvent and a lactic acid ester solvent which are suitable for the step of forming a planarization film of a color filter.

為了解決上述課題經本發明者專心硏究，結果完成本發明。In order to solve the above problems, the present inventors have intensively studied and completed the present invention.

即，第1觀點為一種熱硬化膜形成用感光性聚酯組成物，其為含有(A)成份、(B)成份、(C)成份及(D)成份。In other words, the first aspect is a photosensitive polyester composition for forming a thermosetting film, which comprises (A) component, (B) component, (C) component, and (D) component.

(A)成份：含有下述式(1)所表示的構造單位之聚酯，與具有縮水甘油基及異氰酸酯基中選出的官能基之化合物反應而得的被修飾之聚酯(A) Component: a modified polyester obtained by reacting a polyester having a structural unit represented by the following formula (1) with a compound having a functional group selected from a glycidyl group and an isocyanate group.

(B)成份：具有2個以上環氧基之環氧化合物(B) Component: an epoxy compound having two or more epoxy groups

(C)成份：二胺化合物與二羧酸二酐反應而得的含有胺基之羧酸化合物(C) Component: an amine group-containing carboxylic acid compound obtained by reacting a diamine compound with a dicarboxylic acid dianhydride

(D)成份：1,2-苯醌二疊氮化合物(D) Ingredients: 1,2-benzoquinonediazide

【化1】【化1】

(式中，A為脂環式骨架或脂肪族骨架鍵結4個鍵結鍵之4價有機基，B為脂環式骨架或脂肪族骨架鍵結2個鍵結鍵之2價有機基)。(wherein, A is a tetravalent organic group in which an alicyclic skeleton or an aliphatic skeleton is bonded to four bonding bonds, and B is an alicyclic skeleton or a divalent organic group in which an aliphatic skeleton is bonded to two bonding bonds) .

第2觀點為第1觀點所記載的熱硬化膜形成用感光性聚酯組成物，其中含有前述式(1)所表示的構造單位之聚酯為，含有下述式(i)所表示的四羧酸二酐之四羧酸二酐成份，與含有下述式(ii)所表示的二醇化合物之二醇成份反應而得的聚酯，The second aspect is the photosensitive polyester composition for forming a thermosetting film according to the first aspect, wherein the polyester containing the structural unit represented by the above formula (1) contains the four represented by the following formula (i). a polyester obtained by reacting a tetracarboxylic dianhydride component of a carboxylic acid dianhydride with a diol component containing a diol compound represented by the following formula (ii),

【化2】[Chemical 2]

{式(i)及(ii)中，A及B同前述式(1)之定義}。{In the formulas (i) and (ii), A and B are the same as defined in the above formula (1)}.

第3觀點為如第1或2觀點所記載的熱硬化膜形成用感光性聚酯組成物，其中前述式(1)中，A為下述式(A-1)至(A-8)所表示之基中選出的至少一種基，B為下述式(B-1)至(B-5)所表示之基中選出的至少一種基。The photosensitive polyester composition for forming a thermosetting film according to the above aspect (1), wherein A is represented by the following formulas (A-1) to (A-8). At least one group selected from the group consisting of B is at least one selected from the group represented by the following formulas (B-1) to (B-5).

【化3】[化3]

【化4】【化4】

第4觀點為第1至3觀點中任何一項所記載的熱硬化膜形成用感光性聚酯組成物，其中前述(A)成份之被修飾的聚酯為，具有聚苯乙烯換算下1,000至3,000之重量平均分子量。The photosensitive polyester composition for forming a thermosetting film according to any one of the above aspects, wherein the modified polyester of the component (A) has a polystyrene-converted 1,000 to A weight average molecular weight of 3,000.

第5觀點為第1至4觀點中任何一項所記載的熱硬化膜形成用感光性聚酯組成物，其中前述(C)成份為，二胺化合物1莫耳與二羧酸二酐1.7至2莫耳反應而得的含有胺基之羧酸化合物。The photosensitive polyester composition for forming a thermosetting film according to any one of the above aspects, wherein the component (C) is a diamine compound 1 mol and a dicarboxylic acid dianhydride of 1.7 to An amine group-containing carboxylic acid compound obtained by a molar reaction.

第6觀點為第1至5觀點中任何一項所記載的熱硬化膜形成用感光性聚酯組成物，其中相對於前述(A)成份100質量份各自含有3至50質量份之前述(B)成份、3至50質量份之前述(C)成份及5至80質量份之前述(D)成份。The photosensitive polyester composition for forming a thermosetting film according to any one of the above-mentioned (A) components, which contains 3 to 50 parts by mass each of the above (B) The component, 3 to 50 parts by mass of the above (C) component and 5 to 80 parts by mass of the aforementioned (D) component.

第7觀點為第1至5觀點中任何一項所記載的熱硬化膜形成用感光性聚酯組成物，其中另含有(E)成份之雙馬來醯亞胺化合物。The photosensitive polyester composition for forming a thermosetting film according to any one of the first to fifth aspects, which further comprises the (B) component of the bismaleimide compound.

第8觀點為第6觀點所記載的熱硬化膜形成用感光性聚酯組成物，其中相對於前述(A)成份100質量份含有0.5至50質量份之第7觀點所記載的(E)成份。The eighth aspect is the photosensitive polyester composition for forming a thermosetting film according to the sixth aspect, wherein the component (E) described in the seventh aspect is contained in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the component (A). .

第9觀點為一種硬化膜，其為自第1至8觀點中任何一項所記載的熱硬化膜形成用感光性聚酯組成物形成。The ninth aspect is formed of a photosensitive polyester composition for forming a thermosetting film according to any one of the first to eighth aspects.

第10觀點為一種液晶配向層，其為使用第1至8觀點中任何一項所記載的熱硬化膜形成用感光性聚酯組成物而得。The tenth aspect is a liquid crystal alignment layer obtained by using the photosensitive polyester composition for forming a thermosetting film according to any one of the first to eighth aspects.

本發明之熱硬化膜形成用感光性聚酯組成物可形成具有感光性，及較高平坦化性、較高透明性、較高溶劑耐性、較高耐熱性與液晶配向能之硬化膜，因此適用為液晶配向膜及平坦化膜之形成材料。特別是可一次形成兼具先前獨立形成之液晶配向層及彩色濾光片之保護層兩者的特性之「液晶配向層」，因此可實現製造步驟簡略化及藉由減少步驟數而低成本化等。The photosensitive polyester composition for forming a thermosetting film of the present invention can form a cured film having photosensitivity, high flatness, high transparency, high solvent resistance, high heat resistance, and liquid crystal alignment energy. It is suitable as a material for forming a liquid crystal alignment film and a planarization film. In particular, since the "liquid crystal alignment layer" having the characteristics of both the previously independently formed liquid crystal alignment layer and the protective layer of the color filter can be formed at one time, the manufacturing steps can be simplified and the number of steps can be reduced to reduce the cost. Wait.

又本發明之熱硬化膜形成用感光性聚酯組成物可溶於二元醇系溶劑及乳酸酯系溶劑，因此適用於主要使用此等溶劑之平坦化膜的製作過程中。Further, since the photosensitive polyester composition for forming a thermosetting film of the present invention is soluble in a glycol solvent and a lactic acid ester solvent, it is suitably used in the production process of a planarizing film mainly using such a solvent.

實施發明之形態Form of implementing the invention

如上述般先前提案的丙烯酸樹脂系及聚醯亞胺樹脂系硬化膜為，無法具有充分符合液晶配向膜及平坦化膜所要求的平坦化性、透明性、配向性等全部性能。The acrylic resin-based and the polyimide-based resin-based cured film which have been proposed in the above-mentioned manner cannot have all the properties such as flatness, transparency, and alignment which are required to sufficiently satisfy the liquid crystal alignment film and the planarizing film.

又，目前為止雖有液晶顯示元件之配向材料使用聚酯的提案(參考特開平5-158055號公報、特開2002-229039號公報)，但此等均非具有熱硬化性之物，故所形成的膜之耐溶劑性較差。In addition, there is a proposal to use a polyester for an alignment material of a liquid crystal display device (refer to Japanese Laid-Open Patent Publication No. H5-158055, JP-A-2002-229039), but none of them are thermosetting. The formed film is poor in solvent resistance.

本發明之特徵為，使用熱硬化性之聚酯以提升上述性能。即，本發明為含有(A)成份之聚酯、(B)成份之具有2個以上環氧基的環氧化合物、(C)成份之含有胺基的羧酸化合物及(D)成份之1,2-苯醌二疊氮化合物的熱硬化膜形成用感光性聚酯組成物。又本發明為，除了(A)成份、(B)成份、(C)成份、(D)成份另含有(E)成份之雙馬來醯亞胺化合物的熱硬化膜形成用感光性聚酯組成物。The present invention is characterized in that a thermosetting polyester is used to enhance the above properties. That is, the present invention is a polyester containing (A) component, an epoxy compound having two or more epoxy groups as the component (B), an amine group-containing carboxylic acid compound (C) component, and (D) component 1 A photosensitive polyester composition for forming a thermosetting film of a 2-benzoquinonediazide compound. Further, the present invention is a photosensitive polyester composition for forming a thermosetting film of a bismaleimide compound containing (A) component, (B) component, (C) component, and (D) component (E) component. Things.

下面將詳細說明各成份。The components will be described in detail below.

<(A)成份><(A) ingredient>

(A)成份之聚酯為，含有下述式(1)所表示的構造單位之聚酯(以下亦稱為特定聚合物)，與具有縮水甘油基及異氰酸酯基中選出的官能基之化合物反應而得的被修飾之聚酯。較佳為自下述式(1)所表示的構造單位形成之聚酯，與具有縮水甘油基及異氰酸酯基中選出的官能基之化合物反應而得的被修飾之聚酯。The polyester of the component (A) is a polyester containing a structural unit represented by the following formula (1) (hereinafter also referred to as a specific polymer), and reacted with a compound having a functional group selected from a glycidyl group and an isocyanate group. And the modified polyester. It is preferably a modified polyester obtained by reacting a polyester formed from a structural unit represented by the following formula (1) with a compound having a functional group selected from a glycidyl group and an isocyanate group.

【化5】【化5】

前述A較佳為下述式(1A1)、式(1A2)或(1A3)所表示之基。The above A is preferably a group represented by the following formula (1A1), formula (1A2) or (1A3).

【化6】【化6】

{式(1A1)、(1A2)及(1A3)中，A¹ 為環狀飽和烴基，R¹ 為單鍵、醚鍵、羰基、磺酸基、碳原子數1至8之飽和烴基或被氟原子取代之碳原子數1至8的飽和烴基，又，R² 為碳原子數1至8之飽和烴基}。In the formulae (1A1), (1A2) and (1A3), A ¹ is a cyclic saturated hydrocarbon group, and R ¹ is a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a fluorine atom. The atom-substituted saturated hydrocarbon group having 1 to 8 carbon atoms, and further, R ² is a saturated hydrocarbon group having 1 to 8 carbon atoms}.

前述式中，A¹ 較佳為碳原子數4至8之環狀飽和烴基，更佳為碳原子數4至6之環狀飽和烴基，又，A¹ 基中所含的任意氫原子可各自獨立被脂肪族基取代，且其中2個取代基可相互鍵結形成4至6員環。In the above formula, A ^{1 is} preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms, and further, any hydrogen atom contained in the A ¹ group may be each It is independently substituted with an aliphatic group, and two of the substituents may be bonded to each other to form a 4- to 6-membered ring.

該取代基之脂肪族基較佳為碳原子數1至5之脂肪族基，更佳為碳原子數1至3之脂肪族基。鍵結此等取代基形成環時，例如可為降茨烯基或金剛烷基等之交聯環式烴基、部分或全部氫化之縮合環式烴基。The aliphatic group of the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When the substituents are bonded to form a ring, for example, a crosslinked cyclic hydrocarbon group such as a decyl group or an adamantyl group or a partially or fully hydrogenated condensed cyclic hydrocarbon group may be used.

又，R¹ 較佳為單鍵、醚鍵、羰基、磺酸基、碳原子數1至5之飽和烴基或被氧原子取代之碳原子數1至5的飽和烴基。Further, R ^{1 is} preferably a single bond, an ether bond, a carbonyl group, a sulfonic acid 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 an oxygen atom.

另外R² 較佳為碳原子數1至5之飽和烴基，更佳為碳原子數1至3之飽和烴基。Further, R ^{2 is} preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

上述式(1)中4價有機基之A的較佳具體例如下述式(A-1)至式(A-8)。下述式(A-1)至(A-8)所表示之基中，A特佳為下述式(A-1)或式(A-2)中選出之基。Preferred examples of the A of the tetravalent organic group in the above formula (1) are, for example, the following formulas (A-1) to (A-8). Among the groups represented by the following formulas (A-1) to (A-8), A is particularly preferably a group selected from the following formula (A-1) or formula (A-2).

【化7】【化7】

上述式(1)中，B為脂環式骨架或脂肪族骨架鍵結2個鍵結鍵之2價有機基，較佳為下述式(1B1)或式(1B2)所表示之基。In the above formula (1), B is a divalent organic group in which two bonding bonds are bonded to the alicyclic skeleton or the aliphatic skeleton, and is preferably a group represented by the following formula (1B1) or formula (1B2).

【化8】【化8】

{式(1B1)及(1B2)中，B¹ 為環狀飽和烴基，B² 為伸苯基，又，R³ 為單鍵、醚鍵、羰基、磺酸基、碳原子數1至8之飽和烴基或被氟原子取代之碳原子數1至8的飽和烴基，R⁴ 、R⁵ 各自獨立為單鍵或碳原子數1至5之伸烷基，R⁶ 、R⁷ 各自獨立為碳原子數1至5之伸烷基，又，k為0或1}。In the formulae (1B1) and (1B2), B ¹ is a cyclic saturated hydrocarbon group, B ² is a stretched phenyl group, and further, R ³ is a single bond, an ether bond, a carbonyl group, a sulfonic acid group, and a carbon number of 1 to 8. a saturated hydrocarbon group or a saturated hydrocarbon group having 1 to 8 carbon atoms which is substituted by a fluorine atom, and each of R ⁴ and R ^{5 is} independently a single bond or an alkylene group having 1 to 5 carbon atoms, and R ⁶ and R ⁷ are each independently a carbon atom. The alkyl group is 1 to 5, and k is 0 or 1}.

前述式中，B¹ 較佳為碳原子數4至8之環狀飽和烴基，更佳為碳原子數4至6之環狀飽和烴基，又，B¹ 基中所含的任意氫原子可各自獨立被脂肪族基取代。In the above formula, B ^{1 is} preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms, and further, any hydrogen atom contained in the B ¹ group may be each Independently substituted by an aliphatic group.

其中該取代基之脂肪族基較佳為碳原子數1至5之脂肪族基，更佳為碳原子數1至3之脂肪族基。此等取代基鍵結形成環時，例如可形成降茨烯基或金剛烷基等交聯環式烴基、部分或全部氫化之縮合多環式烴基。The aliphatic group of the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to form a ring, for example, a crosslinked cyclic hydrocarbon group such as a decyl group or an adamantyl group or a partially or fully hydrogenated condensed polycyclic hydrocarbon group can be formed.

R³ 較佳為單鍵、醚鍵、羰基、磺酸基、碳原子數1至5之飽和烴基或被氧原子取代之碳原子數1至5的飽和烴基。R ^{3 is} preferably a single bond, an ether bond, a carbonyl group, a sulfonic acid 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 an oxygen atom.

又，R⁴ 、R⁵ 較佳為單鍵、碳原子數1至3之伸烷基。Further, R ⁴ and R ^{5 are} preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

另外R⁶ 、R⁷ 較佳為碳原子數1至3之伸烷基。Further, R ⁶ and R ^{7 are} preferably an alkylene group having 1 to 3 carbon atoms.

上述式(1)中2價有機基之B的較佳具體例如下述式(B-1)至式(B-5)。下述式(B-1)至(B-5)所表示之基中，B特佳為下述式(B-1)至(B-4)中所選出之基。The B of the divalent organic group in the above formula (1) is preferably, for example, the following formula (B-1) to formula (B-5). Among the groups represented by the following formulae (B-1) to (B-5), B is particularly preferably a group selected from the following formulae (B-1) to (B-4).

【化9】【化9】

特定聚合物較佳為上述式(1)所表示之構造單位中，A含有上述式(1A1)至(1A3)所表示之基所成群中選出的至少一種構造，又可含有上述式(1A1)至(1A3)所表示之基以外的構造。其可為能形成聚酯構造之構造無特別限定，但較佳為下述式(1A4)及式(1A5)所表示之基中所選出的至少一種構造。The specific polymer is preferably a structural unit represented by the above formula (1), and A contains at least one structure selected from the group represented by the above formulas (1A1) to (1A3), and may further contain the above formula (1A1). ) to a structure other than the base represented by (1A3). The structure which can form a polyester structure is not particularly limited, but is preferably at least one selected from the group represented by the following formula (1A4) and formula (1A5).

【化10】【化10】

{式(1A4)及式(1A5)中，R⁸ 、R⁹ 、R¹⁰ 各自獨立為單鍵、醚鍵、羰基、磺酸基、碳原子數1至8之飽和烴基或被氟原子取代之碳原子數1至8的飽和烴基，又，h為0或1}。In the formula (1A4) and the formula (1A5), R ⁸ , R ⁹ and R ¹⁰ are each independently a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a fluorine atom. A saturated hydrocarbon group having 1 to 8 carbon atoms, and h is 0 or 1}.

前述式中，R⁸ 、R⁹ 、R¹⁰ 較佳為單鍵、醚鍵、羰基、磺酸基、碳原子數1至5之飽和烴基或被氟原子取代之碳原子數1至5的飽和烴基。In the above formula, R ⁸ , R ⁹ and R ^{10 are} preferably a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated atomic number of 1 to 5 substituted by a fluorine atom. Hydrocarbyl group.

特佳為R⁸ 為單鍵、醚鍵、羰基、磺酸基、碳原子數1至5之飽和烴基或被氟原子取代之碳原子數1至5的飽和烴基。Particularly preferably, R ⁸ is a single bond, an ether bond, a carbonyl group, a sulfonic acid 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.

又，R⁹ 較佳為醚鍵、碳原子數1至5之飽和烴基或被氟原子取代之碳原子數1至5的飽和烴基。Further, R ^{9 is} preferably an ether bond, 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.

另外R¹⁰ 較佳為醚鍵、羰基、磺酸基、碳原子數1至5之飽和烴基或被氟原子取代之碳原子數1至5的飽和烴基。Further, R ^{10 is} preferably an ether bond, a carbonyl group, a sulfonic acid 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.

前述式(1A4)至(1A5)之較佳具體例如下述式(a1)至(a7)。Preferred examples of the above formulas (1A4) to (1A5) are, for example, the following formulas (a1) to (a7).

【化11】【化11】

特定聚合物中，上述式(1)所表示之構造單位的A較佳為，至少含有60莫耳%以上的上述式(1A1)至(1A3)所表示之基所成群中選出的至少一種構造單位。In the specific polymer, A of the structural unit represented by the above formula (1) is preferably at least one selected from the group consisting of the groups represented by the above formulas (1A1) to (1A3) and containing at least 60 mol% or more. Construction unit.

(A)成份之被修飾的聚酯可如後述為，特定聚合物與具有縮水甘油基及異氰酸酯基中選出的官能基之化合物反應而得。The modified polyester of the component (A) can be obtained by reacting a specific polymer with a compound having a functional group selected from a glycidyl group and an isocyanate group, as will be described later.

(A)成份之被修飾的聚酯之重量平均分子量較佳為，聚苯乙烯換算下1,000至30,000，更佳為1,500至10,000。該聚酯之重量平均分子量小於前述範圍時，傾向降低自本發明之熱硬化膜形成用感光性聚酯組成物形成的硬化膜之配向性及溶劑耐性，超過前述範圍時會降低平坦化性。The weight average molecular weight of the modified polyester of the component (A) is preferably from 1,000 to 30,000, more preferably from 1,500 to 10,000 in terms of polystyrene. When the weight average molecular weight of the polyester is less than the above range, the orientation and solvent resistance of the cured film formed from the photosensitive polyester composition for forming a thermosetting film of the present invention tend to be lowered, and when it exceeds the above range, flatness is lowered.

<特定聚合物之製造方法><Method of Manufacturing Specific Polymer>

本發明中，特定聚合物可自含有下述式(i)所表示之四羧酸二酐之四羧酸二酐成份(以下亦稱為配成份)，與下述式(ii)所表示之二醇化合物(以下亦稱為二醇成份)反應而得。In the present invention, the specific polymer may be derived from a tetracarboxylic dianhydride component (hereinafter also referred to as a component) containing a tetracarboxylic dianhydride represented by the following formula (i), and represented by the following formula (ii). A diol compound (hereinafter also referred to as a diol component) is obtained by reaction.

【化12】【化12】

{式(i)及(ii)中，A及B同上述式(1)之定義}。{In the formulas (i) and (ii), A and B are the same as defined in the above formula (1)}.

又，前述A及B之較佳形態與上述相同。Further, preferred embodiments of the above A and B are the same as described above.

本發明中，前述式(i)所表示之四羧酸二酐、前述式(ii)所表示之二醇化合物可各自獨立為，單獨使用或使用2種以上。In the present invention, the tetracarboxylic dianhydride represented by the above formula (i) and the diol compound represented by the above formula (ii) may be used singly or in combination of two or more kinds.

製造前述特定聚合物時，酸成份除了前述式(i)所表示之四羧酸二酐，可併用其他的四羧酸二酐(以下亦稱為其他酸二酐)。此時之其他酸二酐於無損本發明效果下無特別限定，較佳為下述式(i2)所表示之四羧酸二酐。When the specific polymer is produced, the acid component may be used in combination with the tetracarboxylic dianhydride represented by the above formula (i), and other tetracarboxylic dianhydride (hereinafter also referred to as other acid dianhydride) may be used in combination. The other acid dianhydride at this time is not particularly limited, and is preferably a tetracarboxylic dianhydride represented by the following formula (i2).

【化13】【化13】

{式(12)中，W為上述式(1)所定義的上述式(1A4)及(1A5)所表示之基中選出的至少一種構造，R⁸ 、R⁹ 、R¹⁰ 及h同上述定義}。In the formula (12), W is at least one selected from the group represented by the above formulas (1A4) and (1A5) defined by the above formula (1), and R ⁸ , R ⁹ , R ¹⁰ and h are the same as defined above. }.

另外前述式(1A4)及(1A5)之較佳具體例同如上述式(a1)至(a7)。Further, preferred specific examples of the above formulas (1A4) and (1A5) are the same as the above formulas (a1) to (a7).

本發明較佳為，酸成份中至少含有60莫耳%以上的上述式(i)所表示之四羧酸二酐。In the present invention, the acid component preferably contains at least 60 mol% or more of the tetracarboxylic dianhydride represented by the above formula (i).

前述特定聚合物中，四羧酸二酐之合計量(酸成份之合計量)與二醇化合物之合計量(二醇成份之合計量)的添加比，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>較佳為0.95至1.5。同一般聚縮合反應般，該莫耳比近乎1時可增加所生成的特定聚合物之聚合度，而增加分子量。In the specific polymer, the total ratio 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 components), that is, the total molar number of the diol compound >/<the total number of moles of the tetracarboxylic dianhydride compound> is preferably from 0.95 to 1.5. As with the general polycondensation reaction, when the molar ratio is nearly 1, the degree of polymerization of the specific polymer formed can be increased, and the molecular weight can be increased.

前述特定聚合物之末端會依存於酸成份與二醇成份之添加比而改變。例如以過剩酸成份進行反應時，末端易形成酸酐。The end of the specific polymer described above varies depending on the ratio of addition of the acid component to the diol component. For example, when the reaction is carried out with a residual acid component, an acid anhydride is easily formed at the terminal.

又，使用過剩二醇成份進行聚合時，末端易形成羥基。此時之該末端羥基可與羧酸酐反應，而以酸酐封止末端羥基。該類羧酸酐如，酞酸酐、偏苯三酸酐、馬來酸酐、萘酸酐、氫化酞酸酐、甲基-5-降莰烯-2,3-二羧酸酐、衣康酸酐、四氫酞酸酐等。Further, when polymerization is carried out using an excess diol component, a hydroxyl group is easily formed at the terminal. At this time, the terminal hydroxyl group can react with the carboxylic acid anhydride, and the terminal hydroxyl group is blocked with an acid anhydride. Such carboxylic anhydrides are, for example, phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and the like.

因其後的加成反應中與具有縮水甘油基之化合物反應時，會使所生成的羥基與酸酐反應而凝膠化，故特定聚合物之末端是否為羥基均需以酸酐封止末端羥基。When a reaction with a compound having a glycidyl group is carried out in the subsequent addition reaction, the generated hydroxyl group is reacted with an acid anhydride to be gelated. Therefore, whether or not the terminal of the specific polymer is a hydroxyl group is required to block the terminal hydroxyl group with an acid anhydride.

製造特定聚合物時，酸成份與二醇成份之反應溫度可選用50至200℃，較佳為80至170℃之任意溫度。例如可以反應溫度為100至140℃、反應時間為2至48小時之條件得到特定聚合物。When the specific polymer is produced, the reaction temperature of the acid component and the diol component may be from 50 to 200 ° C, preferably from 80 to 170 ° C. For example, a specific polymer can be obtained under the conditions of a reaction temperature of 100 to 140 ° C and a reaction time of 2 to 48 hours.

又，以酸酐保護末端羥基時之反應溫度可選用50至200℃，較佳為80至170℃之任意溫度。Further, the reaction temperature at the time of protecting the terminal hydroxyl group with an acid anhydride may be any temperature of 50 to 200 ° C, preferably 80 to 170 ° C.

前述酸成份與前述二醇成份之反應一般係於溶劑中進行(以下將使用於聚合特定聚合物時之溶劑稱為「聚合溶劑」)。此時所使用的溶劑可為，不含羥基或胺基等會與酸酐反應之官能基之物無特別限定。例如，N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮、N-乙烯基吡咯烷酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、二甲基碸、六甲基亞碸、m-甲酚、γ-丁內酯、環己酮、環庚酮、甲基乙基酮、甲基異丁基酮、2-庚酮、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇丙基醚乙酸酯、3-甲氧基丙酸甲酯、2-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、2-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、2-乙氧基丙酸乙酯等。The reaction between the acid component and the diol component is generally carried out in a solvent (hereinafter, a solvent used in polymerizing a specific polymer is referred to as a "polymerization solvent"). The solvent to be used at this time is not particularly limited as long as it does not contain a functional group which reacts with an acid anhydride such as a hydroxyl group or an amine group. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylammonium , tetramethyl urea, dimethyl hydrazine, hexamethylarylene, m-cresol, γ-butyrolactone, cyclohexanone, cycloheptanone, methyl ethyl ketone, methyl isobutyl ketone, 2 -heptanone, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, 2 Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

此等溶劑可單獨或混合使用，但就彩色濾光片之保護劑對步驟的適用性觀點較佳為丙二醇單甲基醚乙酸酯。These solvents may be used singly or in combination, but the viewpoint of suitability of the protective agent for the color filter to the step is preferably propylene glycol monomethyl ether acetate.

又，既使為不溶解特定聚合物之溶劑，於不析出聚合反應所生成的特定聚合物之範圍內，可混合使用於前述溶劑。Further, even if it is a solvent which does not dissolve a specific polymer, it can be used in combination with the solvent in the range in which the specific polymer produced by the polymerization reaction is not precipitated.

又前述酸成份(式(i)及式(i2))與前述二醇成份(式(ii))反應時可使用觸媒。Further, a catalyst may be used in the reaction of the above acid component (formula (i) and formula (i2)) with the aforementioned diol component (formula (ii)).

聚合特定聚合物時所使用的觸媒之具體例如，苄基三甲基銨氯化物、苄基三甲基銨溴化物、苄基三乙基銨氯化物、苄基三乙基銨溴化物、苄基三丙基銨氯化物、苄基三丙基銨溴化物、四甲基銨氯化物、四乙基銨溴化物、四丙基銨氯化物、四丙基銨溴化物等四級銨鹽、四苯基鏻氯化物、四苯基鏻溴化物、苄基三苯基鏻氯化物、苄基三苯基鏻溴化物、乙基三苯基鏻氯化物、乙基三苯基鏻溴化物等四級鏻鹽。Specific examples of the catalyst used in polymerizing a specific polymer are, for example, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, a quaternary ammonium salt such as benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide , tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide Wait for the fourth grade of strontium salt.

<製造(A)成份><Manufacture (A) ingredients>

成份(A)之聚酯係自，相對於特定聚合物之羧基添加10至90莫耳%的具有縮水甘油基及異氰酸酯基中選出之官能基的化合物進行反應而得。此時可直接使用特定聚合物之聚合溶液。The polyester of the component (A) is obtained by reacting a compound having a glycidyl group and a functional group selected from an isocyanate group in an amount of 10 to 90 mol% based on the carboxyl group of the specific polymer. At this time, a polymerization solution of a specific polymer can be directly used.

又以共存醇系溶劑可抑制反應中凝膠化而為佳。該類醇系溶劑(以下亦稱為反應溶劑)之具體例如，丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丁基醚、丙二醇丙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、甲基溶纖劑、丁基溶纖劑、乳酸乙酯、乳酸丁酯、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、tert-丁醇、環己醇等。此等溶劑可單獨或2種以上組合使用。Further, it is preferred to coexist the alcohol-based solvent to suppress gelation during the reaction. Specific examples of such an alcohol-based solvent (hereinafter also referred to as a reaction solvent) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol propyl ether, diethylene glycol monomethyl ether, and Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, methyl cellosolve, butyl cellosolve, ethyl lactate, butyl lactate, methanol, ethanol, 1-propanol, 2-propanol, 1 -butanol, 2-butanol, tert-butanol, cyclohexanol, and the like. These solvents may be used alone or in combination of two or more.

附加於特定聚合物之羧基的具有縮水甘油基之化合物的具體例如，縮水甘油基甲基丙烯酸酯、縮水甘油基丙烯酸酯、甲基縮水甘油醚、乙基縮水甘油醚、烯丙基縮水甘油醚、4-tert-丁基苯基縮水甘油醚、縮水甘油基丙基醚、縮水甘油基-2-甲基苯基醚、縮水甘油基丙基醚、縮水甘油基異丙基醚、縮水甘油基丁基醚、縮水甘油基-tert-丁基醚、2-聯苯縮水甘油醚、縮水甘油基-4-甲氧基苯基醚等。Specific examples of the glycidyl group-containing compound added to the carboxyl group of the specific polymer, for example, glycidyl methacrylate, glycidyl acrylate, methyl glycidyl ether, ethyl glycidyl ether, allyl glycidyl ether , 4-tert-butylphenyl glycidyl ether, glycidyl propyl ether, glycidyl-2-methylphenyl ether, glycidyl propyl ether, glycidyl isopropyl ether, glycidyl Butyl ether, glycidyl-tert-butyl ether, 2-biphenyl glycidyl ether, glycidyl-4-methoxyphenyl ether, and the like.

又，附加於特定聚合物之羧基的具有異氰酸酯基之化合物的具體例如，甲基異氰酸酯、乙基異氰酸酯、丙基異氰酸酯、異丙基異氰酸酯、丁基異氰酸酯、異丁基異氰酸酯、tert-丁基異氰酸酯、苯基異氰酸酯、2-甲苯醯異氰酸酯、3-甲苯醯異氰酸酯、4-甲苯醯異氰酸酯、1-萘基異氰酸酯、環己基異氰酸酯、苄基異氰酸酯、2-異氰酸酯乙基甲基丙烯酸酯、2-甲氧基苯基異氰酸酯、3-甲氧基苯基異氰酸酯、4-甲氧基苯基異氰酸酯、戊基異氰酸酯、己基異氰酸酯等。Further, specific examples of the compound having an isocyanate group attached to a carboxyl group of a specific polymer, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, isobutyl isocyanate, tert-butyl isocyanate , phenyl isocyanate, 2-toluene isocyanate, 3-toluene isocyanate, 4-toluene isocyanate, 1-naphthyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, 2-isocyanate ethyl methacrylate, 2-methyl Oxyphenyl isocyanate, 3-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, amyl isocyanate, hexyl isocyanate, and the like.

特定聚合物之羧基與反應用的具有縮水甘油基及異氰酸酯基中選出之官能基的化合物之反應溫度可選用50至160℃，較佳為80至140℃之任意溫度。例如可以反應溫度為100至130℃、反應時間為2至48小時之條件得到本發明用之成份(A)的聚酯。The reaction temperature of the carboxyl group of the specific polymer with the compound having a glycidyl group and a functional group selected from the isocyanate group for the reaction may be selected from any temperature of from 50 to 160 ° C, preferably from 80 to 140 ° C. For example, the polyester of the component (A) used in the present invention can be obtained under the conditions of a reaction temperature of 100 to 130 ° C and a reaction time of 2 to 48 hours.

由此而得的含有(A)成份之聚酯的溶液可直接使用於調製本發明之熱硬化膜形成用感光性聚酯組成物。又，可於水、甲醇、乙醇、二乙基醚、己烷等弱溶劑中沈澱單離聚酯再回收使用。The solution containing the polyester of the component (A) thus obtained can be used as it is for preparing the photosensitive polyester composition for forming a thermosetting film of the present invention. Further, the isolated polyester can be precipitated and reused in a weak solvent such as water, methanol, ethanol, diethyl ether or hexane.

<(B)成份><(B) ingredients>

本發明之(B)成份的具有2個以上環氧基之環氧化合物如，三(2,3-環氧丙基)三聚異氰酸酯、1,4-丁二醇二縮水甘油醚、1,2-環氧-4-(環氧乙基)環己烷、甘油三縮水甘油醚、二乙二醇二縮水甘油醚、2,6-二縮水甘油基苯基縮水甘油醚、1,1,3-三[p-(2,3-環氧丙氧基)苯基]丙烷、1,2-環己烷二羧酸二縮水甘油酯、4,4’-伸甲基雙(N,N-二縮水甘油基苯胺)、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、三羥甲基乙烷三縮水甘油醚、雙酚A二縮水甘油醚及季戊四醇聚縮水甘油醚等。An epoxy compound having two or more epoxy groups as the component (B) of the present invention, such as tris(2,3-epoxypropyl)trimeric isocyanate, 1,4-butanediol diglycidyl ether, 1, 2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1, 3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-extended methyl double (N,N - diglycidyl aniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol A diglycidyl ether And pentaerythritol polyglycidyl ether and the like.

又就易取得性可使用市售之化合物。以下為其具體例(商品名)，但非限定於此等。YH-434、YH434L(東都化成(股)製)等具有胺基之環氧樹脂；耶波星GT-401、GT-403、GT-301、GT-302、歇洛吉2021、歇洛吉3000(泰歇爾化學工業(股)製)等具有環己烯氧化物構造之環氧樹脂；耶皮可1001、1002、1003、1004、1007、1009、1010、828(油化殼環氧(股)(現為日本環氧械脂(股))製)等雙酚A型環氧樹脂；耶皮可807(油化殼環氧(股)(現為日本環氧械脂(股))製)等雙酚F型環氧樹脂；耶皮可152、154(油化殼環氧(股)(現為日本環氧械脂(股))製)、EPPN 201、202(日本化藥(股)製)等苯酚酚醛清漆型環氧樹脂；EOCN-102、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-1025、EOCN-1027(日本化藥(股)製)、耶皮可180S75(油化殼環氧(股)(現為日本環氧械脂(股))製)等甲酚酚醛清漆型環氧樹脂；提那可EX-252(那卡歇(股)製)、CY175、CY177、CY179、艾拉爾CY-182、CY-192、CY-184(CIBA-GEIGY A.G製)、那皮庫200、400(大日本油墨化學工業(股)製)、耶皮可871、872(油化殼環氧(股)(現為日本環氧械脂(股))製)、ED-5661、ED-5662(歇拉尼(股)製)等脂環式環氧樹脂；提那可EX-611、EX-612、EX-614、EX-622、EX-411、EX-512、EX-522、EX-421、EX-313、EX-314、EX-321(那卡歇(股)製)等脂肪族聚縮水甘油醚等。Commercially available compounds can also be used for ease of availability. The following are specific examples (trade names), but are not limited thereto. YH-434, YH434L (Dongdu Chemical Co., Ltd.) and other amine-based epoxy resins; Yevoda GT-401, GT-403, GT-301, GT-302, Shi Luoji 2021, Shi Luoji 3000 Epoxy resin with cyclohexene oxide structure, such as (Taylor Chemical Industry Co., Ltd.); Jupiter 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (oiled shell epoxy) ) (now made by Japan Epoxy Resin Co., Ltd.) and other bisphenol A type epoxy resin; Yapi 807 (oiled shell epoxy (stock) (now Japanese epoxy resin) ) bisphenol F type epoxy resin; yuppie 152, 154 (oiled shell epoxy (stock) (now known as Japan epoxy resin)), EPPN 201, 202 (Nippon Chemicals Co., Ltd.) )) phenol novolac type epoxy resin; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Yippei 180S75 ( A phenolic novolac type epoxy resin such as oleoresin epoxy (stock) (now manufactured by Japan Epoxy Resin Co., Ltd.); Tinaco EX-252 (manufactured by Nakacher Co., Ltd.), CY175, CY177, CY179, Alar CY-182, CY-192, CY-184 (manufactured by CIBA-GEIGY AG), Napiku 200, 400 (made by Dainippon Ink Chemical Industry Co., Ltd.), yeah 871, 872 (oiled shell epoxy (stock) (now manufactured by Japan Epoxy Membrane)), ED-5661, ED-5662 (made by the company) Resin; Tinaco EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (that An aliphatic polyglycidyl ether, etc., such as a Karlscher (stock) system.

又，具有至少2個環氧基之化合物可使用具有環氧基之聚合物。該類聚合物可為具有環氧基之物無特別限制使用。Further, as the compound having at least two epoxy groups, a polymer having an epoxy group can be used. The polymer may be any one having an epoxy group and is not particularly limited.

前述具有環氧基之聚合物可藉由，例如使用具有環氧基之加成聚合性單體的加成聚合而得。其例如，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加成聚合聚合物，或環氧酚醛清漆等縮聚合聚合物。The above epoxy group-containing polymer can be obtained, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. For example, polyglycidyl acrylate, copolymer of glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate and copolymerization of styrene and 2-hydroxyethyl methacrylate Addition polymerized polymer such as a material, or a polycondensation polymer such as an epoxy novolac.

又，前述具有環氧基之聚合物可藉由，具有羥基之高分子化合物與環氧氯丙烷、縮水甘油基對甲苯磺酸酯等具有環氧基之化合物的反應而得。Further, the epoxy group-containing polymer can be obtained by a reaction of a polymer compound having a hydroxyl group with a compound having an epoxy group such as epichlorohydrin or glycidyl p-toluenesulfonate.

該類聚合物之重量平均分子量為，聚苯乙烯換算下例如300至200,000。The weight average molecular weight of such polymers is, for example, from 300 to 200,000 in terms of polystyrene.

此等具有2個以上環氧基之環氧化合物可單獨或2種以上組合使用。These epoxy compounds having two or more epoxy groups may be used singly or in combination of two or more kinds.

本發明之熱硬化膜形成用感光性聚酯組成物中(B)成份的含量，相對於(A)成份之聚酯100質量份較佳為3至50質量份，更佳為5至40質量份，特佳為10至30質量份。該比率過小時，會降低自熱硬化膜形成用感光性聚酯組成物形成的硬化膜之溶劑性及耐熱性，又過大時會降低溶劑耐性及保存安定性。The content of the component (B) in the photosensitive polyester composition for forming a thermosetting film of the present invention is preferably from 3 to 50 parts by mass, more preferably from 5 to 40 parts by mass based on 100 parts by mass of the polyester of the component (A). It is particularly preferably 10 to 30 parts by mass. When the ratio is too small, the solvent property and heat resistance of the cured film formed of the photosensitive polyester composition for forming a thermosetting film are lowered, and when it is too large, solvent resistance and storage stability are lowered.

<(C)成份><(C) ingredients>

(C)成份為，二胺化合物與二羧酸二酐反應而得的含有胺基之羧酸化合物。詳細而言為，下述式(iii)所表示之二胺化合物1莫耳與下述式(iv)所表示之二羧酸酐1.7至2莫耳，較佳為1.8至2莫耳反應而得的含有胺基之羧酸化合物。The component (C) is an amine group-containing carboxylic acid compound obtained by reacting a diamine compound with a dicarboxylic acid dianhydride. Specifically, the diamine compound 1 represented by the following formula (iii) is 1.7 to 2 moles, preferably 1.8 to 2 moles, of the dicarboxylic acid anhydride represented by the following formula (iv). An amine group-containing carboxylic acid compound.

【化14】【化14】

{式(iii)及式(iv)中，P及Q各自獨立為2價有機基}。In the formulae (iii) and (iv), P and Q are each independently a divalent organic group}.

因此藉由前述式(iii)所表示之二胺化合物與前述式(iv)所表示之二羧酸反應，可得下述式(2)所表示之化合物。Therefore, the compound represented by the following formula (2) can be obtained by reacting the diamine compound represented by the above formula (iii) with the dicarboxylic acid represented by the above formula (iv).

【化15】【化15】

{式中，P及Q同前述式(iii)及式(iv)定義}。In the formula, P and Q are the same as defined in the above formulas (iii) and (iv).

本發明中二胺化合物及二羧酸二酐可各自僅使用一種，或使用複數種。因此本發明之(C)成份的含有胺基之羧酸化合物非僅為一種前述式(2)所表示之化合物，可使用複數種。In the present invention, the diamine compound and the dicarboxylic dianhydride may each be used singly or in combination of plural kinds. Therefore, the amine group-containing carboxylic acid compound of the component (C) of the present invention is not limited to only one compound represented by the above formula (2), and a plurality of compounds can be used.

前述P及Q又以各自獨立為具有環構造之2價有機基為佳。該環構造如，苯環、脂環、縮合多環式碳化氫。The above P and Q are preferably each independently a divalent organic group having a ring structure. The ring structure is, for example, a benzene ring, an alicyclic ring, or a condensed polycyclic hydrocarbon.

前述式(iii)中，P所具有的環構造較佳為苯環、碳原子數4至8之脂環、碳原子數7至16之縮合多環式碳化氫。In the above formula (iii), the ring structure of P 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.

因此該類具有環構造之二胺化合物的具體例如下所述：p-伸苯基二胺、m-伸苯基二胺、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、2,4-二胺基苯酚、2,5-二胺基苯酚、4,6-二胺基間苯二酚、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-胺基苄基胺、3-胺基苄基胺、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、3,4’-二胺基聯苯、3,3’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二氟-4,4’-二胺基聯苯、2,2’-三氟甲基-4,4’-二胺基聯苯、3,3’-三氟甲基-4,4’-二胺基聯苯、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’-二胺基二苯基碸、3,3’-二胺基二苯基碸、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)、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、1,3-雙(4-胺基苯基)丙烷、1,3-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-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)十一烷、1,12-雙(4-胺基苯氧基)十二烷、雙(4-胺基苯基)丙烷二醇酯、雙(4-胺基苯基)丁烷二醇酯、雙(4-胺基苯基)戊烷二醇酯、雙(4-胺基苯基)己烷二醇酯、雙(4-胺基苯基)庚烷二醇酯、雙(4-胺基苯基)辛烷二醇酯、雙(4-胺基苯基)壬烷二醇酯、雙(4-胺基苯基)癸烷二醇酯、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-胺基苄基)苯、1,3-雙(4-胺基苄基)苯、雙(4-胺基苯基)對苯二甲酸酯、雙(3-胺基苯基)對苯二甲酸酯、雙(4-胺基苯基)間苯二甲酸酯、雙(3-胺基苯基)間苯二甲酸酯、1,4-伸苯基雙[(4-胺基苯基)甲酮]、1,4-伸苯基雙[(3-胺基苯基)甲酮]、1,3-伸苯基雙[(4-胺基苯基)甲酮]、1,3-伸苯基雙[(3-胺基苯基)甲酮]、1,4-伸苯基雙(4-胺基苯甲酸酯)、1,4-伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、N,N’-(1,4-伸苯基)雙(4-胺基苯醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯醯胺)、雙-(4-胺基苯基)對苯二甲醯胺、雙-(3-胺基苯基)對苯二甲醯胺、雙-(4-胺基苯基)間苯二甲醯胺、雙-(3-胺基苯基)間苯二甲醯胺、2,2-雙-[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙-[4-(4-胺基苯氧基)苯基]六氟丙烷、4,4’-雙(4-胺基苯氧基)二苯基碸、2,6-二胺基吡啶、2,4-二胺基吡啶、2,4-二胺基-1,3,5-三嗪、2,6-二胺基二苯并呋喃、2,7-二胺基二苯并呋喃、3,6-二胺基二苯并呋喃、2,6-二胺基咔唑、2,7-二胺基咔唑、3,6-二胺基咔唑、2,4-二胺基-6-異丙基-1,3,5-三嗪、2,5-雙(4-胺基苯基)-1,3,4-噁二唑、1,4-二胺基環己烷、1,3-二胺基環己烷、雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷等。Therefore, specific examples of such a diamine compound having a ring structure are as follows: p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene , 2,6-diaminotoluene, 2,4-dimethyl-1,3-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3,5, 6-tetramethyl-1,4-diaminobenzene, 2,4-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-di Amino benzoic acid, 3,5-diamino benzoic acid, N,N-diallyl-2,4-diaminoaniline, N,N-diallyl-2,5-diaminoaniline , 4-aminobenzylamine, 3-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 2-(3-aminophenyl)ethylamine, 1,5-naphthalene Diamine, 2,7-naphthalenediamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-di Methyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-di Aminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-difluoro -4,4'-diaminobiphenyl, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl, 3,3'- Fluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodi Phenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamine Diphenyl hydrazine, 3,3'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl), N-methyl ( 3,4'-Diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenyl Methyl ketone, 4,4'-diaminophenyl anilide, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 4,4 '-Diaminodiphenylacetylene, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 2,2-bis(4-aminobenzene) Propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 2,2-bis(4-aminobenzene) Hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylbenzene Hexafluoropropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxyl) Pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminobenzene Oxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane, 1,11-bis(4-amino Phenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, bis(4-aminophenyl)propanediol, bis(4-aminophenyl)butyl An alkanediol ester, bis(4-aminophenyl)pentanediol ester, bis(4-aminophenyl)hexanediolate, bis(4-aminophenyl)heptanediolate, Bis(4-aminophenyl)octanediolate, bis(4-aminophenyl)decanediolate, bis(4-aminophenyl)decanediolate, 1,4-double (4-Aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amine Phenoxy)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, bis(4-aminophenyl)-p-xylylene Acid ester, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate Formate, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1,3- Phenyl bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-amine) Benzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-stretch Phenyl bis(3-aminobenzoate), N,N'-(1,4-phenylene)bis(4-aminophenylguanamine), N,N'-(1,3-stretch Phenyl) bis(4-aminophenylguanamine), N,N'-(1,4-phenylene)bis(3-aminophenylguanamine), N,N'-(1,3-stretch Phenyl) bis(3-aminophenylguanamine), bis-(4-aminophenyl)terephthalamide, bis-(3-aminophenyl)terephthalamide, bis- (4-aminophenyl)m-xylyleneamine, bis-(3-aminophenyl)m-xylyleneamine, 2,2-bis-[4-(4-aminophenoxy) Phenyl]propane, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,6-diaminodibenzofuran, 2,7 -diaminodibenzofuran, 3,6-diaminodibenzo Er, 2,6-diaminocarbazole, 2,7-diaminocarbazole, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3, 5-triazine, 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane , bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, and the like.

又，前述式(iv)中，Q所具有的環構造較佳為苯環、碳原子數4至8之脂環、碳原子數7至16之縮合多環式碳化氫。Q更佳為苯環、碳原子數4至8之脂環、碳原子數7至16之縮合多環式碳化氫。Further, in the above formula (iv), the ring structure of Q 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. More preferably, Q is a benzene ring, an alicyclic ring having 4 to 8 carbon atoms, and a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms.

具有該類環構造之二羧酸二酐的具體例如，酞酸酐、偏苯三酸酐、馬來酸酐、萘二甲酸酐、氫化酞酸酐、甲基-5-降茨烯-2,3-二羧酸酐、衣康酸酐、四氫酞酸酐等。Specific examples of the dicarboxylic dianhydride having such a ring structure include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norzene-2,3-dicarboxylic anhydride, Itaconic anhydride, tetrahydrophthalic anhydride, and the like.

製造上述(C)成份之化合物時，二胺化合物與二羧酸二酐之反應溫度可選用5至80℃，較佳為10至50℃之任意溫度。When the compound of the above (C) component is produced, the reaction temperature of the diamine compound and the dicarboxylic dianhydride may be any temperature of 5 to 80 ° C, preferably 10 to 50 ° C.

前述反應一般係於溶劑中進行。此時所使用的溶劑可為，不含羥基、胺基等會與酸酐反應之官能基之物無特別限定。例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-乙烯基吡咯烷酮、N-甲基己內醯胺、二甲基咪唑、二甲基亞碸、四甲基尿素、二甲基碸、六甲基亞碸、m-甲酚、γ-丁內酯、環己酮、環庚酮、甲基乙基酮、甲基異丁基酮、2-庚酮、丙二醇單甲基醚乙酸酯、丙二醇丙基醚乙酸酯、3-甲氧基丙酸甲酯、2-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、2-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、2-乙氧基丙酸乙酯、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、環己醇、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯等。The foregoing reaction is generally carried out in a solvent. The solvent to be used in this case is not particularly limited as long as it does not contain a functional group which reacts with an acid anhydride such as a hydroxyl group or an amine group. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl Imidazole, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethyl hydrazine, m-cresol, γ-butyrolactone, cyclohexanone, cycloheptanone, methyl ethyl ketone, A Isobutyl ketone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, 3- Ethyl methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, methyl cellosolve acetate, ethyl ester Fibril acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, cyclohexanol, ethyl acetate, butyl acetate, ethyl lactate, lactic acid Butyl ester and the like.

此等溶劑可單獨或混合使用，但就溶解性較佳為丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、二甲基咪唑。These solvents may be used singly or in combination, but the solubility is preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N,N-dimethylacetamide, N-methyl-2-pyrrolidone , dimethylimidazole.

又，既使為不能溶解含有胺基之羧酸化合物的溶劑，於不會析出聚合反應所生成的該化合物之範圍內，可混合前述溶劑使用。Further, even if it is a solvent which cannot dissolve the amine group-containing carboxylic acid compound, it can be used by mixing the above solvent within the range in which the compound formed by the polymerization reaction is not precipitated.

本發明之熱硬化膜形成用聚酯組成物中，(C)成份含量相對於(A)成份之聚酯100質量份較佳為3至50質量份，更佳為5至40質量份。該比率過小時會降低自本發明之熱硬化膜形成用聚酯組成物形成的硬化膜之配向性，又過大時會降低透過率及平坦化型。In the polyester composition for forming a thermosetting film of the present invention, the content of the component (C) is preferably from 3 to 50 parts by mass, more preferably from 5 to 40 parts by mass, per 100 parts by mass of the polyester of the component (A). When the ratio is too small, the alignment property of the cured film formed from the polyester composition for forming a thermosetting film of the present invention is lowered, and when it is too large, the transmittance and the flattening type are lowered.

<(D)成份><(D) ingredient>

(D)成份之1,2-醌二疊氮化合物為，具有羥基或胺基中任何一方，或具有羥基及胺基雙方之化合物，此等羥基或胺基(具有羥基及胺基雙方時為其合計量)中又以使用10至100莫耳%，特佳為20至95莫耳%的經1,2-醌二疊氮磺酸而酯化，或醯胺化之化合物為佳。The (1) component of the 1,2-quinonediazide compound is a compound having either a hydroxyl group or an amine group, or a compound having both a hydroxyl group and an amine group, and such a hydroxyl group or an amine group (when having both a hydroxyl group and an amine group) Further, it is preferred to use a compound of 10 to 100 mol%, particularly preferably 20 to 95 mol%, esterified with 1,2-quinonediazidesulfonic acid, or an amidated compound.

前述具有羥基之化合物如，苯酚、o-甲酚、m-甲酚、p-甲酚、氫醌、間苯二酚、兒茶酚、棓酸甲酯、棓酸乙酯、1,3,3-三(4-羥基苯基)丁烷、4,4-異亞丙基二苯酚、2,2-雙(4-羥基苯基)丙烷、1,1-雙(4-羥基苯基)環己烷、4,4’-二羥基苯基碸、4,4-六氟異亞丙基二苯酚、4,4’,4”-三羥基苯基乙烷、1,1,1-三羥基苯基乙烷、4,4’-[1-[4-[1-(4-羥基苯基)-1-甲基乙基]苯基]亞乙基]雙酚、2,4-二羥基二苯甲酮、2,3,4-三羥基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2,3,4,4’-四羥基二苯甲酮、2,2’,3,4,4’-五羥基二苯甲酮、2,5-雙(2-羥基-5-甲基苄基)甲酯等苯酚化合物、乙醇、2-丙醇、4-丁醇、環己醇、乙二醇、丙二醇、二乙二醇、二丙二醇、2-甲氧基乙醇、2-丁氧基乙醇、2-甲氧基丙醇、2-丁氧基丙醇、乳酸乙酯、乳酸丁酯等脂肪族醇類。The aforementioned compound having a hydroxyl group such as phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl decanoate, ethyl decanoate, 1,3, 3-tris(4-hydroxyphenyl)butane, 4,4-isopropylidenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl) Cyclohexane, 4,4'-dihydroxyphenylhydrazine, 4,4-hexafluoroisopropylidene diphenol, 4,4',4"-trihydroxyphenylethane, 1,1,1-three Hydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 2,4-di Hydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxydiphenyl Phenolic compounds such as ketone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,5-bis(2-hydroxy-5-methylbenzyl)methyl ester, ethanol, 2-propanol , 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxy An aliphatic alcohol such as propyl alcohol, ethyl lactate or butyl lactate.

又，前述含有胺基之化合物如，苯胺、o-甲苯胺、m-甲苯胺、p-甲苯胺、4-胺基二苯基甲烷、4-胺基二苯酯、o-伸苯基二胺、m-伸苯基二胺、p-伸苯基二胺、4,4’-二胺基苯基甲烷、4,4’-二胺基二苯基醚等苯胺類、胺基環己烷。Further, the above amine group-containing compound such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl ester, o-phenylene An amine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, aniline, amine ring alkyl.

又，前述含有羥基及胺基雙方之化合物如，o-胺基苯酚、m-胺基苯酚、p-胺基苯酚、4-胺基甲酚、2,3-二胺基甲酚、2,4-二胺基苯酚、4,4’-二胺基-4”-羥基三苯基甲烷、4-胺基-4’,4”-二羥基三苯基甲烷、雙(4-胺基-3-羧基-5-羥基苯基)醚、雙(4-胺基-3-羧基-5-羥基苯基)甲烷、2,2-雙(4-胺基-3-羧基-5-羥基苯基)丙烷、2,2-雙(4-胺基-3-羧基-5-羥基苯基)六氟丙烷等胺基苯酚類、2-胺基乙醇、3-胺基丙醇、4-胺基環己醇等烷醇胺類。Further, the compound containing both a hydroxyl group and an amine group is, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-aminocresol, 2,3-diaminocresol, 2, 4-diaminophenol, 4,4'-diamino-4"-hydroxytriphenylmethane, 4-amino-4',4"-dihydroxytriphenylmethane, bis(4-amino- 3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxybenzene Aminophenols such as propane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane, 2-aminoethanol, 3-aminopropanol, 4-amine Alkanolamines such as cyclohexanol.

此等1,2-醌二疊氮化合物可單獨或2種以上組合使用。These 1,2-quinonediazide compounds may be used singly or in combination of two or more kinds.

本發明之熱硬化膜形成用感光性聚酯組成物中，(D)成份含量相對於(A)成份100質量份較佳為5至80質量份、更佳為8至60質量份，特佳為10至50質量份。該比率過小時會減少相對於顯像液之溶解速度，而難藉由顯像製圖。又超過100質量份時，短時間曝光將無法充分分解1,2-醌二疊氮化合物，而會降低敏感度，及(D)成份會吸收光而降低硬化膜之透明性。In the photosensitive polyester composition for forming a thermosetting film of the present invention, the content of the component (D) is preferably from 5 to 80 parts by mass, more preferably from 8 to 60 parts by mass, per 100 parts by mass of the component (A). It is 10 to 50 parts by mass. When the ratio is too small, the dissolution rate with respect to the developing solution is reduced, and it is difficult to perform drawing by development. When it exceeds 100 parts by mass, the short-time exposure will not sufficiently decompose the 1,2-quinonediazide compound, which will lower the sensitivity, and the (D) component will absorb light and lower the transparency of the cured film.

<(E)成份><(E) ingredient>

本發明可含有(E)成份用之下述式(3)所表示的雙馬來醯亞胺化合物。The present invention may contain a bismaleimide compound represented by the following formula (3) for the component (E).

(E)成份之雙馬來醯亞胺化合物可提升平坦化性。The (B) component of the bismaleimide compound enhances planarization.

【化16】【化16】

(式中，M₁ 為脂肪族基、含有環式構造之脂肪族基及芳香族基所成群中選出之有機基或此等之群中選出的複數有機基組成之有機基。又M₁ 可含有酯鍵、醚鍵、醯胺鍵、胺基甲酸乙酯等鍵)。(wherein M ₁ is an aliphatic group, an aliphatic group having a cyclic structure, and an organic group selected from the group consisting of an aromatic group or an organic group selected from the plurality of organic groups selected from the group. Further, M ₁ It may contain an ester bond, an ether bond, a guanamine bond, or a urethane bond.

該類雙馬來醯亞胺化合物如，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、3,3-二苯基碸雙馬來醯亞胺、4,4-二苯基碸雙馬來醯亞胺、N,N’-p-二苯甲酮雙馬來醯亞胺、N,N’-二苯基乙烷雙馬來醯亞胺、N,N’-二苯基醚雙馬來醯亞胺、N,N’-(伸甲基二-二四氫苯基)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、N,N’-(3,3-二乙基)-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’-三嗪雙馬來醯亞胺、N,N’-二苯基丙烷馬來醯亞胺、N,N’-萘雙馬來醯亞胺、N,N’-m-伸苯基雙馬來醯亞胺、N,N’-5-甲氧基-1,3-伸苯基雙馬來醯亞胺、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、1,1-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)乙烷、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-(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)苯基)戊烷、1,1,1,3,3,3-六氟-2,2-雙(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,N’-伸乙基二馬來醯亞胺、N,N’-六伸甲基雙馬來醯亞胺、N,N’-十二伸甲基雙馬來醯亞胺、N,N’-m-二甲苯雙馬來醯亞胺、N,N’-p-二甲苯雙馬來醯亞胺、N,N’-1,3-雙伸甲基環己烷雙馬來醯亞胺、N,N’-2,4-伸苄基雙馬來醯亞胺、N,N’-2,6-伸苄基雙馬來醯亞胺等。此等雙馬來醯亞胺化合物無特別限定為上述之物。Such a bismaleimide compound such as N,N'-3,3-diphenylmethane bismaleimide, N,N'-(3,3-diethyl-5,5-di Methyl)-4,4-diphenyl-methane bismaleimide, N,N'-4,4-diphenylmethane bismaleimide, 3,3-diphenylfluorene double horse Indole, 4,4-diphenylfluorene, bismaleimide, N,N'-p-benzophenone, bismaleimide, N,N'-diphenylethane, double horse醯iimine, N,N'-diphenyl ether, bismaleimide, N,N'-(methyl-di-ditetrahydrophenyl)maleimide, N,N'-( 3-ethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dimethyl)-4,4-diphenylmethane bismaleimide , N,N'-(3,3-diethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dichloro)-4,4-di Phenylmethane bismaleimide, N,N'-isophorone bismaleimide, N,N'-triazine bismaleimide, N,N'-diphenylpropane horse醯iimine, N,N'-naphthalene, bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-5-methoxy-1,3- Phenyl 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-maleimide) Oxy)phenyl)propane, 2,2-bis(3-ethyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-propyl-4 -(4-maleimide phenoxy)phenyl)propane, 2,2-bis(3-isopropyl-4-(4-maleimidophenoxy)phenyl)propane, 2 ,2-bis(3-butyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-methoxy-4-(4-mala) Amine phenoxy)phenyl)propane, 1,1-bis(4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-methyl-4-() 4-maleimide phenoxy)phenyl)ethane, 1,1-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)ethane, 1,1 - bis(3-bromo-4-(4-maleimidophenoxy)phenyl)ethane, 3,3-bis(4-(4-maleimidophenoxy)phenyl) Pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-maleimidophenoxy)phenyl)propane, 1,1,1,3,3, 3-hexafluoro-2,2-bis(3,5-dimethyl-4-(4-maleimidophenoxy)phenyl)propane, 1,1,1,3,3,3- Hexafluoro-2,2-bis(3,5-dibromo-4-(4-maleimidophenoxy)phenyl)propane, N,N'-extended ethyl dimale Imine, N, N'-hexa-methyl-m-maleimide, N, N'-dodemethyl-m-maleimide, N, N'-m-xylene double malayan Amine, N, N'-p-xylene bismaleimide, N, N'-1,3-dise methylcyclohexane bismaleimide, N, N'-2,4- Benzyl bismaleimide, N, N'-2,6-extended benzyl bismaleimide and the like. These bismaleimide compounds are not particularly limited to the above.

此等可單獨或2種以上之成份併用。These may be used alone or in combination of two or more.

此等馬來醯亞胺中較佳為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-甲烷雙馬來醯亞胺等芳香族雙馬來醯亞胺。Preferred among these maleimides are 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, N,N'-4,4-diphenylmethane double Aromatic double horses such as maleic imine, N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismaleimide Yttrium.

又，此等芳香族雙馬來醯亞胺中，為了得到更高平坦化性較佳為分子量1,000以下之物。Further, among these aromatic bismaleimine, a polymer having a molecular weight of 1,000 or less is preferable in order to obtain higher flatness.

本發明之熱硬化膜形成用感光性聚酯組成物中，(E)成份含量相對於(A)成份之聚酯100質量份較佳為0.5至50質量份，更佳為1至30質量份，特佳為2至20質量份。該比率過小時會降低自本發明之熱硬化膜形成用感光性聚酯組成物形成的硬化膜之平坦化性，過大時會降低硬化膜之透過率及使塗膜粗糙。In the photosensitive polyester composition for forming a thermosetting film of the present invention, the content of the component (E) is preferably from 0.5 to 50 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the polyester of the component (A). It is particularly preferably 2 to 20 parts by mass. When the ratio is too small, the flattening property of the cured film formed from the photosensitive polyester composition for forming a thermosetting film of the present invention is lowered, and when it is too large, the transmittance of the cured film is lowered and the coating film is roughened.

<溶劑><solvent>

本發明之熱硬化膜形成用感光性聚酯組成物多半係以溶解於溶劑之溶液狀態使用。此時所使用的溶劑為，可溶解(A)成份至(C)成份，必要時使用之(E)成份及/或後述其他添加劑，而具有該類溶解時之溶劑無特別限定其種類及構造等。Most of the photosensitive polyester composition for forming a thermosetting film of the present invention is used in the form of a solution dissolved in a solvent. The solvent to be used at this time is such that the component (A) to the component (C) can be dissolved, and if necessary, the component (E) and/or other additives described later are used, and the solvent in the case of such dissolution is not particularly limited in kind and structure. Wait.

該類溶劑如，聚合特定聚合物時所使用的溶劑及上述反應溶劑，又如乙酸乙酯、乙酸丁酯等。此等溶劑可單獨或二種以上組合使用。Such a solvent is, for example, a solvent used for polymerizing a specific polymer and the above-mentioned reaction solvent, such as ethyl acetate, butyl acetate or the like. These solvents may be used alone or in combination of two or more.

<其他添加劑><Other additives>

又，本發明之熱硬化膜形成用感光性聚酯組成物於無損本發明效果下，必要時可含有表面活性劑、液流調整劑、矽烷偶合劑等接著補助劑、顏料、染料、保存安定劑、消泡劑、多價苯酚及多價羧酸等溶解促進劑等。Further, the photosensitive polyester composition for forming a thermosetting film of the present invention may contain a surfactant, a liquid flow regulator, a decane coupling agent, and the like, a binder, a pigment, a dye, and a storage stability, if the effect of the present invention is not impaired. A dissolution promoter such as a solvent, an antifoaming agent, a polyvalent phenol or a polyvalent carboxylic acid.

<熱硬化膜形成用感光性聚酯組成物><Photosensitive polyester composition for forming a thermosetting film>

本發明之熱硬化膜形成用感光性聚酯組成物可為，含有(A)成份之聚酯、(B)成份之具有2個以上環氧基的環氧化合物、(C)成份之含有胺基的羧酸化合物、(C)成份之1,2-醌二疊氮化合物，及所希望之(E)成份之雙馬來醯亞胺化合物，以及其他添加劑中一種以上之組成物。一般此等多半係以溶解於溶劑之溶液狀使用。The photosensitive polyester composition for forming a thermosetting film of the present invention may be an epoxy compound containing (A) component, (B) component having two or more epoxy groups, and (C) component containing an amine. a carboxylic acid compound of the group, a 1,2-quinonediazide compound of the component (C), and a bismaleimide compound of the desired (E) component, and one or more of the other additives. Generally, most of these are used in the form of a solution dissolved in a solvent.

其中本發明之熱硬化膜形成用感光性聚酯組成物較佳如下述之物。Among them, the photosensitive polyester composition for forming a thermosetting film of the present invention is preferably as follows.

[1]：基於(A)成份100質量份含有3至50質量份之(B)成份、3至50質量份之(C)成份、5至80質量份之(D)成份的熱硬化膜形成用感光性聚酯組成物。[1]: a thermosetting film containing 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), and 5 to 80 parts by mass of the component (D) based on 100 parts by mass of the component (A) A photosensitive polyester composition is used.

[2]：基於(A)成份100質量份含有3至50質量份之(B)成份、3至50質量份之(C)成份、5至80質量份之(D)成份、溶劑的熱硬化膜形成用感光性聚酯組成物。[2]: Based on 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), 5 to 80 parts by mass of the component (D), and heat hardening of the solvent. A photosensitive polyester composition for film formation.

[3]：基於(A)成份100質量份含有3至50質量份之(B)成份、3至50質量份之(C)成份、5至80質量份之(D)成份、0.5至50質量份之(E)成份的熱硬化膜形成用感光性聚酯組成物。[3]: based on 100 parts by mass of the (A) component, 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), 5 to 80 parts by mass of the component (D), and 0.5 to 50 mass. A photosensitive polyester composition for forming a thermosetting film of the component (E).

[4]：基於(A)成份100質量份含有3至50質量份之(B)成份、3至50質量份之(C)成份、5至80質量份之(D)成份、0.5至50質量份之(E)成份、溶劑的熱硬化膜形成用感光性聚酯組成物。[4]: based on 100 parts by mass of the (A) component, 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), 5 to 80 parts by mass of the component (D), and 0.5 to 50 mass. A photosensitive polyester composition for forming a thermosetting film of the component (E) and a solvent.

以溶液狀使用本發明之熱硬化膜形成用感光性聚酯組成物時，添加比率、調製方法等如下詳述。When the photosensitive polyester composition for forming a thermosetting film of the present invention is used in the form of a solution, the addition ratio, the preparation method, and the like are as described in detail below.

本發明之熱硬化膜形成用感光性聚酯組成物中，能將各成份均勻溶解於溶劑時固體成份之比率無特別限定，可為1至80質量%，較佳為5至60質量%，更佳為10至50質量%。該固體成份係指，熱硬化膜形成用感光性聚酯組成物之全部成份去除溶劑後之物。In the photosensitive polyester composition for forming a thermosetting film of the present invention, the ratio of the solid component when the components are uniformly dissolved in the solvent is not particularly limited, and may be from 1 to 80% by mass, preferably from 5 to 60% by mass. More preferably, it is 10 to 50% by mass. The solid content refers to a substance obtained by removing all the components of the photosensitive polyester composition for forming a thermosetting film.

本發明之熱硬化膜形成用感光性聚酯組成物的調製方法無特別限定，該調製方法如，將(A)成份溶解於溶劑後，該溶液以一定比率混合(B)成份、(C)成份、(D)成份及(E)成份，得均勻溶液之方法，或於該調整方法之適當階段另添加混合必要時使用的其他添加劑之方法。The preparation method of the photosensitive polyester composition for forming a thermosetting film of the present invention is not particularly limited. For example, after the component (A) is dissolved in a solvent, the solution is mixed in a certain ratio (B), (C) The component, the component (D) and the component (E) are obtained by a method of uniformly concentrating the solution, or by adding another additive which is necessary if necessary at the appropriate stage of the adjustment method.

調製本發明之熱硬化膜形成用感光性聚酯組成物時，可直接使用溶劑中藉由聚合反應而得的聚酯溶液。此時同前述將(B)成份、(C)成份、(D)成份、(E)成份等加入該(A)成份溶液中形成均勻溶液時，為了調整濃度可另追加溶劑。此時生成聚酯之過程中所使用的溶劑可同或不同於調製熱硬化膜形成用感光性聚酯組成物時調整濃度用之溶劑。When the photosensitive polyester composition for forming a thermosetting film of the present invention is prepared, a polyester solution obtained by a polymerization reaction in a solvent can be used as it is. In this case, when the component (B), the component (C), the component (D), and the component (E) are added to the solution of the component (A) to form a homogeneous solution, a solvent may be additionally added to adjust the concentration. The solvent used in the process of producing the polyester at this time may be the same as or different from the solvent for adjusting the concentration when the photosensitive polyester composition for forming a thermosetting film is prepared.

又以使用孔徑0.2μm之濾器等過濾調製後之熱硬化膜形成用感光性聚酯組成物溶液後再使用為佳。Further, it is preferably used after filtering the prepared photosensitive polyester composition solution for forming a thermosetting film by using a filter having a pore size of 0.2 μm or the like.

<塗膜、硬化膜及液晶配向層><Coating film, cured film, and liquid crystal alignment layer>

將本發明之熱硬化膜形成用感光性聚酯組成物回轉塗佈、流動塗佈、輥塗佈、縫隙塗佈、縫隙加上回轉塗佈、噴墨塗佈、利用印刷等塗佈於基板(例如，矽/二氧化矽被覆基板、氮化矽基板、被金屬，例如鋁、鉬、鉻等被覆之基板、玻璃基板、石英基板、ITO基板等)或薄膜(例如，三乙醯纖維系膜、聚酯膜、丙烯酸膜等樹脂薄膜)等上方後，以熱板或烤箱等預備乾燥(預烤)，可形成塗膜。其後加熱處理該塗膜，形成被膜。The photosensitive polyester composition for forming a thermosetting film of the present invention is applied by spin coating, flow coating, roll coating, slit coating, slit coating, rotary coating, inkjet coating, or printing onto a substrate. (for example, a ruthenium/cerium oxide-coated substrate, a tantalum nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, or the like) or a film (for example, a triethylene fluorene fiber system) After the film or the like, a resin film such as a polyester film or an acrylic film, or the like is applied, it is preliminarily dried (prebaked) by a hot plate or an oven to form a coating film. Thereafter, the coating film is heat-treated to form a coating film.

該加熱處理條件可採用，例如自溫度70至160℃，時間0.3至60分鐘之範圍內選擇的加熱溫度及加熱時間。加熱溫度及加熱時間較佳為80至140℃、0.5至10分鐘。The heat treatment conditions may be, for example, a heating temperature and a heating time selected from a temperature of 70 to 160 ° C and a time of 0.3 to 60 minutes. The heating temperature and heating time are preferably from 80 to 140 ° C for 0.5 to 10 minutes.

又，自熱硬化膜形成用感光性聚酯組成物形成的被膜膜厚例如0.1至30μm，可考量所使用的基板段差及光學、電氣性質後適當選擇。Further, the film thickness of the film formed of the photosensitive polyester composition for forming a thermosetting film is, for example, 0.1 to 30 μm, and can be appropriately selected in consideration of the substrate step difference and optical and electrical properties to be used.

後烤時一般係採因溫度140至250℃之範圍內選出的加熱溫度下，使用熱板時處理5至30分鐘，使用烤箱時處理30至90分鐘之方法。The post-baking method is generally carried out at a heating temperature selected in the range of 140 to 250 ° C, for 5 to 30 minutes when using a hot plate, and for 30 to 90 minutes when using an oven.

藉由上述條件硬化本發明之熱硬化膜形成用感光性聚酯組成物，可形成基板段差充分平坦化、具有高透明性之硬化膜。By curing the photosensitive polyester composition for forming a thermosetting film of the present invention under the above conditions, a cured film having a sufficiently high flatness and a high transparency can be formed.

對所形成的硬化膜進行摩擦處理，可得液晶材配向層，即具有液晶性之化合物經配向的層用之機能。By rubbing the formed cured film, a liquid crystal material alignment layer, that is, a function of a layer having a liquid crystal compound aligned.

摩擦處理之條件一般得使用回轉速度300至1000rpm、運送速度3至200mm/秒、擠壓量0.1至1mm之條件。The conditions of the rubbing treatment generally use a condition of a rotation speed of 300 to 1000 rpm, a conveying speed of 3 to 200 mm/sec, and a pressing amount of 0.1 to 1 mm.

其後使用純水等進行超音波洗淨以去除所生成的殘渣。Thereafter, ultrasonic cleaning is performed using pure water or the like to remove the generated residue.

將相位差材料塗佈於上述形成之液晶配向層後，將相位差材料光硬化為液晶狀態，可形成具有光學各向異性之層。After the phase difference material is applied to the liquid crystal alignment layer formed as described above, the phase difference material is photocured into a liquid crystal state to form a layer having optical anisotropy.

相位差材料例如可使用具有聚合性基之液晶單體或含有其之組成物等。As the phase difference material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the same can be used.

形成液晶配向層之基材為薄膜狀時，適用為光學各向異性薄膜。When the base material forming the liquid crystal alignment layer is in the form of a film, it is suitably used as an optically anisotropic film.

又，介有調距器以液晶配向層面對面方式貼合上述所形成的具有液晶配向層之基板2枚後，將液晶注入此等基板之間，得液晶配向之液晶顯示元件。In addition, a liquid crystal display element in which liquid crystal is aligned is obtained by bonding two liquid crystal alignment layers to each other with a liquid crystal alignment layer facing the surface of the substrate, and then injecting liquid crystal between the substrates.

因此本發明之熱硬化膜形成用感光性聚酯組成物適用於各種光學各向異性薄膜、液晶顯示元件。Therefore, the photosensitive polyester composition for forming a thermosetting film of the present invention is suitable for use in various optically anisotropic films and liquid crystal display elements.

又，因本發明之熱硬化膜形成用感光性聚酯組成物具有至少必要水準之平坦化性，故適用為形成薄膜晶體管(TFT)型液晶顯示元件、有機EL元件等各種顯示器之保護膜、平坦化膜、絕緣膜等硬化膜用之材料，特別是適用為彩色濾光片之保護膜材料、TFT型液晶元件之層間絕緣膜、有機EL元件之絕緣膜等。In addition, since the photosensitive polyester composition for forming a thermosetting film of the present invention has at least a required level of flatness, it is preferably used as a protective film for forming various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element. A material for a cured film such as a flattening film or an insulating film is preferably used as a protective film material for a color filter, an interlayer insulating film for a TFT-type liquid crystal device, an insulating film for an organic EL device, or the like.

實施例Example

下面將舉實施例更詳細說明本發明，但本發明非限定於此等實施例。The invention will be described in more detail below by way of examples, but the invention is not limited thereto.

[實施例所使用的代號][Code used in the embodiment]

下面為實施例所使用之代號的意義。The following is the meaning of the code used in the examples.

<聚酯原料><Polyester raw materials>

BPDA：聯苯四羧酸二酐BPDA: biphenyltetracarboxylic dianhydride

HBPDA：3,3’-4,4’-雙環己基四羧酸二酐HBPDA: 3,3'-4,4'-dicyclohexyltetracarboxylic dianhydride

HBPA：氫化雙酚AHBPA: hydrogenated bisphenol A

THPA：1,2,5,6-四氫酞酸酐THPA: 1,2,5,6-tetrahydrophthalic anhydride

BTEAC：苄基三乙基銨氯化物BTEAC: benzyl triethyl ammonium chloride

TPPB：四苯基鏻溴化物TPPB: tetraphenylphosphonium bromide

GMA：縮水甘油基甲基丙烯酸酯GMA: glycidyl methacrylate

GME：縮水甘油基甲基醚GME: glycidyl methyl ether

DTBC：二-tert-丁基甲酚DTBC: di-tert-butyl cresol

<聚醯亞胺先驅物及含有胺基之羧酸化合物原料><Polyimide precursor and carboxylic acid compound raw material containing an amine group>

CBDA：環己烷四羧酸二酐CBDA: cyclohexane tetracarboxylic dianhydride

DA-4P：1,3-雙(4-胺基苯基)苯DA-4P: 1,3-bis(4-aminophenyl)benzene

DA-1M：4,4’-雙(4-胺基苯氧基)二苯基碸DA-1M: 4,4'-bis(4-aminophenoxy)diphenylanthracene

TA：偏苯三酸酐TA: trimellitic anhydride

DDS：4,4’-二胺基二苯基碸DDS: 4,4'-diaminodiphenylanthracene

pDA：p-伸苯基二胺pDA: p-phenylenediamine

<丙烯酸基共聚物原料><Acrylic based copolymer raw material>

MAA：甲基丙烯酸MAA: Methacrylic acid

MMA：甲基甲基丙烯酸酯MMA: methyl methacrylate

HEMA：2-羥基乙基甲基丙烯酸酯HEMA: 2-hydroxyethyl methacrylate

CHMI：N-環己基馬來醯亞胺CHMI: N-cyclohexylmaleimide

AIBN：偶氮雙丁腈AIBN: azobisbutyronitrile

<環氧化合物><epoxy compound>

CEL：泰歇爾化學工業(股)製歇洛吉P-2021(製品名)(化合物：3,4-環氧環己烯基甲基-3’,4’-環氧環己烯羧酸酯)CEL: Michelle P-2021 (product name) manufactured by Taychel Chemical Industry Co., Ltd. (compound: 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexenecarboxylic acid ester)

<雙馬來醯亞胺化合物><Bismaleimide compound>

BMI1：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BMI1: N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismaleimide

<1,2-醌二疊氮化合物><1,2-醌diazide compound>

QD1：藉由1,3,3-三(4-羥基苯基)丁烷1mol與1,2-萘醌-2-二疊氮-5-磺醯氯化物2mol之縮合反應合成的化合物QD1: a compound synthesized by condensation of 1 mol of 1,3,3-tris(4-hydroxyphenyl)butane with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonium chloride

QD2：藉由α,α,α’-三(4-羥基苯基)-1-乙基-4-異丙基苯1mol與1,2-萘醌-2-二疊氮-5-磺醯氯化物2mol之縮合反應合成的化合物。QD2: 1 mol of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-diazide-5-sulfonate A compound synthesized by condensation of 2 mol of chloride.

<溶劑><solvent>

PGMEA：丙二醇單甲基醚乙酸酯PGMEA: propylene glycol monomethyl ether acetate

PGME：丙二醇單甲基醚PGME: propylene glycol monomethyl ether

DMAc：N,N-二甲基乙醯胺DMAc: N,N-dimethylacetamide

NMP：N-甲基-2-吡咯烷酮NMP: N-methyl-2-pyrrolidone

下述合成例所得的聚酯、聚醯亞胺先驅物及丙烯酸基共聚物之數平均分子量及重量平均分子量係使用日本分光(股)製GPC裝置(Schodex(登記商標)管柱KF803L及KF804L)，以流量1ml/分使溶出溶劑四氫呋喃流入管柱中(管柱溫度40℃)進行溶離之條件測定。又，下述數平均分子量(以下稱為Mn)及重量平均分子量(以下稱為Mw)係以聚苯乙烯換算值表示。The number average molecular weight and the weight average molecular weight of the polyester, the polyimide precursor, and the acrylic copolymer obtained in the following synthesis examples were measured by a GPC apparatus (Schodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation. The conditions for elution of the eluted solvent tetrahydrofuran into the column at a flow rate of 1 ml/min (column temperature: 40 ° C) were measured. In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<合成例1><Synthesis Example 1>

120℃下於PGMEA 241.96g中使HBPDA 40.0g、BPDA 8.23g、HBPA 49.3g、THPA 5.96g、BTEAC 0.18g、TPPB 0.33g反應17小時，得特定聚合物之溶液(固體成份濃度：30.0質量%)(P1)。所得的特定聚合物之Mn為1,500，Mw為3,430。40.0 g of HBPDA, 8.23 g of BPDA, 49.3 g of HBPA, 5.96 g of BPAAC, 0.18 g of BTEAC, and 0.33 g of TPPB were reacted in PGMEA 241.96 g at 120 ° C for 17 hours to obtain a solution of a specific polymer (solid content concentration: 30.0% by mass). ) (P1). The specific polymer obtained had a Mn of 1,500 and a Mw of 3,430.

<合成例2><Synthesis Example 2>

110℃下於合成例1所得的特定聚合物溶液(P1)252.00g中使GMA 18.42g、DTBC 0.057g、PGME 42.99g反應9小時，得聚酯溶液(固體成份濃度：30.0質量%)(P2)。所得的聚酯之Mn為1,260，Mw為6,880。A total of 18.42 g of GMA, 0.057 g of DTBC, and 42.99 g of PGME were reacted at 252.00 g of the specific polymer solution (P1) obtained in Synthesis Example 1 at 110 ° C for 9 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P2) ). The obtained polyester had an Mn of 1,260 and a Mw of 6,880.

<合成例3><Synthesis Example 3>

110℃下於合成例1所得的特定聚合物溶液(P1)252.00g中使GME 11.16g、PGME 26.05g反應9小時，得聚酯溶液(固體成份濃度：30.0質量%)(P3)。所得的聚酯之Mn為1,450，Mw為5,340。GME 11.16 g and PGME 26.05 g were reacted for 9 hours at 252.00 g of the specific polymer solution (P1) obtained in Synthesis Example 1 at 110 ° C to obtain a polyester solution (solid content concentration: 30.0% by mass) (P3). The obtained polyester had an Mn of 1,450 and a Mw of 5,340.

<合成例4><Synthesis Example 4>

23℃下於PGME 60.15g中使DA-1M 15.14g、THPA 10.64g反應24小時，得含有胺基之羧酸化合物溶液(固體成份濃度30.0質量%)(A1)。使用高速液體色譜法確認所得的含有胺基之羧酸化合物未殘存THPA。DA-1M 15.14 g and THPA 10.64 g were reacted in 60.15 g of PGME at 23 ° C for 24 hours to obtain an amine group-containing carboxylic acid compound solution (solid content concentration: 30.0% by mass) (A1). It was confirmed by high-speed liquid chromatography that the obtained amino group-containing carboxylic acid compound did not have THPA remaining.

<合成例5><Synthesis Example 5>

23℃下於PGME 48.71g中使DA-4P 10.23g、THPA 10.64g反應24小時，得含有胺基之羧酸化合物溶液(固體成份濃度30.0質量%)(A2)。使用高速液體色譜法確認所得的含有胺基之羧酸化合物未殘存THPA。DA23P 10.23 g and THPA 10.64 g were reacted in 48.71 g of PGME at 23 ° C for 24 hours to obtain an amine group-containing carboxylic acid compound solution (solid content concentration: 30.0% by mass) (A2). It was confirmed by high-speed liquid chromatography that the obtained amino group-containing carboxylic acid compound did not have THPA remaining.

<合成例6><Synthesis Example 6>

120℃下於PGMEA 175.7g中使BPDA 40.0g、HBPA 35.3g、THPA 3.31g、BTEAC 0.77g反應19小時，得特定聚合物之溶液(固體成份濃度：30.0質量%)所得的特定聚合物之Mn為1,100，Mw為2,580。110℃下於該特定聚合物之溶液252.00g中使GMA 18.42g、DTBC 0.057g、PGME 42.99g反應9小時，得聚酯溶液(固體成份濃度：30.0質量%)(P4)。所得的聚酯之Mn為1,580，Mw為7,540。40.0 g of BPDA, 35.3 g of HBPA, 3.31 g of THPA, and 0.77 g of BTEAC were reacted in 175.7 g of PGMEA at 120 ° C for 19 hours to obtain a specific polymer Mn obtained by a solution of a specific polymer (solid content concentration: 30.0% by mass). 1,100, Mw is 2,580. GMA 18.42 g, DTBC 0.057 g, and PGME 42.99 g were reacted for 9 hours at 1200.00 g of the specific polymer solution at 110 ° C to obtain a polyester solution (solid content concentration: 30.0% by mass). P4). The obtained polyester had an Mn of 1,580 and a Mw of 7,540.

<合成例7><Synthesis Example 7>

23℃下於NMP 66.4g中使CBDA 17.7g、pDA 10.2g反應24小時，得聚醯亞胺先驅物溶液(固體成份濃度30.0質量%)(P5)。所得的聚醯亞胺先驅物之Mw為5,800，Mw為12,500。CBDA 17.7 g and pDA 10.2 g were reacted in 66.4 g of NMP at 23 ° C for 24 hours to obtain a polyimine precursor solution (solid content concentration: 30.0% by mass) (P5). The obtained polybendimimine precursor had a Mw of 5,800 and a Mw of 12,500.

<合成例8><Synthesis Example 8>

所使用的單體成份為MAA 10.9g、CHMI 35.3g、HEMA 25.5g、MMA 28.3g，所使用的自由基聚合引發劑為AIBN 5g，溫度60℃至100℃下於溶劑PGMEA 150g中使此等聚合反應，得丙烯酸基共聚物溶液(固體成份濃度：40.0質量%)(P6)。所得的丙烯酸基共聚之溶液的Mn為3,800，Mw為6,700。The monomer components used were MAA 10.9 g, CHMI 35.3 g, HEMA 25.5 g, MMA 28.3 g, and the radical polymerization initiator used was AIBN 5 g at a temperature of 60 ° C to 100 ° C in a solvent PGMEA 150 g. The polymerization reaction gave an acrylic-based copolymer solution (solid content concentration: 40.0% by mass) (P6). The obtained acrylic-based copolymerized solution had an Mn of 3,800 and a Mw of 6,700.

<實施例1至5及比較例1至5><Examples 1 to 5 and Comparative Examples 1 to 5>

依表1所示組成調製實施例1至5及比較例1至5之各組成物，再評估自該組成物形成之硬化膜的平坦化性、溶劑耐性、配向性、耐熱性、圖型形成性及透過率。Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was prepared in accordance with the composition shown in Table 1, and the planarization property, solvent resistance, alignment property, heat resistance, and pattern formation of the cured film formed from the composition were evaluated. Sex and transmission rate.

[評估平坦化性][Evaluation of flatness]

使用旋塗機將實施例1至實施例5及比較例1至比較例5之各組成物塗佈於高0.5μm、線幅寬10μm、線間空間50μm之段差基板(玻璃製)後，熱板上以110℃預烤120秒，形成膜厚2.8μm之塗膜。膜厚係使用FILMETRICS公司製F20測定。以230℃加熱該塗膜30分鐘，形成膜厚2.5μm之硬化膜。Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was applied to a stepped substrate (made of glass) having a height of 0.5 μm, a line width of 10 μm, and a line space of 50 μm using a spin coater, followed by heat. The plate was prebaked at 110 ° C 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 coating film was heated at 230 ° C for 30 minutes to form a cured film having a film thickness of 2.5 μm.

測定段差基板線上及空間上之塗膜的膜厚差(參考圖1)，利用平坦化率(DOP)=100×[1-{塗膜之膜厚差(μm)/段差基板之高度(0.5μm)}]式求取平坦化率。The film thickness difference of the coating film on the stepped substrate line and the space is measured (refer to FIG. 1), and the flattening ratio (DOP)=100×[1-{film thickness difference (μm) of the coating film/the height of the step substrate (0.5) The μm)}] formula finds the flattening rate.

[評估圖型形成性][Evaluation of pattern formation]

使用旋塗機將實施例1至實施例5及比較例1至比較例5之各組成物塗佈於玻璃基板後，熱板上以110℃預烤120秒，形成膜厚2.8μm之塗膜。使用FILMETRICS公司製F20測定膜厚。介有具有10μm之線與空間圖型之圖罩，使用佳能(股)製紫外線照射裝置PLA-600FA以100mJ/cm² 照射量將365nm之光強度為5.5mW/cm² 的紫外線照射於該塗膜。其後浸漬於0.2質量%之氫氧化四甲基銨(以下稱為TMAH)水溶液中60秒，再以超純水流水洗淨20秒。使用光學顯微鏡觀察所得的線與空間圖型，結果可得同圖罩設計之圖型者視為○，圖型未解像者及顯像時溶解者視為×。Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was applied onto a glass substrate using a spin coater, and then prebaked at 110 ° C for 120 seconds on a hot plate to form a coating film having a film thickness of 2.8 μm. . The film thickness was measured using F20 manufactured by FILMETRICS. A mask having a line and space pattern of 10 μm was interposed, and ultraviolet light having a light intensity of 5.5 mW/cm ² at 365 nm was irradiated to the coating at a dose of 100 mJ/cm ² using a Canon ultraviolet light irradiation apparatus PLA-600FA. membrane. Thereafter, it was immersed in an aqueous solution of 0.2% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with ultrapure water for 20 seconds. The obtained line and space pattern was observed using an optical microscope, and as a result, the pattern of the pattern design of the mask was regarded as ○, and the pattern undissolved and the dissolved person at the time of development were regarded as ×.

[評估溶劑耐性][Evaluation of Solvent Tolerance]

使用旋塗機將實施例1至實施例5及比較例1至比較例5之各組成物塗佈於矽電路板後，熱板上以100℃預烤120秒，形成膜厚2.8μm之塗膜。使用FILMETRICS公司製F20測定膜厚。其後於熱板上以230℃後烤該塗膜30分鐘，形成膜厚2.5μm之硬化膜。Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was applied to a ruthenium circuit board using a spin coater, and then prebaked at 100 ° C for 120 seconds on a hot plate to form a coating having a film thickness of 2.8 μm. membrane. The film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, the coating film was baked at 230 ° C for 30 minutes on a hot plate to form a cured film having a film thickness of 2.5 μm.

將該硬化膜浸漬於PGMEA或NMP中60秒後，各自以100℃乾燥60秒，再測定膜厚。PGMEA或NMP浸漬後膜厚無變化者視為○，浸漬後膜厚會減少者視為×。The cured film was immersed in PGMEA or NMP for 60 seconds, and then dried at 100 ° C for 60 seconds, and the film thickness was measured. The change in film thickness after PGMEA or NMP immersion is regarded as ○, and the decrease in film thickness after immersion is regarded as ×.

[評估光透過率(透明性)][Evaluating light transmittance (transparency)]

使用旋塗機將實施例1至實施例5及比較例1至比較例5之各組成物塗佈於石英基板後，熱板上以100℃預烤120秒，形成膜厚2.8μm之塗膜。使用FILMETRICS公司製F20測定膜厚。將該塗膜浸漬於0.2質量%之TMAH水溶液中60秒後，以超純水流水洗淨20秒，其後使用佳能(股)製紫外線照射裝置PLA-600FA以500mJ/cm² 照射量照射365nm之光強度為5.5mW/cm² 的紫外線。其後於熱板上以230℃後烤該塗膜30分鐘，形成硬化膜。Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was applied to a quartz substrate by a spin coater, and then prebaked at 100 ° C for 120 seconds on a hot plate to form a coating film having a film thickness of 2.8 μm. . The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was immersed in a 0.2% by mass aqueous TMAH solution for 60 seconds, and then washed with ultrapure water for 20 seconds, and then irradiated with 365 nm at 500 mJ/cm ² using a Canon ultraviolet light irradiation apparatus PLA-600FA. The light intensity is ultraviolet light of 5.5 mW/cm ² . Thereafter, the coating film was baked at 230 ° C for 30 minutes on a hot plate to form a cured film.

使用紫外線可視分光光度計(島津製作所(股)製SHIMADSU UV-2550型號)測定該硬化膜於波長400nm時之透過率。The transmittance of the cured film at a wavelength of 400 nm was measured using an ultraviolet visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation).

[評估配向性][Assessing the alignment]

使用旋塗機將實施例1至實施例5及比較例1至比較例5之各組成物塗佈於ITO基板後，熱板上以100℃預烤120秒，形成膜厚2.8μm之塗膜。使用FILMETRICS公司製F20測定膜厚。其後於熱板上以230℃後烤該膜30分鐘，形成硬化膜。Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was applied onto an ITO substrate by a spin coater, and then prebaked at 100 ° C for 120 seconds on a hot plate to form a coating film having a film thickness of 2.8 μm. . The film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, the film was baked at 230 ° C for 30 minutes on a hot plate to form a cured film.

以回轉速度300rpm、運送速度10mm/秒、擠壓量0.45mm對該硬化膜進行摩擦處理。以純水超音波洗淨摩擦處理後之基板5分鐘。使用旋塗機將液晶單體形成的相位差材料塗佈於該基板後，熱板上以100℃預烤40秒後再以55℃預烤30秒，形成膜厚1.1μm之塗膜。氮環境下以2,000mJ將該基板曝光。以偏向板挾持所得的基板，再以目視確認配向性。將基板傾斜45度時相對於未傾斜時光的透過性會明顯變化者視為○，未變化者視為×。The cured film was subjected to a rubbing treatment at a rotation speed of 300 rpm, a conveyance speed of 10 mm/sec, and a pressing amount of 0.45 mm. The substrate after rubbing treatment was washed with pure water ultrasonic for 5 minutes. The phase difference material formed of the liquid crystal monomer was applied onto the substrate by a spin coater, and then prebaked at 100 ° C for 40 seconds on a hot plate, and then prebaked at 55 ° C for 30 seconds to form a coating film having a film thickness of 1.1 μm. The substrate was exposed at 2,000 mJ in a nitrogen atmosphere. The obtained substrate was held by a deflecting plate, and the alignment property was visually confirmed. When the substrate is tilted by 45 degrees, the transmittance of the light with respect to the non-tilted light is significantly changed as ○, and the unchanged person is regarded as ×.

[評估耐熱性][Evaluation of heat resistance]

使用旋塗機將實施例1至實施例5及比較例1至比較例5之各組成物塗佈於石英基板後，熱板上以100℃預烤120秒，熱板上再以230℃後烤30分鐘，形成硬化膜。使用FILMETRICS公司製F20測定膜厚。其後於熱板上以230℃焙燒硬化膜60分鐘，再測定膜厚，算出後烤後之膜厚變化率。又確認為具有耐熱性之硬化膜的條件較佳為，具有至少膜厚變化率未達±5%之性能。Each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 was applied to a quartz substrate using a spin coater, and then prebaked at 100 ° C for 120 seconds on a hot plate, and then at 230 ° C on a hot plate. Bake for 30 minutes to form a cured film. The film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, the cured film was baked at 230 ° C for 60 minutes on a hot plate, and the film thickness was measured, and the film thickness change rate after baking was calculated. Further, it is preferable that the condition of the cured film having heat resistance is such that the film thickness change rate is at least ±5%.

[評估結果][evaluation result]

上述評估結果如下述表2所示。The above evaluation results are shown in Table 2 below.

實施例1至實施例5可形成圖型，具有較高平坦化率及耐熱性，相對於PGMEA、NMP均具有耐性。又任何一種均具有良好配向性，高溫焙燒後均可達成較高透過率(透明性)。Examples 1 to 5 can be formed into a pattern, have a high flatness and heat resistance, and are resistant to both PGMEA and NMP. Any one of them has a good alignment property, and a high transmittance (transparency) can be achieved after high-temperature baking.

比較例1為，未曝光部也會溶解於顯像液無法形成圖型。In Comparative Example 1, the unexposed portion was also dissolved in the developing liquid and the pattern could not be formed.

比較例2為，曝光部未溶解於顯像液無法形成圖型。In Comparative Example 2, the exposed portion was not dissolved in the developing liquid, and the pattern could not be formed.

比較例3為，耐熱性較低也無法形成圖型。In Comparative Example 3, the heat resistance was low and the pattern could not be formed.

比較例4為，平坦化率較低也無法形成圖型。In Comparative Example 4, the pattern was not formed even if the flattening rate was low.

又，比較例5為，可形成圖型且具有良好的平坦化率、耐熱性、溶劑耐性及透過率，但配向性較差。Further, in Comparative Example 5, the pattern was formed and had a good flatness, heat resistance, solvent resistance, and transmittance, but the alignment was inferior.

如上述般，本發明之熱硬化膜形成用感光性聚酯組成物為，形成硬化膜時可使用丙二醇單甲基醚乙酸酯等二元醇系溶劑。又可以鹼顯像液形成圖型，且所得的硬化膜可得優良的光透過性、溶劑耐性、耐熱性、平坦化性及配向性任何良好性能。As described above, the photosensitive polyester composition for forming a thermosetting film of the present invention may be a glycol-based solvent such as propylene glycol monomethyl ether acetate when the cured film is formed. Further, the alkali developing solution can be formed into a pattern, and the obtained cured film can obtain any excellent properties such as excellent light transmittance, solvent resistance, heat resistance, flatness, and alignment.

[產業上利用可能性][Industry use possibility]

本發明之熱硬化膜形成用感光性聚酯組成物非常適合使用為光學各向異性薄膜及液晶顯示元件之液晶配向層，又適用為薄膜晶體管(TFT)型液晶顯示元件、有機EL元件等各種顯示器中形成保護膜、平坦化膜、絕緣膜等硬化膜之材料，特別是形成TFT型液晶元件之層間絕緣膜、彩色濾光片之保護膜、有機EL元件之絕緣膜等之材料。The photosensitive polyester composition for forming a thermosetting film of the present invention is suitably used as an optically anisotropic film and a liquid crystal alignment layer of a liquid crystal display element, and is also suitable as a thin film transistor (TFT) type liquid crystal display element or an organic EL element. A material for forming a cured film such as a protective film, a planarizing film, or an insulating film in the display, in particular, a material for forming an interlayer insulating film of a TFT-type liquid crystal element, a protective film for a color filter, and an insulating film for an organic EL element.

圖1為，將熱硬化性聚酯組成物塗佈於段差基板時所形成的硬化膜模式圖。Fig. 1 is a schematic view showing a cured film formed when a thermosetting polyester composition is applied to a step substrate.

圖2為，使用先前技術之液晶配向層(a)與使用本發明之熱硬化膜形成用感光性聚酯組成物之液晶配向層(b)的對比模式圖。Fig. 2 is a schematic view showing a comparison between a liquid crystal alignment layer (a) of the prior art and a liquid crystal alignment layer (b) using the photosensitive polyester composition for forming a thermosetting film of the present invention.

Claims

一種熱硬化膜形成用感光性聚酯組成物，其特徵為含有(A)成份、(B)成份、(C)成份及(D)成份，(A)成份：含有下述式(1)所表示的構造單位之聚酯，與由縮水甘油基甲基丙烯酸酯、縮水甘油基丙烯酸酯、甲基縮水甘油醚、乙基縮水甘油醚、烯丙基縮水甘油醚、4-tert-丁基苯基縮水甘油醚、縮水甘油基丙基醚、縮水甘油基-2-甲基苯基醚、縮水甘油基丙基醚、縮水甘油基異丙基醚、縮水甘油基丁基醚、縮水甘油基-tert-丁基醚、2-聯苯縮水甘油醚、縮水甘油基-4-甲氧基苯基醚、甲基異氰酸酯、乙基異氰酸酯、丙基異氰酸酯、異丙基異氰酸酯、丁基異氰酸酯、異丁基異氰酸酯、tert-丁基異氰酸酯、苯基異氰酸酯、2-甲苯醯異氰酸酯、3-甲苯醯異氰酸酯、4-甲苯醯異氰酸酯、1-萘基異氰酸酯、環己基異氰酸酯、苄基異氰酸酯、2-異氰酸酯乙基甲基丙烯酸酯、2-甲氧基苯基異氰酸酯、3-甲氧基苯基異氰酸酯、4-甲氧基苯基異氰酸酯、戊基異氰酸酯及己基異氰酸酯中選出之化合物反應而得的被修飾之聚酯(B)成份：具有2個以上環氧基之環氧化合物(C)成份：二胺化合物與二羧酸二酐反應而得的含有胺基之羧酸化合物(D)成份：1,2-苯醌二疊氮化合物 (式中，A為下述式(1A1)、式(1A2)或(1A3)所表示之基， {式(1A1)、(1A2)及(1A3)中，A¹ 為環狀飽和烴基，R¹ 為單鍵、醚鍵、羰基、磺酸基、碳原子數1至8之飽和烴基或被氟原子取代之碳原子數1至8的飽和烴基，又，R² 為碳原子數1至8之飽和烴基}B為下述式(1B1)或式(1B2)所表示之基) {式(1B1)及(1B2)中，B¹ 為環狀飽和烴基，B² 為伸苯基，又，R³ 為單鍵、醚鍵、羰基、磺酸基、碳原子數1至8 之飽和烴基或被氟原子取代之碳原子數1至8的飽和烴基，R⁴ 、R⁵ 各自獨立為單鍵或碳原子數1至5之伸烷基，R⁶ 、R⁷ 各自獨立為碳原子數1至5之伸烷基，又，k為0或1}。A photosensitive polyester composition for forming a thermosetting film, which comprises (A) component, (B) component, (C) component and (D) component, and (A) component: contains the following formula (1) The structural unit of the polyester represented by glycidyl methacrylate, glycidyl acrylate, methyl glycidyl ether, ethyl glycidyl ether, allyl glycidyl ether, 4-tert-butylbenzene Glycidyl ether, glycidyl propyl ether, glycidyl-2-methylphenyl ether, glycidyl propyl ether, glycidyl isopropyl ether, glycidyl butyl ether, glycidyl group - Tert-butyl ether, 2-biphenyl glycidyl ether, glycidyl-4-methoxyphenyl ether, methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, isobutyl Isocyanate, tert-butyl isocyanate, phenyl isocyanate, 2-toluene isocyanate, 3-toluene isocyanate, 4-toluene isocyanate, 1-naphthyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, 2-isocyanate ethyl Methacrylate, 2-methoxyphenyl Modified polyester (B) obtained by reacting a selected one of cyanate ester, 3-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, pentyl isocyanate and hexyl isocyanate: 2 or more Epoxy group epoxy compound (C) component: amine group-containing carboxylic acid compound (D) obtained by reacting diamine compound with dicarboxylic acid dianhydride: 1,2-benzoquinonediazide compound (wherein A is a group represented by the following formula (1A1), formula (1A2) or (1A3), In the formulae (1A1), (1A2) and (1A3), A ¹ is a cyclic saturated hydrocarbon group, and R ¹ is a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a fluorine atom. a saturated hydrocarbon group having 1 to 8 carbon atoms substituted by an atom, and R ² is a saturated hydrocarbon group having 1 to 8 carbon atoms} B is a group represented by the following formula (1B1) or formula (1B2)) In the formulae (1B1) and (1B2), B ¹ is a cyclic saturated hydrocarbon group, B ² is a phenyl group, and R ³ is a single bond, an ether bond, a carbonyl group, a sulfonic acid group, and a carbon number of 1 to 8. a saturated hydrocarbon group or a saturated hydrocarbon group having 1 to 8 carbon atoms which is substituted by a fluorine atom, and each of R ⁴ and R ^{5 is} independently a single bond or an alkylene group having 1 to 5 carbon atoms, and R ⁶ and R ⁷ are each independently a carbon atom. The alkyl group is 1 to 5, and k is 0 or 1}.

如申請專利範圍第1項之熱硬化膜形成用感光性聚酯組成物，其中前述含有式(1)所表示的構造單位之聚酯為，使含有下述式(i)所表示的四羧酸二酐之四羧酸二酐成份，與含有下述式(ii)所表示的二醇化合物之二醇成份反應而得的聚酯， {式(i)及(ii)中，A及B同前述式(1)之定義}。The photosensitive polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the polyester containing the structural unit represented by the formula (1) is a tetracarboxylic acid represented by the following formula (i) a polyester obtained by reacting a tetracarboxylic dianhydride component of an acid dianhydride with a diol component containing a diol compound represented by the following formula (ii), {In the formulas (i) and (ii), A and B are the same as defined in the above formula (1)}.

如申請專利範圍第1項之熱硬化膜形成用感光性聚酯組成物，其中前述式(1)中，A為下述式(A-1)至(A-8)所表示之基中選出的至少一種基，B為下述式(B-1)至(B-5)所表示之基中選出的至少一種基， The photosensitive polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein in the formula (1), A is selected from the groups represented by the following formulas (A-1) to (A-8). At least one group, B is at least one selected from the group represented by the following formulas (B-1) to (B-5),

如申請專利範圍第1項之熱硬化膜形成用感光性聚酯組成物，其中前述(A)成份之被修飾的聚酯為，具有聚苯乙烯換算下1,000至30,000之重量平均分子量。 The photosensitive polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the modified polyester of the component (A) has a weight average molecular weight of 1,000 to 30,000 in terms of polystyrene.

如申請專利範圍第1項之熱硬化膜形成用感光性聚酯組成物，其中前述(C)成份為，二胺化合物1莫耳與二羧酸二酐1.7至2莫耳反應而得的含有胺基之羧酸化合物。 The photosensitive polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (C) is a component obtained by reacting a diamine compound 1 molar with a dicarboxylic dianhydride of 1.7 to 2 mol. Amino-based carboxylic acid compound.

如申請專利範圍第1項之熱硬化膜形成用感光性聚酯組成物，其中基於前述(A)成份100質量份，各自含有3至50質量份之前述(B)成份、3至50質量份之前述(C)成份、5至80質量份之前述(D)成份。 The photosensitive polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (B) is contained in an amount of 3 to 50 parts by mass, and 3 to 50 parts by mass, based on 100 parts by mass of the component (A). The above (C) component, 5 to 80 parts by mass of the above (D) component.

如申請專利範圍第1項之熱硬化膜形成用感光性聚酯組成物，其中另含有(E)成份用之雙馬來醯亞胺化合物。 The photosensitive polyester composition for forming a thermosetting film according to the first aspect of the invention, which further comprises a bismaleimide compound for the component (E).

如申請專利範圍第6項之熱硬化膜形成用感光性聚酯組成物，其中基於前述(A)成份100質量份，含有0.5至50質量份之如申請專利範圍第7項之(E)成份。 The photosensitive polyester composition for forming a thermosetting film according to the sixth aspect of the invention, wherein the component (E) is contained in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the component (A). .

一種硬化膜，其特徵為自如申請專利範圍第1至8項中任何一項之熱硬化膜形成用感光性聚酯組成物形成。 A cured film which is formed by a photosensitive polyester composition for forming a thermosetting film according to any one of claims 1 to 8.

一種液晶配向層，其特徵為使用如申請專利範圍第1至8項中任何一項之熱硬化膜形成用感光性聚酯組成物而得。 A liquid crystal alignment layer obtained by using a photosensitive polyester composition for forming a thermosetting film according to any one of claims 1 to 8.